TW201730325A - A lubricating composition containing nanocomposite particles chelated with metals - Google Patents
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本發明是有關於一種潤滑組成物，特別是指一種包含能自行吸附金屬表面之奈米複合粒子的潤滑組成物。 The present invention relates to a lubricating composition, and more particularly to a lubricating composition comprising nanocomposite particles capable of self-adsorbing a metal surface.
潤滑是任何機械設備或元件在設計上必需要考慮的重要因素，習知已有多種氣體、固體或液體形式的材料能用來支撐金屬對磨面而產生金屬潤滑效果。其中，又以液體形式的潤滑材料被普遍用來潤滑機械或滑動元件中的對磨面，以維持長時間的機械效能穩定性。在經過多年科技進步和發展後，各種潤滑油或潤滑脂已被廣泛應用在工業機械設備或車輛的各種滑動元件上。 Lubrication is an important factor in the design of any mechanical equipment or component. It is known that a variety of materials in the form of gas, solid or liquid can be used to support the metal to the grinding surface to produce metal lubrication. Among them, lubricating materials in liquid form are commonly used to lubricate the facing surfaces in mechanical or sliding elements to maintain long-term mechanical performance stability. After years of technological advancement and development, various lubricants or greases have been widely used in industrial machinery or various sliding elements of vehicles.
於某些條件下，潤滑油或潤滑脂中所使用的基礎油本身的物理或化學性質能決定使用該基礎油之潤滑油或潤滑脂的潤滑性能，但在大多數工業用設備的潤滑應用上，潤滑性能還與潤滑油或潤滑脂中所使用的潤滑油添加劑(additive)有關，在前述情形下，基礎油大部分的功用僅是作為潤滑添加劑的載體(carrier)。 Under certain conditions, the physical or chemical properties of the base oil used in the lubricating oil or grease can determine the lubricating properties of the lubricating oil or grease used in the base oil, but in the lubrication applications of most industrial equipment. Lubricating properties are also related to the lubricating oil additive used in the lubricating oil or grease. In the foregoing case, most of the function of the base oil is only a carrier as a lubricating additive.
減少機械引擎內的摩擦可以增加能源效率和減少機件損耗，而潤滑油的使用便是能減少摩擦力進而增加能源效率和減少機件損耗的必要方法。為了更加提升潤滑油的潤滑性能，除了適當改良潤滑油本身的特性外，添加適合的潤滑油添加劑於潤滑油裡也能降低摩擦係數與磨耗率且同時能提升咬死荷重(即能提升潤滑性)。目前較高級的潤滑油添加劑為有機硫、磷或氯衍生物，雖然此些潤滑油添加劑能提升潤滑油的潤滑性，但皆具有不耐高溫與高壓、壽命短及環境汙染等缺點。而固體潤滑油添加劑如石墨烯、二硫化鉬或奈米鑽石等，雖具有高溫高壓穩定性及較高壽命，但仍必須克服添加劑與潤滑油的相容性不足，以及添加比例過高會造成油路阻塞，因而商業效益不高且無法普及的問題。 Reducing friction in mechanical engines can increase energy efficiency and reduce machine wear, and the use of lubricants is a necessary method to reduce friction and thereby increase energy efficiency and reduce machine wear. In order to improve the lubricating performance of the lubricating oil, in addition to properly improving the characteristics of the lubricating oil itself, adding a suitable lubricating oil additive can also reduce the friction coefficient and the wear rate in the lubricating oil and at the same time increase the sedentary load (ie, improve the lubricity). ). At present, higher-grade lubricating oil additives are organic sulfur, phosphorus or chlorine derivatives. Although these lubricating oil additives can improve the lubricity of lubricating oils, they all have disadvantages such as high temperature and high pressure, short life and environmental pollution. Solid lubricant additives such as graphene, molybdenum disulfide or nanodiamonds have high temperature and high pressure stability and high life, but they must overcome the lack of compatibility between additives and lubricants, and the excessive addition ratio will cause The problem that the oil circuit is blocked, so the commercial benefits are not high and cannot be popularized.
為了克服固體潤滑油添加劑與潤滑油相容性的問題，中國專利CN1186401 C揭示以超音波方式分散奈米金剛石粒子團聚，並藉由添加不同的矽烷表面改質劑，使經表面改質後的奈米金剛石粒子能分散於水相或油相中。而在中國專利CN1695779 A中更進一步揭示以高速剪切機並利用超音波震盪使超分散奈米鑽石解團聚，並加入界面活性劑使其分散於潤滑油中。美國專利US20080248979 A1中便揭示一種潤滑油，藉由同時添加界面活性劑及奈米鑽石，使奈米鑽石能分散於潤滑油中並有效降低摩擦係 數與磨耗率以及提升咬死荷重而能提升潤滑油的潤滑性。前述透過添加界面活性劑並以物理吸附方式吸附奈米鑽石的方法，雖能使奈米鑽石分散於潤滑油中，但此方法除了界面活性劑會影響潤滑油的潤滑特性外，利用物理吸附的方法在高溫情況下也不穩定，所以在潤滑油因機件運作逐漸升溫過程中，當油溫升高到一定溫度時，奈米鑽石會因高溫而與界面活性劑脫附，進而再度團聚成較大的凝結體，此些過大的凝結體不僅不具有潤滑特性反而會使機件產生刮損情況。 In order to overcome the problem of the compatibility of the solid lubricating oil additive with the lubricating oil, the Chinese patent CN1186401 C discloses that the nano diamond particles are dispersed by ultrasonic wave agglomeration, and the surface is modified by adding different decane surface modifying agents. The nanodiamond particles can be dispersed in the aqueous or oil phase. Further, in Chinese patent CN1695779 A, a high-speed shearing machine is used to deagglomerate the super-dispersed nano-diamond by ultrasonic vibration, and a surfactant is added to disperse it in the lubricating oil. U.S. Patent No. 2,028,048, 979 A1 discloses a lubricating oil which can be dispersed in a lubricating oil and effectively reduce the friction system by simultaneously adding a surfactant and a nano diamond. The number and wear rate as well as the increased dead load can improve the lubricity of the lubricant. The method of adsorbing nano diamond by adding a surfactant and physically adsorbing the nano diamond can disperse the nano diamond in the lubricating oil, but the method uses physical adsorption in addition to the surfactant affecting the lubricating property of the lubricating oil. The method is also unstable under high temperature conditions. Therefore, when the lubricating oil is gradually heated due to the operation of the machine parts, when the oil temperature rises to a certain temperature, the nano diamond will desorb with the surfactant due to the high temperature, and then reaggregate again. Larger condensate, these oversized condensate not only does not have lubricating properties but will cause scratching of the machine.
將奈米鑽石表面以共價鍵形式與高分子鍵結是較穩定的方法，可確保奈米鑽石分散在油相和水相時不易受高溫脫附的影響。例如美國專利US20080249229 A1即是將奈米鑽石表面以原子轉移自由基活性聚合(atom-transfer-radical polymerization,ATRP)方法將高分子鏈接枝在奈米鑽石表面，前述方法必需先利用硝酸使氧化奈米鑽石表面形成羧酸根，再進行後續反應使高分子接枝在奈米鑽石的表面，進而促使奈米鑽石能分散於有機溶劑中。然而，前述方法需使用大量強酸氧化奈米鑽石，且還必須使用反應劇烈且必須在無水環境下才能和氧化奈米鑽石進行反應的SOCl2，因此難以在工業量產，且目前也無分散在潤滑油中的實際例子和相關測試數據。 It is a relatively stable method to bond the surface of the nano-diamond with a polymer bond in a covalent bond, which ensures that the nano-diamond is not easily affected by high-temperature desorption when dispersed in the oil phase and the water phase. For example, in U.S. Patent No. 2,028,249,229, A1, the surface of a nano-diamond is atomized by an atomic-transfer-radical polymerization (ATRP) method, and the polymer is grafted on the surface of a nano-diamond. The carboxylate forms a carboxylate on the surface of the diamond, and the subsequent reaction causes the polymer to be grafted on the surface of the nano-diamond, thereby promoting the dispersion of the nano-diamond in the organic solvent. However, the foregoing method requires the use of a large amount of strong acid oxidized nano-diamonds, and it is also necessary to use SOCl 2 which is violently reacted and must be reacted with oxidized nano-diamonds in an anhydrous environment, so that it is difficult to mass-produce in industrial production, and currently there is no dispersion in Practical examples and related test data in lubricants.
美國專利US 8658578 B2揭示利用自由基聚合直接使高分子鍵結在奈米鑽石表面的石墨層而形成奈米複合粒子，雖其簡化了奈米鑽石表面接枝高分子的製程，且解決奈米鑽石與潤滑油間相容性的問題，但前述專利顯示其所使用的奈米複合粒子(即固體潤滑油添加劑)必須在至少1000ppm(以潤滑油與奈米複合粒子的總重為100wt%計)的濃度下才能明顯改善潤滑特性，甚至在2000ppm的濃度下才能完全達到降低摩擦係數與磨耗率以及提升咬死荷重的功效，而添加過高濃度的固體潤滑油添加劑不僅會影響潤滑油本身的物化特性，且成本過高也導致實際商業效應有限。此外，根據現有文獻的記載，大部分添加在潤滑油中的固體潤滑油添加劑，其所使用的固體潤滑油添加劑濃度都至少都在1000ppm以上，例如以二硫化鉬、聚四氟乙烯或氮化硼等作為固體潤滑油添加劑時，其添加比率也都需於1000ppm以上，因此，於實際應用上會因成本考量及影響潤滑油的物化性質而受到諸多限制。 U.S. Patent No. 8,658,7878 B2 discloses the use of free radical polymerization to directly bond a polymer layer to a graphite layer on the surface of a nanodiamond to form a nanocomposite particle, which simplifies the process of grafting a polymer onto the surface of a nanodiamond and solves the problem of nanometer The problem of compatibility between diamond and lubricating oil, but the aforementioned patents show that the nanocomposite particles (ie, solid lubricating oil additive) used must be at least 1000 ppm (based on the total weight of the lubricating oil and nano composite particles of 100 wt%). At the concentration of 5%, the lubricating properties can be significantly improved. Even at a concentration of 2000 ppm, the friction coefficient and the wear rate can be completely reduced, and the sedentary load can be improved. Adding a high concentration of the solid lubricating oil additive not only affects the lubricating oil itself. The physicochemical properties, and the high cost also lead to limited practical commercial effects. In addition, according to the description in the prior literature, most of the solid lubricating oil additives added to the lubricating oil have a solid lubricating oil additive concentration of at least 1000 ppm, for example, molybdenum disulfide, polytetrafluoroethylene or nitriding. When boron or the like is used as a solid lubricating oil additive, the addition ratio thereof is also required to be 1000 ppm or more. Therefore, in practical applications, there are many limitations due to cost considerations and affecting the physical and chemical properties of the lubricating oil.
鑒於習知技術由於固體潤滑油添加劑的濃度都至少在1000ppm以上(以潤滑油與奈米複合粒子的總重為100wt%計)，導致添加過高濃度的固體潤滑油添加劑會影響潤滑油本身的物化特性及產生成本過高的問題。因此，本發明人首先思及改良習知所 使用的固體潤滑油添加劑(奈米複合粒子)，使固體潤滑油添加劑(奈米複合粒子)能完全與礦物油、半合成油或合成油等潤滑油相容，且同時還具有能自行吸附金屬表面的能力，因而無需於潤滑油中添加高濃度的固體潤滑油添加劑，便能達到降低摩擦係數與磨耗率以及提升咬死荷重的功效。 In view of the conventional technology, since the concentration of the solid lubricating oil additive is at least 1000 ppm or more (based on the total weight of the lubricating oil and the nano composite particles is 100% by weight), the addition of an excessively high concentration of the solid lubricating oil additive affects the lubricating oil itself. Physical and chemical properties and the problem of excessive cost. Therefore, the inventor first thought about improving the conventional institute. The solid lubricating oil additive (nano composite particles) is used to make the solid lubricating oil additive (nano composite particles) completely compatible with lubricating oils such as mineral oil, semi-synthetic oil or synthetic oil, and also has the ability to adsorb metal by itself. The ability of the surface, thus eliminating the need to add a high concentration of solid lubricant additives to the lubricating oil, can achieve the effect of reducing the friction coefficient and the wear rate and improving the sedentary load.
因此，本發明之第一目的，即在提供一種潤滑組成物，該潤滑組成物僅需使用極低濃度(500ppm以下)的固體潤滑油添加劑(奈米複合粒子)，便能達到降低摩擦係數與磨耗率以及提升咬死荷重的功效。 Therefore, the first object of the present invention is to provide a lubricating composition which can reduce the friction coefficient by using only a very low concentration (below 500 ppm) of a solid lubricating oil additive (nano composite particle). Abrasive rate and the effect of increasing the weight of the bite.
於是，本發明潤滑組成物包含潤滑油及多個分散於該潤滑油中的奈米複合粒子。 Thus, the lubricating composition of the present invention comprises a lubricating oil and a plurality of nanocomposite particles dispersed in the lubricating oil.
該每一個奈米複合粒子包括奈米碳材及鍵結於該奈米碳材上的共聚寡聚物鏈，該奈米碳材是選自於奈米鑽石、石墨烯、奈米碳管或前述的組合，該共聚寡聚物鏈包括一種含能與金屬螯合之官能基的嵌段及一種含親油性官能基的嵌段，以該潤滑組成物的總重為100wt%計，該等奈米複合粒子的總含量範圍為100~500ppm(0.01~0.05wt%)。 Each of the nano composite particles comprises a nano carbon material and a copolymerized oligomer chain bonded to the nano carbon material, the nano carbon material being selected from the group consisting of nano diamonds, graphene, carbon nanotubes or In the foregoing combination, the copolymerized oligomer chain comprises a block containing a functional group capable of chelation with a metal and a block containing a lipophilic functional group, and the total weight of the lubricating composition is 100% by weight, such The total content of the nanocomposite particles ranges from 100 to 500 ppm (0.01 to 0.05 wt%).
因此，本發明之第二目的，即在提供另一種潤滑組成物，該潤滑組成物同樣僅需使用極低濃度(500ppm以下)的固體潤 滑油添加劑(奈米複合粒子)，便能達到降低摩擦係數與磨耗率以及提升咬死荷重的功效。 Therefore, a second object of the present invention is to provide another lubricating composition which also requires only a very low concentration (500 ppm or less) of solid lubricant. The oil additive (nano composite particles) can reduce the friction coefficient and wear rate and improve the biting load.
於是，本發明潤滑組成物包含潤滑油及多個分散於該潤滑油中的奈米複合粒子。 Thus, the lubricating composition of the present invention comprises a lubricating oil and a plurality of nanocomposite particles dispersed in the lubricating oil.
該每一個奈米複合粒子是由共聚寡聚物所組成，該共聚寡聚物包括一種含能與金屬螯合之官能基的嵌段及一種含親油性官能基的嵌段，以該潤滑組成物的總重為100wt%計，該等奈米複合粒子的總含量範圍為100~500ppm。 Each of the nanocomposite particles is composed of a copolymerized oligomer comprising a block containing a functional group capable of chelation with a metal and a block containing a lipophilic functional group, which is composed of the lubricating composition. The total weight of the material is 100% by weight, and the total content of the nano composite particles ranges from 100 to 500 ppm.
本發明之功效在於藉由奈米複合粒子中的親油性官能基來提升奈米複合粒子與潤滑油間的相容性，使奈米複合粒子能均勻分散於潤滑油中，同時由於該能與金屬螯合之官能基將會螯合於欲潤滑之金屬機械組件的金屬表面，即奈米複合粒子能螯合於金屬表面上，因而使具有潤滑效果的奈米複合粒子能更有效分布於機械組件的金屬與金屬間，進而得以更有效地降低機械組件中金屬與金屬間的摩擦力。因此，本發明的潤滑組成物，相較於習知技術，僅需使用極低濃度(500ppm以下)的固體潤滑油添加劑(奈米複合粒子)，便能達到降低摩擦係數與磨耗率以及提升咬死荷重的功效。 The effect of the invention is to enhance the compatibility between the nano composite particles and the lubricating oil by the lipophilic functional groups in the nano composite particles, so that the nano composite particles can be uniformly dispersed in the lubricating oil, and at the same time The chelated functional group will chelate on the metal surface of the metal mechanical component to be lubricated, that is, the nanocomposite particles can chelate on the metal surface, thereby enabling the lubricated nanocomposite particles to be more effectively distributed to the mechanical component. The metal to the metal, in turn, more effectively reduce the friction between the metal and the metal in the mechanical components. Therefore, the lubricating composition of the present invention can reduce the friction coefficient and the abrasion rate and improve the bite by using only a very low concentration (under 500 ppm) of a solid lubricating oil additive (nano composite particle) as compared with the prior art. The effect of dead weight.
以下將就本發明內容進行詳細說明： The contents of the present invention will be described in detail below:
[潤滑組成物][Lubricating composition]
本發明的潤滑組成物包含潤滑油及多個分散於該潤滑油中且可自吸附金屬的奈米複合粒子，較佳地，依據不同機器或滑動元件的應用，本發明的潤滑組成物還可包含增黏劑、清淨分散劑、抗氧化劑、油性劑、機抗磨劑或消泡劑等添加劑。 The lubricating composition of the present invention comprises a lubricating oil and a plurality of nano composite particles dispersed in the lubricating oil and self-adsorbing the metal. Preferably, the lubricating composition of the present invention can also be applied according to the application of different machines or sliding elements. It contains additives such as tackifiers, detergent dispersants, antioxidants, oily agents, machine anti-wear agents or defoamers.
較佳地，以該潤滑組成物的總重為100wt%計，該等奈米複合粒子的總含量範圍為100~300ppm(0.01~0.03wt%)。 Preferably, the total content of the nano composite particles ranges from 100 to 300 ppm (0.01 to 0.03 wt%) based on 100% by weight of the total weight of the lubricating composition.
以下再針對潤滑油和奈米複合粒子進行說明。 The lubricating oil and the nano composite particles will be described below.
<潤滑油><lubricant>
本發明的潤滑油可為任何習知能降低金屬與金屬間之摩擦力的潤滑油。較佳地，依據不同機器或滑動元件的應用，該潤滑油舉例但不限於為引擎機油、工業齒輪油、冷凍機油、切削油、鑄造油、抽線引拔油、液壓油或潤滑脂。 The lubricating oil of the present invention can be any lubricating oil which is known to reduce the friction between metal and metal. Preferably, the lubricating oil is exemplified by, but not limited to, engine oil, industrial gear oil, refrigeration oil, cutting oil, foundry oil, drawn oil, hydraulic oil or grease, depending on the application of the different machine or sliding element.
<奈米複合粒子><Nano Composite Particles>
本發明中的每一個奈米複合粒子可為包括奈米碳材及鍵結於該奈米碳材上的共聚寡聚物鏈之奈米複合粒子，或是可為由共聚寡聚物所組成之奈米複合粒子。特別值得一提的是，本發明中的奈米複合粒子在添加於各種潤滑油配方中皆能有效彌補現有的有機分子在降低摩擦係數與磨耗率以及提升咬死荷重之功效上的 不足，因而具有高經濟效益。以下再分別針對兩種不同奈米複合粒子進行說明。 Each of the nano composite particles in the present invention may be a nano composite particle including a nano carbon material and a copolymerized oligomer chain bonded to the nano carbon material, or may be composed of a copolymerized oligomer. Nano composite particles. It is particularly worth mentioning that the nano composite particles of the present invention can effectively compensate for the effects of the existing organic molecules on reducing the friction coefficient and the abrasion rate and improving the seizure load in various lubricating oil formulations. Insufficient, thus having high economic benefits. Hereinafter, two different nano composite particles will be separately described.
A.該奈米複合粒子包括奈米碳材及鍵結於該奈米碳材上的共聚寡聚物鏈：A. The nano composite particle comprises a nano carbon material and a copolymerized oligomer chain bonded to the nano carbon material:
該奈米碳材是選自於奈米鑽石、石墨烯、奈米碳管或前述的組合。 The nanocarbon material is selected from the group consisting of nanodiamonds, graphene, carbon nanotubes, or a combination thereof.
較佳地，當該奈米碳材為奈米鑽石時，該奈米鑽石的原始尺寸範圍為4~10nm，且該共聚寡聚物鏈為共價鍵結於該奈米鑽石的表面。 Preferably, when the nano carbon material is a nano diamond, the original size of the nano diamond ranges from 4 to 10 nm, and the copolymerized oligomer chain is covalently bonded to the surface of the nano diamond.
較佳地，該石墨烯的厚度範圍為0.3~20nm。更佳地，該石墨烯的厚度範圍為5~10nm。 Preferably, the graphene has a thickness ranging from 0.3 to 20 nm. More preferably, the graphene has a thickness ranging from 5 to 10 nm.
較佳地，該奈米碳管的平均粒徑範圍為5~100nm。更佳地，該奈米碳管的平均粒徑範圍為20~50nm。 Preferably, the carbon nanotubes have an average particle diameter ranging from 5 to 100 nm. More preferably, the carbon nanotubes have an average particle size ranging from 20 to 50 nm.
該共聚寡聚物鏈包括一種含能與金屬螯合之官能基的嵌段及一種含親油性官能基的嵌段。 The copolymerized oligomer chain includes a block containing a functional group capable of chelation with a metal and a block containing a lipophilic functional group.
較佳地，該能與金屬螯合之官能基是選自於硫醇基(thiol group)、吡咯酮基(pyrrolidone group)、羧基(carboxyl group)或前述的組合。 Preferably, the functional group capable of chelation with a metal is selected from the group consisting of a thiol group, a pyrrolidone group, a carboxyl group, or a combination thereof.
更佳地，當該能與金屬螯合之官能基為硫醇基時，該含能與金屬螯合之官能基的嵌段是由聚甲基丙烯酸縮水甘油酯[poly(glycidyl methacrylate)]嵌段與含羧基的硫醇化合物經開環反應後所形成的嵌段。需特別解釋的是，該含羧基的硫醇化合物亦含能與金屬螯合的硫醇基，此外，該開環反應是透過聚甲基丙烯酸縮水甘油酯嵌段中的環氧基來與含羧基的硫醇化合物中的羧基 進行反應，以形成含結構的連結基，而該硫醇基 能透過該連結基鍵結於該共聚寡聚物鏈上。又更佳地，該含羧基的硫醇化合物舉例但不限於為3-硫基丙酸(3-mercaptopropionic acid，簡稱MPA)。 More preferably, when the functional group capable of chelation with a metal is a thiol group, the block containing a functional group capable of chelation with a metal is embedded by poly(glycidyl methacrylate) [poly(glycidyl methacrylate)] a block formed by a ring-opening reaction with a carboxyl group-containing thiol compound. It should be particularly explained that the carboxyl group-containing thiol compound also contains a thiol group capable of chelating with a metal. Further, the ring opening reaction is carried out through the epoxy group in the polyglycidyl methacrylate block. The carboxyl group in the thiol compound of the carboxyl group is reacted to form a a linking group of the structure, and the thiol group can be bonded to the copolymerized oligomer chain through the linking group. Still more preferably, the carboxyl group-containing thiol compound is exemplified by, but not limited to, 3-mercaptopropionic acid (MPA).
更佳地，當該能與金屬螯合之官能基為吡咯酮基時，該含能與金屬螯合之官能基的嵌段為聚乙烯吡咯烷酮嵌段。 More preferably, when the functional group capable of chelation with a metal is a pyrrolidone group, the block containing a functional group capable of chelation with a metal is a polyvinylpyrrolidone block.
更佳地，當該能與金屬螯合之官能基為羧酸基時，該含能與金屬螯合之官能基的嵌段為聚丙烯酸嵌段。 More preferably, when the functional group capable of chelation with a metal is a carboxylic acid group, the block containing a functional group capable of chelation with a metal is a polyacrylic acid block.
較佳地，該含親油性官能基的嵌段為聚(甲基)丙烯酸烷基酯嵌段，且烷基數為5~22。需特別說明的是，本發明說明書及申請專利範圍中之「聚(甲基)丙烯酸烷基酯」一詞係涵蓋聚甲基丙烯酸烷基酯及聚丙烯酸烷基酯。更佳地，該聚(甲基)丙烯酸烷基酯嵌段之烷基數為15~22。又更佳地，該聚(甲基)丙烯酸烷基酯舉例 但不限於為聚甲基丙烯酸十八烷基酯[poly(stearyl methacrylate)；烷基數為18] Preferably, the lipophilic functional group-containing block is a polyalkyl (meth) acrylate block and the number of alkyl groups is 5-22. It is to be noted that the term "polyalkyl (meth) acrylate" in the specification and claims of the present invention encompasses polyalkyl methacrylate and polyalkyl acrylate. More preferably, the polyalkyl (meth) acrylate block has an alkyl group number of from 15 to 22. Still more preferably, the polyalkyl (meth) acrylate is exemplified But not limited to poly(stearyl methacrylate); the number of alkyl groups is 18]
較佳地，該共聚寡聚物鏈的重量平均分子量範圍為4,000~10,000。更佳地，該共聚寡聚物鏈的重量平均分子量範圍為4,000~6,000。 Preferably, the copolyoligomer chain has a weight average molecular weight ranging from 4,000 to 10,000. More preferably, the copolyoligomer chain has a weight average molecular weight ranging from 4,000 to 6,000.
較佳地，以該每一個奈米複合粒子的總重為100wt%計，該共聚寡聚物鏈的含量範圍為5~20wt%。更佳地，以該每一個奈米複合粒子的總重為100wt%計，該共聚寡聚物鏈的含量範圍為8~15wt%。 Preferably, the copolymerized oligomer chain is contained in an amount ranging from 5 to 20% by weight based on 100% by weight of the total weight of each of the nanocomposite particles. More preferably, the copolymerized oligomer chain is present in an amount ranging from 8 to 15% by weight based on 100% by weight of the total weight of each of the nanocomposite particles.
較佳地，該共聚寡聚物鏈還包括一種與奈米碳材鍵結的嵌段。更佳地，該與奈米碳材鍵結的嵌段是由聚甲基丙烯酸縮水甘油酯嵌段與表面含羧基的奈米碳材(表面含羧基的奈米鑽石、表面含羧基的石墨烯或表面含羧基的奈米碳管)經開環反應後所形成的嵌段。需特別解釋的是，該開環反應是透過聚甲基丙烯酸縮水甘油酯嵌段中的環氧基來與該表面含羧基的奈米碳材中的羧基進行 反應，以形成含結構的連結基，而該共聚寡聚物 鏈能透過該連結基鍵結於該奈米碳材上。 Preferably, the copolymerized oligomer chain further comprises a block bonded to the nanocarbon material. More preferably, the block bonded to the nano carbon material is composed of a polyglycidyl methacrylate block and a surface-containing carboxyl group-containing nanocarbon material (carbon crystal-containing nano-diamond, surface carboxyl group-containing graphene) Or a block formed by a ring-opening reaction of a carboxyl group-containing carbon nanotube. In particular, the ring opening reaction is carried out by reacting an epoxy group in the polyglycidyl methacrylate block with a carboxyl group in the carboxyl group-containing nanocarbon material to form a a linking group of the structure, and the copolymerized oligomer chain can be bonded to the nanocarbon material through the linking group.
更佳的，當前述該表面含羧基的奈米碳材為氧化奈米鑽石時，該氧化奈米鑽石的平均粒徑範圍為4~100nm。更佳地， 該氧化奈米鑽石的平均粒徑範圍為30~80nm。又更佳地，該氧化奈米鑽石的平均粒徑範圍為30~60nm。 More preferably, when the surface carbon-containing nanocarbon material is a oxidized nano-diamond, the oxidized nano-diamond has an average particle diameter ranging from 4 to 100 nm. More preferably, The oxidized nanodiamond has an average particle diameter ranging from 30 to 80 nm. More preferably, the oxidized nanodiamond has an average particle size ranging from 30 to 60 nm.
B.該奈米複合粒子是由共聚寡聚物所組成：B. The nanocomposite particles are composed of copolymerized oligomers:
該共聚寡聚物包括一種含能與金屬螯合之官能基的嵌段及一種含親油性官能基的嵌段，而該共聚寡聚物中含能與金屬螯合之官能基的嵌段及含親油性官能基的嵌段之詳細說明，分別如同前述共聚寡聚物鏈中含能與金屬螯合之官能基的嵌段及含親油性官能基的嵌段之詳細說明。 The copolymerized oligomer comprises a block containing a functional group capable of chelation with a metal and a block containing a lipophilic functional group, and the copolymerized oligomer contains a block of a functional group capable of chelation with a metal and The detailed description of the lipophilic functional group-containing block is as detailed as the block containing the functional group capable of chelation with the metal and the block containing the lipophilic functional group in the copolymer oligomer chain, respectively.
較佳地，該共聚寡聚物的重量平均分子量範圍為4,000~10,000。更佳地，該共聚寡聚物的重量平均分子量範圍為4,000~6,000。 Preferably, the copolymerized oligomer has a weight average molecular weight ranging from 4,000 to 10,000. More preferably, the copolymerized oligomer has a weight average molecular weight ranging from 4,000 to 6,000.
[潤滑組成物的製備方法][Preparation method of lubricating composition]
本發明潤滑組成物的製備方法包含一製備奈米複合粒子的步驟，及一混合潤滑油與奈米複合粒子的步驟。 The preparation method of the lubricating composition of the present invention comprises a step of preparing a nano composite particle, and a step of mixing the lubricating oil with the nano composite particle.
當該奈米複合粒子為包括奈米碳材及鍵結於該奈米碳材上的共聚寡聚物鏈時，該製備奈米複合粒子的步驟是使共聚寡聚物鍵結於奈米碳材上，該奈米碳材是選自於奈米鑽石、石墨烯、奈米碳管或前述的組合，該共聚寡聚物包括一種含能與金屬螯合之官能基的嵌段與一種含親油性官能基的嵌段。 When the nano composite particle is a copolymerized oligomer chain including a nano carbon material and bonded to the nano carbon material, the step of preparing the nano composite particle is to bond the copolymerized oligomer to the nano carbon. In the material, the nano carbon material is selected from the group consisting of nano diamond, graphene, carbon nanotube or a combination of the foregoing, the copolymer oligomer comprising a block containing a functional group capable of chelation with a metal and a A block of lipophilic functional groups.
<該能與金屬螯合之官能基為硫醇基><The functional group capable of chelation with a metal is a thiol group>
較佳地，當該能與金屬螯合之官能基為硫醇基時，該製備奈米複合粒子的步驟包含下列步驟：(1)提供共聚寡聚物，該共聚寡聚物包括一種含環氧基的嵌段，以及一種含親油性官能基的嵌段；(2)於鹼的存在下，使共聚寡聚物中的部分環氧基與表面含羧基的奈米碳材進行開環反應，製得前驅奈米複合粒子；及(3)使前驅奈米複合粒子與含羧基的硫醇化合物進行開環反應，製得奈米複合粒子。 Preferably, when the functional group capable of chelation with a metal is a thiol group, the step of preparing the nano composite particles comprises the steps of: (1) providing a copolymerized oligomer comprising a ring-containing ring a block of an oxy group, and a block containing a lipophilic functional group; (2) ring-opening reaction of a part of the epoxy group in the copolymerized oligomer with a surface-containing carboxyl group-containing nanocarbon material in the presence of a base And preparing the precursor nano composite particles; and (3) subjecting the precursor nano composite particles to the ring-opening reaction of the carboxyl group-containing thiol compound to obtain nano composite particles.
需特別解釋的是，該步驟(3)是透過該共聚寡聚物未在步驟(2)中被反應掉的環氧基來與表面含羧基的硫醇化合物中的羧基進行開環反應。 It is to be particularly explained that the step (3) is a ring-opening reaction with a carboxyl group in a carboxyl group-containing thiol compound through the epoxy group which is not reacted in the copolymerized oligomer in the step (2).
更佳地，在該步驟(1)中，該含環氧基的嵌段為聚甲基丙烯酸縮水甘油酯嵌段，該含親油性官能基的嵌段為聚(甲基)丙烯酸烷基酯嵌段。 More preferably, in the step (1), the epoxy group-containing block is a polyglycidyl methacrylate block, and the lipophilic functional group-containing block is a polyalkyl (meth) acrylate. Block.
更佳地，在該步驟(3)中，該含羧基的硫醇化合物為3-硫基丙酸。 More preferably, in the step (3), the carboxyl group-containing thiol compound is 3-thiopropionic acid.
<該能與金屬螯合之官能基為吡咯酮基或羧酸基><The functional group capable of chelation with a metal is a pyrrolidone group or a carboxylic acid group>
較佳地，當該含能與金屬螯合之官能基為吡咯酮基或羧酸基時，該製備奈米複合粒子的步驟包含下列步驟：(1)提供共聚寡聚物，該共聚寡聚物包括一種含環氧基的嵌段、一種含能與金屬螯合之官能基的嵌段，以及一種含親油性官能基的嵌段；及(2)於鹼的存在下，使該共聚寡聚物中的環氧基與表面含羧基的奈米碳材進行開環反應，製得該奈米複合粒子。 Preferably, when the functional group capable of chelation with a metal is a pyrrolidone group or a carboxylic acid group, the step of preparing the nano composite particles comprises the following steps: (1) providing a copolymerized oligomer, the copolymerization oligomerization The invention comprises an epoxy group-containing block, a block containing a functional group capable of chelation with a metal, and a block containing a lipophilic functional group; and (2) in the presence of a base, the copolymerized oligomer The nano-composite particles are obtained by subjecting an epoxy group in the polymer to a ring-opening reaction with a surface-containing carboxyl group-containing nano carbon material.
更佳地，在該步驟(1)中，該含環氧基的嵌段為聚甲基丙烯酸縮水甘油酯嵌段，該含能與金屬螯合之官能基的嵌段為聚乙烯吡咯烷酮嵌段或聚丙烯酸嵌段，該含親油性官能基的嵌段為聚(甲基)丙烯酸烷基酯嵌段。 More preferably, in the step (1), the epoxy group-containing block is a polyglycidyl methacrylate block, and the block containing a functional group capable of chelation with a metal is a polyvinylpyrrolidone block. Or a polyacrylic acid block, the lipophilic functional group-containing block being a polyalkyl (meth) acrylate block.
更佳地，不論該能與金屬螯合之官能基為硫醇基、吡咯酮基或羧酸基，為了使表面含羧基的奈米碳材能均勻分散地與共聚寡聚物進行開環反應，於反應前皆需先將表面含羧基的奈米碳材先分散於低沸點的非極性有機溶劑中，同時加入分散劑，接著置於含鋯珠球磨材料的連續式球磨機腔槽中進行球磨分散後，才與該共聚寡聚物進行反應。 More preferably, the functional group capable of chelation with the metal is a thiol group, a pyrrolidone group or a carboxylic acid group, and the ring-opening reaction with the copolymerized oligomer can be uniformly dispersed in order to uniformly disperse the surface-containing carboxyl group-containing nano carbon material. Before the reaction, the surface carbon-containing nano carbon material is first dispersed in a low-boiling non-polar organic solvent, and a dispersing agent is added, and then placed in a continuous ball mill cavity containing a zirconium ball ball mill material for ball milling. After the dispersion, the copolymerized oligomer was reacted.
又更佳地，該非極性有機溶劑為四氫呋喃(THF)或正己烷。 Still more preferably, the non-polar organic solvent is tetrahydrofuran (THF) or n-hexane.
又更佳地，該分散劑為油胺(oleylamine)或三正辛基胺。 Still more preferably, the dispersing agent is oleylamine or tri-n-octylamine.
又更佳地，以非極性有機溶劑的總重為100wt%計，表面含羧基的奈米碳材的含量範圍為5~15wt%。又更佳地，以非極性有機溶劑的總重為100wt%計，表面含羧基的奈米碳材的總含量為5wt%。 Still more preferably, the content of the carboxyl group-containing nanocarbon material is in the range of 5 to 15% by weight based on 100% by weight of the total weight of the nonpolar organic solvent. Still more preferably, the total content of the carboxyl group-containing nanocarbon material is 5% by weight based on 100% by weight of the total weight of the nonpolar organic solvent.
又更佳地，以表面含羧基的奈米碳材的總重為100wt%計，分散劑的添加量範圍為20~60wt%。又更佳地，以表面含羧基的奈米碳材的總重為100wt%計，分散劑的添加量範圍為35~45wt%。 Still more preferably, the dispersant is added in an amount ranging from 20 to 60% by weight based on 100% by weight of the total weight of the surface-containing carboxyl group-containing carbon material. Still more preferably, the dispersant is added in an amount ranging from 35 to 45 wt% based on 100% by weight of the total weight of the surface-containing carboxyl group-containing carbon material.
更佳地，不論該能與金屬螯合之官能基為硫醇基、吡咯酮基或羧酸基，共聚寡聚物與表面含羧基的奈米碳材之重量比值範圍為0.5~1.5。又更佳地，共聚寡聚物與表面含羧基的奈米碳材之重量比值為0.8~1.2。 More preferably, the weight ratio of the copolymerized oligomer to the carboxyl group-containing nanocarbon material ranges from 0.5 to 1.5, regardless of whether the functional group capable of chelation with the metal is a thiol group, a pyrrolidone group or a carboxylic acid group. More preferably, the weight ratio of the copolymerized oligomer to the surface-containing carboxyl group-containing nanocarbon material is from 0.8 to 1.2.
更佳地，不論該能與金屬螯合之官能基為硫醇基、吡咯酮基或羧酸基，共聚寡聚物與表面含羧基的奈米碳材進行開環反應的溫度範圍為65~90℃。又更佳地，共聚寡聚物與表面含羧基的奈米碳材進行開環反應的溫度範圍為70~90℃。 More preferably, whether the functional group capable of chelation with a metal is a thiol group, a pyrrolidone group or a carboxylic acid group, the temperature range of the copolymerization oligomer to the surface-containing carboxyl group-containing nanocarbon material is 65~ 90 ° C. More preferably, the temperature at which the copolymerized oligomer is subjected to a ring-opening reaction with the surface-containing carboxyl group-containing nanocarbon material is in the range of 70 to 90 °C.
更佳地，不論該能與金屬螯合之官能基為硫醇基、吡咯酮基或羧酸基，共聚寡聚物與表面含羧基的奈米碳材進行開環反應的時間為0.5~1.5小時。 More preferably, whether the functional group capable of chelation with a metal is a thiol group, a pyrrolidone group or a carboxylic acid group, the copolymerization oligomer is subjected to a ring-opening reaction with a surface-containing carboxyl group-containing nanocarbon material at a time of 0.5 to 1.5. hour.
<共聚寡聚物的製備方法><Preparation method of copolymer oligomer>
前述的共聚寡聚物是藉由混合反應單體、自由基起始劑、烷基硫醇與溶劑，進行共聚合反應後所製得。 The above-mentioned copolymerized oligomer is obtained by carrying out a copolymerization reaction by mixing a reaction monomer, a radical initiator, an alkylthiol and a solvent.
需說明的是，當該能與金屬螯合之官能基為硫醇基時，該反應單體為含環氧基的單體，以及含親油性官能基的單體；當該能與金屬螯合之官能基為吡咯酮基或羧酸基時，該反應單體為含環氧基的單體、含能與金屬螯合之官能基的單體，以及含親油性官能基的單體。 It should be noted that when the functional group capable of chelation with a metal is a thiol group, the reactive monomer is an epoxy group-containing monomer, and a lipophilic functional group-containing monomer; when the energy can be chelated with the metal When the functional group is a pyrrolidone group or a carboxylic acid group, the reactive monomer is an epoxy group-containing monomer, a monomer containing a functional group capable of chelate with a metal, and a lipophilic functional group-containing monomer.
較佳地，當該能與金屬螯合之官能基為硫醇基時，該含親油性官能基的單體與該含環氧基的單體之莫耳數比為1：4~4：1。更佳地，該含親油性官能基的單體與該含環氧基的單體之莫耳數比為1：2。 Preferably, when the functional group capable of chelation with the metal is a thiol group, the molar ratio of the lipophilic functional group-containing monomer to the epoxy group-containing monomer is 1:4 to 4: 1. More preferably, the molar ratio of the lipophilic functional group-containing monomer to the epoxy group-containing monomer is 1:2.
較佳地，當該能與金屬螯合之官能基為吡咯酮基或羧酸基時，該含親油性官能基的單體、該含環氧基的單體與該含能與金屬螯合之官能基的單體之莫耳數比為1：0.1：1~1：1：0.5。更 佳地，該含親油性官能基的單體、該含環氧基的單體與該含能與金屬螯合之官能基的單體之莫耳數比為1：1：1。 Preferably, when the functional group capable of chelation with a metal is a pyrrolidone group or a carboxylic acid group, the lipophilic functional group-containing monomer, the epoxy group-containing monomer and the energy-containing metal are chelated The molar ratio of the monomer of the functional group is 1:0.1:1 to 1:1:0.5. more Preferably, the molar ratio of the lipophilic functional group-containing monomer, the epoxy group-containing monomer, and the monomer having a functional group capable of chelate to the metal is 1:1:1.
較佳地，該自由基起始劑是選自於過氧化物起始劑、偶氮化物起始劑或前述的組合。該自由基起始劑舉例但不限於為過氧化苯(benzoyl peroxide)或偶氮二異丁腈[2,2'-azobis(2-methylpropionitrile)]。 Preferably, the free radical initiator is selected from the group consisting of a peroxide initiator, an azo initiator, or a combination of the foregoing. The radical initiator is exemplified by, but not limited to, benzoyl peroxide or 2,2'-azobis (2-methylpropionitrile).
該烷基硫醇能減緩聚合反應並使聚合分子量較均勻，進而能使共聚反應後所產生的聚合物分子量控制在合理範圍內。較佳地，該烷基硫醇為十八烷基硫醇。 The alkyl mercaptan can slow down the polymerization reaction and make the polymerization molecular weight relatively uniform, thereby controlling the molecular weight of the polymer produced after the copolymerization reaction within a reasonable range. Preferably, the alkyl mercaptan is octadecyl mercaptan.
較佳地，該溶劑例如但不限於為四氫呋喃。 Preferably, the solvent is, for example but not limited to, tetrahydrofuran.
較佳地，共聚反應的溫度為60~90℃。更佳地，共聚反應的溫度為65~75℃。 Preferably, the temperature of the copolymerization reaction is from 60 to 90 °C. More preferably, the temperature of the copolymerization reaction is 65 to 75 °C.
較佳地，共聚反應的時間為20~60分鐘。更佳地，共聚反應的時間為25~35分鐘。 Preferably, the copolymerization reaction takes 20 to 60 minutes. More preferably, the copolymerization time is from 25 to 35 minutes.
較佳地，共聚反應是於油浴及劇烈攪拌下進行。 Preferably, the copolymerization is carried out in an oil bath with vigorous stirring.
較佳地，於該共聚反應後還包含一個透過減壓濃縮方式除去溶劑與烷基硫醇的步驟。 Preferably, after the copolymerization reaction, a step of removing the solvent and the alkyl mercaptan by concentration under reduced pressure is further included.
較佳地，當該能與金屬螯合之官能基為硫醇基時，該含環氧基的單體為甲基丙烯酸縮水甘油酯單體，該含親油性官能基 的單體為(甲基)丙烯酸烷基酯單體；當該能與金屬螯合之官能基為吡咯酮基或羧酸基時，該含環氧基的單體為甲基丙烯酸縮水甘油酯單體，該含親油性官能基的單體為(甲基)丙烯酸烷基酯單體，該含能與金屬螯合之官能基的單體為乙烯吡咯烷酮單體或丙烯酸單體。 Preferably, when the functional group capable of chelation with a metal is a thiol group, the epoxy group-containing monomer is a glycidyl methacrylate monomer, and the lipophilic functional group is contained. The monomer is an alkyl (meth) acrylate monomer; when the functional group capable of chelating with a metal is a pyrrolidone group or a carboxylic acid group, the epoxy group-containing monomer is glycidyl methacrylate The monomer, the lipophilic functional group-containing monomer is an alkyl (meth)acrylate monomer, and the monomer having a functional group capable of chelation with a metal is a vinylpyrrolidone monomer or an acrylic monomer.
本發明將就以下實施例來作進一步說明，但應瞭解的是，該實施例僅為例示說明之用，而不應被解釋為本發明實施之限制。 The present invention will be further illustrated by the following examples, but it should be understood that this embodiment is intended to be illustrative only and not to be construed as limiting.
<製備例1><Preparation Example 1>
製備氧化奈米鑽石(表面含羧基的奈米鑽石)Preparation of oxidized nano-diamonds (nano-diamonds with carboxyl groups on the surface)
參閱反應式a，將100g、原始尺寸範圍為4~10nm的奈米鑽石以高溫爐加熱至450℃後，以200sccm的流速於高溫爐管中持續通入空氣30分鐘，使奈米鑽石表面的富勒烯石磨層或非晶質碳氧化成羧基後，製得氧化奈米鑽石(表面含有羧基的奈米鑽石，重量損失約10~18wt%)。 Referring to the reaction formula a, 100 g of nano diamond having an original size range of 4 to 10 nm is heated to 450 ° C in a high temperature furnace, and air is continuously introduced into the high temperature furnace tube at a flow rate of 200 sccm for 30 minutes to make the surface of the nano diamond. After the fullerene stone layer or the amorphous carbon is oxidized to a carboxyl group, a oxidized nano-diamond (nano-diamond having a carboxyl group on the surface and having a weight loss of about 10 to 18% by weight) is obtained.
<製備例2><Preparation Example 2>
製備共聚寡聚物(能與金屬螯合之官能基為硫醇基)Preparation of copolymerized oligomers (functional groups capable of chelation with metals are thiol groups)
參閱反應式b，製備例2的共聚寡聚物是依據下列步驟製得： Referring to Reaction Formula b, the copolymerized oligomer of Preparation Example 2 was prepared according to the following procedure:
步驟(1)：依據表1選擇成分與各成分添加量後，混合反應單體、自由基起始劑、烷基硫醇與溶劑後，製得反應混合物。其中，該反應單體中，甲基丙烯酸十八烷基酯單體與甲基丙烯酸縮水甘油酯單體的莫耳數比為1：2。 Step (1): After selecting the components and the amounts of the components in accordance with Table 1, the reaction mixture is prepared by mixing a reaction monomer, a radical initiator, an alkylthiol, and a solvent. Wherein, in the reaction monomer, the molar ratio of the octadecyl methacrylate monomer to the glycidyl methacrylate monomer is 1:2.
步驟(2)：先將前述步驟(1)所得的反應混合物以油浴方式加熱至70℃，攪拌迴流30分鐘，再透過減壓濃縮方式除去溶劑 與烷基硫醇後，製得重量平均分子量為4600且具有式(I)結構的共聚寡聚物。 Step (2): first, the reaction mixture obtained in the above step (1) is heated to 70 ° C in an oil bath, stirred and refluxed for 30 minutes, and then the solvent is removed by concentration under reduced pressure. After the alkyl mercaptan, a copolymerized oligomer having a weight average molecular weight of 4,600 and having the structure of the formula (I) was obtained.
<實施例1><Example 1>
製備潤滑組成物(奈米碳材為奈米鑽石、能與金屬螯合之官能基為硫醇基)Preparation of a lubricating composition (nano carbon material is a nano diamond, and the functional group capable of chelation with a metal is a thiol group)
實施例1之潤滑組成物的製備方法包含一製備奈米複合粒子的步驟A，及一混合潤滑油與奈米複合粒子的步驟B。 The method for producing the lubricating composition of Example 1 comprises a step A of preparing a nano composite particle, and a step B of mixing the lubricating oil with the nano composite particle.
A.製備奈米複合粒子的步驟：A. Steps for preparing nano composite particles:
步驟(1)：提供製備例2的共聚寡聚物。 Step (1): The copolymer oligomer of Preparation Example 2 was provided.
步驟(2)：依據下列(i)~(iii)的步驟製備前驅奈米複合粒子. Step (2): preparing the precursor nano composite particles according to the following steps (i) to (iii).
(i)先將由製備例1所製得的氧化奈米鑽石加入4L的THF溶劑，再加入20g三正辛基胺(相對於氧化奈米鑽石重量之40wt%)分散劑，接著置於含50μm鋯珠的連續式球磨腔槽中進行球 磨分散，使氧化奈米鑽石之平均粒徑達到約50nm後，製得奈米碳材分散溶液。 (i) The oxidized nanodiamonds prepared in Preparation Example 1 were first added to 4 L of THF solvent, followed by 20 g of tri-n-octylamine (40 wt% relative to the weight of the oxidized nanodiamonds) dispersant, followed by 50 μm. Ball in a continuous ball mill cavity of zirconium beads After grinding and dispersing, the average particle diameter of the oxidized nano diamond reaches about 50 nm, and a nano carbon material dispersion solution is obtained.
(ii)參閱反應式c，以共聚寡聚物與氧化奈米鑽石之重量比值為1的比例，混合製備例2的共聚寡聚物[式(I)]與前述步驟(i)所得的奈米碳材分散溶液後，加熱至70℃並迴流1小時，使該共聚寡聚物中的部分環氧基會於鹼(三正辛基胺)的存在下和該氧化奈米鑽石中之羧基進行開環反應而形成前驅奈米複合粒子後，製得含數個前驅奈米複合粒子的溶液。 (ii) Referring to the reaction formula c, the copolymerized oligomer of the preparation example 2 [formula (I)] and the naphthalene obtained in the aforementioned step (i) are mixed at a ratio of the weight ratio of the copolymerized oligomer to the oxidized nanodiamond. After dispersing the solution of the rice carbon material, heating to 70 ° C and refluxing for 1 hour, the partial epoxy group in the copolymerized oligomer will be in the presence of a base (tri-n-octylamine) and the carboxyl group in the oxidized nanodiamond. After the ring-opening reaction is carried out to form the precursor nano-composite particles, a solution containing a plurality of precursor nano-composite particles is obtained.
步驟(3)：參閱反應式d，將3-硫基丙酸(表面含羧基的硫醇化合物)加入前述步驟(2)所得含數個前驅奈米複合粒子的溶液中，繼續於70℃下迴流1小時，使該前驅奈米複合粒子與3-硫基丙酸進行開環反應形成奈米複合粒子後，透過離心或過濾方式除去未反應的共聚寡聚物及其它未反應的化學藥品，最終製得含多個奈米鑽石上鍵結有共聚寡聚物鏈之奈米複合粒子的溶液。需說明的是，以該每一個奈米複合粒子的總重為100wt%計，該共聚寡聚物鏈的含量範圍為8~15wt%。 Step (3): Referring to the reaction formula d, 3-thiopropionic acid (the carboxyl group-containing thiol compound) is added to the solution containing the plurality of precursor nano composite particles obtained in the above step (2), and continues at 70 ° C After refluxing for 1 hour, the precursor nanocomposite particles are subjected to ring-opening reaction with 3-thiopropionic acid to form nano composite particles, and then unreacted copolymerized oligomers and other unreacted chemicals are removed by centrifugation or filtration. A solution containing nanocomposite particles having a copolymerized oligomer chain bonded to a plurality of nanodiamonds is finally obtained. It should be noted that the content of the copolymerized oligomer chain ranges from 8 to 15% by weight based on 100% by weight of the total weight of each of the nano composite particles.
B.混合潤滑油與奈米複合粒子：B. Mixed lubricating oil and nano composite particles:
將前述A步驟最終所得含多個奈米複合粒子的溶液加入作為潤滑油的引擎機油(符合API美國石油協會規範SN等級)中，劇烈攪拌並加熱至60℃，接著以減壓濃縮方式除去THF溶劑後，製得本實施例的潤滑組成物。其中，以本實施例之潤滑組成物的總重為100wt%計，該等奈米複合粒子的總含量範圍為100ppm(0.01wt%)。 The solution containing the plurality of nano composite particles finally obtained in the above step A is added to the engine oil (according to the API American Petroleum Institute specification SN grade) as a lubricating oil, stirred vigorously and heated to 60 ° C, and then the THF is removed by concentration under reduced pressure. After the solvent, the lubricating composition of this example was obtained. Here, the total content of the nano composite particles is 100 ppm (0.01% by weight) based on 100% by weight of the total weight of the lubricating composition of the present embodiment.
<實施例2~3><Examples 2 to 3>
製備潤滑組成物(奈米碳材為奈米鑽石、能與金屬螯合之官能基為硫醇基)Preparation of a lubricating composition (nano carbon material is a nano diamond, and the functional group capable of chelation with a metal is a thiol group)
實施例2~3之潤滑組成物的製備方法與實施例1類似，其差別在於，在實施例2~3的步驟B中，以潤滑組成物的總重為100wt%計，該等奈米複合粒子的總含量範圍分別為200ppm(0.02wt%；實施例2)與300ppm(0.03wt%；實施例3)。 The preparation method of the lubricating compositions of Examples 2 to 3 is similar to that of Example 1, except that in the step B of Examples 2 to 3, the total weight of the lubricating composition is 100% by weight, and the nanocomposites are used. The total content of the particles ranged from 200 ppm (0.02 wt%; Example 2) to 300 ppm (0.03 wt%; Example 3).
<製備例3><Preparation Example 3>
製備共聚寡聚物(能與金屬螯合之官能基為吡咯酮基)Preparation of copolymerized oligomers (functional groups capable of chelation with metals are pyrrolidone groups)
製備例3之共聚寡聚物的製備方法與製備例2相似，其差別在於，本製備例的步驟(1)是依據表2選擇成分與各成分添加 量。其中，該反應單體中，甲基丙烯酸十八烷基酯單體、甲基丙烯酸縮水甘油酯單體與乙烯吡咯烷酮單體的莫耳數比為1：1：1。 The preparation method of the copolymerization oligomer of Preparation Example 3 is similar to that of Preparation Example 2, except that the step (1) of the preparation example is based on the selection of components and the addition of each component according to Table 2. the amount. Among them, in the reaction monomer, the molar ratio of the octadecyl methacrylate monomer, the glycidyl methacrylate monomer, and the vinylpyrrolidone monomer is 1:1:1.
<實施例4><Example 4>
製備潤滑組成物(奈米碳材為奈米鑽石、能與金屬螯合之官能基為吡咯酮基)Preparation of a lubricating composition (nano carbon material is a nano-diamond, and the functional group capable of chelation with a metal is pyrrolidone)
實施例4之潤滑組成物的製備方法包含一製備奈米複合粒子的步驟A，及一混合潤滑油與奈米複合粒子的步驟B。 The method for producing the lubricating composition of Example 4 comprises a step A of preparing a nano composite particle, and a step B of mixing the lubricating oil with the nano composite particle.
A.製備奈米複合粒子的步驟：A. Steps for preparing nano composite particles:
步驟(1)：提供製備例3的共聚寡聚物。 Step (1): The copolymer oligomer of Preparation Example 3 was provided.
步驟(2)：依據下列(i)~(ii)的步驟製備前驅奈米複合粒子： Step (2): Prepare the precursor nano composite particles according to the following steps (i) to (ii):
(i)先將由製備例1所製得的氧化奈米鑽石(相對於THF重量之5%)加入4L的THF溶劑，再加入約20g三正辛基胺(相對於表面含羧基的奈米鑽石重量之40wt%)分散劑，接著置於50μm鋯珠連續式球磨腔槽中進行球磨分散，使氧化奈米鑽石之平均粒徑達到約50nm後，製得奈米碳材分散溶液。 (i) First, the oxidized nanodiamonds prepared in Preparation Example 1 (5% relative to the weight of THF) were added to 4 L of THF solvent, and then about 20 g of tri-n-octylamine (relative to the surface-containing carboxyl-containing nanodiamonds). 40% by weight of the dispersant was placed in a 50 μm zirconium bead continuous ball mill chamber for ball-milling dispersion, and the average particle diameter of the oxidized nano-diamond was about 50 nm to prepare a nano-carbon material dispersion solution.
(ii)以共聚寡聚物與氧化奈米鑽石之重量比為1：1的比例，混合製備例3的共聚寡聚物與前述步驟(i)所得的奈米碳材分散溶液後，加熱至70℃並迴流1小時，以使該共聚寡聚物中的環氧基於鹼(三正辛基胺)的存在下和該氧化奈米鑽石中之羧基進行開環反應而形成奈米複合粒子後，製得含多個奈米鑽石上鍵結有共聚寡聚物鏈之奈米複合粒子的溶液。需說明的是，以該每一個奈米複合粒子的總重為100wt%計，該共聚寡聚物鏈的含量範圍為8~15wt%。 (ii) mixing the copolymerized oligomer of Preparation Example 3 with the nanocarbon material dispersion solution obtained in the above step (i) at a ratio of the weight ratio of the copolymerized oligomer to the oxidized nanodiamond to 1:1, and then heating to Reflowing at 70 ° C for 1 hour, so that the epoxy in the copolymerized oligomer is subjected to a ring-opening reaction with a carboxyl group in the oxidized nano-diamond in the presence of a base (tri-n-octylamine) to form a nano-composite particle. A solution comprising nanocomposite particles having a copolymerized oligomer chain bonded to a plurality of nanodiamonds is prepared. It should be noted that the content of the copolymerized oligomer chain ranges from 8 to 15% by weight based on 100% by weight of the total weight of each of the nano composite particles.
B.混合潤滑油與奈米複合粒子：B. Mixed lubricating oil and nano composite particles:
將前述A步驟最終所得含數個奈米複合粒子的溶液加入作為潤滑油的引擎機油(符合API美國石油協會規範SN等級)中，劇烈攪拌並加熱至60℃，接著以減壓濃縮方式除去THF溶劑後，製得本實施例的潤滑組成物。其中，以本實施例之潤滑組成物 的總重為100wt%計，該等奈米複合粒子的總含量範圍為100ppm(0.01wt%)。 The solution containing a plurality of nano composite particles finally obtained in the foregoing step A is added to an engine oil (according to API American Petroleum Institute Standard SN grade) as a lubricating oil, stirred vigorously and heated to 60 ° C, and then THF is removed by concentration under reduced pressure. After the solvent, the lubricating composition of this example was obtained. Wherein the lubricating composition of the embodiment The total weight of the nano composite particles was 100 ppm (0.01 wt%) based on 100 wt%.
<實施例5~6><Examples 5 to 6>
製備潤滑組成物(奈米碳材為奈米鑽石、能與金屬螯合之官能基為吡咯酮基)Preparation of a lubricating composition (nano carbon material is a nano-diamond, and the functional group capable of chelation with a metal is pyrrolidone)
實施例5~6之潤滑組成物的製備方法與實施例4類似，其差別在於，在實施例5~6的步驟B中，以潤滑組成物的總重為100wt%計，該等奈米複合粒子的總含量範圍分別為200ppm(0.02wt%；實施例5)與300ppm(0.03wt%；實施例6)。 The preparation method of the lubricating compositions of Examples 5 to 6 is similar to that of Example 4, except that in the step B of Examples 5 to 6, the total weight of the lubricating composition is 100% by weight, and the nanocomposites are used. The total content of the particles ranged from 200 ppm (0.02 wt%; Example 5) to 300 ppm (0.03 wt%; Example 6).
<實施例7><Example 7>
製備潤滑組成物(奈米碳材為石墨烯、能與金屬螯合之官能基為硫醇基)Preparation of a lubricating composition (nano carbon material is graphene, and the functional group capable of chelation with a metal is a thiol group)
實施例7之潤滑組成物的製備方法與實施例1類似，其差別在於，本實施例是以氧化石墨烯(即表面含羧基的石墨烯，石墨烯厚度為5~10nm，購自Sigma-Aldrich)取代實施例1所使用之表面含羧基的奈米鑽石。 The preparation method of the lubricating composition of Example 7 is similar to that of Example 1, except that the present embodiment is a graphene oxide (ie, graphene having a carboxyl group on the surface, graphene having a thickness of 5 to 10 nm, purchased from Sigma-Aldrich). Instead of the surface-containing carboxyl-containing nanodiamond used in Example 1.
<實施例8~9><Examples 8 to 9>
製備潤滑組成物(奈米碳材為石墨烯、能與金屬螯合之官能基為硫醇基)Preparation of a lubricating composition (nano carbon material is graphene, and the functional group capable of chelation with a metal is a thiol group)
實施例8~9之潤滑組成物的製備方法與實施例7類似，其差別在於，在實施例8~9的步驟B中，以潤滑組成物的總重為100wt%計，該等奈米複合粒子的總含量範圍分別為200ppm(0.02wt%；實施例8)與300ppm(0.03wt%；實施例9)。 The preparation method of the lubricating compositions of Examples 8 to 9 is similar to that of Example 7, except that in the step B of Examples 8 to 9, the total weight of the lubricating composition is 100% by weight, and the nanocomposites are used. The total content of the particles ranged from 200 ppm (0.02 wt%; Example 8) to 300 ppm (0.03 wt%; Example 9).
<製備例4><Preparation Example 4>
製備氧化奈米碳管(表面含羧基的奈米碳管)Preparation of oxidized carbon nanotubes (carbon nanotubes with carboxyl groups on the surface)
混合50g、平均粒徑為20~50nm的奈米碳管與強酸(硫酸與鹽酸體積比3：2)，於130℃下加熱迴流30分鐘，除去奈米碳管中的金屬觸媒且使奈米碳管表面形成羧基後，透過離心方式除去廢酸，以及透過大量去離子水清洗純化，再經乾燥後，製得該氧化奈米碳管(表面含有羧基的奈米碳管)。 Mixing 50g of carbon nanotubes with an average particle diameter of 20~50nm and strong acid (volume ratio of sulfuric acid to hydrochloric acid 3:2), heating and refluxing at 130 °C for 30 minutes, removing the metal catalyst in the carbon nanotubes and allowing Nai After forming a carboxyl group on the surface of the carbon nanotube, the waste acid is removed by centrifugation, and purified by washing with a large amount of deionized water, and then dried to obtain the carbon nanotube (carbon nanotube-containing carbon nanotube).
<實施例10><Example 10>
製備潤滑組成物(奈米碳材為奈米碳管、能與金屬螯合之官能基為硫醇基)Preparation of a lubricating composition (nano carbon material is a carbon nanotube, and a functional group capable of chelation with a metal is a thiol group)
實施例10之潤滑組成物的製備方法與實施例1類似，其差別在於，本實施例是以製備例4所製得之氧化奈米碳管取代實施例1所使用之氧化奈米鑽石。 The preparation method of the lubricating composition of Example 10 was similar to that of Example 1, except that the present embodiment was replaced by the oxidized carbon nanotube obtained in Preparation Example 4 in place of the oxidized nano-diamond used in Example 1.
<實施例11~12><Examples 11 to 12>
製備潤滑組成物(奈米碳材為奈米碳管、能與金屬螯合之官能基為硫醇基)Preparation of a lubricating composition (nano carbon material is a carbon nanotube, and a functional group capable of chelation with a metal is a thiol group)
實施例11~12之潤滑組成物的製備方法與實施例10類似，其差別在於，在實施例11~12的步驟B中，以潤滑組成物的總重為100wt%計，該等奈米複合粒子的總含量範圍分別為200ppm(0.02wt%；實施例11)與300ppm(0.03wt%；實施例12)。 The preparation methods of the lubricating compositions of Examples 11 to 12 were similar to those of Example 10 except that in the step B of Examples 11 to 12, the total weight of the lubricating composition was 100% by weight, and the nanocomposites were used. The total content of the particles ranged from 200 ppm (0.02 wt%; Example 11) to 300 ppm (0.03 wt%; Example 12).
實施例1~12之潤滑組成物的奈米碳材種類、能與金屬螯合之官能基種類，以及奈米複合粒子含量(以潤滑組成物的總重為100wt%計)，分別整理如下表3所示。 The type of the nano carbon material of the lubricating composition of Examples 1 to 12, the type of the functional group capable of chelation with the metal, and the content of the nanocomposite particles (based on the total weight of the lubricating composition of 100% by weight) are respectively arranged as follows. 3 is shown.
<元素分析與熱重分析><Elemental Analysis and Thermogravimetric Analysis>
將奈米鑽石、製備例1的氧化奈米鑽石、氧化石墨烯、奈米碳管、製備例4的氧化奈米碳管，以及實施例1、4、7與10中所製得的奈米複合粒子進行元素分析(C：N：S：H)與熱重分析(重量損失)，所得結果如下表4所示，其中，「~」表示「約」。 Nanodiamond, oxidized nanodiamond of Preparation Example 1, graphene oxide, carbon nanotube, carbon nanotube of Preparation Example 4, and nanoparticles prepared in Examples 1, 4, 7 and 10. The composite particles were subjected to elemental analysis (C:N:S:H) and thermogravimetric analysis (weight loss), and the results are shown in Table 4 below, wherein "~" means "about".
<傅立葉紅外線光譜(FT-IR)分析><Fourier infrared spectroscopy (FT-IR) analysis>
將奈米鑽石、製備例1的氧化奈米鑽石、氧化石墨烯、奈米碳管、製備例4的氧化奈米碳管，以及實施例1、4、7與10中所製得的奈米複合粒子以傅立葉紅外線光譜儀進行分析，所得結果如下表5所示。 Nanodiamond, oxidized nanodiamond of Preparation Example 1, graphene oxide, carbon nanotube, carbon nanotube of Preparation Example 4, and nanoparticles prepared in Examples 1, 4, 7 and 10. The composite particles were analyzed by a Fourier infrared spectrometer, and the results obtained are shown in Table 5 below.
<平均摩擦係數、磨耗率與咬死荷重分析><Average friction coefficient, wear rate and seizure load analysis>
a.測試方法：a. Test method:
平均摩擦係數、磨耗率與咬死荷重測試方法是參照文獻「Wear,vol.268(2010),p960-967」來進行，簡單說明的是，測試實驗是以翼對環模擬滑動元件時之摩擦係數及磨耗情況：先將油杯裝滿測試油品(即潤滑組成物或引擎機油)，再將整個翼對環上下試件浸入油杯內並施加360N的荷重，於滑動速度為6m/s的條件下進行測試，總測試時間約為90分鐘，總滑行距離約26280m。將實施例1~12的潤滑組成物與未含有奈米複合粒子的商業引擎機油(即比較例1)，分別以磨耗試驗機(Falex#6,USA)測試摩擦及磨耗效果。其中，摩擦係數是由數據擷取系統(Red Lion CSMSTRSX,USA)紀錄，下試件之磨耗率是以光學顯微鏡及表面輪郭儀測試，咬死荷重則是利用磨耗試驗機將荷重由400N逐漸增加荷重(每次增加50N)至上下試件咬死時的荷重。實施例1~12(潤滑組成物)與比較例1(引擎機油)所得的平均摩擦係數、磨耗率與咬死荷重數據整理如下表6所示。 The average friction coefficient, the wear rate and the dead load test method are described in the reference " Wear , vol. 268 (2010), p960-967". The test is based on the friction of the wing-to-ring simulation of the sliding element. Coefficient and wear: first fill the oil cup with test oil (ie lubrication composition or engine oil), then immerse the entire wing-to-ring test piece in the oil cup and apply a load of 360N at a sliding speed of 6m/s. The test was carried out under conditions of a total test time of approximately 90 minutes and a total taxi distance of approximately 26,280 m. The lubricating composition of Examples 1 to 12 and the commercial engine oil (i.e., Comparative Example 1) containing no nano composite particles were tested for friction and abrasion by an abrasion tester (Falex #6, USA). Among them, the friction coefficient is recorded by the data extraction system (Red Lion CSMSTRSX, USA). The wear rate of the lower test piece is tested by optical microscope and surface wheel. The bite load is gradually increased by the wear tester from 400N. Load (50N each time) to the load when the upper and lower specimens are killed. The average friction coefficient, the abrasion rate, and the sedentary load data obtained in Examples 1 to 12 (lubricating composition) and Comparative Example 1 (engine oil) are shown in Table 6 below.
b.結果與討論：b. Results and discussion:
由表6的結果顯示，與未添加本發明潤滑組成物的引擎機油(比較例1)相較，實施例1~12皆能有效降低摩擦係數與磨耗率以及提升咬死荷重，因此，相較於現有技術需添加1000ppm以上的固體潤滑油添加劑(奈米複合粒子)才能達到降低摩擦係數與磨耗率以及提升咬死荷重的功效，本發明實施例1~12的潤滑組成物僅添加100~300ppm的固體潤滑油添加劑(奈米複合粒子)即能有效降低摩擦係數與磨耗率以及提升咬死荷重，說明本發明的潤滑組 成物僅需使用極低濃度(500ppm以下)的固體潤滑油添加劑(奈米複合粒子)，便能達到降低摩擦係數與磨耗率以及提升咬死荷重的功效。 From the results of Table 6, it is shown that Examples 1 to 12 can effectively reduce the friction coefficient and the abrasion rate and increase the seizure load as compared with the engine oil (Comparative Example 1) to which the lubricating composition of the present invention is not added, and therefore, compared with In the prior art, it is necessary to add a solid lubricating oil additive (nano composite particle) of 1000 ppm or more in order to achieve the effects of lowering the friction coefficient and the abrasion rate and improving the seizure load. The lubricating composition of the embodiments 1 to 12 of the present invention only adds 100 to 300 ppm. The solid lubricating oil additive (nano composite particle) can effectively reduce the friction coefficient and the wear rate and increase the bite load, indicating the lubricating group of the present invention The product requires only a very low concentration (less than 500 ppm) of solid lubricating oil additive (nano composite particles) to reduce the friction coefficient and wear rate and enhance the sedentary load.
特別值得一提的是，使用接近圓形形狀之零維奈米鑽石的實施例1~6具有較佳降低摩擦係數功效，而能與金屬螯合之官能基為硫醇基的實施例1~3又略為優於為吡咯酮基的實施例4~6。此外，使用二維奈米碳材(石墨烯)的實施例7~9在降低磨耗率與提升咬死荷重上又明顯優於使用奈米鑽石的實施例1~3。因此，由前述說明可知，本發明可依據各種潤滑油的應用特性，選擇適當種類的奈米複合粒子來增強磨潤特性，所以本發明潤滑組成物的應用廣泛，足以涵蓋各種工業用液壓油、齒輪油、引擎機油、壓縮機油或冷凍機油等潤滑油。 It is particularly worth mentioning that Examples 1 to 6 using zero-dimensional nano-diamonds of a nearly circular shape have an effect of lowering the coefficient of friction, and the functional group capable of chelation with a metal is a thiol group. 3 is slightly superior to Examples 4-6 which are pyrrolidone groups. In addition, Examples 7 to 9 using two-dimensional nanocarbon materials (graphene) were significantly superior to Examples 1 to 3 using nanodiamonds in reducing the wear rate and increasing the sedentary load. Therefore, as can be seen from the foregoing description, the present invention can select suitable kinds of nano composite particles to enhance the grinding characteristics according to the application characteristics of various lubricating oils. Therefore, the lubricating composition of the present invention is widely applied to cover various industrial hydraulic oils. Lubricating oils such as gear oil, engine oil, compressor oil or refrigeration oil.
綜上所述，本發明是藉由奈米複合粒子中的親油性官能基來提升奈米複合粒子與潤滑油間的相容性，同時由於該能與金屬螯合之官能基將會螯合於欲潤滑之金屬機械組件的金屬表面，因此，本發明的潤滑組成物僅需使用極低濃度(500ppm以下)的固體潤滑油添加劑(奈米複合粒子)，便能達到降低摩擦係數與磨耗率以及提升咬死荷重的功效，故確實能達成本發明之目的。 In summary, the present invention enhances the compatibility between the nanocomposite particles and the lubricating oil by the lipophilic functional groups in the nanocomposite particles, and at the same time, the functional group capable of chelation with the metal will be chelated to The metal surface of the metal mechanical component to be lubricated, therefore, the lubricating composition of the present invention only needs to use a very low concentration (below 500 ppm) of a solid lubricating oil additive (nano composite particle) to achieve a reduction in friction coefficient and wear rate. The effect of seizing the load is enhanced, so that the object of the present invention can be achieved.
惟以上所述者，僅為本發明之實施例而已，當不能以此限定本發明實施之範圍，凡是依本發明申請專利範圍及專利說明書內容所作之簡單的等效變化與修飾，皆仍屬本發明專利涵蓋之範圍內。 However, the above is only the embodiment of the present invention, and the scope of the invention is not limited thereto, and all the equivalent equivalent changes and modifications according to the scope of the patent application and the patent specification of the present invention are still The scope of the invention is covered.
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