WO2010018749A1 - Système de cylindre refroidisseur et procédé de fabrication d’une membrane microporeuse - Google Patents

Système de cylindre refroidisseur et procédé de fabrication d’une membrane microporeuse Download PDF

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Publication number
WO2010018749A1
WO2010018749A1 PCT/JP2009/063455 JP2009063455W WO2010018749A1 WO 2010018749 A1 WO2010018749 A1 WO 2010018749A1 JP 2009063455 W JP2009063455 W JP 2009063455W WO 2010018749 A1 WO2010018749 A1 WO 2010018749A1
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WO
WIPO (PCT)
Prior art keywords
extrudate
rolls
roll
pair
membrane
Prior art date
Application number
PCT/JP2009/063455
Other languages
English (en)
Inventor
Kotaro Takita
Koichi Kono
Hiroshige Kuzuno
Tetsuro Nogata
Original Assignee
Tonen Chemical Corporation
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Publication date
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Priority to JP2011503692A priority Critical patent/JP5639578B2/ja
Publication of WO2010018749A1 publication Critical patent/WO2010018749A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0083—Thermal after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/002—Organic membrane manufacture from melts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/26—Polyalkenes
    • B01D71/261—Polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/26—Polyalkenes
    • B01D71/262—Polypropylene
    • 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
    • B29C48/04—Particle-shaped
    • 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
    • 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
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/91—Heating, e.g. for cross linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/42—Details of membrane preparation apparatus
    • 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
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/30—Extrusion nozzles or dies
    • B29C48/305—Extrusion nozzles or dies having a wide opening, e.g. for forming sheets
    • 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
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/911—Cooling
    • B29C48/9135—Cooling of flat articles, e.g. using specially adapted supporting means
    • B29C48/914—Cooling of flat articles, e.g. using specially adapted supporting means cooling drums
    • 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
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B29K2023/0608—PE, i.e. polyethylene characterised by its density
    • B29K2023/065—HDPE, i.e. high density polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B29K2023/0658—PE, i.e. polyethylene characterised by its molecular weight
    • B29K2023/0683—UHMWPE, i.e. ultra high molecular weight polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/10—Polymers of propylene
    • B29K2023/12—PP, i.e. polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/25—Solid
    • B29K2105/253—Preform
    • B29K2105/256—Sheets, plates, blanks or films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/755—Membranes, diaphragms

Definitions

  • This disclosure relates generally to a system and method for producing microporous membranes, such as those useful as battery separators.
  • Microporous membranes are useful as separators for primary batteries and secondary batteries such as lithium ion secondary batteries, lithium-polymer secondary batteries, nickel-hydrogen secondary batteries, nickel-cadmium secondary batteries, nickel-zinc secondary batteries, silver- zinc secondary batteries, etc.
  • secondary batteries such as lithium ion secondary batteries, lithium-polymer secondary batteries, nickel-hydrogen secondary batteries, nickel-cadmium secondary batteries, nickel-zinc secondary batteries, silver- zinc secondary batteries, etc.
  • the membrane's characteristics such as flatness and thickness uniformity, significantly affects the properties, productivity and safety of the battery.
  • the aim is to provide a microporous membrane having well-balanced characteristics, where the term "well-balanced" means that the optimization of one membrane characteristic does not result in a significant degradation in another.
  • Microporous polymeric membranes can be produced according to a wet process, where at least one polymer (such as one or more polyolef ⁇ n) and at least one diluent (or solvent) are combined to form a polymeric solution which is then extruded to form an extrudate. The extrudate is then stretched in at least one planar direction. Following stretching, at least a portion of the diluent is removed from the stretched extrudate to form the membrane. Additional steps such as membrane drying, further stretching, thermal treatments, etc. can be used downstream of the diluent removal step. Examples of references disclosing conventional wet processing include U.S. Patent No. 5,051,183, U.S. Patent No.
  • U.S. Patent No. 5,830,554 discloses cooling the extrudate before stretching. The reference discloses that while it is desirable to regulate cooling rate to control membrane pore diameters, cooling at a rate of less than 50°C per minute is said to result in a loss of thickness uniformity, i.e., the extrudate becomes rough.
  • U.S. Patent No. 4,734,196 discloses a method for producing a relatively uniform microporous film from ultra-high-molecular-weight alpha-olefin polymer having a weight-average molecular weight greater than 5x10 5 .
  • the microporous membrane is obtained by forming a gel-like object from a solution of an alpha-olefin polymer having a weight-average molecular weight greater than 5x10 5 , removing at least 10 wt.% of the solvent contained in the gel-like object so that the gel-like object contains 10 to 90 wt.% of alpha-olefin polymer, orientating the gel-like object at a temperature lower than that which is 10°C above the melting point of the alpha-olefin polymer, and removing the residual solvent from the orientated product.
  • a film is produced from the orientated product by pressing the orientated product at a temperature lower than that of the melting point of the alpha-olefin polymer, to provide a relatively uniform product.
  • U.S. Patent Publication No. 2007/0012617 proposes a method for producing a microporous thermoplastic resin membrane comprising the steps of extruding a solution obtained by melt-blending a thermoplastic resin and a membrane- forming solvent through a die, cooling an extrudate to form a gel-like molding, removing the membrane-forming solvent from the gel-like molding by a washing solvent, and then removing the washing solvent.
  • the molten polymer is fed into a first inlet at an end of a first manifold and a second inlet at the end of a second manifold on the opposite side of the first inlet.
  • Two slit currents flow together inside the die. It is theorized that due to the absence of flow divergence of the melt inside the manifold, it may be possible to achieve uniform flow distribution within the die. This is said to result in improved thickness uniformity in the transverse direction of the film or the sheet.
  • the invention relates to an assembly for transferring heat from a molten extrudate comprising polymers and diluent, said assembly comprising: a) first and second rolls positioned to receive opposite surfaces of the extrudate, said first roll contacting the extrudate along an arcuate path traversing first contact angle ⁇ 100° and said second roll contacting the extrudate along an arcuate path traversing a second contact angle ⁇ 100°; and b) a third roll downstream of the first and second rolls, said first, second, and third rolls being aligned so that said third roll receives the extrudate from at least one of the first and second rolls, said third roll contacting the extrudate along an arcuate path traversing a third contact angle to form a cooled extrudate.
  • the third roll contacts the extrudate along an arcuate path of 180° or more. In other embodiments, the third roll contacts the extrudate along an arcuate path traversing a third contact angle of 90° to 180°, preferably 100° to 150°, more preferably 110° to 130°.
  • the rolls act to transfer heat away from the extrudate, they can be referred to as "chill rolls", particularly when the rolls comprise cooling means.
  • the invention relates to a process for producing a microporous membrane comprising: a) combining polyolefin and diluent; b) extruding the combined polyolefin and diluent through an extrusion die to form an extrudate; c) transferring heat from the extrudate through a plurality of rolls to form a cooled extrudate, the plurality of rolls comprising i) first and second rolls positioned to receive opposite surfaces of the extrudate, the first roll contacting the extrudate along an arcuate path traversing a first contact angle ⁇ 100° and the second roll contacting the extrudate along an arcuate path traversing a second contact angle ⁇ 100°; and ii) a third roll downstream of the first and second rolls, the first, second, and third rolls aligned so that the
  • FIG. 1 is a schematic view of one form of a system for producing an oriented film or sheet of thermoplastic material, in accordance herewith;
  • FIG. 2 is a side view of a chill roll assembly for transferring heat from an extrudate formed by extruding a polyolefin solution through an extrusion die, in accordance herewith.
  • Increasing thickness uniformity of the extrudate results in improved processing and yield since, e.g., there are fewer comparatively thin regions of the film that would otherwise pose a risk of tearing during downstream stretching operations. Moreover, greater thickness uniformity of the extrudate results in a finished membrane having improved thickness uniformity, which decreases the need for slitting the membrane along the machine direction to remove abnormally thick or thin regions of the membrane.
  • FIG. 1 shows a system 10 for producing a microporous membrane of thermoplastic material.
  • System 10 includes an extruder 12, extruder 12 having a feed hopper 15 for receiving one or more polymeric materials, processing additives, or the like, fed by a line 14.
  • Extruder 12 also receives a diluent, such as paraffin oil, through a solvent feedline 16.
  • a mixture of polymer and diluent is prepared within extruder 12 by combining the polymer and diluent with heating and mixing.
  • an assembly for transferring heat from an extrudate 100 includes at least one pair of upstream rolls 102 positioned to receive the extrudate 18.
  • each of the at least one pair of upstream rolls 102 may have a diameter of less than about 200 mm, e.g., in the range of 50 mm to 150 mm.
  • At least one pair of upstream rolls 102 includes a first roll 104 and a second roll 106.
  • Assembly 100 also includes at least one downstream roll 114.
  • the at least one pair of upstream rolls 102 and the at least one downstream (or "third") roll 114 are aligned so that the at least one downstream roll 114 receives the extrudate 18 from the at least one pair of upstream rolls 102.
  • the at least one downstream roll 114 has a diameter greater than or equal to about 250 mm, e.g., in the range of 275 mm to 400 mm.
  • each of the at least one pair of upstream rolls 102 has a diameter ⁇ about 150 mm or ⁇ about 100 mm.
  • assembly 100 may also include a second pair of upstream rolls 108.
  • the second pair of upstream rolls 108 includes a first roll 110 and a second roll 112.
  • the second pair of upstream rolls 108 may be positioned downstream of the at least one pair of upstream rolls 102 and upstream of the downstream roll 114.
  • each of the second pair of upstream rolls 108 has a diameter of ⁇ about 200 mm, e.g., in the range of 50 mm to 150 mm.
  • each of the second pair of upstream rolls 108 has a diameter ⁇ about 100 mm.
  • the rolls of the first pair of upstream rolls can have equal diameters.
  • the rolls of the second pair of upstream rolls can have equal diameter, and the diameter is optimally the same as the diameter selected for the first pair of upstream rolls.
  • the rolls constituting the first and second pair of upstream rolls are all of the same diameter and contact the extrudate along arcuate paths of equal contact angle.
  • the cooled extrudate 18' can be conducted to a first orientation apparatus 24, which may be a roll-type stretching machine, as shown.
  • the cooled extrudate 18' is oriented with heating in the machine direction (MD) through the use of the roll-type stretching machine 24 or, optionally, through the use of a tenter-type stretching machine (not shown) and then the cooled extrudate 18' may optionally pass to a second orientation apparatus 26, for orientation in at least the transverse direction (TD), to produce an oriented film or sheet 18".
  • Second orientation apparatus 26 may be a tenter-type stretching machine and may be utilized for further stretching in the MD.
  • the cooled extrudate (or optionally the oriented film or sheet 18") next passes to a solvent extraction device 28 where a readily volatile solvent such as methylene chloride is fed in through line 30.
  • the volatile solvent contacts the extrudate to remove at least a portion of the diluent from the extrudate.
  • the volatile solvent containing extracted diluent (generally a nonvolatile solvent) is recovered from a solvent outflow line 32.
  • the oriented film or sheet 18" next passes to a drying device 34, wherein at least a portion of any remaining volatile species (e.g., the volatile solvent 36) are evaporated from the oriented film or sheet 18".
  • the oriented film or sheet 18" next passes to dry orientation device 38 where the dried membrane is stretched to a magnification of from about 1.1 to about 2.5 fold in at least one direction to form a stretched membrane.
  • the oriented film or sheet 18" passes to the heat treatment device 44 where the oriented film or sheet 18" is annealed so as to adjust porosity and remove stress left in the film or sheet 18", after which oriented film or sheet 18" is rolled up to form product roll 48.
  • FIG. 2 another form of an assembly 200 for transferring heat from an extrudate 18 formed by extruding a polyolefin solution through an extrusion die 20 is shown.
  • Assembly 200 includes at least one support frame 220 and at least one pair of upstream rolls 202 positioned to receive the extrudate 18.
  • Each of the at least one pair of upstream rolls 202 generally has a diameter of less than or equal to about 150 mm.
  • the at least one pair of upstream rolls 202 includes a first roll 204 and a second roll 206 mounted on the at least one support frame 220 and positioned to contact and receive the extrudate 18.
  • each of the at least one pair of upstream rolls 102 has a diameter less than or equal to about 125 mm or less than or equal to about 100 mm.
  • assembly 200 may also include a second pair of upstream rolls 208.
  • the second pair of upstream rolls 208 includes a first roll 210 and a second roll 212.
  • the second pair of upstream rolls 208 may be positioned downstream of the at least one pair of upstream rolls 202 and upstream of the downstream roll 214.
  • each of the second pair of upstream rolls 208 has a diameter of less than about 250 mm.
  • Assembly 200 also includes at least one downstream roll 214 mounted on the at least one support frame 220.
  • the at least one pair of upstream rolls 202 and the at least one downstream roll 214 are aligned so that the at least one downstream roll 214 receives the extrudate 18 from the at least one pair of upstream rolls 202.
  • the at least one downstream roll 214 has a diameter > about 250 mm.
  • the assembly 200 may also include a second downstream roll 222 mounted on the at least one support frame 220 and positioned so as to contact and receive the extrudate 18 from the at least one downstream roll 214. Additional optional downstream rolls 224 and 226 may also be provided.
  • the second downstream roll 214 has a diameter > about 300 mm.
  • chill roll assembly 200 further includes one or more drive motors 230 mounted on support frame 220 and associated with the at least one pair of upstream rolls 202 and the second pair of upstream rolls 208, if provided.
  • One or more drive motors 232 may be provided to rotate the at least one downstream roll 214 and the second downstream roll 222, if provided, through the use, for example of gear box 234.
  • One or more drive motors 236 may be provided to rotate the additional downstream rolls 224 and 226, if provided, through the use, for example of a chain drive mechanism 238, or a gear box (not shown).
  • the drive mechanisms cause extrudate 18 to move through the assembly 200 in contact with the at least one pair of upstream rolls 202 and the at least one downstream roll 214.
  • the drive means may include a plurality of motors 216 that drive a plurality of gears 218 through a chain and sprocket arrangement, as those skilled in the art will plainly recognize.
  • only the at least one downstream roll 214 is driven in rotation.
  • additional rolls may be driven.
  • the rolls can be driven by a single drive, e.g., using suitable linkages, or, alternatively, second, third, fourth, etc. drives can be used. When two or more rolls have independent drives, the drives are generally synchronized to reduce the risk of extrudate tearing.
  • assembly 200 can further include a cooling means associated with the at least one pair of upstream rolls 202 and the at least one downstream roll 214 for cooling extrudate 18.
  • the cooling means may include a plurality of pumps (not shown) to circulate a coolant through one or more cooling circuits (not shown), the cooling circuits in fluid communication with the at least one pair of upstream rolls 202 and the at least one downstream roll 214, each of which have internal passages for circulating coolant and transfer heat from extrudate 18.
  • the upstream and downstream rolls have associated cooling means.
  • the at least one pair of upstream rolls 202 or the at least one downstream roll 214 can comprise cooling means.
  • the second downstream roll 222 can comprise cooling means and can be driven in rotation by drive means.
  • extrudate 18 moves in arcuate paths around the at least one pair of upstream rolls 202 and the at least one downstream roll 214 and in linear paths between the at least one pair of upstream rolls 202 and the at least one downstream roll 214.
  • the pair of upstream rolls have equal diameters in the range of 50 mm to 150 mm, or 75 mm to 125 mm
  • the downstream roll has a diameter in the range of 275 mm to 400 mm.
  • the opposite surfaces of the extrudate contact the upstream rolls along equal arcuate paths traversing a contact angle (as measured along the circumference of the roll from the point where the extrudate first contacts the roll to the point where the extrudate exits the roll) in the range of 55° to 75°, and at least one surface of the extrudate contacts the downstream roll along an arcuate path traversing a contact angle in the range of 120° to 250°, e.g. in the range of 190° to 220°.
  • the opposite surfaces of the extrudate contact the upstream rolls along equal arcuate paths traversing a contact angle in the range of 60° to 70°, and at least one surface of the extrudate contacts the downstream roll along an arcuate path traversing a contact angle in the range of 195° to 205°.
  • These paths may be seen in FIG. 2, where extrudate 18 is shown as a solid line.
  • the at least one pair of upstream rolls 202 can be positioned closely adjacent to each other to define a nip therebetween.
  • a nip roll can be used to increase friction to prevent slippage or movement of the sheet over the roll surface.
  • a gap is established between the first upstream roll 204 and the second upstream roll 206, the gap being equal to or less than thickness of the sheet.
  • the at least one downstream roll 214 may be provided with a relatively rough surface, to produce a relatively large frictional force capable of conveying the sheet through the apparatus 200. Consequently, the use of one or more nip rolls is optional.
  • a gap between first upstream roll 204 and second upstream roll 206 is more than sheet thickness of 1.05 times or more, or 2 to 200 times, or 4 to 100 times. [0034] As indicated above and shown in FIG. 2, a plurality of tandemly-disposed rolls are employed.
  • This multi-stage operation compared to a more conventional; one- stage operation, provides the advantages of uniform cooling on both surfaces of the extrudate, while keeping the extrudate adhered onto the entire surface of the roll. This despite the fact lower tension may be employed, thus minimizing distortion and warping of the extrudate, resulting in improved thickness uniformity in the extrudate and finished membrane. [0035] In operation, a significant amount but less than all of the cooling solidification process is conducted using the upstream chill roll.
  • the extrudate It is generally desired to cool the extrudate from the temperature of the extrudate at the downstream end of the extrusion die (generally at or near the die lip) "T d " until the extrudate reaches its gelation temperature (i.e., the temperature at which the extrudate sheet begins to gel) "Tg" or lower.
  • the average temperature T on the surface of the extrudate following the upstream roll is T g or lower (cooler).
  • the roll assembly has three rolls, e.g., one pair of upstream rolls and the one downstream roll.
  • the extrudate conducted away from the die lip has a surface temperature Ti in the range of 200°C to 235°C.
  • the extrudate conducted away from the upstream rolls has a surface temperature T 2 that is cooler than T 1 , with T 2 in the range of 25°C to 120°C, e.g., 65°C to 115°C.
  • the extrudate conducted away from the downstream roll has a surface temperature T 3 that is less than T 2 , with T 3 in the range of 20°C to 100°C.
  • the temperature reduction (Ti - T 3 ) can be represented by the parameter ⁇ Ti -3 .
  • T 2 is equal to KATi -3 , where K is a multiplicative constant in the range of 40% to 95%, or 45% to 85%, or 50% to 75%.
  • K is a multiplicative constant in the range of 40% to 95%, or 45% to 85%, or 50% to 75%.
  • T c is the average surface temperature of the extrudate conducted away from the pair of upstream rolls.
  • T c is the polyethylene' s crystallization temperature.
  • the films and sheets disclosed herein find particular utility in the critical field of battery separators, e.g., in lithium ion primary and secondary batteries. Such batteries are useful as power sources for, e.g., electric vehicles and hybrid electric vehicles.
  • the films and sheets disclosed herein provide a good balance of key properties, including improved surface smoothness and thickness uniformity.
  • the starting material contains polyethylene.
  • the starting materials contain a first polyethylene (“PE-I”) having an Mw value of less than about 1 x 10 6 or a second polyethylene (“PE-2”) having an Mw value of at least about 1 x 10 6 .
  • the starting materials can contain a first polypropylene ("PP-I").
  • the starting materials comprise one or more of (i) PE-I (PE), (ii) PE-2, (iii) PE-I and PP-I, (iv) PE-I, PE-2, and PP-I, or (v) PE-I and PE-2.
  • the PE-2 can have an Mw in the range of from about 1 x 10 6 to about 15 x 10 6 or from about 1 x 10 6 to about 5 x 10 6 or from about 1 x 10 6 to about 3 x 10 6 .
  • the amount of PE-2 can be in the range of about 0 wt.% to about 40 wt.%, or about 1 wt.% to about 30 wt.%, or about 1 wt.% to 20 wt.%, on the basis of total amount of PE-I and PE-2 in order to obtain a film or sheet having a hybrid structure as hereinafter defined.
  • the PE-2 can be at least one of homopolymer or copolymer.
  • PP-I can be at least one of a homopolymer or copolymer, or can contain no more than about 50 wt.%, on the basis of the total amount of the microporous film or sheet material.
  • the Mw of polyolefin in the microporous film or sheet material can be about 1.5 x 10 6 or less, or in the range of from about 1.0 x 10 5 to about 2.0 x 10 6 or from about 2.0 x 10 5 to about 1.5 x 10 6 in order to obtain a microporous film or sheet having a hybrid structure defined in the later section.
  • PE-I can have an Mw in the range of from about 1 x 10 4 to about 9 x 10 5 , or from about 2 x 10 5 to about 8 x 10 5 , and can be one or more of a high-density polyethylene, a medium-density polyethylene, a branched low- density polyethylene, or a linear low-density polyethylene, and can be at least one of a homopolymer or copolymer.
  • the PE-2 can be an ultra-high molecular weight polyethylene having an Mw in the range of 1 x 10 6 to 2.5 x 10 6 , or 1.5 x 10 6 to 2 x 10 6 .
  • the PP-I can be, for example, one or more of (i) a propylene homopolymer or (ii) a copolymer of propylene and a fifth olefin.
  • the copolymer can be a random or block copolymer.
  • the fifth olefin can be, e.g., one or more of ⁇ -olefins such as ethylene, butene-1, pentene-1, hexene-1, 4-methylpentene-l, octene-1, vinyl acetate, methyl methacrylate, and styrene, etc.; and diolefins such as butadiene, 1,5- hexadiene, 1,7-octadiene, 1 ,9-decadiene, etc.
  • the amount of the fifth olefin in the copolymer may be in a range that does not adversely affect the properties of the microporous membrane such as heat resistance, compression resistance, heat shrinkage resistance, etc.
  • the amount of the fifth olefin can be less than 10% by mol, based on 100% by mol, of the entire copolymer.
  • the polypropylene has one or more of the following properties: (i) the polypropylene has an Mw ranging from about 1 x 10 4 to about 4 x 10 6 , or about 3 x 10 5 to about 3 x 10 6 , or about 6 x 10 5 to about 1.5 x 10 6 , (ii) the polypropylene has an Mw/Mn ranging from about 1.01 to about 100, or about 1.1 to about 50, or about 3 to about 30; (iii) the polypropylene's tacticity may be isotactic; (iv) the polypropylene may have a heat of fusion of at least about 90 Joules/gram or about 100 J/g to 120 J/g; (v) the polypropylene may have a melting peak (second melt) of at least about 160°C, (vi) the polypropylene
  • the microporous film or sheet has a hybrid structure, which is characterized by a pore size distribution exhibiting relatively dense domains having a main peak in a range of 0.01 ⁇ m to 0.08 ⁇ m and relatively coarse domains exhibiting at least one sub-peak in a range of more than 0.08 ⁇ m to 1.5 ⁇ m or less in the pore size distribution curve.
  • the ratio of the pore volume of the dense domains (calculated from the main peak) to the pore volume of the coarse domains (calculated from the sub-peak) is not critical, and can range, e.g., from about 0.5 to about 49.
  • the microporous film or sheet material can optionally contain one or more additional polyolefins, identified as the seventh polyolefin, which can be, e.g., one or more of polybutene-1, polypentene-1, poly-4-methylpentene-l, polyhexene-1, polyoctene-1, polyvinyl acetate, polymethyl methacrylate, polystyrene and an ethylene ⁇ -olefin copolymer (except for an ethylene-propylene copolymer) and can have an Mw in the range of about 1 x 10 4 to about 4 x 10 6 .
  • additional polyolefins identified as the seventh polyolefin, which can be, e.g., one or more of polybutene-1, polypentene-1, poly-4-methylpentene-l, polyhexene-1, polyoctene-1, polyvinyl acetate, polymethyl methacrylate, polystyrene and an ethylene
  • the microporous film or sheet material can further comprise a polyethylene wax, e.g., one having an Mw in the range of about 1 x 10 3 to about 1 x 10 4 .
  • a process for producing a monolayer microporous membrane includes the steps of combining a polyolefin composition and a solvent or diluent to form a polyolefin solution, the polyolefin composition comprising at least a first polyethylene having a crystal dispersion temperature (T Cd ) and polypropylene, extruding the polyolefin solution through an extrusion die to form an extrudate.
  • T Cd crystal dispersion temperature
  • the membrane can be a monolayer membrane, for example.
  • the extrudate is cooled by transferring heat from the extrudate through a plurality of rolls to form a cooled extrudate, the plurality of rolls comprising i) at least one pair of upstream rolls positioned to receive the extrudate, each of the at least one pair of upstream rolls contacting the extrudate along an arcuate path traversing a contact angle of 100° or less, and ii) at least one downstream roll, the at least one pair of upstream rolls and the at least one downstream roll being aligned so that the at least one downstream roll receives the extrudate from the at least one pair of upstream rolls, the at least one downstream roll contacting the extrudate along an arcuate path traversing a contact angle of 180° or more, orienting the cooled extrudate in at least one direction by about two to about 400 fold at a temperature of about T C(1 to T m + 10°C, and removing at least a portion of diluent from the cooled extrudate to form a membrane.
  • the microporous polyolefin membrane is a two-layer membrane.
  • the microporous polyolefin membrane has at least three layers.
  • Such membranes and production methods are described, for example, in PCT Patent Application WO 2008/016174, which is incorporated by reference in its entirety.
  • the production of the microporous polyolefin membrane will be mainly described in terms of two-layer and three-layer membranes, although those skilled in the art will recognize that the same techniques can be applied to the production of membranes or membranes having at least four layers.
  • the three-layer microporous polyolefin membrane comprises first and third microporous layers constituting the outer layers of the microporous polyolefin membrane and a second layer situated between (and optionally in planar contact with) the first and third layers.
  • the first and third layers are produced from the first polyolefin solution and the second (or inner) layer is produced from the second polyolefin solution.
  • the first and third layers are produced from the second polyolefin solution and the second layer is produced from the first polyolefin solution.
  • the first method for producing a multi-layer membrane comprises the steps of (1) combining (e.g., by melt-blending) a first polyolefin composition and diluent to prepare a first mixture, (2) combining a second polyolefin composition and a second diluent to prepare a second mixture, (3) extruding the first and second mixtures through at least one die to form an extrudate, (4) transferring heat from the extrudate through a plurality of chill rolls to form a cooled extrudate, e.g., a multi-layer, gel-like sheet, the plurality of chill rolls comprising i) at least one pair of upstream rolls positioned to receive the extrudate, each of the at least one pair of upstream rolls contacting the extrudate along an arcuate path traversing a contact angle of 100° or less, and ii) at least one downstream roll, the at least one pair of upstream rolls and the at least one downstream roll being aligned so that the at least one downstream roll receives
  • An optional stretching step (6) and an optional hot solvent treatment step (7), etc. can be conducted between steps (4) and (5), if desired.
  • an optional step (8) of stretching a multi-layer, microporous membrane, an optional heat treatment step (9), an optional cross-linking step with ionizing radiation (10), and an optional hydrophilic treatment step (11), etc. can be conducted if desired.
  • the order of the optional steps is not critical.
  • polyolefin e.g., a composition of at least one polyolefin species optionally containing other non-polyolefin or non-polymeric species
  • polyolefin resins as described above are combined, e.g., by dry mixing or melt blending with an appropriate diluent (e.g., a solvent such as liquid paraffin) to produce the first mixture.
  • an appropriate diluent e.g., a solvent such as liquid paraffin
  • the first mixture (which can be described as a solution, slurry, etc.) can contain various additives such as one or more antioxidant, fine silicate powder (pore-forming material), etc., provided these are used in a concentration range that does not significantly degrade the desired properties of the multi-layer, microporous membrane.
  • the first polyolefin composition contains PE-I, and optionally PE-2 and/or PP-I.
  • the amount of PE-I in the first polyolefin composition can be in the range of from 1 wt.% to 100 wt.%
  • the amount of PE-2 in the first polyolefin composition can be in the range of from 0 wt.% to 99 wt.%
  • the amount of PP-I in the first polyolefin composition can be in the range of from 0 wt.% to 80 wt.%, based on the weight of the first polyolefin composition.
  • the amount of PE-I can be in the range of from 1 wt.% to 100 wt.%, the amount of PE-2 can be in the range of from 0 wt.% to 99 wt.%, and the amount of PP-I can be in the range of 0 wt.% to 80 wt.%, based on the weight of the second polyolefin composition.
  • the first and second diluent may be a solvent for polyolefin, e.g., a solvent that is liquid at room temperature.
  • a solvent for polyolefin e.g., a solvent that is liquid at room temperature.
  • Conventional solvents can be used, such as those described in WO 2008/016174.
  • the resins, etc., used to produce the first polyolefin composition are dry mixed or melt-blended in, e.g., a double screw extruder or mixer before they are combined with the solvent or diluent. Conventional mixing, melt-blending, dry mixing, etc. conditions can be used, such as those described in WO 2008/016174.
  • the amount of the first polyolefin composition in the first polyolefin solution is not critical.
  • the amount of first polyolefin composition in the first mixture can range from about 1 wt.% to about 75 wt.%, based on the weight of the polyolefin solution, for example from about 20 wt.% to about 70 wt.%.
  • the amount of the first polyethylene in the first mixture is not critical, and can be, e.g., 1-50% by mass, or 20-40% by mass, per 100% by mass of the first mixture.
  • the second mixture can be prepared by the same methods used to prepare the first mixture.
  • the second diluent can be selected from among the same diluents as the first diluent. And while the second diluent can be (and generally is) selected independently of the first diluent, the second diluent can be the same as the first diluent, and can be used in the same relative concentration as the first diluent is used in the first mixture.
  • the second polyolefin composition is generally selected independently of the first polyolefin composition.
  • the second polyolefin composition can comprise, e.g., the second polyethylene and/or the second polypropylene resin.
  • the first mixture is conducted from a first extruder to a first die and the second mixture is conducted from a second extruder to a second die.
  • a layered extrudate in sheet form i.e., a body significantly larger in the planar directions than in the thickness direction
  • the first and second mixtures are co-extruded from the first and second die with a planar surface of a first extrudate layer formed from the first mixture in contact with a planar surface of a second extrudate layer formed from the second mixture.
  • a planar surface of the extrudate can be defined by a first vector in the machine direction of the extrudate and a second vector in the transverse direction of the extrudate.
  • a die assembly is used where the die assembly comprises the first and second die, as for example when the first die and the second die share a common partition between a region in the die assembly containing the first mixture and a second region in the die assembly containing the second mixture.
  • a plurality of dies is used, with each die connected to an extruder for conducting either the first or second mixture to the die.
  • the first extruder containing the first mixture is connected to a first die and a third die and a second extruder containing the second mixture is connected to a second die.
  • the resulting layered extrudate can be co- extruded from the first, second, and third die (e.g., simultaneously) to form a three-layer extrudate comprising a first and a third layer constituting surface layers (e.g., top and bottom layers) produced from the first mixture; and a second layer constituting a middle or intermediate layer of the extrudate situated between and in planar contact with both surface layers, where the second layer is produced from the second mixture.
  • the same die assembly is used but with the mixtures reversed, i.e., the second extruder containing the second mixture is connected to the first die and the third die, and the first extruder containing the first mixture is connected to the second die.
  • die extrusion can be conducted using conventional die extrusion equipment, e.g., those disclosed in WO 2008/016174.
  • extrusion has been described in terms of forms producing two and three-layer extrudates, the extrusion step is not limited thereto.
  • a plurality of dies and/or die assemblies can be used to produce multi-layer extrudates having four or more layers using the extrusion methods of the preceding forms.
  • each surface or intermediate layer can be produced using either the first mixture and/or the second mixture.
  • the multi-layer extrudate can be formed into a cooled extrudate, e.g., a multi-layer, gel-like sheet, by cooling, for example. Cooling rate and cooling temperature are not particularly critical. In one form, the multi-layer, gel-like sheet can be cooled at a cooling rate of at least about 10°C/minute until the temperature of the multi-layer, gel-like sheet (the cooling temperature) is approximately equal to the multilayer, gel-like sheet's gelation temperature (or lower). In another form, the extrudate is cooled to a temperature of about 100°C or lower in order to form the multi-layer gel- like sheet.
  • the cooling can be accomplished using the apparatus described in any of the preceding embodiments, e.g., a first pair (and optionally a second pair) of upstream chill rolls of equal diameter, with each roll in the pair contacting the extrudate along an arcuate path traversing a contact angle of 100° or less; and a downstream chill roll contacting the extrudate along an arcuate path traversing a contact angle of 180° or more.
  • 50% or more of the cooling of the extrudate is accomplished before the extrudate contacts the downstream roll.
  • first and second diluents are removed (or displaced) from the multi-layer gel-like sheet in order to form a microporous membrane.
  • a displacing (or “washing") solvent can be used to remove (wash away, or displace) the first and second diluent.
  • Conventional washing solvent and washing techniques can be used, e.g., those described in WO 2008/016174.
  • the amount of diluent removed is not particularly critical, generally a higher quality (more porous) membrane will result when at least a major amount of first and second diluents are removed from the gel-like sheet.
  • the membrane-forming solvent is removed from the gel-like sheet (e.g., by washing) until the amount of the remaining diluent in the microporous membrane sheet becomes less than 1 wt.%, based on the weight of the gel-like sheet.
  • the membrane obtained by removing at least a portion of the diluent is dried in order to remove the washing solvent.
  • Any method capable of removing the washing solvent can be used, including conventional methods such as heat-drying, wind-drying (moving air), etc. as described in WO 2008/016174.
  • drying can be conducted until the amount of remaining washing solvent is about 5 wt.% or less on a dry basis, i.e., based on the weight of the microporous membrane. In another form, drying is conducted until the amount of remaining washing solvent is about 3 wt.% or less on a dry basis. Insufficient drying can be recognized because it generally leads to an undesirable decrease in the porosity of the microporous membrane. If this is observed, an increased drying temperature and/or drying time should be used. Removal of the washing solvent, e.g., by drying or otherwise, results in the formation of the microporous membrane.
  • the multi-layer, gel-like sheet Prior to the step for removing the diluent, can be optionally stretched in order to obtain a stretched, multi-layer, gel-like sheet. It is believed that the presence of the first and second diluents in the multi-layer, gel-like sheet results in a relatively uniform stretching magnification. Heating the multi-layer, gel-like sheet, especially at the start of stretching or in a relatively early stage of stretching (e.g., before 50% of the stretching has been completed) is also believed to aid the uniformity of stretching.
  • stretching results in orienting the polymer in the gel-like sheet, stretching can also be referred to as "orientation”.
  • stretching While not wishing to be bound by any theory or model, it is believed that such stretching causes cleavage between polyethylene lamellas, making the polyethylene phases finer and forming large numbers of fibrils. The fibrils form a three-dimensional network structure (three-dimensionally irregularly connected network structure).
  • the stretching when used generally makes it easier to produce a relatively high-mechanical strength multi-layer, microporous polyolefin membrane with a relatively large pore size.
  • Such multi-layer, microporous membranes are believed to be particularly suitable for use as battery separators.
  • the multi-layer, gel-like sheet can be treated with a hot solvent as described in WO 2008/016174 and in WO 2000/20493.
  • the dried multi-layer, microporous membrane of step (6) can be optionally stretched, at least monoaxially.
  • Biaxial stretching can be used, and the amount of stretching along each axis need not be the same.
  • the stretching method selected is not critical, and conventional stretching methods can be used such as by a tenter method, etc. While it is not critical, the membrane can be heated during stretching. While the choice is not critical, the stretching can be monoaxial or biaxial. When biaxial stretching is used, the stretching can be conducted simultaneously in both axial directions, or, alternatively, the multi-layer, microporous polyolefin membrane can be stretched sequentially, e.g., first in the machine direction and then in the transverse direction. In another form, simultaneous biaxial stretching is used.
  • the stretching of the dry multi-layer, microporous polyolefin membrane in step (9) can be called dry-stretching, re-stretching, or dry-orientation.
  • Conventional stretching techniques and conditions can be used, e.g., those described in WO 2008/016174.
  • the dried multi-layer, microporous membrane can be heat-treated following step (5). Conventional heat treatments such as heat set and annealing can be used, as described in WO 2008/016174.
  • the multi-layer, microporous polyolefin membrane can be subjected to a hydrophilic treatment (i.e., a treatment which makes the multi-layer, microporous polyolefin membrane more hydrophilic).
  • the hydrophilic treatment can be, for example, a monomer-grafting treatment, a surfactant treatment, a corona-discharging treatment, etc.
  • the monomer-grafting treatment is used after the cross- linking treatment.
  • any of nonionic surfactants, cationic surfactants, anionic surfactants and amphoteric surfactants can be used, for example, either alone or in combination.
  • a nonionic surfactant is used.
  • the choice of surfactant is not critical.
  • the multi-layer, microporous polyolefin membrane can be dipped in a solution of the surfactant and water or a lower alcohol such as methanol, ethanol, isopropyl alcohol, etc., or coated with the solution, e.g., by a doctor blade method.
  • the thickness of the final membrane is generally in the range of 3 ⁇ m or more.
  • the membrane can have a thickness in the range of from about 3 ⁇ m to about 300 ⁇ m, e.g., from about 5 ⁇ m to about 50 ⁇ m.
  • the thickness of the microporous membrane can be measured, e.g., by a contact thickness meter at 1 cm longitudinal intervals over the width of 10 cm, and then averaged to yield the membrane thickness. Thickness meters such as the Litematic available from Mitsutoyo Corporation are suitable. Non-contact thickness measurement methods are also suitable, e.g. optical thickness measurement methods.
  • the microporous membrane exhibits a standard deviation of thickness values 1 micron or less, for example from about 0.25 microns to about 0.75 microns, making it a superior battery separator, especially for lithium ion batteries.
  • the membranes produced by prior art processes exhibit significant thickness variation along the membrane's TD. Some of this thickness variation results from deformities along the edge of the membrane from, e.g., the tenter clips gripping the membrane during processing. The thickness variation also results from variations in the thickness of the cooled extrudate. Selvage is cut from the edges of the extrudate and/or membrane to produce a membrane having an acceptable standard deviation of thickness values, generally less than 1 micron, e.g., in the range of 0.25 to 0.75 microns.
  • Selvage removal can be operated continuously, e.g., by locating cutting blades oriented parallel to the membrane's MD at a desired distance inward (along TD) from the edge of the membrane. The selvage is then conducted away from the process.
  • the ratio of the weight of the membrane per unit length to the weight of the selvage per unit length is 75% or greater.
  • the process of the invention is advantageous because the improved thickness uniformity of the cooled extrudate is carried through the process and results in a membrane having improved thickness uniformity along TD. Thus, less slitting is required to produce a membrane having the desired amount of thickness variation or less, thereby producing less selvage and improving microporous membrane yield.
  • the ratio of the weight of the membrane per unit length to the weight of the selvage per unit length is in the range of 75% to 99%.
  • the slitting of the membrane to remove the selvage reduces the width of the membrane by a factor of about 90% to about 99% of the width of the membrane exiting the heat setting step.
  • This slitting step can be referred to as a "first" slitting step when additional slitting is used downstream, e.g., in order to produce microporous membrane of a desired final width for battery manufacturing.
  • the membrane's average thickness can be measured at selected points along TD (i.e., across the membrane).
  • a plurality of measurement points approximately equally spaced along TD and referenced to the center line of the membrane are used to determine the membrane's average thickness and the standard deviation of the measured values. Since the thickness values are measured at a plurality of points referenced to the center line of the membrane, the measurements can be made before or after slitting. [0080] In an embodiment, the selected thickness measurement points are along
  • the distance between the initial point and final point can be, e.g., about 75%, or alternatively about 80%, or alternatively 90%, or alternatively about 95% of the width of the membrane after the heat setting step but before slitting, i.e., before first slitting and any slitting downstream of first slitting.
  • While average thickness and the standard deviation of the measured thickness values can be determined with an initial point and final point only, typically those points and a plurality of points along TD are used to determine those values; e.g., at least five points, or at least ten points, or at least 20 points, or at least 40 points.
  • the number of points can be in the range of 10 to 30 points, and, optionally, the points can be equally spaced along TD at a convenient interval, e.g., the distance between adjacent measurement points can be in the range of about 25 mm to about 100 mm.
  • ⁇ refers to the arithmetic mean of the measured thickness values (measured in microns) determined at the measurement points along TD.
  • the standard deviation of the measured thickness values " ⁇ " is defined as the square root of the variance, i.e.,
  • the microporous membrane of the present invention also has at least one of the following properties.
  • the normalized air permeability is 30 sec/100 cm 3 / ⁇ m or less, e.g., in the range of 10 sec/100 cm 3 / ⁇ m to
  • Pin puncture strength is defined as the maximum load measured (in grams Force or "gF") when a microporous membrane having a thickness Of T 1 is pricked with a needle of 1 mm in diameter with a spherical end surface (radius R of curvature: 0.5 mm) at a speed of 2 mm/second.
  • the pin puncture strength is normalized to a value at a membrane thickness of 1.0 ⁇ m using the equation
  • L 2 (Li )/Ti j
  • L 1 is the measured pin puncture strength
  • L 2 is the normalized pin puncture strength
  • Ti is the average thickness of the membrane.
  • the normalized pin puncture strength is in the range of
  • the membrane's MD tensile strength is in the range of 1000 Kg/cm 2 to 2,000 Kg/cm 2
  • TD tensile strength is in the range of 900 Kg/cm 2 to 1300 Kg/cm 2 .
  • Tensile elongation is measured according to ASTM D-882A.
  • the membrane's MD and TD tensile elongation are each in the range of 50% to 350%.
  • the membrane's MD tensile elongation is in the range of, e.g., 150% to 300% and TD tensile elongation is in the range of, e.g., 150% to 400%.
  • the shutdown temperature of the microporous membrane is measured by a thermomechanical analyzer (TMA/SS6000 available from Seiko Instruments, Inc.) as follows: A rectangular sample of 3 mm x 50 mm is cut out of the microporous membrane such that the long axis of the sample is aligned with the transverse direction of the microporous membrane and the short axis is aligned with the machine direction. The sample is set in the thermomechanical analyzer at a chuck distance of 10 mm, i.e., the distance from the upper chuck to the lower chuck is 10 mm. The lower chuck is fixed and a load of 19.6 mN applied to the sample at the upper chuck.
  • shutdown temperature is defined as the temperature of the inflection point observed at approximately the melting point of the polymer having the lowest melting point among the polymers used to produce the membrane. In an embodiment, the shutdown temperature is 140°C or less, e.g., in the range of l28°C to l33°C. (g) Meltdown temperature of 142°C or higher
  • Meltdown temperature is measured by the following procedure: A rectangular sample of 3 mm x 50 mm is cut out of the microporous membrane such that the long axis of the sample is aligned with the transverse direction of the microporous membrane as it is produced in the process and the short axis is aligned with the machine direction.
  • the sample is set in the thermomechanical analyzer (TMA/SS6000 available from Seiko Instruments, Inc.) at a chuck distance of 10 mm, i.e., the distance from the upper chuck to the lower chuck is 10 mm.
  • the lower chuck is fixed and a load of 19.6 mN applied to the sample at the upper chuck.
  • the chucks and sample are enclosed in a tube which can be heated.
  • the temperature inside the tube is elevated at a rate of 5°C/minute, and sample length change under the 19.6 mN load is measured at intervals of 0.5 second and recorded as temperature is increased.
  • the temperature is increased to 200°C.
  • the meltdown temperature of the sample is defined as the temperature at which the sample breaks, generally at a temperature in the range of about 142°C to about 200 0 C.
  • the meltdown temperature is in the range of from
  • Microporous membrane composition 143°C to 190 0 C.
  • the microporous membrane generally comprises the same polymers used to produce the polymeric composition, in generally the same relative amounts. Washing solvent and/or process solvent (diluent) can also be present, generally in amounts less than 1 wt.% based on the weight of the microporous membrane. A small amount of polymer molecular weight degradation might occur during processing, but this is acceptable.
  • molecular weight degradation during processing causes the value of Mw/Mn of the polyolefin in the membrane to differ from the Mw/Mn of the polymer used to produce the polyolefin composition by no more than about 5%, or no more than about 1 %, or no more than about 0.1 %.
  • the microporous membrane comprises the first and second polyethylene, for example from about 25 wt.% to about 35 wt.% of the first polyethylene and from about 65 wt.% to about 75 wt.% of the second polyethylene, based on the weight of the membrane.
  • the membrane contains about 30 wt.% of the first polyethylene and about 70 wt.% of the second polyethylene.
  • the microporous membrane of any of the preceding embodiments is useful for separating electrodes in energy storage and conversion devices such as lithium ion batteries.
  • microporous membranes of the invention are useful as battery separators in e.g., lithium ion primary and secondary batteries. Such batteries are described in PCT publication WO 2008/016174.
  • EXAMPLES The Extrudate [0096] The extrudate used in Examples 1 , 2, and 3 and in Comparative Examples
  • Extrudate thickness (measuring at the extrusion die lip) is provided in the Table 1.
  • a polyolefin composition comprising 20% by mass of ultra-high-molecular-weight polyethylene (UHMWPE) having a weight-average molecular weight (Mw) of 2.0 x 10 6 , a molecular weight distribution (Mw/Mn) of 5.0, a melting point (T m ) of 135°C, and a crystal dispersion temperature (T C( j) of 100°C is dry blended with 80% by mass of high-density polyethylene (HDPE) having a Mw of 5.6 x 10 5 and Mw/Mn of 4.6, T m of 135°C, and T cd of 100°C, and 0.2 parts by mass of tetrakis [methylene-3 -(3,5-ditertiary-butyl-4-hydroxyphenyI)-propionate] methane as an antioxidant.
  • the polyolefin composition has an Mw/Mn of 8.6, a T m of 135°
  • Mw and Mw/Mn of each UHMWPE and HDPE are measured by a gel permeation chromatography (GPC) method under the following conditions.
  • Mw and Mn of the polyethylenes are determined using a High Temperature Size Exclusion Chromatograph, or "SEC", (GPC PL 220, Polymer Laboratories), equipped with a differential refractive index detector (DRJ). Three PLgel Mixed-B columns (available from Polymer Laboratories) are used. The nominal flow rate is 0.5 cm /min, and the nominal injection volume was 300 ⁇ L. Transfer lines, columns, and the DRI detector were contained in an oven maintained at 145°C. The measurement is made in accordance with the procedure disclosed in "Macromolecules, Vol. 34, No. 19, pp. 6812-6820 (2001)".
  • the GPC solvent used is filtered Aldrich reagent grade 1,2,4- Trichlorobenzene (TCB) containing approximately 1000 ppm of butylated hydroxy toluene (BHT).
  • TCB 1,2,4- Trichlorobenzene
  • BHT butylated hydroxy toluene
  • Polymer solutions were prepared by placing dry polymer in a glass container, adding the desired amount of above TCB solvent, then heating the mixture at 160°C with continuous agitation for about 2 hours.
  • the concentration of UHMWPE solution was 0.25 to 0.75mg/ml.
  • Sample solution will be filtered off-line before injecting to GPC with 2 ⁇ m filter using a model SP260 Sample Prep Station (available from Polymer Laboratories).
  • the separation efficiency of the column set is calibrated with a calibration curve generated using seventeen individual polystyrene standards ranging in Mp from about 580 to about 10,000,000, which is used to generate the calibration curve.
  • the polystyrene standards are obtained from Polymer Laboratories (Amherst, MA).
  • a calibration curve (logMp vs. retention volume) is generated by recording the retention volume at the peak in the DRI signal for each PS standard, and fitting this data set to a 2nd-order polynomial. Samples are analyzed using IGOR Pro, available from Wave Metrics, Inc.
  • the polyolefin solution is supplied from its double-screw extruder to a monolayer-sheet-forming T-die having a 250mm width at 210°C, to form an extrudate having a first surface and a second surface.
  • the extrudate is cooled, using chill roll assemblies as discussed in the following Examples and Comparative Examples.
  • Example 1 The extrudate produced at a thickness of 1.2 mm is conducted to a first chill roll (CR-I) having a diameter of 100 mm, and a surface temperature of 15 0 C, as shown in Table 1.
  • the first surface of the extrudate contacts the chill roll at a contact angle of 65° to cool the extrudate.
  • the cooled extrudate conducted away from the first chill roll to a second chill roll (CR-2) having a diameter of 100 mm and a surface temperature of 15°C.
  • the second chill roll contacts the second surface of the extrudate (opposite the first surface) at a contact angle of 70°.
  • the first and second chill rolls comprise an upstream pair of chill rolls.
  • the extrudate is conducted away from the first upstream pair of chill rolls to a second upstream pair of chill rolls, the second pair comprising a third (CR-3) and a fourth (CR-4) chill roll.
  • the third chill roll has a diameter of 100 mm, a surface temperature of 15°C, and contacts the first surface of the extrudate at a contact angle of 70°.
  • the extrudate is conducted to the fourth chill roll having a diameter of 100 mm and a surface temperature of 15°C.
  • the second surface of the extrudate contacts the fourth chill roll at a contact angle of 70°.
  • the extrudate is conducted away from the second pair of chill rolls to a downstream chill roll (CR-5) having a diameter of 300 mm, a surface temperature of 15°C, and a contact angle of 200°.
  • the extrudate conducted away from the downstream chill roll (the "cooled extrudate") has a temperature of 35°C and an average thickness of 1040 ⁇ m and a thickness deviation from the average value in the range of 5 ⁇ m to 11 ⁇ m.
  • Example 2 is the same as Example 1 except that the thickness of the extrudate as produced from the die is 0.6 mm, the thickness of the cooled extrudate prior to biaxial stretching is 520 ⁇ m, the cooled extrudate has a temperature of 30°C, the thickness deviation is in the range of 5 ⁇ m to 10 ⁇ m, and the heat set temperature is 124.5°C.
  • the properties of the final membrane are shown in Table 1.
  • Example 3 is the same as Example 1 except that the thickness of the extrudate as produced from the die is 2.3 mm, the cooled extrudate has a temperature of 40°C, the thickness of the cooled extrudate is 2070 ⁇ m, the thickness deviation is in the range of 5 ⁇ m to 13 ⁇ m, the biaxial stretching temperature is 116.5°C, and the heat set temperature is 123.5°C.
  • the properties of the final membrane are shown in Table 1. Comparative Example 1
  • Comparative Example 1 is the same as Example 1 except that the diameter of the first chill roll is 300 mm with a contact angle of 210°, the diameter of the second and third chill rolls are each 300 mm with a contact angle of 170°, the diameter of the fourth chill roll is 300 mm with a contact angle of 150°, the diameter of the downstream chill roll is 100 mm with a contact angle at 80°, the cooled extrudate has a temperature of 35°C, the thickness of the cooled extrudate is 960 ⁇ m, and the thickness deviation is in the range of 15 ⁇ m to 35 ⁇ m.
  • the properties of the final membrane are shown in Table 1. Comparative Example 2
  • Comparative Example 2 is the same as Comparative Example 1 except that the thickness of the extrudate produced from the die is 0.6 mm, the cooled extrudate has a temperature of 30°C, the thickness of the cooled extrudate is 480 ⁇ m, the thickness deviation is 15 ⁇ m to 30 ⁇ m, and the biaxial stretching temperature is 1 14.4.
  • the properties of the final membrane are shown in Table 1. Comparative Example 3
  • Comparative Example 3 is the same as Comparative Example 1 except that the thickness of the extrudate produced from the die is 0.9 mm, the cooled extrudate has a temperature of 35°C, the contact angle of the first chill roll is 165°, the contact angle of the second chill roll is 150°, the diameter of the third chill roll is 450 mm with a contact angle of 225°, the diameter of the fourth chill roll is 450 mm with a contact angle of 200°, the downstream chill roll has a diameter of 200 mm with a contact angle of 170°, the thickness of the cooled extrudate is 810 ⁇ m, the thickness deviation is in the range of 15 ⁇ m to 30 ⁇ m, the biaxial stretching temperature is 1 14.8°C, and heat setting is conducted at 125.3°C for 10 seconds. Comparative Example 4
  • Comparative Example 4 is the same as Comparative Example 2 except that the thickness of the extrudate produced from the die is 1.4 mm, the first chill roll has a contact angle of 40°, the fourth chill roll has a contact angle of 170°, there is no downstream chill roll, the thickness of the cooled extrudate is 1220 ⁇ m, the thickness deviation is in the range of 20 ⁇ m to 35 ⁇ m, the biaxial stretching temperature is 116.4°C, and the heat setting temperature is 125.5 0 C.
  • Table 1 The properties of the finished membrane are shown in Table 1. Table 1

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Cell Separators (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L’invention concerne un ensemble destiné à transférer de la chaleur depuis un extrudat formé en extrudant une solution de polyoléfine par une filière d’extrusion. L’ensemble comprend au moins une paire de rouleaux en amont positionnés de manière à recevoir des surfaces opposées de l’extrudat, et au moins un rouleau en aval, la paire de rouleaux en amont et le rouleau en aval étant alignés de manière à ce que le rouleau en aval reçoive l’extrudat de la paire de rouleaux en amont. L’invention concerne également un procédé de fabrication d’une membrane microporeuse.
PCT/JP2009/063455 2008-08-15 2009-07-22 Système de cylindre refroidisseur et procédé de fabrication d’une membrane microporeuse WO2010018749A1 (fr)

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JP5857151B2 (ja) * 2013-02-27 2016-02-10 東レバッテリーセパレータフィルム株式会社 ポリオレフィン多孔質膜、それを用いた電池用セパレータおよびそれらの製造方法
WO2016132808A1 (fr) * 2015-02-20 2016-08-25 東レバッテリーセパレータフィルム株式会社 Procédé de production d'une feuille plastique microporeuse
WO2016132807A1 (fr) * 2015-02-20 2016-08-25 東レバッテリーセパレータフィルム株式会社 Procédé de production d'une feuille plastique microporeuse
WO2016132806A1 (fr) * 2015-02-20 2016-08-25 東レバッテリーセパレータフィルム株式会社 Procédé de production de film plastique microporeux
CN106103556A (zh) * 2014-03-24 2016-11-09 东丽电池隔膜株式会社 微多孔塑料膜的制造方法
CN107108945A (zh) * 2014-11-18 2017-08-29 东丽株式会社 聚烯烃微多孔膜、电池用隔膜及其制造方法
JPWO2016132810A1 (ja) * 2015-02-20 2017-12-07 東レ株式会社 微多孔プラスチックフィルムの製造方法
US20180043598A1 (en) * 2015-02-20 2018-02-15 Toray Industries, Inc. Method of producing microporous plastic film
EP3438177A4 (fr) * 2016-03-31 2020-01-08 Toray Industries, Inc. Membrane microporeuse en polyoléfine, procédé de production pour membrane microporeuse en polyoléfine, séparateur de batterie et batterie
CN111182818A (zh) * 2017-08-07 2020-05-19 贝瑞全球有限公司 用于热成型制品的方法和装置
US10770707B2 (en) 2015-12-04 2020-09-08 Toray Industries, Inc. Battery separator and method of manufacturing same
EP2670577B1 (fr) 2011-02-03 2021-04-07 battenfeld-cincinnati Germany GmbH Dispositif de refroidissement et procédé de refroidissement d'un produit d'extrusion
US10978721B2 (en) 2015-12-24 2021-04-13 Toray Industries, Inc. Polyolefin microporous membrane, battery separator and production method
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JPWO2017170288A1 (ja) * 2016-03-31 2019-02-07 東レ株式会社 ポリオレフィン微多孔膜及びその製造方法、電池用セパレータ並びに電池
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JPWO2014132791A1 (ja) * 2013-02-27 2017-02-02 東レバッテリーセパレータフィルム株式会社 ポリオレフィン多孔質膜、それを用いた電池用セパレータおよびそれらの製造方法
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US20180043598A1 (en) * 2015-02-20 2018-02-15 Toray Industries, Inc. Method of producing microporous plastic film
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US10770707B2 (en) 2015-12-04 2020-09-08 Toray Industries, Inc. Battery separator and method of manufacturing same
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