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WO2002064670A1 - Produit composite polymere, son procede de fabrication et ses applications - Google Patents

Produit composite polymere, son procede de fabrication et ses applications Download PDF

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Publication number
WO2002064670A1
WO2002064670A1 PCT/DK2002/000085 DK0200085W WO02064670A1 WO 2002064670 A1 WO2002064670 A1 WO 2002064670A1 DK 0200085 W DK0200085 W DK 0200085W WO 02064670 A1 WO02064670 A1 WO 02064670A1
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WO
WIPO (PCT)
Prior art keywords
fibres
product
mapp
polypropylene
lay
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/DK2002/000085
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English (en)
Inventor
Tom Løgstrup ANDERSEN
David Victor Plackett
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.)
Riso National Laboratory
Original Assignee
Riso National Laboratory
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 Riso National Laboratory filed Critical Riso National Laboratory
Publication of WO2002064670A1 publication Critical patent/WO2002064670A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/045—Reinforcing macromolecular compounds with loose or coherent fibrous material with vegetable or animal fibrous material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene

Definitions

  • the present invention relates to a process for the manufacture of a polymer composite product with improved properties, said product consisting of a thermoplastic matrix material reinforced by one or more layers of natural fibres, optionally blended with synthetic fibres, in which the fibres are in the form of woven or non-woven mats or filament- wound fibre yarn, whereby the fibres are placed between layers of the matrix material, each layer comprising at least one sheet or foil of the matrix material, where- after the lay-up is subjected to an elevated temperature followed by cooling under pressure to produce a composite product.
  • the invention also relates to said polymer composite product manufactured by the process and to the use of the product within definite fields of industry, such as the automotive industry, the building industry, the furniture industry and the windmill industry.
  • plant fibre composites can readily be burned to create energy at the end of the useful service life of the product
  • EP 0 201 367 Bl discloses a fibre-reinforced thermoplastic polymeric composite material and a second thermoplastic polymer (different from the first one, but compatible with it) placed between the first polymer and the fibres, which are predominantly glass fibres. This second polymer promotes the wetting of the mineral fibres.
  • a bonding agent in the form of a web-shaped non- woven material is continuously inserted between a plastic web and a web of reinforce- ment glass fibres, and the joined webs are fused using the effects of pressure and temperature.
  • the bonding agent is maleic anhydride in the form of a non- woven made up of a number of extruded, non-needled individual fibres.
  • compatibili- sers such as polypropylene functionalised with maleic anhydride, to treat natural fibres, specifically flax fibres, thereby obtaining products capable of competing with traditional glass fibre-reinforced products.
  • the MAPP polymer has predominantly been used in the form of an additive for the treatment of fibres, for example during extrusion processes. While such treatments lead to products with adequate properties for many purposes, an alternative, simple and versatile method of compatibilisation would expand the range of process options available for high-performance plant fibre composites.
  • the present invention is based upon a specific use of compatibilising agents, e.g. MAPP, in the form of a sheet, a foil, a fabric or the like in combination with plant fibres to produce composites with optimum properties, especially with regard to tensile strength.
  • compatibilising agents e.g. MAPP
  • the key point is to use the compatibihser foil at the interface between the fibres in mat form or another suitable form (e.g. unidirectional yarn lay-up) on the one hand and the polymer (e.g. polypropylene) in the form of foils on the other hand.
  • the present invention relates to a process for the manufacture of a polymer composite product with improved properties, said product consisting of a thermoplastic matrix material reinforced by one or more layers of natural fibres, in which the fibres are in the form of woven or non- woven mats or filament- wound fibre yarn, whereby the fibres are placed between layers of the matrix material, each layer comprising at least one sheet or foil of the matrix material, whereafter the lay-up is subjected to an elevated temperature followed by cooling under pressure to produce a composite product.
  • the process of the invention is characterised in that the fibrous sheet and the matrix material are compatibilised in situ by means of a layer of a compatibihser material, said layer being in the form of a sheet, a foil, a fabric or the like, placed in between the fibrous material and the matrix.
  • thermoplastic material is preferably polypropylene (PP), but other thermoplastic materials are useful as well, e.g. polyethylene, polystyrene, polylactide, polyhydroxybutyrate, co-polyethyleneterephthalate and polyethylene/polypropylene copolymers.
  • PP polypropylene
  • a preferred compatibihser material is maleated polypropylene (MAPP) or a blend of MAPP with polypropylene in combination with polypropylene as the matrix material.
  • MAPP maleated polypropylene
  • Other preferred compatibihser materials are selected from the group consisting of a maleated polyethylene (MAPE), a maleated polylactide, a maleated polyhydroxybutyrate and a maleated polystyrene in the form of foils used in combination with polyethylene, polylactide, polyhydroxybutyrate and polystyrene, respectively.
  • the fibrous reinforcement in the composite product manufactured by the process of the invention consists of either:
  • the synthetic fibres may be any kinds of artificial or chemical fibres, including e.g. polypropylene (PP), polyethylene (PE), PP/PE copolymers, glass, aramid, carbon etc.
  • the invention also concerns the polymer composite product perse manufactured by the inventive process from a lay-up comprising:
  • thermoplastic matrix material one or more sheets or foils of a thermoplastic matrix material, said lay-up being subjected to an elevated temperature followed by cooling under pressure to produce a composite product.
  • the present invention provides a number of advantages over the prior art, including:
  • the process and the products according to the invention will find use within a number of different fields of industry.
  • One of the key areas will be the automotive industry.
  • the automotive industry has taken a major lead in using plant fibre composites in automotive interiors.
  • the industry has been particularly interested in the environmental advantages of such composites, as requirements for eventual disposal or recycling of car components become still more stringent.
  • the weight and cost advantages of these composites are also particularly important to the industry.
  • the main benefit of the technology that forms the basis of the present invention in contrast to the known techniques is the ability to maximise the key mechanical properties (e.g. tensile strength) in "one shot” through a film-stacked lay-up technique.
  • the process will be amenable to semi-continuous application through feeding of polymer and compatibihser films in-line with fibre mats to provide the required sandwich lay-up.
  • the placement of the compatibihser directly at the fibre/polymer interface is the main feature of the inventive technology.
  • Fig. 1 is a schematic view of the composite lay-up
  • Fig. 2 is a diagram showing the influence of the compatibihser location on the resulting tensile strength
  • Fig. 3 is a graph showing the tensile strength as a function of the MAPP content for a product according to the invention comprising a random jute fibre mat, and
  • Fig. 4 is a graph showing the tensile strength as a function of the MAPP content for a product according to the invention comprising a random wood/binder fibre mat.
  • the present invention is based upon a specific use of compatibilising agents, e.g. MAPP, in the form of sheets, foils, fabrics or the like in combination with plant fibres to produce composites with optimum properties, especially with regard to tensile strength. More specifically, it has surprisingly been found that the exact location of the compatibihser, e.g. MAPP, relative to the fibrous material is of utmost importance, and therefore the fibrous sheet and the matrix material are compatibilised in situ by means of a layer of a compatibihser material, said layer being in the form of a sheet, a foil, a fabric or the like, placed in between the fibrous material and the matrix.
  • compatibilising agents e.g. MAPP
  • the polymer composite product according to the present invention consists in principle of a large number of reinforcing fibres, e.g. jute fibres, held together by a thermoplastic matrix material, e.g. polypropylene (PP). It is primarily the reinforcing fibres which give the composite product its desirable properties, whereas the matrix material must be capable of distributing any strains equally between the fibres. The adhesion or bonding between the fibres and the matrix material is therefore crucial to the properties of the product.
  • a thermoplastic matrix material e.g. polypropylene
  • the typical lay-up (film stacking) used in the invention is known perse.
  • the lay-up may consist of a stack of fibre sheets, e.g. jute, said stack being covered on each side by a sheet or foil of a compatibihser, preferably MAPP, said sheet or foil in turn being covered by one or more layers of a matrix material, preferably PP.
  • the lay-up is heated under vacuum in contact with the heating elements, causing the PP matrix material and the MAPP interface foil to melt, thereby wetting the jute fibres.
  • the lay-up is subsequently cooled under pressure (consolidation) whereby the plastics solidify, leading to the formation of the desired composite material (a laminate).
  • the MAPP foil is placed directly in contact with the stack of fibre sheets, because it is the maleic anhydride (MA) part of the MAPP which is capable of establishing a strong chemical bonding to the fibres, thereby providing an improved bond/compatibilisation between the reinforcing fibres and the PP matrix material.
  • MA maleic anhydride
  • Figs. 3 and 4 show the tensile strength vs. the MAPP content for a jute fibre mat and a wood/binder fibre mat, respectively.
  • a MAPP content of 0 % (w/w) corresponds to the starting material.
  • tensile strengths 30 - 50 % above those of the reference material may be obtained by using a MAPP foil as an in situ compatibilising agent.
  • the fibres used in the experiments were either jute or mixed softwood in the form of mats.
  • a needle-punched jute mat was obtained from JB Plant Fibres Ltd., UK, and an air-laid mat was prepared from mixed spruce and pine wood fibres using a Dan- Web machine.
  • the wood fibre mat contained 9 % (w/w) of a commercial bicomponent polypropylene (PP)/polyethylene (PE) fibre as a binder.
  • PP polypropylene
  • PE polyethylene
  • the basis weight of the jute mat was 250 g/m 2 and that of the wood fibre mat was 300 g/m 2 under ambient laboratory conditions. The moisture content of the mats under these conditions was in the range 8 - 10 % (w/w).
  • the PP selected for the experiments was Dow Inspire H710-05, a general purpose inj ection-moulding grade homopolymer with good flow properties and a melt flow index of 6.0 as measured by ISO standard 1133. Temperatures in the extruder were set at 160 °C at the inlet, 180 °C in the first section of the extruder barrel, 200 °C in the second section of the extruder barrel, and 200 °C in the extruder die. The roll temperature was set at 65 °C. PP films were extruded with thicknesses in the range 0.15 - 0.25 mm and a width of approximately 120 mm.
  • the MAPP product Polybond 3002 was obtained from Uniroyal Chemicals; this product was used for most of the experiments. This grade of MAPP has a melt flow index in the range of 7.0 - 12.0 dg/min, a MAH index in the range 0.5 - 0.8 and a maximum moisture content of 0.1 % as supplied. Extruder temperatures were set at the same values as those used for extruding PP. The roll temperature was reduced to 55 °C to optimise film quality. Film thicknesses and width were the same as for the PP films.
  • Another MAPP product, Fusabond MD 51 ID from DuPont was also used in the experimental series. The extrusion temperatures for Fusabond were the same as those used for Polybond 3002, but the roll temperature was increased to 65 °C to obtain the best film quality.
  • Composite lay-ups were prepared by sandwiching a number of fibre mat layers between layers of PP film. Films of MAPP or MAPP/PP blends were then placed at the interface between the jute fibre mats and PP films. Typically,five layers of jute mat were used with five to seven layers of PP film on either side. Knowing fibre and polymer densities, the ratio of fibre weight to polymer weight was chosen so as to achieve a targeted fibre weight fraction of 40 % or a fibre volume fraction of 30 %. In the case of the wood fibre mats, films of MAPP or MAPP/PP blends were placed between the fibre and the PP films or were interspersed between layers of PP film and jute mats in a multi-layer construction.
  • the fibre mat/polymer film lay-ups were placed carefully between Teflon release foils and secured in a metal frame. The frame was then used to convey the lay-up into the press. The importance of placing the MAPP film at the fibre mat/PP interface was demonstrated by preparing a number of lay-ups in which the compatibihser film was placed either at the interface (as shown schematically in Fig. 1), in the middle of the layer of PP films, or at the top and bottom surfaces of the entire lay-up.
  • Composite panels were cut into sections allowing for at least three tensile test specimens in each case.
  • the specimens were dogbone-shaped, measuring 180 mm in length, 25 mm in maximum width and 15 mm in minimum width.
  • samples for tensile testing were cut both in the direction in which the mat was formed and in right angles to this direction. These samples were taken because of the known differences in properties of the jute mat in these two directions and were labelled 0° and 90°, respectively.
  • Tensile testing was undertaken using an Instron machine operated in displacement control at a speed of 2 mm/min with a 5 kN load cell. The longitudinal strain of each specimen was recorded with two back-to-back extensometers.
  • Readings of load and strain were sampled at 4 Hz with a PC-based data acquisition system. The average strain was used and the stress was calculated as load divided by initial cross- section. The results were expressed as plots of stress (MPa) against strain (%). The ultimate tensile strength or tensile strength at yield and the tensile stiffness, as determined by the slope of the tangent to the stress-strain curve drawn through the origin, were established from the stress-strain plots.
  • the fibre volume fraction and the porosity of the composite samples were determined by gravimetric measurement using a slightly modified version of ASTM Standard D 3171-76.
  • the measured fibre volume fractions and porosity values are shown in Tables 1-4.
  • the tensile properties of fibre-reinforced composites are affected by changes n fibre volume fraction and porosity; however, the variations shown in Tables 1-4 and especially in Tables 2-3 do not alter the trends in tensile properties described above.
  • the tensile strength of composites prepared from a sandwich-type fibre/polymer lay- up is maximised when a MAPP compatibiliser film is placed at the fibre/polymer interface.
  • Composite tensile strength increases as a function of MAPP compatibiliser content in a sandwich-type fibre/polymer lay-up and reaches a plateau at a MAPP concentration that varies with fibre type and with the construction of the lay-up.
  • More than one MAPP product can be used to achieve the observed increases in composite tensile strength.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Reinforced Plastic Materials (AREA)

Abstract

L'invention porte sur un produit composite polymère, aux propriétés améliorées et obtenues par superposition. Ledit produit renferme a) un matériau de renfort fibreux de type noyau constitué d'une ou plusieurs couches de fibres naturelles recouvertes sur chaque côté par b) une feuille compatibilisante réalisant une compatibilisation sur place des fibres naturelles et du matériau à matrice thermoplastique, alors que sur la partie supérieure de la feuille compatibilisante se trouve(nt) c) une ou plusieurs feuille(s) d'un matériau à matrice thermoplastique, ladite superposition étant soumise à une température élevée puis à un refroidissement sous pression de manière à obtenir un produit composite. L'invention porte également sur un procédé de fabrication dudit produit et sur ses applications industrielles, notamment dans l'industrie de l'automobile, l'industrie du bâtiment, l'industrie du mobilier et l'industrie des éoliennes. L'invention présente un certain nombre d'avantages par rapport à l'art antérieur, notamment la compatibilisation sur place en une seule étape de matelas de fibres, une plus grande souplesse de traitement pour le fabricant, une manipulation/automatisation facilitée du traitement de compatibilisation et un processus de superposition amélioré ainsi que de meilleures performances du matériau composite.
PCT/DK2002/000085 2001-02-09 2002-02-07 Produit composite polymere, son procede de fabrication et ses applications Ceased WO2002064670A1 (fr)

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DKPA200100208 2001-02-09

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008101937A3 (fr) * 2007-02-23 2008-10-09 Basf Se Matériaux composites et leur procédé de préparation
US8637789B2 (en) 2007-02-20 2014-01-28 Basf Se Method for producing metallised textile surfaces using electricity-generating or electricity-consuming elements
CN106573437A (zh) * 2014-07-29 2017-04-19 乐天化学株式会社 连续纤维复合材料和用于产生连续纤维复合材料的方法
CN114213760A (zh) * 2022-01-12 2022-03-22 安徽工程大学 一种大麻-椰壳混杂聚丙烯复合材料及其制备方法和应用
CN115320198A (zh) * 2022-08-09 2022-11-11 安徽工程大学 一种质轻、环保可代替玻璃纤维的聚丙烯基汽车用复合材料
CN116199962A (zh) * 2023-02-21 2023-06-02 常州市灵犀医疗用品有限公司 一种纤维增韧聚乙烯尸体隔离袋及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5187018A (en) * 1985-03-24 1993-02-16 Atochem Fiber-reinforced thermoplastic polymer composite and process for preparation thereof
DE4331328A1 (de) * 1993-09-15 1994-04-07 Thueringisches Inst Textil Verfahren zur Haftverbesserung von Verstärkungsmaterial in thermoplastischen Kunststoffen
US5340642A (en) * 1992-03-07 1994-08-23 Basf Aktiengesellschaft Sheetlike composite
WO2000000351A1 (fr) * 1998-06-30 2000-01-06 Symalit Ag Procede de production d'un corps composite a partir d'un plastique renforce par des fibres et corps composite ainsi obtenu

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5187018A (en) * 1985-03-24 1993-02-16 Atochem Fiber-reinforced thermoplastic polymer composite and process for preparation thereof
US5340642A (en) * 1992-03-07 1994-08-23 Basf Aktiengesellschaft Sheetlike composite
DE4331328A1 (de) * 1993-09-15 1994-04-07 Thueringisches Inst Textil Verfahren zur Haftverbesserung von Verstärkungsmaterial in thermoplastischen Kunststoffen
WO2000000351A1 (fr) * 1998-06-30 2000-01-06 Symalit Ag Procede de production d'un corps composite a partir d'un plastique renforce par des fibres et corps composite ainsi obtenu

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MIECK K.-P. ET AL: "Needle-Punched hybrid nonwovens of flax and PPfibers-textile semiproducts for manufacturing of fiber composites.", POLYMER COMPOSITES, vol. 17, no. 6, 1996, pages 873 - 878, XP002902510 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8637789B2 (en) 2007-02-20 2014-01-28 Basf Se Method for producing metallised textile surfaces using electricity-generating or electricity-consuming elements
WO2008101937A3 (fr) * 2007-02-23 2008-10-09 Basf Se Matériaux composites et leur procédé de préparation
CN106573437A (zh) * 2014-07-29 2017-04-19 乐天化学株式会社 连续纤维复合材料和用于产生连续纤维复合材料的方法
US20170217140A1 (en) * 2014-07-29 2017-08-03 Lotte Chemical Corporation Continuous fiber composite and method for preparing continuous fiber composite
EP3175980A4 (fr) * 2014-07-29 2018-03-21 Lotte Chemical Corporation Composite à fibres continues et procédé de préparation de composite à fibres continues
CN106573437B (zh) * 2014-07-29 2020-02-14 乐天化学株式会社 连续纤维复合材料和用于产生连续纤维复合材料的方法
CN114213760A (zh) * 2022-01-12 2022-03-22 安徽工程大学 一种大麻-椰壳混杂聚丙烯复合材料及其制备方法和应用
CN115320198A (zh) * 2022-08-09 2022-11-11 安徽工程大学 一种质轻、环保可代替玻璃纤维的聚丙烯基汽车用复合材料
CN116199962A (zh) * 2023-02-21 2023-06-02 常州市灵犀医疗用品有限公司 一种纤维增韧聚乙烯尸体隔离袋及其制备方法
CN116199962B (zh) * 2023-02-21 2024-05-28 常州市灵犀医疗用品有限公司 一种纤维增韧聚乙烯尸体隔离袋及其制备方法

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