• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    Biodegradable compound for use as a lubricating grease that comprises a thickener made up of at least one clay, in a ratio between 10% and 60% by weight; at least one vegetable oil, in a ratio between 40% and 90% by weight; and at least one natural antioxidant agent, in a ratio between 0.5% and 3% by weight; and where its production process comprises a previous stage of pre-conditioning of a mixture between the oil and the clay that comprises an initial weighing of both compounds and a subsequent mixing without stirring; and a homogenization of the mixture resulting from the previous step together with the antioxidant agents using a rotor-stator device. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2802877A1
    申请号:ES201930653
    申请日:2019-07-15
    公开日:2021-01-21
    发明作者:Alfonso José Enrique Martin；Gomez José María Franco；Barragan Concepción Valencia
    申请人:Universidad de Huelva；
    IPC主号:
    专利说明:

    [0002] BIODEGRADABLE COMPOUND FOR USE AS A LUBRICATING GREASE AND
    [0004] Object of the invention
    [0006] The present invention refers to the development of a new type of biodegradable compound from a layered silicate, preferably montmorillonite, and a vegetable oil, where the result has industrial applications in the lubricants sector, and in particular, said compound is used as a lubricating grease.
    [0008] State of the art
    [0010] In general, clays in their natural state (without modifications) have a highly hydrophilic character and are only miscible with fluids or highly hydrophilic polymeric matrices, hence, on many occasions, mixing with some polymeric materials such as polyolefins or fluids such as bitumens. or oils give rise to completely immiscible systems. For this reason, these clays have been modified with surfactants (such as ammonium salts) to make them more related to this type of materials. Furthermore, with this modification it is possible to increase the interlaminar (basal) spacing of the clay. Hence, the size of the surfactant chains is of great influence to obtain a greater or less interlaminar spacing. In recent years, interest in the mixing and study of the compatibility of smectite-type clays (such as montmorillonite) in all types of fluids and polymeric matrices has grown exponentially, due on the one hand to the large aspect ratio of the lamellae that they form this type of laminar silicates, and on the other hand, the great availability of this type of clay compared to others.
    [0012] Lamellar silicates have been used for various industrial applications, such as additives for the manufacture of polymeric matrix nanocomposites, matrices for catalytic purposes or in the design of construction materials, but they have not been used so far as thickeners of vegetable oils to the production of biodegradable lubricating greases. Currently, most of the biodegradable greases that are marketed are made from anhydrous calcium soaps and vegetable oils for lossy greasing applications (bearings, blades, etc.).
    [0013] On the other hand, there are numerous patents that describe procedures for obtaining lubricating greases. The manufacture of lubricating greases, with in situ generation of a metallic soap that acts as a thickening agent, is a complex process that consists of carrying out the saponification reaction between fatty acids and an alkaline solution, followed by dehydration, heating to temperature transition, cooling stage and, finally, a homogenization process. The traditional process for manufacturing lubricating greases thickened with fatty acid metal soaps and, mainly, with lithium or calcium 12-hydroxystearate is well described in various American patents from the 1950s and 1960s.
    [0015] In reference to obtaining lubricating greases, considered biodegradable, in US patent US4115282, the objective of providing a biodegradable grease for rails, points, crossings and railway vehicles is described, consisting of a lubricating oil, water, a thickener and optionally additional additives. Specifically, the composition of the fat of the present invention differs in its composition and results, which comprises a biodegradable vegetable or animal oil in an aqueous mixture containing a thickening or gelling agent of vegetable origin with a differentiated composition.
    [0017] European patent EP / 0806470 / A2 refers to a vegetable oil, an alkali metal or alkaline earth metal carboxylate as a thickening agent and the process for preparing the same. The thickener is preferably prepared in situ in the oil.
    [0019] International patent WO97 / 46642 refers to the use of esters as biodegradable lubricating bases in two-stroke engine oils.
    [0021] International patent WO03 / 018/29 A1 refers to the use of a non-toxic biodegradable grease composed of glycerin oil, one or more stearates, one or more long-chain esters and bentonite to lubricate mechanisms that are exposed to high loads, such as such as curved rails in railways and flanges in cars and locomotives, as well as other different applications where biodegradable lubricants are required.
    [0022] Patent ES2524603A1 refers to lubricating greases that comprise: residual oleins resulting from the refining process of sunflower oils, high oleic sunflower, olive pomace, soybean, rapeseed or a mixture thereof, a metal hydroxide and an oxidizing agent.
    [0024] US8507421B2 refers to lubricating greases that include calcium lignosulphonates as a lubricating grease additive that reacts with the thickener and is incorporated as part of the thickener.
    [0025] However, the use of biodegradable lubricating greases based on smectite-type clays (such as montmorillonite) and vegetable oils is not known. This provides the technical advantage of having viscosity reversibility against shear and of being used at high temperatures, which is not possible to obtain by means of other types of known formulations or a combination of them. In this sense, the present invention refers to the definition of the process for obtaining lubricating greases and their formulation.
    [0027] Description of the invention
    [0029] The object of the present invention is to develop new formulations of biodegradable lubricating greases, from smectite-type clays, such as montmorillonite, modified with ammonium salts and vegetable oils with possible applications in the lubricant sector and their production process.
    [0031] A first aspect of the present invention refers to a biodegradable compound, which is a lubricating product that has a use as a lubricating grease, where the compound has the following composition (according to dry matter):
    [0033] a) Between 10% and 60% by weight of a smectite-type clay, such as montmorillonite, modified with ammonium salts selected from the group consisting of cloisite 10A, cloisite 15A, cloisite 20A, cloisite 25A, cloisite 93A, cloisite 30B, cloisite Na +, or combinations of these.
    [0035] b) Between 90% and 40% by weight of a vegetable oil selected from the group consisting of castor oil, olive oil, sunflower oil, high oleic oil, linseed oil, soybean oil, rapeseed oil , palm oil or combinations of these.
    [0037] c) Between 0.5% and 3% by weight of a natural antioxidant agent selected from the group consisting of tocopherol, propyl gallate, ascorbyl palmitate or combinations thereof.
    [0039] A second aspect of the present invention refers to a procedure for obtaining lubricating grease as described above, which comprises the following steps:
    [0041] a) Pre-conditioning of the oil-clay mixture in a reactor comprising:
    [0042] - the initial weighing of the amounts of clay and oil depending on their percentages by mass and
    [0043] - its subsequent mixing without stirring for a time between 1 and 60 minutes so that a first interaction between both components takes place and the processing is facilitated in the second stage.
    [0045] b) Homogenization of the mixture resulting from the previous stage together with antioxidant additives, or of another type, using a rotor-stator device, colloid mill type under the following conditions:
    [0047] i) Homogenization speed between 1000 and 15000 rpm.
    [0049] ii) Homogenization time between 1 and 60 minutes.
    [0051] iii) Homogenization temperature between -10 and 100 ° C.
    [0053] According to another aspect of the present invention, it relates to the use of the proposed formulations as lubricating greases. Said formulations can be used for general applications in bearings, stub pivots in automobiles, bearings and gears for sealing, bearings, elevators, chains, bearings, conveyor belts, couplings, hinges, or the like.
    [0055] In addition, they have good resistance to water and good adhesion capacity to surfaces, working temperatures below 170 ° C and are easy to handle at low temperatures. Depending on the clay concentration (20-40% by weight), lubricating greases with different consistencies (000-4), rheological and tribological behavior are obtained.
    [0057] It should be noted that, throughout the description and claims, the term "comprises" and its variants are not intended to exclude other technical characteristics or additional elements.
    [0059] Brief description of the figures
    [0061] In order to complete the description and to help a better understanding of the characteristics of the invention, a set of figures and drawings is presented in which the following is represented by way of illustration and not limitation:
    [0063] Figure 1: Shows the mechanical spectra (storage moduli, G ', and losses, G ”), within the linear viscoelasticity range for the fats corresponding to examples 1-3, prepared with castor oil as a function of the concentration of clay used.
    [0065] Figure 2: Shows the mechanical spectra (storage moduli, G ', and losses, G ”) within the range of linear viscoelasticity for fats corresponding to examples 4-7, prepared with a clay concentration of 30% by weight depending on the type of vegetable oil used.
    [0067] Figure 3: Shows the evolution of the apparent viscosity with the shear rate for the fats corresponding to examples 1-3, prepared with castor oil as a function of the concentration of clay used.
    [0069] Figure 4: Shows the same as Figure 3 for Examples 4-7.
    [0071] Figure 5: Micrographs of the 4x footprint obtained by tribological contact of fats with 30% by weight of clays prepared with castor oil (A), high oleic oil (B), sunflower oil (C) and linseed oil ( D), obtained with an optical microscope.
    [0073] Detailed description of some embodiments of the invention.
    [0075] Next, and taking into account the previous figures, they are illustrated in detail with the following non-limiting examples of embodiment of the invention:
    [0077] Example 1:
    [0079] Castor oil (80% by weight) and clay (20% by weight) were introduced into a reactor at room temperature. This mixture was kept without stirring for 1 hour. Finally, a high shear mixing process was carried out with a rotorestator homogenizer for 15 min at 8800 rpm.
    [0081] Example 2:
    [0083] Castor oil (70% by weight) and clay (30% by weight) were introduced into a reactor at room temperature. This mixture was kept without stirring for 1 hour. Finally, a high shear mixing process was carried out with a rotorestator homogenizer for 15 min at 8800 rpm.
    [0085] Example 3:
    [0087] Castor oil (60% by weight) and clay (40% by weight) were introduced into a reactor at room temperature. This mixture was kept without stirring for 1 hour. Finally, a high shear mixing process was carried out with a rotorestator homogenizer for 15 min at 8800 rpm.
    [0089] Example 4:
    [0091] Soybean oil (70% by weight) and clay (30% by weight) were introduced into a reactor at room temperature. This mixture was kept without stirring for 1 hour. Finally A high shear mixing process was carried out with a rotorestator homogenizer for 15 min at 8800 rpm.
    [0093] Example 5:
    [0095] Linseed oil (70% by weight) and clay (30% by weight) were introduced into a reactor at room temperature. This mixture was kept without stirring for 1 hour. Finally, a high shear mixing process was carried out with a rotorestator homogenizer for 15 min at 8800 rpm.
    [0097] Example 6:
    [0099] Sunflower oil (70% by weight) and clay (30% by weight) were introduced into a reactor at room temperature. This mixture was kept without stirring for 1 hour. Finally, a high shear mixing process was carried out with a rotorestator homogenizer for 15 min at 8800 rpm.
    [0101] Example 7:
    [0103] High oleic oil (70% by weight) and clay (30% by weight) were introduced into a reactor at room temperature. This mixture was kept without stirring for 1 hour. Finally, a high shear mixing process was carried out with a rotor-stator homogenizer for 15 min at 8800 rpm.
    [0105] In all the cited examples, after the homogenization process, a homogeneous mixture was obtained, without any separation of oil.
    [0107] Table 1 shows the penetration values, NLGI grades (according to ASTM D1403 and D217 standards, respectively) of the greases corresponding to Examples 1 to 7. The NLGI grade provides a measure of the consistency of the lubricating grease. As can be seen, different consistencies can be obtained depending on the concentration of clay and the type of oil used.
    [0111] Table 1
    [0113] Table 2 shows the values of the storage modulus (G ') at 1 rad / s measured within the linear viscoelastic range and the viscosity at 1 s-1 for the greases corresponding to examples 1 to 7, as a function of the percentage of clay used as a thickener and of the type of oil used.
    [0118] Table 2
    [0120] The National Lubricating Grease Institute (NLGI) establishes a classification of lubricating greases based on their consistency. The system for classifying the consistencies of greases is defined by the penetration produced by the fall of a standard cone in a grease sample (ASTM-D-217). Depending on the value obtained in this test, the fat is classified in one of the grades defined for this purpose by the NLGI. These grades range from 000 for the most fluid fats, to 6 for the most consistent fats.
    [0121] As can be seen in Table 1, depending on the formulation (different content of thickener and vegetable oil) we can obtain greases with different NLGI grades, ranging from 000 to 4. These degrees of consistency indicate the main application. which may have a grease, the most common applications being bearings, gears and gaskets. Example 1 (NLGI 000, liquid grease) can be applied in closed gearboxes due to its ability to flow and re-seat, while greases (NLGI 0 and NLGI 1, semi-fluid) can be applied in bearings and centralized systems . While example 3 (NLGI 4, semi-hard) can be applied to perform sealing tasks on valves, armatures, guides or others.
    权利要求:
    Claims (13)
    [1]
    1. Biodegradable compound, which is a lubricant product characterized in that it comprises a composition with:
    - at least one clay as a thickening agent, in a ratio between 10% and 60% by weight;
    - at least one vegetable oil, in a ratio between 40% and 90% by weight; Y
    - at least one natural antioxidant agent, in a ratio between 0.5% and 3% by weight.
    [2]
    2. Biodegradable compound according to claim 1, wherein the clay is a smectite modified with ammonium salts.
    [3]
    3. Biodegradable compound according to claim 2, wherein the smectite is a montmorillonite.
    [4]
    4. Biodegradable compound according to claim 2, wherein the montmorillonite is selected from cloisite 10A, cloisite 15A, cloisite 20A, cloisite 25A, cloisite 93A, cloisite 30B, cloisite Na +, or combinations of these.
    [5]
    5. Biodegradable compound according to claim 1, where the vegetable oil is selected from castor oil, olive oil, sunflower oil, high oleic oil, linseed oil, soybean oil, rapeseed oil, palm oil or combinations of these.
    [6]
    6. Biodegradable compound according to claim 1, wherein the antioxidant agent is selected from tocopherol, propyl gallate, ascorbyl palmitate or combinations of these.
    [7]
    7. Biodegradable compound comprising a composition according to any of claims 1 to 6 for use as a lubricating grease.
    [8]
    8. Process for obtaining a compound according to any of claims 1 to 7, comprising the steps of:
    a) a pre-conditioning of a mixture between the oil and the clay comprising an initial weighing of both compounds and a subsequent mixing without stirring, using a reactor; and b) homogenizing the mixture resulting from the previous step together with the antioxidant agent using a rotor-stator device.
    [9]
    9. Process according to claim 8, wherein the pre-conditioning of the mixture of step (a) is carried out without stirring for a time between 1 and 60 minutes.
    [10]
    10. Process according to claim 8, wherein the homogenization of the mixture resulting from the precursor composition of step (b) is carried out at a homogenization speed between 1000 and 15000 rpm.
    [11]
    11. Process according to claim 8, wherein the homogenization of the mixture resulting from the precursor composition of step (b) is carried out with a homogenization time of between 1 and 60 minutes.
    [12]
    12. Process according to claim 8, wherein the homogenization of the mixture resulting from the precursor composition of step (b) is carried out at a homogenization temperature of between -10 and 100 ° C.
    [13]
    13. Process according to claim 8, wherein the homogenization of the mixture resulting from the precursor composition of step (b) is carried out in a rotor-stator device of the colloid mill type.
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    同族专利:
    公开号 | 公开日
    WO2021009396A1|2021-01-21|
    ES2802877B2|2021-07-09|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US5405543A|1989-07-04|1995-04-11|Kabushiki Kaisha Tokai Rika Denki Seisakusho|Grease for copper contact|
    US5364544A|1990-08-31|1994-11-15|Kabushiki Kaisha Tokai Rika Denki Seisakusho|Grease for a slide contact|
    ZA962705B|1995-04-13|1996-10-09|Engen Petroleum Limited|Lubricant|
    WO1997003117A1|1995-07-12|1997-01-30|Caschem, Inc.|Polypropylene compatible grease compositions for optical fiber cable|
    ES2525892A1|2013-06-25|2014-12-30|Universidad De Huelva|Biodegradable fats and process for obtaining them from residual oleins |
    CN104342233A|2014-09-25|2015-02-11|苏州长盛机电有限公司|Metal antiwear lubricating oil|
    CN105567378B|2015-12-28|2018-05-18|大庆市加通石油化工有限公司|A kind of Biodegradation Lubricating Oil|
    CN108456584A|2018-03-13|2018-08-28|合肥择浚电气设备有限公司|A kind of lube oil additive and preparation method thereof|
    法律状态:
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    优先权:
    申请号 | 申请日 | 专利标题
    ES201930653A|ES2802877B2|2019-07-15|2019-07-15|BIODEGRADABLE COMPOUND FOR USE AS A LUBRICATING GREASE AND PROCEDURE TO OBTAIN IT|ES201930653A| ES2802877B2|2019-07-15|2019-07-15|BIODEGRADABLE COMPOUND FOR USE AS A LUBRICATING GREASE AND PROCEDURE TO OBTAIN IT|
    PCT/ES2020/070418| WO2021009396A1|2019-07-15|2020-06-30|Biodegradable compound for use as a lubricating grease and method for obtaining it|
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