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WO2014123478A1 - Procédé pour procurer un matériau composite comprenant une matrice thermoplastique et des fibres de cellulose - Google Patents

Procédé pour procurer un matériau composite comprenant une matrice thermoplastique et des fibres de cellulose Download PDF

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Publication number
WO2014123478A1
WO2014123478A1 PCT/SE2014/050149 SE2014050149W WO2014123478A1 WO 2014123478 A1 WO2014123478 A1 WO 2014123478A1 SE 2014050149 W SE2014050149 W SE 2014050149W WO 2014123478 A1 WO2014123478 A1 WO 2014123478A1
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WO
WIPO (PCT)
Prior art keywords
fibers
cellulose
composite
fiber
cellulose fiber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/SE2014/050149
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English (en)
Inventor
Antal Boldizar
Ruth Arino
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SODRA SKOGSAGARNA EKONOMISK FORENING
Original Assignee
SODRA SKOGSAGARNA EKONOMISK FORENING
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SODRA SKOGSAGARNA EKONOMISK FORENING filed Critical SODRA SKOGSAGARNA EKONOMISK FORENING
Priority to EP14749372.0A priority Critical patent/EP2953780A4/fr
Publication of WO2014123478A1 publication Critical patent/WO2014123478A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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 drums
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • B29B7/48—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws
    • B29B7/482—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws provided with screw parts in addition to other mixing parts, e.g. paddles, gears, discs
    • B29B7/483—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft with intermeshing devices, e.g. screws provided with screw parts in addition to other mixing parts, e.g. paddles, gears, discs the other mixing parts being discs perpendicular to the screw axis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58—Component parts, details or accessories; Auxiliary operations
    • B29B7/72—Measuring, controlling or regulating
    • B29B7/726—Measuring properties of mixture, e.g. temperature or density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/82—Heating or cooling
    • B29B7/823—Temperature control
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/82—Heating or cooling
    • B29B7/826—Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B29B7/90—Fillers or reinforcements, e.g. fibres
    • B29B7/92—Wood chips or wood fibres
    • 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
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • 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
    • 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
    • B29C48/285—Feeding the extrusion material to the extruder
    • B29C48/288—Feeding the extrusion material to the extruder in solid form, e.g. powder or granules
    • B29C48/2886—Feeding the extrusion material to the extruder in solid form, e.g. powder or granules of fillers or of fibrous materials, e.g. short-fibre reinforcements
    • 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
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • 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
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B29C48/425—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders using three or more screws
    • 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
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/40—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft
    • B29B7/42—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft with screw or helix
    • B29B7/421—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft with screw or helix with screw and additionally other mixing elements on the same shaft, e.g. paddles, discs, bearings, rotor blades of the Banbury type
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B29C2948/9259—Angular velocity
    • 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
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • 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
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0022—Combinations of extrusion moulding with other shaping operations combined with cutting
    • 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
    • B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns

Definitions

  • the present invention relates to a method for providing composite materials comprising a thermoplastic matrix and cellulose fibers.
  • glass-fiber reinforced plastic is a fiber reinforced polymer made of a plastic matrix reinforced by fine glass fibers.
  • examples of glass-fiber reinforced plastics are boat hulls and pipes.
  • the fibers for reinforcement have traditionally been synthetic such as glass fibers more recent research and development has shown excellent results also for reinforcement with natural fibers.
  • Cellulose fibers are natural fibers that have attracted particular interest in the context of composite materials due to their properties such as renewability, biodegradability, low density, high specific stiffness, low abrasiveness, physiological harmlessness, high availability and low cost.
  • manufacture of cellulose fiber-reinforced composite materials is associated with challenges since short cellulose fibers such as wood pulp fibers are difficult to feed in a continuous way and disperse evenly in a matrix.
  • the cellulose fibers may be subjected to breaking and thermal degradation during processing.
  • the low density and high bulkiness of cellulose fibers make them difficult to use in continuous industrial processes.
  • the cellulose fibers In order to facilitate mixing of cellulose fibers with thermoplastic polymers in continuous processes the cellulose fibers have been converted into granules or pellets. However, such granulating or pelletizing leads to severe fiber breakage resulting in composite materials with poor mechanical performance.
  • the cellulose fibers may be converted into a fiber roving or tow that is fed into the process, but unfortunately this does not work well when the fibers are short such as in the case of wood pulp fibers.
  • the cellulose fibers are evenly distributed within the matrix of the composite material as individual fibers will form a better reinforcing fibrous network in the composite material than will bundles or clusters of fibers.
  • An even distribution of fibres in the polymeric matrix is also beneficial for the further processability of the composite material into articles having high surface finish and detail definition.
  • Fiber dispersion may be improved by using compatibilizers improving adhesion between the fibers and the matrix and/or by using appropriate processing conditions. For example, in extrusion the amount of shear forces to which the material undergoing extrusion is subjected will depend on the extruder screw configuration used. The shear forces required to break the fiber bundles will also reduce fiber length thereby negatively influencing the mechanical properties of the resulting material. Therefore, achieving breakage of fiber bundles while minimizing fiber breakage during extrusion in order to produce a composite material with good mechanical performance is a difficult task.
  • EP 2 51 1 323 discloses processes such as extrusion mixing for manufacturing cellulose fiber-reinforced ethylene acrylic acid copolymer (EAA). No compatibilizer or coupling agent is required to promote the compatibility between the EAA and the cellulose fibers. Agglomerates, i.e. pellets of cellulosic fibers and EAA, are used for producing the composite materials. This way of extrusion mixing does not allow for complete dispersion of the cellulose fibers into the matrix of EAA.
  • EAA cellulose fiber-reinforced ethylene acrylic acid copolymer
  • the manufacturing of cellulose fiber- re info reed composite materials with good mechanical performance is a complex task due to the difficulties associated with handling and feeding of the cellulose fibers as well as the large number of parameters being interrelated in a non-straightforward way and affecting the mechanical properties.
  • a method for producing a composite material comprising cellulose fibers and a thermoplastic matrix by means of an extruder.
  • the extruder comprises a twin screw,
  • co-extrusion is understood to mean extrusion of the one or more cellulose fiber-based webs in a mixture with a melted thermoplastic matrix material.
  • the web may be provided in roll form or in the form of a stack or pile of Z-folded web material so that the desired amount of fibers can be easily fed into the extruder.
  • the cellulose fiber-based web may also be provided as individual sheets.
  • the amount of added fibers is also determined by the basis weight of the fiber- based web, the width of the fiber-based web and by the number of webs or plies that are fed into the extruder. Accordingly, with the same equipment, composite materials having different fiber content may be produced by varying one or more of process speed, basis weight of the web, width of the web and number of webs or plies used in the process.
  • the web will be broken and mixed with the melted thermoplastic matrix material in an efficient way so that a composite material is formed with the cellulose fibers well dispersed within the thermoplastic matrix. It has been found that introducing the web into a melted thermoplastic matrix material in accordance with the invention helps to minimize fiber length reduction resulting in improved mechanical performance and evenness of the resulting composite material. This is in contrast to the use of fibers which have been pre-processed into solid pellets or granules together with thermoplastic polymer. Pre-processing of the fibers and the matrix polymer into pellets or granules involves mechanical working of the materials resulting in grinding of the fibers and causing the fiber length to diminish. Thus, in addition to the improved handling aspects the use of a cellulose fiber-based web has a positive impact on the properties of the resulting composite material as the web allows for improved fiber dispersion within the thermoplastic matrix with minimal fiber length reduction during processing.
  • the composite article obtained in step b) may be subsequently formed into a composite material of desired shape such as a sheet shape or a three-dimensional shape and allowed to assume room temperature by cooling.
  • the cooling speed may be increased by using cooled rollers, cooling air, etc. as known in the art.
  • the method may further comprise the steps of:
  • the composite article may be given its final shape at this stage or may be further processed, e.g. from a sheet or pellet-form by thermoforming methods such as form pressing or molding techniques. Measurement of properties such as fiber length, aspect ratio, area percentage of cellulose fiber aggregates in the thermoplastic matrix, tensile modulus (E), tensile strength (a ) and strain at break (s ) were used to characterize the formed composite article. It was found that extrusion generally resulted in shorter fiber length and lower aspect ratio to some minor extent; while fiber dispersion was very good as measured visually or by microscopy analysis. In order to achieve complete or almost complete fiber dispersion the formed composite article may be further subjected to additional melting and extrusion.
  • E tensile modulus
  • a tensile strength
  • s strain at break
  • the method may further comprise subjecting the composite article to the steps of: e) melting and extruding by means of one or more twin screws or one or more single screws to provide a composite material,
  • thermoplastic matrix material and/or cellulose fiber-based web material may be added during step e).
  • the additional thermoplastic matrix material and/or the cellulose fiber-based web material may be the same or different as those used for making the composite material resulting from steps a) and b).
  • the thermoplastic matrix material is melted prior to extrusion with the one or more cellulose fiber-based webs. If using more than one extruder screw in step e), the screws may be sequentially arranged in the extruder or the composite material may be passed more than once through the same extruder screw arrangement.
  • a twin screw is required in process step b) in order to achieve satisfactory fiber dispersion, further processing of the material may be carried out using either a single screw or a twin screw or any combination of two or more extruder screws as set out herein.
  • a barrier screw is an example of a single screw that may be used.
  • a twin screw is understood to be two screws placed side by side.
  • the twin screw may be co-rotating or counter-rotating.
  • the twin screw used in step b) is preferably operated in a co-rotating manner.
  • the configurations of the screws may be varied using forward conveying elements, reverse conveying elements, kneading blocks, and other means for achieving particular mixing characteristics.
  • a fiber-based web as used herein is implied a continuous coherent structure having an undefined length, a defined width and a defined thickness. The thickness is small in comparison with the width such that the web is a generally two-dimensional structure.
  • the webs used in the mixing process of the invention may comprise any type of cellulosic fibers such as wood pulp fibers, cotton fibers, viscose fibers, flax, hemp, etc., with wood pulp fibers being preferred. Mixtures of different kinds of cellulosic fibers may also be used.
  • the cellulose fiber-based web may be an air-laid cellulose fiber-based web or a paper web.
  • the paper web may be a creped or non-creped tissue paper web, i.e. a lightweight paper web. It will be appreciated that tissue paper is wet-formed paper while airlaid paper is dry-formed paper.
  • the cellulose fiber-based web may comprise one, two, three, four or more plies. Each individual ply may have a basis weight of from 10 to 50 g/m 2 . For instance, tissue paper typically has a basis weight of from 15 to 40 g/m 2 .
  • the fiber-based webs used in the methods of the invention may comprise additives such as pigments and fillers.
  • the amount of additives should preferably not exceed 20 % by volume, by that limiting the processing difficulties arising from an increased viscosity.
  • a further advantage of the method disclosed herein is that the cellulose fiber-based web may comprise softwood fibers, hardwood fibers or mixtures thereof. This is in contrast to, for example, roving and carding techniques where short wood pulp fibers are difficult to use.
  • the method also provides a way of using recycled fibers which due to having been previously subjected to various processing steps generally have a smaller fiber length as compared to corresponding virgin fibers i.e. fibers that are used for the first time.
  • the method of the invention and the composite materials and/or composite articles produced therefrom offer high versatility as well as increased environmental benefits.
  • the moisture content is from 0 to 10 weight% ( wt %), from 0 to 7 wt%, from 6 to 8 wt%, from 5 to 6 wt%, from 2 to 4 wt% or about 3 wt% based on the cellulose fiber-based web.
  • the amount of cellulose fibers incorporated into the thermoplastic matrix influences the properties of the formed composite material. The best results have been found when the cellulose fiber content is from 20 to 30 wt % or from 25 to 30 wt% based on the weight of the composite material. Thus, the cellulose fiber-based web should provide from 20 to 30 wt % or from 25 to 30 wt% of cellulose fibers to the composite composition. It was found that the tensile modulus and tensile strength decreased or remained relatively constant when the cellulose fiber content was increased from about 25 to 30 wt%. A cellulose fiber content above about 30 wt% did not afford additional benefits to the mechanical properties of the composite material, but an increased level of fiber content was found to lead to more difficulties with the flow properties of the material mixture.
  • thermoplastic polymer or a mixture of different thermoplastic polymers may be used as the thermoplastic matrix material.
  • the thermoplastic polymer or polymers may be derived from recycled or non-recycled thermoplastic resources. It is desirable that the
  • thermoplastic polymer has a softening or melting temperature that is less than about 100° C since cellulose fibers may deteriorate above this temperature.
  • the thermoplastic matrix may be prepared according to conventional methods such as grinding, shredding, pelletizing and the like.
  • the thermoplastic polymer or polymers may be independently selected from one or more in the group consisting of: ethylene acrylic acid copolymer, polyethylene, polypropylene, polyimide, polyvinylchloride, acrylonitrile butadiene styrene polymer, aliphatic polyester, aromatic polyester and mixtures thereof.
  • the thermoplastic polymer may be ethylene acrylic acid copolymer (EAA).
  • EAA ethylene acrylic acid copolymer
  • Use of EAA as the thermoplastic matrix has the advantages that no compatibilizers are required to promote adhesion between the EAA and the cellulose fibers, and the low melting point of the EAA allows using a low operating temperature.
  • the amount of acrylic acid in the EAA may vary between 3 and 15 weight % (wt%). For instance, the amount of acrylic acid may be 7 wt%.
  • Compatibilizers are substances that improve the interfacial bond between the cellulose fibers and the thermoplastic matrix. The compatibilizers create a bridge between the fibers and the thermoplaxtic matrix which improves the tensile and flexural properties of the thermoplastic composite under load.
  • compatibilizers add to the cost of manufacturing the composite material.
  • examples of compatibilizers are maleic anhydride grafted polyethylene and maleic anhydride grafted polypropylene.
  • the amount of compatibilizers is usually less than 10 wt% based on the thermoplastic matrix.
  • thermoplastic matrix optionally in conjunction with up to 10 wt% of maleic acid anhydride polyethylene.
  • the extruded fiber-reinforced composite material may be provided with a desired shape by passing the composite material through a die.
  • the composite material may be formed through hot compression molding. Once extracted from the die or mold, the finished composite article may be allowed to assume ambient temperature through cooling with air or water.
  • a particular benefit of the highly uniform fiber/polymer composite materials of the invention is that they can be shaped into three-dimensional objects having high surface definition.
  • the high degree of individualized fibers in the fiber/polymer mixtures of the invention results in a very even mixture both with regard to homogeneity and with regard to surface properties.
  • the composites of the invention are practically free from fiber bundles they can be formed into products with very good surface definition and with a minimum of irregularities in the surface. Accordingly, the composites of the invention are highly useful in articles such as screw-on caps and other devices where a high definition is required in small details on the surface of the article.
  • the composites of the invention can be formed into sheets having excellent smoothness and surface finish.
  • the extrusion of the mixture of thermoplastic matrix material with the one or more cellulose fiber-based webs may take place at a temperature that is equal to or above the melting temperature of the thermoplastic matrix material.
  • the temperature may be the same throughout the extruder, i.e. the temperature is the same within the barrel from the hopper to the die.
  • a cellulose-fiber reinforced thermoplastic composite article in which the cellulose fibers are completely dispersed within the thermoplastic matrix, i.e. no or very few bundles of fibers are detectable. The presence of fiber bundles may be detected visually or by microscopy analysis as described in the experimental part of this document.
  • This composite article exhibits excellent mechanical performance when the cellulose fiber content is from 20 to 30 wt% or 25 to30 wt% based on the composite material, and the polymer matrix is ethylene acrylic acid copolymer.
  • a cellulose-fiber reinforced thermoplastic composite article in which the cellulose fibers constitute about 25 wt% and are completely dispersed within the thermoplastic matrix consisting of ethylene acrylic acid copolymer
  • the composite material and/or composite article is characterized in that the cellulose fibers are completely dispersed within the thermoplastic matrix, i.e. no or very few bundles of fibers are detectable. The presence of fiber bundles may be detected visually or by microscopy analysis as described in the experimental part of this document.
  • the composite article produced in accordance with the method described herein may be used in packaging components such as bottles and screw caps or any other article that may be formed by molding techniques. Furthermore, sheets of the composite materials disclosed herein may be provided with a three-dimensional shape by hot pressing and formed into articles such as containers, ornamental items, furnishing, etc.
  • Aspect ratio as used herein is refers to the ratio fiber length/ fiber diameter.
  • thermoplastic or “thermoplastic polymer” refer to polymers that become pliable or moldable above a specific temperature, and returns to a solid state upon cooling.
  • Basis weight stands for the weight divided by the area of a piece of cellulose fiber-based web such as tissue paper. Basis weight is usually expressed in grams per square meter (g/m 2 ) or gsm. Rpm is an abbreviation of revolutions per minute and is a measure of rotation frequency.
  • TP is an abbreviation for tissue paper.
  • D is an abbreviation for diaper paper.
  • Figure 1 shows composite materials having a cellulose fiber content of 30 wt% and being made from a two-ply tissue paper (TP) and EAA % by means of extrusion in accordance with the method described herein.
  • TP tissue paper
  • Figure 2 shows composite materials having a cellulose fiber content of 30 wt% and being made from four-ply diaper paper (D) and EAA by means of extrusion in accordance with the method described herein.
  • Figure 3 is a schematic view of an extruder system used in the method for producing cellulose-fiber reinforced composite material as described herein.
  • Figure 4 is a graph showing the tensile modulus versus the cellulose content for composite articles made from two-ply tissue paper (TP) and EAA, and four-ply diaper paper (D) and EAA, respectively.
  • Figure 1 shows composite articles having a cellulose fiber content of 30 wt% and being made from a two-ply tissue paper (TP) and EAA by means of extrusion in accordance with the method described herein.
  • the composite article denoted with the letter a results from extrusion of TP with melted EAA using a twin screw.
  • Visual inspection shows aggregates of cellulose fibers as light regions. The area percentage of the light regions as determined by microscopy analysis was determined to be 2.1 %.
  • the composite article denoted with the letter b results from melting and extrusion of the composite article denoted with the letter a using a barrier screw, i.e. a single screw.
  • Visual inspection shows that that the number of aggregates of cellulose fibers has diminished compared to the material denoted with the letter a.
  • the area percentage of the light regions as determined by microscopy analysis was determined to be 0.2 %.
  • FIG 1 the composite article denoted with the letter c results from melting and extrusion of the composite article denoted with the letter a using a twin screw. Visual inspection shows that that the number of aggregates of cellulose fibers has diminished compared to the material denoted with the letter a. The area percentage of the light regions as determined by microscopy analysis was determined to be 0 %, i.e. no aggregates of cellulose fibers were detected.
  • Figure 2 shows composite articles having a cellulose fiber content of 30 wt% and being made from four-ply diaper paper (D) and EAA by means of extrusion in accordance with the method described herein.
  • the composite article denoted with the letter a results from extrusion of a four- ply diaper paper (D) and EAA using a twin screw. Visual inspection shows the presence of aggregates of cellulose fibers as light regions. The area percentage of the light regions as determined by microscopy analysis was determined to be 13 %.
  • the composite article denoted with the letter b results from melting and extrusion of the composite article denoted with the letter a using a barrier screw.
  • Visual inspection shows the presence of aggregates of cellulose fibers as light regions. The area percentage of the light regions as determined by microscopy analysis was determined to be 1.1 %.
  • the composite article denoted with the letter c results from melting and extrusion of the composite article denoted with the letter a using a twin screw.
  • Visual inspection shows the presence of aggregates of cellulose fibers as light regions. The area percentage of the light regions as determined by microscopy analysis was determined to be 0.4 %.
  • Comparison of the results for the TP based composite articles denoted with the letters b and c in figure 1 show that a second run with the twin screw is better for providing a composite article with evenly distributed cellulose fibers than the barrier screw.
  • inspection of the results for the D based composite articles denoted with the letters b and c in figure 2 shows that a second run with the twin screw provides better fiber dispersion than the barrier screw.
  • Figure 3 is a schematic representation of the processing used to compound the cellulose fiber-based web with the thermoplastic matrix, and the extruder screw configuration.
  • Pellets of thermoplastic matrix material are fed into the hopper 1 and melted in
  • FIG. 4 shows the tensile modulus versus the cellulose content for articles made from two-ply tissue paper (TP) and EAA, and articles made from four-ply diaper paper (D). The articles were obtained after two consecutive extrusions with twin extruder.
  • the tensile strength had a maximum when the cellulose fiber content was 25 wt%.
  • the tensile modulus remained relatively constant when the cellulose content was increased from 25 to 30 wt%.
  • the polymer used as matrix material was EAA Primacor 3540 from Dow Chemical Company.
  • the EAA had a 7% acrylic acid content, average molecular mass of 16100 g/mol, melt flow rate (MFR) (190°C/2.16 kg, ISO 1 133) of 8 g/10 min and a density of 0.932 g/cm 3 .
  • the cellulose fibers used in this work were in form of tissue. Two different tissues were used: a two-ply tissue with 100% primary fibers from Metsa Tissue and a four- plytissue DG2490 from Swedish Tissue AB, denoted herein as TP and D respectively.
  • the TP tissue consisted in 75% birch and 25% softwood fibers with no additives and a basis weight of 34 g/m 2 .
  • the D material contained 2 wt% wet strength and 0.3 wt% dry strength agents and consisted in 20% birch fibers and the rest softwood fibers.
  • the basis weight was approximately 96 g/m 2 . In this case, the cellulose fibers were less loosely bonded than in the TP tissue.
  • the compounding of the tissue with the polymer was performed with a co-rotating twin screw Werner & Pfleiderer ZSK 30 M9/2 (Stuttgart, Germany) with a screw diameter of 30 mm and 966 mm length and provided with 5 heating zones and the die zone.
  • the temperatures profile used from the hopper to the die was: 100, 130, 140, 140, 150, 150°C. Since the polymer was fed into the extruder in a controlled manner, it was possible to calculate the cellulose content by the dragging speed of the tissue. In this case, the screw speed was fixed for each material and the polymer feeding was adjusted depending on the desired cellulose content.
  • the screw speed used with the TP tissue was 96 rpm while for the four layered tissue a lower speed had to be used, specifically 60 rpm.
  • a schematic representation of the processing and the screw configuration are shown in Fig. 3.
  • the tissue which was in drying chamber was fed into the extruder and then dragged by the screws through an opening in the zone C.
  • a tube was used to connect the drying chamber with the entry of the extruder.
  • the tissue was dried for 3 days at 75°C resulting in a water content of 3 wt% before the compounding.
  • Fig. 3. is a schematic representation of the processing used to compound the cellulose tissue with the polymer and the screw configuration.
  • the type and number of elements of the screw from the hopper to the die was: 1 pressure element, 9 fast transport elements, 1 slow transport element, 1 mixing element, 4 fast transport elements, 1 slow transport element, 2 pressure elements, 5 mixing (kneading) elements, 1 pressure element with contrary direction to the flow and 5 pressure elements.
  • the second extrusion performed with the twin screw extruder was done with the same screw speed and the same screw configuration that was used for compounding the tissue with the polymer.
  • the material obtained with TP tissue was 96 rpm and 60 rpm for the four layered tissue.
  • a Maillefer barrier-flighted screw (Maillefer, 1960, 1967) with a compression ratio 2.5: 1 with a Saxton distributive mixer element at the screw end was used.
  • the temperature profile along the barrel from hopper to die was 90, 130, 140 and 140°C and the screw speed was 100 rpm.
  • the second extrusion performed with the twin screw is denoted TS while in case of the barrier-flighted screw is BS.
  • the injection molding was performed with an injection molding machine Arburg Allrounder, 221 M-250-55, Austria.
  • the temperature profile from the hopper to the die was 90, 130, 140, 150 and 150°C, the injection pressure was 125 MPa, the cycle time 50 s and the mold was at room temperature.
  • the mold used had a single cavity, producing a test bar with a shape according to DIN 53455 with a mass of about 6 g.
  • the flow path from the cylinder nozzle to the cavity was a sprue diverging from diameter 3.5 Millimeters (mm) to diameter 6.5 mm along the sprue length of 54 mm; a first runner of 80 mm length with a cross section of 35 mm 2 , a second runner of 35 mm length with a cross section of 25 mm 2 and a rectangular cavity gate with dimensions of 15 x 1 mm and a land length of 1.5 mm.
  • the fiber content was measured using Soxhlet extraction with xylene.
  • a small sample piece of the composite sample was cut, weighed and placed into a sample container, i.e. a thimble. The thimble was weighed prior to use.
  • the thimble containing the composite sample was placed in a Soxhlet apparatus containing xylene. Heating to reflux during Soxhlet extraction using xylene was performed for approximately 96 h. After this time, the thimble containing the cellulose fibers was dried and weighed. The weight difference between the dried thimble containing cellulose fibers and the weight of the thimble prior to use was calculated to yield the fiber weight.
  • the fiber content was calculated by dividing the fiber weight in the composite sample by the sum of the fiber weight in the composite sample and the weight of the pure polymer in the composite sample. The given values are based on one measurement.
  • the fiber content was also measured by determining the weight difference between the composite sample and a sample of pure polymer (the matrix polymer EAA). A total of 10 samples were weighed and the average value was calculated. The average value for the composite sample was subtracted with the weight value for the sample of pure polymer to yield the weight of the fibers in the composite sample. The fiber content was calculated by dividing the fiber weight in the composite sample by the sum of the fiber weight in the composite sample and the weight of the pure polymer in the composite sample. For the above calculations of the fiber content it was assumed that the volume of the composite sample was the same as for the sample of pure polymer, i.e. 1.8 cm 3 .
  • This volume was set to be equal to the fiber weight in the composite sample divided by the fiber density plus the unknown weight for the pure polymer divided by the pure polymer density.
  • the weight of the pure polymer in the composite sample was obtained.
  • the calculations were based on a fiber density of 1 ,5 g/cm 3 and 0,932 g/cm 3 for the pure polymer, i.e. EAA.
  • the middle region of each injection-molded sample was milled from 4 mm to a thickness of 1 mm.
  • the analysis was performed with a stereomicroscope type SteREO discovery. V20 from Carl Zeiss, Germany.
  • the total characterized area was 10 x 20 mm 2 .
  • the number of aggregates and the relative area percentage were assessed with the digital image processing software AxioVision from Carl Zeiss Microimaging GmbH, Germany.
  • Fiber length measurements were made with an optical analyzer Kajaani FS300, Metso Automation, Finland, based on light polarization measurements of fibers in water.
  • the polymer was extracted directly with xylene during approximately 12h.
  • the cellulose fibers were washed and kept in water before performing the measurements.
  • the fiber length distribution and the width distribution obtained were calculated according to the standardized methods TAPPI T271 0-7.60 mm and ISO 16065 0.20-7.00 mm.
  • the mean value of the fiber length and the standard deviation was calculated based on three measurements.
  • the tensile mechanical properties were measured with a tensile testing machine equipped with a free-standing clip-on extensometer with adjustable gauge length Zwick 1455, Germany, and according to IS0527-1. A cross-head speed of 6 m/min corresponding to a strain rate of about 1.4x10 "3 s "1 was used and the gauge length of the extensometer was 60 mm. The tensile modulus was calculated from data points between 0.1 and 0.25 % strain. The mean value and the standard deviation of all mechanical properties were calculated based on seven measurements.
  • Fig. 1 The middle part of injection-molded specimens of TP materials containing 30 wt% cellulose fibers are shown in Fig. 1. It could be observed that the specimen having more cellulose aggregates was the one obtained after just compounding the tissue with the polymer, i.e. after only one pass with the twin screw (specimen a, Fig. 1). Almost no cellulose aggregates were observed in specimens obtained after a second extrusion with the barrier-flighted screw (specimen b, Fig. 1) while the specimen obtained after two passes in the twin screw presented no detectable cellulose aggregates (specimen c, Fig. 1). The same trend was observed for materials with lower cellulose content.
  • TP materials a) 30% TP b)30% TP BS c) 30% TP TS
  • Tables 4 and Table 5 show the measured fiber length of the specimens made with the TP tissue and the D tissue, respectively.
  • the original fiber length in the D tissue which contained more softwood fibers, was greater than for the TP tissue.
  • the fiber length was reduced more than 25% after compounding with the twin screw extruder and even more after a second extrusion.
  • the fiber shortening was more pronounced after a second extrusion with the twin screw than with the barrier screw.
  • the fiber length was also affected by the fiber content, as higher fiber loading increases the melt viscosity and thus the shear forces responsible for the fiber breakage.
  • the fiber length shortening was about 50 % after two passes of the material through the twin screw extruder, at 25 % cellulose fiber content obtained with both tissue TP and tissue D. With an increased fiber content of 30 - 35 % and still two passes through the twin screw extruder, the fiber length reduction increased to about 65 %, with no significant difference between using tissue TP or tissue D, as can be estimated from tables 4 and 5.
  • Table 4 Average values of three fiber length measurements and aspect ratio of specimens made with TP tissue. The standard deviation values are in parentheses.
  • Table 5 Average values of three fiber length measurements and aspect ratio of specimens made with D tissue. The standard deviation values are in parentheses. * Mold not completely filled.
  • the tensile mechanical properties of all injection-molded specimens are shown from Table 6 to Table 9.
  • E tensile modulus
  • o tensile strength
  • the lower aspect ratio of the fibers after two consecutive extrusions could explain the lower reinforcing effect of the fibers while the better dispersion achieved by the two consecutive extrusions with the twin screw could explain the higher elongation at break since the interaction fiber-matrix could be improved by a better wettability of the fibers with the polymer.
  • the second extrusion with the barrier screw also had a beneficial effect on the mechanical properties.
  • Fiber content also influenced the mechanical properties. As expected, the tensile modulus increased with increasing fiber content and the opposite trend was observed for the elongation at break. Only in the case of two consecutive extrusions with the twin screw extruder, shown in Fig. 4 no improvement in stiffness was observed when increasing the fiber content from 25 wt% to 30 wt% which could indicate that in this particular case the maximum packing fraction is 25 wt%. The same trend was observed for the tensile strength where the maximum value was obtained at 25 wt% of cellulose fibers.

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Abstract

La présente invention concerne un procédé pour procurer des matériaux composites comprenant une matrice thermoplastique et des fibres de cellulose. Le procédé comprend l'extrusion d'une ou de plusieurs toiles à base de fibres de cellulose dans un mélange avec un matériau de matrice thermoplastique fondu au moyen d'une double vis sans fin, ce qui permet de former un matériau composite extrudé qui peut ensuite être transformé en un objet composite renforcé par des fibres de cellulose, dans lequel les fibres de cellulose sont distribuées de manière uniforme au sein de la matrice thermoplastique. Le procédé concerne des possibilités améliorées pour une fabrication à grande échelle par une alimentation améliorée en partie cellulosique. Les objets composites renforcés par des fibres de cellulose présentent d'excellentes propriétés mécaniques, les meilleurs résultats étant obtenus lorsque la teneur en fibres de cellulose est située entre 20 et 30 % en poids sur base de l'objet composite.
PCT/SE2014/050149 2013-02-07 2014-02-06 Procédé pour procurer un matériau composite comprenant une matrice thermoplastique et des fibres de cellulose Ceased WO2014123478A1 (fr)

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CN109563350A (zh) * 2016-07-27 2019-04-02 Fp创新研究所 柔性纤维的真空辅助共挤出和所生产的可模制热塑性复合材料
EP3541864A4 (fr) * 2016-11-17 2020-07-15 Fibria Celulose S.A. Procédé d'obtention de granulés composites thermoplastiques renforcés par de la pâte de cellulose et de la pâte de cellulose supplémentaire
WO2021248219A1 (fr) * 2020-06-10 2021-12-16 Artecola Química S.A. Composite hybride de matrice polymère et procédé de traitement

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WO2021248219A1 (fr) * 2020-06-10 2021-12-16 Artecola Química S.A. Composite hybride de matrice polymère et procédé de traitement

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