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DE102008008035A1 - Preparing polyamide foam, comprises heating scrap tire granulates containing polyamide fiber cords and gum powder in an extruder under formation of melting mass and carrying out a thermal decomposition of gum powder in e.g. cracked gas - Google Patents

Preparing polyamide foam, comprises heating scrap tire granulates containing polyamide fiber cords and gum powder in an extruder under formation of melting mass and carrying out a thermal decomposition of gum powder in e.g. cracked gas Download PDF

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DE102008008035A1
DE102008008035A1 DE102008008035A DE102008008035A DE102008008035A1 DE 102008008035 A1 DE102008008035 A1 DE 102008008035A1 DE 102008008035 A DE102008008035 A DE 102008008035A DE 102008008035 A DE102008008035 A DE 102008008035A DE 102008008035 A1 DE102008008035 A1 DE 102008008035A1
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gum powder
thermal decomposition
extruder
foam
scrap tire
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DE102008008035B4 (en
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Oleksandr Gitelman
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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
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3442—Mixing, kneading or conveying the foamable material
    • B29C44/3446—Feeding the blowing agent
    • 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
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/3442—Mixing, kneading or conveying the foamable material
    • B29C44/3446—Feeding the blowing agent
    • B29C44/3457—Feeding the blowing agent in solid form to the plastic material
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • 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
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2030/00—Pneumatic or solid tyres or parts thereof
    • 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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/03—Extrusion of the foamable blend
    • 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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/046—Elimination of a polymeric phase
    • 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
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/30—Polymeric waste or recycled polymer
    • 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
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

Preparation of polyamide foam (2) using scrap tire granulates containing polyamide fiber cords and gum powder, comprises uniquely heating the scrap tire granulates in an extruder (1) under formation of a melting mass (3) and simultaneously carrying out a thermal decomposition (pyrolysis) of the gum powder in dust-fine technical carbon and cracked gas, where the cracked gas serves as gas pore forming material for foaming the melting mass, and the technical carbon (polycarbon) as sheathing filler material for increasing the stability of the polyamide foam.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von Polyamidschaum, das sich durch eine gute Umweltverträglichkeit auszeichnet.The Invention relates to a process for the production of polyamide foam, which is characterized by good environmental compatibility.

Bekannt sind Verfahren zur Plastschaumgewinnung, bei denen eine Erwärmung von Mischungen aus flüssigen oder festen Ausgangskomponenten (Halbfabrikaten) gemeinsam mit Treibmitteln und Füllstoffen erfolgt.Known are processes for plastic foam extraction, where a warming mixtures of liquid or solid starting components (Semi-finished products) together with blowing agents and fillers he follows.

So wird in der DD 133 806 A ein Verfahren beschrieben, bei dem mit vorgewärmten Formen gearbeitet wird. Dabei ist es notwendig, Sondertreibmittel zu verwenden. Das ist ein wesentlicher Mangel dieser Technologie. Ferner ist das Verfahren diskontinuierlich und hat eine niedrige Produktivität bei hohen Kosten.So will in the DD 133 806 A a method is described, is worked in the preheated molds. It is necessary to use special blowing agents. That's a major shortcoming of this technology. Further, the process is discontinuous and has low productivity at a high cost.

Aus der CH 520 736 B ist ein weiteres Verfahren zur Polyamidschaumgewinnung bekannt. Hier werden in einem Sonderaktivator gasbildende bzw. gasabspaltende Produkte in die polymerisierte Polyamidmischung "Lactam" gegeben. Im Ergebnis wird die Mischung mit Gas gesättigt. Die Polyamide werden hier einer Anfangs- und Endpolymerisation in den vorgewärmten Formen unterworfen.From the CH 520 736 B Another method for polyamide foam recovery is known. Here gas-forming or gas-releasing products are added to the polymerized polyamide mixture "lactam" in a special activator. As a result, the mixture is saturated with gas. The polyamides are here subjected to initial and final polymerization in the preheated molds.

Zu den Mängeln dieses Verfahrens gehören Sonderaktivatoren und Sondertreibmittel. Auch dieses Verfahren zeichnet sich durch eine mehrstufige Polyamidschaumgewinnung aus.To The deficiencies of this procedure include special activators and special blowing agents. This method is also characterized a multi-stage polyamide foam extraction.

Aus Khoshaba N., Sabsay O., Barshtein G., Kuleznev V, Technological properties of the expanded and filled polyolefins, Plastics (J. Plast. Massy), 1991, 11, s. 46–48 ist eine Technologie der Gewinnung von geschäumten extrudierten Thermoplasten bekannt. Bei diesem Verfahren wird Polyäthylen von hoher und niedriger Dichte unter Verwendung der Füllstoffe Kreide und Glasfasern verarbeitet. Alle diese Komponenten werden zuerst im Granulator und dann im Extruder bei entsprechender Temperatur zusammengemischt. Im zweiten Schritt wird in die Mischung ein Treibmittel (Gasporenbilder) beigefügt. Im Ergebnis erfolgt die Gewinnung vom schäumenden Thermoplasten.Out Khoshaba N., Sabsay O., Barshtein G., Kuleznev V, Technological Properties of the Expanded and Filled Polyolefins, Plastics (J. Plast. Massy), 1991, 11, p. 46-48 is a technology of recovery of foamed extruded thermoplastics known. In this process, high and low density polyethylene is processed using the chalk and glass fiber fillers. All of these components are mixed together first in the granulator and then in the extruder at the appropriate temperature. In the second step, a blowing agent (gas pore images) is added to the mixture. As a result, the recovery of the foaming thermoplastic.

Zu den Mängeln dieses Verfahrens gehören ihre niedrige Produktivität, die Notwendigkeit von Sonderfüllstoffen und Treibmitteln, Zweistufigkeit und die vergleichsweise hohen Kosten vom aufgeschäumten Thermoplasten.To The shortcomings of this procedure include their low ones Productivity, the need for special fillers and blowing agents, two-stage and the comparatively high cost from the foamed thermoplastic.

Weiterhin ist ein Verfahren zur Herstellung von Polystyrolschaum im Extruder bekannt ( PENOPLEX in STRON Magazine, 11, 2002. ) In diesem Fall wird ein Treibmittel (Freon und Kohlendioxid (CO2)) bei hoher Temperatur und unter Druck zugefügt.Furthermore, a process for the production of polystyrene foam in the extruder is known (US Pat. PENOPLEX in STRON Magazine, 11, 2002. In this case, a blowing agent (freon and carbon dioxide (CO 2 )) is added at high temperature and under pressure.

Zu den Mängeln dieses Verfahrens zur Plastschaumgewinnung auf Polystyrolbasis gehören einmal die Notwendigkeit der Anwendung nicht nur von speziellen Treibmitteln sondern auch die Mischung mit Polystyrol beim Erwärmen im Extruder und weiter die beschränkten Festigkeitseigenschaften.To the shortcomings of this process for plastic foam extraction On polystyrene basis belong once the need of Application not only of special propellants but also the Mixture with polystyrene during heating in the extruder and continue the limited strength properties.

Aufgabe der Erfindung ist es, Polystyrolschäume billiger, kontinuierlich und unter Verwendung von Abfallstoffen herzustellen.task The invention is polystyrene foams cheaper, continuous and using waste materials.

Gelöst wird diese Aufgabe mit den Merkmalen des Anspruches 1, vorteilhafte Ausgestaltungen sind Gegenstand der Unteransprüche.Solved This object is achieved with the features of claim 1, advantageous Embodiments are the subject of the dependent claims.

Erfindungsgemäß wird ein Verfahren zur Herstellung von Polyamidschaum vorgeschlagen unter Verwendung von Altreifengranulat enthaltend Polyamidkordfasern und Gummipulver, die in einem Extruder unter Bildung einer Schmelzmasse einmalig erwärmt werden, wobei gleichzeitig eine thermische Zerlegung (Pyrolyse) des Gummipulvers in staubfeinen technischen Kohlenstoff und Spaltgas erfolgt und wobei das Spaltgas als Gasporenbildner zum Verschäumen der Schmelzmasse dient und der technische Kohlenstoff (Polycarbon) als armierender Füllstoff zur Erhöhung der Festigkeit des Polyamidschaumes.According to the invention a method of producing polyamide foam has been proposed Use of used tire granules containing polyamide cord fibers and Rubber powder used in an extruder to form a melt be heated once, while a thermal decomposition (Pyrolysis) of rubber powder in dusty technical carbon and cracking gas takes place and wherein the cracked gas as a gas-pore-forming agent used for foaming the melt and the technical Carbon (polycarbon) as reinforcing filler for Increasing the strength of the polyamide foam.

Ein solches Verfahren dient nicht nur der Ressourcen- und Energieeinsparung sondern stellt auch eine sinnvolle Alternative für eine Altreifenverwertung durch umweltschädliches Verbrennen dar.One such a method is not only the resource and energy savings but also provides a useful alternative for one Used tire recycling by environmentally harmful burning represents.

Anhand der 1 soll das Verfahren erläutert werden. Als bisher nicht verwertbare und deshalb zur Verbrennung vorgesehene Abfallprodukte aus der Altreifenverwertung verbleibt eine schwer trennbare Mischung 4 aus staubfeinen und bis zum Beispiel 8 mm langen Polyamidkordfasern und Gummipulver, das Altreifengranulat als eine Ausgangsmischung der Altreifenbearbeitung. Diese Mischung 4 wird in den Extruder 1 zwangsweise und dosiert eingebracht.Based on 1 the procedure should be explained. As previously unrecognizable and therefore intended for incineration waste products from the old tire recycling remains a difficult to separate mixture 4 from dust and, for example, 8 mm long polyamide cord fibers and rubber powder, the scrap tire granules as a starting mixture of scrap tire processing. This mixture 4 will be in the extruder 1 Forcibly and metered introduced.

Im Extruder 1 erfolgt das Erwärmen der Mischung 4 auf eine Temperatur von 216–220°C bis zur Bildung der Schmelzmasse 3 von Polyamiden. Gleichzeitig erfolgt eine thermische Zerlegung (Pyrolyse) des Gummipulvers in staubfeinen technischen Kohlenstoff (Pyrocarbon) und Spaltgas.In the extruder 1 the heating of the mixture takes place 4 to a temperature of 216-220 ° C until the formation of the melt 3 of polyamides. At the same time there is a thermal decomposition (pyrolysis) of the rubber powder in dust-fine technical carbon (pyrocarbon) and cracked gas.

Pyrocarbon (technischer Kohlenstoff) erfüllt die Funktion von armierenden Füllstoffen und bewirkt so einen Plastschaum von höherer Festigkeit (bis auf 200–250%).pyrocarbon (technical carbon) fulfills the function of reinforcing Fillers and thus causes a plastic foam of higher Strength (up to 200-250%).

Das Spaltgas dient als Gasporenbildner, der die Schmelzmasse 3 verschäumt und so einstufig Plastschaum (Polyamidschaum) 2 entstehen lässt.The cracked gas serves as a gas-pore-forming agent, which is the melt 3 foamed and thus one-stage plastic foam (polyamide foam) 2 can arise.

Der warme Polyamidschaum, der den Ausgang aus dem Extruder 1 erreicht, wird ohne jegliche zusätzliche nochmalige Erwärmung ausgeformt (Erhärtung) zu verschiedenen wärmeisolierenden Erzeugnissen z. B. flache Blockbaukonstruktionen, Schalen für die Wärmeisolierung von Rohrleitungen u. a. Da die thermische Zerlegung (Pyrolyse) von Gummi (Gummipulver) bei 80–85°C ein klar ausgeprägter exothermer Prozess ist, steht eine große Energiemenge für den Verfahrensprozess zur Verfügung. Dies bedeutet eine Energieeinsparung, da weniger Wärme dem Extruder von außen zugeführt werden muss für das Erwärmen der Ausgangsmischung 4 und die Schmelze 3.The warm polyamide foam, which is the exit from the extruder 1 achieved is formed without any additional reheating (hardening) to various heat-insulating products such. As the thermal decomposition (pyrolysis) of rubber (rubber powder) at 80-85 ° C is a clearly exothermal process, a large amount of energy for the process process is available. This means an energy saving, since less heat must be supplied to the extruder from the outside for the heating of the starting mixture 4 and the melt 3 ,

Bis heute werden die genannten Abfälle aus der Verarbeitung von abgenutzten Reifen nicht verwendet. Dabei geht es um bis zu 20% der Masse von verwertbaren Altreifen.To Today, the waste is processed not used by worn tires. It's about up to 20% of the mass of recyclable used tires.

Jährlich fallen nur in Deutschland 900.000 t von Abfälle aus Gummireifen an, die der Verwertung unterliegenden. Darum kann der Umfang ihrer ressourcensparenden rationalen Verarbeitung in Plastschaum (Polyamidschaum) 180.000 t erreichen. Außerdem kann mit dem Verfahren die umweltschädliche Verbrennung reduziert werden.Yearly Only in Germany 900,000 t of rubber tire waste which are subject to recovery. That is why the scope of their Resource-saving rational processing in plastic foam (polyamide foam) Reach 180,000 t. In addition, with the method the environmentally harmful combustion can be reduced.

ZITATE ENTHALTEN IN DER BESCHREIBUNGQUOTES INCLUDE IN THE DESCRIPTION

Diese Liste der vom Anmelder aufgeführten Dokumente wurde automatisiert erzeugt und ist ausschließlich zur besseren Information des Lesers aufgenommen. Die Liste ist nicht Bestandteil der deutschen Patent- bzw. Gebrauchsmusteranmeldung. Das DPMA übernimmt keinerlei Haftung für etwaige Fehler oder Auslassungen.This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Zitierte PatentliteraturCited patent literature

  • - DD 133806 A [0003] - DD 133806 A [0003]
  • - CH 520736 B [0004] CH 520736 B [0004]

Zitierte Nicht-PatentliteraturCited non-patent literature

  • - Khoshaba N., Sabsay O., Barshtein G., Kuleznev V, Technological properties of the expanded and filled polyolefins, Plastics (J. Plast. Massy), 1991, 11, s. 46–48 [0006] Khoshaba N., Sabsay O., Barshtein G., Kuleznev V, Technological Properties of the Expanded and Filled Polyolefins, Plastics (J. Plast. Massy), 1991, 11, p. 46-48 [0006]
  • - PENOPLEX in STRON Magazine, 11, 2002. [0008] - PENOPLEX in STRON Magazine, 11, 2002. [0008]

Claims (6)

Verfahren zur Herstellung von Polyamidschaum unter Verwendung von Altreifengranulat enthaltend Polyamidkordfasern und Gummipulver, die in einem Extruder unter Bildung einer Schmelzmasse einmalig erwärmt werden, wobei gleichzeitig eine thermische Zerlegung (Pyrolyse) des Gummipulvers in staubfeinen technischen Kohlenstoff und Spaltgas erfolgt und wobei das Spaltgas als Gasporenbildner zum Verschäumen der Schmelzmasse dient und der technische Kohlenstoff (Polycarbon) als armierender Füllstoff zur Erhöhung der Festigkeit des Polyamidschaumes.Process for the production of polyamide foam using scrap tire granules containing polyamide cord fibers and rubber powder which is unique in an extruder to form a melt be heated, at the same time a thermal decomposition (Pyrolysis) of rubber powder in dusty technical carbon and cracking gas takes place and wherein the cracked gas as a gas-pore forming agent for Foaming serves the melt and the technical carbon (Polycarbon) as reinforcing filler to increase the strength of the polyamide foam. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Altreifengranulat eine Ausgangsmischung der Altreifenbearbeitung ist.Method according to claim 1, characterized in that that the used tire granulate is a starting mixture of scrap tire processing is. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die notwendige Energie für das Erwärmen durch äußere Wärmezufuhr und den exothermen Vorgang der thermischen Zerlegung von Gummi in Summe bereitgestellt wird.Method according to claim 1 or 2, characterized that the necessary energy for heating by external Heat input and the exothermic process of thermal Disassembly of rubber is provided in total. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die bei der thermischen Zerlegung freigesetzte Wärme zum Vorwärmen des Granulates eingesetzt wird.Method according to one of claims 1 to 3, characterized in that in the thermal decomposition released heat to preheat the granules is used. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass der Polyamidschaum kontinuierlich dem Extruder entnommen und geformt wird.Method according to one of claims 1 to 4, characterized in that the polyamide foam continuously removed from the extruder and molded. Verfahren nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die Herstellung des Polyamidschaumes im Extruder als einstufiger Prozess erfolgt.Method according to one of claims 1 to 5, characterized in that the production of the polyamide foam in the extruder as a one-step process.
DE102008008035A 2008-02-05 2008-02-05 Process for the production of polyamide foam Expired - Fee Related DE102008008035B4 (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD133806A1 (en) 1977-11-08 1979-01-24 Karin Baum PROCESS FOR PREPARING POLYAMIDE FOAM

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH52036A (en) * 1910-04-15 1911-10-16 Wilhelm Reutter Collapsible hood for motor vehicles
US4003408A (en) * 1974-02-26 1977-01-18 George C. Ballas, trustee Underground irrigation porous pipe

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD133806A1 (en) 1977-11-08 1979-01-24 Karin Baum PROCESS FOR PREPARING POLYAMIDE FOAM

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Khoshaba N., Sabsay O., Barshtein G., Kuleznev V, Technological properties of the expanded and filled polyolefins, Plastics (J. Plast. Massy), 1991, 11, s. 46-48
PENOPLEX in STRON Magazine, 11, 2002.

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