CN116239626A - 一种氟改性硼酸酯及其制备方法和包含该氟改性硼酸酯的制动液 - Google Patents
一种氟改性硼酸酯及其制备方法和包含该氟改性硼酸酯的制动液 Download PDFInfo
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- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims abstract description 6
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/04—Esters of boric 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
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/78—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing boron
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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
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
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- C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
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- 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
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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
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/061—Esters derived from boron
- C10M2227/0615—Esters derived from boron used as base material
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- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
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Abstract
Description
技术领域
本发明属于制动液技术领域,特别提供了一种氟改性硼酸酯及其制备方法和包含该氟改性硼酸酯的制动液。
背景技术
硼酸酯是一个结构独特、性能优良的无机酸酯类化合物。其自身和衍生物可以应用在众多领域中,例如:润滑油添加剂、偶联剂、表面活性剂等。在汽车制动液领域,硼酸酯制动液也存在诸多优势,中国专利CN107573998A一种以三乙二醇甲醚硼酸酯为基础液复配而成DOT6硼酸酯型制动液。它具有良好的高低温性能,又具有憎水性,对钢、黄铜、铜、铸铁、铝等金属无腐蚀性,对橡胶不溶胀,受温度变化影响小。然而,现有的研究仍在致力于提升硼酸酯型制动液的平衡回流沸点和低温运动粘度等主要性能,对其疏水性能的关注不足。硼酸酯遇到少量水时,虽然能够通过自身的水解具备一定的抗水性,但若长时间暴露在湿度较大的环境中时,大量硼酸酯的水解产物—硼酸会以固体的形式从制动液中析出,而硼酸不仅会腐蚀金属,还会对制动液的性能有严重影响(陶佃彬,广东化工,2021,10,99)。随着中国汽车市场的快速发展,对高端制动液的需求也越发紧迫,因此,如何在保证制动液主要性能的同时进一步提升其疏水性能就成为了亟待解决的问题。
含氟材料由于其具高疏水性,高的热稳定性,低折射率以及良好的生物相容性等等在多个领域都得到了广泛的应用。利用氟改性提升材料的疏水性能已有诸多报道,例如,在经典的疏水材料聚丙烯中空纤维膜中,通过全氟硅烷的加入使得其水接触角由73°增加到97°(Zhihao Xu,Desalination,2017,414,10),疏水能力明显增强;在疏水性涂料的配方中,提升十三氟辛基三乙氧基硅烷的加入比例,水接触角由100°增加到110°(MohammadReza Heshmati,Polymer Bulletin,2022,79,9427);此外,在热敏性材料聚(N-异丙烯酰胺)中(Jae Min Bak,Polym.Chem.,2013,4,2219),通过控制分子末端的甲基上氟原子的个数,达到调节材料疏水能力的目的。
但是,目前并没有含氟制动液的相关研究。
发明内容
发明目的:为了解决现有技术存在的问题,本发明提供了一种氟改性硼酸酯及其制备方法和包含该氟改性硼酸酯的制动液。该化合物由于在硼酸酯上引入氟,使其具有更高的抗水性。方法具有原料易得、成本低、污染小、操作简单、产率较高、便于分离等优点。另外,复配出了一种氟改性硼酸酯型制动液,其不仅具有高的干湿沸点还具有良好的低温运动粘度。
技术方案:本发明提供了一种氟改性硼酸酯,其结构式如下所示:
其中,R1为氟取代的C1-C5烷基;R2为氢或C1-C5烷基;n=2~8。
优选的,R1为二氟乙基、三氟乙基或四氟丙基;R2为氢、甲基或乙基;n=2~8。
所述的氟改性硼酸酯的制备方法,包括以下步骤:
(1)将氟代醇在碱催化的条件下与环氧烷烃发生聚合反应,制备氟改性聚醇醚;
(2)将氟改性聚醇醚与硼酸或六元环状硼酸发生酯化反应,制备氟改性链状或环状硼酸酯;
其中,R1、R2和n同权利要求1或2所述。
优选的,步骤(1)中,所述的碱为氢氧化钠、氢氧化钾、甲醇钠、碳酸钠、碳酸氢钠、碳酸氢钾或三乙胺中的一种或几种。
优选的,步骤(1)中,所述聚合反应时间为2~10h,聚合温度为120~240℃,氟代醇与环氧烷烃的摩尔比为1:2~10,碱用量为氟代醇摩尔当量的2.5%~20%,聚合压力为0.2~6MPa。
优选的,步骤(2)中,所述氟改性聚醇醚与硼酸发生酯化反应,制备氟改性链状硼酸酯的反应中,酯化反应时间为3~15h,酯化反应温度为100~200℃,硼酸与氟改性硼酸酯的摩尔比为1:3~6。
优选的,步骤(2)中,所述氟改性聚醇醚与六元环状硼酸发生酯化反应,制备氟改性环状硼酸酯的反应中,酯化反应时间为3~15h,酯化反应温度为100~200℃,硼酸与氟改性硼酸酯的摩尔比为1:1~5。
本发明还提供了一种制动液,包含所述的氟改性硼酸酯。
优选的,所述制动液包含氟改性硼酸酯、稀释剂和制动液添加剂。
进一步优选的,所述稀释剂为三乙二醇单甲醚、三乙二醇单乙醚、三乙二醇单丁醚中的一种或几种;所述制动液添加剂为pH调节剂、橡胶溶胀剂、抗氧剂、防锈剂、水解稳定剂中的一种或几种。
有益效果:与现有技术相比,本发明具有如下优势:
(1)本发明通过聚合、酯化的步骤制备氟改性硼酸酯的步骤,具有反应后处理简单、反应条件温和、便于分离等优点;
(2)在硼酸酯中引入含氟基团,该化合物由于在硼酸酯上引入了氟,使其具有更高的抗水性;
(3)提供了两种氟改性硼酸酯型制动液,其具有高的干湿平衡回流沸点和良好的高低温运动粘度,性能可以达到DOT6标准。
因此,本发明提供了一种全新的性能能够达到DOT6标准的制动液,并且进一步提升了疏水性能。
附图说明
图1本发明聚丙醇二氟乙醚二聚物的1H NMR谱图。
图2本发明聚丙醇二氟乙醚二聚物的19F NMR谱图。
图3本发明聚丙醇二氟乙醚链状硼酸酯的FT-IR谱图。
图4本发明聚丙醇二氟乙醚环状硼酸酯的FT-IR谱图。
图5本发明制动液的含水量测试结果。
具体实施方式
下述实施例中所述实验方法,如无特殊说明,均为常规方法;所述试剂和材料,如无特殊说明,均可从商业途径获得。
实施例1
(一)氟改性聚醇醚的制备
将16.41g(0.2mol)二氟乙醇,23.23g(0.4mol)环氧丙烷加入到250mL的高压釜中,再加入1.6g(0.04mol)NaOH固体。通入氩气至高压釜压力为1MPa,100℃下搅拌2h。随后冷却至室温,向体系内加入二氯甲烷稀释,经硅藻土助滤得到36.35g无色油状聚丙醇二氟乙醚二聚物,收率为91.8%。1H NMR(400MHz,CDCl3):δ1.04-1.09(m,6H),δ3.23-3.65(m,6H),δ3.67-3.88(m,2H),δ5.67-5.95(m,1H);19F NMR(376MHz,CDCl3):δ-125.16~-125.43(m,2F).
(二)氟改性硼酸酯的制备
将19.82g(0.1mol)聚丙醇二氟乙醚二聚物,1.5g(0.025mol)硼酸依次加入到50mL三口烧瓶中,120℃下搅拌4h。反应结束后,向体系内滴加5mL甲苯真空分水,得17.62g淡黄色油状聚丙醇二氟乙醚链状硼酸酯,收率为88.2%。IR(thin film,υcm-1):3425,2973,2932,1456,1374,1284,1165.
将19.82g(0.1mol)聚丙醇二氟乙醚二聚物,6.77g(0.067mol)六元环状硼酸依次加入到50mL三口烧瓶中,100℃下搅拌4h。反应结束后,向体系内滴加10mL甲苯真空分水,得23.74g淡黄色油状聚丙醇二氟乙醚环状硼酸酯,收率为93.5%。IR(thin film,υcm-1):3420,2973,2932,1425,1374,1278,1114.
实施例2制动液的复配
将15g的聚丙醇二氟乙醚链状硼酸酯(实施例1所得),10g三乙二醇单甲醚,1.0gpH调节剂,1.0g制动液添加剂依次加入到100mL单口烧瓶中,40℃搅拌1h得氟改性硼酸酯制动液1。
或者:
将15g的聚丙醇二氟乙醚环状硼酸酯(实施例1所得),10g三乙二醇单甲醚,1.0gpH调节剂,1.0g制动液添加剂依次加入到100mL单口烧瓶中,40℃搅拌1h得氟改性硼酸酯制动液2。
实施例3
1、含水量测试
在温度25℃,湿度为100%的环境下,测试不同时间下10mL制动液的含水量,取样量为1μL,测试仪器为:WS-6型微量水分测定仪(山东淄博分析仪器厂)。聚丙醇乙醚环状硼酸酯是采用实施例1方法,将二氟乙醇替换为乙醇所制得。测试结果如图5所示。
2、制动液具体性能见表一。
表一氟改性硼酸酯制动液性能
本发明的上述实施例仅为说明本发明所作的举例,而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其他不同形式的变化和变动。这里无法对所有的实施方式予以穷举。凡是属于本发明的技术方案所引申出的显而易见的变化或变动仍处于本发明的保护范围之列。
Claims (10)
2.根据权利书要求1所述的氟改性硼酸酯,其特征在于,R1为二氟乙基、三氟乙基或四氟丙基;R2为氢、甲基或乙基;n=2~8。
4.根据权利要求3所述的氟改性硼酸酯的制备方法,其特征在于,步骤(1)中,所述的碱为氢氧化钠、氢氧化钾、甲醇钠、碳酸钠、碳酸氢钠、碳酸氢钾或三乙胺中的一种或几种。
5.根据权利要求3所述的氟改性硼酸酯的制备方法,其特征在于,步骤(1)中,所述聚合反应时间为2~10h,聚合温度为120~240℃,氟代醇与环氧烷烃的摩尔比为1:2~10,碱用量为氟代醇摩尔当量的2.5%~20%,聚合压力为0.2~6MPa。
6.根据权利要求3所述的氟改性硼酸酯的制备方法,其特征在于,步骤(2)中,所述氟改性聚醇醚与硼酸发生酯化反应,制备氟改性链状硼酸酯的反应中,酯化反应时间为3~15h,酯化反应温度为100~200℃,硼酸与氟改性硼酸酯的摩尔比为1:3~6。
7.根据权利要求3所述的氟改性硼酸酯的制备方法,其特征在于,步骤(2)中,所述氟改性聚醇醚与六元环状硼酸发生酯化反应,制备氟改性环状硼酸酯的反应中,酯化反应时间为3~15h,酯化反应温度为100~200℃,硼酸与氟改性硼酸酯的摩尔比为1:1~5。
8.一种制动液,包含权利要求1或2所述的氟改性硼酸酯。
9.根据权利要求8所述的制动液,其特征在于,所述制动液包含氟改性硼酸酯、稀释剂和制动液添加剂。
10.根据权利要求9所述的制动液,其特征在于,所述稀释剂为三乙二醇单甲醚、三乙二醇单乙醚、三乙二醇单丁醚中的一种或几种;所述制动液添加剂为pH调节剂、橡胶溶胀剂、抗氧剂、防锈剂、水解稳定剂中的一种或几种。
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