BR102013013758B1 - METHOD OF OBTAINING HYBRID OR NANOCOMPOSITE MATERIALS - Google Patents
METHOD OF OBTAINING HYBRID OR NANOCOMPOSITE MATERIALS Download PDFInfo
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- BR102013013758B1 BR102013013758B1 BR102013013758-8A BR102013013758A BR102013013758B1 BR 102013013758 B1 BR102013013758 B1 BR 102013013758B1 BR 102013013758 A BR102013013758 A BR 102013013758A BR 102013013758 B1 BR102013013758 B1 BR 102013013758B1
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- organic
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- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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- 239000011787 zinc oxide Substances 0.000 description 1
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Abstract
método de obtenção de materiais híbridos ou nanocompósitos. a invenção descreve um método de obtenção de materiais híbridos ou nanocompósitos a partir de nanoparticulas de áxidos não metálicos e metálicos, obtidas pelo processo solgel, em uma matriz polimérica solúvel em solventes orgânicos. o processo consiste na formação de uma suspensão coloidal das nanopartículas dos referidos áxidos, estável em sistemas de solventes orgânicos ou misturas destes, e a incorporação de polímeros ou oligômeros orgânicos, formando uma dispersão estável. a eliminação do solvente promove a formação de filmes híbridos e ou nanocompósitos com excepcional dispersão das nanopartículas.method of obtaining hybrid materials or nanocomposites. The invention describes a method of obtaining hybrid materials or nanocomposites from nanoparticles of non-metallic and metallic oxides, obtained by the solgel process, in a polymeric matrix soluble in organic solvents. the process consists of the formation of a colloidal suspension of nanoparticles of the aforementioned oxides, stable in organic solvent systems or mixtures thereof, and the incorporation of organic polymers or oligomers, forming a stable dispersion. the elimination of the solvent promotes the formation of hybrid films and/or nanocomposites with exceptional nanoparticle dispersion.
Description
[001] Esta invenção se insere no ramo da nanotecnologia, mais especificamente no que diz respeito à obtenção de nano materiais, e descreve um método de obtenção de materiais híbridos ou nanocompósitos de óxidos não metálicos e óxidos metálicos a partir de dispersões de nanopartículas em solventes orgânicos compatíveis com polímeros orgânicos de interesse.[001] This invention is part of the field of nanotechnology, more specifically with regard to obtaining nanomaterials, and describes a method of obtaining hybrid materials or nanocomposites of non-metallic oxides and metallic oxides from dispersions of nanoparticles in solvents organic compounds compatible with organic polymers of interest.
[002] O material híbrido ou o nanocompósito obtido pode ser processado na forma de filmes híbridos e ou nanocompósitos com excepcional dispersão das nanopartículas.[002] The hybrid material or nanocomposite obtained can be processed in the form of hybrid films and/or nanocomposites with exceptional dispersion of nanoparticles.
[003] Materiais híbridos e nanocompósitos são definidos como sistemas formados por componentes distintos, intimamente associados por meio de uma interface bem definida.[003] Hybrid materials and nanocomposites are defined as systems formed by distinct components, intimately associated through a well-defined interface.
[004] No caso dos nanocompósitos poliméricos, um elemento de reforço ou carga, com uma de suas dimensões em escala nanométrica, está disperso em uma matriz polimérica contínua.[004] In the case of polymeric nanocomposites, a reinforcing element or filler, with one of its dimensions in nanometer scale, is dispersed in a continuous polymeric matrix.
[005] As nanopartículas podem apresentar diversos formatos (esféricos, lamelares, fibrilares e ocos, dentre outros) e os termos “híbridos” e “nanocompósitos” serão utilizados de modo indistinto ao longo da presente descrição.[005] Nanoparticles can have different shapes (spherical, lamellar, fibrillar and hollow, among others) and the terms "hybrid" and "nanocomposite" will be used interchangeably throughout this description.
[006] Os materiais híbridos e os nanocompósitos podem ser aplicados em uma grande diversidade de sistemas, inclusive como filmes finos de espessura nanométrica em revestimentos e em dispositivos ópticos e eletrônicos não convencionais.[006] Hybrid materials and nanocomposites can be applied in a wide variety of systems, including as thin films of nanometer thickness in coatings and in unconventional optical and electronic devices.
[007] Devido à sinergia entre os constituintes dos materiais compósitos orgânico e inorgânico, novas aplicações surgiram para os mesmos.[007] Due to the synergy between the constituents of organic and inorganic composite materials, new applications have emerged for them.
[008] Um exemplo de nova aplicação de alta tecnologia é na fabricação de dispositivos orgânicos emissores de luz ou células fotovoltaicas orgânicas. Filmes de material ativo, em geral formados por um polímero eletroluminescente ou fotovoltaico, pode ser constituído de um compósito formado a partir de polímeros com uma nanocarga, tal como TiO2, com capacidade de capturar elétrons. Esses filmes apresentam espessuras que variam de 100 a 500 nm e, por isso, apenas nanocompósitos com cargas de dimensões inferiores a 100 nm podem ser empregados.[008] An example of a new application of high technology is in the manufacture of organic light-emitting devices or organic photovoltaic cells. Films of active material, generally formed by an electroluminescent or photovoltaic polymer, may consist of a composite formed from polymers with a nanocharge, such as TiO2, with the ability to capture electrons. These films have thicknesses that vary from 100 to 500 nm and, therefore, only nanocomposites with fillers smaller than 100 nm can be used.
[009] Uma segunda aplicação para materiais poliméricos de TiO2 é na produção de filmes fotodegradáveis, visto que este composto, na presença de traços de água e sob ação de radiação UV, forma radicais livres que aceleram o processo de degradação de polímeros orgânicos, tais como filmes de polietileno e polipropileno.[009] A second application for TiO2 polymeric materials is in the production of photodegradable films, since this compound, in the presence of traces of water and under the action of UV radiation, forms free radicals that accelerate the degradation process of organic polymers, such as such as polyethylene and polypropylene films.
[010] Dentre os materiais que podem ser utilizados como carga ou reforço em materiais poliméricos, podemos citar a mica, a sílica, o carbono, a argila, o carbonato de cálcio, o dióxido de titânio (TiO2), o óxido de zinco, o dióxido de silício, os óxidos de magnésio e de alumínio, dentre outros.[010] Among the materials that can be used as filler or reinforcement in polymeric materials, we can mention mica, silica, carbon, clay, calcium carbonate, titanium dioxide (TiO2), zinc oxide, silicon dioxide, magnesium and aluminum oxides, among others.
[011] O grande desafio na área de materiais nanocompósitos está na dispersão das nanocargas, que, por apresentarem elevada energia de superfície, tendem à aglomeração. De um modo geral, as nanocargas são produzidas em fase aquosa e, uma vez isoladas no estado sólido, tendem a se aglomerar e, assim, inviabilizam os sistemas.[011] The great challenge in the area of nanocomposite materials is in the dispersion of nanofillers, which, due to their high surface energy, tend to agglomeration. In general, nanofillers are produced in an aqueous phase and, once isolated in the solid state, tend to agglomerate and, thus, make the systems unfeasible.
[012] A obtenção de nanocompósitos a partir desses materiais apresenta muitas dificuldades, não sendo útil para formar filmes poliméricos com espessura nanométrica.[012] Obtaining nanocomposites from these materials presents many difficulties, not being useful to form polymeric films with nanometric thickness.
[013] Nanocompósitos com boa dispersão dos materiais são produzidos, em geral, a partir das suspensões aquosas desses materiais utilizando polímeros hidrossolúveis (tal como descrito nos documentos de anterioridade PI 0806021-5 e PI 0801349-7). Embora apresente excelentes resultados, esse método apresenta uso limitado a matrizes hidrofílicas e hidrossolúveis.[013] Nanocomposites with good dispersion of materials are generally produced from aqueous suspensions of these materials using water-soluble polymers (as described in prior documents PI 0806021-5 and PI 0801349-7). Although it presents excellent results, this method has limited use to hydrophilic and water-soluble matrices.
[014] No caso das matrizes poliméricas não solúveis em água, em especial aquelas de média ou baixa polaridade, diversos métodos têm sido utilizados, tais como a funcionalização das nanopartículas para aumentar a sua compatibilidade com as matrizes e o uso de técnicas de incorporação das nanopartículas sólidas por processos de elevado poder de mistura.[014] In the case of non-water soluble polymer matrices, especially those of medium or low polarity, several methods have been used, such as the functionalization of nanoparticles to increase their compatibility with the matrices and the use of incorporation techniques of the solid nanoparticles by high mixing power processes.
[015] Demais processos envolvem a síntese da nanopartícula em meio orgânico, seguida da precipitação e redispersão em um solvente orgânico. O documento WO 2012/001579, por exemplo, descreve sistemas com nanopartículas de óxidos metálicos, mais especificamente o óxido de ferro, as quais são produzidas na presença de ácido oleico e de solventes orgânicos, sendo precipitadas ao final do processo e redispersas em outro solvente orgânico, podendo formar aglomerados.[015] Other processes involve the synthesis of the nanoparticle in an organic medium, followed by precipitation and redispersion in an organic solvent. WO 2012/001579, for example, describes systems with nanoparticles of metallic oxides, more specifically iron oxide, which are produced in the presence of oleic acid and organic solvents, being precipitated at the end of the process and redispersed in another solvent. organic and can form agglomerates.
[016] No documento WO 2007/015248 A2, surfactantes não iônicos são utilizados para dispersar nanopartículas em pó, formando suspensões estáveis de nanopartículas tratadas em um solvente orgânico apolar, podendo, também, levar à formação de agregados.[016] In WO 2007/015248 A2, nonionic surfactants are used to disperse nanoparticles in powder, forming stable suspensions of treated nanoparticles in a nonpolar organic solvent, which can also lead to the formation of aggregates.
[017] Já na patente EP 2 206 682 A1, partículas em forma de escamas de dimensões micrométricas preparadas em suspensão aquosa são centrifugadas ou liofilizadas para, então, serem redispersas em um solvente orgânico.[017] Already in the patent EP 2 206 682 A1, particles in the form of scales of micrometric dimensions prepared in aqueous suspension are centrifuged or lyophilized to then be redispersed in an organic solvent.
[018] Outro processo descrito na patente EP 0 236 945 B1 é baseado em nanopartículas sintetizadas em um meio aquoso e / ou composto por um solvente hidroxilado polar, tal como um glicol ou um álcool.[018] Another process described in patent EP 0 236 945 B1 is based on nanoparticles synthesized in an aqueous medium and/or composed of a polar hydroxylated solvent, such as a glycol or an alcohol.
[019] Com exceção das matrizes polares e hidrossolúveis, que permitem uma excelente distribuição das nanopartículas, as matrizes apolares representam um grande desafio, uma vez que a dispersão de nanopartículas no estado sólido requer processos intensivos e complexos e, invariavelmente, levam à formação de aglomerados de nanopartículas.[019] With the exception of polar and water-soluble matrices, which allow an excellent distribution of nanoparticles, apolar matrices represent a great challenge, since the dispersion of nanoparticles in the solid state requires intensive and complex processes and, invariably, lead to the formation of nanoparticle clusters.
[020] Em vista de todos os problemas expostos, a presente invenção se refere a um método de obtenção de materiais híbridos ou nanocompósitos a partir de dispersões coloidais de nanopartículas de óxidos não metálicos e metálicos em solventes orgânicos compatíveis com os polímeros.[020] In view of all the problems exposed, the present invention refers to a method of obtaining hybrid materials or nanocomposites from colloidal dispersions of nanoparticles of non-metallic and metallic oxides in organic solvents compatible with the polymers.
[021] Em seguida, a partir deste sistema, promove-se a remoção do solvente e a obtenção do material híbrido ou nanocompósito, o qual pode ser processado na forma de filmes híbridos e ou nanocompósitos com excepcional dispersão das nanopartículas.[021] Then, from this system, the solvent removal is promoted and the hybrid material or nanocomposite is obtained, which can be processed in the form of hybrid films and/or nanocomposites with exceptional dispersion of nanoparticles.
[022] A presente invenção descreve um método de obtenção de materiais híbridos ou nanocompósitos a partir de dispersões coloidais de nanopartículas em solventes orgânicos.[022] The present invention describes a method of obtaining hybrid materials or nanocomposites from colloidal dispersions of nanoparticles in organic solvents.
[023] O processo consiste na troca do solvente aquoso da suspensão de nanopartículas por um solvente orgânico e a posterior incorporação do polímero orgânico solúvel na suspensão de nanopartículas em fase orgânica, seguido da evaporação do solvente para gerar o material híbrido ou nanocompósito.[023] The process consists of exchanging the aqueous solvent of the suspension of nanoparticles for an organic solvent and the subsequent incorporation of the soluble organic polymer in the suspension of nanoparticles in the organic phase, followed by the evaporation of the solvent to generate the hybrid material or nanocomposite.
[024] Os materiais ou nanocompósitos obtidos apresentam ótima dispersão e distribuição de nanopartículas, inibindo a ocorrência de aglomerados e permitindo a produção de filmes híbridos e ou nanocompósitos.[024] The materials or nanocomposites obtained show great dispersion and distribution of nanoparticles, inhibiting the occurrence of agglomerates and allowing the production of hybrid films and/or nanocomposites.
[025] Breve descrição das figuras:[025] Brief description of the figures:
[026] A presente invenção pode ser mais bem entendida mediante referência as figuras anexas e suas descrições:[026] The present invention can be better understood by referring to the attached figures and their descriptions:
[027] A Figura 1 mostra o fluxograma do método de obtenção de materiais híbridos ou nanocompósitos descrito no Exemplo da presente patente.[027] Figure 1 shows the flowchart of the method for obtaining hybrid or nanocomposite materials described in the Example of the present patent.
[028] As Figuras 2A, 2B, 2C e 2D representam graficamente as curvas de distribuição do tamanho de partícula (em nm) das suspensões coloidais preparadas a partir da dispersão do N-butil titanato em água (Figura 2D), seguida da substituição desta água pelos solventes N-metil pirolidona - NMP (Figura 2C), dimetil sulfóxido - DMSO (Figura 2B) e etileno glicol - EG (Figura 2A), obtidas pela técnica de espalhamento de luz.[028] Figures 2A, 2B, 2C and 2D graphically represent the particle size distribution curves (in nm) of colloidal suspensions prepared from the dispersion of N-butyl titanate in water (Figure 2D), followed by the replacement of this water by the solvents N-methyl pyrolidone - NMP (Figure 2C), dimethyl sulfoxide - DMSO (Figure 2B) and ethylene glycol - EG (Figure 2A), obtained by the light scattering technique.
[029] As Figuras 3A e 3B representam imagens de microscopia eletrônica de varredura das nanopartículas obtidas pela evaporação da suspensão em DMSO.[029] Figures 3A and 3B represent scanning electron microscopy images of the nanoparticles obtained by evaporating the suspension in DMSO.
[030] A Figura 4 representa uma micrografia obtida por Microscopia Eletrônica de Transmissão das nanopartículas de dióxido de titânio obtidas após evaporação do DMSO.[030] Figure 4 represents a micrograph obtained by Transmission Electron Microscopy of titanium dioxide nanoparticles obtained after evaporation of DMSO.
[031] A Figura 5 representa uma micrografia obtida por Microscopia Eletrônica de Transmissão de um filme do material híbrido/nanocompósito obtido a partir do sistema dióxido de titânio / polímero em DMSO.[031] Figure 5 represents a micrograph obtained by Transmission Electron Microscopy of a film of the hybrid/nanocomposite material obtained from the titanium dioxide / polymer system in DMSO.
[032] A Figura 6 representa uma micrografia obtida por Microscopia Eletrônica de Transmissão de um filme do material híbrido/nanocompósito obtidos a partir do sistema dióxido de titânio / polímero em DMSO, evidenciando, na área marcada, uma nanopartícula isolada com diâmetro de aproximadamente de 5 nm.[032] Figure 6 represents a micrograph obtained by Transmission Electron Microscopy of a film of the hybrid/nanocomposite material obtained from the titanium dioxide / polymer system in DMSO, showing, in the marked area, an isolated nanoparticle with a diameter of approximately 5 nm.
[033] As Figuras 7A, 7B, 7C e 7D mostram os difratogramas de raio-X dos materiais após secagem obtido diretamente da suspensão aquosa (Figura 7D) e das suspensões em DMSO após tratamento a 50, 130 e 200°C (respectivamente, Figuras 7C, 7B e 7A).[033] Figures 7A, 7B, 7C and 7D show the X-ray diffractograms of the materials after drying obtained directly from the aqueous suspension (Figure 7D) and from the suspensions in DMSO after treatment at 50, 130 and 200°C (respectively, Figures 7C, 7B and 7A).
[034] A presente invenção descreve um método de obtenção de materiais híbridos ou nanocompósitos de óxidos não metálicos e óxidos metálicos a partir de dispersões de nanopartículas em solventes orgânicos compatíveis com os polímeros orgânicos de interesse.[034] The present invention describes a method of obtaining hybrid materials or nanocomposites of non-metallic oxides and metallic oxides from nanoparticle dispersions in organic solvents compatible with the organic polymers of interest.
[035] O método consiste nas etapas de: a) síntese de nanopartículas de óxidos metálicos ou não metálicos em suspensão coloidal por meio do processo sol/gel, em que a suspensão final apresenta concentração que varia de 0,25 a 20%, preferencialmente entre 0,5 e 10% em massa; b) substituição da fase aquosa da suspensão obtida na etapa (a) por um solvente orgânico solúvel em água, em que o sistema solvente final é composto por pelo menos 90 % de solvente orgânico, preferencialmente 99% de solvente orgânico; c) adição de um ou mais polímeros orgânicos, de forma direta ou em solução do mesmo solvente usado na etapa (b), à suspensão de nanopartículas em fase orgânica, em que a concentração final de polímero orgânico em solução é entre 1 e 25 %, preferencialmente entre 2 e 15%; e d) evaporação do solvente para obtenção do material híbrido ou nanocompósitos com excepcional distribuição das nanopartículas.[035] The method consists of the steps of: a) synthesis of nanoparticles of metallic or non-metallic oxides in colloidal suspension through the sol/gel process, in which the final suspension has a concentration ranging from 0.25 to 20%, preferably between 0.5 and 10% by mass; b) replacing the aqueous phase of the suspension obtained in step (a) by a water-soluble organic solvent, wherein the final solvent system is composed of at least 90% organic solvent, preferably 99% organic solvent; c) addition of one or more organic polymers, directly or in solution of the same solvent used in step (b), to the suspension of nanoparticles in organic phase, in which the final concentration of organic polymer in solution is between 1 and 25% , preferably between 2 and 15%; and d) evaporation of the solvent to obtain the hybrid material or nanocomposites with exceptional distribution of the nanoparticles.
[036] É fundamental que a suspensão coloidal se mantenha estável durante todas as etapas do método, a fim de que o produto final apresente as nanopartículas individuais não aglomeradas e bem dispersas pela matriz polimérica. Nesse caso, a desestabilização, caracteriza-se pela aglomeração das nanopartículas inorgânicas e sua sedimentação, provocando turvação do meio.[036] It is essential that the colloidal suspension remains stable during all stages of the method, so that the final product presents the individual nanoparticles not agglomerated and well dispersed by the polymer matrix. In this case, destabilization is characterized by the agglomeration of inorganic nanoparticles and their sedimentation, causing turbidity in the medium.
[037] Abaixo, as etapas do método de obtenção de materiais híbridos ou nanocompósitos são mais bem descritas:[037] Below, the steps of the method of obtaining hybrid or nanocomposite materials are better described:
[038] A etapa (a) do método descrito na presente invenção consiste no preparo de uma suspensão coloidal de material óxido metálico ou não metálico através de processo sol/gel.[038] Step (a) of the method described in the present invention consists of preparing a colloidal suspension of metallic or non-metallic oxide material through a sol/gel process.
[039] Materiais úteis no preparo da suspensão coloidal podem ser quaisquer óxidos de metais ou não-metais selecionados do grupo que consiste em: dióxido de silício, dióxido de titânio, dióxido de zinco, dióxido de manganês, óxido de zircônio, óxidos de ferro, óxido de cério, óxido de magnésio, óxido de estanho, óxido de tântalo, óxido de platina, óxidos de cobre, hidróxido/óxido de alumínio, pentóxido de nióbio, trióxido de boro, sulfato de bário, não se limitando aos mesmos.[039] Materials useful in preparing the colloidal suspension can be any metal or non-metal oxides selected from the group consisting of: silicon dioxide, titanium dioxide, zinc dioxide, manganese dioxide, zirconium oxide, iron oxides , cerium oxide, magnesium oxide, tin oxide, tantalum oxide, platinum oxide, copper oxides, aluminum hydroxide/oxide, niobium pentoxide, boron trioxide, barium sulfate, but not limited to the same.
[040] Os óxidos são hidrolisados em meio aquoso ácido e, em seguida, sofrem um processo de peptização, produzindo uma suspensão coloidal de nanopartículas com dimensões de 1 a 500 nm, preferencialmente de 5 a 100 nm, tipicamente em torno de 20 nm.[040] The oxides are hydrolyzed in an acidic aqueous medium and then undergo a peptization process, producing a colloidal suspension of nanoparticles with dimensions from 1 to 500 nm, preferably from 5 to 100 nm, typically around 20 nm.
[041] Para os óxidos selecionados, um reagente, tal como o tetracloreto de titânio ou um alcóxido como o tetra isopropil-titanato ou tetra n-butil-titanato, é hidrolisado em meio aquoso e a dispersão coloidal obtida é peptitizada, ou seja, passa por um tratamento térmico que promove a formação de partículas com tamanho bem definido e grande estabilidade.[041] For the selected oxides, a reagent, such as titanium tetrachloride or an alkoxide such as tetra isopropyl titanate or tetra n-butyl titanate, is hydrolyzed in aqueous medium and the colloidal dispersion obtained is peptitized, that is, undergoes a heat treatment that promotes the formation of particles with a well-defined size and great stability.
[042] O tratamento térmico consiste na introdução da amostra em uma estufa ou em um forno à temperatura desejada por um tempo pré-determinado. A temperatura depende do tipo de material e deve ser definida com base no tipo de estrutura cristalina desejada. No caso específico do dióxido de titânio, a temperatura deve estar compreendida entre 100 e 600 °C, preferencialmente entre 200 e 300 °C.[042] The heat treatment consists of introducing the sample into an oven or an oven at the desired temperature for a predetermined time. The temperature depends on the type of material and should be set based on the type of crystal structure desired. In the specific case of titanium dioxide, the temperature must be between 100 and 600 °C, preferably between 200 and 300 °C.
[043] A concentração das nanopartículas deve ser definida em função da concentração final desejada. Se em excesso, pode-se provocar a desestabilização da suspensão.[043] The concentration of nanoparticles must be defined as a function of the desired final concentration. If in excess, it can cause the suspension to destabilize.
[044] Em muitos casos, pode ser necessária a estabilização das suspensões coloidais pelo uso de agentes estabilizantes tais como surfactantes, polímeros não iônicos ou iônicos, álcoois de cadeia longa ou outro material orgânico que tenha capacidade de interagir com ambas as porções inorgânica e orgânica do sistema.[044] In many cases, stabilization of colloidal suspensions may be necessary by the use of stabilizing agents such as surfactants, non-ionic or ionic polymers, long-chain alcohols or other organic material that has the ability to interact with both the inorganic and organic portions. of the system.
[045] Na etapa (b) do método ora descrito, a suspensão é submetida à troca da fase aquosa por um solvente orgânico miscível em água, cujo ponto de ebulição é superior ao da água.[045] In step (b) of the method described herein, the suspension is subjected to the exchange of the aqueous phase by a water-miscible organic solvent, whose boiling point is higher than that of water.
[046] Os solventes orgânicos que podem ser empregados são selecionados do grupo que consiste em álcoois (n-butanol, n-pentanol e álcool benzílico); dialcoóis (glicóis como o etilenoglicol, propilenoglicol, dietilenoglicol, trietileno glicol); glicerol; N,N-dimetilformamida; dimetil sulfóxido (DMSO); N-metil-2-pirolidona; piridina; acetofenona e etanolamina, bem como suas misturas.[046] The organic solvents that can be used are selected from the group consisting of alcohols (n-butanol, n-pentanol and benzyl alcohol); dial-alcohols (glycols such as ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol); glycerol; N,N-dimethylformamide; dimethyl sulfoxide (DMSO); N-methyl-2-pyrolidone; pyridine; acetophenone and ethanolamine, as well as mixtures thereof.
[047] A substituição da fase aquosa é realizada por meio da adição do solvente à suspensão, seguida da evaporação da fase aquosa com o sistema sob agitação, por meio de um processo de destilação simples.[047] The replacement of the aqueous phase is carried out by adding the solvent to the suspension, followed by the evaporation of the aqueous phase with the system under agitation, through a simple distillation process.
[048] Nessa etapa, pode ser necessário reduzir a pressão para acelerar a remoção da água.[048] At this stage, it may be necessary to reduce the pressure to accelerate the removal of water.
[049] Por fim, traços remanescentes de água são removidos por meio de agentes dessecantes que podem ser reciclados, como peneira molecular e sulfato de magnésio anidro. Outras técnicas para a remoção da água, como osmose e destilação azeotrópica, também podem ser empregadas.[049] Finally, remaining traces of water are removed using desiccant agents that can be recycled, such as molecular sieve and anhydrous magnesium sulfate. Other techniques for removing water, such as osmosis and azeotropic distillation, can also be used.
[050] Adição de um ou mais polímeros orgânicos, de forma direta ou em solução do mesmo solvente usado na etapa (b), à suspensão de nanopartículas em fase orgânica:[050] Addition of one or more organic polymers, directly or in solution of the same solvent used in step (b), to the suspension of nanoparticles in organic phase:
[051] Na etapa (c), o polímero orgânico é adicionado à suspensão. O polímero pode ser diretamente adicionado ou previamente solubilizado no mesmo solvente utilizado na etapa (b). Em ambos os casos, a adição deve ser controlada para evitar uma desestabilização da suspensão coloidal. Preferencialmente, a adição é lenta e deve-se observar a formação de precipitado. Em caso positivo, a velocidade de adição dever ser reduzida.[051] In step (c), the organic polymer is added to the suspension. The polymer can be directly added or previously solubilized in the same solvent used in step (b). In both cases, the addition must be controlled to avoid destabilization of the colloidal suspension. Preferably, the addition is slow and the formation of precipitate should be observed. If so, the addition speed should be reduced.
[052] O polímero deve ser completamente solúvel no solvente escolhido e não provocar a desestabilização do sistema.[052] The polymer must be completely soluble in the chosen solvent and not cause the destabilization of the system.
[053] Matrizes poliméricas úteis são selecionadas dentre os polímeros condutores, tais como: poli (p- fenilenovinileno) (PPV), polianilina, poliacetileno poli (o- metoxianilina) (POMA), dentre outros.[053] Useful polymer matrices are selected among conductive polymers, such as: poly (p-phenylenevinylene) (PPV), polyaniline, polyacetylene poly (o-methoxyaniline) (POMA), among others.
[054] Dentre os polímeros condutores emissores de luz, podem ser utilizados: poli[2-metoxi-5-(2-etilhexiloxi)- 1,4-fenileno-vinileno]; poli[2-metoxi-5-(2-etilhexiloxi)- 1,4-fenileno-vinileno]- com terminações de demetilfenila (DMP); poli[2-metoxi-5-(2-etilhexiloxi)-1,4-fenileno- vinileno]; poli[2-metoxi-5-(2-etilhexiloxi)-1,4-fenileno- vinileno] com terminações de polisilsesquioxano; poli[2- metoxi-5-(2-etilhexiloxi)-1,4-fenileno-vinileno]-co-(4,4’- bifenileno-vinileno)]; poli[2-metoxi-5-(3,7- dimetiloctiloxi)-1,4-fenileno-vinileno]; poli[2-metoxi-5- (3,7-dimetiloctiloxi)-1,4-fenileno-vinileno] com terminações dimetilfenila (DMP); poli[2-metoxi-5-(3,7-dimetiloctiloxi)- 1,4-fenileno-vinileno]; poli[2-metoxi-5-(3,7- dimetiloctiloxi)-1,4-fenileno-vinileno]- com terminações polisilsesquioxano; poli[(9,9-dioctil-2,7- divinilenofluorenileno)-alt-co-(9,10-antraceno)]; poli[(9,9- dioctil-2,7-divinilenofluorenileno)-alt-co-(4,4’- bifenileno)]; poli[(9,9-dioctil-2,7-divinilenofluorenileno)- alt-co-{2-metoxi-5-(2-ethilhexiloxi)-1,4-fenileno}]; poli[(9,9-dioctil-2,7-bis{2-cianovinilenofluorenileno})-alt- co-(2-metoxi-5-{2-ethilhexiloxi}-1,4-fenileno)]; poli[2- metoxi-5-(2-etilhexiloxi)-1,4-(1-cianovinileno-1,4- fenileno)]; poli[{9,9-dihexil-2,7-bis(1- cianovinileno)fluorenilene}-alt-co-{2,5-bis(n,n’- difenilamino)-1,4-fenileno}]; poli[{2-metoxi-5-(2- etilhexiloxi)-1,4-(1-cianovinilenofenileno)}-co-{2,5- bis(n,n’-difenilamino)-1,4-fenileno}]; poli[2-(5-ciano-5- metilhexiloxi)-1,4-fenileno]; poli[2-(5-ciano-5- metilhexiloxi)-1,4-fenileno] com terminações dimetilfenila (DMP); poli[2,5-dioctil-1,4-fenileno]; poli[2,5-dioctil-1,4- fenileno] - com terminação DMP; poli[{9,9-dioctil fluorenil- 2,7-diil}-co-{1,4-(2,5-dimetoxi)benzeno}]; poli [{9,9- dioctilfluorenil-2,7-diil}-co-{1,4-(2,5-dimetoxi) benzeno}]- com terminação DMP; poli[(9,9-dioctilfluorenil-2,7-diil)-co- (1,4-difenileno-vinileno-2-metoxi-5-{2-etil hexiloxi}- benzeno)]; poli[(9,9-dihexil-2,7-(2-ciano divinileno) - fluorenilenil-2,7-diil)]; poli[(9,9-dioctil-2,7- divinilenofluorenileno)-alt-co-(1,4-fenileno)]; poli [9,9- dioctilfluorenil-2,7-diil]; poli[9,9-dioctilfluorenil-2,7- diil] - com terminação DMP; poli[9,9-dioctilfluorenil-2,7- diil]; poli[9,9-dioctilfluorenil-2,7-diil] - com terminação polisilsesquioxane; poli[9,9-dioctilfluorenil-2,7-diil]; poli[9,9-dioctilfluorenil-2,7-diil] - com terminação n,n- bis(4-metilfenil)-anilina; poli[9,9-dioctilfluorenil-2,7- diil]; poli[9,9-dioctilfluorenil-2,7-diil] - com terminação 2,5-difenil-1,2,4-oxadiazol; poli[9,9-diexilfluorenil-2,7- diil]; poli[9,9-diexil fluorenil -2,7-diil] - com terminação DMP; poli[9,9-di-(2-etilhexilo)-fluorenil-2,7-diil]; poli[9,9-di-(2-etilhexilo) -fluorenil-2,7-diil] - com terminação DMP; poli[9,9-di-(2-etilhexilo)-fluorenil-2,7- diil]; poli[9,9-di-(2-etilhexilo) -fluorenil-2,7-diil] - com terminação polisilsesquioxano; poli[9,9-di-(2-etilhexilo)- fluorenil-2,7-diil]; poli[9,9-di-(2-etilhexilo)-fluorenil- 2.7- diil] - com terminação n,n-bis(4-metilfenilo)-aniline; poli[9,9-di-(2-etilhexilo)-fluorenil-2,7-diil]; poli[9,9-di- (2-etilhexilo)-fluorenil-2,7-diil] - com terminação 2,5- difenil-1,2,4-oxadiazole; poli[(9,9-dioctilfluorenil-2,7- diil)-co-(n,n’-difenil)-n,n’ -di(pbutilenil)-1,4-diamino- benzeno)]; poli[(9,9-dioctil fluorenil-2,7-diil)-alt-co-(1,4- benzo-{2,1’,3}-tiadiazole)]; poli[(9,9-dioctilfluorenil-2,7- diil)-co-(1,4-benzo-{2,1’,3}-thiadiazole)]10% benzotiadiazole (i); poli [(9,9-diexilfluorenil-2,7-diil)-co- (9,10-antraceno)]; poli[(9,9-dioctilfluorenil-2,7-diil)-alt- co-(n,n’-bis{4-butilfenil}-benzidinen,n’-{1,4-difenileno})]; poli[(9,9-diexilfluorenil-2,7-diil)-alt-co-(2-metoxi-5-{2- etiloxiloxi}-1,4-fenileno)]; poli[(9,9-diexilfluorenil-2,7- diil)-alt-co-(2-metoxi-5-{2-etilhexiloxi}-1,4-fenileno)]; poli[(9,9-dioctilfluorenil-2,7-diil)-alt-co-(9-hexil-3,6- carbazol)]; poli[(9,9-dioctilfluorenil-2,7-diil)-co-(9- hexil-3,6-carbazol)]; poli[(9,9-dioctilfluorenil-2,7-diil)- co-(9-hexil-3,6-carbazol)]- com terminação DMP; poli[(9,9- dihexilfluorenil-2,7-diil)-alt-co-(9,9’-spiro-bifluoreno- 2,7-diil)]; poli[(9,9-dioctilfluorenil-2,7-diil)-co-(2,5-p- xileno)]; poli[(9,9-dioctilfluorenil-2,7-diil)-alt-co-(2,6- piridino)]; poli[(9,9-dioctilfluorenil-2,7-diil)-co-(1,4- fenileno)]; poli[(9,9-dioctilfluorenil-2,7-diil)-co-(1,4- fenileno)]- com a terminação DMP; poli[(9,9-dioctil fluorenil- 2,7-diil)-alt-co-(9,9-di-{5’-pentanil}-fluorenil-2,7-diil)]; poli[(9,9-dioctilfluorenil-2,7-diil)-alt-co- (6,6’-{2,2’- bipiridino})]; poli[(9,9-dioctil fluorenil-2,7-diil)-alt-co- (6,6’-{2,2’:6’,2’’-terpiridino})]; poli[2-metoxi -5-(2- etilexiloxi)-1,4-fenileno]; poli[2-metoxi-5-(2-etilexiloxi)- 1,4-fenileno];poli[2-metoxi-5-(2-etilexil oxi)-1,4- fenileno]- com a terminação DMP; poli[(9,9-dioctil-2,7- fluorenileno)-co-(3,8-fenantrolino)];poli[(9,9-dioctil-2,7- fluorenileno)-co-(3,8-fenantrolino)]; poli[(9,9-dioctil-2,7- fluorenileno)-co-(3,8-fenantrolino)];poli[(9,9-dioctil-2,7- fluorenileno)-co-(3,8-fenantrolino)]- com terminação DMP.[054] Among the light-emitting conductive polymers, the following can be used: poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene-vinylene]; poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene-vinylene]-terminated with demethylphenyl (DMP); poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene-vinylene]; poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene-vinylene] terminated with polysilsesquioxane; poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene-vinylene]-co-(4,4'-biphenylene-vinylene)]; poly[2-methoxy-5-(3,7-dimethyloctyloxy)-1,4-phenylene-vinylene]; poly[2-methoxy-5-(3,7-dimethyloctyloxy)-1,4-phenylene-vinylene] with dimethylphenyl (DMP) ends; poly[2-methoxy-5-(3,7-dimethyloctyloxy)-1,4-phenylene-vinylene]; poly[2-methoxy-5-(3,7-dimethyloctyloxy)-1,4-phenylene-vinylene]-terminated polysilsesquioxane; poly[(9,9-dioctyl-2,7-divinylenefluorenylene)-alt-co-(9,10-anthracene)]; poly[(9,9-dioctyl-2,7-divinylenefluorenylene)-alt-co-(4,4'-biphenylene)]; poly[(9,9-dioctyl-2,7-divinylenefluorenylene)-alt-co-{2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene}]; poly[(9,9-dioctyl-2,7-bis{2-cyanovinylenefluorenylene})-alt-co-(2-methoxy-5-{2-ethylhexyloxy}-1,4-phenylene)]; poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-(1-cyanovinylene-1,4-phenylene)]; poly[{9,9-dihexyl-2,7-bis(1-cyanovinylene)fluorenylene}-alt-co-{2,5-bis(n,n'-diphenylamino)-1,4-phenylene}]; poly[{2-methoxy-5-(2-ethylhexyloxy)-1,4-(1-cyanovinylenephenylene)}-co-{2,5-bis(n,n'-diphenylamino)-1,4-phenylene}] ; poly[2-(5-cyano-5-methylhexyloxy)-1,4-phenylene]; poly[2-(5-cyano-5-methylhexyloxy)-1,4-phenylene] with dimethylphenyl (DMP) ends; poly[2,5-dioctyl-1,4-phenylene]; poly[2,5-dioctyl-1,4-phenylene] - with DMP termination; poly[{9,9-dioctyl fluorenyl-2,7-diyl}-co-{1,4-(2,5-dimethoxy)benzene}]; DMP-terminated poly [{9,9-dioctylfluorenyl-2,7-diyl}-co-{1,4-(2,5-dimethoxy)benzene}]-; poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(1,4-diphenylene-vinylene-2-methoxy-5-{2-ethylhexyloxy}-benzene)]; poly[(9,9-dihexyl-2,7-(2-cyano divinylene)-fluorenylenyl-2,7-diyl)]; poly[(9,9-dioctyl-2,7-divinylenefluorenylene)-alt-co-(1,4-phenylene)]; poly[9,9-dioctylfluorenyl-2,7-diyl]; poly[9,9-dioctylfluorenyl-2,7-diyl] - with DMP termination; poly[9,9-dioctylfluorenyl-2,7-diyl]; poly[9,9-dioctylfluorenyl-2,7-diyl] - terminated with polysilsesquioxane; poly[9,9-dioctylfluorenyl-2,7-diyl]; poly[9,9-dioctylfluorenyl-2,7-diyl]-terminated n,n-bis(4-methylphenyl)-aniline; poly[9,9-dioctylfluorenyl-2,7-diyl]; poly[9,9-dioctylfluorenyl-2,7-diyl]-terminated 2,5-diphenyl-1,2,4-oxadiazole; poly[9,9-dihexylfluorenyl-2,7-diyl]; poly[9,9-dihexyl fluorenyl-2,7-diyl] - with DMP termination; poly[9,9-di-(2-ethylhexyl)-fluorenyl-2,7-diyl]; poly[9,9-di-(2-ethylhexyl)-fluorenyl-2,7-diyl] - DMP-terminated; poly[9,9-di-(2-ethylhexyl)-fluorenyl-2,7-diyl]; poly[9,9-di-(2-ethylhexyl)-fluorenyl-2,7-diyl]-terminated polysilsesquioxane; poly[9,9-di-(2-ethylhexyl)-fluorenyl-2,7-diyl]; poly[9,9-di-(2-ethylhexyl)-fluorenyl-2,7-diyl]-terminated n,n-bis(4-methylphenyl)-aniline; poly[9,9-di-(2-ethylhexyl)-fluorenyl-2,7-diyl]; poly[9,9-di-(2-ethylhexyl)-fluorenyl-2,7-diyl]-terminated 2,5-diphenyl-1,2,4-oxadiazole; poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(n,n'-diphenyl)-n,n'-di(pbutylenyl)-1,4-diaminobenzene)]; poly[(9,9-dioctyl fluorenyl-2,7-diyl)-alt-co-(1,4-benzo-{2,1',3}-thiadiazole)]; poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(1,4-benzo-{2,1',3}-thiadiazole)]10% benzothiadiazole (i); poly[(9,9-dihexylfluorenyl-2,7-diyl)-co-(9,10-anthracene)]; poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-co-(n,n'-bis{4-butylphenyl}-benzidinen,n'-{1,4-diphenylene})]; poly[(9,9-dihexylfluorenyl-2,7-diyl)-alt-co-(2-methoxy-5-{2-ethyloxyloxy}-1,4-phenylene)]; poly[(9,9-dihexylfluorenyl-2,7-diyl)-alt-co-(2-methoxy-5-{2-ethylhexyloxy}-1,4-phenylene)]; poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-co-(9-hexyl-3,6-carbazole)]; poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(9-hexyl-3,6-carbazole)]; DMP-terminated poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(9-hexyl-3,6-carbazole)]-; poly[(9,9-dihexylfluorenyl-2,7-diyl)-alt-co-(9,9'-spiro-bifluorene-2,7-diyl)]; poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(2,5-p-xylene)]; poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-co-(2,6-pyridine)]; poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(1,4-phenylene)]; poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(1,4-phenylene)]-terminated DMP; poly[(9,9-dioctyl fluorenyl-2,7-diyl)-alt-co-(9,9-di-{5'-pentanyl}-fluorenyl-2,7-diyl)]; poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-co-(6,6'-{2,2'-bipyridine})]; poly[(9,9-dioctyl fluorenyl-2,7-diyl)-alt-co-(6,6'-{2,2':6',2''-terpyridine})]; poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene]; poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene];poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylene]-terminated DMP; poly[(9,9-dioctyl-2,7-fluorenylene)-co-(3,8-phenanthroline)];poly[(9,9-dioctyl-2,7-fluorenylene)-co-(3,8- phenanthroline)]; poly[(9,9-dioctyl-2,7-fluorenylene)-co-(3,8-phenanthroline)];poly[(9,9-dioctyl-2,7-fluorenylene)-co-(3,8- phenanthroline)]- with DMP termination.
[055] Dentre os oligômeros condutores emissores de luz, têm-se: 4,4’-bis(9-etil-3-carbazovinileno)-1,1’-bifenil; 9,10-bis[(9-etil-3-carbazol) -vinilenol] -antraceno; 1,4- bis(9-etil-3-carbazovinileno)-2-metoxi-5-(2- etilhexiloxi)benzeno; 4,4’-bis(difenilvinilenol) - antraceno; 9,9,9’,9’,9’’,9’’-hexaquis(hexil)-2,7’;2’,7’’-trifluoreno; 9,9,9’,9’,9’’,9’’-hexaquis(octil)-2,7’;2’,7’’-trifluoreno; 9,9,9’,9’,9’’,9’’, 9’’’,9’’’,9’’’’,9’’’’-decaquis(hexil)- 2’’’,7’’’’-pentafluoreno; 2t9,9,9’,9’,9’’,9’’,9’’’,9’’’, 9’’’’,9’’’’, 9’’’’’, 9’’’’’’, 9’’’’’’-dodecaquis 2’’,7’’’;2’’’,7’’’’, 2’’’’,7’’’’’, heptafluoreno; 3,7-bis-(9,9-di-n-hexil fluorenila-2,7-diil)- dibenzotiofeno-s,s-dióxido; 3,7-bis[7-(9,9-di-n- hexilfluorenila-2,7-diil)]-9,9-di-n-hexil fluoreno-2-il] dibenzotiofeno-s,s-dióxido.[055] Among the light-emitting conductive oligomers, there are: 4,4'-bis(9-ethyl-3-carbazovinylene)-1,1'-biphenyl; 9,10-bis[(9-ethyl-3-carbazole)-vinylenol]-anthracene; 1,4-bis(9-ethyl-3-carbazovinylene)-2-methoxy-5-(2-ethylhexyloxy)benzene; 4,4'-bis(diphenylvinylenol)-anthracene; 9,9,9',9',9'',9''-hexakis(hexyl)-2,7';2',7''-trifluorene; 9,9,9',9',9'',9''-hexakis(octyl)-2,7';2',7''-trifluorene; 9,9,9',9',9'',9'', 9''',9''',9'''',9''''-decakis(hexyl)- 2''', 7''''-pentafluorene; 2t9,9,9',9',9'',9'',9''',9''', 9'''',9'''', 9''''', 9'' '''', 9''''''-dodecaki 2'',7''';2''',7'''', 2'''',7''''', heptafluorene; 3,7-bis-(9,9-di-n-hexylfluorenyl-2,7-diyl)-dibenzothiophene-s,s-dioxide; 3,7-bis[7-(9,9-di-n-hexylfluorenyl-2,7-diyl)]-9,9-di-n-hexylfluoren-2-yl]dibenzothiophene-s,s-dioxide.
[056] Ainda, polímeros para transporte de buraco ou polímeros tipo p são selecionados dentre poli[(9,9- dihexilfluorenila-2,7-diil)-alt-co-(n,n’bis{p-butilfenila}- 1,4-diaminofenileno)]; poli[(9,9-dioctilfluorenila-2,7- diil)-alt-co-(n,n’-bis{p-butilfenila}-1,1’-bifenileno-4,4’- diamino)]; poli[(9,9-bis{1’-penten-5’-il}fluorenila-2,7- diil)-alt-co-(n,n’bis{p-butilfenila}-1,4-diaminofenileno)]; poli[n,n’-bis(4-butilfenila)-n,n’-bis(fenila)-benzidina]; poli[(9,9-dioctilfluorenil-2,7-diil)-co-(4,4’-(n-(p- butilfenila))difenilamina)].[056] Also, hole transport polymers or p-type polymers are selected from poly[(9,9-dihexylfluorenyl-2,7-diyl)-alt-co-(n,n'bis{p-butylphenyl}-1 ,4-diaminophenylene)]); poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-co-(n,n'-bis{p-butylphenyl}-1,1'-biphenylene-4,4'-diamino)]; poly[(9,9-bis{1'-penten-5'-yl}fluorenyl-2,7-diyl)-alt-co-(n,n'bis{p-butylphenyl}-1,4-diaminophenylene) ]; poly[n,n'-bis(4-butylphenyl)-n,n'-bis(phenyl)-benzidine]; poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(n-(p-butylphenyl))diphenylamine)].
[057] Polímeros ou moléculas para transporte de buraco são selecionados dentre: n,n’-bis(3-metilfenil)-n,n’- bis(fenil) benzidina; n,n’-bis(4-metilfenil)-n,n’- bis(fenil)benzidina n,n’-bis(2-naftalenila)-n-n’- bis(fenilbenzidina); 1,3,5-tris (3-metildifenilamino)benzeno; n,n’-bis(1-naftalenila)-n-n’-bis(fenilbenzidina); 2,2’,5,5’- tetra(n-bis(4-metoxifenila)amino)spiro-9,9’-bifluoreno; 4,4’,4’’-tris (n,n-fenil-3-metilfenilamino)trifenilamina; 4,4’,n,n’-difenilcarbazol.[057] Polymers or molecules for hole transport are selected from: n,n'-bis(3-methylphenyl)-n,n'-bis(phenyl) benzidine; n,n'-bis(4-methylphenyl)-n,n'-bis(phenyl)benzidine n,n'-bis(2-naphthalenyl)-n-n'-bis(phenylbenzidine); 1,3,5-tris(3-methyldiphenylamino)benzene; n,n'-bis(1-naphthalenyl)-n-n'-bis(phenylbenzidine); 2,2',5,5'-tetra(n-bis(4-methoxyphenyl)amino)spiro-9,9'-bifluorene; 4,4',4''-tris(n,n-phenyl-3-methylphenylamino)triphenylamine; 4,4',n,n'-diphenylcarbazole.
[058] Polímeros derivados do politiofeno também podem ser utilizados e são selecionados dentre: poli[3-butiltiofeno- 2,5-diil]; poli[3-hexiltiofeno-2,5-diil]; poli[3-octil tiofeno-2,5-diil]; poli[3-decitiofeno-2,5-diil]; poli[3-metil -4-butiltiofeno -2,5- diil]; poli[3-metil -4-hexil tiofeno - 2,5-diil]; poli[3-metil-4-octiltiofeno-2,5-diil]; poli[3- metil-4-deciltiofeno-2,5-diil]; poli[3-butiltiofeno-2,5- diil]; poli[3-hexiltiofeno-2,5-diil]; poli[3-octil tiofeno- 2,5-diil]; poli[3-deciltiofeno-2,5-diil]; poli[3-(2-etil- isocianato-octadecanil)tiofeno]; poli[2-(3-tienil) etiloxi-4- butilsulfonato] sal sódio sal; poli[(9,9-dihexilfluorenil- 2,7-diil)-alt-co-(bitiofeno)]; poli[(9,9-dioctilfluorenil- 2,7-diil)-alt-co-(bitiofeno)]; poli (3,3’’’- didodecil quarter tiofeno).[058] Polythiophene-derived polymers can also be used and are selected from: poly[3-butylthiophene-2,5-diyl]; poly[3-hexylthiophene-2,5-diyl]; poly[3-octyl thiophene-2,5-diyl]; poly[3-decythiophene-2,5-diyl]; poly[3-methyl-4-butylthiophene-2,5-diyl]; poly[3-methyl-4-hexyl thiophene-2,5-diyl]; poly[3-methyl-4-octylthiophene-2,5-diyl]; poly[3-methyl-4-decylthiophene-2,5-diyl]; poly[3-butylthiophene-2,5-diyl]; poly[3-hexylthiophene-2,5-diyl]; poly[3-octyl thiophene-2,5-diyl]; poly[3-decylthiophene-2,5-diyl]; poly[3-(2-ethyl-isocyanato-octadecanyl)thiophene]; poly[2-(3-thienyl)ethyloxy-4-butylsulfonate] sodium salt; poly[(9,9-dihexylfluorenyl-2,7-diyl)-alt-co-(bitiophene)]; poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-co-(bitiophene)]; poly (3,3'''-didodecyl quarter thiophene).
[059] Polímeros polares compreendem aqueles contendo grupos hidroxila, como, por exemplo, poli(álcool vinílico) e seus copolímeros, poliacrilatos hidroxilados, dentre outros. Além desses, há ainda os polímeros contendo grupos iônicos, como polipirrol (PPi), poli (N-vinil carbazol) (PNVC), poli (estireno sulfonato) (PSS), poli (triaril amina) (PTAA), polivil pirrolidona, ácido poliacrílico, poliaminas, dentre outros.[059] Polar polymers comprise those containing hydroxyl groups, such as poly(vinyl alcohol) and its copolymers, hydroxylated polyacrylates, among others. In addition to these, there are also polymers containing ionic groups, such as polypyrrole (PPi), poly (N-vinyl carbazole) (PNVC), poly (styrene sulfonate) (PSS), poly (triaryl amine) (PTAA), polyvil pyrrolidone, polyacrylic, polyamines, among others.
[060] A classe de polímeros acrilatos também pode ser utilizada, sendo estes selecionados dentre: poli(metil metacrilato de metila), poli(acrilato de glicidila) e outros, além do ácido poli(acrílico).[060] The class of acrylate polymers can also be used, these being selected from: poly(methyl methyl methacrylate), poly(glycidyl acrylate) and others, in addition to poly(acrylic acid).
[061] Outros polímeros úteis pertencem à classe dos polímeros vinílicos como poliestireno, poli(alfa metil estireno), poli(cloreto de vinila), poliacrionitrila.[061] Other useful polymers belong to the class of vinyl polymers such as polystyrene, poly(alpha methyl styrene), poly(vinyl chloride), polyacryonitrile.
[062] São também úteis os poliésteres tanto aromáticos como alifáticos, como o poli(etileno tereftalato), poli(butileno tereftalato), as poliamidas, poliuretanas e poliimidas, bem como seus copolímeros.[062] Both aromatic and aliphatic polyesters are also useful, such as poly(ethylene terephthalate), poly(butylene terephthalate), polyamides, polyurethanes and polyimides, as well as their copolymers.
[063] Na última etapa do processo, o solvent orgânico é removido por evaporação ou por meio de alguma técnica de formação de pós ou péletes, tal como a secagem por pulverização (“spray-drying”). A remoção deve ser conduzida de modo a manter a suspensão coloidal estável, evitando, assim, a aglomeração da carga.[063] In the last step of the process, the organic solvent is removed by evaporation or by means of some technique for forming powders or pellets, such as spray-drying. Removal must be conducted in such a way as to keep the colloidal suspension stable, thus avoiding agglomeration of the filler.
[064] Assim, é obtido o material híbrido ou o nanocompósito na forma de filme ou na forma de pós ou péletes, adequados para o processamento futuro por fusão, por exemplo.[064] Thus, the hybrid material or the nanocomposite is obtained in the form of a film or in the form of powders or pellets, suitable for future processing by melting, for example.
[065] O material híbrido ou nanocompósito obtido pode ainda ser disperso em uma matriz polimérica no estado fundido (termoplásticos, elastômeros ou resinas), sendo utilizado como concentrado em vez de produto final.[065] The hybrid or nanocomposite material obtained can also be dispersed in a polymer matrix in the molten state (thermoplastics, elastomers or resins), being used as a concentrate instead of a final product.
[066] A concentração de nanopartículas dispersas no material híbrido é, tipicamente, superior a 25 % em massa. Todavia, qualquer concentração de nanopartículas no material seco pode ser obtida de acordo com o método descrito na presente invenção.[066] The concentration of nanoparticles dispersed in the hybrid material is typically greater than 25% by mass. However, any concentration of nanoparticles in the dry material can be obtained according to the method described in the present invention.
[067] A concentração ideal depende da utilização do produto final. No caso de filmes ativos de células fotovoltaicas, por exemplo, a concentração é, em geral, superior a 30 %. No caso de sensores, essa concentração pode variar de 1 a 50 % e, para filmes de poliolefinas ou materiais para uso geral (“commodity”), a concentração típica pode variar de 0,25 a 5% em massa.[067] The ideal concentration depends on the use of the final product. In the case of active films from photovoltaic cells, for example, the concentration is generally higher than 30%. In the case of sensors, this concentration can vary from 1 to 50% and, for polyolefin films or materials for general use (“commodity”), the typical concentration can vary from 0.25 to 5% by mass.
[068] A presente invenção é mais bem descrita pelo Exemplo abaixo e Figuras que o acompanham, ambos de caráter unicamente demonstrativo e não limitativo desta invenção.[068] The present invention is best described by the Example below and accompanying Figures, both of which are purely demonstrative and not limitative of this invention.
[069] O presente exemplo refere-se ao método de obtenção de um filme híbrido de um polímero com atividade fotovoltaica e nanopartículas de dióxido de titânio sobre um substrato de vidro recoberto com um filme condutor de índio/estanho, através das etapas descritas a seguir e conforme fluxograma apresentado na Figura 1:[069] The present example refers to the method of obtaining a hybrid film of a polymer with photovoltaic activity and titanium dioxide nanoparticles on a glass substrate covered with a conductive indium/tin film, through the steps described below. and according to the flowchart shown in Figure 1:
[070] Uma mistura composta por 60 ml de tetra-n-butil titanato e 60 ml de 2-propanol foi adicionada lentamente, por cerca de 15 minutos, a 600 ml de água destilada, na qual foram previamente adicionados 4 ml de ácido nítrico 70%, sob agitação constante.[070] A mixture composed of 60 ml of tetra-n-butyl titanate and 60 ml of 2-propanol was slowly added, for about 15 minutes, to 600 ml of distilled water, in which 4 ml of nitric acid were previously added. 70% under constant stirring.
[071] A solução resultante foi agitada por 2 horas a 30 °C e a mistura obtida foi aquecida sob agitação a 80 °C por 4 horas.[071] The resulting solution was stirred for 2 hours at 30 °C and the mixture obtained was heated under stirring at 80 °C for 4 hours.
[072] Ao final, o aquecimento foi retirado e a solução obtida foi mantida sob agitação por mais 12 horas. A suspensão coloidal foi caracterizada pela técnica de espalhamento de luz (Dynamic Light Scattering - DLS), sendo o diâmetro médio das nanopartículas de dióxido de titânio de 20 nm. A curva obtida por DLS da suspensão em água é apresentada na Figura 2D .[072] At the end, the heating was removed and the solution obtained was kept under stirring for another 12 hours. The colloidal suspension was characterized by the technique of light scattering (Dynamic Light Scattering - DLS), and the average diameter of the titanium dioxide nanoparticles was 20 nm. The curve obtained by DLS of the suspension in water is shown in Figure 2D.
[073] A concentração de nanopartículas de dióxido de titânio foi determinada pela técnica de gravimetria, obtendo- se aproximadamente 24 mg/ml.[073] The concentration of titanium dioxide nanoparticles was determined by the gravimetry technique, obtaining approximately 24 mg/ml.
[074] A técnica de Difração de Raios-X (X-Ray Diffraction - XRD) foi utilizada para a determinação das formas cristalinas de dióxido de titânio obtidas no processo, detectando a fase cristalina anatase e bruquita.[074] The X-Ray Diffraction (XRD) technique was used to determine the crystalline forms of titanium dioxide obtained in the process, detecting the crystalline phase anatase and bruquite.
[075] O produto final foi caracterizado por meio de medida de espalhamento de luz para se determinar o tamanho das partículas. De modo complementar, foi obtido um filme com a suspensão, que foi analisado por microscopia eletrônica de varredura.[075] The final product was characterized by measuring light scattering to determine the size of the particles. In addition, a film with the suspension was obtained, which was analyzed by scanning electron microscopy.
[076] Para uma parte (500 mL) de suspensão coloidal em água, foi adicionado lentamente sob agitação 500 mL de dimetil sulfóxido.[076] To one part (500 ml) of colloidal suspension in water, 500 ml of dimethyl sulfoxide was slowly added under stirring.
[077] A estabilidade da suspensão deve ser monitorada durante a adição. A mistura obtida é transferida para um rotoevaporador com banho de água aquecido a 70 - 80°C e a evaporação da água é realizada sob pressão reduzida.[077] Suspension stability should be monitored during addition. The mixture obtained is transferred to a rotoevaporator with a water bath heated to 70 - 80°C and the evaporation of the water is carried out under reduced pressure.
[078] O processo deve ser mantido até que o volume seja reduzido pela metade e se observe um aumento na temperatura de destilação, também acompanhado da sua diminuição.[078] The process must be maintained until the volume is reduced by half and an increase in the distillation temperature is observed, also accompanied by its decrease.
[079] O produto final foi caracterizado por meio de medida de espalhamento de luz para se determinar o tamanho das partículas. A curva de distribuição de tamanho das nanopartículas em DMSO é apresentada na Figura 2B. Curvas de distribuição de tamanho obtidas por DLS em NMP e em EG são apresentadas nas Figuras 2C e 2A, respectivamente.[079] The final product was characterized by measuring light scattering to determine the size of the particles. The size distribution curve of the nanoparticles in DMSO is shown in Figure 2B. Size distribution curves obtained by DLS in NMP and in EG are shown in Figures 2C and 2A, respectively.
[080] De modo complementar, foi obtido um filme com a suspensão, que foi analisado por microscopia eletrônica de varredura e de transmissão, respectivamente, apresentadas nas figuras 3A e 3B e 4. As nanopartículas de dióxido de titânio obtidas após evaporação do DMSO também foram analisadas por microscopia eletrônica de transmissão, estando representada na Figura 4.[080] In addition, a film with the suspension was obtained, which was analyzed by scanning and transmission electron microscopy, respectively, shown in figures 3A and 3B and 4. The titanium dioxide nanoparticles obtained after evaporation of DMSO also were analyzed by transmission electron microscopy, being represented in Figure 4.
[081] 160 mg de {di-tert-butil 3,3’-[2-(2,1,3-benzo tiadiazol-4-il)-7-(4-hexil-2-tienil)-9H-fluoreno-9,9-diil] dipropanoato} (OFeBT) foram dissolvidos em 10 mL de DMSO.[081] 160 mg of {di-tert-butyl 3,3'-[2-(2,1,3-benzothiadiazol-4-yl)-7-(4-hexyl-2-thienyl)-9H-fluorene -9,9-diyl]dipropanoate} (OFeBT) were dissolved in 10 ml of DMSO.
[082] A solução obtida foi filtrada em filtro de membrana de teflon com porosidade de 0,25 μm. A solução resultante foi adicionada lentamente à suspensão de dióxido de titânio / DMSO sob agitação constante.[082] The solution obtained was filtered through a teflon membrane filter with porosity of 0.25 μm. The resulting solution was slowly added to the titanium dioxide/DMSO suspension under constant stirring.
[083] A quantidade de suspensão utilizada foi de 71 μL, de modo que a concentração final resultante de nanopartículas, com base na quantidade de polímero, fosse de 1% em massa. A mistura resultante foi aquecida a 60 °C sob agitação por 8 h.[083] The amount of suspension used was 71 μL, so that the resulting final concentration of nanoparticles, based on the amount of polymer, was 1% by mass. The resulting mixture was heated at 60 °C under stirring for 8 h.
[084] A suspensão preparada em (c) é espalhada sobre o substrato de vidro/ITO e submetida à evaporação em estufa a 200°C por 1h para produzir um filme com 100 nm de espessura, composto por 99 % de polímero e 1% de dióxido de titânio.[084] The suspension prepared in (c) is spread over the glass/ITO substrate and subjected to evaporation in an oven at 200°C for 1h to produce a 100 nm thick film, composed of 99% polymer and 1% of titanium dioxide.
[085] Um filme de menor espessura foi também preparado diretamente em um suporte para microscopia eletrônica de transmissão e analisado por essa técnica. O resultado é apresentado em duas ampliações, uma de menor e outra de maior magnitude, respectivamente nas Figuras 5 e 6.[085] A thinner film was also prepared directly on a support for transmission electron microscopy and analyzed by this technique. The result is presented in two magnifications, one of smaller and one of greater magnitude, respectively in Figures 5 and 6.
[086] Os filmes produzidos foram tratados termicamente a 50, 130 e 200°C. Esses filmes foram analisados por difração de raio-X. Os difratogramas de raio-X para a amostra não tratada e tratada a 50, 150 e 200 °C são apresentados nas Figuras 7D, 7C, 7B e 7A, respectivamente.[086] The films produced were heat treated at 50, 130 and 200°C. These films were analyzed by X-ray diffraction. X-ray diffractograms for the untreated and treated sample at 50, 150 and 200°C are shown in Figures 7D, 7C, 7B and 7A, respectively.
[087] O método da presente invenção resolve a problemática da aglomeração da carga, um dos maiores desafios no preparo de nanocompósitos, em especial nanocompósitos de cargas de elevada energia de superfície em matrizes de baixa energia de superfície.[087] The method of the present invention solves the problem of filler agglomeration, one of the biggest challenges in the preparation of nanocomposites, especially nanocomposites of high surface energy fillers in low surface energy matrices.
[088] O método ora descrito apresenta eficiência muito superior quando comparados a processos do estado da técnica nos quais há a dispersão direta de nanopartículas no estado sólido, e constitui um avanço com relação aos processos que empregam matrizes poliméricas hidrossolúveis.[088] The method described here presents much higher efficiency when compared to state-of-the-art processes in which there is a direct dispersion of nanoparticles in the solid state, and constitutes an advance in relation to processes that employ water-soluble polymeric matrices.
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