WO2007006489A1 - Use of bleached biodiesel as a plasticizer - Google Patents

Use of bleached biodiesel as a plasticizer Download PDF

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Publication number
WO2007006489A1
WO2007006489A1 PCT/EP2006/006623 EP2006006623W WO2007006489A1 WO 2007006489 A1 WO2007006489 A1 WO 2007006489A1 EP 2006006623 W EP2006006623 W EP 2006006623W WO 2007006489 A1 WO2007006489 A1 WO 2007006489A1
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Prior art keywords
biodiesel
silane
modified
activated
use according
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PCT/EP2006/006623
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German (de)
French (fr)
Inventor
Tobias Austermann
Andreas Brey
Michael Duetsch
Helmut Mack
Laurent Marc
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Construction Research & Technology Gmbh
Evonik Degussa Gmbh
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Application filed by Construction Research & Technology Gmbh, Evonik Degussa Gmbh filed Critical Construction Research & Technology Gmbh
Priority to EP06762467A priority Critical patent/EP1913068A1/en
Publication of WO2007006489A1 publication Critical patent/WO2007006489A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers

Definitions

  • the present invention relates to the use of decolorized biodiesel as a plasticizer for polymers and / or resins and / or binders.
  • Plastics, adhesives and sealants, coatings, paints and varnishes, floors, sports floors, potting compounds, etc. contain polymers, binders and / or resins, which are responsible for the main properties of the products mentioned. But also important are the additives despite their z. T. small amount added, since they greatly affect the expected properties of the corresponding products.
  • the plasticizer plays an important role as an additive.
  • Plasticizers are substances added to a polymer, binder and / or resin to improve its ductility, softness and flexibility for processing and use. However, plasticizers do not undergo chemical reaction with the polymer, binder and / or resin, but only change it physically.
  • an ideal softener should be odorless, solid or liquid, colorless, resistant to light, temperature and water, not harmful to health, hardly combustible, as volatile as possible and inexpensive.
  • Plasticizers also escape from PVC soils, especially at high temperatures and newly produced soils, and thus, especially for toddlers playing on the ground Problem dar. Phthalate are biologically difficult to decompose and therefore accumulate in the environment. Due to the high amount of plasticizer used, phthalic acid esters are now widely used in soils and water sediments and can be detected at elevated concentrations. As a plasticizer z. B. also ecologically also questionable chloroparaffins used. Alternative and ecologically harmless plasticizers are therefore increasingly in demand.
  • plasticizers are trimellitates, aliphatic dicarboxylic acid esters, polyether polyols, polyester polyols, phosphoric acid esters, fatty acid esters, hydroxycarboxylic acid esters, alkylated benzenes, aromatic and aliphatic hydrocarbons, silicone oils, alkylsulfonic acid esters, sulfoxides / sulfones, etc.
  • a class of greener plasticizers is made from natural oils.
  • the most commonly used natural softener is epoxidized soybean oil (ESO).
  • ESO epoxidized soybean oil
  • Other epoxidized oils used in flexible PVC are castor oil and epoxidized tall oil.
  • plasticizers are natural esters. Stearic and oleic esters are known. They are used as plasticizers for z. B. Polystyrene, celluloid, ethylcellulose, etc. used. Sebacic acid, a component of castor oil, is used in the form of the ester as plasticizer for PVC.
  • the present invention was therefore based on the object to provide a new plasticizer, which does not have the disadvantages mentioned in the prior art, but has environmentally friendly properties and can be produced at the same time cost.
  • biodiesel which has been decolorized as a plasticizer and has a color number of APHA ⁇ 300 (according to ISO 6271). It has surprisingly been found that decolored biodiesel has excellent properties as a plasticizer and can be used excellently, for example, in pigmented or transparent products.
  • Biodiesel is the name given to a fatty acid methyl ester mixture produced from vegetable oils.
  • Vegetable oil is a generic term for "fat” oil that is derived from plants, as opposed to the essential oils, which are also referred to as “drying oils”.
  • fat oil that is derived from plants, as opposed to the essential oils, which are also referred to as “drying oils”.
  • drying oils In the plant seeds, the oil occurs in the form of lipids, which represent cell membrane building blocks and energy reserves. Comprehensive one speaks of oils and fats, because the difference results only from the respective consistency at different temperatures.
  • oils consist of triglycerides.
  • argan argan, algae, avocado, thistle, flax, hazelnut, Hemp, jojoba, coconut, pumpkin seed, corn, almond, apricot, poppy, evening primrose, olive, palm, rapeseed, castor, sea buckthorn, black cumin, sesame, soya , Sunflower, walnut, grape seed and wheat germ oil, etc.
  • Vegetable oils are normally used as foodstuffs (eg olive oil, etc.) and as margarine (also hardened fat), as cosmetics and as base material in the chemical industry. Recently, vegetable oils have become increasingly important as a starting material for diesel fuel.
  • biodiesel In order to find use as fuel for diesel engines, the transesterification to the so-called biodiesel is necessary.
  • the technical term for biodiesel is PME (vegetable methyl ester) or FAME (fatty acid methylene ester).
  • a major advantage of using vegetable oils as fuel is the substantial CO 2 neutrality. In the case of incineration, essentially the amount of CO 2 released by the plants from the atmosphere by photosynthesis is released.
  • To produce the vegetable oil with about 10 wt .-% methanol and various catalysts such. As alcoholates, etc. added. At atmospheric pressure and temperatures around 60 0 C, the ester bonds of the triglycerides of the vegetable oil are separated and the fatty acids then esterified with the methanol.
  • decolourised biodiesel which has a color number of APHA (according to Iso 6271) ⁇ 300, more preferably ⁇ 280, even more preferably ⁇ 250, and most preferably ⁇ 200.
  • the amount of biodiesel used can be varied within wide limits, but it has proved to be particularly advantageous, this in an amount of 1 to 80 wt .-%, in particular 5 to 50 wt .-% and particularly preferably 10 to 30 parts by weight. %, based on the weight of the polymers and / or resins and / or binders to use.
  • the plasticizer proposed according to the invention is suitable for all customary polymers and / or resins and / or binders, in particular based on PVC, epoxides, polyurethanes, polyacrylates, polymethacrylates, polysulfides and silicones, synthetic or natural rubbers, silane-modified polyurethanes, silane-modified polyethers (eg MS polymer), silane-modified acrylates, silane-modified methacrylates and / or silane-modified polysulfides.
  • the decolourised biodiesel can be used for all sorts of products, in particular in plastics, adhesives and sealants, coatings, paints and varnishes, floors, sports floors, potting compounds, etc.
  • the preparation of the decolourised biodiesel can be done in various ways. Surprisingly, it was found that the biodiesel gently and inexpensively by contacting with suitable adsorbents, eg. Activated charcoal (eg Norit® ) can be decolorized.
  • suitable adsorbents eg. Activated charcoal (eg Norit® )
  • the decolorization process may be carried out batchwise by contacting the biodiesel with pulverulent or shaped activated carbon in a stirred reactor or continuously. As adsorbents are z. B.
  • activated carbons in addition to the activated carbons also activated silica (Precipitated silica, flame silica, etc.), silicates of all kinds (e.g., kaolins, etc.), magnesium phosphates, metal hydroxides, metal oxides (e.g., aluminas, etc.), metal carbonates, clays (e.g., bentonites, etc .), etc.
  • the adsorbents can be used individually or in combination.
  • the decolorization of the biodiesel is preferably carried out in a continuous manner.
  • the biodiesel to be decolored is passed over an activated carbon bed, which is arranged in a reactor, in trickle bed or in bubbling mode and thereby contacted with the activated activated carbon.
  • an activated carbon bed which is arranged in a reactor, in trickle bed or in bubbling mode and thereby contacted with the activated activated carbon.
  • a strongly colored biodiesel (color number APHA> 1000) is almost completely decolorized.
  • decolored biodiesel having a color number of APHA ⁇ 300, more preferably ⁇ 280, even more preferably ⁇ 250, and most preferably ⁇ 200 is obtained.
  • the surface area of the activated carbon used according to the invention is in particular 20 to 2500 m 2 / g, preferably 100 to 2000 m 2 / g and particularly preferably 200 to 1500 m 2 / g.
  • the amount of activated carbon used is in particular between 0.01 and 20 wt .-%, preferably between 0.1 and 5 wt .-% and particularly preferably between 0.2 and 3 wt .-%.
  • the activated carbons used according to the invention are usually chemically activated, for. B. by phosphoric acid.
  • the decolorization capacity of an activated carbon depends to a large extent on the physico-chemical properties of the activated carbon. With increasing loading of the activated carbon with the coloring constituents of the biodiesel (eg soap residues, etc.) increases the activity or adsorption capacity of the activated carbon from and at the same time increases the color number of the treated biodiesel. As soon as an initially defined target color number of the treated biodiesel is exceeded, the activated carbon is preferably replaced or regenerated and used again for decolorization after the regeneration. This regeneration can z. B. as described in DE 101 222 66 A1.
  • Biodiesel belongs to the group “Renewable resources”, contains no benzene or other aromatics, is readily biodegradable, does not endanger ground or groundwater in accidents, is not a dangerous good (its flashpoint is at least 12O 0 C) and is sulfur-free ( ⁇ 0.001 wt .-%) •
  • Biodiesel is available worldwide and can be produced particularly inexpensively.
  • Biodiesel is liquid, almost odorless, light, temperature and water resistant, not harmful to health, difficult to burn, low viscosity and low volatility.
  • decolourised biodiesel is particularly suitable as a plasticizer on an industrial scale.
  • Discolored biodiesel (Novance manufacturer from France) is one with activated charcoal (Norit ® SA Super activated by means of steam) filled column (height 40 cm, diameter 2 cm), an activated carbon bed fed.
  • the bed density is about 400 g / l.
  • the contact is made with a dosing of about 50 ml / h, corresponding to about two hours of contact time. Over a period of about 48 hours will be a discoloration of the biodiesel to a color number APHA ⁇ 200 achieved.
  • the activated carbon used at a color number of APHA ⁇ 200 without regeneration is approx. 10 kg.
  • silane-terminated polyurethane polymer manufactured by the manufacturer Kerr Mc-Gee
  • 225 g of silane-terminated polyurethane polymer manufactured by the manufacturer Kerr Mc-Gee
  • another 5.75 g of vinyl silane manufactured by the manufacturer Kerr Mc-Gee
  • 22.5 g of hydrophobized flame silica manufactured by the manufacturer Kerr Mc-Gee
  • stabilizer manufactured by the manufacturer Kerr Mc-Gee was added and worked into the mixture over about two hours.
  • white pigment titanium dioxide Manufacturer Kerr Mc-Gee was added and worked into the mixture over about two hours.
  • the pressure in the working space of the mixer is lowered to 100 mbar. This removes volatile components from the compound within ten minutes.
  • the DTC analysis of the sealant with biodiesel shows no pronounced glass transition temperature. Glass transition temperatures show only defined chemical compounds such. Phthalates, adipates, stearic acid methyl ester, etc.).

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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)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to the use of bleached biodiesel having a color number APHA < 300 (according to ISO 6271) as a plasticizer for polymers and resins and/or binders. Surprisingly, bleached biodiesel has excellent properties as a plasticizer and is suitable for use in products based on PVC, epoxides, polyurethanes, polyacrylates, polymethacrylates, polysulfides and silicones, synthetic and natural rubbers, silane-modified polyurethanes, silane-modified polyethers, silane-modified acrylates, silane-modified methacrylates and/or silane-modified polysulfides. Due to its specific ecological and economic advantages, bleached biodiesel is especially suitable for large-scale use as a plasticizer.

Description

Verwendung von entfärbtem Biodiesel als Weichmacher Use of discolored biodiesel as plasticizer
Beschreibungdescription
Die vorliegende Erfindung betrifft die Verwendung von entfärbtem Biodiesel als Weichmacher für Polymere und/oder Harze und/oder Bindemittel.The present invention relates to the use of decolorized biodiesel as a plasticizer for polymers and / or resins and / or binders.
Kunststoffe, Kleb- und Dichtstoffe, Beschichtungen, Farben und Lacke, Fußböden, Sportböden, Vergussmassen, usw. enthalten Polymere, Bindemittel und/oder Harze, welche für die Haupteigenschaften der erwähnten Produkte verantwortlich sind. Wichtig sind aber auch die Additive trotz ihrer z. T. kleinen Zusatzmenge, da sie die erwarteten Eigenschaften der entsprechenden Produkte sehr stark beeinflussen. Eine bedeutende Rolle spielt hierbei der Weichmacher als Additiv.Plastics, adhesives and sealants, coatings, paints and varnishes, floors, sports floors, potting compounds, etc. contain polymers, binders and / or resins, which are responsible for the main properties of the products mentioned. But also important are the additives despite their z. T. small amount added, since they greatly affect the expected properties of the corresponding products. The plasticizer plays an important role as an additive.
Als Weichmacher werden Stoffe bezeichnet, die einem Polymer, Bindemittel und/oder Harz zugegeben werden, um dessen Dehnbarkeit, Weichheit und Biegsamkeit für Verarbeitung und Gebrauch zu verbessern. Dabei gehen Weichmacher aber keine chemische Reaktion mit dem Polymer, Bindemittel und/oder Harz ein, sondern verändern es nur physikalisch.Plasticizers are substances added to a polymer, binder and / or resin to improve its ductility, softness and flexibility for processing and use. However, plasticizers do not undergo chemical reaction with the polymer, binder and / or resin, but only change it physically.
Neben seiner weich machenden Wirkung sollte ein idealer Weichmacher geruchlos, fest oder flüssig, farblos, licht-, temperatur- und wasserbeständig, nicht gesundheitsschädlich, schwer brennbar, möglichst wenig flüchtig und kostengünstig sein.In addition to its softening effect, an ideal softener should be odorless, solid or liquid, colorless, resistant to light, temperature and water, not harmful to health, hardly combustible, as volatile as possible and inexpensive.
In großem Umfang werden Weichmacher bei bestimmten Kunststoffen (z. B. Polyvinylchlorid = PVC) verwendet; andere Kunststoffe enthalten hingegen keine Weichmacher (z. B. Polyethylen, Polypropylen). Die PVC-Produktion stellt den größten Verbraucher (fast 90%) von Weichmacher dar. Diese können bis zu 55 Gew.-% im PVC enthalten sein. Am häufigsten werden neben Phthalsäureestem (Jayflex®, usw.) unter anderem Sulfonsäureester (Mesamoll®, usw.) und Dicarbonsäureester (Plastomoll®, usw.) verwendet. Di(2-ethylhexyl)phthalat (= DEHP), der am häufigsten verwendete Phthalsäureester, wurde in den USA als krebserzeugend eingestuft. Weichmacher gelangen über Kunststoffverpackungen in Lebensmittel (z. B. Milch) und stellen somit eine Gesundheitsgefährdung dar. Aus PVC-Böden entweichen ebenfalls Weichmacher, insbesondere bei hohen Temperaturen und neu produzierten Böden und stellen somit, besonders für Kleinkinder, die am Boden spielen, ein Problem dar. Phthalsäureester sind biologisch nur schwer abbaubar und reichern sich daher in der Umwelt an. Durch die hohe Einsatzmenge der Weichmacher sind Phthalsäureester heute in Böden und Gewässersedimenten weit verbreitet und in erhöhten Konzentrationen nachweisbar. Als Weichmacher werden z. B. auch die ökologisch ebenfalls bedenklichen Chlorparaffine verwendet. Alternative und ökologisch unbedenkliche Weichmacher werden deshalb verstärkt nachgefragt.Plasticizers are widely used in certain plastics (eg polyvinylchloride = PVC); however, other plastics contain no plasticizers (eg polyethylene, polypropylene). PVC production is the largest consumer (almost 90%) of plasticizers. These can be up to 55% by weight in PVC. Most frequently, in addition to phthalic acid esters (Jayflex ®, etc.), among other sulfonic acid esters (mesamoll ®, etc.) and dicarboxylic acid (Plastomoll®, etc.). Di (2-ethylhexyl) phthalate (= DEHP), the most commonly used phthalic acid ester, was classified as a carcinogen in the United States. Softeners enter into food (eg milk) via plastic packaging and pose a health hazard. Plasticizers also escape from PVC soils, especially at high temperatures and newly produced soils, and thus, especially for toddlers playing on the ground Problem dar. Phthalate are biologically difficult to decompose and therefore accumulate in the environment. Due to the high amount of plasticizer used, phthalic acid esters are now widely used in soils and water sediments and can be detected at elevated concentrations. As a plasticizer z. B. also ecologically also questionable chloroparaffins used. Alternative and ecologically harmless plasticizers are therefore increasingly in demand.
Weitere Stoffgruppen, aus denen Verbindungen als Weichmacher Verwendung finden, sind Trimellitate, aliphatische Dicarbonsäureester, Polyetherpolyole, Polyesterpolyole, Phosphorsäureester, Fettsäureester, Hydroxycarbonsäureester, alkylierte Benzole, aromatische und aliphatische Kohlenwasserstoffe, Silikonöle, Alkylsulfonsäureester, Sulfoxide/Sulfone, usw.Other groups of substances from which compounds are used as plasticizers are trimellitates, aliphatic dicarboxylic acid esters, polyether polyols, polyester polyols, phosphoric acid esters, fatty acid esters, hydroxycarboxylic acid esters, alkylated benzenes, aromatic and aliphatic hydrocarbons, silicone oils, alkylsulfonic acid esters, sulfoxides / sulfones, etc.
Eine Klasse von umweltfreundlicheren Weichmachern wird aus natürlichen ölen hergestellt. Der am häufigsten verwendete natürliche Weichmacher ist epoxidiertes Sojaöl (epoxidized soybean oil = ESO). ESO (Vikoflexreg®, usw.) wird als Weichmacher in flexiblem PVC eingesetzt. Andere epoxidierte öle, die in flexiblem PVC verwendet werden, sind Rizinusöl und epoxidiertes Tallöl.A class of greener plasticizers is made from natural oils. The most commonly used natural softener is epoxidized soybean oil (ESO). ESO (Vikoflexreg ®, etc.) is used as a plasticizer in flexible PVC. Other epoxidized oils used in flexible PVC are castor oil and epoxidized tall oil.
Eine andere Klasse von Weichmachern sind natürliche Ester. Bekannt sind Stearinsäure- und ölsäureester. Sie werden als Weichmacher für z. B. Polystyrol, Celluloid, Ethylcellulose, usw. verwendet. Sebacinsäure, eine Komponente des Castoröls, wird in Form des Esters als Weichmacher für PVC verwendet.Another class of plasticizers are natural esters. Stearic and oleic esters are known. They are used as plasticizers for z. B. Polystyrene, celluloid, ethylcellulose, etc. used. Sebacic acid, a component of castor oil, is used in the form of the ester as plasticizer for PVC.
Nachteilig bei diesen Weichmachern auf Basis von natürlichen Ölen und Estern ist die Tatsache, dass die Herstellung beziehungsweise Aufreinigung dieser Verbindungen relativ aufwendig und kostenintensiv ist.A disadvantage of these plasticizers based on natural oils and esters is the fact that the preparation or purification of these compounds is relatively complicated and expensive.
Der vorliegenden Erfindung lag daher die Aufgabe zu Grunde, einen neuen Weichmacher bereitzustellen, der die genannten Nachteile entsprechend dem Stand der Technik nicht aufweist, sondern umweltfreundliche Eigenschaften aufweist und gleichzeitig kostengünstig hergestellt werden kann.The present invention was therefore based on the object to provide a new plasticizer, which does not have the disadvantages mentioned in the prior art, but has environmentally friendly properties and can be produced at the same time cost.
Diese Aufgabe wurde erfindungsgemäß dadurch gelöst, dass man als Weichmacher entfärbten Biodiesel mit einer Farbzahl von APHA < 300 (nach ISO 6271) einsetzt. Es hat sich nämlich überraschenderweise gezeigt, dass entfärbter Biodiesel ausgezeichnete Eigenschaften als Weichmacher besitzt und hervorragend zum Beispiel in pigmentierten oder transparenten Produkten eingesetzt werden kann.This object is achieved according to the invention by using biodiesel which has been decolorized as a plasticizer and has a color number of APHA <300 (according to ISO 6271). It has surprisingly been found that decolored biodiesel has excellent properties as a plasticizer and can be used excellently, for example, in pigmented or transparent products.
Biodiesel ist die Bezeichnung für ein aus Pflanzenölen hergestelltes Fettsäuremethylestergemisch. Pflanzenöl ist ein Oberbegriff für „fettes" Öl, welches aus Pflanzen gewonnen wird, im Gegensatz zu den ätherischen Ölen, welche auch als „trocknende öle" bezeichnet werden. In den Pflanzensamen kommt das Öl in Form von Lipiden vor, die Zellmembran- Bausteine und Energiereserven darstellen. Umfassend spricht man von Ölen und Fetten, denn der Unterschied ergibt sich nur aus der jeweiligen Konsistenz bei unterschiedlichen Temperaturen.Biodiesel is the name given to a fatty acid methyl ester mixture produced from vegetable oils. Vegetable oil is a generic term for "fat" oil that is derived from plants, as opposed to the essential oils, which are also referred to as "drying oils". In the plant seeds, the oil occurs in the form of lipids, which represent cell membrane building blocks and energy reserves. Comprehensive one speaks of oils and fats, because the difference results only from the respective consistency at different temperatures.
Chemisch gesehen bestehen Öle aus Triglyceriden. Man unterscheidet nach der Herkunftspflanze Argan-, Algen-, Avocado-, Distel-, Lein-, Haselnuss-, Hanf-, Jojoba-, Kokos-, Kürbiskern-, Mais-, Mandel-, Marillenkern-, Mohn-, Nachtkerzen-, Oliven-, Palm-, Raps-, Rizinus-, Sanddornkern-, Schwarzkümmel-, Sesam-, Soja-, Sonnenblumen-, Walnuss-, Traubenkern- und Weizenkeim-Öl, usw.Chemically, oils consist of triglycerides. A distinction is made according to the origin plant argan, algae, avocado, thistle, flax, hazelnut, Hemp, jojoba, coconut, pumpkin seed, corn, almond, apricot, poppy, evening primrose, olive, palm, rapeseed, castor, sea buckthorn, black cumin, sesame, soya , Sunflower, walnut, grape seed and wheat germ oil, etc.
Pflanzenöle werden normalerweise als Nahrungsmittel verwendet (z. B. Olivenöl, usw.) und als Margarine (auch gehärtetes Fett), als Kosmetika und als Grundstoff in der chemischen Industrie eingesetzt. In jüngster Zeit gewinnen Pflanzenöle als Ausgangsmaterial für Kraftstoff für Dieselmotoren zunehmend an Bedeutung.Vegetable oils are normally used as foodstuffs (eg olive oil, etc.) and as margarine (also hardened fat), as cosmetics and as base material in the chemical industry. Recently, vegetable oils have become increasingly important as a starting material for diesel fuel.
Um als Kraftstoff für Dieselmotoren Verwendung zu finden, ist die Umesterung zum so genannten Biodiesel notwendig. Der Fachbegriff für Biodiesel lautet PME (Pflanzen Methyl Ester) beziehungsweise FAME (Fatty Acid Methylene Ester). Ein großer Vorteil der Verwendung von Pflanzenölen als Treibstoff ist die weitgehende CO2-Neutralität. Bei der Verbrennung wird im Wesentlichen die Menge CO2 freigesetzt, die die Pflanzen vorher durch Photosynthese aus der Atmosphäre entnommen haben. Zur Herstellung wird das Pflanzenöl mit ca. 10 Gew.-% Methanol und verschiedenen Katalysatoren wie z. B. Alkoholaten, usw. versetzt. Bei Normaldruck und Temperaturen um 600C werden die Esterbindungen der Triglyzeride des Pflanzenöls getrennt und die Fettsäuren dann mit dem Methanol verestert. Das dabei entstehende Glycerin muss dann vom Biodiesel getrennt werden. Durch diese Umesterung hat das Endprodukt eine deutlich geringere Viskosität als das Pflanzenöl, weist aber nach wie vor eine relativ hohe Eigenfärbung (Farbzahl) auf. Die hohe Eigenfärbung ist von Nachteil für die Verwendung als Weichmacher in z. B. unpigmentierten Beschichtungen oder Dichtstoffen. Erfindungsgemäß wird deshalb entfärbter Biodiesel eingesetzt, der eine Farbzahl von APHA (nach Iso 6271 ) < 300, stärker bevorzugt ≤ 280, nochmals stärker bevorzugt ≤ 250 und am stärksten bevorzugt ≤ 200 besitzt. Gemäß einer bevorzugten Ausführungsform wird als entfärbter Biodiesel ein pflanzlicher Methylester (PME) nach DIN E 51 606, Rapsöl-Methylester (RME) nach DIN E 51 606, Soja-Methylester (SME) oder Sonnenblumen- Methylester, Altfett-Methylester (AME) und Fett-Methylester (FME) aus sonstigen Pflanzen- und Tierstoffen nach DIN V 51 606 verwendet. Die Menge des eingesetzten Biodiesels ist in weiten Grenzen variierbar, doch hat es sich als besonders vorteilhaft erwiesen, diesen in einer Menge von 1 bis 80 Gew.-%, insbesondere 5 bis 50 Gew.-% und besonders bevorzugt 10 bis 30 Gew.-%, bezogen auf das Gewicht der Polymere und/oder Harze und/oder Bindemittel, einzusetzen.In order to find use as fuel for diesel engines, the transesterification to the so-called biodiesel is necessary. The technical term for biodiesel is PME (vegetable methyl ester) or FAME (fatty acid methylene ester). A major advantage of using vegetable oils as fuel is the substantial CO 2 neutrality. In the case of incineration, essentially the amount of CO 2 released by the plants from the atmosphere by photosynthesis is released. To produce the vegetable oil with about 10 wt .-% methanol and various catalysts such. As alcoholates, etc. added. At atmospheric pressure and temperatures around 60 0 C, the ester bonds of the triglycerides of the vegetable oil are separated and the fatty acids then esterified with the methanol. The resulting glycerine must then be separated from the biodiesel. As a result of this transesterification, the end product has a significantly lower viscosity than the vegetable oil, but still has a relatively high intrinsic coloration (color number). The high intrinsic color is disadvantageous for use as a plasticizer in z. B. unpigmented coatings or sealants. Therefore, according to the invention, decolourised biodiesel is used which has a color number of APHA (according to Iso 6271) <300, more preferably ≦ 280, even more preferably ≦ 250, and most preferably ≦ 200. According to a preferred embodiment, a vegetable methyl ester (PME) according to DIN E 51 606, rapeseed oil methyl ester (RME) according to DIN E 51 606, soybean methyl ester (SME) or sunflower methyl ester, old fat methyl ester (AME) and as biodegraded biodiesel Fat methyl ester (FME) from other plant and animal substances according to DIN V 51 606 used. The amount of biodiesel used can be varied within wide limits, but it has proved to be particularly advantageous, this in an amount of 1 to 80 wt .-%, in particular 5 to 50 wt .-% and particularly preferably 10 to 30 parts by weight. %, based on the weight of the polymers and / or resins and / or binders to use.
Der erfindungsgemäß vorgeschlagene Weichmacher eignet sich für alle üblichen Polymere und/oder Harze und/oder Bindemittel insbesondere auf Basis von PVC, Epoxiden, Polyurethanen, Polyacrylaten, Polymethacrylaten, Polysulfiden sowie Silikonen, synthetischen oder natürlichen Kautschuken, silanmodifizierten Polyurethanen, silanmodifizierten Polyethern (z. B. MS Polymer), silanmodifizierten Acrylaten, silanmodifizierten Methacrylaten und/oder silanmodifizierten Polysulfiden.The plasticizer proposed according to the invention is suitable for all customary polymers and / or resins and / or binders, in particular based on PVC, epoxides, polyurethanes, polyacrylates, polymethacrylates, polysulfides and silicones, synthetic or natural rubbers, silane-modified polyurethanes, silane-modified polyethers (eg MS polymer), silane-modified acrylates, silane-modified methacrylates and / or silane-modified polysulfides.
Aufgrund seiner besonderen Eigenschaften als Weichmacher kann der entfärbte Biodiesel für alle möglichen Produkte, insbesondere in Kunststoffen, Kleb- und Dichtstoffen, Beschichtungen, Farben und Lacken, Fußböden, Sportböden, Vergussmassen usw., eingesetzt werden.Due to its special properties as a plasticizer, the decolourised biodiesel can be used for all sorts of products, in particular in plastics, adhesives and sealants, coatings, paints and varnishes, floors, sports floors, potting compounds, etc.
Die Herstellung des entfärbten Biodiesels kann auf verschiedenem Wege erfolgen. Überraschenderweise wurde gefunden, dass der Biodiesel schonend und kostengünstig durch Kontaktieren mit geeigneten Adsorbentien, z. B. aktivierter Aktivkohle (z. B. Norit®), entfärbt werden kann. Das Entfärbungsverfahren kann diskontinuierlich durch Kontaktieren des Biodiesels mit pulverförmiger oder geformter Aktivkohle in einem Rührreaktor oder kontinuierlich durchgeführt werden. Als Adsorbentien eignen sich z. B. neben den aktivierten Aktivkohlen auch Kieselsäuren (Fällungskieselsäure, Flammkieselsäure, usw.), Silikate aller Art (z. B. Kaoline, usw.), Magnesiumphosphate, Metallhydroxide, Metalloxide (z. B. Aluminiumoxide, usw.), Metallcarbonate, Tonerden (z. B. Bentonite, usw.), usw.. Die Adsorbentien können einzeln oder auch in Kombination eingesetzt werden.The preparation of the decolourised biodiesel can be done in various ways. Surprisingly, it was found that the biodiesel gently and inexpensively by contacting with suitable adsorbents, eg. Activated charcoal (eg Norit® ) can be decolorized. The decolorization process may be carried out batchwise by contacting the biodiesel with pulverulent or shaped activated carbon in a stirred reactor or continuously. As adsorbents are z. B. in addition to the activated carbons also activated silica (Precipitated silica, flame silica, etc.), silicates of all kinds (e.g., kaolins, etc.), magnesium phosphates, metal hydroxides, metal oxides (e.g., aluminas, etc.), metal carbonates, clays (e.g., bentonites, etc .), etc. The adsorbents can be used individually or in combination.
Die Entfärbung des Biodiesels wird bevorzugt in kontinuierlicher Weise durchgeführt. Hierbei wird der zu entfärbende Biodiesel über ein aktiviertes Aktivkohlebett, das in einem Reaktor angeordnet ist, in Rieselbett- oder in Blasenfahrweise geleitet und dabei mit der aktivierten Aktivkohle kontaktiert. Bei geeigneter Auswahl der aktivierten Aktivkohle sowie ausreichender Kontaktzeit wird auch ein stark gefärbter Biodiesel (Farbzahl APHA > 1000) nahezu vollständig entfärbt. Üblicherweise wird entfärbter Biodiesel mit einer Farbzahl APHA < 300, stärker bevorzugt ≤ 280, nochmals stärker bevorzugt ≤ 250 und am stärksten bevorzugt ≤ 200 erhalten.The decolorization of the biodiesel is preferably carried out in a continuous manner. In this case, the biodiesel to be decolored is passed over an activated carbon bed, which is arranged in a reactor, in trickle bed or in bubbling mode and thereby contacted with the activated activated carbon. With a suitable selection of the activated carbon and sufficient contact time, a strongly colored biodiesel (color number APHA> 1000) is almost completely decolorized. Usually, decolored biodiesel having a color number of APHA <300, more preferably ≦ 280, even more preferably ≦ 250, and most preferably ≦ 200 is obtained.
Der Flächeninhalt der erfindungsgemäß eingesetzten aktivierten Aktivkohle beträgt insbesondere 20 bis 2500 m2/g, bevorzugt 100 bis 2000 m2/g und besonders bevorzugt 200 bis 1500 m2/g. Die eingesetzte Menge der Aktivkohle liegt insbesondere zwischen 0,01 und 20 Gew.-%, bevorzugt zwischen 0,1 und 5 Gew.-% und besonders bevorzugt zwischen 0,2 und 3 Gew.-%. Gut geeignet für die Entfärbung von Biodiesel sind z. B. aktivierte Aktivkohlen mit guter Adsorptionskapazität für hochmolekulare Verbindungen (um z. B. Reste von Seifen im Biodiesel zu entfernen). Gute Filtrationseigenschaften der aktivierten Aktivkohle sind ebenfalls wichtig. Die erfindungsgemäß eingesetzten aktivierten Aktivkohlen sind üblicherweise chemisch aktiviert, z. B. mittels Phophorsäure.The surface area of the activated carbon used according to the invention is in particular 20 to 2500 m 2 / g, preferably 100 to 2000 m 2 / g and particularly preferably 200 to 1500 m 2 / g. The amount of activated carbon used is in particular between 0.01 and 20 wt .-%, preferably between 0.1 and 5 wt .-% and particularly preferably between 0.2 and 3 wt .-%. Well suited for the decolorization of biodiesel z. Activated carbons with good adsorption capacity for high molecular weight compounds (for example, to remove residues of soaps in biodiesel). Good filtration properties of the activated carbon are also important. The activated carbons used according to the invention are usually chemically activated, for. B. by phosphoric acid.
Die Entfärbungskapazität einer aktivierten Aktivkohle hängt in starkem Umfang von den physikalisch-chemischen Eigenschaften der aktivierten Aktivkohle ab. Mit zunehmender Beladung der aktivierten Aktivkohle mit den farbgebenden Bestandteilen des Biodiesels (z. B. Seifenreste, usw.) nimmt die Aktivität oder Adsorptionskapazität der aktivierten Aktivkohle ab und gleichzeitig nimmt die Farbzahl des behandelten Biodiesels zu. Sobald eine zunächst festgelegte Zielfarbzahl des behandelten Biodiesels überschritten wird, wird vorzugsweise die aktivierte Aktivkohle ersetzt oder regeneriert und nach der Regenerierung erneut zur Entfärbung verwendet. Diese Regenerierung kann z. B. wie in DE 101 222 66 A1 beschrieben durchgeführt werden.The decolorization capacity of an activated carbon depends to a large extent on the physico-chemical properties of the activated carbon. With increasing loading of the activated carbon with the coloring constituents of the biodiesel (eg soap residues, etc.) increases the activity or adsorption capacity of the activated carbon from and at the same time increases the color number of the treated biodiesel. As soon as an initially defined target color number of the treated biodiesel is exceeded, the activated carbon is preferably replaced or regenerated and used again for decolorization after the regeneration. This regeneration can z. B. as described in DE 101 222 66 A1.
Die Vorteile des erfindungsgemäß vorgeschlagenen Biodiesels lassen sich folgendermaßen zusammenfassen:The advantages of the biodiesel proposed according to the invention can be summarized as follows:
Biodiesel gehört zu der Gruppe „Nachwachsende Rohstoffe", enthält kein Benzol oder andere Aromaten, ist biologisch leicht abbaubar, gefährdet bei Unfällen nicht Boden oder Grundwasser, ist kein Gefahrgut (sein Flammpunkt liegt bei mindestens 12O0C) und ist schwefelfrei (<0,001 Gew.- %)•Biodiesel belongs to the group "Renewable resources", contains no benzene or other aromatics, is readily biodegradable, does not endanger ground or groundwater in accidents, is not a dangerous good (its flashpoint is at least 12O 0 C) and is sulfur-free (<0.001 wt .-%) •
Außerdem ist Biodiesel weltweit verfügbar und besonders kostengünstig herstellbar. Darüberhinaus ist Biodiesel flüssig, fast geruchlos, licht-, temperatur- und wasserbeständig, nicht gesundheitsschädlich, schwer brennbar, niederviskos und wenig flüchtig.In addition, biodiesel is available worldwide and can be produced particularly inexpensively. In addition, Biodiesel is liquid, almost odorless, light, temperature and water resistant, not harmful to health, difficult to burn, low viscosity and low volatility.
Aufgrund dieser besonderen ökologischen und ökonomischen Vorteile ist entfärbter Biodiesel in besonderem Maße als Weichmacher im großtechnischen Umfang geeignet.Due to these particular ecological and economic advantages, decolourised biodiesel is particularly suitable as a plasticizer on an industrial scale.
Die nachfolgenden Beispiele sollen die Erfindung näher veranschaulichen. BeispieleThe following examples are intended to illustrate the invention in more detail. Examples
Entfärbung von BiodieselDiscoloration of biodiesel
Beispiel 1example 1
Diskontinuierliche Entfärbung von BiodieselDiscontinuous discoloration of biodiesel
a) 1 I verfärbter Biodiesel (Hersteller ADM-Ölmühle Hamburg AG) wird in einem Rührbehälter mit 10 g aktivierter Aktivkohle (Norit® CA 1 , chemisch mit Phosphorsäure aktiviert) versetzt; nach einer Stunde wird abgefiltert und die Farbe des Biodiesels bestimmt. Die Farbzahl beträgt nach der Behandlung APHA 250.a) 1 l of discolored biodiesel (manufacturer ADM-Ölmühle Hamburg AG) is in a stirred tank with 10 g of activated carbon activated (Norit ® CA 1, chemically activated with phosphoric acid); After one hour, it is filtered off and the color of the biodiesel is determined. The color number after treatment is APHA 250.
b) Der Versuch a) wird wiederholt, jedoch wird vorher die aktivierte Aktivkohle gemörsert und auf eine Fraktion von > 125 μm abgesiebt. Mit 1 Gew.-% dieser gemörserten aktivierten Aktivkohle wird eine Farbzahl von APHA 200 erreicht.b) The experiment a) is repeated, but previously activated activated carbon is triturated and sieved to a fraction of> 125 microns. With 1 wt .-% of this triturated activated activated carbon, a color number of APHA 200 is achieved.
Beispiel 2Example 2
Diskontinuierliche Entfärbung von BiodieselDiscontinuous discoloration of biodiesel
1 I verfärbter Biodiesel (Hersteller ADM-Ölmühle Hamburg AG) wird in einem Rührbehälter mit 10 g aktivierter Aktivkohle (Norit® SA Super, aktiviert mittels Wasserdampf) versetzt; nach einer Stunde wird abgefiltert und die Farbe des Biodiesels bestimmt. Die Farbzahl beträgt nach der Behandlung APHA 265. Beispiel 31 I discolored biodiesel (manufacturer ADM Hamburg AG mill oil) is placed in a stirred vessel with 10 g of activated charcoal (Norit ® SA Super activated by means of steam); After one hour, it is filtered off and the color of the biodiesel is determined. The color number after treatment is APHA 265. Example 3
Diskontinuierliche Entfärbung von BiodieselDiscontinuous discoloration of biodiesel
1 I verfärbter Biodiesel (Hersteller Biodiesel Kärnten GmbH) wird in einem Rührbehälter mit 10 g aktivierter Aktivkohle (Norit® CA 1 , chemisch mit Phosphorsäure aktiviert) versetzt; nach einer Stunde wird abgefiltert und die Farbe des Biodiesels bestimmt. Die Farbzahl beträgt nach der Behandlung APHA 185.1 I discolored biodiesel (biodiesel manufacturer Carinthia GmbH) is placed in a stirred vessel with 10 g of activated charcoal (Norit ® CA 1, chemically activated with phosphoric acid); After one hour, it is filtered off and the color of the biodiesel is determined. The color number after treatment is APHA 185.
Beispiel 4Example 4
Diskontinuierliche Entfärbung von BiodieselDiscontinuous discoloration of biodiesel
1 I verfärbter Biodiesel (Hersteller Biodiesel Kärnten GmbH) wird in einem Rührbehälter mit 10 g aktivierter Aktivkohle (Norit® SA Super, aktiviert mittels Wasserdampf) versetzt; nach einer Stunde wird abgefiltert und die Farbe des Biodiesels bestimmt. Die Farbzahl beträgt nach der Behandlung APHA 245.1 I discolored biodiesel (biodiesel manufacturer Carinthia GmbH) is placed in a stirred vessel with 10 g of activated charcoal (Norit ® SA Super activated by means of steam); After one hour, it is filtered off and the color of the biodiesel is determined. The color number after treatment is APHA 245.
Beispiel 5Example 5
Kontinuierliche Entfärbung von BiodieselContinuous decolorization of biodiesel
Verfärbter Biodiesel (Hersteller Novance aus Frankreich) wird über eine mit aktivierter Aktivkohle (Norit® SA Super, aktiviert mittels Wasserdampf) gefüllte Säule (Höhe 40 cm, Durchmesser 2 cm), ein aktiviertes Aktivkohlebett, geleitet. Die Bettdichte beträgt ca. 400 g/l. Die Kontaktierung erfolgt mit einer Dosierleistung von ca. 50 ml/h, entsprechend einer ca. zweistündigen Kontaktzeit. Über einen Zeitraum von ca. 48 Stunden wird eine Entfärbung des Biodiesels auf eine Farbzahl APHA < 200 erreicht. Pro 1000 I Biodiesel beträgt der Einsatz der aktivierten Aktivkohle bei einer Farbzahl von APHA < 200 ohne Regenerierung ca. 10 kg.Discolored biodiesel (Novance manufacturer from France) is one with activated charcoal (Norit ® SA Super activated by means of steam) filled column (height 40 cm, diameter 2 cm), an activated carbon bed fed. The bed density is about 400 g / l. The contact is made with a dosing of about 50 ml / h, corresponding to about two hours of contact time. Over a period of about 48 hours will be a discoloration of the biodiesel to a color number APHA <200 achieved. For every 1000 l of biodiesel, the activated carbon used at a color number of APHA <200 without regeneration is approx. 10 kg.
Beispiel 6Example 6
Verwendung von entfärbtem Biodiesel als Weichmacher in einem silylierten PolyurethandichtstoffUse of discolored biodiesel as plasticizer in a silylated polyurethane sealant
In das Arbeitsgefäß (1 I Dose) eines Laborplanetenmischers (Typ Labmax®, Hersteller Molteni) werden 150 g entfärbter Biodiesel (Hersteller Biodiesel Kärnten GmbH) gemäß Beispiel 3 als Weichmacher und 300 g gefällte Kreide (Hersteller Solvay) als Füllstoff eingewogen. Nach der Zugabe von 11 ,5 g Vinylsilan (Hersteller Degussa) wird zehn Minuten bei 200 Umdrehungen/Minute vermischt. Anschließend werden 225 g silanterminiertes Polyurethanpolymer (Hersteller Hanse-Chemie), weitere 5,75 g Vinylsilan (Hersteller Degussa), 22,5 g hydrophobierte Flammkieselsäure (Hersteller Degussa), 3,4 g Stabilisator (Hersteller Ciba) und 20 g Weißpigment Titandioxid (Hersteller Kerr Mc-Gee) zugegeben und im Verlauf von ca. zwei Stunden in die Mischung eingearbeitet. Nach vollständiger Einarbeitung wird der Druck im Arbeitsraum des Mischers auf 100 mbar gesenkt. Dadurch werden innerhalb von zehn Minuten flüchtige Bestandteile aus der Masse entfernt. Dann werden 0,75 g Zinnkatalysator (Hersteller Acima) und 11 g primäres Aminosilan (Hersteller Degussa AG) zugegeben und unter Rühren der Druck erneut auf 100 mbar erniedrigt. Nach einer Behandlungsdauer von ca. fünf Minuten wird die Dose mit der Masse dem Mischer entnommen. Die fertige Dichtmasse wird aus der Ansatzdose in Kartuschen umgefüllt.In the working vessel (1 I can) of a laboratory planetary mixer (type Labmax ® , manufacturer Molteni) 150 g of decolourised biodiesel (manufacturer Biodiesel Kärnten GmbH) according to Example 3 as a plasticizer and 300 g precipitated chalk (manufacturer Solvay) are weighed as a filler. After the addition of 11.5 g of vinylsilane (manufacturer Degussa) is mixed for ten minutes at 200 revolutions / minute. Subsequently, 225 g of silane-terminated polyurethane polymer (manufacturer Hanse-Chemie), another 5.75 g of vinyl silane (manufacturer Degussa), 22.5 g of hydrophobized flame silica (manufacturer Degussa), 3.4 g of stabilizer (manufacturer Ciba) and 20 g of white pigment titanium dioxide ( Manufacturer Kerr Mc-Gee) was added and worked into the mixture over about two hours. After complete incorporation, the pressure in the working space of the mixer is lowered to 100 mbar. This removes volatile components from the compound within ten minutes. Then 0.75 g of tin catalyst (manufacturer Acima) and 11 g of primary aminosilane (manufacturer Degussa AG) are added and the pressure is lowered again to 100 mbar with stirring. After a treatment time of about five minutes, the can with the mass is removed from the mixer. The finished sealant is transferred from the batch box into cartridges.
Die Prüfung der erfindungsgemäß hergestellten Dichtmasse nach einschlägig bekannten Prüfvorschriften ergibt Härtung nach 7 Tagen: 6 mmThe examination of the sealant according to the invention according to relevant known test specifications results Hardening after 7 days: 6 mm
Haftung auf Glas: sehr gutAdhesion to glass: very good
Haftung auf PVC: sehr gutAdhesion to PVC: very good
Haftung auf Aluminium: sehr gutAdhesion to aluminum: very good
Zugfestigkeit: 1 ,5 MPaTensile strength: 1.5 MPa
Bruchdehnung: 300%Elongation at break: 300%
Spannungswert bei 100%: 0,65 MPaVoltage value at 100%: 0.65 MPa
Löschblattest („Fettrand"): bestandenBlotter test ("fat margin"): passed
Die DTC-Analyse der Dichtmasse mit Biodiesel (Fettsäuremethylestergemisch) zeigt keine ausgeprägte Glasübergangstemperatur. Glasübergangstemperaturen zeigen nur definierte chemische Verbindungen wie z. B. Phthalate, Adipate, Stearinsäuremethylester, usw.). The DTC analysis of the sealant with biodiesel (fatty acid methyl ester mixture) shows no pronounced glass transition temperature. Glass transition temperatures show only defined chemical compounds such. Phthalates, adipates, stearic acid methyl ester, etc.).

Claims

Patentansprüche claims
1. Verwendung von entfärbtem Biodiesel mit einer Farbzahl von APHA1. Use of discolored biodiesel having a color number of APHA
< 300 (nach ISO 6271 ) als Weichmacher für Polymere und/oder Harze und/oder Bindemittel.<300 (according to ISO 6271) as a plasticizer for polymers and / or resins and / or binders.
2. Verwendung nach Anspruch 1 , dadurch gekennzeichnet, dass man als Biodiesel einen pflanzlichen Methylester (PME) nach DIN E 51 606, Rapsöl-Methylester (RME) nach DIN E 51 606, Soja-Methylester (SME) oder Sonnenblumen-Methylester, Altfett-Methylester (AME) und Fett- Methylester (FME) aus sonstigen Pflanzen- und Tierstoffen nach DIN V 51 606 einsetzt.2. Use according to claim 1, characterized in that the biodiesel is a vegetable methyl ester (PME) according to DIN E 51 606, rapeseed oil methyl ester (RME) according to DIN E 51 606, soybean methyl ester (SME) or sunflower methyl ester, used fat -Methylester (AME) and fat methyl ester (FME) from other plant and animal substances according to DIN V 51 606 used.
3. Verwendung nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass man den entfärbten Biodiesel in einer Menge von 1 bis 80 Gew.-%, vorzugsweise 5 bis 50 Gew.-% und besonders bevorzugt 10 bis 30 Gew.-%, bezogen auf das Gewicht der Polymere und/oder Harze und/oder Bindemittel, einsetzt.3. Use according to claim 1 or 2, characterized in that the decolourised biodiesel in an amount of 1 to 80 wt .-%, preferably 5 to 50 wt .-% and particularly preferably 10 to 30 wt .-%, based on the weight of the polymers and / or resins and / or binders used.
4. Verwendung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Polymere und/oder Harze und/oder Bindemittel aus PVC, Epoxiden, Polyurethanen, Polyacrylaten, Polymethacrylaten, Polysulfiden sowie Silikonen, synthetischen oder natürlichen Kautschuken, silanmodifizierten Polyurethanen, silanmodifizierten Polyethern (z. B. MS Polymer), silanmodifizierten Acrylaten, silanmodifizierten Methacrylaten, und/oder silanmodifizierten Polysulfiden bestehen.4. Use according to one of claims 1 to 3, characterized in that the polymers and / or resins and / or binders of PVC, epoxies, polyurethanes, polyacrylates, polymethacrylates, polysulfides and silicones, synthetic or natural rubbers, silane-modified polyurethanes, silane-modified polyethers (eg, MS polymer), silane-modified acrylates, silane-modified methacrylates, and / or silane-modified polysulfides.
5. Verwendung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Polymere und/oder Harze und/oder Bindemittel in Kunststoffen, Kleb- und Dichtstoffen, Beschichtungen, Farben und Lacken, Fußböden, Sportböden, Vergussmassen und so weiter, eingesetzt werden.5. Use according to one of claims 1 to 4, characterized in that the polymers and / or resins and / or binders in plastics, adhesives and sealants, coatings, Paints and varnishes, floors, sports floors, potting compounds and so on, are used.
6. Verwendung des entfärbten Biodiesels nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass der Biodiesel durch Behandlung mit einer aktivierten Aktivkohle, mit einer spezifischen Oberfläche von 20 bis 2500 m2/g, vorzugsweise 100 bis 2000 m2/g und besonders bevorzugt 200 bis 1500 m2/g, hergestellt wurde.6. Use of the decolourised biodiesel according to one of claims 1 to 5, characterized in that the biodiesel by treatment with an activated activated carbon, with a specific surface area of 20 to 2500 m 2 / g, preferably 100 to 2000 m 2 / g and especially preferably 200 to 1500 m 2 / g, was prepared.
7. Verwendung nach Anspruch 6, dadurch gekennzeichnet, dass die eingesetzte Menge der aktivierten Aktivkohle zwischen 0,01 und 20 Gew.-%, vorzugsweise 0,1 und 5 Gew.-% und besonders bevorzugt zwischen 0,2 und 3 Gew.-%, bezogen auf die Menge des zu entfärbenden Biodiesels betrug.7. Use according to claim 6, characterized in that the amount of activated charcoal used is between 0.01 and 20 wt .-%, preferably 0.1 and 5 wt .-% and particularly preferably between 0.2 and 3 wt. %, based on the amount of biodiesel to be decolored.
8. Verwendung nach Anspruch 6 oder 7, dadurch gekennzeichnet, dass der Biodiesel kontinuierlich über ein aktiviertes Aktivkohlebett geleitet wurde.8. Use according to claim 6 or 7, characterized in that the biodiesel was passed continuously over an activated activated carbon bed.
9. Verwendung nach einem der Ansprüche 6 bis 8, dadurch gekennzeichnet, dass man die aktivierte Aktivkohle nach Überschreiten einer festgelegten Farbzahl des behandelnden und zumindest teilweise entfärbten Biodiesels regeneriert und anschließend wieder zur Entfärbung einsetzte.9. Use according to one of claims 6 to 8, characterized in that regenerating the activated activated carbon after exceeding a predetermined color number of the treated and at least partially decolourised biodiesel and then used again for decolorization.
10. Verwendung nach einem der Ansprüche 6 bis 9, dadurch gekennzeichnet, dass Phosphorsäure-aktivierte Aktivkohle verwendet wurde. 10. Use according to one of claims 6 to 9, characterized in that phosphoric acid-activated activated carbon was used.
PCT/EP2006/006623 2005-07-08 2006-07-06 Use of bleached biodiesel as a plasticizer WO2007006489A1 (en)

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