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WO2007036171A1 - A method for recycling a mixture of engineering thermoplastics to obtain a tough thermoplastic material and a mixture of engineering materials - Google Patents

A method for recycling a mixture of engineering thermoplastics to obtain a tough thermoplastic material and a mixture of engineering materials Download PDF

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Publication number
WO2007036171A1
WO2007036171A1 PCT/CZ2006/000064 CZ2006000064W WO2007036171A1 WO 2007036171 A1 WO2007036171 A1 WO 2007036171A1 CZ 2006000064 W CZ2006000064 W CZ 2006000064W WO 2007036171 A1 WO2007036171 A1 WO 2007036171A1
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WO
WIPO (PCT)
Prior art keywords
mixture
weight percent
styrene
maximum
fact
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/CZ2006/000064
Other languages
French (fr)
Inventor
Jan RYBNÍCEK
Josef Steidl
Zdenek Krulis
Ralf Lach
Wolfgang Grellmann
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.)
Czech Technical University In Prague
Original Assignee
Czech Technical University In Prague
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 Czech Technical University In Prague filed Critical Czech Technical University In Prague
Publication of WO2007036171A1 publication Critical patent/WO2007036171A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/0026—Recovery of plastics or other constituents of waste material containing plastics by agglomeration or compacting
    • B29B17/0036—Recovery of plastics or other constituents of waste material containing plastics by agglomeration or compacting of large particles, e.g. beads, granules, pellets, flakes, slices
    • 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
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/04—Disintegrating plastics, e.g. by milling
    • B29B17/0412—Disintegrating plastics, e.g. by milling to large particles, e.g. beads, granules, flakes, slices
    • 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
    • B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
    • B29K2033/04—Polymers of esters
    • B29K2033/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
    • 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
    • B29K2055/00—Use of specific polymers obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of main groups B29K2023/00 - B29K2049/00, e.g. having a vinyl group, as moulding material
    • B29K2055/02—ABS polymers, i.e. acrylonitrile-butadiene-styrene polymers
    • 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
    • B29K2069/00—Use of PC, i.e. polycarbonates or derivatives thereof, as moulding material
    • 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 input material can be technological scrap generated during plastics processing, especially the scrap generated during the production of car lighting components.
  • the input material can also be end-of-life plastic products, especially car lighting components from scrapped cars.
  • mixture B shows a higher value of toughness (see values of J-integral Jia) .
  • the method for recycling a mixture of engineering thermoplastics to obtain a tough thermoplastic material, and a mixture which is prepared in this way, will be applied in the disposal of waste engineering thermoplastics generated by the production, for example, of car rear lights, or products that have reached the end of their service life, for example, rear lights from scrapped cars.

Landscapes

  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

This invention refers to a method for recycling a mixture of engineering thermoplastics to obtain a tough thermoplastic material . The subject matter of the invention is that the input material is disintegrated to a size of 1 mm to 10 mm. Then, a mixture is created containing 40 to 80 weight percent of polycarbonate, 10 to 50 weight percent of terpolymer acrylonitrile-butadiene- styrene, a maximum of 10 weight percent of poly (methyl methacrylate) and a maximum of 10 weight percent of thermoplastic elastomer on the basis of styrene-ethylene/butylene-styrene block copolymer or styrene-butadiene-styrene block copolymer. As the last step, the mixture is processed into the final product . The invention also refers to a mixture of engineering materials which contains 40 to 80 weight percent of polycarbonate, 10 to 50 weight percent of terpolymer acrylonitrile-butadiene-styrene, a maximum of 10 weight percent of poly (methyl methacrylate) and maximum of 10 weight percent of thermoplastic elastomer on the basis of styrene-ethylene/butylene-styrene block copolymer or styrene -butadiene styrene block copolymer. The input material can be technological scrap generated during plastics processing, especially scrap generated during the production of car lighting components. The input material can be also end-of-life plastic products, especially car lighting components from scrap cars.

Description

A method for recycling a mixture of engineering thermoplastics to obtain a tough thermoplastic material and a mixture of engineering materials.
Technical field
This invention refers to a method for recycling a mixture of engineering thermoplastics to obtain a tough thermoplastic material and a mixture of engineering materials.
Background of the invention
At the present time, engineering thermoplastics generated from production waste, e.g. car rear lights and other products which have reached the end of their service life, such as rear lights from scrapped cars, is commonly disposed of in landfills or is incinerated. However, these disposal processes are uneconomical and unfriendly to the environment, and they waste the material and energetic content of the disposed polymers. The most effective way to use the material and energetic input in the production of a virgin polymer is to recycle the material. Material recycling involves supplying mechanical energy and additives, i.e. stabilizers, colorants, fillers, etc., to upgrade the waste material to a new material with mechanical and esthetical properties which will be close to those of the virgin material .
Recycling of production waste plastics is mainly limited to well-separated mono-material wastes from the production of plastic components. The main restriction on broader utilization of recycling procedures for waste plastics is the fact that the waste components tend to be composed of several plastics that are hard to dismantle. The individual parts are usually produced from PC - polycarbonate, ABS - acrylonitrile-butadiene-styrene, PMMA - poly (methyl methacrylate) , TPE - thermoplastic elastomer or blends of PC/ABS, ABS/PMMA, PC/PMMA, etc. Separating the mono- material waste demands high investment in machinery, and the operating costs are high in relation to relatively low productivity. Another problem with the separating procedures is their low efficiency: in practice, not more than 95% purity of the separated fraction is achieved.
The above-mentioned problems of separating mono-material plastic wastes are solved when the plastic waste is recycled as a multi-material mixture. Recycling a mixture of polycarbonate with polymers on the basis of styrene and with the addition of elastomer was studied, for example, in invention JP 2004352762. Recycling a ternary mixture is addressed in invention US 5,232,986, which focuses on a mixture of PMMA/ABS/PC with a major component of PMMA. Extrusion of thermoplastic mixtures in a closed loop recycling system, especially mixtures of PC/PMMA, with the addition of a compatibilizator on the basis of MBS - methylmethacrylate-butadiene-styrene or terpolymer consisting of butadiene - is described in invention US 5,569,713. Recycling quaternary mixtures of PET/ABS/PC/SBS or PET/ABS/PC/SEBS, where PET is a major component, is discussed in invention US 2004209985.
In the case of a multi-material engineering thermoplastics mixture, a primary condition for the economic practicability of the recycling process is that the recyclate should have a high level of final utilizable properties. When the material properties of mixtures of PC, ABS, PMMA and TPE were investigated, it was surprisingly found that these mixtures of a certain composition exhibit essentially higher toughness than their individual components. Furthermore, it was proved that increased thermo-mechanical loading of these mixtures during melt processing, e.g. regranulation, leads to undesirable deterioration of the mechanical properties of the final product. These considerations are fundamental to the method for recycling a mixture of PC, ABS, PMMA and TPE according to the invention.
Summary of the invention
The above-mentioned deficiencies are eliminated to a large extent in the method according to this invention for recycling a mixture of engineering thermoplastics to obtain a tough thermoplastic material. The subject matter of the invention is that the input material is disintegrated to a size of 1 mm to 10 mm. Then, a mixture is created containing 40 to 80 weight percent of polycarbonate, 10 to 50 weight percent of terpolymer acrylonitrile-butadiene-styrene, a maximum of 10 weight percent of poly (methyl methacrylate) and a maximum of 10 weight percent of thermoplastic elastomer on the basis of styrene- ethylene/butylene-styrene block copolymer or styrene-butadiene- styrene block copolymer. In the last step, the mixture is processed into the final product .
Advantageous implementation involves magnetic and induction separation of metallic impurities from the disintegrated material .
The invention also refers to a mixture of engineering materials, which contains 40 to 80 weight percent of polycarbonate, 10 to 50 weight percent of terpolymer acrylonitrile-butadiene-styrene, a maximum of 10 weight percent of poly (methyl methacrylate) and a maximum of 10 weight percent of thermoplastic elastomer on the basis of styrene- -A- ethylene/butylene-styrene block copolymer or styrene-butadiene- styrene block copolymer.
The input material can be technological scrap generated during plastics processing, especially the scrap generated during the production of car lighting components. The input material can also be end-of-life plastic products, especially car lighting components from scrapped cars.
Any of the components can be a virgin material .
The considerable advantage of this method for recycling a mixture of engineering thermoplastics according to the invention is that the toughness of the final recyclate is usually higher than the toughness of the virgin materials PC, ABS, PMMA, while a balanced complex of utilizable properties is retained.
Another advantage of the method for recycling a mixture of engineering thermoplastics according to the invention is that there is no regranulation of the grind, which guarantees low thermo-mechanical loading of the mixture melt and, as a consequence, retention of the physical properties of the thermoplastic mixture according to the invention, especially the toughness. In addition/ omitting the regranulation step saves power costs for processing the mixture.
The advantages of the method for recycling a mixture of engineering thermoplastics to obtain a tough thermoplastic material according to the invention are further clarified by the following examples. Detailed description of the preferred embodiments
In the following invention implementation examples, materials were used (see Tab.l) which occur in the production of car rear light assemblies. The materials were mainly as follows:
Polycarbonate (Lexan LS2, GEPlastics) , acrylonitrile-butadiene- styrene (Cycolac X37, GEPlastics), poly(methyl methacrylate)
(Lucryl G88, BASF) and styrene-ethylene/butylene-styrene
(Bergaflex BFI K70A, Bergmann) .
The toughness of the mixtures was evaluated on the basis of fracture mechanics, mainly using the concept of the J-integral (Jid) • The methodology, the preparation of the samples and the equipment for J-integral determination are described in the literature, e.g. W. Grellmann, S. Seidler: Deformation and Fracture Behaviour of Polymers. Springer Verlag, Berlin Heidelberg, 2001.
Example 1
A mixture was obtained by grinding scrap material of car rear lights. The mixture corresponds to the composition of A according to Tab.l.
Grinding was performed with the help of a PH TRIA 47-30/CN granulator with three rotating cutting knives . The average grind size was 5mm. The ground material was de-dusted using an Allgier dust separator, and the metal particles were detected using a Mesurtronic metal detector.
The ground mixture was dried for a minimum of 6 hours at a temperature of 105 0C in a hot-air drier. The mixture was processed using a Battenfeld 500 injection molding machine with a screw diameter of 35 mm and a length-to- diameter ratio of 75. The melt was injected into a mold for the production of standard ISO 179 specimens. The injection molding unit temperature was set to 245°C, the screw speed reached 128 revolutions per minute, and the backpressure was set to 10 MPa. The mold temperature was 900C.
In comparison with virgin (original) materials 1, 2, 3 according to Tab.l, mixture A shows a higher value of toughness (see values of J-integral Jid) •
Example 2
As in the case of example 1, except that the mixture corresponds to composition B according to Tab.l.
In comparison with virgin (original) materials 1, 2, 3 according to Tab.l, mixture B shows a higher value of toughness (see values of J-integral Jia) .
Example 3
As in the case of example 1, except that the mixture corresponds to composition C according to Tab.l.
In comparison with virgin (original) materials 1, 2, 3 according to Tab.l, mixture C shows a slightly higher value of toughness (see values of J-integral Jτd) .
Example 4
As in the case of example 1, except that the mixture corresponds to composition D according to Tab.l. In comparison with virgin (original) materials 1, 2, 3 according to Tab.l, mixture D shows a slightly higher value of toughness (see values of J-integral JId) .
Table 1. Toughness of the investigated mixtures
Mixture 1 2 3 A B C D
PC [%] Too - ~ 80 40 60 60
ABS [%] 100 10 50 20 20
PMMA [%] 100 10 10 10 10
SEBS [%] _ 1 100 _
SBS [%] 10 ~J^ [kJ/m2] 11.0 10.2 0~~8 14, 8 12, 6 11,6 11,5
Industrial applications
The method for recycling a mixture of engineering thermoplastics to obtain a tough thermoplastic material, and a mixture which is prepared in this way, will be applied in the disposal of waste engineering thermoplastics generated by the production, for example, of car rear lights, or products that have reached the end of their service life, for example, rear lights from scrapped cars.

Claims

Claims
1. The method for recycling a mixture of engineering thermoplastics to obtain a tough thermoplastic material is characterized by the fact that it uniquely comprises the following steps: disintegrating the input material to a size of 1 mm to 10 mm; creating a mixture containing 40 to 80 weight percent of polycarbonate, 10 to 50 weight percent of terpolymer acrylonitrile-butadiene-styrene and a maximum of 10 weight percent of poly (methyl methacrylate) ; processing the mixture to a final product.
2. The method according to claim 1 is characterized by the fact that a maximum of 10 weight percent of thermoplastic elastomer on the basis of block copolymer styrene-ethylene/butylene- styrene is added to the mixture.
3. The method according to claim 1 is characterized by the fact that a maximum of 10 weight percent of thermoplastic elastomer on the basis of block copolymer styrene-butylene -styrene is added to the mixture .
4. The method according to claim 1, 2 or 3 is characterized by the fact that the metallic impurities are separated from the disintegrated material using magnetic and induction separation.
5. The mixture of thermoplastic materials is characterized by the fact that it essentially contains 40 to 80 weight percent of polycarbonate, 10 to 50 weight percent of terpolymer acrylonitrile-butadiene-styrene and a maximum of 10 weight percent of poly (methyl methacrylate).
6. The mixture according to claim 5 is characterized by the fact that the mixture contains an additional amount of a maximum of 10 weight percent of thermoplastic elastomer on the basis of block copolymer styrene-ethylene/butylene-styrene .
7. The mixture according to claim 5 is characterized by the fact that the mixture contains an additional amount of a maximum of 10 weight percent of thermoplastic elastomer on the basis of block copolymer styrene-butylene-styrene .
8. The mixture according to any one of claims 5 to 7 is characterized by the fact that the input material is technological scrap generated during plastics processing.
9. The mixture according to any one of claims 5 to 7 is characterized by the fact that the input material comprises end- of-life plastic products.
PCT/CZ2006/000064 2005-09-30 2006-09-29 A method for recycling a mixture of engineering thermoplastics to obtain a tough thermoplastic material and a mixture of engineering materials Ceased WO2007036171A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CZPV2005-624 2005-09-30
CZ20050624A CZ297698B6 (en) 2005-09-30 2005-09-30 Tenacious thermoplastic material and process for producing thereof

Publications (1)

Publication Number Publication Date
WO2007036171A1 true WO2007036171A1 (en) 2007-04-05

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2058102A1 (en) * 2007-11-09 2009-05-13 Canon Kabushiki Kaisha Process for producing thermoplastic resin composition, and thermoplastic resin composition produced by the same
CN109880337A (en) * 2019-02-25 2019-06-14 宁波公牛精密制造有限公司 The spray painting polycarbonate compositions and preparation method thereof that high efficiente callback recycles
CN110256804A (en) * 2019-06-28 2019-09-20 祥兴(福建)箱包集团有限公司 A kind of preparation method of the anti-scratch PMMA/ABS tank material of toughening type
CN114716803A (en) * 2022-05-16 2022-07-08 东莞市国亨塑胶科技有限公司 Regeneration preparation method and regeneration material of ocean recycled polycarbonate

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EP0906817A1 (en) * 1996-04-14 1999-04-07 Suzuka Fuji Xerox Co., Ltd. Coated molded article, method of recycling the same and apparatus therefor
EP1193039A1 (en) * 2000-09-29 2002-04-03 Fuji Photo Film Co., Ltd. Method of recycling plastic parts for photosensitive material
EP1291378A1 (en) * 2001-03-28 2003-03-12 Sony Corporation Method of reclaiming resin
DE10256305A1 (en) * 2002-12-03 2004-06-24 Der Grüne Punkt - Duales System Deutschland Ag Method for processing mixed waste materials comprises identifying materials of several different types as recyclable, separating them and wet-digesting, while residual waste stream is sorted and disposed of
EP1479502A1 (en) * 2002-01-23 2004-11-24 Suzuka Fuji Xerox Co., Ltd. Process for producing molded article of reclaimed thermoplastic resin
US20040253405A1 (en) * 2003-05-30 2004-12-16 Yasuhito Inagaki Method for recycling optical disk, resin composition for forming film, and resin molded article
EP1609573A1 (en) * 2003-04-01 2005-12-28 Suzuka Fuji Xerox Co., Ltd. Molded article of reclaimed thermoplastic resin

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US5232986A (en) * 1990-04-28 1993-08-03 Rohm Gmbh Chemische Fabrik Thermoplastic moulding composition comprising a polymer blend based on poly(meth)acrylate(s), abs-type polymer and polycarbonate
CZ236098A3 (en) * 1998-07-27 2000-02-16 Vladimír Prof. Ing. Drcs. Kubánek Process for preparing curing compounds from devulcanized rubber and recycled polymers
US20040209985A1 (en) * 2003-04-18 2004-10-21 Woei-Min Tsai Resin composition for injection molding

Patent Citations (8)

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Publication number Priority date Publication date Assignee Title
US5424013A (en) * 1993-08-09 1995-06-13 Lieberman; Mark Thermoplastic closed loop recycling process
EP0906817A1 (en) * 1996-04-14 1999-04-07 Suzuka Fuji Xerox Co., Ltd. Coated molded article, method of recycling the same and apparatus therefor
EP1193039A1 (en) * 2000-09-29 2002-04-03 Fuji Photo Film Co., Ltd. Method of recycling plastic parts for photosensitive material
EP1291378A1 (en) * 2001-03-28 2003-03-12 Sony Corporation Method of reclaiming resin
EP1479502A1 (en) * 2002-01-23 2004-11-24 Suzuka Fuji Xerox Co., Ltd. Process for producing molded article of reclaimed thermoplastic resin
DE10256305A1 (en) * 2002-12-03 2004-06-24 Der Grüne Punkt - Duales System Deutschland Ag Method for processing mixed waste materials comprises identifying materials of several different types as recyclable, separating them and wet-digesting, while residual waste stream is sorted and disposed of
EP1609573A1 (en) * 2003-04-01 2005-12-28 Suzuka Fuji Xerox Co., Ltd. Molded article of reclaimed thermoplastic resin
US20040253405A1 (en) * 2003-05-30 2004-12-16 Yasuhito Inagaki Method for recycling optical disk, resin composition for forming film, and resin molded article

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2058102A1 (en) * 2007-11-09 2009-05-13 Canon Kabushiki Kaisha Process for producing thermoplastic resin composition, and thermoplastic resin composition produced by the same
CN109880337A (en) * 2019-02-25 2019-06-14 宁波公牛精密制造有限公司 The spray painting polycarbonate compositions and preparation method thereof that high efficiente callback recycles
CN110256804A (en) * 2019-06-28 2019-09-20 祥兴(福建)箱包集团有限公司 A kind of preparation method of the anti-scratch PMMA/ABS tank material of toughening type
CN114716803A (en) * 2022-05-16 2022-07-08 东莞市国亨塑胶科技有限公司 Regeneration preparation method and regeneration material of ocean recycled polycarbonate
CN114716803B (en) * 2022-05-16 2024-02-20 东莞市国亨塑胶科技有限公司 Regeneration preparation method of ocean recovered polycarbonate and regenerated material thereof

Also Published As

Publication number Publication date
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CZ297698B6 (en) 2007-03-07

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