CN113677781A - 含有支化醇丙氧基化物的金属加工流体 - Google Patents
含有支化醇丙氧基化物的金属加工流体 Download PDFInfo
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- CN113677781A CN113677781A CN202080027915.5A CN202080027915A CN113677781A CN 113677781 A CN113677781 A CN 113677781A CN 202080027915 A CN202080027915 A CN 202080027915A CN 113677781 A CN113677781 A CN 113677781A
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- tert
- butyl
- branched
- bis
- propoxylate
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- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
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- LZGVDNRJCGPNDS-UHFFFAOYSA-N trinitromethane Chemical compound [O-][N+](=O)C([N+]([O-])=O)[N+]([O-])=O LZGVDNRJCGPNDS-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/24—Polyethers
- C10M145/26—Polyoxyalkylenes
- C10M145/36—Polyoxyalkylenes etherified
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M173/00—Lubricating compositions containing more than 10% water
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
- C10M145/18—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M145/24—Polyethers
- C10M145/26—Polyoxyalkylenes
- C10M145/30—Polyoxyalkylenes of alkylene oxides containing 3 carbon atoms only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M173/00—Lubricating compositions containing more than 10% water
- C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/1006—Petroleum or coal fractions, e.g. tars, solvents, bitumen used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
- C10M2203/106—Naphthenic fractions
- C10M2203/1065—Naphthenic fractions used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
- C10M2207/046—Hydroxy ethers
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
- C10M2207/128—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids containing hydroxy groups; Ethers thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/18—Tall oil acids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
- C10M2209/1055—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only used as base material
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Abstract
本发明涉及一种加工工件的方法,包括使工具与工件接触以实现工件形状的改变,和将金属加工流体施加到所述工具与所述工件接触的表面区域,其中金属加工流体含有式R‑O‑(C3H6O)n‑H的丙氧基化物,其中R为支化C6‑C20烷基且n为3‑30。本发明进一步涉及金属加工流体,和丙氧基化物作为添加剂在金属加工流体中的用途。
Description
本发明涉及一种加工工件的方法,包括使工具与工件接触以实现工件形状的改变,和将金属加工流体施加到所述工具与所述工件接触的表面区域,其中金属加工流体含有式R-O-(C3H6O)n-H的丙氧基化物,其中R为支化C6-C20烷基且n为3-30。本发明进一步涉及金属加工流体,和丙氧基化物作为添加剂在金属加工流体中的用途。优选实施方案与其他优选实施方案的组合在本发明范围内。
金属加工流体(MWF)在全世界的车间中用于金属的切割和成形。它们的主要目的是冷却和润滑工具、工件和机器,抑制腐蚀和去除切屑。
在MWF领域,最小量润滑(MQL)的应用稳定地增加。通常,与数百立方米淹没工件相比,MQL产品仅以最小量使用(大约每8小时轮班1升)。如果有效地使用,这种形式的加工产生干的工件和干的切屑,这又产生优于湿加工的许多益处。
目前持续需要改进MWF和MQL的各种性能,例如减少发泡、增加储存稳定性、减少磨痕和保护加工工具。
该目的通过一种加工工件的方法来解决,该方法包括
a)使工具与工件接触以实现工件形状的改变,和
b)将金属加工流体施加至所述工具与所述工件接触的表面区域,其中金属加工流体含有式R-O-(C3H6O)n-H的丙氧基化物,其中R为支化C6-C20烷基且n为3-30。
成型方法例如是机加工、车削、磨削、开槽、剪切、挤压、冲压、仿形加工、弯曲、拉伸、钻削、冲切、刨削、攻丝或锯切。用于工件成型的合适工具是本领域技术人员已知的并且是商业上可获得的。
工件可以由各种材料制成,例如纯金属、金属合金、非金属、复合材料、塑料、耐火材料、陶瓷和其他可加工材料。复合材料是例如包含两种或更多种选自纯金属、金属合金、非金属、塑料、耐火材料和陶瓷的材料的组合或物理混合物。优选地,工件由纯金属或金属合金制成。
在步骤b)中将MWF施加到表面区域可以通过喷涂、喷射、溢流、喷雾、滴落或以其他方式引导MWF接触表面区域来进行。通常,MWF渗透和/或填充由工具和/或工件上的表面粗糙形成的微观区域。
当施加MWF时,应以足以润湿或渗透表面区域并填充表面上粗糙之间的区域的最小量施加MWF。施加到表面区域的MWF的量取决于成型方法和机器,并且是本领域技术人员已知的。
在优选的形式中,MWF用于MQL。金属加工流体可以以5-50ml/h的量施加,通常与压缩空气组合。
在另一形式中,MWF应用于低温冷却,其中工件通常用液氮、液氦或固体CO2冷却。在低温加工期间,由工件或研磨工具产生的切屑可能是个问题,并且可能需要被去除。由于工件的低温,使用具有低倾点的合适流体作为去除剂。
金属加工流体含有式R-O-(C3H6O)n-H的丙氧基化物,其中R为支化C6-C20烷基且n为3-30。
丙氧基化物重复单元(C3H6O)优选为(CH2-CH(CH3)-O)。丙氧基化物优选具有式R-O-(CH2-CH(CH3)-O)n-H。
指数n优选为5-25,特别是6-20的实数。在一种形式中,n为6-10。在另一形式中,n为12-18。
R除了支化烷基之外,还可以含有线性C6-C20烷基。通常,R含有小于30mol%、20mol%或5mol%的线性烷基。
R优选为支化C8-C16烷基,特别是C12-C14烷基。R可以含有支化烷基的混合物。在另一形式中,R是支化C10-C13烷基。在优选的形式中,R是支化C13烷基或支化C10烷基。在另一优选的形式中,R是2-丙基庚基。在另一优选的形式中,R是支化C13烷基。
在特定的形式中,R是十三烷醇混合物,其包含单、双重和三重支化十三烷醇。
该十三烷醇混合物可以通过异构十二碳烯混合物的加氢甲酰化和氢化得到,优选通过异构十二碳烯混合物的加氢甲酰化和氢化得到。
该异构十二碳烯混合物可以通过使包含丁烯类的烃混合物在非均相催化剂上反应得到,优选通过使包含丁烯类的烃混合物在非均相催化剂上反应得到。
在由包含丁烯类的烃混合物开始的多步方法中,第一步将丁烯类二聚而得到异构辛烯类和十二碳烯类的混合物。这里生产的主产物是辛烯类,而生产的十二碳烯类的比例基于反应器排出料通常为5-20重量%。然后将十二碳烯类从反应混合物中分离,加氢甲酰化得到相应C13醛类,然后氢化而得到异十三烷醇类。
因此,优选通过使包含丁烯类的烃混合物与包含氧化镍的非均相催化剂接触而得到该异构十二碳烯混合物。该烃混合物的异丁烯含量优选为5重量%或更小,尤其是3重量%或更小,特别优选2重量%或更小,最优选1.5重量%或更小,在每种情况下基于丁烯总含量。合适的烃料流是已知为C4馏分的料流—一种由丁烯类和丁烷类构成的混合物,它可以由FCC装置或蒸汽裂解装置大量得到。特别优选使用萃余液II作为原料,这是贫含异丁烯的C4馏分。
一种优选的原料包含50-100重量%,优选80-95重量%丁烯类和0-50重量%,优选5-20重量%丁烷类。丁烯级分的下列组成可以作为一般定量指标给出:1-99重量%1-丁烯,1-50重量%顺式-2-丁烯,1-99重量%反式-2-丁烯,1-5重量%异丁烯。
可以使用的催化剂是包含氧化镍的本身已知催化剂。可以使用负载型氧化镍催化剂,其中合适的载体材料是二氧化硅、氧化铝、硅铝酸盐、具有页硅酸盐结构的硅铝酸盐和沸石。特别合适的催化剂是通过混合镍盐和硅酸盐的水溶液,例如混合硅酸钠和硝酸镍,合适的话与其他成分,如铝盐,例如硝酸铝混合,以及煅烧得到的沉淀催化剂。
特别优选基本由NiO、SiO2、TiO2和/或ZrO2以及合适的话还有Al2O3构成的催化剂。最优选其主要活性成分是10-70重量%氧化镍、5-30重量%二氧化钛和/或二氧化锆和0-20重量%氧化铝,达到100重量%的其余材料是二氧化硅的催化剂。这类催化剂可以通过将包含硝酸镍的水溶液加入包含二氧化钛和/或二氧化锆的碱金属水玻璃溶液中而在5-9的pH下沉淀该催化剂组合物、过滤、干燥和在350-650℃下退火而得到。
优选使包含丁烯的烃混合物在30-280℃,尤其是30-140℃,特别优选40-130℃下与该催化剂接触。这里的压力优选为10-300巴,尤其是15-100巴,特别优选20-80巴。有用地调节该压力以使得该富含烯烃的烃混合物在选取的温度下为液体或者呈超临界状态。
适合使该包含丁烯类的烃混合物与该非均相催化剂接触的设备的实例管束式反应器和竖式炉。优选竖式炉,因为资本支出成本更低。二聚可以在单一反应器中进行,其中该齐聚催化剂可以排列在一个或多个固定床中。另一方式是使用由两个或更多个,优选两个串联排列的反应器构成的反应器级联,其中在通过该级联的最后反应器之前的一个或多个反应器时仅引起反应混合物中的丁烯二聚达到部分转化,并且所需的最终转化率直到反应混合物通过该级联的最后反应器时才达到。丁烯二聚优选在绝热反应器或绝热反应器级联中进行。
在离开反应器或者级联的最后反应器之后,将形成的十二碳烯类与反应器排出料中的辛烯类以及合适的话高级齐聚物及未转化丁烯类和丁烷类分离。辛烯类通常是主产物。
在该方法的第二步中,将所得十二碳烯类以本身已知的方式通过使用合成气的加氢甲酰化转化成分子延长一个碳原子的醛类。加氢甲酰化在均匀溶解于反应介质中的催化剂存在下进行。这里所用催化剂通常是第VIII过渡族金属的化合物或配合物,尤其是Co、Rh、Ir、Pd、Pt或Ru的化合物或配合物,这些未被改性或者例如被含胺-或膦的化合物改性。
对本发明而言,该加氢甲酰化优选在钴催化剂存在下,优选在120-240℃,尤其是160-200℃下在150-400巴,尤其是250-350巴的合成气压力下进行。该加氢甲酰化优选在水存在下进行。所用合成气中氢气与一氧化碳的混合比优选在70:30-50:50体积%,尤其是65:35-55:45体积%范围内。
该钴催化加氢甲酰化方法可以作为包括下列4个步骤的多步方法进行:制备该催化剂(预羰基化),催化剂萃取,烯烃加氢甲酰化和催化剂从反应产物除去(脱钴)。在该方法的第一步—预羰基化中,所用原料为钴盐,例如甲酸钴或乙酸钴的水溶液,使其与一氧化碳和氢气反应而制备加氢甲酰化所需催化剂配合物(HCo(CO)4)。在该方法的第二步—催化剂萃取中,使用有机相,优选使用待加氢甲酰化烯烃将在该方法的第一步中制备的钴催化剂从水相中萃取。除了该烯烃外,有时有用的是将来自加氢甲酰化的反应产物和副产物用于催化剂萃取,只要这些不溶于水中并且在选取的反应条件下为液体。在分离各相之后,将负载有钴催化剂的有机相供入该方法的第三步—加氢甲酰化中。在该方法的第四步—脱钴中,在无配合物的工艺水存在下通过用氧气或空气处理而从反应器排出料的有机相中除去羰基钴配合物。在此过程中,钴催化剂氧化分解并且将所得钴盐萃取回水相中。将由脱钴得到的钴盐水溶液再循环到该方法的第一步—预羰基化中。可以将所得粗加氢甲酰化产物直接供入氢化。作为替换,可以以常规方式,例如通过蒸馏将C13醛级分与其分离,并供入氢化中。钴催化剂的形成、将钴催化剂萃取到有机相中和烯烃的加氢甲酰化还可以在该加氢甲酰化反应器中以一步法进行。
可以使用的钴化合物的实例是氯化钴(II),硝酸钴(II),这些的胺或水合物配合物,羧酸钴,如甲酸钴、乙酸钴、乙基己酸钴或环烷酸钴,以及还有己内酰胺钴配合物。在加氢甲酰化条件下,催化活性钴化合物作为羰基钴就地形成。还可以使用钴的羰基配合物,如八羰基二钴、十二羰基四钴或十六羰基六钴。
将在加氢甲酰化过程中得到的醛混合物还原而得到伯醇。通常在加氢甲酰化条件下发生一定程度的还原,并且在这里也可以控制加氢甲酰化,从而使得发生基本完全还原。然而,所得加氢甲酰化产物通常在该方法的另一步中使用氢气或含氢气体氢化。氢化通常在非均相氢化催化剂存在下进行。所用氢化催化剂可以是适合氢化醛而得到伯醇的任何所需催化剂。合适市售催化剂的实例是亚铬酸铜,钴,钴化合物,镍,镍化合物,它们合适的话可以包含少量铬或其他促进剂,以及铜、镍和/或铬的混合物。镍化合物通常呈在载体材料如氧化铝或硅藻土上的负载形式。还可以使用包含贵金属,如铂或钯的催化剂。
氢化可以通过滴流法进行,其中使待氢化混合物和氢气或者含氢气体例如同时在氢化催化剂固定床上通过。氢化优选在50-250℃,尤其是100-150℃以及50-350巴,尤其是150-300巴的氢气压力下进行。可以使用分馏将所需异十三烷醇级分与存在于氢化过程中得到的反应排出料中的C8烃和更高沸点产物分离。
对本发明目的而言特别优选的所得异十三烷醇类具有异构体的特征分布,这例如可以借助气相色谱法更详细定义。该十三烷醇混合物包含一定百分数的线性或支化十三烷醇,其中百分数由气相色谱法测定。百分数通常相对于包含在被分析混合物种的所有十三烷醇类的总面积。可以将气相色谱图分成3个保留区域,例如如Kovacs(Z.Anal.Chem.181(1961),第351页;Adv.Chromatogr.1(1965),第229页)所述借助保留指数(“RI”)并使用正十一烷醇、正十二烷醇和正十三烷醇作为参照物:
区域1:保留指数小于1180
区域2:保留指数为1180-1217
区域3:保留指数大于1217
存在于区域1中的物质主要是至少三重支化的十三烷醇,存在于区域2中的那些主要是双重支化的异十三烷醇类以及存在于区域3中的那些主要是单支化异十三烷醇类和/或正十三烷醇。该方法通过比较在气相色谱曲线相应部分下面的区域(面积%)而对异十三烷醇类的组成给出足够准确的测定。
该十三烷醇混合物包含20-60%,优选25-50%,尤其是40-48%至少三重支化的十三烷醇。
该十三烷醇混合物包含10-50%,优选20-45%,尤其是30-40%双重支化的十三烷醇。
该十三烷醇混合物包含5-30%,优选10-25%,尤其是15-20%单支化和/或线性十三烷醇。
在另一形式中,该十三烷醇混合物包含25-50%至少三重支化的十三烷醇,20-45%双重支化的十三烷醇和10-25%单支化和/或线性十三烷醇。
在另一形式中,该十三烷醇混合物包含40-48%至少三重支化的十三烷醇,30-40%双重支化的十三烷醇和15-20%单支化和/或线性十三烷醇。
该十三烷醇混合物通常包含至少85重量%,优选至少95重量%,尤其是至少98重量%线性或支化十三烷醇,例如由气相色谱法测定。
该十三烷醇混合物通常包含小于15%,优选小于5重量%,尤其是小于2重量%的十二烷醇,例如由气相色谱法测定。
该十三烷醇混合物通常包含小于5%,优选小于3重量%,尤其是小于1重量%的十四烷醇,例如由气相色谱法测定。
该十三烷醇混合物的密度通常为0.8-0.9g/cm3,优选0.82-0.86g/cm3,特别优选0.84-0.845g/cm3。
该十三烷醇混合物的折射率nD 20通常为1.4-1.5,优选1.44-1.46,特别优选1.446-1.45。
该十三烷醇混合物的沸程通常为230-280℃,优选240-275℃,特别优选250-270℃。
该十三烷醇混合物通常具有在1.1-3.5,优选1.5-3.0,尤其是1.9-2.4范围内的支化度,例如由H-NMR测定。
式R-O-(C3H6O)n-H的丙氧基化物可通过用环氧丙烷将相应醇R-OH烷氧基化而获得。
进行烷氧基化是本领域技术人员原则上已知的。本领域技术人员同样已知的是,烷氧基化物的分子量分布可受反应条件,尤其是催化剂选择的影响。
烷氧基化可为碱催化的烷氧基化。为此,可在加压反应器中将醇与碱金属氢氧化物,优选氢氧化钾,或与碱金属醇盐,如甲醇钠混合。由于压力降低(如<100毫巴)和/或温度增加(30-150℃),可排除仍存在于混合物中的水。醇则以相应的醇盐存在。用惰性气体(如氮气)使体系呈惰性并将氧化烯在60-180℃的温度以及至多最大10巴的压力下逐步加入。在反应结束时,可通过加入酸(如乙酸或磷酸)而将催化剂中和,以及需要的话将其过滤掉。任选烷氧基化也可在溶剂存在下进行。溶剂例如可为甲苯、二甲苯、二甲基甲酰胺或碳酸亚乙酯。
然而,醇的烷氧基化也可借助其他方法,如通过酸催化的烷氧基化而进行。此外,例如可使用DE 43 25 237A1中所述的双氢氧化物粘土,或可使用双金属氰化物催化剂(DMC催化剂)。合适的DMC催化剂例如公开在WO2003/066706或DE 102 43 361A1中,尤其是[0029]至[0041]部分以及其中引用的文献。例如可使用Zn-Co型的催化剂。为进行反应,可将醇与催化剂混合,如上所述将混合物脱水并如上所述使其与氧化烯反应。
金属加工流体可以配制成各种配制剂,其可以在施加前稀释或不稀释而施加。
金属加工流体可以被配制成
-直馏油,其含有至少80重量%的丙氧基化物,并且其在没有水稀释的情况下施加;
-可溶性油,其含有30-85重量%矿物油和至多20重量%丙氧基化物,并且其在用水稀释之后作为水乳液施加;或
-半合成流体,其含有5-30重量%矿物油、30-50重量%水和至多20重量%丙氧基化物,并且其在没有水稀释的情况下施加。
在优选的形式中,金属加工流体被配制成直馏油。在另一优选的形式中,金属加工流体被配制成可溶性油。在另一优选的形式中,金属加工流体被配制成半合成流体。
优选地,金属加工流体被配制成直馏油,其含有至少90重量%丙氧基化物和任选的抗氧化剂。优选地,直馏油不含水。
在另一优选的形式中,金属加工流体被配制成可溶性油,其含有30-85重量%矿物油、至多30重量%水和至多10重量%丙氧基化物。
矿物油可以选自根据美国石油学会API定义的I、II、III、IV和V组油的基础油或其混合物。
I组基础油含有小于90%的饱和物(ASTM D 2007)和/或大于0.03%的硫(ASTM D2622)并且具有大于或等于80且小于120的粘度指数(ASTM D 2270)。
II组基础油含有大于或等于90%的饱和物和小于或等于0.03%的硫并且具有大于或等于80且小于120的粘度指数。
III组基础油含有大于或等于90%的饱和物和小于或等于0.03%的硫并且具有大于或等于120的粘度指数。
IV组基础油含有聚-α-烯烃。聚-α-烯烃(PAO)包括通常包含α-烯烃—包括但不限于C2至约C32-α-烯烃,优选C8至约C16-α-烯烃,如1-辛烯、1-癸烯、1-十二碳烯等—的相对低分子量氢化聚合物或齐聚物的已知PAO材料。优选的聚-α-烯烃是聚-1-辛烯、聚-1-癸烯和聚-1-十二碳烯。
V组基础油含有任何未被I-VI组描述的基础油。V组基础油的实例包括烷基萘、氧化烯聚合物、硅油和磷酸酯。
金属加工流体可以附加含有添加剂,加入这些添加剂是为了进一步改进它们的基本性能。这些包括:抗氧化剂、金属钝化剂、防锈剂、粘度指数改进剂、倾点下降剂、分散剂、清净剂、增粘剂、触变助洗剂(thixotropic builder)、脱水剂、消泡剂、破乳剂、高压添加剂和抗磨添加剂。就此而言,该类添加剂在每种情况中以常规的量添加,各自为0.01-10.0重量%。附加添加剂的实例如下:
1.酚类抗氧化剂
1.1.烷基化单酚:2,6-二叔丁基-4-甲基酚、2-丁基-4,6-二甲基酚、2,6-二叔丁基-4-乙基酚、2,6-二叔丁基-4-正丁基酚、2,6-二叔丁基-4-异丁基酚、2,6-二环戊基-4-甲基酚、2-(α-甲基环己基)-4,6-二甲基酚、2,6-双十八烷基-4-甲基酚、2,4,6-三环己基酚、2,6-二叔丁基-4-甲氧基甲基酚、线性壬基酚或在侧链中支化的壬基酚,例如2,6-二壬基-4-甲基酚、2,4-二甲基-6-(1'-甲基-十一烷-1'-基)-酚、2,4-二甲基-6-(1'-甲基十七烷-1'-基)-酚、2,4-二甲基-6-(1'-甲基十三烷-1'-基)-酚及其混合物
1.2.烷基硫甲基酚:2,4-二辛基硫甲基-6-叔丁基酚、2,4-二辛基硫甲基-6-甲基酚、2,4-二辛基硫甲基-6-乙基酚、2,6-双十二烷基硫甲基-4-壬基酚
1.3.氢醌和烷基化氢醌:2,6-二叔丁基-4-甲氧基酚、2,5-二叔丁基氢醌、2,5-二-叔戊基氢醌、2,6-二苯基-4-十八烷氧基酚、2,6-二叔丁基氢醌、2,5-二叔丁基-4-羟基茴香醚、3,5-二叔丁基-4-羟基茴香醚、3,5-二叔丁基-4-羟苯基硬脂酸酯、双(3,5-二叔丁基-4-羟苯基)己二酸酯
1.4.生育酚:α-、β-、γ或δ-生育酚及其混合物(维生素E)
1.5.羟基化硫代二苯醚:2,2'-硫代-双(6-叔丁基-4-甲基酚)、2,2'-硫代-双(4-辛基酚)、4,4'-硫代-双(6-叔丁基-3-甲基酚)、4,4'-硫代-双(6-叔丁基-2-甲基酚)、4,4'-硫代-双(3,6-二-仲戊基酚)、4,4'-双(2,6-二甲基-4-羟苯基)二硫
1.6.亚烷基双酚:2,2'-亚甲基-双(6-叔丁基-4-甲基酚)、2,2'-亚甲基-双(6-叔丁基-4-乙基酚)、2,2'-亚甲基-双[4-甲基-6-(α-甲基环己基)酚]、2,2'-亚甲基-双(4-甲基-6-环己基酚)、2,2'-亚甲基-双(6-壬基-4-甲基酚)、2,2'-亚甲基-双(4,6-二叔丁基酚)、2,2'-亚乙基-双(4,6-二叔丁基酚)、2,2'-亚乙基-双(6-叔丁基-4-异丁基酚)、2,2'-亚甲基-双[6-(α-甲基苄基)-4-壬基酚]、2,2'-亚甲基-双[6-(α,α-二甲基-苄基)-4-壬基酚]、4,4'-亚甲基双(2,6-二叔丁基酚)、4,4'-亚甲基-双(6-叔丁基-2-甲基酚)、1,1-双(5-叔丁基-4-羟基-2-甲基苯基)丁烷、2,6-双(3-叔丁基-5-甲基-2-羟苄基)-4-甲基酚、1,1,3-三(5-叔丁基-4-羟基-2-甲基苯基)丁烷、1,1-双(5-叔丁基-4-羟基-2-甲基苯基)-3-n-十二烷基巯基丁烷、乙二醇双[3,3-双(3'-叔丁基-4'-羟苯基)-丁酸酯]、双(3-叔丁基-4-羟基-5-甲基苯基)二环戊二烯、双[2-(3'-叔丁基-2'-羟基-5'-甲基苄基)-6-叔丁基-4-甲基苯基]对苯二甲酸酯、1,1-双(3,5-二甲基-2-羟苯基)丁烷、2,2-双(3,5-二叔丁基-4-羟苯基)-丙烷、2,2-双(5-叔丁基-4-羟基-2-甲基苯基)-4-n-十二烷基巯基丁烷、1,1,5,5-四(5-叔丁基-4-羟基-2-甲基苯基)戊烷
1.7.O-、N-和S-苄基化合物:3,5,3',5'-四-叔丁基-4,4'-二羟基二苄基醚、十八烷基-4-羟基-3,5-二甲基苄基-巯基乙酸酯、十三烷基-4-羟基-3,5-二叔丁基苄基-巯基乙酸酯、三(3,5-二叔丁基-4-羟苄基)铵、双(4-叔丁基-3-羟基-2,6-二甲基苄基)二硫代对苯二甲酸酯、双(3,5-二叔丁基-4-羟苄基)硫、异辛基-3,5-二叔丁基-4-羟苄基-巯基乙酸酯
1.8.羟苄基化丙二酸酯:双十八烷基-2,2-双(3,5-二叔丁基-2-羟苄基)丙二酸酯、双十八烷基-2-(3-叔丁基-4-羟基-5-甲基苄基)丙二酸酯、双十二烷基-巯乙基-2,2-双(3,5-二叔丁基-4-羟苄基)丙二酸酯、二[4-(1,1,3,3-四甲基丁基)-苯基]-2,2-双(3,5-二叔丁基-4-羟苄基)丙二酸酯
1.9.羟苄基芳族化合物:1,3,5-三(3,5-二叔丁基-4-羟苄基)-2,4,6-三甲基苯、1,4-双(3,5-二叔丁基-4-羟苄基)-2,3,5,6-四甲基苯、2,4,6-三(3,5-二叔丁基-4-羟苄基)酚
1.10.三嗪化合物:2,4-双-辛基巯基-6-(3,5-二叔丁基-4-羟基苯胺基)-1,3,5-三嗪、2-辛基巯基-4,6-双(3,5-二叔丁基-4-羟基苯胺基)-1,3,5-三嗪,2-辛基巯基-4,6-双(3,5-二叔丁基-4-羟基苯氧基)-1,3,5-三嗪、2,4,6-三(3,5-二叔丁基-4-羟基苯氧基)-1,2,3-三嗪、1,3,5-三(3,5-二叔丁基-4-羟苄基)异氰脲酸酯、1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)异氰脲酸酯、2,4,6-三(3,5-二叔丁基-4-羟苯基乙基)-1,3,5-三嗪、1,3,5-三(3,5-二叔丁基-4-羟苯基丙酰基)六氢-1,3,5-三嗪、1,3,5-三(3,5-二环己基-4-羟苄基)异氰脲酸酯
1.11.酰氨基酚:4-羟基月桂酰苯胺、4-羟基硬脂酰苯胺、N-(3,5-二叔丁基-4-羟苯基)-氨基甲酸辛基酯
1.12.β-(3,5-二叔丁基-4-羟苯基)丙酸与一元或多元醇,例如与甲醇、乙醇、正辛醇、异辛醇、十八烷醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二乙二醇、二乙二醇、三乙二醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N'-双(羟乙基)草酰胺、3-硫杂十一烷醇、3-硫杂十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷的酯
1.13.β-(5-叔丁基-4-羟基-3-甲基苯基)丙酸与一元或多元醇,例如与甲醇、乙醇、正辛醇、异辛醇、十八烷醇、1,6-己二醇、1,9-壬二醇、乙二醇、1,2-丙二醇、新戊二醇、硫代二乙二醇、二乙二醇、三乙二醇、季戊四醇、三(羟乙基)异氰脲酸酯、N,N'-双(羟乙基)草酰胺、3-硫杂十一烷醇、3-硫杂十五烷醇、三甲基己二醇、三羟甲基丙烷、4-羟甲基-1-磷杂-2,6,7-三氧杂双环[2.2.2]辛烷的酯
1.14.β-(3,5-二环己基-4-羟苯基)丙酸与一元或多元醇,例如13下所述醇的酯
1.15.3,5-二叔丁基-4-羟苯基乙酸与一元或多元醇,例如13下所述醇的酯
1.16.β-(3,5-二叔丁基-4-羟苯基)丙酸的酰胺:N,N'-双(3,5-二叔丁基-4-羟苯基丙酰基)六亚甲基二胺、N,N'-双(3,5-二叔丁基-4-羟苯基丙酰基)三亚甲基二胺、N,N'-双(3,5-二叔丁基-4-羟苯基丙酰基)肼
1.17.抗坏血酸(维生素C)
1.18.胺类抗氧化剂:N,N'-二异丙基-对苯二胺、N,N'-二-仲丁基-对苯二胺、N,N'-双(1,4-二甲基戊基)-对苯二胺、N,N'-双(1-乙基-3-甲基戊基)-对苯二胺、N,N'-双(1-甲基庚基)-对苯二胺、N,N'二环己基-对苯二胺、N,N'-二苯基-对苯二胺、N,N'-二(萘-2-基)-对苯二胺、N-异丙基-N'-苯基-对苯二胺、N-(1,3-二甲基丁基)-N'-苯基-对苯二胺、N-(1-甲基庚基)-N'-苯基-对苯二胺、N-环己基-N'-苯基-对苯二胺、4-(对甲苯磺酰氨基)-二苯基胺、N,N'-二甲基-N,N'-二-仲丁基-对苯二胺、二苯基胺、N-烯丙基二苯基胺、4-异丙氧基二苯基胺、N-苯基-1-萘基胺、N-(4-叔辛基苯基)-1-萘基胺、N-苯基-2-萘基胺、辛基化二苯胺(例如p,p'-二叔辛基二苯基胺)、4-正丁基氨基酚、4-丁酰基氨基酚、4-壬酰基氨基酚、4-十二烷酰基氨基酚、4-十八烷酰基氨基酚、二(4-甲氧基苯基)胺、2,6-二叔丁基-4-二甲基氨基甲基酚、2,4'-二氨基二苯甲烷、4,4'-二氨基二苯甲烷、N,N,N',N'-四甲基-4,4'-二氨基二苯甲烷、1,2-二[(2-甲基苯基)氨基]-乙烷、1,2-二(苯基氨基)丙烷、(邻甲苯基)双胍、二[4-(1',3'-二甲基丁基)苯基]胺、叔辛基化N-苯基-1-萘基胺、单-和二-烷基化叔丁基/叔辛基-二苯基胺的混合物、单-和二-烷基化壬基二苯基胺的混合物、单-和二-烷基化十二烷基二苯基胺的混合物、单-和二-烷基化异丙基/异己基二苯基胺的混合物、单-和二-烷基化叔丁基二苯基胺的混合物、2,3-二氢-3,3-二甲基-4H-1,4-苯并噻嗪、吩噻嗪、单-和二烷基化叔丁基/叔辛基-吩噻嗪的混合物、单-和二-烷基化叔辛基吩噻嗪的混合物、N-烯丙基吩噻嗪、N,N,N',N'-四苯基-1,4-二氨基丁-2-烯、N,N-双(2,2,6,6-四甲基哌啶-4-基)己二胺、双(2,2,6,6-四甲基哌啶-4-基)癸二酸酯、2,2,6,6-四甲基哌啶-4-酮、2,2,6,6-四甲基哌啶-4-醇。
2.附加抗氧化剂:脂族或芳族亚磷酸酯、硫代二丙酸或硫代二乙酸的酯或二硫代氨基甲酸或二硫代磷酸的盐、2,2,12,12-四甲基-5,9-二羟基-3,7,11-三硫杂十三烷和2,2,15,15-四甲基-5,12-二羟基-3,7,10,14-四硫杂十六烷。
3.附加金属减活剂:
3.1.苯并三唑及其衍生物:2-巯基苯并三唑、2,5-二巯基苯并三唑、4-或5-烷基苯并三唑(例如甲苯三唑)及其衍生物、4,5,6,7-四氢苯并三唑、5,5'-亚甲基-双-苯并三唑;苯并三唑或甲苯三唑的曼尼希碱,如1-[二(2-乙基己基氨基甲基)]甲苯三唑和1-[二(2-乙基己基氨基甲基)]苯并三唑;烷氧基烷基苯并三唑,如1-(壬氧基-甲基)苯并三唑、1-(1-丁氧基乙基)-苯并三唑和1-(1-环己氧基丁基)-甲苯三唑
3.2.1,2,4-三唑及其衍生物:3-烷基(或芳基)-1,2,4-三唑、1,2,4-三唑的曼尼希碱,如1-[二(2-乙基己基)氨基甲基]-1,2,4-三唑;烷氧基烷基-1,2,4-三唑,如1-(1-丁氧基乙基)-1,2,4-三唑;酰化3-氨基-1,2,4-三唑
3.3.咪唑衍生物:4,4'-亚甲基-双(2-十一烷基-5-甲基)咪唑和双[(N-甲基)咪唑-2-基]甲醇-辛基醚
3.4.含硫杂环化合物:2-巯基苯并噻唑、2,5-二巯基-1,3,4-噻二唑、2,5-二巯基苯并噻二唑及其衍生物;3,5-双[二(2-乙基己基)氨基甲基]-1,3,4-噻二唑啉-2-酮
3.5.氨基化合物:亚水杨基-丙二胺、水杨基氨基胍及其盐。
4.防锈剂:
4.1.有机酸、它们的酯、金属盐、胺盐和酐:烷基-和烯基琥珀酸和它们与醇、二醇或羟基羧酸的偏酯、烷基-和烯基-琥珀酸的偏酰胺(partial amides)、4-壬基苯氧基乙酸、烷氧基-和烷氧基乙氧基-羧酸,如十二烷氧基乙酸、十二烷氧基(乙氧基)乙酸及其胺盐、山梨糖醇酐单油酸酯、单油酸钠、环烷酸铅、烯基琥珀酸酐,例如十二烯基琥珀酸酐、2-(2-羧乙基)-1-十二烷基-3-甲基甘油及其盐,尤其是钠盐和三乙醇胺盐。
4.2.含氮化合物:
4.2.1.叔脂族和脂环族胺和有机和无机酸的胺盐,例如油溶性烷基铵羧酸盐,以及还有1-[N,N-双(2-羟乙基)氨基]-3-(4-壬基苯氧基)丙-2-醇
4.2.2.杂环化合物,例如取代咪唑啉和噁唑啉,例如2-十七烯基-1-(2-羟乙基)-咪唑啉
5.含硫化合物:二壬基萘磺酸钡、石油磺酸钙、烷硫基取代的脂族羧酸、脂族2-磺基羧酸的酯及其盐。
6.粘度指数改进剂:聚丙烯酸酯、聚甲基丙烯酸酯、乙烯基吡咯烷酮/甲基丙烯酸酯共聚物、聚乙烯基吡咯烷酮、聚丁烯、烯烃共聚物、苯乙烯/丙烯酸酯共聚物、聚醚。
7.倾点下降剂:聚(甲基)丙烯酸酯、乙烯-乙酸乙烯酯共聚物、烷基聚苯乙烯、富马酸酯共聚物、烷基化萘衍生物。
8.分散剂/表面活性剂:聚丁烯基琥珀酰胺或聚丁烯基琥珀酰亚胺、聚丁烯基膦酸衍生物、碱性镁、钙和钡磺酸盐和酚盐。
9.高压和抗磨添加剂:含硫和含卤素的化合物,例如氯化石蜡、磺化烯烃或植物油(大豆油、菜籽油)、烷基-或芳基-二-或-三-硫化物、苯并三唑或其衍生物,如双(2-乙基己基)氨基甲基甲苯三唑,二硫代氨基甲酸酯,如亚甲基-双-二丁基二硫代氨基甲酸酯,2-巯基苯并噻唑的衍生物,如1-[N,N-双(2-乙基己基)氨基甲基]-2-巯基-1H-1,3-苯并噻唑,2,5-二巯基-1,3,4-噻二唑的衍生物,如2,5-双(叔壬基二硫代)-1,3,4-噻二唑。
10.摩擦系数降低剂:猪油、油酸、动物脂、菜籽油、硫化脂肪、胺。
11.用于水/油流体的特殊添加剂:
11.1乳化剂:石油磺酸盐、胺如聚氧乙基化脂肪胺、非离子表面活性物质
11.2缓冲剂:链烷醇胺
11.3杀生物剂:三嗪、噻唑啉酮、三-硝基甲烷、吗啉、吡啶硫醇钠
11.4加工速度改进剂:钙磺酸盐和钡磺酸盐。
11.5增粘剂:丙烯酰胺共聚物、聚异丁烯树脂。
11.6触变助洗剂:微晶蜡、氧化蜡和氧化酯
11.7脱水剂:聚乙二醇醚、丁基二甘醇。
本发明还涉及如上定义的金属加工流体。
本发明还涉及丙氧基化物作为金属加工流体中的添加剂的用途。
实施例
实施例1-十三烷醇混合物
十三烷醇的工业混合物如US 2003/0187114所述由工业C4萃余液开始制备。使丁烷和丁烯异构体的工业混合物在非均相催化剂上进行二聚而生产辛烯异构体和和十二碳烯异构体的混合物。十二碳烯异构体通过蒸馏分离。将异构十二碳烯用包含氢气和一氧化碳的合成气加氢甲酰化,然后用氢气氢化。所得十三烷醇混合物通过分馏分离。
该异十三烷醇混合物的密度为0.843g/cm3,折射率nD 20为1.448,粘度为34.8mPas且沸程为251-267℃(根据DIN 51751)。
十三烷醇异构体的比例由气相色谱法根据DIN 55685测定为至少99.0面积%。十二烷醇和十四烷醇的含量由气相色谱法测定为各自低于1面积%。
十三烷醇混合物如US 2003/0187114所述使用Kovacs方法通过气相色谱法分析:
在80℃下使用1ml N-甲基-N-三甲基甲硅烷基三氟乙酰胺/100μl样品将异十三烷醇样品三甲基甲硅烷基化60分钟。为了通过气相色谱法分离,使用具有一根长50m、基于100%甲基化硅橡胶、内径0.32mm的分离柱的Hewlett Packard Ultra。注射口温度和检测器温度为250℃并且柱温为160℃(等温)。分离为80ml/min。载气为氮气。将入口压力设定为2巴。将1μl样品注入气相色谱仪,并借助FID检测分离的成分。
这里所用参照物为:正十一烷醇:保留指数(“RI”)1100;正十二烷醇:保留指数1200;和正十三烷醇:保留指数1300。为了评价的目的,将该气相色谱图细分为下列区域:
区域1:保留指数小于1180
区域2:保留指数为1180-1217
区域3:保留指数大于1217
将十三烷醇峰面积设定为100面积%。结果总结于表A中。
表A
保留指数 | 支化 | 十三烷醇混合物 |
小于1180 | 至少三重支化 | 46% |
1180-1217 | 双重支化 | 35% |
大于1217 | 单支化和/或线性 | 19% |
实施例2-丙氧基化物
丙氧基化物A
在2L高压釜中,将双金属氰化物(DMC)催化剂(23mg,根据WO 2003/066706第13-14页制备)悬浮于十三烷醇混合物(170.3g)中。关闭反应器,并应用三个真空吹扫循环。然后将混合物加热至135℃。在该温度下,在6.25小时内稳定加入环氧丙烷(740.5g)。然后将混合物在相同温度下再搅拌5小时,最后冷却至室温。得到产物(900g),为淡黄色油。
得到丙氧基化物A,其具有平均15个环氧丙烷单元,酸值0.24(DGF C-V 2),倾点-51℃(DIN ISO 3016),40℃下的运动粘度为56mm2/s,100℃下的运动粘度为10mm2/s(ASTM D445)。
丙氧基化物B
将KOH(8g)的水(8g)溶液加入到十三烷醇混合物(1200g)中,在100℃和真空下,在圆底烧瓶中搅拌2小时。然后将混合物装入高压釜中,加热至130℃。然后在66小时内加入环氧丙烷(2788g),再搅拌混合物6小时,冷却至100℃。加入硅酸镁吸收剂(120g),在100℃搅拌混合物2小时,然后过滤。获得产物(3980g),为淡黄色油。
得到丙氧基化物B,其具有平均8个环氧丙烷单元,酸值0.1,倾点-54℃,40℃下的运动粘度为29mm2/s,100℃下的运动粘度为6mm2/s。
丙氧基化物C
丙氧基化物C根据丙氧基化物A和B基于2-丙基庚醇制备。得到具有平均8个环氧丙烷单元的丙氧基化物C
实施例3-应用试验
如下所述进行应用试验,结果总结于表1中。为了比较,使用市售可得的AL G 16(2-己基癸烷-1-醇Guerbet醇)(倾点-60℃,40℃下的运动粘度为19mm2/s,100℃下的运动粘度为2.8mm2/s)。使用以下测试方法:
Reichert磨痕:以20重量%在T 22(用于金属加工流体的中等粘度加氢处理环烷油,KV40约22cSt)中测试。Reichert磨损测试机包括两个由不锈钢制成的圆筒(V2A)。一个用作固定磨损件,第二圆筒用作与固定磨损件成90度操作的旋转磨损件。流体容器填充有1%的测试物质水溶液。在100m后,停止旋转,用乙醇洗涤金属圆筒,并分析固定磨损元件的磨痕(以mm2测量)。
结果显示磨痕减少和VI增加方面的改进。
表1:
实施例4-配制剂稳定性
表2:
通过将该液体在室温下在40℃下储存2个月,然后在室温下储存12个月(“长期”)来测试该金属加工流体配制剂的稳定性。目测检查显示在试验期结束时为澄清液体。
表3:
实施例5-发泡
用自来水稀释实施例4的配制剂,以产生含有5重量%配制剂的透明乳液。如下评价摇动泡沫:在100ml带塞子的量筒中,小心地填充70ml稀释的配制剂,不产生泡沫。上下摇动圆筒20次,其中一次向上-向下-向上过程作为一次记录。作为表4中给出的开始时间和时间间隔立即记录最大泡沫高度。
数据表明丙氧基化物A、B和C产生的发泡比对比配制剂少。
表4:泡沫量[ml]
实施例6
测量丙氧基化物A、B和C的倾点(DIN ISO 3016)并与具有2.2个环氧乙烷单元的C16/18丙氧基化物比较。表5中的数据表明倾点极低。
表5:
实施例7
表6:
Claims (14)
1.一种加工工件的方法,包括
a)使工具与工件接触以实现工件形状的改变,和
b)将金属加工流体施加至所述工具与所述工件接触的表面区域,其中金属加工流体含有式R-O-(C3H6O)n-H的丙氧基化物,其中R为支化C6-C20烷基且n为3-30。
2.根据权利要求1的方法,其中n为5-25。
3.根据权利要求1或2的方法,其中R为支化C10-C13烷基。
4.根据权利要求1-3中任一项的方法,其中R为支化C13烷基。
5.根据权利要求1-4中任一项的方法,其中R为十三烷醇混合物,其包含单、双重和三重支化十三烷醇。
6.根据权利要求5的方法,其中所述十三烷醇混合物包含:
-20-60%至少三重支化的十三烷醇,
-10-50%双重支化的十三烷醇,和
-5-30%单支化和/或线性十三烷醇,
其中百分数由气相色谱法测定。
7.根据权利要求1-6中任一项的方法,其中丙氧基化物具有式R-O-(CH2-CH(CH3)-O)n-H。
8.根据权利要求1-7中任一项的方法,其中金属加工流体被配制成
-直馏油,其含有至少80重量%的丙氧基化物,并且其在没有水稀释的情况下施加;
-可溶性油,其含有30-85重量%矿物油和至多20重量%丙氧基化物,并且其在用水稀释之后作为水乳液施加;或
-半合成流体,其含有5-30重量%矿物油、30-50重量%水和至多20重量%丙氧基化物,并且其在没有水稀释的情况下施加。
9.根据权利要求1-8中任一项的方法,其中金属加工流体被配制成直馏油,其含有至少90重量%丙氧基化物和任选的抗氧化剂。
10.根据权利要求1-9中任一项的方法,其中金属加工流体被配制成可溶性油,其含有30-85重量%矿物油、至多30重量%水和至多10重量%丙氧基化物。
11.根据权利要求1-10中任一项的方法,其中金属加工流体以5-50ml/h的量施加。
12.根据权利要求1-11中任一项的方法,其中工件由纯金属或金属合金制成。
13.如权利要求1-12中任一项所定义的金属加工流体。
14.如权利要求1-7中任一项所定义的丙氧基化物作为金属加工流体中的添加剂的用途。
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DE10243361A1 (de) | 2002-09-18 | 2004-04-01 | Basf Ag | Alkoxylatgemische und diese enthaltende Waschmittel |
US20160186032A1 (en) | 2013-09-26 | 2016-06-30 | Dow Global Technologies Llc | Drilling fluid composition and method useful for reducing accretion of bitumin on drill components |
JP6283552B2 (ja) * | 2014-03-28 | 2018-02-21 | 出光興産株式会社 | 水溶性金属加工油および金属加工用クーラント |
CA3001600A1 (en) * | 2015-10-15 | 2017-04-20 | Ingevity South Carolina, Llc | Lubricating compositions and methods for the use thereof |
RU2019122807A (ru) * | 2016-12-20 | 2021-01-22 | Басф Се | Применение смеси комплексного сложного эфира с монокарбоновой кислотой для уменьшения трения |
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2020
- 2020-04-01 CN CN202080027915.5A patent/CN113677781A/zh active Pending
- 2020-04-01 EP EP20716370.0A patent/EP3953441A1/en active Pending
- 2020-04-01 JP JP2021559992A patent/JP2022527603A/ja active Pending
- 2020-04-01 WO PCT/EP2020/059319 patent/WO2020207881A1/en unknown
- 2020-04-01 US US17/602,871 patent/US11795414B2/en active Active
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US20220162514A1 (en) | 2022-05-26 |
US11795414B2 (en) | 2023-10-24 |
JP2022527603A (ja) | 2022-06-02 |
WO2020207881A1 (en) | 2020-10-15 |
EP3953441A1 (en) | 2022-02-16 |
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