• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
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    • 专利摘要:
    COMPOSITION, AND, METHOD FOR PREPARING A COMPOSITION. A composition comprising 65 to 90 weight percent chemical wood kraft pulp fibers and a thermoplastic polymer and a method of making the composition. In one embodiment, amounts of about 5-10%, and in another 0.2-5% of the coupling agent are incorporated into the composite formulations and melt-processable compositions. Fillers and fibers in addition to chemical wood pulp fibers can be added to the fiber/polymer combination to impart desirable physical characteristics or reduce the amount of polymer needed for a given application.
    公开号:BR112013018613B1
    申请号:R112013018613-5
    申请日:2012-02-10
    公开日:2021-05-25
    发明作者:Robert T. Hamilton；Harshadkumar M. Shah；Jeffrey Jacob Cernohous；Neil R. Granlund；David E. Fish
    申请人:Weyerhaeuser Nr Company；
    IPC主号:
    专利说明:

    Cross Reference to Related Order
    This application is entitled and claims priority benefit under 35 USC §119 of US Provisional Patent Application Serial No. 61/442,716 filed February 14, 2011, and entitled "Polymer Composites", the contents of which are incorporated herein by reference. Field of Invention
    The present invention relates to polymeric composites which are derived from the molten mass of a polymer matrix with chemical wood pulp fiber. Fundamentals
    There are three steps in molding composite polymer materials. The first is the formation of a standard mixing material. The second is the composition of the standard mixing material into a composite material. The third step is the molding of the composite material into a final molded product. In some cases steps one and two can be combined. Brief Description of Drawings
    Figs. 1-5 are diagrams of a globule used to produce the polymer composite.
    Fig. 6 is a diagram of a mixer
    Figs. 7 and 8 are diagrams of a globule mill.
    Fig. 9 is a diagram of a single screw extruder useful for producing the present globule. Detailed Description
    The present invention is directed to a solution for providing an economical means of producing composite polymeric materials that include 65 to 90% by weight of chemical wood pulp fiber from a sheet of chemical wood pulp. The composites of this invention have chemical wood pulp fibers uniformly dispersed within a polymeric matrix.
    In one embodiment the chemical wood pulp fiber is a bleached chemical wood pulp fiber. There are reasons for using a bleached chemical wood pulp fiber instead of an unbleached wood pulp fiber.
    One reason is color. A bleached chemical wood pulp fiber is substantially all cellulose and hemicellulose. Cellulose and hemicellulose have no natural color so they impart little or no color to a composite. On the other hand, unbleached fibers such as natural fibers like kenaf or integral wood fibers are up to 50% lignin and other compounds can be colored in their natural state or will be colored when heated to thermoplastic processing temperatures. A composite with unbleached, natural or whole wood fibers would become colored, likely a dark brown color.
    Another reason is odor. Cellulose has no odor so a composite with bleached wood pulp fibers has very little odor contributed by the cellulose. Lignin and other components in unbleached fibers have strong characteristic odors when melted, imparting a strong odor to the resulting composite, limiting their use in confined areas such as the interior of an automobile.
    There are problems associated with uniformly dispersing chemical wood pulp fibers through a polymeric matrix. The fibers are initially in a sheet of dry pulp. Drying collapses the pulp fibers. Drying also causes pulp fibers to bond through hydrogen bonds. The hydrogen bonds must be broken in order to obtain substantially individual fibers. Some of the fibers will remain attached. These are called nodes or meshes, depending on the size. There will usually be few knots and meshes remaining after breaking the hydrogen bonds between the fibers.
    There are also problems associated with providing the chemical wood pulp fibers at levels of 65% by weight or higher of the total polymer/fiber blend weight. The smaller amount of polymer means that it is more difficult to disperse the fiber in the polymer matrix. The smaller amount of polymer means that it is more difficult to disperse the fiber evenly throughout the polymer matrix. The fiber/polymer mixture becomes more viscous as the amount of fiber increases and it is therefore more difficult to move the fibers within the matrix to promote dispersion. The purpose is to have very few fiber clumps.
    The problems to be solved are to supply the fibers in a polymeric matrix in a substantially individual form and to measure the fibers to the polymer in a substantially uniform amount so that the composite/wood pulp fiber has substantially uniformly dispersed wood pulp fibers through the composite. The present invention loads the diced chemical wood pulp particles removed from the wood pulp sheet and measures them into the polymer and substantially separates the wood pulp fibers while mixing the wood pulp with the polymer.
    The polymer matrix serves as the host polymer and is a component of the melt processable composition including the chemical wood pulp feedstock. Melt processing is used to combine the polymer and fiber of chemical wood pulp. In melt processing the polymer is heated and melted and the chemical wood pulp fiber is combined with the polymer.
    The polymer is thermoplastic.
    A wide variety of polymers recognized in the art as suitable for melt processing are useful as a polymer matrix. The polymer matrix substantially includes polymers which are sometimes referred to as being difficult to melt, especially when combined with an interfering element or other immiscible polymer. They include both hydrocarbon and non-hydrocarbon polymers. Examples of useful polymeric matrices include, but are not limited to, high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), polypropylene (PP), polyolefin copolymers (e.g., ethylene -butene, ethylene-octene, ethylene vinyl alcohol), polystyrene, polystyrene copolymers (eg high impact polystyrene, acrylonitrile butadiene styrene copolymer), polyacrylates, polymethacrylates, polyesters, polyvinyl chloride (PVC), fluoropolymers , Liquid Crystal Polymers, polyamides, poly(ether imides), poly(phenylene sulfides), polysulfones, polyacetals, polycarbonates, poly(phenylene oxides), polyurethanes, thermoplastic elastomers, epoxies, alkyds, melamines, phenolics, ureas, esters vinyls or combinations thereof. In certain embodiments, the most suitable polymeric matrices are polyolefins.
    Polymeric matrices that are derived from recycled plastics are also applicable as they are often lower in cost. However, because such materials are often derived from materials coming from multiple waste sources, they can have vastly different melting mass rheologies. This can make the material very problematic to process. The addition of cellulosic feedstock to a recycled polymer matrix should increase melt viscosity and reduce overall variability, thus improving processing.
    A partial list of plastic or polymeric materials that can utilize cellulose from wood pulp fibers may include polyolefins, polyethylene, polypropylene, poly(vinyl chloride), ABS, polyamides, blends thereof, poly(ethylene terephthalate), poly (butylene terephthalate), poly(methyl terephthalate), ethylene-carbon monoxide and mixtures of styrene copolymers such as thermoplastic polymers of styrene/acrylonitrile and styrene/maleic anhydride, polyacetals, cellulose butyrate, acrylonitrile-butadiene-styrene, certain methyl methacrylates, and polychlorotrifluoroethylene polymers. A complete list of thermosetting or thermoplastic material, which can utilize wood pulp fiber cellulose, is known to those skilled in the art.
    In one embodiment, the chemical wood pulp feedstock is melt processed with an incompatible polymer matrix (eg, polyolefin). In another embodiment, the chemical wood pulp feedstock is fused with a compatible polymeric matrix (eg modified cellulosic polymers). For example, it has been found that when the chemical wood pulp feedstock of this invention is fused with cellulose propionate (Tenite1M 350E), the resulting composite has excellent fiber dispersion and mechanical properties.
    The present invention also contemplates the use of coupling agents in the composite formulation. Coupling agents are typically used to improve the interfacial interaction of fillers with the polymer matrix. The addition of coupling agents or compatibilizers often improves mechanical properties of the resulting composite material. The present invention uses coupling agents to improve the interaction between the chemical wood pulp fiber of this invention and the polymer matrix as it is conventionally known. However, we have also found that the addition of a coupling agent improves melt processing and dispersion of the chemical wood pulp feedstock for this invention with some polymers.
    Preferred coupling agents for use with polyolefins are polyolefin-graft-maleic anhydride copolymers. In one embodiment, the polymer matrix and cellulosic feedstock are fused with a polyolefin-graft-maleic anhydride copolymer. Commercially available coupling agents of this invention include those sold under the brand names Polybond (Chemtura), Exxelor (Exxon Mobil), Fusabond™ (DuPont), Lotader™ (Arkema), Bondyram 1M (Maroon), Integrate rM (Equistar). The polymer matrix can contain one or more fillers in addition to the chemical wood pulp feed filler. The polyolefin in the graft copolymer will be the same polyolefin used as the polymer in the polymer matrix. For example, polyethylene-graft-maleic anhydride would be used with polyethylene and polypropylene-graft-maleic anhydride would be used with polypropylene.
    In one embodiment, amounts of about 5-10% and in the other 0.2-5% of coupling agent are incorporated into composite formulations and melt-processable compositions.
    Fillers and fibers in addition to chemical wood pulp fibers can be added to the fiber/polymer combination to impart desirable physical characteristics or reduce the amount of polymer needed for a given application. Fillers often contain moisture and therefore reduce the effectiveness of a compatibilizer present in a polymer matrix. Non-limiting examples of fillers and fibers include wood flour, natural fibers in addition to chemical wood pulp fiber, glass fiber, calcium carbonate, talc, silica, clay, magnesium hydroxide, and aluminum trihydroxide. ,
    In another aspect of the invention, the melt processable composition may contain other additives. Non-limiting examples of conventional additives include antioxidants, light stabilizers, fibers, blowing agents, foam additives, antiblocking agents, heat stabilizers, impact modifiers, biocides, flame retardants, plasticizers, tackifiers, colorants, processing aids , lubricants, compatibilizers and pigments. Additives can be incorporated into the melt processable composition in the form of powders, granules, granules, or in any other extrudable or prepareable form. The amount and type of conventional additives in the melt processable composition may vary depending on the polymer matrix and physical properties desired in the finished composition. Those skilled in the melt processing art are able to select appropriate amounts and types of additives to combine with a specific polymer matrix in order to achieve desired physical properties in the finished material.
    In one embodiment, the chemical wood pulp feedstock of this invention is produced by mechanically cutting a chemical wood pulp sheet material. In one embodiment, the chemical wood pulp feedstock is cut into a hexagonal shape that is conducive for use with conventional feeding equipment. In other embodiments the shapes can be triangular, rectangular or pentagonal shaped particles. The composites of this invention are produced by melt processing a polymeric matrix with chemical wood pulp feed. In one embodiment, the chemical wood pulp feedstock is evenly dispersed within the polymer matrix after melt processing.
    The present invention is directed to a solution for providing an economical means of producing composite materials that contain well-dispersed chemical wood pulp fibers. This is achieved by utilizing a chemical wood pulp feedstock that has an increased specific mass and that is capable of being fed by melt processing equipment using conventional feed technology. The composites of this invention have chemical wood pulp fibers well dispersed in the polymer matrix.
    The present invention can utilize a number of tree species as the source of pulp, paperboard and paper fibers. Coniferous and broadleaf species and mixtures of these can be used. These are also known as softwood and hardwood. Typical softwood species are various spruces (eg Sitka spruces), spruce (Douglas spruce), various hemlocks (Western hemlock), American larch, larch, various pine (Southern Pine, white pine, Caribbean pine), cypress, redwood or mixtures thereof. Typical softwood species are ash, black beech, poplar, linden, birch, beech, chestnut, gum, elm, eucalyptus, maple oak, poplar, and maple or mixtures thereof.
    The use of softwood or hardwood species may depend in part on the desired fiber length. Hardwood or broadleaf species have a fiber length of 1-2 mm. Softwood or coniferous species have a fiber length of 3.5 to 7 mm. Douglas fir, great spruce, western hemlock, western larch, and southern pine have fiber lengths in the range of 4 to 6 mm. Pulping and bleaching and cutting can reduce the average length slightly because of fiber breakage.
    In pulp production, woody material is broken down into fibers in a chemical pulping process. The fibers can then optionally be subjected to bleaching. The fibers are then combined with water in a storage cylinder to form a slurry. The slurry then passes to a feed box and is then placed on a wire, subjected to dewatering and dried to form a pulp sheet. Additives can be combined with fibers in the storage cylinder, feed box or both. The materials can also be sprayed onto the pulp sheet before, during or after dewatering and drying. The kraft pulping process is typically used in the production of wood pulp.
    Cellulosic wood pulp fibers can be in the form of commercial cellulosic wood pulps. Material is typically delivered in roll or baled form. The thickness of the pulp sheet is a factor that can determine particle thickness. The pulp sheet has two substantially parallel opposite faces and the distance between faces will be the particle thickness. A typical pulp sheet might have a thickness of 0.1mm to 4mm. In some modalities the thickness can be from 0.5 mm to 4 mm. One of the other factors affecting particle thickness is the presence of pretreatment to the fiber sheet. Thus the particle can be thicker or thinner than the fiber sheet.
    The fiber sheet, and the particles, can have a basis weight of 2 2 • 'li* 12g/m (gsm) to 2000 g/m . In one embodiment the particles could have a basis weight of 600 g/m to 1900 g/m . In another embodiment the particles could have a basis weight of 500 g/m2 to 900 g/m2. For a sheet of paper a mod could have a basis weight of 70gsm to 120gsm. In another embodiment a paperboard could have a basis weight of 100gsm to 350gsm. In another embodiment a fiber sheet for specialized use could have a basis weight of 350 gsm to 500 gsm.
    Pulp or pretreatment additives can also change the character of the particle. A pulp that is treated with separating materials will provide a looser particle than a pulp that has no separating materials. A looser particle can more readily disperse in the material being combined.
    The particle has a hexagonal shape, the modality of which is shown in Figure 1. The hexagon can be any type from totally equilateral to totally asymmetric. If not equilateral, the major axis can be 4 to 8 millimeters (mm) and the minor axis can be 2 to 5 mm. Some of the sides of the hexagon can be the same length and some or all sides can be different lengths. The circumference or perimeter of the hexagon can be from 12 mm to 30 mm and the area of the top or bottom 24 or 26 of the particle can be from 12 to 32 mm. In one embodiment the particles could have a thickness of 0.1 to 1.5 mm, a length of 4.5 to 6.5 mm, a width of 3 to 4 mm and an area on a face of 15 to 20 mm. In another embodiment the particles could have a thickness of 1 to 4 mm, a length of 5 to 8 mm, a width of 2.5 to 5 mm and an area on a face of 12 to 20 mm~.
    Two examples of a hexagonally formed particle are shown.
    In Figs. 1-3, particle 10 is hexagon-shaped and has two opposite sides 12 and 18 that are equal in length and longer than the other four sides 14, 16, 20 and 22. The other four sides 14, 16, 20 and 22 can be the same length as shown, or the four sides can be different lengths. Two of the sides, one at each end such as 14 and 20 or 14 and 22 can be the same length, and the other two at each end, 16 and 22 or 16 and 20, can be the same length or have different lengths. In each of these variations, sides 10 and 18 can be the same length or different lengths. The edges of particles can be sharp or rounded.
    The distance between the top 24 and the bottom 26 of the particle 10 can be from 0.1 mm to 4 mm.
    Figs. 4 and 5 illustrate an embodiment in which each of the six sides of the hexagon is of a different length. The mode shown is illustrative and the order of the side lengths and the size of the side lengths may vary.
    Particles of the shape, size and basis weight described above can be measured in weight loss and volumetric feed systems known in the art.
    The alignment of fibers within the particle can be parallel to the major axis of the hexagon or perpendicular to the major axis of the hexagon or any orientation in between.
    The hexagonal particles can be formed in a Henion cutter, but other means could be used to produce a hexagonal particle.
    The hydrogen bonded wood pulp cellulose fibers are then dispersed in the polymer. One method is to prepare a masterbatch which is rich in fibers having from 65 to 85% by weight of wood pulp cellulose fiber and 15 to 35% by weight of polymer. Part of the polymer can be a compatibilizer if one is needed. This material would then be prepared at the same location or at a different location to reduce the amount of cellulose fiber from wood pulp and increase the amount of polymer. Other additives and fillers can be added to the material in the compounding operation. The prepared material would then be molded.
    The initial addition of cellulose pulp fiber to the polymer is a two-step operation.
    In the first step the hexagonal globules are combined and mixed with the polymer in a mixing operation. Mixing can take place in a thermokinetic mixer or a Gelimat mixer. The amount of chemical wood pulp cellulose fiber in the material is from 65 to 85% by weight and the amount of polymer is from 15 to 35% by weight. If a compatibilizer is used then the amount of polymer will be reduced by the amount of compatibilizer. If 5% by weight of compatibilizer is used then the amount of polymer will be reduced by 5% by weight. Apolar polymers, such as olefins, would use a compatibilizer. Typical compatibilizers are graft copolymers such as polypropylene maleic anhydride or polyethylene maleic anhydride. If polypropylene is the polymer then up to 0.5% by weight of antioxidant will also be used. The fiber and polymer will come out of the thermokinetic mixer as a soft material.
    A mixer 30 is shown in Figure 6. The mixer 30 has a hopper through which materials are fed. Materials are conveyed by a screw feeder 34 to mixing chamber 36 in which paddles 38 are rapidly rotated by motor 40. Paddles 38 rotate through the mixture and the centrifugal force created by paddles 38 moves the material outwardly against the mixture. mixing chamber wall 42. The frictional heat fuses the polymer materials, polymer and compatibilizer, and mixes the fiber with the polymer. After mixing the polymer is removed from mixing chamber 36 through port 44.
    Another method that can be used in the first step is a twin-screw opener extruder. The twin screw extruder has an opening at the exit end so that material flow from the extruder is not impaired. The amounts of fiber, polymer and compatibilizer are the same as described for the thermokinetic mixer. The material will come out of the twin screw extruder as a grainy material.
    This material will then be further treated in a pellet mill, such as the California pellet mill, or a single screw extruder, such as the Bonnot single screw extruder.
    A laboratory version of a globule mill is shown in Figures 7 and 8. The globule mill 50 has a hopper 52 into which the fiber/polymer composite material 54 from the thermokinetic mixer or twin screw extruder is transferred. The composite material 54 falls onto a perforated plate 56. Apertures 58 in perforated plate 56 are the size of the diameter of extruded beads 60. A pair of wheels 62 forces the composite through openings 58 to form beads 60. Wheels 62 are mounted on shafts 64. Shafts 64 are mounted on a rotor 66. Rotor 66 is rotated by a motor (not shown) to rotate wheels 62 around perforated plate 56. Globules 60 are removed from the apparatus and collected.
    Several experiments were needed to determine how the single screw extruder could be used to provide a material in which the pulp cellulose fiber was dispersed through the polymer. The tendency of fibers at high fiber levels is to clump together. It was discovered that it was necessary to divert the flow of material through the extruder in order to obtain fiber dispersion. This is done by placing pins extending from the extruder outer wall into the extruder cavity. Material is forced from the apparatus through holes to form extruded globules. Material may have a tendency to get stuck behind the plate and not pass through the hole in an efficient manner. The addition of a wiper at the rear of the plate face moves the composite material through the holes more efficiently.
    A single screw extruder is shown in Figure 9. The extruder 80 has a hopper 82 into which the fiber composite material from the mixer is placed. Hopper 82 connects to cylinder 84 and bolt 86 extending through cylinder 84. Bolt 86 is rotated by a motor (not shown) and drives material in cylinder toward plate 88. Bolt design can place more or less pressure in the composite as it travels through the cylinder. Pins 90 are placed along the cylinder. Pins 90 can be moved in or out to divert material flow through the cylinder and assist in dispersing the fibers within the polymer. Plate 86 has a number of openings 92 through which material passes to form globules.
    In one embodiment the first twin screw mixer can be directly connected to the second single screw extruder and the material will pass directly from the first mixer to the second. The same engine can operate both.
    The beadlets of the masterbatch contain from 65 to 90% by weight of chemical wood pulp fiber and from 15 to 35% by weight of polymer.
    权利要求:
    Claims (9)
    [0001]
    1. Composition, characterized in that it comprises at least 85 and up to 90 percent by weight of wood kraft chemical pulp fibers and a thermoplastic polymer.
    [0002]
    2. Composition according to claim 1, characterized in that the chemical wood pulp fiber has a separating material.
    [0003]
    3. Composition according to claim 1, characterized in that the chemical wood pulp fiber does not have a separating material.
    [0004]
    4. Composition according to claim 1, characterized in that the chemical wood pulp fiber is a chemical wood pulp fiber subjected to bleaching.
    [0005]
    5. Composition according to claim 1, characterized in that the thermoplastic polymer comprises a compatibilizer.
    [0006]
    6. Composition according to claim 1, characterized in that it comprises an antioxidant.
    [0007]
    7. Composition according to claim 1, characterized in that the composition is a globule.
    [0008]
    8. Composition according to claim 1, characterized in that the polymer is not poly(vinyl chloride).
    [0009]
    9. Method for preparing a composition as defined in claim 1, characterized in that it comprises: providing chemical wood pulp fibers in the form of a particle to a mixer in the form of a thermokinetic mixer or a mixing device having at least two interwoven rotors, supplying a thermoplastic polymer to the blender, wherein for every 100 weight percent material supplied to the blender the pulp fibers are 85 to 90 weight percent of the material, mixing the fiber particles and polymer in the blender to forming a fiber/polymer blend in which the fibers are dispersed within the polymer, another blend of the fiber/polymer blend in a second blending device, wherein the second blending device uses split flow to disperse the fibers in the fiber blend /polymer, and thereby forming globules with the fiber/polymer combination.
    类似技术:
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-07-09| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2020-08-11| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2020-12-08| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-04-13| B09X| Decision of grant: republication|
    2021-05-25| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 10/02/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201161442716P| true| 2011-02-14|2011-02-14|
    US61/442,716|2011-02-14|
    PCT/US2012/024705|WO2012112398A1|2011-02-14|2012-02-10|Polymeric composites|
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