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WO1998003586A1 - Melange de polymeres - Google Patents

Melange de polymeres Download PDF

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Publication number
WO1998003586A1
WO1998003586A1 PCT/AU1997/000460 AU9700460W WO9803586A1 WO 1998003586 A1 WO1998003586 A1 WO 1998003586A1 AU 9700460 W AU9700460 W AU 9700460W WO 9803586 A1 WO9803586 A1 WO 9803586A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
polyisobutylene
polymer blend
cellulosic material
die
Prior art date
Application number
PCT/AU1997/000460
Other languages
English (en)
Inventor
Ru Yu Wu
Lawrence David Mccarthy
Original Assignee
Crc For Polymers Pty. Ltd.
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 Crc For Polymers Pty. Ltd. filed Critical Crc For Polymers Pty. Ltd.
Priority to AU34303/97A priority Critical patent/AU3430397A/en
Publication of WO1998003586A1 publication Critical patent/WO1998003586A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • 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
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/20—Recycled plastic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
    • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08L23/22—Copolymers of isobutene; Butyl rubber; Homopolymers or copolymers of other iso-olefins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • the present invention relates to a fibre reinforced polymer and to a process for the production of a fibre reinforced polymer.
  • the present invention relates to a thermoplastic polymer incorporating cellulosic fibres and to a process for the manufacture thereof.
  • the present invention may find particular application in the recycling and/or reusing of spent materials such as waste paper and waste thermoplastics.
  • Thermoplastic polymers have, in general, a low elastic modulus. It is well known that the elastic modulus of a polymer may be increased by the addition of fibrous reinforcing agents and/or inert fillers. The resulting polymer composites are generally more rigid and have reduced materials costs since the cost of fibrous reinforcing agents may be significantly less than the cost of the base polymer. Mineral fillers and glass fibres may be used to increase modulus, however, these "hard” fillers generally result in extruder wear and weight increase in the composite. While cellulosic materials such as wood flour and paper pulp have been used in thermosetting molding compounds in order to provide low density, high modulus and high strength, the use of cellulosic materials in thermoplastic polymers has been limited.
  • thermoplastic polymers such as polypropylene
  • the process requires a high degree of mixing, such as with twin screw extruders, in order to obtain an acceptable blend.
  • the wood flour generally remains poorly dispersed.
  • Waste paper is a potentially inexpensive source of cellulosic fibres. Fibres from waste paper are tangled and it is not easy to disperse them. Waste paper may also be hammer milled into bulky fibre form but feeding the bulky fibres into extruder is very difficult. Paper granules can be made from hammer milled fibres for the ease of feeding. Irrespective of the form of cellulosic fibres, intensive and prolonged mixing is usually required to impregnate and disperse the fibres. We have found that batch type mixers are usually required for prolonged mixing which is not economical both in terms of energy consumption and man-power. Prolonged mixing also results in extensive breakage of fibres, reducing their effectiveness as reinforcing agents.
  • cellulosic particles it is desirable for cellulosic particles to be incorporated into thermoplastic polymers whereby the cellulosic particles are evenly dispersed throughout the thermoplastic polymer and that the thermoplastic polymer wets the cellulosic particles.
  • the degree of dispersion of the cellulosic particles as well as the degree of wetting determines the mechanical properties of the composite materials.
  • polyisobutylene polymers includes homopolymers and copolymers of isobutylene such as the range of homopolymers known as polyisobutylenes and the range of copolymers known as polybutenes.
  • Polybutenes are copolymers of isobutylene and at least one of the n-butenes.
  • Polyisobutylene polymers are generally known as tackifiers and have been used for hot melt adhesives, pressure-sensitive adhesives, stretch and cling films. We have found that these tackifiers provide improved dispersion and wetting and result in composites having improved mechanical properties.
  • a polymer blend comprising at least one thermoplastic polymer, cellulosic material and at least one polyisobutylene polymer.
  • the thermoplastic polymer used in the polymer blend of the present invention may be any thermoplastic polymer which may be processed below the thermal decomposition temperature of the cellulosic material (about 200° C). It is preferable that the thermoplastic polymer not be sensitive to water vapour at the processing temperature.
  • the thermoplastic polymer may be in the form of a blend of one or more thermoplastic polymers.
  • Thermoplastic polymers suitable for use in the polymer blends of the present invention include polymers and copolymers of ethylene, modified polyethylene, propylene, styrene, vinyl chloride and other polyolefins. It will be understood by those skilled in the art that the term 'copolymers' includes polymers formed from two or more monomers. Copolymers formed from three monomers for instance, often referred to as terpolymers, are included within the meaning of the term 'copolymer' .
  • Polyethylene suitable for use in the process of the present invention may include very low, low, linear low, medium and high density polyethylene. Modified polyethylenes have hydrogens on a tertiary C-atom substituted by other groups, such as cross-linked, chlorinated, sulfonated, and chlorosulfonated polyethylenes.
  • Ethylene copolymers suitable for use in the present invention include ethylene/vinyl acetate copolymers, ethylene/vinyl alcohol copolymers, ethylene/ethyl acrylate copolymers and ethylene/methacrylate copolymers.
  • Other polyethylenes suitable for use in the process of present invention include ionomers.
  • lonomers such as those copolymers of ethylene and acrylic or methacrylic acids, which have been neutralised wid metal ions such as sodium, lithium or zinc, are exemplified by the commercial products "Surlyn” (manufactured by Du Pont).
  • Polypropylene suitable for use in the process of the present invention may include isotactic polypropylene, syndiotactic polypropylene, functionalised polypropylene and modified polypropylene.
  • Modified polypropylene includes block copolymers with ethylene, but-1-ene and higher ⁇ -olefin; ethylene / propylene (diene) copolymers, polypropylene / ethylene propylene blends.
  • Functionalised polypropylene includes maleic anhydride grafted polypropylene.
  • the polymers which may be used in the present invention can be derived from waste plastics materials, especially co-mingled plastics wastes such as multi- layered films and bottles, polymer blends, car bumpers, shrink, stretch and cling films; or contaminated plastics, such as waste detergent, engine oil and edible oil containers, printed botdes and films, agriculture films contaminated with soil or dirt etc. Waste stretch or cling films may be advantageously incorporated into the polymer blend as these waste materials incorporate polyisobutylene polymers.
  • Cellulosic materials may conveniently be derived from finely ground products of wood pulp, agricultural products such as the shells of peanuts or walnuts, corn cobs, rice hulls, vegetable fibres, bamboo, cotton, hemp or fibres from fruit and vegetable skins such as pineapple and banana skins. It is preferred that cellulosic material be in the form of fibres as fibres present considerable advantages in the reinforcement of thermoplastic polymers.
  • a particularly convenient source of cellulosic fibres is waste paper and/or newsprint.
  • Waste paper, newsprint and die like typically contain lignin or other incidental components such as dyes, printing pigments, printing binders, trace oils etc. While the properties of the polymer blend may be improved by removing one or more of these incidental components we have found that it is unnecessary as acceptable properties may be obtained in the polymer blend notwithstanding presence of these incidental components.
  • the cellulosic material is either milled or beaten in order to promote particle or fibre separation. Pretreatment of the cellulosic materials is preferred although not necessary to produce acceptable materials.
  • Cellulosic materials may be thermally pretreated immediately prior to blending to improve their compatibility with the thermoplastic polymer thereby further reducing die compounding time required to produce a homogeneous polymer blend.
  • Thermal pretreatment of the cellulosic materials is performed by heating to temperature which results in dehydration without destruction of the particles.
  • Hammer milled newspaper fibre heated to temperatures between 80 and 200°C in an inert atmosphere results in dehydration without significant destruction of the fibre. It is believed that this dehydration of die fibres renders die fibres less hydrophilic and more susceptible to polymer adsorption.
  • tiiat such thermal treatment results in increased homogenity in the polymer blend. While a degree of dehydration will occur during the compounding of the fibres into the polymer blend, the compounding times are reduced by the use of thermal pretreatments which it is believed to be as a result of the partial dehydration of the cellulose.
  • the cellulosic particles may be heated in an oven under an oxygen depleted atmosphere at a temperature approaching the decomposition temperature of the cellulose. If oxygen is present, present rapid decomposition of the paper occurs at this temperature and any fibrous structure may be lost. For example, when using hammer milled newsprint, heating in the range of from 80 to 200°C for 20 minutes under forced nitrogen was found to be advantageous. Other fibrous cellulosic materials which contain water may also be pretreated at temperatures dependant on die impurity content, chain length and cellulose chemistry.
  • the polymer blends of d e present invention may incorporate cellulosic materials in amounts from 1 to 99% by weight of the polymer blend, preferably in the range of from 5 to 75 % by weight of the polymer blend.
  • At least one polyisobutylene polymer may be a polyisobutylene homopolymer or a polyisobutylene copolymer or a mixture thereof.
  • Polyisobutylene homopolymers range from low molecular weight semi-liquids to high molecular weight elastomers.
  • Polyisobutylene copolymers are generally obtained from a mixture of C relieH 8 isomers in the form of the C 4 fraction of processes that crack petroleum fractions and natural gas.
  • the four C H 8 isomers are 1-butene, cis-2-butene, trans-2-butene and isobutylene.
  • Copolymers of these C H g isomers are useful polyisobutylene copolymers.
  • Other comonomers such as isoprene may be used in the polyisobutylene copolymers.
  • polyisobutylene homopolymers and copolymers have a low molecular weight form of a highly viscous liquid.
  • Polyisobutylene polymers having a molecular weight average of from 200 to 10,000 are particularly suitable, preferably polyisobutylene has a weight average molecular weight from 300 to 10,000 and most preferable a weight average molecular weight of about 1500.
  • polyisobutylene assists the dispersion of cellulosic materials and improves their adhesion to the thermoplastic polymer.
  • Tackifiers used for stretch or cling wrap applications such as low molecular weight polyisobutylene polymer may advantageously be used. It is particularly convenient for the polyisobutylene polymer to be provided in die form of recycled stretch or cling wrap whereby die thermoplastic polymer or polymers also present in the recycled material may be incorporated into die polymer blend of the present invention.
  • mat die polyisobutylene polymer be present in the polymer blend in an amount of from 0.1 to 10% by weight of the polymer blend, dependent upon the amount of cellulosic material.
  • the process may be applied to recycled materials such as polymer films including shrink wrap and which hitherto have presented an environmental problem in tiiat applications for the recycled materials have not been available.
  • the polymer blend of d e present invention may also incorporate various other additives typical of those incorporated into thermoplastic blends.
  • additives may include pigment, colorants, antioxidants, UV stabilizers, plasticisers, lubricants, flame retardants, nucleating agents, powdery and fibrous fillers and chemical blowing agents.
  • a process for die production of a polymer blend comprising mixing cellulosic material witii at least one polyisobutylene polymer and at least one tiiermoplastic polymer.
  • the polyisobutylene polymer it is preferable for the polyisobutylene polymer to be blended with at least a portion of the thermoplastic polymer prior to the incorporation of the cellulosic material into the blend.
  • the compounding of the polymer blend can be done on conventional polymer processing mixers or by any mixer capable of compounding highly viscous polymeric systems at elevated temperatures. Continuous mixing equipment may also be used. Preferably a twin screw extruder is used to blend d e components of the polymer blend. Solvents or heat may be used to aid adsorption. Typically die mixer is heated to a suitable temperature and the required amount of polymer is added. After the polymer is completely molten the polyisobutylene polymer is added. The cellulosic materials are added as rapidly as possible, keeping torque below the equipment maximum. It is conventional to allow mixing for a fixed time or until die torque has dropped to a prescribed minimum.
  • the process of the present invention incorporates a pre-treatment step whereby die cellulosic material is treated by heating to a temperature which results in the dehydration of the cellulosic material without the destruction of the particles or fibre.
  • a pre-treatment step whereby die cellulosic material is treated by heating to a temperature which results in the dehydration of the cellulosic material without the destruction of the particles or fibre.
  • hammer milled newspaper fibre may be treated at temperatures between 80 and
  • the polymer blend may be removed from d e blender, divided into smaller pieces and allowed to cool. These pieces may then be taken and platten press molded into plaques and bars. Alternately the material could be taken directly from die mixer and moulded while hot. Certain compositions within the scope of the invention have low enough viscosity to be further processed by extrusion or injection molding vastly extending d e possible applications.
  • EXAMPLE 1 5 Hammer milled newsprint was dried for 8 hours at 90°C under a forced draught of nitrogen. During ti ⁇ s time the paper released approximately 10 % W/W of water. 98.6 gram of stretch wrap waste (comprising 5 % W W of polyisobutylene in linear low density polyethylene) was softened at 200°C (5 minutes) in a 242 cc batch mixer attached to a Brabender PL2000 unit. 239.3 gram (70% W W) of die dried newsprint was mixed in as quickly as possible (approx. 10 20 minutes). Maximum torque was 7,000 m-gram and final torque was 3,400 m-gram. The resulting composite was a homogeneous plastic mass with a dark grey colouration.
  • Anotiier composite material was prepared according to the method of example 1 , with the 20 substitution of pure LLDPE for stretch wrap waste.
  • the time required to add the dry newsprint was 34 minutes (an increase of 14 minutes over Example 1).
  • the maximum torque in the mixer was 8,600 m-gram and the final torque was 4,600 m-gram (compared to 7,000 m-gram and 3,400 m-gram in Example 1). 25
  • Breaking stress was found to be 25 MPa, breaking strain was found to be 0.015 mm/mm and flex modulus was found to be 2,627 MPa.
  • a composite material was prepared according to d e method of Example 11 , with the addition of 5% polyisobutylene Ultravis (BP Chemicals) as used to produce stretch wrap.
  • the electrical current reading was 2.0 Ampere for stable extrusion.
  • Extrudate breakages was significantly less than in example 11.
  • the improved incorporation of the paper in the plastic meant mat the extrudate could no longer be handled by bare hands as in example 11 , the molten plastic made up d e majority of the extrudate surface.
  • Flexural modulus was found to be 471 Mpa. Strain at break was found to be 2.7% and the flexural strength was found to be 7.4 Mpa. The high speed puncture impact strength was 5.9 Joule.
  • Car interior boards made of 50% polypropylene, 45% wood flour and 5 % talc were cut into small pieces and fed into a Brabender 242 cc batch mixer and mixed at 190° C for two minutes.
  • Another composite material was prepared according to die method of example 14 with the addition of 2% w/w of polyisobutylene (Ultravis) also included in the Brabender mixture.
  • Ultravis polyisobutylene
  • the resulting compression moulded plaque looked very homogenous and wood flour aggregates could not be detected.
  • Plaques were pressed at 80 kg/cm 2 and 190°C from the above mixed materials. Impact resistance of the plaques were evaluated by using ICI Instrumented Impact Tester. Mechanical properties were also evaluated by tiiree point bend flexual test. The results are shown in Table 2.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Sustainable Development (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Cette invention concerne un mélange de polymères comportant au moins un polymère thermoplastique, une matière cellulosique et au moins un polymère de polyisobutylène. La matière cellulosique utilisée dans le mélange de polymères peut avantageusement être composée de papier journal recyclé. Des polyisobutylènes sont souvent incorporés aux polymères thermoplastiques tels que le polyéthylène lors de la fabrication de films étirables ou autocollants. Le fait de mélanger du papier journal recyclé à un film d'emballage étirable ou autocollant recyclé permet de fabriquer un matériau utile à partir de déchets. L'incorporation de matière cellulosique et de polymères thermoplastiques à des polymères de polyisobutylène permet aussi avantageusement d'améliorer la dispersion et le mouillage des particules cellulosiques et elle entraîne une amélioration correspondante des propriétés mécaniques du mélange.
PCT/AU1997/000460 1996-07-22 1997-07-21 Melange de polymeres WO1998003586A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU34303/97A AU3430397A (en) 1996-07-22 1997-07-21 Polymer blend

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AUPO1162 1996-07-22
AUPO1162A AUPO116296A0 (en) 1996-07-22 1996-07-22 Polymer blend

Publications (1)

Publication Number Publication Date
WO1998003586A1 true WO1998003586A1 (fr) 1998-01-29

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WO (1) WO1998003586A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002077077A3 (fr) * 2001-03-22 2003-04-17 Cycletec Ltd Materiaux composites a faible cout, durables et resistants, fabriques a partir de cellulose et de plastique traites
US6863971B2 (en) 2001-03-22 2005-03-08 Cycletec Ltd. Strong durable low cost composite materials made from treated cellulose and plastic
WO2010100836A1 (fr) * 2009-03-04 2010-09-10 Toyota Jidosha Kabushiki Kaisha Composition de résine contenant des fibres naturelles et produit moulé la contenant
KR101595999B1 (ko) * 2014-09-12 2016-02-23 이응우 친환경 수지 복합 조성물 및 이를 이용한 제품
CN108314820A (zh) * 2018-02-08 2018-07-24 青岛软盛塑业有限公司 拉伸膜及其制备方法
EP3632581A1 (fr) * 2009-01-15 2020-04-08 U.B.Q. Materials Ltd. Matériau composite et son procédé de préparation à partir de déchets sensiblement non triés

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4013616A (en) * 1971-11-22 1977-03-22 Wallace Richard A Mixed polymeric structural material and method
US4176097A (en) * 1978-04-25 1979-11-27 Standard Oil Company (Indiana) Asbestos-free tape sealant
EP0009238A1 (fr) * 1978-09-23 1980-04-02 BASF Aktiengesellschaft Matières à mouler contenant un mélange polypropylène-polyisobutylène-polyéthylène résistant aux chocs à basse température et leur utilisation pour la production d'articles moulés
AU5760286A (en) * 1985-05-21 1986-11-27 Pluess Staufer Ag Thermoplastic compositions containing powdered inorganic substances
WO1993010916A1 (fr) * 1991-11-27 1993-06-10 Southern Research Institute Procede d'elimination d'elements contaminants contenus dans des polyolefines a des fins de recyclage

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4013616A (en) * 1971-11-22 1977-03-22 Wallace Richard A Mixed polymeric structural material and method
US4176097A (en) * 1978-04-25 1979-11-27 Standard Oil Company (Indiana) Asbestos-free tape sealant
EP0009238A1 (fr) * 1978-09-23 1980-04-02 BASF Aktiengesellschaft Matières à mouler contenant un mélange polypropylène-polyisobutylène-polyéthylène résistant aux chocs à basse température et leur utilisation pour la production d'articles moulés
AU5760286A (en) * 1985-05-21 1986-11-27 Pluess Staufer Ag Thermoplastic compositions containing powdered inorganic substances
WO1993010916A1 (fr) * 1991-11-27 1993-06-10 Southern Research Institute Procede d'elimination d'elements contaminants contenus dans des polyolefines a des fins de recyclage

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002077077A3 (fr) * 2001-03-22 2003-04-17 Cycletec Ltd Materiaux composites a faible cout, durables et resistants, fabriques a partir de cellulose et de plastique traites
US6863971B2 (en) 2001-03-22 2005-03-08 Cycletec Ltd. Strong durable low cost composite materials made from treated cellulose and plastic
EP3632581A1 (fr) * 2009-01-15 2020-04-08 U.B.Q. Materials Ltd. Matériau composite et son procédé de préparation à partir de déchets sensiblement non triés
WO2010100836A1 (fr) * 2009-03-04 2010-09-10 Toyota Jidosha Kabushiki Kaisha Composition de résine contenant des fibres naturelles et produit moulé la contenant
KR101595999B1 (ko) * 2014-09-12 2016-02-23 이응우 친환경 수지 복합 조성물 및 이를 이용한 제품
CN108314820A (zh) * 2018-02-08 2018-07-24 青岛软盛塑业有限公司 拉伸膜及其制备方法
CN108314820B (zh) * 2018-02-08 2020-09-04 青岛软盛塑业有限公司 拉伸膜及其制备方法

Also Published As

Publication number Publication date
AUPO116296A0 (en) 1996-08-15

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