WO1998007777A1 - Use of cashew nut husk oil in rubber and duroplastics recycling - Google Patents

Use of cashew nut husk oil in rubber and duroplastics recycling Download PDF

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Publication number
WO1998007777A1
WO1998007777A1 PCT/PT1997/000006 PT9700006W WO9807777A1 WO 1998007777 A1 WO1998007777 A1 WO 1998007777A1 PT 9700006 W PT9700006 W PT 9700006W WO 9807777 A1 WO9807777 A1 WO 9807777A1
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WO
WIPO (PCT)
Prior art keywords
rubber
recycling
cashew nut
duroplastics
hcnc
Prior art date
Application number
PCT/PT1997/000006
Other languages
French (fr)
Inventor
Martin Ernst Stielau
Original Assignee
Martin Ernst Stielau
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
Priority claimed from PT10190796A external-priority patent/PT101907A/en
Priority claimed from PT10192996A external-priority patent/PT101929A/en
Application filed by Martin Ernst Stielau filed Critical Martin Ernst Stielau
Priority to AU37888/97A priority Critical patent/AU3788897A/en
Priority to BR9711222A priority patent/BR9711222A/en
Priority to CA 2263990 priority patent/CA2263990A1/en
Priority to EP97934807A priority patent/EP0922068A1/en
Priority to JP51063598A priority patent/JP2001504523A/en
Publication of WO1998007777A1 publication Critical patent/WO1998007777A1/en

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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
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
    • C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L19/00—Compositions of rubbers not provided for in groups C08L7/00 - C08L17/00
    • C08L19/003—Precrosslinked rubber; Scrap rubber; Used vulcanised rubber
    • 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
    • C08J2321/00—Characterised by the use of unspecified rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
    • 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 the field of recycling rubbers and thermosetting plastics.
  • Cashew shell oil (henceforth HCNC) is a by-product of the food industry, of the preparation of cashew nuts.
  • This liquid which is located under the shell of the nut and which is released when it is opened, is a 9: 1 mixture of a fatty acid (anacardic acid, which carries a phenolic group to the benzene ring) with a diphenol (Cardol), both with side chains with 15 carbon atoms and 27 hydrogen and one to three double bonds.
  • a fatty acid anacardic acid, which carries a phenolic group to the benzene ring
  • Cardol diphenol
  • HCNC can, at a higher or lower temperature, "melt" vulcanized recycling rubbers and other thermosets.
  • the mixture is heated by kneading at a temperature between 200 and 300 ° C, and newly crosslinkable and / or vulcanizable liquids are obtained.
  • Preparation - even when cold - of old rubber with HCNC improves - thanks to the causticity of this product - the "recasting" in new rubber.
  • This crosslinking can be carried out - as the patent application PT 101,761 teaches us - cited above - thanks to a di- and / or polyisocyanate or with sulfur or with both.
  • PT 101,761 teaches us - cited above - thanks to a di- and / or polyisocyanate or with sulfur or with both.
  • the mechanical results improve greatly, if sulfur treated with HCNC is used.
  • the acceleration and modification systems seem to react in the same way.
  • HCNC Recycled rubber can be cold mixed with HCNC, sulfur, possibly accelerators and additives, and heated to a temperature around 150 ° C for 15 min. , to obtain appreciable "jumps" between particles of old rubber and / or new rubber.
  • HCNC 100 g of HCNC are heated with 20 g of rubber powder from a car tire at 180 ° C. until the powder is "diluted" completely. The mixture is allowed to cool and 33 g of an MD1 (type 44V20 from Bayer) are added. A rubber of good elasticity and mechanical resistance is obtained.

Abstract

The invention concerns the use of cashew nut husk oil in rubber and duroplastics recycling. It describes how this natural substance can eat into or even dissolve the vulcanised rubber car tyres and be involved in their re-vulcanisation.

Description

DESCRIPTION DESCRIPTION
L'UTILISATION DE L'HUILE DE COQUILLE DE NOIX DE CAJOU DANS LE DOMAINE DU RECYCLAGE DU CAOUTCHOUC ET DES PLASTIQUES THERMODURCISSABLESTHE USE OF CASHEW NUT OIL IN THE FIELD OF RUBBER RECYCLING AND THERMOSETTING PLASTICS
Domaines d'emploiAreas of use
La présente invention concerne le domaine des caoutchoucs de recyclage et des plastiques theπnodurcissables.The present invention relates to the field of recycling rubbers and thermosetting plastics.
AntécédentsBackground
L'huile de coquille de noix de Cajou (dorénavant HCNC) est un sous-produit de l'industrie alimentaire, de la préparation de la noix de cajou.Cashew shell oil (henceforth HCNC) is a by-product of the food industry, of the preparation of cashew nuts.
Ce liquide, qui se trouve sous la coquille de la noix et qui se libère au moment de son ouverture, est un mélange 9: 1 d'un acide gras (acide anacardique, qui porte un groupement phénolique a l'anneau benzénique ) avec un diphenol (Cardol), les deux avec des chaînes latérales avec 15 atomes de carbone et 27 d'hydrogène et une à trois doubles liaisons.This liquid, which is located under the shell of the nut and which is released when it is opened, is a 9: 1 mixture of a fatty acid (anacardic acid, which carries a phenolic group to the benzene ring) with a diphenol (Cardol), both with side chains with 15 carbon atoms and 27 hydrogen and one to three double bonds.
Les utilisations actuelles de ce produit se trouvent principalement dans le domaine des phenoplastes, ou en négligeant les chaînes avec leurs doubles liaisons, on fait: - après avoir descarboxylé l'acide gras grâce à une petite quantité d'acide sulfurique,The current uses of this product are mainly in the field of phenoplasts, or by neglecting the chains with their double bonds, we do: - after descarboxylating the fatty acid with a small amount of sulfuric acid,
- réagir les groupements phénoliques avec des aldéhydes. 11 en résulte, des produits qui se caractérisent surtout par leur grande résistance à la chaleur et à l'abrasion.- react the phenolic groups with aldehydes. 11 results, products which are characterized above all by their high resistance to heat and abrasion.
En ce qui concerne le domaine du caoutchouc, un chercheur américain, Mortimer T. Harvey, avait découvert et breveté des nombreuses possibilités de combiner l'HCNC a cette matière. (Brevets US 1 ,819,416 du 8.08.1931 ; n° 1,771,785 du 28. 1 1. 1925). Il est évident que ces découverts se réfèrent à la matière "caoutchouc naturel" étant donné que les caoutchoucs synthétiques n'ont commencé à être importants qu'après la deuxième guerre mondiale. Aujourd'hui, les dérivés du pétrole présentent plus de 60% dans la production des caoutchoucs en générale. Ainsi, les inventions de M. Harvey n'ont pu gagner l'importance économique qu'elles méritaient. Par contre, la présente invention se réfère au caoutchouc de recyclage provenant des pneus de voiture, qui selon le niveau de la technique, se composent de plus de 50% de caoutchouc synthétique. Dans le domaine du recyclage, la préparation ou incorporation des particules du vieux caoutchouc avant ou pendant agglomération ou revulcanisation est toujours problématique. La présente invention - tant la préparation des surfaces que leur agglomération - apporte des solutions simples et économiques.With regard to the rubber sector, an American researcher, Mortimer T. Harvey, had discovered and patented numerous possibilities for combining HCNC with this material. (US Patents 1, 819,416 of 8.08.1931; n ° 1,771,785 of 28. 1 1. 1925). It is obvious that these discoveries refer to the material "natural rubber" since synthetic rubbers only began to be important after the Second World War. Today, petroleum derivatives account for more than 60% in the production of rubbers in general. Thus, Mr. Harvey's inventions could not gain the economic importance they deserved. On the other hand, the present invention refers to recycling rubber from car tires, which, depending on the level of technology, consists of more than 50% of synthetic rubber. In the recycling field, the preparation or incorporation of old rubber particles before or during agglomeration or revulcanization is always problematic. The present invention - both the preparation of surfaces and their agglomeration - provides simple and economical solutions.
Dans une demande de brevet antérieur du même auteur (demande de brevet n° PT 101 761 du 21.08.95) il a été expliqué comment les polyisocyanates peuvent réticuler le HCNC grâce à ses groupements phénoliques des anneaux benzéniques. La présente invention fait plus d'attention aux chaînes latérales des composés avec leurs doubles liaisons, ainsi qu'à une capacité évidente de l'HCNC à dépolymeriser les caoutchoucs de recyclage (i.e. principalement, le mélange de caoutchouc naturel et synthétique) et d'autres thermodurcissables.In an earlier patent application by the same author (patent application no. PT 101 761 of August 21, 95) it was explained how polyisocyanates can crosslink HCNC thanks to its phenolic groups of benzene rings. The present invention pays more attention to the side chains of the compounds with their double bonds, as well as to an obvious capacity of the HCNC to depolymerize the recycling rubbers (ie mainly, the mixture of natural and synthetic rubber) and of other thermosets.
Contenu de l'inve tiContents of the invention
11 a été découvert que l'HCNC peut, à une température plus ou moins élevée, "fondre" les caoutchoucs vulcanisés de recyclage et d'autres thermodurcissables. Selon la composition et granulométrie de l'échantillon, on chauffe le mélange en malaxant à une températures d'entre 200 et 300°C, et on obtient des liquides nouvellement réticulables et/ou vulcanisables. Une préparation - même à froid - du vieux caoutchouc avec de l'HCNC améliore - grâce à la causticité de ce produit - la "refonte" dans le caoutchouc neuf. Cette réticulation peut se réaliser - comme nous l'enseigne la demande de brevet PT 101.761 - cité ci-dessus - grâce à un di- et/ou polyisocyanate ou avec du soufre ou avec l'un et l'autre. 11 a été également découvert que, pour agglomérer la poudre ou les fibres de caoutchouc provenant des pneus de voiture, les résultats mécaniques s'améliorent de beaucoup, si on utilise du soufre traité par l'HCNC. Les systèmes d'accélération et de modification semblent réagir de la même façon.It has been discovered that HCNC can, at a higher or lower temperature, "melt" vulcanized recycling rubbers and other thermosets. Depending on the composition and grain size of the sample, the mixture is heated by kneading at a temperature between 200 and 300 ° C, and newly crosslinkable and / or vulcanizable liquids are obtained. Preparation - even when cold - of old rubber with HCNC improves - thanks to the causticity of this product - the "recasting" in new rubber. This crosslinking can be carried out - as the patent application PT 101,761 teaches us - cited above - thanks to a di- and / or polyisocyanate or with sulfur or with both. It has also been found that, to agglomerate the powder or the rubber fibers from car tires, the mechanical results improve greatly, if sulfur treated with HCNC is used. The acceleration and modification systems seem to react in the same way.
Description de l'inventi nDescription of the invention
En chauffant la poudre de caoutchouc qui provient de pneus de voiture dans l'HCNC, on constate qu'au fur et à mesure que la température dépasse 180°C le caoutchouc de recyclage se dissout dans ce liquide. Pour une résine de polyester ou d'époxy réticulée, on constate un phénomène analogue à une température plus élevée. Après refroidissement, les mélanges obtenus sont repolymérisables. On a également découvert une manièred'utiliser l'HCNC comme liant : Le caoutchouc recyclé peut être mélangé à froid avec l'HCNC, le soufre, éventuellement des accélérateurs et des additifs, et chauffé à une température autour de 150°C pendant 15 min, pour obtenir des "bonds" appréciables entre particules du vieux caoutchouc et/ou du caoutchouc neuf. Ces résultats peuvent être améliorés grâce à la préalable préparation, suivie du vulcanisant: l'HCNC et le soufre sont mélangés p. ex. dans une proportion de 1 :2 et laissés réagir pendant au moins 24 heures avant leurs emplois.By heating the rubber powder from car tires in the HCNC, we see that as the temperature exceeds 180 ° C the recycling rubber dissolves in this liquid. For a crosslinked polyester or epoxy resin, a similar phenomenon is observed at a higher temperature. After cooling, the mixtures obtained are repolymerizable. We have also discovered a way to use HCNC as a binder: Recycled rubber can be cold mixed with HCNC, sulfur, possibly accelerators and additives, and heated to a temperature around 150 ° C for 15 min. , to obtain appreciable "jumps" between particles of old rubber and / or new rubber. These results can be improved thanks to the prior preparation, followed by the vulcanizer: HCNC and sulfur are mixed p. ex. in a proportion of 1: 2 and left to react for at least 24 hours before their use.
Exemple 1Example 1
On chauffe 100 g de l'HCNC avec 20 g de poudre de caoutchouc d'un pneu de voiture à 180°C jusqu'à la "dilution" complète de la poudre. On laisse refroidir et ajoute 33 g d'un MD1 (genre 44V20 de Bayer). On obtient un caoutchouc d'une bonne élasticité et résistance mécanique.100 g of HCNC are heated with 20 g of rubber powder from a car tire at 180 ° C. until the powder is "diluted" completely. The mixture is allowed to cool and 33 g of an MD1 (type 44V20 from Bayer) are added. A rubber of good elasticity and mechanical resistance is obtained.
Exemple 2Example 2
On prend 10 g de l'HNCN, on mélange avec 20g de soufre en poudre, et on les malaxe jusqu'à l'obtention d'une pâte homogène. Après maturation de 24 heures, on peut ajouter des plastifiants et d'auties additifs pour réaliser un liant pour caoutchouc de recyclage. 10 g of the HNCN are taken, mixed with 20 g of powdered sulfur, and kneaded until a homogeneous paste is obtained. After 24 hours of maturation, plasticizers and other additives can be added to make a binder for recycling rubber.

Claims

REVENDICATIONS
1. L'utilisation de l'huile de la coquille de la noix de cajou (HCNC) caractérisée par le fait que cet HNCN soit utilisé en tant que dépolymerisant réticulable.1. The use of cashew nut oil (HCNC) characterized in that this HNCN is used as a crosslinkable depolymerizer.
2. L'utilisation de l'huile de la coquille de la noix de cajou caractérisée par le fait qu'elle soit utilisée en tant que liant pour caoutchouc de recyclage.2. The use of the oil from the cashew nut shell, characterized in that it is used as a binder for recycling rubber.
3. L'utilisation en accord avec la revendication 1 , caractérisée par le fait qu'un di et/ou polyisocyanate soit employé pour réticuler le mélange de l'HNCN avec un composant thermodurcissable dépolymerisé.3. The use in accordance with claim 1, characterized in that a di and / or polyisocyanate is used to crosslink the mixture of HNCN with a depolymerized thermosetting component.
4. Le procédé de fabrication caractérisé par le fait que l'HNCN soit ajouté au soufre afin d'obtenir une préparation vulcanisante pour caoutchouc.4. The manufacturing process characterized in that the HNCN is added to the sulfur in order to obtain a vulcanizing preparation for rubber.
5. Produits caractérisés par le fait qu'ils résultent des procès qui emploient les utilisations mentionées aux revendications 1,2, 3 et 4. 5. Products characterized by the fact that they result from the trials which employ the uses mentioned in claims 1,2, 3 and 4.
PCT/PT1997/000006 1996-08-20 1997-08-19 Use of cashew nut husk oil in rubber and duroplastics recycling WO1998007777A1 (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
AU37888/97A AU3788897A (en) 1996-08-20 1997-08-19 Use of cashew nut husk oil in rubber and duroplastics recycling
BR9711222A BR9711222A (en) 1996-08-20 1997-08-19 Use of cashew nut house oil and product obtained from its use
CA 2263990 CA2263990A1 (en) 1996-08-20 1997-08-19 Use of cashew nut husk oil in rubber and duroplastics recycling
EP97934807A EP0922068A1 (en) 1996-08-20 1997-08-19 Use of cashew nut husk oil in rubber and duroplastics recycling
JP51063598A JP2001504523A (en) 1996-08-20 1997-08-19 Use of cashew nut shell oil as a polymerizable depolymerizer in the regeneration of rubber and thermoset plastics

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
PT101907 1996-08-20
PT10190796A PT101907A (en) 1996-08-20 1996-08-20 Use of cashew nut oil - in recycling rubber and duroplastics.
PT101929 1996-10-24
PT10192996A PT101929A (en) 1996-10-24 1996-10-24 Method for the vulcanisation of cashew nut shell oil and the product thus obtained

Publications (1)

Publication Number Publication Date
WO1998007777A1 true WO1998007777A1 (en) 1998-02-26

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PCT/PT1997/000006 WO1998007777A1 (en) 1996-08-20 1997-08-19 Use of cashew nut husk oil in rubber and duroplastics recycling

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EP (1) EP0922068A1 (en)
JP (1) JP2001504523A (en)
AU (1) AU3788897A (en)
BR (1) BR9711222A (en)
CA (1) CA2263990A1 (en)
WO (1) WO1998007777A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6180686B1 (en) 1998-09-17 2001-01-30 Thomas M. Kurth Cellular plastic material
KR20020064038A (en) * 2001-01-31 2002-08-07 금호산업 주식회사 Rubber composition with edible oil
ES2207995A1 (en) * 2000-08-25 2004-06-01 Angel Corbera Alarcon Tires are recycled by means of revulcanization of rubber with rubber extracted from used tires by scraping process
US9045581B2 (en) 2005-03-03 2015-06-02 Rhino Linings Corporation Polyols derived from a vegetable oil using an oxidation process

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7595094B2 (en) 1998-09-17 2009-09-29 Urethane Soy Systems, Co. Vegetable oil-based coating and method for application
US20020058774A1 (en) 2000-09-06 2002-05-16 Kurth Thomas M. Transesterified polyol having selectable and increased functionality and urethane material products formed using the polyol
JP2015117275A (en) * 2013-12-17 2015-06-25 住化バイエルウレタン株式会社 Use of cashew nutshell liquid as raw material for polyurethane resin

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1819416A (en) * 1928-08-08 1931-08-18 Harvel Corp Compositions of materials and method for producing them

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1819416A (en) * 1928-08-08 1931-08-18 Harvel Corp Compositions of materials and method for producing them

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
N.D. GHATGE ET AL.: "Reclaiming scrap rubber", RUBBER AGE, vol. 105, no. 7, July 1973 (1973-07-01), NEW YORK, pages 35 - 38, XP002044758 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6180686B1 (en) 1998-09-17 2001-01-30 Thomas M. Kurth Cellular plastic material
ES2207995A1 (en) * 2000-08-25 2004-06-01 Angel Corbera Alarcon Tires are recycled by means of revulcanization of rubber with rubber extracted from used tires by scraping process
KR20020064038A (en) * 2001-01-31 2002-08-07 금호산업 주식회사 Rubber composition with edible oil
US9045581B2 (en) 2005-03-03 2015-06-02 Rhino Linings Corporation Polyols derived from a vegetable oil using an oxidation process

Also Published As

Publication number Publication date
JP2001504523A (en) 2001-04-03
AU3788897A (en) 1998-03-06
EP0922068A1 (en) 1999-06-16
CA2263990A1 (en) 1998-02-26
BR9711222A (en) 1999-08-17

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