• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    Microcapsules comprising corrosión inhibitors. Microcapsule comprising at least one corrosión inhibitor and one resin. Procedure for obtaining the microcapsule and its use in the prevention of corrosión, preferably in reinforced concrete structures (eha). (Machine-translation by Google Translate, not legally binding)
    公开号:ES2650976A1
    申请号:ES201630830
    申请日:2016-06-20
    公开日:2018-01-23
    发明作者:David MARTÍNEZ BASTIDAS
    申请人:Consejo Superior de Investigaciones Cientificas CSIC；
    IPC主号:
    专利说明:

    The present invention relates to microcapsules comprising at least one corrosion inhibitor and a resin. Also, the present invention relates to its method of obtaining and its use in the prevention of corrosion, preferably in reinforced concrete structures (EHA).
    STATE OF THE TECHNIQUE
    Natural resins such as rosin are environmentally friendly.
    Rosin also reduces porosity in concrete, and also improves its mechanical properties due to its plastic behavior.
    Microencapsulated corrosion inhibitors in pine resins are an attractive solution for reinforced concrete structures in civil engineering, architecture, building and construction.
    The use of corrosion inhibitors is known to prevent corrosion and increase the shelf life of EHA corrugated steel. However, in all the applications described, high amounts of such corrosion inhibitors are needed, which implies a high economic cost and an environmental problem because they are polluting compounds.
    Thus, the advantages of microencapsulated corrosion inhibitors are their environmental compatibility and the reduction of economic cost. Since it is not necessary to use so many quantities due to the controlled release effect caused by microencapsulation in natural resins.
    Therefore, it would be desirable to have corrosion inhibitors, preferably in reinforced concrete (EHA) structures capable of acting over time.
    In a first aspect, the present invention relates to a microcapsule that
    understands:
    i) at its core at least one corrosion inhibitor; Y
    ii) a resin as a core coating.
    In another embodiment the invention relates to the microcapsule as defined above, where the corrosion inhibitor is selected from Zn (N02h. Zn (OH h. Pb (NO,), and Pb (OH) ,.
    In another embodiment the invention relates to the microcapsule as defined above, where the corrosion inhibitor is selected from Pb (N02h and Pb (OH) ,.
    In another embodiment the invention relates to the microcapsule as defined above, where the corrosion inhibitor is Pb (N02k
    In another embodiment the invention relates to the microcapsule as defined above, where the corrosion inhibitor is Pb (OHh.
    In another embodiment the invention relates to the microcapsule as defined above, where the corrosion inhibitor is Zn (N02h.
    In another embodiment the invention relates to the microcapsule as defined above, where the corrosion inhibitor is Zn (OHh,
    In another embodiment the invention relates to the microcapsule as defined above, where the resin is a natural resin, and preferably where the resin is rosin.
    In another embodiment the invention relates to the microcapsule as defined above, comprising: i) at its core at least one corrosion inhibitor selected from Pb (NO,) "Pb (OH)" Zn (NO, ), and Zn (OH); and ii) a resin as a core coating.
    In another embodiment the invention relates to the microcapsule as defined above, where the ratio between the corrosion inhibitor and the resin is between 1: 1 and 1: 6, and preferably between 1: 2 and 1: 5.
    In another embodiment the invention relates to the microcapsule as defined.
    above, the present invention relates to a microcapsule comprising: i) in its core at least one corrosion inhibitor; and ii) a resin as a core coating,
    where the ratio between the corrosion inhibitor and the resin is between 1: 1 and 1: 6, and preferably between 1: 2 and 1: 5.
    In another embodiment the invention relates to the microcapsule as defined above, comprising: i) at its core at least one corrosion inhibitor selected from Pb (NO,) "Pb (OH)" Zn (NO, ), and Zn (OH); Y
    ii) a resin as a core coating. where the ratio between the corrosion inhibitor and the resin is between 1: 1 and 1: 6, and preferably between 1: 2 and 1: 5.
    In another embodiment the invention relates to the microcapsule as defined above, comprising: i) at its core at least one corrosion inhibitor selected from Pb (NO, ¡"Pb (OH)" Zn (NO, ), and Zn (OH) ,; and
    ii) a resin as a core coating. where: the ratio between the corrosion inhibitor and the resin is between 1: 1 and 1: 6, and preferably between 1: 2 and 1: 5; and -the resin is rosin.
    Another aspect of the invention relates to the method of obtaining the microcapsule as defined above, which comprises the double emulsion stage W1 / OfW2 (aqueous phase / organic phase / aqueous phase) where: - a first emulsion is formed W1 / O between an aqueous solution of the corrosion inhibitor and a solution of the resin in an organic solvent; and W1 / O and an aqueous solution of the emulsifier.
    In another embodiment, the invention relates to the method of obtaining the microcapsule as defined above, where the emulsifier is polyvinyl alcohol (PVA).
    In another embodiment, the invention relates to the method of obtaining the microcapsule as defined above, wherein the organic solvent is diethyl ether.
    Another aspect of the present invention relates to the use of the microcapsule as defined above, in the prevention of corrosion, preferably in the prevention of corrosion of building materials, paints and coatings, and more preferably in corrosion. of building materials where the building material is reinforced concrete (EHA).
    Another aspect of the invention relates to a composition comprising: i) the microcapsule as defined above; and ii) a building material, a paint or a coating; preferably a building material; and more preferably where the building material is reinforced concrete.
    Therefore, the present invention demonstrates that microencapsulation in natural rosins prevents the effectiveness of corrosion inhibitors from being lost during the curing time of the concrete due to leaching processes since the rosin prevents the corrosion inhibitor from reacting With the cement.
    Throughout the present invention, the term "corrosion inhibitor" refers to a substance or compound that inhibits / minimizes / decreases the corrosion deterioration process. Examples include Zn (NO,) "Zn (OH)" Pb (NO,), and Pb (OH) ,.
    The term "resin" refers to an organic substance or compound that is used to coat the microcapsule, constituting the structure of the cortex thereof. And it includes "natural resins" that refer to a family of resins of natural origin obtained directly from natural products, that is, non-synthetic.
    Examples include among others rosin, shellac, dammar, almaciga, starch, agar, gelatin, dextrin and latex, preferably rosin, agar and gelatin, and more preferably rosin.
    5 Rosin is a pine resin of natural origin, composed mainly of: -resinic acids, such as abietic acid where the -COOH group is the hydrophilic group and the rest of the molecule constitutes the hydrophobic group (see acid formula abietic); and -a minor fraction of other non-acidic compounds.
    Abietic Acid Formula-a minor fraction of other non-acidic compounds.
    15 The rosin has hydrophobic and hydrophilic characteristics, which have some influence on the physical-chemical properties of Portland cement, such as air content, water absorption, adhesive capacity and some mechanical properties. The rosin contributes favorably to the improvement of the properties of the cement mortar, particularly acting as aerating, improving the
    20 porosity, increasing the impermeability, improving the adhesion of the paste to the aggregate, and increasing the resistance to flexotraction and absorption. In addition, rosin has the advantages of being a natural, renewable and economical product.
    In addition to the inhibitor release reaction encapsulates: lo, the acids in the
    The rosin microcapsule can react with Ca (OHh present in the concrete phases by saponification, forming a calcium ester. However, this reagent heating at temperatures around 20crC, and even so, it is a reaction of very slow kinetics.In industrial reactions of esterification of rosin with alcohols such as glycerol are used, among others;
    5 CaO or Ca (OHh as reaction catalysts.
    The term "microcapsule" refers to a micrometric size capsule, which contains the corrosion inhibitor.
    The term "double emulsion W, / OIW2" refers to the aqueous phase / organic phase / aqueous phase. The preparation of a double emulsion water - in-oil-in-water 0! V, / 01W2), unlike the simple emulsion 0! V10), is usually carried out for water-soluble active substances.
    The term "emulsifier" refers to a compound or substance that makes an emulsion possible by serving as a dispersing agent when added in the mixture of two phases that are not miscible with each other. The emulsifier is an active surface agent that reduces interfacial tension so that extremely small drops of the emulsified liquid can be formed. Examples include among others the egg yolk,
    Acacia, tragacanth, pectin, methylcellulose, sulphonates, alkyl phenols and pOlivinyl alcohol (PVA).
    Polyvinyl alcohol (PVA) is a water soluble polymer whose main function is to stabilize the emulsion formed by stirring (emulsifying agent) by
    25 increase in surface tension between the aqueous and organic phases. The PVA is composed of monomers and its operation is based on the formation of micelles within the solution, stabilizing the formation of the microcapsules until the membrane polymerizes. In its structure it can be seen that it has hydrophilic groups (the -OH groups) and a hydrophobic chain (the rest of the polymer) (see PVA formula).
    PVA formula
    The active matter is dissolved in a small amount of water, which is emulsified with the organic solution of the membrane polymer to form a first water-in-oil emulsion. This emulsion is added to a water solution containing an emulsifier, such as PVA, to obtain the double emulsion W / ONl /. The organic solvent is removed by evaporation until an aqueous suspension is obtained with microcapsules containing the active material dissolved in small drops of water. These microcapsules are isolated by centrifugation, washing and drying.
    The term "reinforced concrete" refers to a composite material of ceramic matrix and metallic reinforcement, where the matrix can generally be formed by Portland cement and the reinforcement consists of corrugated steel bars. Examples include Portland cement.
    The expression "at least one corrosion inhibitor" means the possibility of including one or more corrosion inhibitors, and preferably 1 or 2 corrosion inhibitors.
    Throughout the description and the claims the word "comprises" and its variants are not intended to exclude other technical characteristics, additives, components or steps. For those skilled in the art, other objects, advantages and features of the invention will be derived partly from the description and partly from the practice of the invention. The following examples and figures are provided by way of illustration, and are not intended to be limiting of the present invention.
    BRIEF DESCRIPTION OF THE FIGURES
    FIG. 1 shows the scheme of synthesis of encapsulation of inhibitor in microcapsules by double emulsion W1 / ONl / 2. A) Aqueous solution of inhibitor and PVA, B) organic solution (diethyl ether) of rosin, C) stirring of the emulsion W / O, D) aqueous solution of PVA, E) stirring of the double emulsion W / OIW, F) Solvent removal by evaporation at 50 ° C in the presence of agitation. FIG. 2 shows the synthesized microcapsules FIG. 3 shows the spherical morphology of the microcapsule
    FIG. 5 shows the mechanism of inhibitor release. A) stable microcapsule; B)increased porosity; C) inhibitor release.FIG. 6 shows the zero order release kinetics, represented the concentrationof inhibitor versus time.FIG. 7 shows the Eeorr variation as a function of [CIl and [inhibitor]FIG. 8 shows the iCOlT variation based on [CIl and [Inhibitor]
    EXAMPLES
    Abbreviations:
    Rpm: revolutions per minuteiJm: micrometersEcoJT: corrosion potentialleo ,, corrosion density[inhibitor]: inhibitor concentration1 / [inhibitor): inverse of the inhibitor concentrationLn [inhibitor]: neperian logarithm of the inhibitor concentrationRp: polarization resistanceVco ,, corrosion rate
    The invention will now be illustrated by tests carried out by theinventors, which highlights the effectiveness of the product of the invention.
    Obtaining the microcapsulesThe process of obtaining, has been carried out according to the procedure described in theintroduction referred to double emulsions W 1 / 01W2, and as shown in theFig. 1.
    Starting from an aqueous solution of 100 mL in which 5 g of dissolvedinhibitor (Pb (NO,), and Pb (OH),) and 1 9 of PVA, are taken 5 mL and taken to a glass ofprecipitates This, which will be the internal aqueous phase, is mixed with the organic phase of1 g of rosin powder dissolved in 10 mL of diethyl ether, stirring at 500 rpmfor 5 min at room temperature, forming the first W / O emulsion.
    This first emulsion is taken to another 30 mL aqueous solution of 4% PVA, stirring at a speed between 300-250 rpm for 30 min so that the first drops form within the solution. Subsequently, and maintaining the stirring speed, the temperature is raised to facilitate the evaporation of the organic solvent, maintaining the stirring until it has been completely removed from the suspension, obtaining a dispersion of rosin microcapsules containing small drops of inhibitor in its interior (Fig. 2).
    To form the rosin solution in diethyl ether, the resin crystals are ground before grinding until they are finely divided.
    To heat the emulsion and bring it to the boiling temperature of the organic solvent (such as diethyl ether whose boiling temperature is 34.5 OC), a heated magnetic stirrer was used.
    Lastly, mechanical stirrers with "Heidolph RZR 2021" model blades, equipped with a four-bladed glass stirring rod, were used to form the emulsion.
    The volume ratio between solutions was maintained at 1: 2. The explanation is that the solution with the largest volume should be the one that "encapsulates" the one with the lowest volume (in the first step the organic phase encapsulates the aqueous inhibitor phase and in the second step the aqueous PVA phase does the same to W / O emulsion). Even so, the volume ratio was one of the parameters that were optimized.
    To keep the microcapsules intact, they were kept in suspension in the aqueous reaction solution until such time as the subsequent tests were to be carried out, both the determination of the release and the electrochemical measurements. At that time they were filtered and weighed on an analytical balance.
    In addition, to evaluate the encapsulation efficacy, once the microcapsules were filtered, the filtrate waters were diluted and analyzed by Flame Atomic Absorption Spectroscopy (MS) to determine the amount of encapsulated inhibitor by difference to that found in the solution.
    It is also worth mentioning the porous structure observed in the microcapsule surface, Fig. 2, Fig. 3 and Fig. 4, thanks to which the release of the encapsulated inhibitor occurs. It should be noted that as the microcapsule decreases in size, the surface structure is much more polished and homogeneous, and the number of pores decreases.
    Efficiency of encapsulation The concentration of inhibitor in the filtrate waters (once the microcapsules have been filtered) has been determined by AAS in duplicate, obtaining similar values of the encapsulation performance of the inhibitor in rosin capsules.
    The encapsulation performance values have been satisfactory (around 85%), and have been similar in all microcapsule synthesis carried out.
    Determination of release capacity. Release mechanism In addition to the aforementioned advantages of the use of rosin, there is one more reason to use this resin for the microcapsule membranes: the porosity they present under certain conditions.
    When corrosion occurs, the oxygen reduction reaction releases OH-o ions Under these conditions, the rosin is slightly soluble in aqueous solution, and therefore, the capsules increase their porosity, releasing the inhibitor inside, stopping the corrosion process. when necessary This process is described in Fig. 5.
    The microcapsules have been shown to have a certain porosity because a small amount of them were kept in a desiccator for 15 days. After that time it was found that the capsules had dried both externally and internally, thus confirming their porosity.
    Results The release assay was carried out by preparing 7 test tubes in which 10 mL of a solution of Ca (saturated OHh was added to which a certain amount of encapsulated inhibitor was added (the same amount of inhibitor in the 7 tubes.) 1 mL aliquots were taken in duplicate of the solutions from time to time, prolonging the test up to 60 days. These aliquots were taken to volumetric flasks up to 50 mL volume and analyzed by MS.
    The concentration results obtained are shown below in Table 1 and Table 2 and Fig. 6 shows the study of release kinetics performed.
    Table 1. Results of the release test.
    [Inhibitor] (mgfL)
    Time (days) Aliquot AAlicuota BMiddle value
    one 0.380.370.375
    3 0.470.410.44
    7 0.460.460.46
    fifteen 0.510.490.5
    30 0.670.670.67
    Four. Five 0.780.750.765
    60 0.890.890.89
    Table 2. Study of release kinetics.
    Zero Order Order OneOrder Two
    Time (days) [Inhibitor]Ln [Inhibitor]1f [inhibitor]
    one 0.375~ O, 98082,6667
    3 0.44-0, 82102.2727
    7 0.46-0, 77652.1739
    fifteen 0.5-0, 69312,0000
    30 0.67-0,40051.4925
    Four. Five 0.765~ O, 26791,3072
    60 0.89-0, 11651.1236
    As can be seen, from the linear regression coefficient (R2) of the different kinetics, the one that is closest to a straight line is the zero order kinetics.
    15 This indicates, on the one hand, that inhibitor release is not a function of the concentration of the inhibitor in the solution. In addition, it has been proven that, after 60 days, inhibitor is still released. Therefore, the threshold of 28 days in which the concrete setting process occurs during which there may be leaching of the inhibitor has been exceeded.
    Electrochemical tests Once the values of Rp, i cofT and VCOfT have been determined, the level of attack on the steel structure must be determined. The assessment criteria to determine the level of corrosion of the reinforcement are shown in Table 3. Although these
    5 values are referred to specimens embedded in concrete mortar, they will be used as a reference for this study by similarity.
    Table 3. Limit values to identify the level of corrosion.
    Density d. Intensity d. Corrosion, icon (! -IA / cm2) <0.1 0.1 to 0.5 0.5 to 1> 1 Corrosion Speed, vc ,, "Corrosion Level (! -1 m / year) <1.6 Negligible 1.6a5.8 Low 5.8a11, 6 Moderate> 11, 6 Alla
    10 The solutions of the electrochemical electrolytes next to the test tubes are continued in Table 4.employees for the different measures used for each are collected at
    Table 4. Solutions of the Eleetrolitos.
    Test tube ElectrolyteDissolution
    White Ca (OH) 2 salted
    one White'Ca (OH) 2 salt + NaCl 0.4%
    White" Ca (OH) 2 salt + NaCI 3.5%
    2 Measure l 'Ca (OH) 2 sat + NaCI 0.4% + lnh free ibidor
    Half way 1 " Ca (OH n sat + NaCI 3.5% + Inhibitor
    3 Half way 2 'Ca (OH n sat + NaCI 0.4% + Inh encapsulated ibidor
    Midway 2 " Ca (OH) 2 salt + 3.5% NaCl + encapsulated inhibitor
    15 The necessary quantity to be added as a free and encapsulated inhibitor was calculated taking into account the ratio Chlorides: inhibitor (1: 1). All solutions were prepared in 100 mL volumetric flasks. The results obtained are presented in Table 5.
    20 Table 5. Results of electrochemical tests.
    Test tube MeasurementsEc ,, "(V)Rp (O · cm2)ichor, (~ cm2)ro (mg / dm 2d)v ~ "(! -1m / year)Corrosion Level
    one White-0, 2251.06E + 060.0250.0610.284Negligible
    White' 0,3491.60E + 050.1630.4061,885Low
    White" -0, 3921.12E + 050.2320.5812,692Low
    2 Measure l '-0, 1951.23E + 060.0210.0530.245Negligible
    1 "measure -0, 1927.36E + 050.0350.0880.410Negligible
    3 2 'measure-0, 3484.00E + 050.0650.1630.754Negligible
    2 "measure -0, 4449.45E + 040.2750.6883,191Low
    The Eco measurements "lasted until a time t = 1200 s, or until it stabilized at a constant potential.
    The graphs (Fig. 7 and Fig. 8) of Eco "and icorr are shown below depending on the chloride concentration and the inhibitor concentration.
    权利要求:
    Claims (13)
    [1]
    1. Microcapsule comprising:
    i) at its core at least one corrosion inhibitor; Yii) a resin as a core coating.
    [2]
    2. The microcapsule according to claim 1, wherein the corrosion inhibitor is selected from Zn (NO,) "Zn (OH)" Pb (NO,), and Pb (OH) ,.
    [3]
    3. The microcapsule according to claim 2, wherein the corrosion inhibitor is selected from Pb (NO,), and Pb (OH) ,.
    [4 ]
    Four . The microcapsule according to any one of claims 1 to 3, wherein the resin is selected from rosin.
    [5]
    5. The microcapsule according to any one of claims 1 to 4, wherein the ratio between the corrosion inhibitor and the resin is between 1: 1 and 1: 6.
    [6]
    6. Method for obtaining the microcapsule defined in any one of claims 1 to 5, comprising the double emulsion stage W, / 0M / 2 (aqueous organic organophosphate phase) wherein: - a first emulsion W, / O is formed between a solution aqueous corrosion inhibitor and a solution of the resin in an organic solvent; and -after a second emulsion W, IOM / 2 is formed between the first emulsion W 1/0 and an aqueous solution of the emulsifier.
    [7]
    7. The process according to claim 6, wherein the emulsifier is polyvinyl alcohol (PVA).
    [8]
    8. The process according to any of claims 6 or 7, wherein the organic solvent is diethyl ether.
    [9]
    9. Use of the microcapsule defined in any of claims 1 to 5, in the prevention of corrosion.
    [10]
    10. The use according to claim 9, in the prevention of corrosion of building materials, paints and coatings.
    [11]
    eleven. The use according to claim 10, wherein the construction material is reinforced concrete.
    [12]
    12. Composition comprising: i) the microcapsule defined in any one of claims 1 to 5; and ii) a building material, a paint or a coating.
    [13]
    13. The composition according to claim 12, wherein the construction material is reinforced concrete.
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    同族专利:
    公开号 | 公开日
    WO2017220836A1|2017-12-28|
    ES2650976B1|2018-11-23|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JPH0542388B2|1985-05-02|1993-06-28|Ube Industries|
    US8974594B2|2011-03-29|2015-03-10|Empire Technology Development Llc|Microcapsule corrosion control in reinforced concrete|
    CN103011667B|2012-12-03|2014-05-28|深圳大学|Method for preparing polystyrene/sodium monofluorophosphate microcapsule corrosion inhibitor|
    CN102992673B|2012-12-11|2015-01-14|同济大学|Chlorine salt corrosion resistant system with chemical microcapsule for underground structure concrete|
    CN104725563B|2013-12-19|2017-04-12|中国科学院金属研究所|Corrosion inhibitor gel microsphere with intelligent pH value controlled release function and its preparation method and use|
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    优先权:
    申请号 | 申请日 | 专利标题
    ES201630830A|ES2650976B1|2016-06-20|2016-06-20|MICROCAKES THAT INCLUDE CORROSION INHIBITORS|ES201630830A| ES2650976B1|2016-06-20|2016-06-20|MICROCAKES THAT INCLUDE CORROSION INHIBITORS|
    PCT/ES2017/070445| WO2017220836A1|2016-06-20|2017-06-20|Microcapsules comprising corrosion inhibitors|
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