• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
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    • 专利摘要:
    The present invention relates to a process for the preparation of polymerizable resins with graphene derivatives comprising the following steps: A) mixing the graphene derivative with the solid component of the polymerizable resin and homogenizing the mixture, B) polymerization of the compound obtained in step a) And does not comprise the addition of solvents. Furthermore, the present invention relates to the polymerizable resin obtained by the process of the present invention and to the use thereof for medical and dental applications, thermosetting coatings, thermosetting adhesives and sealants in construction and civil engineering, thermostable adhesives in space engineering and aeronautics, and thermoset adhesives and sealants in the automotive industry. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2547476A1
    申请号:ES201530933
    申请日:2015-06-29
    公开日:2015-10-06
    发明作者:José Miguel MARTÍN MARTÍNEZ；María Alejandra MOYANO；Miguel Ángel TORRES DEL CASTILLO；Antonio GARCÍA PELLICER
    申请人:Dental Global Training Sl；Dental Global Training S L；Universidad de Alicante；
    IPC主号:
    专利说明:

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    evaporate the solvent for 24 hours in vacuo. They tested various types of solvents. As for the in situ polymerization method, the PMMA was prepared by emulsion polymerization of free radicals in a jacketed reactor, introducing a dispersion of CNF in water into the reactor together with a surfactant and an initiator and heated to 70 ° C. Subsequently, over a period of one hour they slowly added the methyl methacrylate monomer and the reaction was continued for a further 3 hours. Finally the mixture was placed on a flat surface and allowed to dry under vacuum for 24 hours. The conclusions of these studies indicated that the stirring conditions in the melt mixing method decreased the length of carbon nanofibers making their incorporation into the PMMA less effective. As regards solvent-casting and in-situ polymerization methods, the conditions of agitation were not as aggressive, so they did not observe rupture of the nanoparticles, but their functionalization was crucial to guarantee the stability of the dispersions in the solvents organic
    The process of incorporating carbon or graphene nanoparticles into acrylic resins is not yet optimized, and the proposed methods are complex, require the use of organic solvents or water, lead to poor dispersions of the nanoparticles in the polymer matrix, and require applying ultrasound or heating and forced evaporation.
    There is therefore a need to find a method of incorporating carbon or graphene nanoparticles into acrylic resins that overcome all the problems described in the state of the art. Brief Description of the Invention
    The present invention solves the problems described in the state of the art, since it provides a process for the preparation of polymerizable resin consisting of adding a graphene derivative (graphene nanollamines, graphene nanofibers) using a rapid in situ polymerization technique that it does not require the use of organic solvents or water, nor ultrasound, high temperatures, nor long reaction times.
    Thus, in a first aspect, the present invention relates to a process for the preparation of polymerizable resins with graphene derivatives (hereinafter, the process of the present invention) comprising the following steps:
    a) mixing the graphene derivative with the solid component of the polymerizable resin and homogenizing the mixture,
    b) polymerization of the compound obtained in step a) and does not include the addition of solvents.
    In the present invention, "polymerizable resins" refers to bicomponent polymerizable resins and those monocomponent resins that have a solid consistency.
    or semi-solid. Preferably, the invention relates to acrylic resins, epoxy resins, unsaturated polyester resins, vinyl ester resins, polyurethane resins, polyimide resins, cyanoacrylate resins, polybenzimidazole resins, polyarylsulfone resins, polyphenylquinoxaline resins, and derived resins. of siloxane.
    In a more particular aspect of the present invention, graphene derivatives are selected from graphene nanollamines and / or graphene nanofibers.
    In a more particular aspect of the present invention, between step a) and step b) of the process of the present invention, there is an additional step of adding the liquid component of the resin to the homogenate obtained in step a).
    In a more particular aspect of the present invention, the homogenization of the mixture of step a) is carried out by centrifugation at speeds between 20004000 rpm.
    In a more particular aspect of the present invention, graphene derivatives are found in a maximum percentage of 5% by weight.
    In a more particular aspect of the present invention, step b) of polymerization is carried out at room temperature without applying pressure or at 40-65 ° C applying pressure (2-4 bar).
    In a second aspect, the present invention relates to a polymerizable resin with graphene derivatives (resin of the present invention) obtained by the process of the present invention.
    In another aspect, the present invention relates to the use of the resin of the present invention for dental and / or medical applications, thermosetting coatings, thermosetting and sealant adhesives in construction and civil engineering, thermosetting adhesives in space and aeronautical engineering, and adhesives thermosets and sealants in automotive, among others. BRIEF DESCRIPTION OF THE FIGURES
    Figure 1 shows the transmission electron microscopy (TEM) images of the polymerized Auto Kiero acrylic resin containing: a) 0.12%, b) 0.49%, and c) 1.01% by weight of graphene nanofibers (GNF).
    Figure 2 shows the stress-strain curve of composites of the polymerized Auto Kiero acrylic resin containing different amounts of graphene nanofibers (GNF). Compression tests
    Figure 3 shows the transmission electron microscopy (TEM) images of the polymerized Auto Kiero acrylic resin containing: a) 0.13%, b) 0.50%, and c) 1.00% by weight graphene nanolines (GNP).
    Figure 4 shows the stress-strain curve of the polymerized Auto Kiero acrylic resin containing different amounts of graphene nanolines (GNP). Compression tests
    Figure 5 shows the variation of the storage module (E ’) with the temperature of the polymeric resins Auto Kiero, New Outline and Pi-Ku-Plast polymerized containing graphene nanofibers. Experiments of mechanical dynamic-thermal analysis (DMTA).
    Figure 6 shows the stress-strain curve of polymerized Auto Kiero, New Outline and Pi-Ku-Plast acrylic resins containing graphene nanofibers (GNF). Compression tests Detailed description of the invention
    The polymerizable resin prepared according to this invention is obtained by first mixing the solid component of the acrylic resin consisting of polymer spheres (polymethylmethacrylate), the initiator and the pigments, with graphene nanofibers or nanofilms in the Speed-Mixer equipment using a rotational speed of 3400 rpm for 6 minutes. Once the mixture has been homogenized, the liquid component consisting of the methyl methacrylate monomer, an inhibitor and plasticizer is slowly added and mixed manually with a spatula. The setting time of these mixtures is 30 seconds, the fluid phase lasts 2-3 minutes and finally the plastic phase lasts 3-8 minutes. The resin must be handled during the fluid phase, so once the mixture is made, it is poured into silicone molds. To carry out the polymerization, the molds with the resin are placed in a pressure cooker (2 bars) for 30 minutes, covering them with water at 55 ° C. Subsequently, the samples are taken out of the pot and allowed to dry at room temperature on absorbent paper for 2 hours. EXAMPLE 1:
    Mixtures of the self-curing commercial acrylic resin Auto Kiero (Kuss Dental, Madrid, Spain) with different amounts of graphene nanofibers (Graphenano, Yecla, Murcia, Spain) were prepared and characterized. A powder (polymer) / liquid (monomer) ratio of 2 / 1.2 g / g was used.
    As a white, Auto Kiero acrylic resin was prepared by slowly adding the powder (polymer) to the liquid (monomer), mixing them manually with a spatula to homogenize the mixture. The mixture was poured into a silicone mold (Dubli-Basic 1: 1, BasicDental, Petrer, Alicante, Spain) and the polymerization was carried out in a pressure cooker (2 bars) with water at 55 ° C for 30 minutes. Subsequently, the polymerized mixture was removed from the pot and allowed to dry at room temperature on absorbent paper for 2 hours.
    To prepare the mixtures of Auto Kiero acrylic resin and graphene nanofibers (GNF), the corresponding amount of GNF (which was deducted from the total amount of powder) was added to the polymer and the mixture was homogenized in a Speed orbital double centrifugal equipment -Mixer (Hauschild Engineering, Hamm, Germany) at 3400 rpm for 6 minutes. Mixtures of Auto Kiero acrylic resin with 0.12, 0.49 and 1.01% by weight of graphene nanofibers (GNF) were prepared. The mixture was poured into a silicone mold (Dubli-Basic 1: 1, BasicDental, Petrer, Alicante, Spain) and polymerization was carried out in a pressure cooker (2 bar) with water at 55 ° C for 30 minutes. Subsequently, the polymerized mixtures were removed from the pot and allowed to dry at room temperature on absorbent paper for 2 hours.
    The degree of dispersion of graphene nanofibers in the self-curing acrylic resin matrix was determined by transmission electron microscopy (TEM). A JEOL model JEM-1400 Plus transmission electron microscope equipped with an image acquisition camera GATAN model ORIUS was used using a 120 kV beam. The samples were cut by microtomy to obtain sections between 80 and 100 nm thick and deposited on a copper grid. Images were obtained with magnifications between 5 μm and 50 nm. The TEM photos of the polymerized Auto Kiero acrylic resin containing 0.12, 0.49 and 1.01% by weight of graphene nanofibers respectively are shown in Figure 1.a-c. The addition of small amounts of GNF produces a good dispersion of the nanofibers that are homogeneously separated and dispersed within the acrylic resin matrix. By increasing the amount of GNF to 1.01% by weight (Figure 1.c), the formation of some nanofiber aggregates is observed.
    The thermomechanical properties of Auto Kiero acrylic resin and polymerized GNF were studied by mechanical dynamic-thermal analysis (DMTA). Films of dimensions 30x13x3 mm were prepared. A dynamic thermal-mechanical DMA analyzer was used
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    Spain). The optimal amount of graphene nanofibers (GNF) was added to each resin, which was 0.49% by weight of GNF to Auto Kiero resin, 0.10% by weight of GNF to New Outline resin, and 0.10% by weight of GNF to the Pi-Ku-Plast resin.
    As a white, Auto Kiero acrylic resin was prepared by slowly adding the powder (polymer) to the liquid (monomer), mixing them manually with a spatula to homogenize the mixture. The mixture was poured into a silicone mold (Dubli-Basic 1: 1, BasicDental, Petrer, Alicante, Spain) and the polymerization was carried out in a pressure cooker (2 bars) with water at 55 ° C for 30 minutes. Subsequently, the polymerized mixture was removed from the pot and allowed to dry at room temperature on absorbent paper for 2 hours. The white of the New Outline acrylic resin was prepared following the same procedure as for the Auto Kiero resin except that the powder (polymer) / liquid (monomer) ratio was 2/1 g / g respectively and the polymerization was carried out in a pressure cooker (2 bars) with water at 40 ° C for 2 minutes. The white of the Pi-Ku-Plast resin was prepared following the same procedure as for the Auto Kiero resin except that it was polymerized by the "salt and pepper" technique using a powder (polymer) / liquid (monomer) ratio of 1.8 / 0.6 g / g respectively.
    To prepare the mixture of Auto Kiero acrylic resin and 0.49% by weight of graphene nanofibers (GNF), the corresponding amount of GNF (which was deducted from the total amount of powder) was added to the polymer and the mixture was homogenized in a set Dual Speed-Mixer orbital centrifuge (Hauschild Engineering, Hamm, Germany) at 3400 rpm for 6 minutes. The mixture was poured into a silicone mold (Dubli-Basic 1: 1, BasicDental, Petrer, Alicante, Spain) and polymerization was carried out in a pressure cooker (2 bar) with water at 55 ° C for 30 minutes. Subsequently, the polymerized mixtures were removed from the pot and allowed to dry at room temperature on absorbent paper for 2 hours. The mixture of the New Outline acrylic resin with 0.10% by weight of graphene nanofibers (GNF) was prepared in the same way as the Auto Kiero and GNF resin mixture but the powder (polymer) / liquid (monomer) ratio was 2/1 g / g respectively and polymerization was carried out in a pressure cooker (2 bars) with water at 40 ° C for 2 minutes. The mixture of acrylic resin Pi-Ku-Plast with 0.10% by weight of graphene nanofibers (GNF) was prepared in the same way as the mixture of Auto Kiero resin and GNF except that it was polymerized by the technique of “salt and pepper ”Using a powder (polymer) / liquid (monomer) ratio of 1.8 / 0.6 g / g respectively.
    The thermomechanical properties of the composites of the Auto Kiero, New Outline and Pi-Ku-Plast acrylic resins with graphene nanofibers were studied by mechanical dynamicmicothermal analysis (DMTA). Films of dimensions 30x13x3 mm were prepared. It was used
    a dynamic thermal-mechanical analyzer DMA Q800 (TA Instruments, Lukens Drive, New Castle, UK) working with a three-point bending geometry, a 10 µm deformation amplitude and a frequency of 1 Hz. The temperature scanning was carried out between -30 ° C and 200 ° C with a heating rate of 5 ° C / min. Figure 5 5 shows the variation curves of the elastic or storage module (E ’) with the temperature for Auto Kiero, New Outline and Pi-Ku-Plast acrylic resins polymerized with graphene nanofibers. Both the polymerized Auto Kiero resin + 0.49% by weight of GNF and the polymerized New Outline resin + 0.10% by weight of GNF show an elastic modulus greater than that of the polymerized Pi-Ku-Plast resin + 0.10% by weight of GNF in the entire temperature range, although the glass transition temperature (Tg) of the latter is lower. Table 3 shows that the elastic modulus at 37 ° C of the polymerized New Outline resin increases substantially (71%) when 0.10% by weight of GNF is added, and so does, although to a lesser extent, the elastic modulus of the Auto Kiero resin polymerized by adding 0.49% by weight of GNF (41%). In the Pi-Ku-Plast resin
    15 polymerized, on the other hand, module E ’decreases slightly (-0-1%) by adding 0.10% by weight of GNF. Therefore, the acrylic resin formulation determines the effectiveness of the addition of GNF.
    TABLE 3: Storage module (E ’) at 37ºC of Auto Kiero, New Outline and Pi-Ku-Plast polymerized acrylic resins without and with graphene nanofibers (GNF). Experiments of
    20 mechanical dynamic-thermal analysis (DMTA).
    Polymerizable acrylic resin E '(MPa) at 37 ° C
    Without GNF With optimal amount of GNFIncrease in E ’(%)
    Kiero car 1302218941
    New outline 683237971
    Pi-Ku-Plast 14391332-0.1
    The mechanical properties of Auto Kiero, New Outline and Pi-Ku-Plast resins polymerized with graphene nanofibers (GNF) were measured by compression tests of solid cylinders (5.5 mm in diameter and 7.5 mm in height) on a machine 25 Instron 4411 trials (Instron Spain and Portugal, Cerdanyola, Barcelona, Spain). The compression rate was 1 mm / min and the test was stopped by applying a load of 5 kN. The stress-strain curves of Auto Kiero, New Outline and Pi-Ku-Plast resins polymerized with graphene nanofibers (GNF) are shown in Figure 6 and Table 4 shows
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    权利要求:
    Claims (1)
    [1]
    image 1
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    同族专利:
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    引用文献:
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    ES2674178A1|2016-12-27|2018-06-27|Universidad De Sevilla|Composite biomaterials for 3D printing of medical devices |US20090176891A1|2007-12-06|2009-07-09|Sami Chogle|Dental composition and method of use|
    CN103565651B|2013-11-20|2015-01-07|桂林理工大学|Preparation method of tooth-filling composite resin|
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    ES201530933A|ES2547476B1|2015-06-29|2015-06-29|Process for the preparation of polymerizable resins with graphene derivatives|ES201530933A| ES2547476B1|2015-06-29|2015-06-29|Process for the preparation of polymerizable resins with graphene derivatives|
    PCT/ES2016/070462| WO2017001713A1|2015-06-29|2016-06-17|Method for the production of polymerisable resins with graphene derivatives|
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