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DE102014014177B4 - Use of plant-based silicates as an additive to improve the material properties of mixtures - Google Patents

Use of plant-based silicates as an additive to improve the material properties of mixtures Download PDF

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DE102014014177B4
DE102014014177B4 DE102014014177.2A DE102014014177A DE102014014177B4 DE 102014014177 B4 DE102014014177 B4 DE 102014014177B4 DE 102014014177 A DE102014014177 A DE 102014014177A DE 102014014177 B4 DE102014014177 B4 DE 102014014177B4
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plant
silicates
acid
silicate
based silicates
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DE102014014177A1 (en
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Matthias Schmidt
Frank Kose
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Green Sugar Ag De
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Green Sugar AG
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/28—Compounds of silicon
    • C09C1/30—Silicic acid
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic

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

Abstract

Verwendung von pflanzenbasierten Silikaten als Zuschlagsstoff für Kunststoffe, Elastomere, Farben, Lacke, Leime oder Dichtmassen, gekennzeichnet dadurch, dass:a) die Silikate aus silikatreichen Biomassen gewonnen werden, indemb) diese silikatreichen Biomassen mittels Säure behandelt werden undc) diese Säure durch ein Agens verdrängt wird, das frei von Metallen, Metallionen oder anderen metallhaltigen Substanzen ist, undd) die so behandelte Biomasse verbrannt wird, und dasse) diese so erhaltenen pflanzenbasierten Silikate in einer Dosis von 1 bis 25 mg/kg zu Kunststoffen, Elastomeren, Farben, Lacken, Leimen oder Dichtmassen zugemischt werden.Use of plant-based silicates as an additive for plastics, elastomers, paints, lacquers, glues or sealing compounds, characterized in that: a) the silicates are obtained from silicate-rich biomasses, by treating these silicate-rich biomasses with acid and c) this acid by an agent is displaced, which is free of metals, metal ions or other metal-containing substances, and d) the biomass treated in this way is burned, and e) these plant-based silicates obtained in this way in a dose of 1 to 25 mg / kg to plastics, elastomers, paints, varnishes , Glues or sealants are added.

Description

Die Erfindung betrifft die Verwendung von pflanzenbasierten Silikaten als Zuschlagsstoff für Kunststoffe, Elastomere, Farben, Lacke, Leime oder Dichtmassen, gemäß den Verwendungsansprüchen 1 bis 6.The invention relates to the use of plant-based silicates as an additive for plastics, elastomers, paints, lacquers, glues or sealants, according to the use claims 1 to 6.

Die Verwendung von Salzsäure zur Herstellung von pflanzlichen Silikaten wird mit der Druckschrift CA 2 860 482 A1 beschrieben, jedoch in einem Konzentrationsbereich von 3 bis 10 Gew.-%, welches nicht dem bekannten Bergius-Verfahren entspricht.The use of hydrochloric acid for the production of vegetable silicates is described in the document CA 2 860 482 A1 described, but in a concentration range of 3 to 10 wt .-%, which does not correspond to the known Bergius process.

Die Druckschrift US 6 406 678 B1 beschreibt die Verwendung einer oxidativ wirkenden Substanz zur Entfernung metallischer Komponenten aus der Biomasse. Zur Frage der damit erzielbaren Qualität der gewonnenen Silikate sind keine Ergebnisse bekannt geworden.The publication US 6 406 678 B1 describes the use of an oxidative substance to remove metallic components from the biomass. No results have been published on the question of the quality of the silicates obtained.

Die Verwendung von Silikaten als Additiv für Kunststoffe wird auch mit der WO 2007/081431 A1 beschrieben, wobei dort die Verwendung von Beimischungsanteilen von unter 1 % als nicht effizient angesehen wird.The use of silicates as an additive for plastics is also associated with the WO 2007/081431 A1 described, wherein the use of admixtures below 1% is considered inefficient.

Die mit der vorliegenden Erfindung erzeugbaren pflanzenbasierten Silikate zeigen bereits bei Zumischungen von 1 mg/kg (Kunststoffe, Elastomere, Farben, Lacke, Leime oder Dichtmassen) die beschriebenen positiven Effekte.The plant-based silicates which can be produced with the present invention show the described positive effects even when admixtures of 1 mg / kg (plastics, elastomers, paints, varnishes, glues or sealants).

In eigenen Testreihen konnte herausgefunden werden, dass diese pflanzlichen Silikate als Additiv in Kunststoffen, Elastomeren, Farben, Lacken, Leimen und Dichtmassen zu stark veränderten Eigenschaften der Mischungen führen.In our own test series, it was found that these vegetable silicates as additives in plastics, elastomers, paints, varnishes, glues and sealants lead to greatly changed properties of the mixtures.

Dies liegt vor allem an den Eigenschaften der pflanzlichen Silikate selbst, wie z.B. die hohe Festigkeit, geringe Schüttdichte und wie sich zeigte vor allem die inhomogene Mikro- und Nanostruktur, welche die Scheinstruktur der Zellbiomasse nachbildet.This is mainly due to the properties of the vegetable silicates themselves, e.g. the high strength, low bulk density and as was shown above all the inhomogeneous micro and nanostructure, which simulates the apparent structure of the cell biomass.

Insgesamt konnte herausgefunden werden, dass die Zumischung von pflanzlichen Silikaten bei Kunststoffen und Elastomeren, Farben und Lacken oder Leimen und Dichtmassen u.a. zu einer Erhöhung der Festigkeit bei gleichzeitiger Verringerung der Dichte führt.Overall, it was found that the admixture of vegetable silicates in plastics and elastomers, paints and varnishes or glues and sealants, etc. leads to an increase in strength while reducing density.

Des Weiteren konnte herausgefunden werden, dass die Beimischung von z.B. 25 mg Silikatpulver (welches auf Basis von Reisstroh gewonnen wurde) zu einem Kilogramm handelsüblichen Polyethylen zu einer signifikant erhöhten Kratz- und Abriebfestigkeit führte. Ähnliche Ergebnisse ergaben sich für die Kunststoffe PP und Polyacetaten.It was also found that the addition of e.g. 25 mg of silicate powder (which was obtained on the basis of rice straw) to one kilogram of commercially available polyethylene led to a significantly increased scratch and abrasion resistance. Similar results were obtained for the plastics PP and polyacetates.

Handelsübliche Silikate, die durch Fällung von gelösten Kieselsäuren hergestellt werden, zeigten diesen Effekt nicht. Dies hat, unserer Auffassung gemäß, folgende Gründe.Commercial silicates, which are produced by the precipitation of dissolved silicic acids, did not show this effect. In our opinion, this has the following reasons.

Erstens, die Partikel der gefällten Kieselsäuren haben eine eher kugelförmige Form. Zweitens, bilden pflanzenbasierte Silikate die Nano- und Mikrostruktur der pflanzlichen Biomasse (Scheinstruktur) nach, da die eigentlichen in der Pflanze eingelagerten Silikate in ihrer Struktur durch den Herstellungsprozess der pflanzenbasierten Silikate mittels saurer Hydrolyse, Verdrängung der Säure und anschließender Verbrennung nicht verändert wird. Die pflanzlichen Silikatpartikel zeigen eine eher faserartige Partikelform mit einer stark zerklüfteten Oberfläche. Dies führt in der Mischung zu einer anderen Verzahnung mit dem umgebenden Medium und damit zu anderen mechanischen Eigenschaften als dies für handelsübliche Silikate aus gefällten Kieselsäuren der Fall ist. Die porösen und ungeordneten Strukturen bilden Anker, welche den Kraftfluss zwischen den festen Silikatstrukturen und elastischen Strukturen des umgebenden Mediums besser gewährleisten als handelsübliche Silikate aus gefällten Kieselsäuren. Die Eigenschaften von Silikaten bezüglich Druck- und Zugfestigkeit und der elastischen Eigenschaften des umgebenden Mediums können sich dadurch besser kombinieren und zur Wirkung kommen.First, the precipitated silica particles are more spherical in shape. Second, plant-based silicates reproduce the nano- and microstructure of the plant biomass (apparent structure), since the structure of the actual silicates stored in the plant is not changed by the manufacturing process of the plant-based silicates by means of acid hydrolysis, displacement of the acid and subsequent combustion. The vegetable silicate particles show a rather fibrous particle shape with a strongly jagged surface. In the mixture, this leads to different interlocking with the surrounding medium and thus to different mechanical properties than is the case for commercially available silicates from precipitated silicas. The porous and disordered structures form anchors, which better guarantee the flow of force between the solid silicate structures and elastic structures of the surrounding medium than commercially available silicates from precipitated silicas. The properties of silicates in terms of compressive and tensile strength and the elastic properties of the surrounding medium can thus combine better and come into effect.

Die Herstellung dieser pflanzenbasierten Silikate erfolgt mittels Behandlung von silikatreichen Biomassen mittels Säuren (vorzugsweise Salzsäure), nachfolgender Verdrängung dieser Säuren mittels eines Agens, das frei von Metallen, Metalloxiden oder anderen metallhaltigen Stoffen ist und der anschließenden Verbrennung.These plant-based silicates are produced by treating silicate-rich biomass with acids (preferably hydrochloric acid), then displacing these acids with an agent that is free of metals, metal oxides or other metal-containing substances and then burning them.

Silikatreiche Biomasse sind solche Biomassen, die nach Verbennung einen Rückstand von mindestens 0,5 % Silikatasche (bezogen auf die trockene Ausgangsmasse der Biomasse) ergeben. Dazu gehören sämtliche Stroharten (seien es Reisstroh oder Weizenstroh), Gräser oder landwirtschaftliche Abfälle wie Reisspelzen, u.a. pflanzliche Biomassen.Biomass rich in silicate are those biomass which, after being banished, result in a residue of at least 0.5% of silicate ash (based on the dry starting mass of the biomass). This includes all types of straw (be it rice straw or wheat straw), grasses or agricultural waste such as rice husks, etc. vegetable biomass.

Claims (6)

Verwendung von pflanzenbasierten Silikaten als Zuschlagsstoff für Kunststoffe, Elastomere, Farben, Lacke, Leime oder Dichtmassen, gekennzeichnet dadurch, dass: a) die Silikate aus silikatreichen Biomassen gewonnen werden, indem b) diese silikatreichen Biomassen mittels Säure behandelt werden und c) diese Säure durch ein Agens verdrängt wird, das frei von Metallen, Metallionen oder anderen metallhaltigen Substanzen ist, und d) die so behandelte Biomasse verbrannt wird, und dass e) diese so erhaltenen pflanzenbasierten Silikate in einer Dosis von 1 bis 25 mg/kg zu Kunststoffen, Elastomeren, Farben, Lacken, Leimen oder Dichtmassen zugemischt werden.Use of plant-based silicates as an additive for plastics, elastomers, paints, varnishes, glues or sealing compounds, characterized in that: a) the silicates are obtained from silicate-rich biomasses by b) treating these silicate-rich biomasses with acid and c) this acid by displacing an agent which is free of metals, metal ions or other metal-containing substances, and d) the biomass treated in this way is burned, and that e) these plant-based silicates thus obtained are mixed in a dose of 1 to 25 mg / kg to plastics, elastomers, paints, varnishes, glues or sealing compounds. Verwendung von pflanzenbasierten Silikaten nach Anspruch 1, gekennzeichnet dadurch, dass als Säure eine in Wasser gelöste Halogenwasserstoffsäure verwendet wird.Use of plant-based silicates after Claim 1 , characterized in that a hydrohalic acid dissolved in water is used as the acid. Verwendung von pflanzenbasierten Silikaten nach Anspruch 1 bis 2, gekennzeichnet dadurch, dass als Säure Salzsäure verwendet wird.Use of plant-based silicates after Claim 1 to 2nd , characterized in that hydrochloric acid is used as the acid. Verwendung von pflanzenbasierten Silikaten nach Anspruch 1 bis 3, gekennzeichnet dadurch, dass als Agens zur Verdrängung der Säure a) ein organisches Lösungsmittel, das frei von Metallen, Metallionen oder metallhaltigen Substanzen ist, oder b) ein Gas oder c) entionisiertes oder destilliertes Wasser verwendet wird.Use of plant-based silicates after Claim 1 to 3rd , characterized in that a) an organic solvent which is free of metals, metal ions or metal-containing substances, or b) a gas or c) deionized or distilled water is used as the agent for displacing the acid. Verwendung von pflanzenbasierten Silikaten nach Anspruch 1 bis 4, gekennzeichnet dadurch, dass solche Biomassen verwendet werden, die einen Silikatgehalt von mindestens 0,5 % (nach Verbrennung bezogen auf die trockene Ausgangsmasse der Biomasse) besitzen.Use of plant-based silicates after Claim 1 to 4th , characterized in that those biomasses are used which have a silicate content of at least 0.5% (after combustion based on the dry starting mass of the biomass). Verwendung von pflanzenbasierten Silikaten nach Anspruch 1 bis 5, gekennzeichnet dadurch, dass sämtliche Stroharten (beispielsweise Weizen- oder Reisstroh), Gräser und/oder Spelzen (beispielsweise Reisspelzen) als Rohmaterial verwendet werden.Use of plant-based silicates after Claim 1 to 5 , characterized in that all types of straw (for example wheat or rice straw), grasses and / or husks (for example rice husks) are used as raw material.
DE102014014177.2A 2014-09-19 2014-09-19 Use of plant-based silicates as an additive to improve the material properties of mixtures Expired - Fee Related DE102014014177B4 (en)

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DE102017000114A1 (en) 2016-02-24 2017-08-24 Green Sugar Ag Process for the fixation of metals, transition metals and their oxides on silicate materials of plant origin and use of these modified silicate materials as catalyst and as additive for paints, lacquers, plastics, elastomers and glues

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6406678B1 (en) * 2001-03-26 2002-06-18 Process Management, Inc. Process for production of high purity amorphous silica from biogenic material
WO2007081431A1 (en) * 2006-01-05 2007-07-19 Dow Corning Corporation Curable silicone compositions containing silica derived from biogenic matter
CA2860482A1 (en) * 2012-01-05 2013-07-11 Wuhan Kaidi General Research Institute Of Engineering & Technology Co., Ltd. Comprehensive utilization method for biomass containing amorphous silicon dioxide

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6406678B1 (en) * 2001-03-26 2002-06-18 Process Management, Inc. Process for production of high purity amorphous silica from biogenic material
WO2007081431A1 (en) * 2006-01-05 2007-07-19 Dow Corning Corporation Curable silicone compositions containing silica derived from biogenic matter
CA2860482A1 (en) * 2012-01-05 2013-07-11 Wuhan Kaidi General Research Institute Of Engineering & Technology Co., Ltd. Comprehensive utilization method for biomass containing amorphous silicon dioxide

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