BRPI1102638B1 - zeolite and mesoporous materials organized as filler for the formulation of rubber compounds, thermoplastic rubber, plastic and product manufacturing - Google Patents

zeolite and mesoporous materials organized as filler for the formulation of rubber compounds, thermoplastic rubber, plastic and product manufacturing Download PDF

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BRPI1102638B1
BRPI1102638B1 BRPI1102638-3A BRPI1102638A BRPI1102638B1 BR PI1102638 B1 BRPI1102638 B1 BR PI1102638B1 BR PI1102638 A BRPI1102638 A BR PI1102638A BR PI1102638 B1 BRPI1102638 B1 BR PI1102638B1
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rubber
organized
zeolite
parts
materials
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Michéle Oberson De Souza
Diana Exenberger Finkler
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Universidade Federal Do Rio Grande Do Sul
Frenzel Indústria De Plástico E Borracha Ltda
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Priority to PCT/BR2012/000200 priority patent/WO2012171090A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/405—Compounds of aluminium containing combined silica, e.g. mica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds

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

Abstract

ZEÓLITA E MATERIAIS MESOPOROSOS ORGANIZADOS COMO CARGA PARA A FORMULAÇÃO DE COMPOSTOS DE BORRACHA, BORRACHA TERMOPLÁSTICA, PLÁSTICO E FABRICAÇÃO DE PRODUTOS A presente invenção consiste na utilização de zeólitas e materiais mesoporosos organizados na formulação de composto de borracha, borracha termoplástica e plástico, como cargas inorgânicas, para sua aplicação na obtenção de artefatos usados em diversos segmentos da indústria, como, por exemplo, componentes de peças automotivas, peças mecânicas, peças de segurança, materiais 10 esportivos, pneus, máquinas agrícolas, embalagens, máquinas alimentícias e máquinas de fabricação de fármacos, entre outros, beneficiando-se do aumento de resistência mecânica, química e da diminuição da permeabilidade a líquidos e vapores.ZEOLITE AND MESOPOROUS MATERIALS ORGANIZED AS A LOAD FOR THE FORMULATION OF RUBBER COMPOUNDS, THERMOPLASTIC RUBBER, PLASTIC AND PRODUCT MANUFACTURING The present invention consists in the use of zeolites and mesoporous materials organized in the formulation of rubber compound, inorganic and plastic rubber, as thermoplastic and plastic fillers, , for its application in obtaining artifacts used in various segments of the industry, such as, for example, components of automotive parts, mechanical parts, safety parts, sports materials, tires, agricultural machinery, packaging, food machinery and machinery for manufacturing drugs, among others, benefiting from increased mechanical and chemical resistance and decreased permeability to liquids and vapors.

Description

Campo da InvençãoField of the Invention

A presente invenção consiste na utilização de zeólitas e materiais mesoporosos organizados na formulação de composto de borracha, borracha termoplástica e plástico, como cargas inorgânicas, para sua aplicação na obtenção de artefatos usados em diversos segmentos da indústria, como, por exemplo, componentes de peças automotivas, peças mecânicas, peças de segurança, materiais esportivos, pneus, máquinas agrícolas, embalagens, máquinas alimentícias e máquinas de fabricação de fármacos, entre outros, beneficiando-se do aumento de resistência mecânica, química e da diminuição da permeabilidade a líquidos e vapores. A contribuição da zeólita e do material mesoporoso organizado como carga inorgânica é devida a suas altas áreas específicas decorrentes de suas estruturas cristalinas e organizadas na escala nanométrica.The present invention consists of the use of zeolites and mesoporous materials organized in the formulation of rubber compounds, thermoplastic rubber and plastics, as inorganic fillers, for their application in obtaining artifacts used in various segments of the industry, such as parts components automotive, mechanical parts, safety parts, sporting materials, tires, agricultural machinery, packaging, food machinery and pharmaceutical manufacturing machines, among others, benefiting from increased mechanical and chemical resistance and reduced permeability to liquids and vapors . The contribution of zeolite and mesoporous material organized as an inorganic charge is due to their high specific areas resulting from their crystalline structures and organized on the nanometer scale.

Uso de zeólitas e de materiais mesoporosos organizados como carga nas borrachas Nitrílica (NBR), Nitrílica Hidrogenada (HNBR), Poliacrílica (ACM / AEM), Policloropreno (CR), Epicloridrina (ECO), Polietileno cloro-sulfonado (CSP), Silicone (MVQ), Elastômero de óxido de propeno, silicone fluorado (FMVQ), elastômero fluorado (FKM), elastômero perfluorado (FFKM), Poliuretano (PU), Natural (NR), Poliisopreno (IR), Polibutadieno (BR), Polibutadieno-estireno (SBR), Poli-etileno-propileno-dieno (EPDM), Poli-etilenopropileno (EPR), Butílica (HR), Butílica halogenada, Polietileno dorado (CPE), Fluorelastomero fosfonitrlico, Etileno vinil acetato (EVA) e Termoplásticas (TPU/ TPV/ TPO/ TPE/ TR), usadas para a confecção de peças com formato de membranas, foles, tubos e mangueiras para combustível e mangueiras para aplicações hidráulicas e/ou pneumáticas ou, pára transporte de hidrocarbonetos alifáticos, transporte de solventes, transporte de petróleo, transporte de alimentos, peças de borracha usadas na indústria do petróleo e da petroquímica, correias transportadoras, material de fricção, cobertura de rolos ou ainda para a confecção de peças de vedação, peças automotivas, peças mecânicas, peças de segurança, peças de funilaria, materiais esportivos, calçados, pneus, peças de construção civil, peças para a preparação de artigos de borrachas técnicas, máquinas agrícolas, embalagens, máquinas alimentícias e máquinas de fabricação de fármacos entre outros.Use of zeolites and mesoporous materials organized as fillers in rubbers Nitrile (NBR), Hydrogenated Nitrile (HNBR), Polyacrylic (ACM / AEM), Polychloroprene (CR), Epichlorohydrin (ECO), Chlorosulfonated polyethylene (CSP), Silicone ( MVQ), propylene oxide elastomer, fluorinated silicone (FMVQ), fluorinated elastomer (FKM), perfluorinated elastomer (FFKM), Polyurethane (PU), Natural (NR), Polyisoprene (IR), Polybutadiene (BR), Polybutadiene-styrene (SBR), Polyethylene-propylene-diene (EPDM), Poly-ethylene-propylene (EPR), Butyl (HR), Halogenated butyl, Dorado polyethylene (CPE), Phosphonitrile fluorelastomer, Ethylene vinyl acetate (EVA) and Thermoplastics (TPU / TPV / TPO / TPE / TR), used to make parts with the shape of membranes, bellows, tubes and hoses for fuel and hoses for hydraulic and / or pneumatic applications or, for the transportation of aliphatic hydrocarbons, solvent transportation, transportation of oil, food transport, used rubber parts those in the oil and petrochemical industry, conveyor belts, friction material, roller cover or even for the manufacture of sealing parts, automotive parts, mechanical parts, safety parts, body parts, sporting goods, shoes, tires, civil construction parts, parts for the preparation of technical rubber articles, agricultural machinery, packaging, food machinery and drug manufacturing machines, among others.

ESTADO DA ARTESTATE OF ART

A tecnologia atual de produção de artefatos de borracha empregados nas mais diversas aplicações da indústria utiliza cargas pretas e cargas brancas que auxiliam na melhoria de propriedades mecânicas, propriedades químicas e na diminuição da permeabilidade a gases e líquidos, mas que tem a desvantagem de prejudicar a processabilidade, proporcionalmente à quantidade de carga adicionada. Tais problemas constituem limitações significativas à aplicabilidade industrial de tais materiais.The current technology for the production of rubber artifacts used in the most diverse applications in the industry uses black charges and white charges that help to improve mechanical properties, chemical properties and decrease the permeability to gases and liquids, but which has the disadvantage of damaging the processability, in proportion to the amount of load added. Such problems constitute significant limitations to the industrial applicability of such materials.

Para aumentar a ação da carga para melhoria das propriedades da borracha procura-se aumentar a interação entre a borracha e a superfície da carga. Isso pode ser obtido empregando materiais inorgânicos com alta área específica, como carga, combinados a um agente de acoplamento, que é misturado fisicamente aos compostos da formulação da borracha. Esses agentes proporcionam um aumento de compatibilidade entre a carga e a borracha. Um exemplo típico é a melhoria das interações entre as hidroxilas da sílica e as duplas ligações carbono-carbono conjugadas da borracha. Por exemplo, a patente americana US Patent 6.279.633, de 20/04/2005, descreve a utilização de sílica precipitada, de área específica entre 110 e 130 m2 g'1, e organosilanos sulfurados como agente de acoplamento em uma borracha EPDM (terpolímero etileno-propileno-dieno).In order to increase the action of the load to improve the properties of the rubber, an attempt is made to increase the interaction between the rubber and the load surface. This can be achieved by employing inorganic materials with a high specific area, such as filler, combined with a coupling agent, which is physically mixed with the compounds of the rubber formulation. These agents provide an increased compatibility between the load and the rubber. A typical example is the improvement of interactions between silica hydroxyls and the conjugated carbon-carbon double bonds of rubber. For example, the US patent 6,279,633, of 04/20/2005, describes the use of precipitated silica, with a specific area between 110 and 130 m2 g'1, and sulfurized organosilanes as a coupling agent in an EPDM rubber ( ethylene-propylene-diene terpolymer).

Melhorias são encontradas no uso de agentes de acoplamento de tipo organomercaptosilanos modificados com fórmula geral (X)n(R7O)3-n Si R8-SH, sendo X um halogênio, R um radical alquil contendo de 1 a 18 carbonos como descrito na patente EP 1752488 (A2) (03/08/2006) que corresponde à obtenção de borracha destinada à fabricação de pneus.Improvements are found in the use of modified organomercaptosilane coupling agents with general formula (X) n (R7O) 3-n Si R8-SH, where X is a halogen, R is an alkyl radical containing from 1 to 18 carbons as described in the patent EP 1752488 (A2) (03/08/2006) which corresponds to obtaining rubber for the manufacture of tires.

A adição de cargas usuais como, por exemplo, negro de fumo, sílica e argila à borracha é acompanhada de melhoria relacionada às propriedades mecânicas, mas paralelamente o material apresenta um aumento nos valores de viscosidade Mooney. Esse comportamento da borracha contendo carga de reforço indica uma diminuição da fluidez do material e consequentemente corresponde a uma diminuição ou até a uma impossibilidade de processabilidade desse material conforme descrito para as borrachas nitrílicas em “Ohm, R. F., The Vanderbilt Rubber Handbook, 13a. Ed., Norwalk, 1990, páginas 478 e 479”. Esse efeito nefasto da adição de carga sobre a fluidez do material corresponde a uma limitação para alcançar melhorias das propriedades mecânicas das borrachas processadasfindustrialmente. Assim encontrar uma carga que melhor as propriedades mecânicas e de barreira sem prejudicar as propriedades de processabilidade, ou seja que permite a obtenção de uma borracha com índices de fluidez adequado para o processamento industrial é um objetivo a ser alcançado.The addition of usual fillers such as carbon black, silica and clay to rubber is accompanied by an improvement related to mechanical properties, but in parallel the material shows an increase in Mooney viscosity values. This behavior of rubber containing reinforcement load indicates a decrease in the fluidity of the material and consequently corresponds to a decrease or even an impossibility of processability of this material as described for the nitrile rubbers in “Ohm, R. F., The Vanderbilt Rubber Handbook, 13a. Ed., Norwalk, 1990, pages 478 and 479 ”. This harmful effect of the addition of charge on the fluidity of the material corresponds to a limitation to achieve improvements in the mechanical properties of industrially processed rubbers. Thus, finding a load that improves the mechanical and barrier properties without impairing the processability properties, in other words, that allows obtaining a rubber with adequate fluidity indexes for industrial processing is an objective to be achieved.

OBJETIVO DA INVENÇÃOOBJECTIVE OF THE INVENTION

A presente invenção corresponde à utilização de compostos silicoaluminatos cristalinos que possuem poros na escala nanométrica, chamados zeólitas e materiais mesoporosos organizados, como carga inorgânica, fazendo parte da formulação de borracha, borracha termoplástica ou plástico, utilizada para a manufatura de peças usadas em diversos segmentos da indústria que utilizam artefatos de borracha, borracha termoplástica ou plástico que necessitem possuir resistência mecânica, resistência química e resistência à permeação de líquidos e vapores e que apresentam elasticidade. O uso de zeólitas e materiais mesoporosos organizados permite a obtenção de matérias que apresentam melhorias relativas às propriedades de resistência mecânicas e resistência ao ataque por produtos químicos sendo que esses materiais continuem possuindo uma fluidez compatível com a processabilidade industrial.The present invention corresponds to the use of crystalline silicoaluminates that have pores on the nanoscale, called zeolites and organized mesoporous materials, such as inorganic filler, forming part of the formulation of rubber, thermoplastic rubber or plastic, used for the manufacture of parts used in various segments of the industry that use rubber, thermoplastic rubber or plastic artifacts that need mechanical resistance, chemical resistance and resistance to the permeation of liquids and vapors and that have elasticity. The use of zeolites and organized mesoporous materials allows the obtaining of materials that present improvements related to the mechanical resistance properties and resistance to attack by chemical products, with these materials still having a fluidity compatible with industrial processability.

DESCRIÇÃO DA INVENÇÃODESCRIPTION OF THE INVENTION

A adição de compostos silico-aluminatos cristalinos que possuem poros na escala nanométrica, chamados zeólitas ou materiais mesoporosos organizados, como componentes da carga para a borracha, borracha termoplástica ou plástico, que confere ao material o aumento de sua resistência em relação ao ataque por produtos químicos líquidos ou gasosos como, por exemplo, solventes e gasolina.The addition of crystalline silico-aluminate compounds that have pores on the nanoscale, called zeolites or organized mesoporous materials, as load components for rubber, thermoplastic rubber or plastic, which gives the material an increase in its resistance to attack by products liquid or gaseous chemicals such as solvents and gasoline.

Essa maior resistência química permite a obtenção de compostos mais eficientes para a produção de peças de vedação usadas em sistemas em contato com solventes voláteis líquidos ou vapores de solventes. A presença de compostos do tipo zeólitas e/ou materiais mesoporosos organizados, incorporados aos compostos de borracha, representa uma melhoria em termos de propriedade de barreira física e química do composto sem que suas propriedades de processabilidade sejam modificadas.This greater chemical resistance makes it possible to obtain more efficient compounds for the production of sealing parts used in systems in contact with liquid volatile solvents or solvent vapors. The presence of zeolite-type compounds and / or organized mesoporous materials, incorporated into the rubber compounds, represents an improvement in terms of the physical and chemical barrier properties of the compound without changing its processability properties.

A formulação do composto objeto comporta os seguintes elementos: a matriz polimérica, o sistema de carga, constituído por negro de fumo, sílica, zeólita e/ou material mesoporoso organizado, o agente de vulcanização, os aceleradores químicos, como por exemplo óxido de zinco; o agente plastificante; o auxiliar de processo; o antiozonante, o antioxidante e o agente de acoplamento. Esses elementos são misturados fisicamente em um misturador fechado ou aberto. Após o processo de mistura obtém-se o composto e com ele é realizada a vulcanização durante a qual ocorre a formação de ligações cruzadas através de reações químicas obtendo-se assim o artefato.The formulation of the object compound comprises the following elements: the polymeric matrix, the charging system, consisting of carbon black, silica, zeolite and / or organized mesoporous material, the vulcanizing agent, chemical accelerators, such as zinc oxide ; the plasticizer; the process assistant; the antiozonant, the antioxidant and the coupling agent. These elements are physically mixed in a closed or open mixer. After the mixing process, the compound is obtained and vulcanization is performed, during which cross-links are formed through chemical reactions, thus obtaining the artifact.

As propriedades reométricas do composto foram avaliadas, medindo o parâmetro de torque mínimo (ML), torque máximo (MH), tempo de Scorch (ts2) e tempo ótimo de vulcanização (t90).The rheometric properties of the compound were evaluated, measuring the minimum torque parameter (ML), maximum torque (MH), Scorch time (ts2) and optimal vulcanization time (t90).

Comparando-se compostos obtidos com adição de zeólita com materiais obtidos sem tal adição observa-se: i) o valor de ML não é alterado, o que indica que o material é adequado para ser processado; ii) o valor de MH apresenta um aumento proporcional à quantidade de zeólita adicionada, o que corresponde a um aumento na resistência mecânica ao alongamento; iii) os valores de ts2 e t90 diminuem o que significa que o composto inicia a sua vulcanização num tempo menor, o que corresponde a um efeito das interações da carga com a borracha.Comparing compounds obtained with the addition of zeolite with materials obtained without such addition, it is observed: i) the ML value is not changed, which indicates that the material is suitable for processing; ii) the MH value shows an increase proportional to the amount of zeolite added, which corresponds to an increase in the mechanical resistance to elongation; iii) the values of ts2 and t90 decrease which means that the compound starts its vulcanization in a shorter time, which corresponds to an effect of the interactions of the load with the rubber.

Comparando-se compostos obtidos com adição de zeólita com materiais obtidos sem tal adição, a dureza, medida conforme a norma ASTM D 2240, dos compostos contendo zeólita apresentam um aumento da dureza proporcional à quantidade de zeólita adicionada.Comparing compounds obtained with the addition of zeolite with materials obtained without such addition, the hardness, measured according to ASTM D 2240, of the compounds containing zeolite shows an increase in hardness proportional to the amount of zeolite added.

Comparando-se compostos obtidos com adição de zeólita com materiais obtidos sem tal adição, a tensão de ruptura, medida conforme a norma ASTM D 412, dos compostos contendo zeólita apresentam um aumento da tensão de ruptura proporcional à quantidade de zeólita adicionada. Esse resultado traduz o efeito da resistência mecânica associada à adição da zeólita para a borracha. A avaliação da propriedade do alongamento na ruptura, medida conforme a norma ASTM D 412, indica que a elasticidade do produto é conservada após a adição da zeólita.When comparing compounds obtained with the addition of zeolite with materials obtained without such addition, the rupture stress, measured according to the ASTM D 412 standard, of the compounds containing zeolite show an increase in the rupture stress proportional to the amount of zeolite added. This result reflects the effect of mechanical resistance associated with the addition of zeolite to rubber. The evaluation of the elongation property at break, measured in accordance with ASTM D 412, indicates that the product's elasticity is preserved after the addition of zeolite.

As propriedades acima avaliadas, ou seja, propriedades mecânicas, tensão de ruptura e o alongamento na ruptura, sendo que essa última caracteriza a elasticidade do material, podem ser modificas através da variação da quantidade de agente de acoplamento empregada.The properties evaluated above, that is, mechanical properties, tensile strength and elongation at break, the latter characterizing the elasticity of the material, can be modified by varying the amount of coupling agent employed.

A avaliação da resistência química foi feita através da imersão do produto utilizando a norma ASTM 471 em uma mistura de solventes composta de (expressa em % volumétrica): 42,2 % tolueno, 25,4 % isoctano, 12,7 % isobutileno, 4,2 % etanol, 15,0 % metanol, 0,5 % água deionizada, à qual são adicionados 20 ppm de ácido fórmico. Foi registrada a variação do volume do produto após uma imersão de 48 horas a 23° C. Em comparação com um composto sem zeólita ou sem materiais mesoporosos organizados, o valor de inchamento é reduzido comprovando que a adição de zeólita permite obter materiais com maior resistência química.The chemical resistance was evaluated by immersing the product using the ASTM 471 standard in a solvent mixture composed of (expressed in% volumetric): 42.2% toluene, 25.4% isoctane, 12.7% isobutylene, 4 , 2% ethanol, 15.0% methanol, 0.5% deionized water, to which 20 ppm formic acid are added. The variation in the volume of the product was recorded after immersion for 48 hours at 23 ° C. Compared to a compound without zeolite or without organized mesoporous materials, the swelling value is reduced, proving that the addition of zeolite allows to obtain materials with greater resistance chemistry.

A viscosidade Mooney do composto prevê o comportamento do composto para os processos que dependem do fluxo de material (no interior do molde ou durante o processo de injeção). Avalia-se através da viscosidade Mooney, conforme a norma ASTM 1646, que o material contendo zeólita ou materiais mesoporosos organizados como carga de reforço possui propriedade de processabilidade. Observa-se que o aumento da quantidade de zeólita não altera a processabilidade.The Mooney viscosity of the compound predicts the behavior of the compound for processes that depend on the material flow (inside the mold or during the injection process). It is evaluated through the Mooney viscosity, according to the ASTM 1646 standard, that the material containing zeolite or mesoporous materials organized as reinforcement filler has a processability property. It is observed that the increase in the amount of zeolite does not change the processability.

Comparando o invento com as formulações atuais que utilizam sistemas de cargas tradicionais (sílica, negro de fumo, carbonato de cálcio ou caulim) evidencia-se que quando incorporada à borracha, a zeólita ou os materiais mesoporosos organizados atuam como carga de reforço e agentes de resistência química (resistência ao inchamento quando em contado com solvente) e permite obter um composto de boa processabilidade levando a produtos cuja elasticidade é conservada.Comparing the invention with current formulations using traditional filler systems (silica, carbon black, calcium carbonate or kaolin), it is evident that when incorporated into rubber, zeolite or organized mesoporous materials act as reinforcing fillers and chemical resistance (resistance to swelling when in contact with solvent) and allows to obtain a compound of good processability leading to products whose elasticity is conserved.

EXEMPLOSEXAMPLES Exemplo 1:Example 1:

Obtenção de uma borracha NBR contendo 20 phr (phr do inglês parts per hundred of rubber1)de uma zeólita sintética do tipo Faujasita na forma sódica com uma área específica de 400 m2 g‘1 como carga de reforço. A formulação da borracha contem além da zeólita agentes de vulcanização, plastificante, auxiliar de processo, antiozonante e antioxidante.Obtaining an NBR rubber containing 20 phr (phr from English parts per hundred of rubber1) of a synthetic zuolite of the Faujasite type in sodium form with a specific area of 400 m2 g‘1 as reinforcement load. The rubber formulation contains, in addition to zeolite, vulcanizing agents, plasticizers, process aids, antiozones and antioxidants.

As propriedades reométricas do composto são: ML = 1,14 lb/in; MH = 33,2 lb/in; ts2 = 43 s e t90 = 146 s. A dureza (Shore A), medida conforme a norma ASTM D 2240 é igual a 73. A tensão de ruptura, medida conforme a norma ASTM D 412, é igual a 8,1 MPa. O alongamento do corpo de prova na ruptura, medido conforme a norma ASTM D 412, é de 223 %. A avaliação da resistência química é feita através da imersão do produto utilizando a norma ASTM 471 em uma mistura de solventes composta de (expressa em % volumétrica): 42,2 % tolueno, 25,4 % isoctano, 12,7 % isobutileno, 4,2 % etanol, 15,0 % metanol, 0,5 % água deionizada, à qual são adicionados 20 ppm de ácido fórmico. É registrada uma variação do volume do corpo de prova após uma imersão de 48 horas a 23° C de 30,1 %. É registrada uma variação do volume do produto após uma imersão de 48 horas a 23° C de 32,0 %. A viscosidade Mooney do composto medida conforme a norma ASTM 1646, é de 29.The rheometric properties of the compound are: ML = 1.14 lb / in; MH = 33.2 lb / in; ts2 = 43 s and t90 = 146 s. The hardness (Shore A), measured according to the ASTM D 2240 standard is equal to 73. The tensile strength, measured according to the ASTM D 412 standard, is 8.1 MPa. The elongation of the specimen at break, measured in accordance with ASTM D 412, is 223%. The chemical resistance is assessed by immersing the product using the ASTM 471 standard in a solvent mixture composed of (expressed in% volumetric): 42.2% toluene, 25.4% isoctane, 12.7% isobutylene, 4 , 2% ethanol, 15.0% methanol, 0.5% deionized water, to which 20 ppm formic acid are added. A variation in the volume of the specimen is recorded after an immersion of 48 hours at 23 ° C of 30.1%. A variation in the volume of the product is recorded after immersion of 48 hours at 23 ° C of 32.0%. The Mooney viscosity of the compound measured in accordance with ASTM 1646, is 29.

Exemplo 2:Example 2:

Obtenção de uma borracha NBR com a formulação do exemplo 1, mas com 30 phr de uma zeólita sintética do tipo Faujasita Y na forma sódica com uma área específica de 400 m2 g‘1 como carga de reforço.Obtaining an NBR rubber with the formulation of example 1, but with 30 phr of a synthetic zeolite of the type Faujasita Y in sodium form with a specific area of 400 m2 g'1 as reinforcement load.

As propriedades reométricas do composto são: ML = 1,17 I b/in; MH = 34,1 lb/in; ts2 = 42 s e t90 = 141 s. A dureza (Shore A), medida conforme a norma ASTM D 2240 é igual a 75. A tensão de ruptura, medida conforme a norma ASTM D 412, é igual a 8,1 MPa. O alongamento do corpo de prova na ruptura, medido conforme a norma ASTM D 412, é de 219 %. A avaliação da resistência química é feita através da imersão do produto utilizando a norma ASTM 471 em uma mistura de solventes composta de (expressa em % volumétrica): 42,2 % tolueno, 25,4 % isoctano, 12,7 % isobutileno, 4,2 % etanol, 15,0 % metanol, 0,5 % água deionizada, à qual são adicionados 20 ppm de ácido fórmico. É registrada uma variação do volume do corpo de prova após uma imersão de 48 horas a 23° C de 28,0 %. É registrada uma variação do volume do produto após uma imersão de 48 horas a 23° C de 30,1 %. A viscosidade Mooney do composto medida conforme a norma ASTM 1646, é de 28.The rheometric properties of the compound are: ML = 1.17 I b / in; MH = 34.1 lb / in; ts2 = 42 s and t90 = 141 s. The hardness (Shore A), measured according to the ASTM D 2240 standard, is equal to 75. The tensile strength, measured according to the ASTM D 412 standard, is 8.1 MPa. The elongation of the specimen at break, measured in accordance with ASTM D 412, is 219%. The chemical resistance is assessed by immersing the product using the ASTM 471 standard in a solvent mixture composed of (expressed in% volumetric): 42.2% toluene, 25.4% isoctane, 12.7% isobutylene, 4 , 2% ethanol, 15.0% methanol, 0.5% deionized water, to which 20 ppm formic acid are added. A variation in the volume of the specimen is recorded after an immersion of 48 hours at 23 ° C of 28.0%. A variation in the volume of the product is recorded after immersion of 48 hours at 23 ° C of 30.1%. The Mooney viscosity of the compound, measured according to ASTM 1646, is 28.

Exemplo 3:Example 3:

Obtenção de um composto de borracha fluorada (68,5 % em massa de flúor) cuja formulação é expressa em cem partes de borracha ou phr, contendo 7 phr de uma zeólita sintética do tipo A, na forma sódica com área específica 400 m2 g"1, como carga de reforço. A formulação da borracha contém além da zeólita, ativador, pigmento, auxiliar de processo.Obtaining a fluorinated rubber compound (68.5% fluorine by weight) whose formulation is expressed in one hundred parts of rubber or phr, containing 7 phr of a synthetic zeolite type A, in the sodium form with a specific area 400 m2 g " 1, as reinforcement filler.The rubber formulation contains in addition to zeolite, activator, pigment, process aid.

As propriedades reométricas do composto são: ML = 1,96 lb/in; MH = 31,55 lb/in; ts2 = 115 s e t90 = 147 s. A dureza (Shore A), medida conforme a norma ASTM D 2240 é igual a 67. A tensão de ruptura, medida conforme a norma ASTM D 412, é igual a 6,4 MPa. O alongamento do corpo de prova na 5 ruptura, medido conforme a norma ASTM D 412, é de 220 %. A avaliação da resistência química é feita através da imersão do produto utilizando a norma ASTM 471 em uma mistura de solventes composta de (expressa em % volumétrica): 42,2 % tolueno, 25,4 % isoctano, 12,7 % isobutileno, 4,2 % etanol, 15,0 % metanol, 0,5 % água deionizada, à qual são adicionados 20 ppm io de ácido fórmico. É registrada uma variação do volume do corpo de prova após uma imersão de 48 horas a 23° C de 23,0 %.The rheometric properties of the compound are: ML = 1.96 lb / in; MH = 31.55 lb / in; ts2 = 115 s and t90 = 147 s. The hardness (Shore A), measured in accordance with the ASTM D 2240 standard, is equal to 67. The tensile strength, measured in accordance with the ASTM D 412 standard, is equal to 6.4 MPa. The elongation of the specimen at 5 rupture, measured according to the ASTM D 412 standard, is 220%. The chemical resistance is assessed by immersing the product using the ASTM 471 standard in a solvent mixture composed of (expressed in% volumetric): 42.2% toluene, 25.4% isoctane, 12.7% isobutylene, 4 , 2% ethanol, 15.0% methanol, 0.5% deionized water, to which 20 ppm formic acid are added. A variation in the volume of the specimen is recorded after an immersion of 48 hours at 23 ° C of 23.0%.

Deve ficar evidente aos conhecedores da técnica que a presente invenção pode ser configurada de muitas outras formas específicas sem apartar-se do espírito ou do escopo da invenção. Particularmente, deve-se 15 compreender que a invenção pode ser configurada nas formas descritas.It should be apparent to those skilled in the art that the present invention can be configured in many other specific ways without departing from the spirit or scope of the invention. In particular, it should be understood that the invention can be configured in the ways described.

Portanto, os exemplos e configurações presentes devem ser considerados como ilustrativos e não restritivos, e a invenção não deve ser limitada aos detalhes fornecidos neste documento, mas podem ser modificados dentro do escopo e equivalência das reivindicações anexas.Therefore, the examples and configurations present should be considered as illustrative and not restrictive, and the invention should not be limited to the details provided in this document, but can be modified within the scope and equivalence of the attached claims.

Claims (9)

1. USO DE ZEÓLITA E MATERIAIS MESOPOROSOS ORGANIZADOS COMO CARGA PARA O PROCESSO DE OBTENÇÃO DE COMPOSTOS DE BORRACHA, fazendo parte da formulação da borracha, caracterizado pelo uso de zeólita, de materiais zeolíticos sulfurados, sendo que para esses materiais, podem ser variadas a natureza dos cátions compensadores de carga, a relação entre os átomos compondo a estrutura e a natureza dos átomos que formam sua estrutura porosa.1. USE OF ZEOLITE AND MESOPOROUS MATERIALS ORGANIZED AS A LOAD FOR THE PROCESS OF OBTAINING RUBBER COMPOUNDS, forming part of the rubber formulation, characterized by the use of zeolite, sulfurized zeolitic materials, and for these materials, the nature can be varied of charge-compensating cations, the relationship between the atoms composing the structure and the nature of the atoms that form their porous structure. 2. USO DE ZEÓLITAS E MATERIAIS MESOPOROSOS ORGANIZADOS, de acordo com a reivindicação 1, caracterizado por fazer parte da formulação das seguintes borrachas: Nitrílica (NBR), Nitrílica Hidrogenada (HNBR), Poliacrílica (ACM / AEM), Policloropreno (CR), Epicloridrina (ECO), Polietileno clorosulfonado (CSP), Silicone (MVQ), Elastômero de óxido de propeno, silicone fluorado (FMVQ), elastômero fluorado (FKM), elastômero perfluorado (FFKM), Poliuretano (PU), Natural (NR), Poliisopreno (IR), Polibutadieno (BR), Polibutadieno-estireno (SBR), Poli-etileno-propileno-dieno (EPDM), Poli-etilenopropileno (EPR), Butílica (IIR), Butílica halogenada, Polietileno clorado (CPE), Fluorelastomero fosfonitrlico, Etileno vinil acetato (EVA) e Termoplásticas (TPU/ TPV/ TPO/ TPE/ TR).2. USE OF ORGANIZED MESOPOROUS MATERIALS AND ZEOLITES, according to claim 1, characterized by being part of the formulation of the following rubbers: Nitrile (NBR), Hydrogenated Nitrile (HNBR), Polyacrylic (ACM / AEM), Polychloroprene (CR), Epichlorohydrin (ECO), Chlorosulfonated polyethylene (CSP), Silicone (MVQ), Propylene oxide elastomer, fluorinated silicone (FMVQ), fluorinated elastomer (FKM), perfluorinated elastomer (FFKM), Polyurethane (PU), Natural (NR), Polyisoprene (IR), Polybutadiene (BR), Polybutadiene-styrene (SBR), Polyethylene-propylene-diene (EPDM), Polyethylenepropylene (EPR), Butyl (IIR), Halogenated butyl, Chlorinated polyethylene (CPE), Fluorelastomer phosphonitrile, Ethylene vinyl acetate (EVA) and Thermoplastics (TPU / TPV / TPO / TPE / TR). 3. USO DE ZEÓLITAS E MATERIAIS MESOPOROSOS ORGANIZADOS, de acordo com a reivindicação 1, caracterizado pelas formulações conterem de A a F conforme abaixo (A) Uso de uma ou mais borrachas bases correspondendo a um total de 100 phr (B) 10 a 120 phr de carga reforçante, tais como negro de fumo, carbonato de cálcio ou caulim (C) 10 a 110 phr, de sílica (D) 6 a 110 phr de zeólita ou materiais mesoporosos organizados sendo que para as zeólitas, os materiais zeolíticos sulfurados, podem ser variadas a natureza dos cátions compensadores de carga, a relação entre os átomos compondo a estrutura e a natureza dos átomos que formam sua estrutura porosa (E) 0 a 7 phr de agentes de acoplamento tais como compostos organomercaptosilanos tais como: mercaptometiltrimetoxisilano, mercaptoetiltrimetoxisilano, mercaptopropiltrimetoxisilano, mercaptometiltrimetoxisilano, mercaptoetiltripropoxisilano e do composto mercaptopropiltrietoxisilano (F) 5 a 100 phr de plastificantes como: Aromático, Parafínico, Naftênico, Ésteres de ácido adípico, Éster sintético, Plastificante Resinoso Éster, DOS (Dioctil Sebaçato), DBP (Dibutil Ftalato), DOP (Dioctil Ftalato), BBP (Butilbenzil Ftalato), DIDP (Diisodelil Ftalato), DTDP (Ditridecil Ftalato), DUP (Diendercil Ftalato), DBEA (Dibutoxietil Adipato), DBEEA (Dibutoxietoxietil Adipato), DOA (Dioctil Adipato), DIDA (Diisodecil Adipato), DINA (Diisononil Adipato), ESO (Óleo de soja epoxidado), IDdPF (Isodecil Difenil Fosfato), TrAF Trialil Fosfato, Polimérico Sebaçato (Viscosidade 200.000 CPS), Polimérico (Viscosidade 3.300 CPS/ 5.800 CPS), Polimérico Gluterato (Viscosidade 12.000 CPS/ 24.000 CPS), TOTM (Trioctil Trimelitato), TIDTM (Triisodecil Trimelitato), TIOTM (Triisooctil Trimelitato), DBEEG (Di Dibutoxietil Gluterato), ou DBEG (Glutaratos butoxietoxietil Gluterato).3. USE OF ORGANIZED MESOPOROUS MATERIALS AND ZEOLITES, according to claim 1, characterized by the formulations containing from A to F as below (A) Use of one or more base rubbers corresponding to a total of 100 phr (B) 10 to 120 reinforcing charge phr, such as carbon black, calcium carbonate or kaolin (C) 10 to 110 phr, silica (D) 6 to 110 phr of zeolite or organized mesoporous materials and for zeolites, sulfurized zeolitic materials, the nature of the charge-compensating cations can be varied, the relationship between the atoms composing the structure and the nature of the atoms that form their porous structure (E) 0 to 7 phr of coupling agents such as organomercaptosilane compounds such as: mercaptomethyltrimethoxysilane, mercaptoethyltrimethoxysilane , mercaptopropyltrimethoxysilane, mercaptomethyltrimethoxysilane, mercaptoethyltripropoxysilane and the mercaptopropyltriethoxysilane compound (F) 5 to 100 phr of plasticizers such as: Aromatic, Paraffinic, Naf tonic, Adipic acid esters, Synthetic ester, Resin plasticizer Ester, DOS (Dioctyl Sebaceous), DBP (Dibutyl Phthalate), DOP (Dioctyl Phthalate), BBP (Butylbenzyl Phthalate), DIDP (Diisodelil Phthalate), DTDP (Ditridecyl Ftal) DUP (Diendercil Phthalate), DBEA (Dibutoxyethyl Adipate), DBEEA (Dibutoxyethoxyethyl Adipate), DOA (Dioctyl Adipate), DIDA (Diisodecyl Adipate), DINA (Diisononyl Adipate), ESO (Epoxidized Soybean Oil), IDdPil (IDDPF) IsodFil (IDDFF) Isod , TrAF Trialil Phosphate, Sebaçato Polymeric (Viscosity 200,000 CPS), Polymeric (Viscosity 3,300 CPS / 5,800 CPS), Polymeric Gluterate (Viscosity 12,000 CPS / 24,000 CPS), TOTM (Trioctyl Trimellitate), TIDTM (Triisodecyl Trimellitate), TIOTM ), DBEEG (Di Dibutoxyethyl Gluterate), or DBEG (Glutarates butoxyethoxyethyl Gluterate). 4. USO DE ZEÓLITAS E MATERIAIS MESOPOROSOS ORGANIZADOS, de acordo com a reivindicação 1, caracterizado pela zeólita e o composto mesoporoso organizado serem cargas de reforço fazendo parte da formulação que aumentam as propriedades mecânicas do composto de borracha e dos produtos com ele obtidos.4. USE OF ORGANIZED MESOPOROUS MATERIALS AND ZEOLITES, according to claim 1, characterized in that the zeolite and the organized mesoporous compound are reinforcing charges forming part of the formulation that increase the mechanical properties of the rubber compound and the products obtained with it. 5. USO DE ZEÓLITAS E MATERIAIS MESOPOROSOS ORGANIZADOS, de acordo com a reivindicação 1, caracterizado pela zeólita e o composto mesoporoso organizado aumentarem a resistência química da borracha.5. USE OF ORGANIZED MESOPOROUS MATERIALS AND ZEOLITES, according to claim 1, characterized by zeolite and the organized mesoporous compound increasing the chemical resistance of rubber. 6. USO DE ZEÓLITAS E MATERIAIS MESOPOROSOS ORGANIZADOS, de acordo com a reivindicação 1, caracterizado por aumentar a impermeabilidade a líquidos, gases e vapores.6. USE OF ORGANIZED MESOPOROUS MATERIALS AND ZEOLITES, according to claim 1, characterized by increasing the impermeability to liquids, gases and vapors. 7. USO DE ZEÓLITAS E MATERIAIS MESOPOROSOS ORGANIZADOS, de acordo com a reivindicação 1, caracterizado pela zeólita e o composto mesoporoso organizado permitirem obter um composto com melhoria de suas propriedades mecânicas, químicas de resistência à permeabilidade de líquidos, gases e vapores sem comprometer as propriedades de processabilidade para os processos que dependem do fluxo de material (no interior do molde ou durante o processo de injeção).7. USE OF ORGANIZED MESOPOROUS ZEOLITES AND MATERIALS, according to claim 1, characterized by the zeolite and the organized mesoporous compound allowing to obtain a compound with improvement of its mechanical, chemical properties of resistance to the permeability of liquids, gases and vapors without compromising the Processability properties for processes that depend on the material flow (inside the mold or during the injection process). 8. USO DE ZEÓLITAS E MATERIAIS MESOPOROSOS ORGANIZADOS, de acordo com a reivindicação 1, caracterizado por conservar as propriedades de elasticidade.8. USE OF ORGANIZED MESOPOROUS MATERIALS AND ZEOLITES, according to claim 1, characterized by conserving the elastic properties. 9. USO DE ZEÓLITAS E MATERIAIS MESOPOROSOS ORGANIZADOS, de acordo com a reivindicação 1, caracterizado pelo composto obtido após vulcanização poder ser usado para a confecção de peças com formato de membranas, foles, tubos e mangueiras para combustível e mangueiras para aplicações hidráulicas e/ou pneumáticas ou, para transporte de hidrocarbonetos alifáticos, transporte de solventes, transporte de petróleo, transporte de alimentos, peças de borracha usada na indústria do petróleo e da petroquímica, correias transportadoras, materiais de fricção, cobertura de rolos ou ainda para a confecção de peças de vedação, peças automotivas, peças mecânicas, peças de segurança, peças de funilaria, materiais esportivos, calçados, pneus, peças de construção civil, peças para a preparação de artigos de borrachas técnicas, máquinas agrícolas, embalagens, máquinas alimentícias e máquinas de fabricação de fármacos entre outros.9. USE OF ORGANIZED ZEOLIT AND MESOPOROUS MATERIALS, according to claim 1, characterized by the compound obtained after vulcanization can be used for the manufacture of parts with the shape of membranes, bellows, tubes and hoses for fuel and hoses for hydraulic and / or hydraulic applications or pneumatic or, for the transportation of aliphatic hydrocarbons, solvent transportation, oil transportation, food transportation, rubber parts used in the petroleum and petrochemical industry, conveyor belts, friction materials, roller covers or for the manufacture of sealing parts, automotive parts, mechanical parts, safety parts, body shop parts, sporting goods, shoes, tires, civil construction parts, parts for the preparation of technical rubber articles, agricultural machinery, packaging, food machinery and machinery manufacture of drugs, among others.
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