WO2011019408A1 - Composite multicouche utile en tant qu’additif polymère - Google Patents

Composite multicouche utile en tant qu’additif polymère Download PDF

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Publication number
WO2011019408A1
WO2011019408A1 PCT/US2010/002250 US2010002250W WO2011019408A1 WO 2011019408 A1 WO2011019408 A1 WO 2011019408A1 US 2010002250 W US2010002250 W US 2010002250W WO 2011019408 A1 WO2011019408 A1 WO 2011019408A1
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Prior art keywords
composite
layers
polymer
layer
alternating
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PCT/US2010/002250
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English (en)
Inventor
Nathan A. Mehl
David A. Schiraldi
Yuxin Wang
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Milliken & Company
Connor, Daniel M.
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Publication of WO2011019408A1 publication Critical patent/WO2011019408A1/fr

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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
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • 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
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/365—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using pumps, e.g. piston pumps
    • 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
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/50—Details of extruders
    • B29C48/695—Flow dividers, e.g. breaker plates
    • B29C48/70—Flow dividers, e.g. breaker plates comprising means for dividing, distributing and recombining melt flows
    • B29C48/71—Flow dividers, e.g. breaker plates comprising means for dividing, distributing and recombining melt flows for layer multiplication
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • 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
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/23—Articles comprising two or more components, e.g. co-extruded layers the components being layers with means for avoiding adhesion of the layers, e.g. for forming peelable layers
    • 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
    • C08J2400/00—Characterised by the use of unspecified polymers
    • C08J2400/14—Water soluble or water swellable polymers, e.g. aqueous gels
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils

Definitions

  • This invention is directed to a multilayer polymer composite, which may be provided in the form of a pellet, and incorporated in a matrix polymer, to improve one or more of the physical, chemical or electrical properties of the matrix polymer.
  • Reinforcement of polymer products is well known to be successfully accomplished using a range of inorganic fillers, including glass fibers and flakes, smectite clays, talc and many other minerals. While such fillers can substantially increase the moduli and thermal properties (heat deflection temperature, glass transition temperature, onset of thermal degradation), these property enhancements generally come at the expense of ductility and processability. Inorganic fillers used to reinforce organic polymers also often require the use of specialized
  • exfoliated layered silicate material derived from intercalates formed by contacting the layer material, e.g., a phyllosilicate, with an intercalant polymer to sorb or intercalate the polymer between adjacent platelets of the layered material.
  • Sufficient intercalant polymer is sorbed between adjacent platelets to expand the adjacent platelets to a spacing of at least about 10 A (as measured after water removal), up to about 100 A and preferably in the range of about 30-45 A, so that the intercalate easily can be exfoliated, e.g., when mixed with a thermoplastic or thermosetting matrix polymer melt, to provide a matrix polymer/platelet nanocomposite material-the platelets being exfoliated from the intercalate.
  • Bagrodia et al., US Patent No. 6,395,386 B2 disclose multilayer formed articles including, but not limited to containers such as bottles, tubes, pipes, preforms and films (including oriented films such as biaxially oriented) comprising a melt processible resin having dispersed therein a platelet filler.
  • Suitable platelet particles are derived from clay materials, such as mica-type layered phyllosilicates, including clays, smectite clays, sodium montmorillonite, sodium hectorite, bentonites, nontronite, beidellite, volkonskoite, saponite, sauconite, magadiite, kenyaite, synthetic sodium hecotorites, and the like.
  • the coextrusion of multilayer sheets and other articles wherein individual layer thicknesses are on the order of microns is known in the art.
  • Schrenk U.S. Pat. Nos. 3,773,882 and 3,884,606, teaches devices which prepare multilayered coextruded thermoplastic polymeric materials having substantially uniform layer thicknesses.
  • the feedblock of the coextrusion device receives streams of the diverse thermoplastic polymeric materials from sources such as heat plastifying extruders.
  • the streams of resinous materials are passed to a mechanical manipulating section within the feedblock. This section serves to rearrange the original streams into a multilayered stream having the number of layers desired in the final body.
  • this multilayered stream may be subsequently passed through a series of layer multiplying means (sometimes termed interfacial surface generators) in order to further increase the number of layers in the final body as is described in Schrenk et al, U.S. Pat. No. 3,759,647.
  • the multilayered stream is then passed into an extrusion die which is so constructed and arranged that streamlined flow is maintained therein.
  • an extrusion device is described in Chisholm et al, U.S. Pat. No. 3,557,265.
  • the resultant product is extruded to form a multilayered body in which each layer is generally parallel to the major surface of adjacent layers.
  • This technology may be termed microlayer coextrusion technology because of the thinness of the layers which are formed.
  • Microlayer coextrusion is to be distinguished from conventional multilayer coextrusion which typically involves the production of less than about fifteen layers each having thicknesses which may be from one to two orders of magnitude greater than the layer thicknesses produced in microlayer coextrusion
  • the present invention includes a multilayer composite, a method of improving the properties of a matrix polymer by mixing the multilayer composite and matrix polymer together, followed by melt extruding the mixture, and a matrix polymer composition obtained from incorporating the multilayer composite in the matrix polymer according to the foregoing method.
  • the multilayer composite is comprised of at least eight layers of one or more polymers.
  • Each polymer layer is contiguous with at least one other polymer layer, that is, each polymer layer is in contact with at least one adjacent polymer layer, as distinguished from prior art additives such as clays having a layer of a polymer disposed between alternating inorganic layers.
  • the components of the various alternating layers may be the same or different, as long as at least one component includes a polymer that can melt when extruded with a matrix polymer, i.e. the target polymer that is intended to be modified by incorporation of the multilayer composite.
  • the number of organic polymer layers in the composite may be 16, 32, 64, 128, 256, 512 or more.
  • multilayer composites having as many as 5000 layers may be fabricated by those skilled in art.
  • the multilayer composite may be fabricated by a multilayer coextrusion forced assembly process, as described in greater detail herein. Briefly, the process employs coextrusion using multiple extruders to create a multilayer film structure, that is, one layer for each of the extruders. The original film structure is then split in two, the two sections are stacked together, and the stacked sections are
  • the process can be repeated to fabricate a composite with the desired number of layers and layer thicknesses.
  • the thickness of each of the layers of the composite need not be the same.
  • organic polymers that have a similar melt viscosity.
  • all of the polymers in the composite may be selected to have a melt viscosity within a factor of four of each other, as measured by melt rheometry.
  • the thickness of the polymer layers in the composite may range from 15 nm to 100 ⁇ m, as measured perpendicular to the plane of the layer. In particular, polymer layers having a thickness ranging from 200 nm to 10 ⁇ m, or from 400 nm to 1 ,500 nm are believed to be useful.
  • the final shape of the multilayer composite particles may be selected to provide individual layers with an aspect ratio that optimizes the performance of the composite when the composite is mixed with a matrix polymer and melt extruded.
  • platelets of one or more of the organic polymers that comprise the layers of the composite may have an aspect ratio of at least 4, particularly at least 10, and more particularly having ranges from 50 to 20,000, or from 100 to 10,000, as determined by comparing the thickness of an individual layer to its maximum dimension parallel to the plane of such layer.
  • the multilayer composite may be provided in the shape of a pellet, having a diameter of from 2 mm to 6 mm, determined by the maximum width measured parallel to the plane of the layers.
  • the composite is not stranded and cut into pellets, but collected in sheet, tape or strand form. In such a case, the layers of the composite would exist as tapes or ribbons, but not platelets.
  • sheets, tapes or strands can then be fed into the throat of the matrix polymer extruder or alternatively fed downstream into a port on the matrix polymer extruder.
  • the sheet, tape or strand is fed into the throat or downstream port on an injection molder, thermoformer or extrusion blow molder.
  • the multi-layer composite structure, which exits the multiplier block assembly of the extruder is fed directly into the matrix polymer extruder as described above, with or without partial cooling. Comminution of the multilayer composite structure occurs during melt extruding.
  • the multilayer composite has at least two alternating layers, identified as first and second polymer layers.
  • first and second polymer layers When the multilayer composite is employed as an additive to improve the properties of a matrix polymer, the first polymer softens and flows readily during the melt extrusion process, whereas the second polymer does not flow readily.
  • the multilayer composite can be understood to undergo an exfoliation process, whereby the individual layers of the second polymer or platelets are dispersed throughout the matrix polymer, forming a two-phase system, when the layers of the first polymer soften and flow readily.
  • the use of the multilayer composite as an additive provides a method to disperse layers (platelets) of the second polymer and thereby improve the properties of the matrix polymer.
  • the first polymer is also dispersed throughout the matrix polymer as well, during the melt extrusion step.
  • the first polymer may be miscible, partially miscible or immiscible in the matrix polymer.
  • the first polymer and the matrix polymer may be the same class of polymers, for example polyolefins, and the first polymer of the composite is miscible in the matrix polymer.
  • the multilayer composite may be mixed with the matrix polymer to provide a concentration of the composite of from 3 to 33 weight %, based on the total weight of the mixture, and thus in the final product.
  • T f is the temperature above which a polymer will readily flow under normal shear rates experienced during typical processing conditions.
  • T f is defined as the larger of either the T 9 or the T m of a polymer.
  • T m is defined as the polymer melting point.
  • T f T 9 .
  • the T f of the polymer in the first layer of the composite is selected to be relatively close to or less than the processing temperature of the matrix polymer, for example, the T f of the first polymer is not greater than the processing temperature of the matrix polymer.
  • the polymer in the second layer is not intended to flow and preferably retains its shape, so the T f of the second polymer should be selected to be greater than the processing temperature of the matrix polymer, for example, by at about 10 °C or more.
  • the difference in the T f of the polymers in the first and second layers should be such that the first polymer will readily melt or flow during melt extrusion and the second polymer will not.
  • the difference between the T f of the first and the second polymers may be at least 10 0 C. In other embodiments of the invention, the difference in T f is at least 20 0 C or 30 0 C.
  • the polymer of the second layer may have one or more additives incorporated therein to improve the stiffness of the polymer, which has the effect of minimizing distortion during processing, as well as positively affecting the properties of the matrix polymer.
  • the first and second polymers comprising layers of the multilayer composite are characterized by the second layer having a flexural modulus that is at least 2 times greater, preferably 5 times greater, than the flexural modulus of the first layer, as measured by ASTM D-790.
  • the multilayer composite is mixed with the matrix polymer to provide a concentration of the layers of the second polymer (platelets), as is desired to improve the properties in the matrix polymer.
  • the layers of the second polymer may be present in a concentration of 1 to 50 weight %, or 3 to 33 weight %, based on the weight of the matrix polymer and multilayer composite mixture.
  • the polymer layers comprising the multilayer composite are selected to provide layers of first and second polymer that both flow, when the multilayer composite and matrix polymer are melt extruded.
  • the multilayer composite is fabricated from two polymers that are stacked in alternating layers, then both layers of the composite material are melted and dispersed in the matrix polymer.
  • at least one of the polymer layers has an additive incorporated therein, which is released into the matrix polymer, when that layer of the composite softens and flows.
  • the present invention is particularly useful in regard to additives that function as a reinforcing agent in the matrix polymer, such as high aspect ratio, inorganic additives, including reinforcing agents in the form of whiskers, fibers, platelets and the like.
  • additives having an aspect ratio of at least 4, which neither dissolve nor melt in the matrix polymer during melt extrusion with the matrix polymer may be employed as additives to improve the performance of the matrix material.
  • certain fabrication processes for creating multilayer composite materials such as the multilayer coextrusion forced assembly process, orient high aspect ratio additives that are dispersed in one or more of the polymer layers.
  • the additive dispersed in the matrix polymer retains at least some of the orientation, resulting in improved properties in the matrix polymer, as compared to traditional methods of mixing and melt extruding the additive and matrix polymer.
  • the multilayer composite functions as a means for delivering and dispersing an additive in the matrix polymer.
  • the multilayer composite is mixed with the matrix polymer to provide a desired concentration of the additive, which is dispersed in one or more of the polymer layers of the composite, to improve the properties in the matrix polymer.
  • the concentration of the additive which is dispersed in one or more of the polymer layers of the composite, may be present in a concentration of 3 to 33 weight %, based on the weight of the matrix polymer and multilayer composite mixture. Accordingly, in one embodiment, the concentration of the additive in at least one of the layers of the polymer in the multilayer composite may range from 5 to 80 weight % of such polymer, typically from 10 to 30 weight %. Alternatively measured, the concentration of the additive in at least one of the layers of the polymer in the multilayer composite may range from 3 to 50 volume %.
  • Various properties of the matrix polymer may be improved by practicing the methods outlined above, such as the tensile modulus, elongation at break and flexural modulus of the matrix polymer. For example, by selecting various combinations of the matrix polymer.
  • combinations of polymers in the multilayer composite, additives in the polymer layers and concentrations relative to the matrix polymer, the tensile modulus and flexural modulus of the matrix polymer may be increased by at least 50%, 75% or 100%.
  • the elongation at break of the matrix polymer may also be increased by at least 25% or more.
  • Figure 1 is a flow diagram of a multilayer coextrusion forced assembly process for a two polymer system.
  • Figures 2A, 2B, 2C, and 2D are a series of cross-sectional views illustrating the manner in which coextruded polymer melts can be divided and combined in a multilayer extrusion process.
  • Figures 3A, 3B, and 3C are atomic force microscopy images of the multilayer film produced in Example 1 taken at various levels of magnification.
  • Figures 4A and 4B are scanning electron micrographs of the multilayered extrudate produced in Example 1 taken in the flow direction.
  • Figures 4C and 4D are scanning electron micrographs of the multilayered extrudate produced in Example 1 taken in the transverse direction (i.e.,
  • polymer or "polymeric material” as used in the present application denotes a material having a weight average molecular weight (Mw) of at least 5,000. Such polymeric materials can be amorphous, crystalline or elastomeric polymeric materials.
  • polymer as used in the present application is not intended to include inorganic materials, such as clays, silicates, metals, metal oxides,
  • oligomer or "oligomeric material” as used in the present application denotes a material with a weight average molecular weight of from 1 ,000 to less than 5,000.
  • the multilayer composite of the present invention is comprised of at least eight layers of one or more organic polymers.
  • a film comprising two, three, four or more organic polymers forms an alternating structure throughout the multilayer composite.
  • the multilayer composite may have as may as 5000 layers. Typically, all of the layers in the multilayer composite will be comprised of one or more polymers. By way of example, multilayer composites having from 20 to 5000 layers are believed to be particularly useful.
  • substantially all of the polymer layers for example, at least 90%, are contiguous with two polymer layers, or even all of the polymer layers, except the end layers, are contiguous with two polymer layers.
  • the multilayer composite is comprised of repeating film structures having at least two different polymer layers in each structure.
  • the layers may differ in one or more of the following characteristics: type of polymer, additives within the polymer, flexural modulus, processing temperature, Tg and tensile strength.
  • At least one of the polymers is selected to be processable, that is, it melts, when the multilayer composite is melt extruded with a matrix polymer.
  • the multilayer film can be made of two alternating layers (e.g. ABABA . . .) of a first polymer referred to as a polymer "(a)” and a second polymer referred to as polymer "(b)".
  • multilayer structure of the invention may include additional types of layers. For instance, a three component structure of alternating layers
  • (ABCBABCBA. . .) of components (a), (b) and (c) is represented by (ABC)x, where x is as defined above and (c) is a third material.
  • the components of the various alternating layers may be the same or different, as long as at least one component includes a polymer that can melt when extruded with a matrix polymer, i.e. the target polymer that is intended to be modified by incorporation of the multilayer composite.
  • a film comprising three or more layers can be made, wherein the layers may be the same or different in composition.
  • the film may be used to fabricate the multilayer composite of the present invention.
  • One of the layers for example, may be a compatibilizing or decompatibilizing layer.
  • the third layer can act to destabilize the adhesion between layers one and two and thus facilitate the separation of the layers when mixed into the matrix polymer.
  • Multilayer extrusion is a well-known method which is widely used to produce products, such as decorative packaging films, vacuum-packed packages of goods, such as coffee, and bottles used to store products, such as catsup.
  • the multilayer composite of the present invention can be fabricated using a multilayer coextrusion forced assembly technique.
  • a typical multilayer coextrusion apparatus is illustrated in Fig. 1.
  • the two component (AB) coextrusion system consists of two 3 A inch single screw extruders each connected by a melt pump to a coextrusion feedblock.
  • the feedblock for this two component system combines polymeric material (a) and polymeric material (b) in an (AB) layer configuration or film.
  • the melt pumps control the two melt streams that are combined in the feedblock as two parallel layers. By adjusting the melt pump speed, the relative layer thickness, that is, the ratio of A to B can be varied. From the feedblock, the melt goes through a series of multiplying elements.
  • a multiplying element first slices the AB structure vertically, and subsequently spreads the melt horizontally. The flowing streams recombine, doubling the number of layers.
  • An assembly of n multiplier elements produces an extrudate with the layer sequence (AB)x where x is equal to (2) ⁇ and n is the number of multiplier elements. It is understood by those skilled in the art that the number of extruders used to fabricate the structure of the invention equals the number of components. Thus, a three-component multilayer (ABC . . .), requires three extruders.
  • Multilayer extrusion offers a means by which two or more polymers can be easily arrayed in an alternating structure.
  • This extrusion process can operate at standard polymer film line throughputs, making use of commercial polymers and composite materials as its constituents, subject to melt temperature/rheological match requirements.
  • the multilayer coextrusion forced assembly process is shown below in the following figures.
  • two or more polymeric materials are melt coextruded into a channel (commonly rectangular in cross section) to produce a molten flow that appears as depicted in Figure 2A. While still in molten flow, the polymer is divided “cut” into two halves, as depicted in Figure 2B. The cut layers are then directed to flow (are “stretched") back to their original widths, with reduced thicknesses, as depicted in Figure 2C. The stretched layers are then assembled through flow channels so they are "stacked" upon one another to produce a "layer doubled” structure, as depicted in Figure 2D.
  • a multilayered structure produced by layer multiplying with an outside "skin layer" which serves to protect the product from physical damage in handling.
  • skin layer may be left in place, or peeled away from the multilayered structure, depending on the
  • a layer multiplication technology useful in conjunction with the present invention is disclosed in Baer et al., US Patent No. 6,582,807 B2 and Baer et al., US Patent No. 7,002,754 B2, and in "Processing and Properties of Polymer Multilayered Systems", by E. Baer, J. Kerns, and A. Hiltner, in Structure Development During Polymer Processing, A. M. Cunha and S. Fakirov, eds., pp 327-344, 2000, Kluwer Academic Publishers, The Netherlands.
  • the individual layer thickness can be controlled.
  • the thickness of the individual layers can range from 15 nm to 100 ⁇ m, 20 nm to 50 ⁇ m, or 50 nm to 10 ⁇ m.
  • the multilayer film or sheet has an overall thickness ranging from 10 nanometers to 1000 mils, preferably from 0.1 mils to 125 mils and any increments therein.
  • the multilayer films may be formed into a variety of useful shapes including pellets, profiles, tubes and the like.
  • a polymer "skin" may be added to either side of the multilayer composite, as is known in the art.
  • the multilayer composite may be fabricated from thermoplastic polymers, thermosetting polymers, or a combination thereof.
  • Thermoplastic polymers are particularly useful for fabricating the multilayer composite.
  • Useful polymers include, but are not limited to, melt processible synthetic polymeric materials, such as polyesters (including, but not limited to PET, PBT, PTT, PLA, polyglycolic acid, polycaprolactone, wholly aromatic polyesters and water dispersible polyesters), polyamides (i.e.
  • nylon 6,6, 6, 11 , 12, 6,12, MXD6® copolymers of ethylene and vinyl alcohol, ethyl-vinyl acetate copolymer, polyimides, polycarbonate, polystyrene, polyvinylchloride (PVC), polyacrylates, polymethacrylates, polyvinylethers, thermoplastic fluoro-based polymers (FEP, PFA, ETFE, EFEP), polyolefins, polysulfones, polyether ketones, polysulfides (such as PPS), polyamide-imides, polyacetals, recycled polymers and mixtures thereof.
  • olefin polymers are polymers and copolymers of aliphatic monoolefins containing 2 to about 8 carbon atoms which have an average molecular weight of from about 10,000 to about 2,000,000, preferably from about 30,000 to about 300,000, such as, without limitation, polyethylene, linear low density
  • polyethylene isotactic polypropylene, syndiotactic polypropylene, crystalline ethylene propylene copolymer, poly(i-butene), poly(4-methyl)pentene, 1-hexene, 1- octene, homo and copolymer of norbornene such as COC and COP polymers, ethylene-octene copolymers, SEBS, and vinyl cyclohexane.
  • the polyolefin polymers may include aliphatic polyolefins and copolymers made from at least one aliphatic olefin and one or more ethylenically unsaturated co-monomers.
  • the co- monomers if present, will be provided in a minor amount, e.g., about 10 percent or less or even about 5 percent or less, based upon the weight of the polyolefin (e.g. random copolymer polypropylene), but copolymers containing up to 25% or more of the co-monomer (e.g., impact copolymers) are also envisaged.
  • Other polymers such as acrylic acids and vinyl acetate) or rubber (such as EPDM, SBS, SEBS or EPR) may also be compounded with the polyolefin to obtain desired characteristics.
  • the polyolefins of the present invention may be described as basically linear, regular polymers that may optionally contain side chains such as are found, for instance, in conventional low density polyethylene.
  • thermosetting polymers or a combination of thermoplastic and thermosetting polymers may be used to fabricate the multilayer composite.
  • the thermosetting polymer may be provided uncured, for example, without cross-linking, and then cured after fabrication is complete.
  • the thermosetting polymer may be cured prior to melt extruding the multilayer composite and a matrix polymer.
  • thermosetting polymers examples include photocrosslinkable polymers, such as (but not limited to) acrylic copolymers, epoxy resins, and unsaturated polyester resins.
  • the "polymer” comprising a particular layer of the composite may be a mixture of one or more individual polymers.
  • additives normally used in any of the above polymers may be used if desired.
  • Such additives include, but are not limited to colorants, pigments, carbon black, glass fibers, fillers, impact modifiers, antioxidants, stabilizers, flame retardants, reheat aids, acetaldehyde reducing compounds, oxygen scavaging compounds and the like.
  • reinforcing agents as described below in more detail, may be incorporated into one or more of the polymers comprising repeating layers of the multilayer composite.
  • the multilayer composite can be mixed with a matrix polymer, and the mixture can be melt extruded, to improve one or more of the properties of the matrix polymer.
  • polystyrene resins Particularly useful as the matrix polymers are polyolefins, for example, the
  • the multilayer composite / matrix polymer system In selecting the multilayer composite / matrix polymer system, one should bear in mind whether it is desirable for one or more of the polymers comprising layers of the composite not to melt during melt extrusion with the matrix polymer, or whether it is desirable for all of the polymers comprising the layers of the composite to melt during melt extrusion with the matrix polymer. Persons skilled in the art of injection molding of polymers will be able to select materials that are consistent with the intended mechanism and desired properties of the resulting product.
  • the multilayer composite may be provided with alternating structures, with each structure comprising a layer of first and second polymers.
  • the multilayer composite is employed as an additive to improve the properties of a matrix polymer, and the first polymer flows readily during the melt extrusion process, whereas the second polymer does not flow readily, whereby the individual layers of the second polymer or platelets are dispersed throughout the matrix polymer, forming a two-phase system, when the layers of the first polymer melt.
  • useful polymer combinations include: for the matrix polymer: polyolefins; for the first polymer: polyethylene, polypropylene or their compolymers; and for the second polymer: polysulfone or poly(ether ketones).
  • the polymer layers comprising the multilayer composite are selected to provide layers of first and second polymer that both melt, when the multilayer composite and matrix polymer are melt extruded.
  • at least one of the polymer layers has an additive incorporated therein, which is released into the matrix polymer, when that layer of the composite melts.
  • both the first and second layers may have an additive incorporated therein, which is capable of improving the properties of a matrix polymer.
  • additives that function as reinforcing agents in the matrix polymer, for example, to increase the tensile strength, flexural modulus, heat deflection temperature ("HDT") and / or the elongation at break.
  • one or more of the following additives may be incorporated into the first or second polymer layer, or both, of the multilayer composite, as a reinforcing agent: glass fibers, carbon fibers, carbon nanotubes, boron fibers, basalt fibers, metal oxide fibers, inorganic fibers, such as metal fibers, inorganic whiskers, such as metal oxide whiskers, nanocrystalline cellulose, cellulosic fibers and cellulose whiskers, and textile fibers, such as aramid fibers.
  • Inorganic whiskers are largely a family composed of single crystal inorganic materials with rod-like, fiber-like, or ribbon-like morphologies. They are often characterized by high aspect ratios (>5), diameters from 10 nm to 10 microns and lengths from 50 nm to several hundred microns.
  • magnesium oxysulfate aragonite calcium carbonate, calcium sulfate, calcium silicic acid, calcium sodium metaphosphate, calcium silicate, boron nitride, zinc oxide, zinc oxide tetrapods, magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium borate, magnesium oxide-aluminum oxide, magnesium perborate, nickel borate, silicon carbide, silicon nitride, tin oxide, copper oxide, sodium titanate, potassium titanate, potasium hexatitante, potassium octatitanate, calcium hydroxyapatite, aluminum nitride, aluminum oxide, aluminum borate, mulite, titanium dioxide, aluminum silicate, zirconia, alpha chitin, carbon whiskers such as GraskersTM, aluminum zirconate, magnesium oxychlohde, aluminophosphate zeolites, alumina, calcium metaphosphate, and others.
  • Examples of preferred inorganic whiskers include magnesium oxysulfate, sold by Milliken Chemical as Hyperform® HPR-803, calcium carbonate aragonite whiskers, sold by Maruo Calcium of Japan, calcium sulfate whiskers, magnesium borate whiskers, and calcium silicate whiskers such as Zono HigeTM sold by Ube Materials.
  • Other useful reinforcing agents could include plate-like materials like talcs, clays, metal oxide flakes, graphite or graphene, nanocrystalline silica, glass plates, zirconium phosphate nanoplatelets, Beohmites, magnesium hydroxide nano- materials, synthetic clays such as Perkalite® from Akzo Nobel and a wide range of other plate-like reinforcing agents.
  • Reinforcing agents and fillers can be surface treated or blended with by a range of materials known by those skilled in the art to increase compatibility and/or dispersion or other properties. Examples include coupling agents, nucleating agents, compatibilizing agents, and others known to those skilled in the art. It can be understood that the use of additives, particularly a reinforcing agent, may be employed in various ways to improve the performance of the multilayer composite, that is, in improving the properties of a matrix polymer.
  • the multilayer composite / matrix polymer system may be designed so that the first polymer layers melt and the second polymer layers of the composite do not melt, during melt extrusion with a matrix polymer.
  • the exfoliated second polymer layer is able to perform at or near maximum level in the matrix polymer, because it less likely to lose its planar shape when heated and stressed during melt extrusion.
  • the invention may be further understood in view of the following examples.
  • a multilayered composite film of PSF and EO 1 with 4096 alternating layers was melt extruded at 285°C on a laboratory scale coextrusion line, employing layer- multiplying technology as described above. Both polymer melts were controlled at the same temperature during this extrusion.
  • the total extruded multilayer strand thickness measured 4 mm, including two protective 1.08 mm EO skin layers.
  • the composition of PSF/EO alternative layers 50/50 was by volume (i.e. the same volumes of "A" and "B" layer polymers were used in these examples).
  • the multilayer extruded strand was cut into pellet size (about 4mm x 5mm) using a Flexible Plastic Blade (Model 3001 EVO/13, Accucutter Company, Carlisle, PA). With such cutting into pellets, the multilayered material could be handled and processed in the normal manner of commercial polymers. These pellets are referred to as PSF/EO "Smart Pellets" below.
  • the thickness of individual PSF and EO layers in the extruded product of Example 1 were measured by atomic force microscopy (AFM, Nanoscope Ilia, Digital
  • a multilayered composite film of PP and FP, with 64 alternating layers was melt extruded at 195°C on a laboratory scale coextrusion line, employing layer- multiplying technology as described above. Both polymer melts were controlled at the same temperature during this extrusion.
  • the total film thickness was targeted at 76.8 ⁇ m; the composition of FP/PP alternating layers was 50/50 by volume.
  • the thickness of individual PP and FP layer was targeted at 1.2 ⁇ m and later measured by scanning electron microscopy microtomed samples using Philips XL scanning electron microscope. The samples were sputter coated with palladium to provide enhanced conductivity, and were studied with the microscope operating at 15 or 20 kV. Images of the alternating FP/PP multilayered extrudate are shown in the Figure 4 below. After extrusion, 20 individual multilayer films were stacked and
  • Polymer pellets of PSF and EO (10/90 wt/wt% respectively) were melt- blended and pelletized using a twin-screw extruder (Haake Fisons Rheodrive 5000) at 28O 0 C prior to injection-molding shaken to combine the two materials.
  • the bended pellets were then injection molded under the same conditions as were used in Comparative Example 1.
  • Example 1 PSF/EO Smart Pellets of Example 1 were combined by shaking with pellets of EO * polymer in a 10/90 wt/wt% ratio, respectively, then injection molded in the same manner as was used in Comparative Example 3.
  • Example 2 The FP/PP smart pellets of Example 2 were combined by shaking with PP pellets in a 30:70 wt/wt% ratio respectively, to produce an overall fiber loading of 5 wt%. This blend of pellets was injection molded under the same conditions use for Comparative Examples 4 and 5.
  • Examples 1 and 2 and from Example 3 are compared in Table 3 below.
  • Use of the PSF/EO Smart Pellet system produced a product with noticeably higher tensile modulus than was obtained with the starting EO polymer or from a simple PSF/EO polymer blend.
  • Table 3 Tensile test results of PSF/EO injection-molding samples.
  • Example 4 Examples 4 and 5, and from Example 5 are compared in Table 5 below.
  • Use of the FP/PP Smart Pellet system produced a product with noticeably higher tensile modulus than was obtained with the starting PP polymer, and matched that obtained with a fiber masterbatch/PP blend.
  • Table 5 Tensile test results of FP/PP injection-molding samples.
  • Example 3 is compared in Table 7 below.
  • Use of the PSF/EO Smart Pellet system produced a product with a noticeably higher flexural than was obtained with the starting EO * polymer.
  • Table 7 Flexural test results of PSF/EO * injection-molding samples.
  • Example 4 Examples 4 and 5, and from Example 5 are compared in Table 8 below.
  • Use of the PF/PP Smart Pellet system produced a product with noticeably higher flexural modulus than was obtained with the starting PP polymer or from a simple fiber filled polymer.

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

Selon la présente invention, un système de composite multicouche / « préforme intelligente » unique a été introduit en tant que procédé pour produire des polymères de matrice renforcés ayant des propriétés mécaniques supérieures. Un copolymère éthylène-octène / un polysulfone et un polypropylène / une fibre inorganique ont été choisis en tant que systèmes modèles avec lesquels soumettre à essai ce concept. Les agents de renforcement étaient présents dans le composite multicouche et mélangés avec le polymère de matrice dans un moulage par injection. Les propriétés mécaniques des produits de polymère de matrice résultants ont été étudiées en effectuant des essais de résistance à la traction, à la flexion et aux chocs. Les comportements de morphologie des composites multicouches et des produits de polymère de matrice ont été étudiés par microscopie électronique à balayage, microscopie à force atomique, et microscopie optique. Dans un essai, les couches de polysulfone ressemblent à une morphologie de lamelles d’argile dispersées dans un polymère de matrice.
PCT/US2010/002250 2009-08-14 2010-08-13 Composite multicouche utile en tant qu’additif polymère WO2011019408A1 (fr)

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EP3350818A4 (fr) * 2015-09-14 2019-05-15 Polymerplus, LLC Film diélectrique stratifié multicomposant et ses utilisations
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WO2013013070A3 (fr) * 2011-07-21 2013-05-02 Entegris, Inc. Compositions à base de nanotubes et de composés polymères de fibre de carbone finement broyée et leur procédé de fabrication
EP2836361A4 (fr) * 2012-04-13 2016-01-20 Univ Case Western Reserve Production de microfibres et de nanofibres par coextrusion de microcouches continue
US11111606B2 (en) 2012-04-13 2021-09-07 Case Western Reserve University Production of micro- and nano-fibers by continuous microlayer coextrusion
WO2013155519A1 (fr) 2012-04-13 2013-10-17 Case Western Reserve University Production de microfibres et de nanofibres par coextrusion de microcouches continue
US10077509B2 (en) 2012-04-13 2018-09-18 Case Western Reserve University Production of micro- and nano-fibers by continuous microlayer coextrusion
CN104245309A (zh) * 2012-04-13 2014-12-24 卡斯西部储备大学 通过连续微米层的共挤出来制备微米和纳米纤维
CN104245309B (zh) * 2012-04-13 2018-05-15 卡斯西部储备大学 通过连续微米层的共挤出来制备微米和纳米纤维
FR2995815A1 (fr) * 2012-09-26 2014-03-28 Peugeot Citroen Automobiles Sa Procede d'elaboration d'un materiau composite thermoplastique renforce par des nanotubes de carbone
WO2014048755A1 (fr) * 2012-09-26 2014-04-03 Peugeot Citroen Automobiles Sa Procede d'elaboration d'un materiau composite thermoplastique renforce par des nanotubes de carbone
CN103336098A (zh) * 2013-07-15 2013-10-02 四川大学 一种预测功能粒子对聚合物基体有效作用范围的方法
WO2015066588A1 (fr) 2013-11-04 2015-05-07 The Procter & Gamble Company Compositions de polymères thermoplastiques ayant une morphologie lamellaire co-continue
US10286585B2 (en) * 2015-08-17 2019-05-14 Case Western Reserve University Fiber reinforced hydrogels and methods of making same
EP3350818A4 (fr) * 2015-09-14 2019-05-15 Polymerplus, LLC Film diélectrique stratifié multicomposant et ses utilisations
US10759139B2 (en) 2015-09-14 2020-09-01 Polymerplus Llc Multicomponent layered dielectric film and uses thereof
US20230219135A1 (en) * 2022-01-08 2023-07-13 M4 Sciences, Llc Composite materials and composite manufacturing methods

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