WO2014009584A1 - Method for coating polymer surfaces with a carbon-containing coating, and product obtained by said method - Google Patents
Method for coating polymer surfaces with a carbon-containing coating, and product obtained by said method Download PDFInfo
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- WO2014009584A1 WO2014009584A1 PCT/ES2013/070490 ES2013070490W WO2014009584A1 WO 2014009584 A1 WO2014009584 A1 WO 2014009584A1 ES 2013070490 W ES2013070490 W ES 2013070490W WO 2014009584 A1 WO2014009584 A1 WO 2014009584A1
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- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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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
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
Definitions
- the present invention relates to a method of coating polymeric surfaces with a coating containing carbon material and the product obtained by said method.
- the coated polymer obtained by the method of the invention is especially applicable to the mechanical reinforcement of materials, protective coating and as an electrical conductor.
- reinforced polymers are especially attractive due to their low weight and excellent mechanical and electrical properties.
- reinforced polymers loaded with graphite due to their electrical conductivity, antistatic properties and also good thermal behavior, have been used in fields such as electrochemistry, packaging and aeronautical industry.
- carbon-modified polymeric composite materials are produced by mixing the original polymeric materials with graphite or carbon black powders.
- patent application with publication number US 2009/0189125 shows a process by mixing in solution to prepare an electrically conductive reinforced polymer with a weight ratio of carbon to the polymer greater than 0.1 1. The process comprises the steps of mixing the non-pre-dispersed carbon with an emulsion containing the polymer in a liquid solvent to achieve carbon dispersion in the polymer matrix and subsequent removal of the liquid solvent from the dispersion.
- the patent application with publication number US 2010/0190924 refers to electrically reinforced polymeric materials that are produced by in-situ polymerization in the presence of carbon-based fillers.
- Graphite coatings in non-polymeric materials are also known, such as that described in the patent application with publication number US2004 / 0129313, where a graphite coating for lubricating elements of an engine is described.
- a process is described for applying a graphite coating inside a battery case.
- the inventors have found a method of coating polymeric surfaces with a carbon coating, as well as the products obtained by said process and the uses given thereto.
- the method of the invention can cover polymeric objects that have any shape, the method of the invention provides very good adhesion between the polymeric surface and the coating, in addition to requiring minimal amounts of carbon material to carry out the coating.
- a first aspect of the present invention relates to a method of coating a polymeric substrate with a carbon coating, said method comprising the steps of:
- step b) adding the polymeric substrate to the suspension obtained in step a);
- step c) ultrasonically treating the suspension of step b) containing the polymeric substrate; d) isolate, wash and dry the product obtained in step c).
- the suspension of the carbon allotrope it is not necessary that the suspension of the carbon allotrope be stable in solution.
- the carbon allotrope suspension can be recycled and reused many times for various polymeric substrates.
- a second aspect of the invention is the coated polymer product obtained by the method of the first aspect of the invention.
- the coating method of the invention improves the electrical conductivity of the coated polymer with respect to the same uncoated polymer.
- a third aspect of the invention relates to the use of the coated polymeric product obtained according to the method of the invention as an electrical conductive material.
- Young's modulus and tensile strength at breakage are increased;
- the reinforced and improved mechanical properties of the coated polymer make the polymer product of the invention suitable for use as a mechanical reinforcement of materials.
- a fourth aspect of the invention relates to a use of the coated polymeric product obtained according to the method of the invention for the mechanical reinforcement of materials.
- FIG. 1A and FIG. 1 B show scanning electron microscopy micrographs of graphite-coated polyurethane films obtained in example 1.
- FIG. 2A and FIG. 2B show scanning electron microscopy micrographs of graphite-coated polyvinyl butyral films obtained in example 2.
- FIG. 3A and FIG. 3B show scanning electron microscopy micrographs of poly (p-phenylene terephthalamide), Kevlar fibers, coated with graphite obtained in Example 3.
- FIG. 4 shows an uncoated polyurethane foam (0 mg / ml) and foams of polyurethane coated with graphite suspensions of different.
- the first aspect of the invention is a method of coating a polymeric surface with a carbon coating, said method comprises the steps of:
- step b) adding the polymeric substrate to the suspension obtained in step a);
- step c) ultrasonically treating the suspension of step b) containing the polymeric substrate; d) isolate, wash and dry the product obtained in step c).
- polymeric substrate refers to the polymeric material on which the carbon coating is deposited.
- the polymeric substrate can be solid or porous.
- inflatable polymer refers to a polymer that can be swell in the presence of a solvent. When the polymer swells it increases the size and facilitates the partial penetration of the carbon allotropes suspended in the solvent on the polymer surface so that the adhesion of the carbon allotrope to the polymer surface is improved.
- Non-limiting examples of the carbon allotrope or derivative thereof that can be used in the present invention are amorphous carbon, graphite, graphene, graphene oxide and carbon black or mixtures thereof.
- the carbon allotrope is graphite.
- Non-limiting examples of the solvent that can be used in step a) of the method of the invention are water, cyclohexane, heptane, toluene, n-methyl pyrrolidone (NMP), dimethyl formamide (DMF), xylene and in general organic amides, amines , ethers, esters, aldehydes, ketones and mixtures thereof.
- the solvent is cyclohexane.
- the polymeric substrate used in the method of the invention has to be insoluble in the solvent.
- the polymeric substrate may be swellable in the solvent.
- Non-limiting examples of the polymeric substrate that can be used in the present invention are: polyurethane, polyvinyl butyral, polyolefin, polyester, polyamide and poly (p-phenylene terephthalamide).
- the polymeric substrate is selected from the group consisting of polyurethane, poly (vinyl butyral) and poly (p-phenylene terephthalamide).
- the polymer is a solvent swellable polymer.
- the polymeric substrate can be presented in any form such as threads, fibers, tapes, films, sponges, foams.
- the washing step is carried out with an alcohol or with an ether.
- the ultrasonic treatment of the polymer is carried out at a temperature between 25 e C and 300 e C.
- the ultrasound treatment of the polymer is carried out at a temperature between 25 e C and 100 e C.
- the ultrasound treatment is carried out in a time between 1 second and 4 weeks.
- the treatment with Ultrasound is performed in a time between 1 minute and 12 hours.
- the thickness of the coating can be controlled by the concentration of the carbon allotrope in the suspension or by the time of the ultrasonic treatment.
- concentration of the carbon allotrope in the solvent is up to 50% by mass with respect to the total mass.
- Ultrasonic equipment for treatment may include ultrasonic bath, ultrasonic probe or oven.
- a third aspect of the invention relates to the use of the coated polymeric product obtained according to the method of the invention as a conductive material.
- the conductive material of the invention can be used as an electronic packaging or as flexible electrodes in screens and batteries. Therefore, an electronic packaging made with the coated polymer obtained according to the method of the invention, an electrode made with the coated polymer obtained according to the method of the invention and a battery made with the coated polymer obtained according to the method of the invention are part of the invention. the invention.
- the reinforced and improved mechanical properties of the coated polymer make the polymer product of the invention suitable for use as a material reinforcement.
- a fourth aspect of the invention relates to a use of the coated polymer product obtained according to the method of the invention for the reinforcement of materials.
- a embodiment of the invention is a bulletproof laminated glass made of the coated polymer obtained according to the method of the invention, as well as a bulletproof suit made of the coated polymer obtained according to the method of the invention.
- Example 1 coating of polyurethane samples
- Polyurethane (PU) foam samples containing 30% and 40% rigid segment were treated in a graphite suspension (1 mg / mL) in cyclohexane for 15 min each, using a bath of ultrasound Each sample was then washed with ethanol and dried in air. It was found that the pieces with 30 and 40% rigid segment were well coated by graphite. It was repeated for graphite suspensions with concentrations of 0.05mg / ml, 0.1 mg / ml, and 0.5 mg / ml.
- FIG. 4 shows polyurethane foams without gratin coating (0 mg / ml) and coated with the graphite suspensions of the different concentrations. The amount of graphite in the final foam increases as the concentration of graphite in the suspension increases.
- FIG. 1 A and in FIG. 1 B shows scanning electron microscopy micrographs for PU with 30% rigid segment coated with graphite for the case where the graphite suspension is 1 mg / ml. It was found that the conductivity of the piece of PU coated with graphite was significantly increased (the resistance of the samples after coating was of the order of 9 kOhm).
- This example demonstrates that the invention can be used to produce an antistatic coating on polymers or be used for galvanizing - electroplating the polymer surface. These materials can be used in electronic packaging or as flexible electrodes in screens, batteries and other devices.
- Example 2 coating of polyvinyl butyral films
- Poly (vinyl butyral) (PVB) films with graphite suspension (1 mg / mL) in cyclohexane were treated for 15 min using an ultrasonic bath.
- the modified polymer was cleaned with ethanol and dried.
- FIG. 2A and FIG. 2B show scanning electron microscopy micrographs for graphite coated PVB.
- the control sample of PVB, ultrasonic in pure hexane without graphite showed a decrease of the order of 20% in both Young's modulus and tensile strength at breakage.
- This example shows that this invention can be used to produce mechanically reinforced materials for use in various applications, including bulletproof laminated glass (PVB is a common material for glass lamination) or protective clothing (bulletproof suits).
- Example 3 Coating of poly (p-phenylene terephthalamide) threads and fibers A similar experiment was also carried out with threads and fibers of
- FIG. 3A and FIG. 3B show scanning electron microscopy micrographs of Keviar fibers treated with graphite.
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Description
MÉTODO DE RECUBRIMIENTO DE SUPERFICIES POLIMÉRICAS CON UN METHOD OF COATING POLYMER SURFACES WITH A
RECUBRIMIENTO QUE CONTIENE CARBONO Y PRODUCTO OBTENIDO POR DICHOCOATING CONTAINING CARBON AND PRODUCT OBTAINED BY SUCH
MÉTODO METHOD
Campo de la invención Field of the Invention
La presente invención se refiere a un método de recubrimiento de superficies poliméricas con un recubrimiento que contiene material carbono y el producto obtenido por dicho método. El polímero recubierto obtenido por el método de la invención es especialmente aplicable al refuerzo mecánico de materiales, revestimiento protector y como conductor eléctrico. The present invention relates to a method of coating polymeric surfaces with a coating containing carbon material and the product obtained by said method. The coated polymer obtained by the method of the invention is especially applicable to the mechanical reinforcement of materials, protective coating and as an electrical conductor.
Antecedentes de la invención Background of the invention
Existe una demanda creciente de nuevos materiales poliméricos mejorados debido a sus propiedades únicas que los hacen adecuados para un amplio rango de aplicaciones. There is a growing demand for new improved polymeric materials due to their unique properties that make them suitable for a wide range of applications.
De entre los polímeros reforzados, los polímeros reforzados que contienen carbono son especialmente atractivos debido a su bajo peso y propiedades mecánicas y eléctricas excelentes. Por ejemplo, los polímeros reforzados cargados con grafito, debido a su conductividad eléctrica, propiedades antiestáticas y también buena conducta térmica, se han utilizado en campos como electroquímica, envasado e industria aeronáutica. Among reinforced polymers, reinforced carbon-containing polymers are especially attractive due to their low weight and excellent mechanical and electrical properties. For example, reinforced polymers loaded with graphite, due to their electrical conductivity, antistatic properties and also good thermal behavior, have been used in fields such as electrochemistry, packaging and aeronautical industry.
Actualmente todas las aproximaciones existentes para la fabricación de polímeros mejorados conteniendo carbono utilizan técnicas estándar de procesado como preparación en solución, fundido, moldeo, extrusión y polimerización in situ. Currently all existing approaches for the manufacture of improved polymers containing carbon use standard processing techniques such as solution preparation, melting, molding, extrusion and in-situ polymerization.
En la mayoría de estas técnicas los materiales compuestos poliméricos modificados con carbono se producen mezclando los materiales poliméricos originales con polvos de grafito o negro de carbono. Por ejemplo, la solicitud de patente con número de publicación US 2009/0189125 muestra un proceso por mezclado en solución para preparar un polímero reforzado eléctricamente conductor con una relación en peso de carbono al polímero superior a 0,1 1 . El proceso comprende las etapas de mezclar el carbono no-pre-dispersado con una emulsión que contiene el polímero en un solvente líquido para conseguir la dispersión del carbono en la matriz polimérica y posterior eliminación del solvente líquido de la dispersión. La solicitud de patente con número de publicación US 2010/0190924 se refiere a materiales poliméricos reforzados eléctricamente que se producen por polimerización in situ en presencia de cargas basadas en carbono. In most of these techniques, carbon-modified polymeric composite materials are produced by mixing the original polymeric materials with graphite or carbon black powders. For example, patent application with publication number US 2009/0189125 shows a process by mixing in solution to prepare an electrically conductive reinforced polymer with a weight ratio of carbon to the polymer greater than 0.1 1. The process comprises the steps of mixing the non-pre-dispersed carbon with an emulsion containing the polymer in a liquid solvent to achieve carbon dispersion in the polymer matrix and subsequent removal of the liquid solvent from the dispersion. The patent application with publication number US 2010/0190924 refers to electrically reinforced polymeric materials that are produced by in-situ polymerization in the presence of carbon-based fillers.
En todas estas técnicas el carbono o el grafito deben ser incorporados en la solución del polímero, el polímero fundido o mezclados con el monómero inicial antes de la formación del producto final. In all these techniques carbon or graphite must be incorporated into the solution of the polymer, the molten polymer or mixed with the initial monomer before the formation of the final product.
Son también conocidos los recubrimientos de grafito en materiales no poliméricos, como el descrito en la solicitud de patente con número de publicación US2004/0129313, donde se describe un recubrimiento de grafito para lubricar elementos de un motor. En la patente con número de publicación US6841 194 se describe un proceso para aplicar un recubrimiento de grafito en el interior de una carcasa de una pila. Graphite coatings in non-polymeric materials are also known, such as that described in the patent application with publication number US2004 / 0129313, where a graphite coating for lubricating elements of an engine is described. In the patent with publication number US6841 194 a process is described for applying a graphite coating inside a battery case.
Las aproximaciones actualmente existentes para los recubrimientos basados en grafito o carbono incluyen: esprayado, pintado, recubrimiento por inmersión, deposición a alta temperatura y con vacío. Sin embargo, estas técnicas no son adecuadas para recubrir polímeros, por ejemplo, la deposición a alta temperatura no es adecuada debido a los bajos puntos de fusión y a la baja estabilidad térmica de los polímeros. La mayoría de las técnicas existentes tienen problemas de adhesión o requieren aditivos de unión especiales si se quieren usar para el recubrimiento de polímeros. Por ejemplo, las técnicas de esprayado y recubrimiento requieren la preparación de suspensiones estables de partículas de grafito o carbono en solventes así como la adición de agentes de unión y estabilizantes específicos. Finalmente, la mayoría de estas técnicas son exigentes energéticamente y bastante costosas, requiriendo equipamiento especial caro así como una adecuada preparación del personal. Por tanto, de lo que es conocido en el estado de la técnica, se deriva que es de gran interés el desarrollo de un método que permita la incorporación de carbono en productos poliméricos en la superficie de los mismos, sin afectar a las partes internas de la matriz polimérica, y que resulten en polímeros reforzados con propiedades mecánicas, térmicas y eléctricas mejoradas y protegiéndolos de la oxidación de manera que se incrementa la durabilidad. Objeto de la invención Currently existing approaches for graphite or carbon based coatings include: spray, painted, dip coating, high temperature deposition and vacuum. However, these techniques are not suitable for coating polymers, for example, high temperature deposition is not suitable due to the low melting points and low thermal stability of the polymers. Most existing techniques have adhesion problems or require special bonding additives if they are to be used for polymer coating. For example, spray and coating techniques require the preparation of stable suspensions of graphite or carbon particles in solvents as well as the addition of specific bonding agents and stabilizers. Finally, most of these techniques are energy demanding and quite expensive, requiring expensive special equipment as well as adequate staff preparation. Therefore, from what is known in the state of the art, it is derived that it is of great interest to develop a method that allows the incorporation of carbon into polymeric products on the surface thereof, without affecting the internal parts of the polymer matrix, and resulting in reinforced polymers with improved mechanical, thermal and electrical properties and protecting them from oxidation so that durability is increased. Object of the invention
Los inventores han encontrado un método de recubrimiento de superficies poliméricas con un recubrimiento de carbono, así como los productos obtenidos por dicho procedimiento y los usos dados a los mismos. The inventors have found a method of coating polymeric surfaces with a carbon coating, as well as the products obtained by said process and the uses given thereto.
El método de la invención puede recubrir objetos poliméricos que presenten cualquier forma, el método de la invención proporciona muy buena adhesión entre la superficie polimérica y el recubrimiento, además de requerir mínimas cantidades de material carbono para poder llevar a cabo el recubrimiento. The method of the invention can cover polymeric objects that have any shape, the method of the invention provides very good adhesion between the polymeric surface and the coating, in addition to requiring minimal amounts of carbon material to carry out the coating.
No hay nada en la técnica que sugiera un método de recubrimiento de polímeros con carbono, que sea sencillo, que requiera mínimas cantidades de carbono, y que consiga la adhesión del recubrimiento adecuada al polímero. There is nothing in the art that suggests a method of coating polymers with carbon, that is simple, that requires minimal amounts of carbon, and that achieves adhesion of the suitable coating to the polymer.
Por tanto, un primer aspecto de la presente invención se refiere a un método de recubrimiento de un substrato polimérico con un recubrimiento de carbono, dicho método comprende las etapas de: Therefore, a first aspect of the present invention relates to a method of coating a polymeric substrate with a carbon coating, said method comprising the steps of:
a) suspender un alótropo de carbono o derivado del mismo en un disolvente; a) suspending a carbon allotrope or derivative thereof in a solvent;
b) adicionar el substrato polimérico a la suspensión obtenida en la etapa a); b) adding the polymeric substrate to the suspension obtained in step a);
c) tratar con ultrasonidos la suspensión de la etapa b) que contiene el substrato polimérico; d) aislar, lavar y secar el producto obtenido en la etapa c). En el método de la invención no es necesario que la suspensión del alótropo de carbono sea estable en solución. Se puede reciclar la suspensión del alótropo de carbono y reutilizarla muchas veces para varios substratos poliméricos. c) ultrasonically treating the suspension of step b) containing the polymeric substrate; d) isolate, wash and dry the product obtained in step c). In the method of the invention it is not necessary that the suspension of the carbon allotrope be stable in solution. The carbon allotrope suspension can be recycled and reused many times for various polymeric substrates.
Con el método de la invención se obtiene un polímero recubierto con un recubrimiento de carbono. Por lo tanto, un segundo aspecto de la invención es el producto polimérico recubierto obtenido mediante el método del primer aspecto de la invención. With the method of the invention a polymer coated with a carbon coating is obtained. Therefore, a second aspect of the invention is the coated polymer product obtained by the method of the first aspect of the invention.
El método de recubrimiento de la invención mejora la conductividad eléctrica del polímero recubierto respecto al mismo polímero sin recubrir. Por tanto un tercer aspecto de la invención se refiere al uso del producto polimérico recubierto obtenido según el método de la invención como material conductivo eléctrico. Por último con el método de recubrimiento de la invención se incrementa el módulo de Young y la resistencia de tracción a la rotura; las propiedades mecánicas reforzadas y mejoradas del polímero recubierto hacen que el producto polimérico de la invención sea adecuado para utilizarlo como refuerzo mecánico de materiales. Por tanto un cuarto aspecto de la invención se refiere a un uso del producto polimérico recubierto obtenido según el método de la invención para el refuerzo mecánico de materiales. The coating method of the invention improves the electrical conductivity of the coated polymer with respect to the same uncoated polymer. Thus a third aspect of the invention relates to the use of the coated polymeric product obtained according to the method of the invention as an electrical conductive material. Finally, with the coating method of the invention, Young's modulus and tensile strength at breakage are increased; The reinforced and improved mechanical properties of the coated polymer make the polymer product of the invention suitable for use as a mechanical reinforcement of materials. Thus a fourth aspect of the invention relates to a use of the coated polymeric product obtained according to the method of the invention for the mechanical reinforcement of materials.
Breve descripción de las figuras La FIG. 1A y la FIG. 1 B muestran micrografías de microscopía de barrido electrónico de películas de poliuretano recubiertas con grafito obtenidas en el ejemplo 1 . Brief description of the figures FIG. 1A and FIG. 1 B show scanning electron microscopy micrographs of graphite-coated polyurethane films obtained in example 1.
La FIG. 2A y la FIG. 2B muestran micrografías de microscopía de barrido electrónico de películas de poli(vinil butiral) recubiertas con grafito obtenidas en el ejemplo 2. FIG. 2A and FIG. 2B show scanning electron microscopy micrographs of graphite-coated polyvinyl butyral films obtained in example 2.
La FIG. 3A y la FIG. 3B muestran micrografías de microscopía de barrido electrónico de fibras de poli(p-fenilen tereftalamida), fibras Kevlar, recubiertas con grafito obtenidas en el ejemplo 3. La FIG.4 muestra un espuma de poliuretano sin recubrir (0 mg/ml) y espumas de poliuretano recubiertas con suspensiones de grafito de diferente. FIG. 3A and FIG. 3B show scanning electron microscopy micrographs of poly (p-phenylene terephthalamide), Kevlar fibers, coated with graphite obtained in Example 3. FIG. 4 shows an uncoated polyurethane foam (0 mg / ml) and foams of polyurethane coated with graphite suspensions of different.
Descripción detallada de la invención Como se ha mencionado arriba el primer aspecto de la invención es un método de recubrimiento de una superficie polimérica con un recubrimiento de carbono, dicho método comprende las etapas de: DETAILED DESCRIPTION OF THE INVENTION As mentioned above the first aspect of the invention is a method of coating a polymeric surface with a carbon coating, said method comprises the steps of:
a) suspender un alótropo de carbono o derivado del mismo en un disolvente; a) suspending a carbon allotrope or derivative thereof in a solvent;
b) adicionar el substrato polimérico a la suspensión obtenida en la etapa a); b) adding the polymeric substrate to the suspension obtained in step a);
c) tratar con ultrasonidos la suspensión de la etapa b) que contiene el substrato polimérico; d) aislar, lavar y secar el producto obtenido en la etapa c). c) ultrasonically treating the suspension of step b) containing the polymeric substrate; d) isolate, wash and dry the product obtained in step c).
El término "substrato polimérico" como se utiliza aquí se refiere al material polimérico sobre el que se deposita el recubrimiento de carbono. El substrato polimérico puede ser sólido o poroso. The term "polymeric substrate" as used herein refers to the polymeric material on which the carbon coating is deposited. The polymeric substrate can be solid or porous.
El término "polímero hinchable" como se utiliza aquí se refiere a un polímero que se puede hinchar en presencia de un disolvente. Cuando el polímero se hincha incrementa el tamaño y facilita la penetración parcial de los alótropos de carbono suspendidos en el disolvente en la superficie del polímero de manera que se mejora la adhesión del alotropo de carbono a la superficie del polímero. The term "inflatable polymer" as used herein refers to a polymer that can be swell in the presence of a solvent. When the polymer swells it increases the size and facilitates the partial penetration of the carbon allotropes suspended in the solvent on the polymer surface so that the adhesion of the carbon allotrope to the polymer surface is improved.
Ejemplos no limitantes del alotropo de carbono o derivado del mismo que puede ser utilizado en la presente invención son carbono amorfo, grafito, grafeno, óxido de grafeno y negro de carbono o mezclas de ellos. En una materialización particular el alotropo de carbono es grafito. Non-limiting examples of the carbon allotrope or derivative thereof that can be used in the present invention are amorphous carbon, graphite, graphene, graphene oxide and carbon black or mixtures thereof. In a particular materialization the carbon allotrope is graphite.
Ejemplos no limitantes del disolvente que pueden ser utilizados en la etapa a) del método de la invención son agua, ciclohexano, heptano, tolueno, n-metil pirrolidona (NMP), dimetil formamida (DMF), xileno y en general amidas orgánicas, aminas, éteres, ésteres, aldehidos, cetonas y mezclas de ellos. En una materialización particular el disolvente es ciclohexano. Non-limiting examples of the solvent that can be used in step a) of the method of the invention are water, cyclohexane, heptane, toluene, n-methyl pyrrolidone (NMP), dimethyl formamide (DMF), xylene and in general organic amides, amines , ethers, esters, aldehydes, ketones and mixtures thereof. In a particular embodiment the solvent is cyclohexane.
El substrato polimérico utilizado en el método de la invención tiene que ser insoluble en el disolvente. El substrato polimérico puede ser hinchable en el disolvente. Ejemplos no limitantes del substrato polimérico que pueden ser utilizados en la presente invención son: poliuretano, poli(vinil butiral), poliolefina, poliéster, poliamida y poli(p-fenilen tereftalamida). En una materialización particular el substrato polimérico se selecciona del grupo consistente en poliuretano, poli(vinil butiral) y poli(p-fenilen tereftalamida). En una materialización preferente del primer aspecto de la invención el polímero es un polímero hinchable en el disolvente. El substrato polimérico puede presentarse en cualquier forma como por ejemplo hilos, fibras, cintas, películas, esponjas, espumas. The polymeric substrate used in the method of the invention has to be insoluble in the solvent. The polymeric substrate may be swellable in the solvent. Non-limiting examples of the polymeric substrate that can be used in the present invention are: polyurethane, polyvinyl butyral, polyolefin, polyester, polyamide and poly (p-phenylene terephthalamide). In a particular embodiment the polymeric substrate is selected from the group consisting of polyurethane, poly (vinyl butyral) and poly (p-phenylene terephthalamide). In a preferred embodiment of the first aspect of the invention, the polymer is a solvent swellable polymer. The polymeric substrate can be presented in any form such as threads, fibers, tapes, films, sponges, foams.
En una materialización preferente de la invención la etapa de lavado se realiza con un alcohol o con un éter. In a preferred embodiment of the invention, the washing step is carried out with an alcohol or with an ether.
Preferentemente el tratamiento con ultrasonidos del polímero se realiza a temperatura comprendida entre 25 eC y 300 eC. En una materialización más preferente el tratamiento con ultrasonidos del polímero se realiza a una temperatura comprendida entre 25 eC y 100 eC. Preferably, the ultrasonic treatment of the polymer is carried out at a temperature between 25 e C and 300 e C. In a more preferred embodiment, the ultrasound treatment of the polymer is carried out at a temperature between 25 e C and 100 e C.
Preferentemente el tratamiento con ultrasonidos se realiza en un tiempo comprendido entre 1 segundo y 4 semanas. En una materialización más preferente el tratamiento con ultrasonidos se realiza en un tiempo comprendido entre 1 minuto y 12 horas. Preferably, the ultrasound treatment is carried out in a time between 1 second and 4 weeks. In a more preferred embodiment the treatment with Ultrasound is performed in a time between 1 minute and 12 hours.
El espesor del recubrimiento puede controlarse por la concentración del alótropo de carbono en la suspensión o por el tiempo del tratamiento de ultrasonidos. Preferentemente la concentración del alótropo de carbono en el disolvente es de hasta el 50% en masa respecto a la masa total. The thickness of the coating can be controlled by the concentration of the carbon allotrope in the suspension or by the time of the ultrasonic treatment. Preferably the concentration of the carbon allotrope in the solvent is up to 50% by mass with respect to the total mass.
El equipamiento ultrasónico para el tratamiento puede incluir baño ultrasónico, sonda ultrasónica u horno. Ultrasonic equipment for treatment may include ultrasonic bath, ultrasonic probe or oven.
Como se ha dicho más arriba un tercer aspecto de la invención se refiere al uso del producto polimérico recubierto obtenido según el método de la invención como material conductivo. El material conductivo de la invención puede utilizarse como un embalaje electrónico o como electrodos flexibles en pantallas y baterías. Por tanto forman parte de la invención un embalaje electrónico hecho con el polímero recubierto obtenido según el método de la invención, un electrodo hecho con el polímero recubierto obtenido según el método de la invención y una batería hecha con el polímero recubierto obtenido según el método de la invención. Las propiedades mecánicas reforzadas y mejoradas del polímero recubierto hacen que el producto polimérico de la invención sea adecuado para utilizarlo como refuerzo de materiales. Por tanto un cuarto aspecto de la invención se refiere a un uso del producto polimérico recubierto obtenido según el método de la invención para el refuerzo de materiales. Una materialización de la invención es un vidrio laminado antibalas hecho del polímero recubierto obtenido según el método de la invención, así como un traje antibalas hecho del polímero recubierto obtenido según el método de la invención. As stated above, a third aspect of the invention relates to the use of the coated polymeric product obtained according to the method of the invention as a conductive material. The conductive material of the invention can be used as an electronic packaging or as flexible electrodes in screens and batteries. Therefore, an electronic packaging made with the coated polymer obtained according to the method of the invention, an electrode made with the coated polymer obtained according to the method of the invention and a battery made with the coated polymer obtained according to the method of the invention are part of the invention. the invention. The reinforced and improved mechanical properties of the coated polymer make the polymer product of the invention suitable for use as a material reinforcement. Thus a fourth aspect of the invention relates to a use of the coated polymer product obtained according to the method of the invention for the reinforcement of materials. A embodiment of the invention is a bulletproof laminated glass made of the coated polymer obtained according to the method of the invention, as well as a bulletproof suit made of the coated polymer obtained according to the method of the invention.
Ejemplos A continuación se detallan unos ejemplos concretos de realización de la invención que sirven para ilustrar la invención. Examples Specific examples of embodiments of the invention that serve to illustrate the invention are detailed below.
Ejemplo 1 : recubrimiento de muestras de poliuretano Se trataron muestras de espuma de poliuretano (PU) conteniendo 30% y 40% de segmento rígido en una suspensión de grafito (1 mg/mL) en ciclohexano durante 15 min cada una, empleando un baño de ultrasonidos. Después cada muestra se lavó con etanol y se secó en aire. Se encontró que las piezas con 30 y 40% de segmento rígido estaban bien recubiertas por el grafito. Se repitió para suspensiones de grafito con concentraciones de 0.05mg/ml, 0.1 mg/ml, y 0.5 mg/ml. La FIG. 4 muestra espumas de poliuretano sin recubrimiento de gratito (0 mg/ml ) y recubiertas con las suspensiones de grafito de las diferentes concentraciones. La cantidad de grafito en la espuma final aumenta al aumentar la concentración de grafito en la suspensión. Example 1: coating of polyurethane samples Polyurethane (PU) foam samples containing 30% and 40% rigid segment were treated in a graphite suspension (1 mg / mL) in cyclohexane for 15 min each, using a bath of ultrasound Each sample was then washed with ethanol and dried in air. It was found that the pieces with 30 and 40% rigid segment were well coated by graphite. It was repeated for graphite suspensions with concentrations of 0.05mg / ml, 0.1 mg / ml, and 0.5 mg / ml. FIG. 4 shows polyurethane foams without gratin coating (0 mg / ml) and coated with the graphite suspensions of the different concentrations. The amount of graphite in the final foam increases as the concentration of graphite in the suspension increases.
En la FIG. 1 A y en la FIG. 1 B se muestran micrografías de microscopía de barrido electrónico para PU con 30% de segmento rígido recubierto con grafito para el caso en que la suspensión de grafito es 1 mg/ml. Se encontró que la conductividad de la pieza de PU recubierta con grafito se incrementaba significativamente (la resistencia de las muestras después del recubrimiento era del orden de 9 kOhm). Este ejemplo demuestra que se puede utilizar la invención para producir un recubrimiento antiestático en polímeros o ser utilizada para galvanizado - electrochapeado de la superficie del polímero. Estos materiales se pueden emplear en embalaje electrónico o como electrodos flexibles en pantallas, baterías y otros dispositivos. In FIG. 1 A and in FIG. 1 B shows scanning electron microscopy micrographs for PU with 30% rigid segment coated with graphite for the case where the graphite suspension is 1 mg / ml. It was found that the conductivity of the piece of PU coated with graphite was significantly increased (the resistance of the samples after coating was of the order of 9 kOhm). This example demonstrates that the invention can be used to produce an antistatic coating on polymers or be used for galvanizing - electroplating the polymer surface. These materials can be used in electronic packaging or as flexible electrodes in screens, batteries and other devices.
Ejemplo 2: recubrimiento de películas de poli(vinil butiral) Example 2: coating of polyvinyl butyral films
Se trataron películas de poli(vinil butiral) (PVB) con suspensión de grafito (1 mg/mL) en ciclohexano durante 15 min utilizando un baño ultrasónico. Poly (vinyl butyral) (PVB) films with graphite suspension (1 mg / mL) in cyclohexane were treated for 15 min using an ultrasonic bath.
El polímero modificado se limpió con etanol y se secó. The modified polymer was cleaned with ethanol and dried.
Se comprobó que el PVB recubierto presentaba un incremento de 1 ,5 veces en el módulo de Young y de 1 ,4 veces en la resistencia de tracción a rotura. La FIG. 2A y la FIG. 2B muestran micrografías de microscopía de barrido electrónico para el PVB recubierto con grafito. Por otra parte, la muestra control de PVB, ultrasonicada en hexano puro sin grafito mostraba un decrecimiento del orden del 20% tanto en el módulo de Young como en la resistencia de tracción a la rotura. Este ejemplo muestra que esta invención se puede emplear para producir materiales mecánicamente reforzados para su uso en aplicaciones diversas, que incluyen vidrio laminado antibalas (el PVB es un material común para la laminación de vidrios) o ropa protectora (trajes antibalas). Ejemplo 3: recubrimiento de hilos y fibras de poli(p-fenilen tereftalamida) Se realizó también un experimento similar con hilos y fibras de It was found that the coated PVB showed an increase of 1.5 times in Young's modulus and 1.4 times in tensile strength at break. FIG. 2A and FIG. 2B show scanning electron microscopy micrographs for graphite coated PVB. On the other hand, the control sample of PVB, ultrasonic in pure hexane without graphite, showed a decrease of the order of 20% in both Young's modulus and tensile strength at breakage. This example shows that this invention can be used to produce mechanically reinforced materials for use in various applications, including bulletproof laminated glass (PVB is a common material for glass lamination) or protective clothing (bulletproof suits). Example 3: Coating of poly (p-phenylene terephthalamide) threads and fibers A similar experiment was also carried out with threads and fibers of
poli(p-fenilen tereftalamida). Se trató un hilo de poli(p-fenilen tereftalamida), Keviar 129, con suspensión de grafito (1 mg/mL) en ciciohexano durante 15 min. Posteriormente se limpió el hilo con etanol y se secó. La FIG. 3A y la FIG. 3B muestran micrografías de microscopía de barrido electrónico de las fibras de Keviar tratadas con grafito. poly (p-phenylene terephthalamide). A strand of poly (p-phenylene terephthalamide), Keviar 129, was treated with graphite suspension (1 mg / mL) in cytohexane for 15 min. Subsequently the thread was cleaned with ethanol and dried. FIG. 3A and FIG. 3B show scanning electron microscopy micrographs of Keviar fibers treated with graphite.
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| ES201231103A ES2442765B1 (en) | 2012-07-13 | 2012-07-13 | METHOD OF COATING POLYMER SURFACES WITH A COATING CONTAINING CARBON AND PRODUCT OBTAINED BY SUCH METHOD |
| ESP201231103 | 2012-07-13 |
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| WO2014009584A1 true WO2014009584A1 (en) | 2014-01-16 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1098946A1 (en) * | 1982-06-08 | 1984-06-23 | Всесоюзный научно-исследовательский и проектно-технологический институт электроугольных изделий | Composition for producing electrically conducting coatings on polymeric materials |
| KR20050024541A (en) * | 2003-09-03 | 2005-03-10 | (주)맨투맨테크놀로지 | method for manufacturing the open-cell type metalfoam for filter of clean water device and open-cell type metalfoam using this method |
| WO2007136559A2 (en) * | 2006-05-16 | 2007-11-29 | Michigan State University | Conductive coatings produced by monolayer deposition on surfaces |
| US20120012796A1 (en) * | 2009-01-16 | 2012-01-19 | Yongsheng Chen | Conductive films based on graphene and process for preparing the same |
-
2012
- 2012-07-13 ES ES201231103A patent/ES2442765B1/en active Active
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2013
- 2013-07-08 WO PCT/ES2013/070490 patent/WO2014009584A1/en not_active Ceased
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1098946A1 (en) * | 1982-06-08 | 1984-06-23 | Всесоюзный научно-исследовательский и проектно-технологический институт электроугольных изделий | Composition for producing electrically conducting coatings on polymeric materials |
| KR20050024541A (en) * | 2003-09-03 | 2005-03-10 | (주)맨투맨테크놀로지 | method for manufacturing the open-cell type metalfoam for filter of clean water device and open-cell type metalfoam using this method |
| WO2007136559A2 (en) * | 2006-05-16 | 2007-11-29 | Michigan State University | Conductive coatings produced by monolayer deposition on surfaces |
| US20120012796A1 (en) * | 2009-01-16 | 2012-01-19 | Yongsheng Chen | Conductive films based on graphene and process for preparing the same |
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| CHEMICAL ABSTRACTS, vol. 03, 1985, Columbus, Ohio, US; abstract no. 1985-018019 * |
| DATABASE WPI. accession no. 005-0539498 * |
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