WO2011050427A1 - Polymer coating for metal pipes and production method - Google Patents

Polymer coating for metal pipes and production method Download PDF

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Publication number
WO2011050427A1
WO2011050427A1 PCT/BR2009/000358 BR2009000358W WO2011050427A1 WO 2011050427 A1 WO2011050427 A1 WO 2011050427A1 BR 2009000358 W BR2009000358 W BR 2009000358W WO 2011050427 A1 WO2011050427 A1 WO 2011050427A1
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WO
WIPO (PCT)
Prior art keywords
epoxy resin
film
metal
coatings
coating
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Application number
PCT/BR2009/000358
Other languages
French (fr)
Portuguese (pt)
Inventor
Marly Grinapel Lachtermacher
Peter Libimor Polak
Ronaldo Domingues Mansano
Paulo Roberto De Souza Mendes
Original Assignee
Petróleo Brasileiro S.A. - Petrobras
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Priority to PCT/BR2009/000358 priority Critical patent/WO2011050427A1/en
Publication of WO2011050427A1 publication Critical patent/WO2011050427A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L58/00—Protection of pipes or pipe fittings against corrosion or incrustation
    • F16L58/02—Protection of pipes or pipe fittings against corrosion or incrustation by means of internal or external coatings
    • F16L58/04—Coatings characterised by the materials used
    • F16L58/10—Coatings characterised by the materials used by rubber or plastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2254/00—Tubes
    • B05D2254/04—Applying the material on the interior of the tube
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B05D5/083—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified

Definitions

  • the present invention relates to polymeric metal pipe coatings, more specifically to two-layer polymeric coatings, an inner layer of an epoxy-fluorine fluoropolymer film in the range of 15% to 60% by mass.
  • Such coatings are useful in preventing corrosion and controlling deposit formation, especially paraffinic formed in metal piping for the transportation of petroleum and its derivatives.
  • Petroleum is a complex mixture of hydrocarbons, including high molecular weight n-paraffins. It is common in the petroleum industry during the production, transport and treatment stages that such paraffins form deposits as a result of changes in thermodynamic variables that alter their solubility.
  • paraffin deposits in subsea metal pipes, surface equipment, production column or reservoir rock can cause significant and increasing oil losses.
  • phase equilibrium is a function of the intrinsic characteristics of the oil and the variations in temperature and pressure during production.
  • the appearance of paraffinic deposits is manifested by the breakdown of this equilibrium, caused by the oil cooling and / or detachment of the lighter fractions originally dissolved in this oil.
  • Ideal internal coatings to minimize the formation of paraffin deposits in metal pipelines for oil transportation should therefore have low roughness, high hydrophobicity, and high adherence to the metal surface of the pipelines.
  • US 2006/0051561 describes a method for obtaining superhydrophobic coatings comprising the steps of applying a polymeric material, more specifically polybutadiene, to the surface of a substrate; plasma fluorination of the surface of the polymeric material employing gases such as SF 6 and compounds of formula CH X F. X , where x is an integer ranging from 0 to 3 ; followed by curing at least part of the polymeric material.
  • WO 2007/106611 describes a two-step process for depositing a fluorinated polymeric thin film with a 3% oxygen atomic percentage on the surface of a substrate with the aid of radio frequency (RF) plasma fluorination. ).
  • RF radio frequency
  • the first step comprises film deposition by exposing the surface of a substrate to an RF plasma comprising fluorine-containing molecular fragments generated by a precursor, more specifically hexafluoropropylene (C 3 F 6 ).
  • a precursor more specifically hexafluoropropylene (C 3 F 6 ).
  • the active sites of the formed film react with stable gas molecules. containing fluorine in the absence of plasma, making such films more stable and less susceptible to oxidation.
  • the polymeric films thus obtained have hydrophobic characteristics and lower susceptibility to oxidation, they still have difficulty adhering when applied directly to smooth surfaces such as metallic surfaces.
  • the present invention relates to polymeric metal pipe coatings consisting of an epoxy resin film having deposited on it a fluorine fluoropolymer film having a concentration of 15% to 60% by weight.
  • Such coatings have average roughness in the range of 0.1 to 1 pm, are superhydrophobic, ie, have contact angle with water greater than 140 degrees, and have good adhesion to metallic surfaces.
  • Another aspect of the invention is a method of depositing a film of a fluoropolymer on epoxy resin by plasma polymerization of fluorinated gases, where the plasma employed is so-called cold plasma, or non-thermal plasma.
  • cold plasma the reactions involved occur at low temperatures, close to room temperature, which prevents thermal degradation of the epoxy resin.
  • fluorinating agents, CF 4 , CHF 3 and SF 6 employed in such method present low toxicity and minimal environmental contamination.
  • the accompanying Figure 1 illustrates the paraffin deposition rate, represented by the ratio of mass variation (g) to deposition time (minutes), for the following surfaces: blasted carbon steel, commercial epoxy resin (B resins) and C) and for commercial epoxy resin B after deposition of a film of a fluoropolymer obtained by plasma polymerization of gases CF 4 and SF 6 .
  • the attached Figure 2 illustrates the paraffin detachment stress for the following surfaces: commercial epoxy resin C and commercial epoxy resin B after deposition of a fluoropolymer film obtained by plasma polymerization of gases such as: CF 4 , CHF 3 and SF 6 .
  • the accompanying Figure 3 illustrates the contact angle measurement of commercial epoxy resin B without the deposition of the fluoropolymer film.
  • the accompanying Figure 4 illustrates the contact angle measurement of commercial epoxy resin B following deposition of a fluoropolymer film by CF 4 plasma polymerization.
  • the accompanying Figure 5 illustrates the contact angle measurement of commercial epoxy resin B after deposition of a fluoropolymer film by SF 6 plasma plasma polymerization.
  • the polymeric coatings described below are applicable to the simultaneous control of corrosion and deposit formation in metal pipelines, especially paraffinic, formed in metal pipelines for petroleum transport.
  • Such coatings have a roughness between 0.1 pm and 1 pm and a contact angle of more than 140 degrees, consisting of two layers: a first layer comprising an epoxy resin film with a thickness ranging from 250 Mm to 550 pm; and a second a layer comprising a film of a fluoropolymer, with a thickness ranging from 10 nm to 5 pm, and with fluorine concentration ranging from 15% to 60% by weight.
  • the epoxy resins used are two-component, high solids, around 80% to 99% by mass, and low VOC (volatile organic products), preferably in the range of 130 g / kg to 160 g / kg of resin.
  • VOC volatile organic products
  • the adhesion capacity of these resins is a consequence of the polarity of the aliphatic ether and hydroxyl groups which often constitute the polymeric chain of the initial resin and the network of the cured system.
  • the polarity of these groups serves to create interaction forces between the polymeric chain of the epoxy resin and the metal surface adjacent to it.
  • a film of a fluoropolymer is deposited on the resin film.
  • epoxy by plasma polymerization of fluorinated gases.
  • the plasma polymerization process used in the present invention involves so-called cold plasma, or non-thermal plasma, as that the reactions involved occur at low temperatures, or even at room temperature, which prevents thermal degradation of the epoxy resin.
  • epoxy resin surface reactions In this process, epoxy resin surface reactions, corrosion reactions, and polymerization reactions of the gases employed as fluorinating agents occur simultaneously.
  • the predominance of either reaction will depend on the fluorinating agent employed, the operating parameters, and the chemical characteristics inherent in epoxy resin.
  • Highly fluorinated compounds such as CF 4 and SF 6 are useful as fluorinating agents as they are non-toxic and non-corrosive in their natural state and therefore easy to handle.
  • SF 6 is also used due to the properties of SF 4 species generated in its dissociation, which simultaneously promote oxygen extraction and surface dehydrofluorination / fluorination reaction mechanisms.
  • paraffin deposits already formed on the pipes treated in accordance with the present invention have less adherence to the coatings proposed herein, which is represented by the lower peel stress when compared to commercial coatings, as illustrated by figure 2.
  • Another aspect of the invention is a method for preparing polymeric coatings for metal pipes by RF plasma treatment of epoxy resin films. Said method comprises the following steps:
  • The. Prepare the surface of a metal pipe to obtain a surface with average roughness between 10 pm and 100 pm;
  • d. deposit a fluoropolymer film onto the surface of the epoxy resin film by radio frequency (RF) plasma polymerization employing fluorinated gases at a flow rate of 10 to 500 sccm, pressure ranging from 0.67 to 133.30 Pa and power RF in the range 10 W to 1200 W for a period of 1 to 180 minutes;
  • RF radio frequency
  • the application of the epoxy resin film to the surface of metal pipes should be preceded by the preparation of such surfaces by any of the known cleaning methods, such as mechanical cleaning, blasting, chemical cleaning, cleaning with the aid of steam and others to provide maximum adhesion of the epoxy resin film to the metal surface of the pipe.
  • cleaning methods such as mechanical cleaning, blasting, chemical cleaning, cleaning with the aid of steam and others to provide maximum adhesion of the epoxy resin film to the metal surface of the pipe.
  • the epoxy resins undergo the curing process.
  • solvent-free aromatic polyamine-based curing agents promote crosslinking in the structure of the epoxy resin, making them thermo-rigid materials with excellent mechanical, chemical and electrical insulation resistance.
  • the curing agent does not alter the characteristics of the rich film. in fluorine formed after plasma fluorination, provided that the fluorination is done on the cured resin, thus the importance of the order in which the steps are performed is clear.

Abstract

A polymer coating for metal pipes is described, more specifically a polymer coating with two layers, an internal layer formed by a film of epoxy resin and an external layer made of a fluoropolymer film with a fluorine concentration ranging from 15% to 60% by mass. This coating is useful for preventing corrosion and suppressing the formation of deposits in metal pipes.

Description

REVESTIMENTO POL1MÉR1CO PARA TUBULAÇÕES METÁLICAS E  POLYMERIC COATING FOR METAL PIPES AND
MÉTODO DE PREPARO PREPARATION METHOD
CAMPO DA INVENÇÃO FIELD OF INVENTION
A presente invenção diz respeito a revestimentos poliméricos para tubulações metálicas, mais especificamente a revestimentos poliméricos em duas camadas, uma camada interna de um filme de resina epóxi e uma camada externa de um filme de um fluorpolímero com concentração de flúor na faixa de 15% a 60%, em massa. Tais revestimentos são úteis na prevenção da corrosão e no controle da formação de depósitos, especialmente os parafínicos formados em tubulações metálicas para o transporte de petróleo e seus derivados.  The present invention relates to polymeric metal pipe coatings, more specifically to two-layer polymeric coatings, an inner layer of an epoxy-fluorine fluoropolymer film in the range of 15% to 60% by mass. Such coatings are useful in preventing corrosion and controlling deposit formation, especially paraffinic formed in metal piping for the transportation of petroleum and its derivatives.
FUNDAMENTOS DA INVENÇÃO BACKGROUND OF THE INVENTION
O petróleo é uma mistura complexa de hidrocarbonetos, incluindo n-parafinas de alto peso molecular. É comum na indústria de petróleo, durante as etapas de produção, transporte e tratamento, que tais parafinas formem depósitos em decorrência de modificações nas variáveis termodinâmicas que alteram sua solubilidade.  Petroleum is a complex mixture of hydrocarbons, including high molecular weight n-paraffins. It is common in the petroleum industry during the production, transport and treatment stages that such paraffins form deposits as a result of changes in thermodynamic variables that alter their solubility.
A formação de depósitos parafínicos, tanto nas tubulações metálicas submarinas, quanto nos equipamentos de superfície, na coluna de produção, ou na rocha reservatório, pode provocar significativas e crescentes perdas de petróleo.  The formation of paraffin deposits in subsea metal pipes, surface equipment, production column or reservoir rock can cause significant and increasing oil losses.
Tal fenómeno está associado ao equilíbrio de fases, sendo função das características intrínsecas do petróleo e das variações de temperatura e de pressão durante a produção. Assim sendo, o aparecimento de depósitos parafínicos se manifesta pela quebra deste equilíbrio, provocada pelo resfriamento do petróleo e/ou desprendimento das frações mais leves originalmente dissolvidas neste petróleo.  This phenomenon is associated with phase equilibrium, being a function of the intrinsic characteristics of the oil and the variations in temperature and pressure during production. Thus, the appearance of paraffinic deposits is manifested by the breakdown of this equilibrium, caused by the oil cooling and / or detachment of the lighter fractions originally dissolved in this oil.
Atualmente existem diversos métodos para evitar, ou ao menos minimizar a formação de depósitos de parafina em tubulações metálicas que compõe as linhas de transferência de petróleo, tais como: uso de inibidores químicos, tratamentos microbiológicos, uso de isolamento e aquecimento das tubulações metálicas, tratamento termoquímico, aplicação de revestimentos internos a parede das tubulações metálicas, dentre outros. There are currently several methods to prevent, or at least minimize the formation of paraffin deposits in metal pipes that make up the oil transfer lines, such as: chemical inhibitors, microbiological treatments, use of insulation and heating of metal pipes, thermochemical treatment, application of internal coatings to the wall of metal pipes, among others.
Os revestimentos internos ideais para minimizar a formação de depósitos parafínicos em tubulações metálicas para o transporte de petróleo devem possuir, portanto, baixa rugosidade, alta hidrofobicidade, além de alta aderência à superfície metálica das tubulações.  Ideal internal coatings to minimize the formation of paraffin deposits in metal pipelines for oil transportation should therefore have low roughness, high hydrophobicity, and high adherence to the metal surface of the pipelines.
Inúmeros estudos têm sido efetuados com o objetivo de se obter revestimentos com tais características.  Numerous studies have been performed with the objective of obtaining coatings with such characteristics.
O documento US 2006/0051561, descreve um método para obtenção de revestimentos super-hidrofóbicos, compreendendo as etapas de aplicação de um material polimérico, mais especificamente o polibutadieno, a superfície de um substrato; a fluoração por plasma da superfície do material polimérico, empregando gases tais como o SF6 e compostos de fórmula CHXF .X, onde x é um número inteiro variando de 0 a 3; seguida da cura de pelo menos parte do material polimérico. Embora este método proporcione a obtenção de revestimentos super-hidrofóbicos, há o inconveniente de levar a um aumento da rugosidade da superfície do material polimérico após a fluoração, o que pode levar a formação de depósitos sobre o revestimento. US 2006/0051561 describes a method for obtaining superhydrophobic coatings comprising the steps of applying a polymeric material, more specifically polybutadiene, to the surface of a substrate; plasma fluorination of the surface of the polymeric material employing gases such as SF 6 and compounds of formula CH X F. X , where x is an integer ranging from 0 to 3 ; followed by curing at least part of the polymeric material. Although this method provides for obtaining super hydrophobic coatings, there is the disadvantage of leading to increased surface roughness of the polymeric material after fluorination, which may lead to deposits on the coating.
No documento WO 2007/106611 é descrito um processo em duas etapas para a deposição de um filme fino polimérico fluorado, com percentual atómico de oxigénio de 3%, sobre a superfície de um substrato com o auxílio da fluoração por plasma de rádio frequência (RF).  WO 2007/106611 describes a two-step process for depositing a fluorinated polymeric thin film with a 3% oxygen atomic percentage on the surface of a substrate with the aid of radio frequency (RF) plasma fluorination. ).
A primeira etapa compreende a deposição do filme pela exposição da superfície de um substrato a um plasma de RF, compreendendo fragmentos moleculares contendo flúor, gerados por um precursor, mais especificamente o hexafluoropropileno (C3F6). Numa segunda etapa, os sítios ativos do filme formado reagem com moléculas de gases estáveis contendo flúor, na ausência de plasma, tornando tais filmes mais estáveis e menos suscetíveis a oxidação. The first step comprises film deposition by exposing the surface of a substrate to an RF plasma comprising fluorine-containing molecular fragments generated by a precursor, more specifically hexafluoropropylene (C 3 F 6 ). In a second step, the active sites of the formed film react with stable gas molecules. containing fluorine in the absence of plasma, making such films more stable and less susceptible to oxidation.
Embora os filmes poliméricos assim obtidos tenham características hidrofóbicas, e menor suscetibilidade à oxidação, estes ainda apresentam dificuldade de adesão quando aplicados diretamente a superfícies lisas, tais como superfícies metálicas.  Although the polymeric films thus obtained have hydrophobic characteristics and lower susceptibility to oxidation, they still have difficulty adhering when applied directly to smooth surfaces such as metallic surfaces.
Portanto, não há na literatura, descrição nem sugestão de revestimentos que apresentem simultaneamente alta hidrofobicidade, rugosidade reduzida, e, portanto, propriedade antiaderente, sem prejuízo da aderência de tais revestimentos a superfície em que serão aplicados. SUMÁRIO DA INVENÇÃO  Therefore, there is no literature, description or suggestion of coatings that present simultaneously high hydrophobicity, reduced roughness, and therefore non-stick property, without prejudice to the adhesion of such coatings to the surface to which they will be applied. SUMMARY OF THE INVENTION
De um modo amplo, a presente invenção trata de revestimentos poliméricos para tubulações metálicas constituídos por um filme de resina epóxi tendo depositado sobre ele um filme de um fluorpolímero com concentração de flúor variando de 15% a 60% em massa.  Broadly, the present invention relates to polymeric metal pipe coatings consisting of an epoxy resin film having deposited on it a fluorine fluoropolymer film having a concentration of 15% to 60% by weight.
Tais revestimentos apresentam rugosidade média na faixa de 0,1 a 1 pm, são super-hidrofóbicos, ou seja, apresentam ângulo de contato com a água superior a 140 graus, além de possuírem boa aderência a superfícies metálicas.  Such coatings have average roughness in the range of 0.1 to 1 pm, are superhydrophobic, ie, have contact angle with water greater than 140 degrees, and have good adhesion to metallic surfaces.
Estas características permitem a aplicação destes revestimentos como revestimentos anticorrosivos e antiaderentes em tubulações metálicas, em especial em tubulações metálicas para transporte de petróleo, já que sua propriedade antiaderente minimiza a formação de depósitos parafínicos.  These characteristics allow the application of these coatings as anti-corrosion and non-stick coatings on metal pipelines, especially metal pipelines for oil transport, as their non-stick property minimizes the formation of paraffin deposits.
Outro aspecto da invenção é um método de deposição de um filme de um fluorpolímero sobre resina epóxi, pela polimerização por plasma de gases fluorados, onde o plasma empregado é o chamado plasma a frio, ou plasma não-térmico. No plasma a frio as reações envolvidas ocorrem a baixas temperaturas, próximas à temperatura ambiente, o que evita a degradação térmica da resina epóxi. Além disso, os agentes de fluoração, CF4, CHF3 e SF6, empregados em tal método apresentam baixa toxicidade e mínima contaminação ambiental. Another aspect of the invention is a method of depositing a film of a fluoropolymer on epoxy resin by plasma polymerization of fluorinated gases, where the plasma employed is so-called cold plasma, or non-thermal plasma. In cold plasma the reactions involved occur at low temperatures, close to room temperature, which prevents thermal degradation of the epoxy resin. In addition, fluorinating agents, CF 4 , CHF 3 and SF 6 , employed in such method present low toxicity and minimal environmental contamination.
BREVE DESCRIÇÃO DOS DESENHOS BRIEF DESCRIPTION OF DRAWINGS
A Figura 1 , anexa, ilustra a taxa de deposição de parafina, representada pela relação entre a variação de massa (g) em relação ao tempo de deposição (minutos), para as seguintes superfícies: aço carbono jateado, resina epóxi comercial (resinas B e C) e para a resina epóxi comercial B após deposição de um filme de um fluorpolímero, obtido pela polimerização por plasma dos gases CF4 e SF6. The accompanying Figure 1 illustrates the paraffin deposition rate, represented by the ratio of mass variation (g) to deposition time (minutes), for the following surfaces: blasted carbon steel, commercial epoxy resin (B resins) and C) and for commercial epoxy resin B after deposition of a film of a fluoropolymer obtained by plasma polymerization of gases CF 4 and SF 6 .
A Figura 2, anexa, ilustra a tensão de descolamento da parafina para as seguintes superfícies: resina epóxi comercial C e para a resina epóxi comercial B após deposição de um filme de um fluorpolímero, obtido pela polimerização por plasma de gases como o: CF4, CHF3 e SF6. The attached Figure 2 illustrates the paraffin detachment stress for the following surfaces: commercial epoxy resin C and commercial epoxy resin B after deposition of a fluoropolymer film obtained by plasma polymerization of gases such as: CF 4 , CHF 3 and SF 6 .
A Figura 3, anexa, ilustra a medida do ângulo de contato da resina epóxi comercial B sem a deposição do filme de fluorpolímero.  The accompanying Figure 3 illustrates the contact angle measurement of commercial epoxy resin B without the deposition of the fluoropolymer film.
A Figura 4, anexa, ilustra a medida do ângulo de contato da resina epóxi comercial B, após a deposição de um filme de um fluorpolímero pela polimerização por plasma de CF4. The accompanying Figure 4 illustrates the contact angle measurement of commercial epoxy resin B following deposition of a fluoropolymer film by CF 4 plasma polymerization.
A Figura 5, anexa, ilustra a medida do ângulo de contato da resina epóxi comercial B, após a deposição de um filme de um fluorpolímero pela polimerização por plasma do gás SF6. The accompanying Figure 5 illustrates the contact angle measurement of commercial epoxy resin B after deposition of a fluoropolymer film by SF 6 plasma plasma polymerization.
DESCRIÇÃO DETALHADA DA INVENÇÃO  DETAILED DESCRIPTION OF THE INVENTION
Os revestimentos poliméricos descritos a seguir são aplicáveis ao controle simultâneo da corrosão e da formação de depósitos em tubulações metálicas, especialmente os parafí nicos, formados em tubulações metálicas para o transporte de petróleo.  The polymeric coatings described below are applicable to the simultaneous control of corrosion and deposit formation in metal pipelines, especially paraffinic, formed in metal pipelines for petroleum transport.
Tais revestimentos apresentam rugosidade entre 0,1 pm e 1 pm e ângulo de contato superior a 140 graus, sendo constituídos por duas camadas: uma primeira camada que compreende um filme de resina epóxi, com espessura que varia entre 250 Mm e 550 pm; e uma segunda camada que compreende um filme de um fluorpolímero, de espessura que varia entre de 10 nm a 5 pm, e com concentração de flúor variando de 15% a 60 % em massa. Such coatings have a roughness between 0.1 pm and 1 pm and a contact angle of more than 140 degrees, consisting of two layers: a first layer comprising an epoxy resin film with a thickness ranging from 250 Mm to 550 pm; and a second a layer comprising a film of a fluoropolymer, with a thickness ranging from 10 nm to 5 pm, and with fluorine concentration ranging from 15% to 60% by weight.
As resinas epóxi utilizadas são bi-componente, com alto teor de sólidos, em torno de 80% a 99% em massa, e de baixo teor de VOC (produtos orgânicos voláteis), preferencialmente na faixa de 130 g/kg a 160 g/kg de resina. O uso de tais resinas deve-se ao fato destas apresentarem alta capacidade de adesão a superfícies metálicas e excelente resistência química.  The epoxy resins used are two-component, high solids, around 80% to 99% by mass, and low VOC (volatile organic products), preferably in the range of 130 g / kg to 160 g / kg of resin. The use of such resins is due to their high adhesion capacity to metallic surfaces and excellent chemical resistance.
A capacidade de adesão destas resinas é consequência da polaridade dos grupos éteres e hidroxilas alifáticas que, frequentemente, constituem a cadeia polimérica da resina inicial e a rede do sistema curado. A polaridade desses grupos serve para criar forças de interação entre a cadeia polimérica da resina epóxi e a superfície metálica adjacente a ela.  The adhesion capacity of these resins is a consequence of the polarity of the aliphatic ether and hydroxyl groups which often constitute the polymeric chain of the initial resin and the network of the cured system. The polarity of these groups serves to create interaction forces between the polymeric chain of the epoxy resin and the metal surface adjacent to it.
As resinas epóxi tradicionais, embora apresentem alta adesividade, são susceptíveis a absorção de umidade, devido à presença dos grupos hidroxil em sua estrutura molecular. A difusão da água absorvida até a interface metal-resina pode promover a corrosão da superfície metálica em ambientes de alta umidade. Além disto, os revestimentos de resinas epóxi tradicionais possuem alta tensão superficial, o que acaba por facilitar a aderência e o acúmulo de depósitos de compostos orgânicos em geral sobre tais revestimentos.  Traditional epoxy resins, although highly adhesive, are susceptible to moisture absorption due to the presence of hydroxyl groups in their molecular structure. Diffusion of absorbed water to the metal-resin interface can promote corrosion of the metal surface in high humidity environments. In addition, traditional epoxy resin coatings have high surface tension, which facilitates the adhesion and buildup of deposits of organic compounds on such coatings.
Para modificar a tensão superficial de revestimentos à base de resinas epóxi tradicionais e também aumentar o seu caráter hidrofóbico, minimizando assim a formação de depósitos e a absorção/difusão de água em tais revestimentos, é depositado um filme de um fluorpolímero sobre o filme de resina epóxi, pela polimerização por plasma de gases fluorados.  To modify the surface tension of traditional epoxy resin coatings and also increase their hydrophobic character, thereby minimizing deposit formation and water absorption / diffusion in such coatings, a film of a fluoropolymer is deposited on the resin film. epoxy, by plasma polymerization of fluorinated gases.
O processo de polimerização por plasma utilizado na presente invenção envolve o chamado plasma frio, ou plasma não-térmico, visto que as reações envolvidas ocorrem a baixas temperaturas, ou até mesmo à temperatura ambiente, o que evita a degradação térmica da resina epóxi. The plasma polymerization process used in the present invention involves so-called cold plasma, or non-thermal plasma, as that the reactions involved occur at low temperatures, or even at room temperature, which prevents thermal degradation of the epoxy resin.
Neste processo, ocorrem simultaneamente, reações na superfície da resina epóxi, reações de corrosão, e de polimerização dos gases empregados como agentes de fluoração. A predominância de uma ou outra reação vai depender do agente de fluoração empregado, dos parâmetros de operação, além das características químicas inerentes a resina epóxi.  In this process, epoxy resin surface reactions, corrosion reactions, and polymerization reactions of the gases employed as fluorinating agents occur simultaneously. The predominance of either reaction will depend on the fluorinating agent employed, the operating parameters, and the chemical characteristics inherent in epoxy resin.
Compostos altamente fluorados tais como o CF4 e o SF6 são úteis como agentes de fluoração, já que são não-tóxicos e não-corrosivos em seu estado natural e, portanto, de fácil manuseio. Highly fluorinated compounds such as CF 4 and SF 6 are useful as fluorinating agents as they are non-toxic and non-corrosive in their natural state and therefore easy to handle.
A interação de plasmas de CF com a resina epóxi resulta na formação de grupos CF e CF2 na superfície da resina, promovendo a polimerização por plasma do CF4 e a deposição de um filme de um fluorpolimero na superfície da resina epóxi, com concentração de flúor superior a 40% em massa. The interaction of CF plasmas with epoxy resin results in the formation of CF and CF 2 groups on the resin surface, promoting CF 4 plasma polymerization and the deposition of a fluoropolymer film on the epoxy resin surface, with a concentration of fluorine exceeding 40% by weight.
Além da polimerização por plasma do CF4( há, em menor extensão, a incorporação de flúor, proveniente da dissociação do CF4, à cadeia polimérica da resina epóxi. Esta incorporação de flúor à resina promove o ancoramento do filme de fluorpolimero formado à resina epóxi, devido à substituição dos átomos de hidrogénio da cadeia polimérica da resina epóxi por átomos de flúor. In addition to CF 4 plasma polymerization ( there is, to a lesser extent, fluorine incorporation from CF 4 dissociation into the polymer chain of the epoxy resin. epoxy, due to the replacement of hydrogen atoms in the polymeric chain of the epoxy resin with fluorine atoms.
O SF6 é também utilizado devido às propriedades das espécies SF4 geradas na sua dissociação, que promovem simultaneamente a extração do oxigénio e os mecanismos de reação superficiais de dehidro-fluoração/ fluoração. SF 6 is also used due to the properties of SF 4 species generated in its dissociation, which simultaneously promote oxygen extraction and surface dehydrofluorination / fluorination reaction mechanisms.
Tais propriedades levam à deposição de um filme de um fluorpolimero sobre a resina epóxi, com concentração de flúor de aproximadamente 20% em massa, havendo a incorporação simultânea de enxofre à resina epóxi de cerca de 25% em massa. A formação de filmes finos poliméricos sobre a superfície da resina epóxi promove a redução da tensão superficial e um aumento do ângulo de contato com a água, para valores superiores a 140 graus, o que caracteriza tais superfícies como super-hidrofóbicas, como podemos observar nas figuras 4 e 5. Such properties lead to the deposition of a fluoropolymer film on the epoxy resin, with fluorine concentration of approximately 20 wt%, with the simultaneous incorporation of sulfur into the epoxy resin of about 25 wt%. The formation of polymeric thin films on the surface of the epoxy resin promotes the reduction of surface tension and an increase of contact angle with water to values above 140 degrees, which characterizes such surfaces as superhydrophobic, as we can see in the Figures 4 and 5.
Os revestimentos compostos pela resina epóxi, tendo depositados sobre esta filmes finos altamente fluorados por polimerização por plasma, tal como os aqui descritos, apresentam uma menor taxa de deposição de parafina, se comparados aos revestimentos à base de resina epóxi tradicionais, como pode ser visto através das retas de tendência de formação de depósitos parafinicos apresentadas na figura 1. Além disso, a tendência de deposição apresenta-se mais significativa após 10 minutos de teste, conforme a figura 1 , mostrando que a quantidade de parafina depositada nos revestimentos da presente invenção diminui ao longo do tempo.  Coatings composed of epoxy resin, having deposited thereon highly fluorinated plasma polymerization thin films, such as those described herein, have a lower paraffin deposition rate compared to traditional epoxy resin coatings, as can be seen. In addition, the deposition tendency is more significant after 10 minutes of testing, as shown in Figure 1, showing that the amount of paraffin deposited on the coatings of the present invention. decreases over time.
Ainda há que se destacar que os depósitos de parafina já formados sobre as tubulações tratadas de acordo com a presente invenção, possuem menor aderência aos revestimentos aqui propostos, o que é representado pela menor tensão de descolamento, quando comparadas a revestimentos comerciais, conforme ilustra a figura 2.  It should also be noted that paraffin deposits already formed on the pipes treated in accordance with the present invention have less adherence to the coatings proposed herein, which is represented by the lower peel stress when compared to commercial coatings, as illustrated by figure 2.
Outro aspecto da invenção é um método para preparo de revestimentos poliméricos para tubulações metálicas, pelo tratamento por plasma de RF de filmes de resina epóxi. O dito método compreende as seguintes etapas:  Another aspect of the invention is a method for preparing polymeric coatings for metal pipes by RF plasma treatment of epoxy resin films. Said method comprises the following steps:
a. Preparar a superfície de uma tubulação metálica, de modo a obter uma superfície com rugosidade média entre 10 pm e 100 pm;  The. Prepare the surface of a metal pipe to obtain a surface with average roughness between 10 pm and 100 pm;
b. aplicar um filme de resina epóxi compreendendo um agente de cura totalmente disperso na resina epóxi, à superfície metálica previamente preparada; c. promover a cura do filme de resina epóxi, por aquecimento a temperaturas variando na faixa de 20°C a 45°C, num período de 1 a 6 horas; B. applying an epoxy resin film comprising a fully dispersed curing agent on the epoxy resin to the previously prepared metal surface; ç. promote curing of the epoxy resin film by heating at temperatures ranging from 20 ° C to 45 ° C over a period of 1 to 6 hours;
d. depositar um filme de um fluorpolímero sobre a superfíce do filme de resina epóxi por polimerização por plasma de radio frequência (RF), empregando gases fluorados, numa vazão de 10 a 500 sccm, pressão variando de 0,67 a 133,30 Pa e potência RF na faixa de 10 W a 1200 W, por um período de 1 a 180 minutos ;  d. deposit a fluoropolymer film onto the surface of the epoxy resin film by radio frequency (RF) plasma polymerization employing fluorinated gases at a flow rate of 10 to 500 sccm, pressure ranging from 0.67 to 133.30 Pa and power RF in the range 10 W to 1200 W for a period of 1 to 180 minutes;
Preferencialmente, a aplicação do filme de resina epóxi sobre a superfície de tubulações metálicas deve ser precedida pelo preparo de tais superfícies, por quaisquer dos métodos de limpeza conhecidos, tais como a limpeza mecânica, o jateamento, a limpeza química, a limpeza com auxílio de vapor e outras, de modo a proporcionar o máximo de aderência do filme de resina epóxi à superfície metálica da tubulação.  Preferably, the application of the epoxy resin film to the surface of metal pipes should be preceded by the preparation of such surfaces by any of the known cleaning methods, such as mechanical cleaning, blasting, chemical cleaning, cleaning with the aid of steam and others to provide maximum adhesion of the epoxy resin film to the metal surface of the pipe.
A aplicação de tais resinas a superfícies metálicas de dutos é efetuada de acordo com os métodos já conhecidos, como a aplicação pela utilização de spray, por meio de pistolas.  The application of such resins to metal duct surfaces is carried out in accordance with known methods such as spray application by means of spray guns.
Após a aplicação, as resinas epóxi são submetidas ao processo de cura. Neste processo, os agentes de cura, líquidos à base de poliamina aromática, livres de solventes, promovem a formação de ligações cruzadas na estrutura da resina epóxi, tornando-as materiais termorrígidos, com excelente resistência mecânica, química e de isolação elétrica.  After application, the epoxy resins undergo the curing process. In this process, solvent-free aromatic polyamine-based curing agents promote crosslinking in the structure of the epoxy resin, making them thermo-rigid materials with excellent mechanical, chemical and electrical insulation resistance.
Ainda deve-se esclarecer que a fluoração por plasma da resina epóxi não seria possível antes de a cura ser efetuada, já que materiais voláteis, tais como os agentes de cura, que compõe a resina epóxi, ao serem expostos ao vácuo, seriam degradados pela vaporização em alta velocidade, comprometendo as propriedades do revestimento final obtido.  It should also be clarified that plasma fluorination of the epoxy resin would not be possible before curing was performed, as volatile materials such as the curing agents that make up the epoxy resin upon exposure to vacuum would be degraded by vaporization at high speed, compromising the properties of the final coating obtained.
O agente de cura, porém, não altera as características do filme rico em flúor formado após a fluoração por plasma, desde que a fluoração seja feita na resina já curada, ficando, portanto, clara a importância da ordem em que as etapas são efetuadas. The curing agent, however, does not alter the characteristics of the rich film. in fluorine formed after plasma fluorination, provided that the fluorination is done on the cured resin, thus the importance of the order in which the steps are performed is clear.

Claims

REIVINDICAÇÕES
1- REVESTIMENTO POLIMÉRICO PARA TUBULAÇÕES METÁLICAS, caracterizado por ser constituído por pelo menos duas camadas: uma camada interna de um filme de resina epóxi com espessura entre 250 e 550 μιτι, e uma camada externa de um filme de um fluorpolímero com espessura entre 10 nm e 5 pm com concentração de flúor na faixa entre 15% a 60% em massa, de modo a apresentar rugosidade média de 0,1 Mm a 1 Mm e ângulo de contato com a água maior que 140 graus. 1- POLYMERIC COATING FOR METAL PIPES, characterized in that it consists of at least two layers: an inner layer of an epoxy resin film between 250 and 550 μιτι, and an outer layer of a fluoropolymer film between 10 nm. and 5 pm with fluorine concentration in the range of 15% to 60% by mass, so as to present average roughness of 0.1 Mm to 1 Mm and contact angle with water greater than 140 degrees.
2- Revestimento, de acordo com a reivindicação 1 , caracterizado por a resina epóxi ser uma resina epóxi bi-componente, com alto teor de sólidos, na faixa de 80% a 99% em massa. Coating according to Claim 1, characterized in that the epoxy resin is a high solids two-component epoxy resin in the range of 80% to 99% by mass.
3- Revestimento, de acordo com a reivindicação 1 , caracterizado por a resina epóxi possuir teor de VOC (produtos orgânicos voláteis) variando de 130 g/Kg a 160 g/Kg de resina.  Coating according to Claim 1, characterized in that the epoxy resin has a VOC content ranging from 130 g / kg to 160 g / kg of resin.
4- MÉTODO DE PREPARAÇÃO DE REVESTIMENTO, definido de acordo com a reivindicação 1 , caracterizado por compreender as seguintes etapas:  4. COATING PREPARATION METHOD, defined according to claim 1, characterized in that it comprises the following steps:
a. preparar a superfície de uma tubulação metálica, de modo a obter uma rugosidade média entrei 0 pm e 100 Mm; b. aplicar um filme de resina epóxi, compreendendo um agente de cura totalmente disperso na resina epóxi, a superfície metálica previamente preparada;  The. preparing the surface of a metal pipe to obtain an average roughness between 0 pm and 100 Mm; B. applying an epoxy resin film comprising a fully dispersed curing agent to the epoxy resin, the previously prepared metal surface;
c. promover a cura do filme de resina epóxi, por aquecimento a temperaturas variando na faixa de 20°C a 45°C, por um período de 1 a 6 horas;  ç. promote curing of the epoxy resin film by heating at temperatures ranging from 20 ° C to 45 ° C for a period of 1 to 6 hours;
d. depositar um filme de um fluorpolímero sobre a superfíce do filme de resina epóxi por polimerização por plasma de rádio frequência (RF), empregando gases fluorados, numa vazão de 10 a 500 sccm, pressão variando de 0,67 Pa a 133,33 Pa e potência RF na faixa de 10 W a 1200 W, por um período de 1 a 180 minutos; d. deposit a film of a fluoropolymer on the surface of the epoxy resin film by radio frequency plasma (RF) polymerization employing fluorinated gases at a flow rate of 10 to 500 sccm, pressure ranging from 0.67 Pa to 133.33 Pa and RF power in the range 10 W to 1200 W for a period of 1 to 180 minutes;
5- Método, de acordo com a reivindicação 4, caracterizado por a superfície da tubulação metálica ser preparada por um dos seguintes métodos: limpeza mecânica, jateamento, limpeza química ou limpeza com auxílio de vapor.  Method according to Claim 4, characterized in that the surface of the metal pipe is prepared by one of the following methods: mechanical cleaning, blasting, chemical cleaning or steam cleaning.
6- Método, de acordo com a reivindicação 4, caracterizado por o agente de cura disperso na resina epóxi ser um líquido à base de poli-amina aromática, livre de solvente.  Method according to Claim 4, characterized in that the curing agent dispersed in the epoxy resin is a solvent-free aromatic polyamine-based liquid.
7- Método, de acordo com a reivindicação 4, caracterizado por o gás fluorado ser escolhidos dentre: CF4, CHF3 ou SF6. Method according to Claim 4, characterized in that the fluorinated gas is chosen from: CF 4 , CHF 3 or SF 6 .
PCT/BR2009/000358 2009-10-30 2009-10-30 Polymer coating for metal pipes and production method WO2011050427A1 (en)

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