CN117467492A - 一种氢氟烃用冷冻机油组合物及其制备方法 - Google Patents
一种氢氟烃用冷冻机油组合物及其制备方法 Download PDFInfo
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 32
- 239000011737 fluorine Substances 0.000 claims abstract description 32
- 150000004996 alkyl benzenes Chemical class 0.000 claims abstract description 30
- 239000002199 base oil Substances 0.000 claims abstract description 27
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
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- 239000003112 inhibitor Substances 0.000 claims abstract description 8
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 19
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- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
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- 239000012964 benzotriazole Substances 0.000 claims description 5
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- 125000000217 alkyl group Chemical group 0.000 claims description 3
- HRWYHCYGVIJOEC-UHFFFAOYSA-N 2-(octoxymethyl)oxirane Chemical compound CCCCCCCCOCC1CO1 HRWYHCYGVIJOEC-UHFFFAOYSA-N 0.000 claims description 2
- RAAGZOYMEQDCTD-UHFFFAOYSA-N 2-fluorobenzoyl chloride Chemical compound FC1=CC=CC=C1C(Cl)=O RAAGZOYMEQDCTD-UHFFFAOYSA-N 0.000 claims description 2
- SYVNVEGIRVXRQH-UHFFFAOYSA-N 3-fluorobenzoyl chloride Chemical compound FC1=CC=CC(C(Cl)=O)=C1 SYVNVEGIRVXRQH-UHFFFAOYSA-N 0.000 claims description 2
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- 230000000052 comparative effect Effects 0.000 description 20
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- 238000005191 phase separation Methods 0.000 description 8
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- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 3
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 description 3
- 238000005057 refrigeration Methods 0.000 description 3
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- VUHMHACHBVTPMF-UHFFFAOYSA-N nonyl benzoate Chemical compound CCCCCCCCCOC(=O)C1=CC=CC=C1 VUHMHACHBVTPMF-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- UMPRJGKLMUDRHL-UHFFFAOYSA-N ethyl 4-fluorobenzoate Chemical compound CCOC(=O)C1=CC=C(F)C=C1 UMPRJGKLMUDRHL-UHFFFAOYSA-N 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
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- OSTIHFXUTPZJQL-UHFFFAOYSA-N fluoro benzoate Chemical compound FOC(=O)C1=CC=CC=C1 OSTIHFXUTPZJQL-UHFFFAOYSA-N 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- -1 fluorobenzoate ester Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
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- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
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- 230000008569 process Effects 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
- C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
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- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/06—Well-defined aromatic compounds
- C10M2203/065—Well-defined aromatic compounds used as base material
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Abstract
本发明涉及润滑油技术领域,具体涉及一种氢氟烃用冷冻机油组合物及其制备方法。该组合物按重量份数包括如下组分:90‑180份基础油、1‑2份抗磨剂、0.5‑1份稳定剂、0.1‑0.5份抗泡剂、0.05‑0.1份酸捕获剂和0.01‑0.02份缓蚀剂;所述基础油按重量份数包括如下组分:80‑100份直链烷基苯、10‑80份含氟苯甲酸酯。该发明提供的冷冻机油于氢氟烃类制冷剂具有优异的相容性,在冷冻机油领域具有广泛应用前景。
Description
技术领域
本发明涉及润滑油技术领域,尤其涉及一种氢氟烃用冷冻机油组合物及其制备方法。
背景技术
冷冻机油是一种应用于制冷***的润滑油,它扮演着冷冻循环中润滑、密封和冷却的重要角色。然而,传统的冷冻机油在与氢氟烃接触时存在一些问题。
传统的冷冻机油通常使用烷基苯作为基础油成分,但是,烷基苯与氢氟烃的相容性较差,容易产生相分离或沉淀的问题,导致冷冻机油的性能下降。其次,冷冻机油需要具备良好的润滑性能、抗磨损性能、抗氧化性能和防泡性能,以确保制冷***的高效运行和长期稳定性。然而,在低温条件下,传统的冷冻机油可能无法满足这些要求。
专利技术文献CN112048355B公开了一种冷冻机油及冷冻机用工作流体组合物,该冷冻机油以烷基苯作为基础油,所述烷基苯具有250℃以上的5%馏出温度及460℃以下的95%馏出温度。虽然该发明采用了特定的烷基苯作为基础油以改善其与氢氟烃之间的相溶性,但是,由于烷基苯本身的性质影响,仍旧与氢氟烃存在较差的相溶性。
因此,十分有必要开发一种以烷基苯作为基础油且适用于氢氟烃的冷冻机油。
发明内容
有鉴于此,本发明的目的在于提出一种氢氟烃用冷冻机油组合物及其制备方法,以解决烷基苯作为基础油与氢氟烃的相溶性欠佳的问题。
基于上述目的,本发明提供了一种氢氟烃用冷冻机油组合物,按重量份数包括如下组分:90-180份基础油、1-2份抗磨剂、0.5-1份稳定剂、0.1-0.5份抗泡剂、0.05-0.1份酸捕获剂和0.01-0.02份缓蚀剂;
其中,所述基础油按重量份数包括如下组分:80-100份直链烷基苯、10-80份含氟苯甲酸酯;
其中,所述含氟苯甲酸酯的结构式如下:
其中,R选自C8-C14直链烷基中的一种。
优选的,所述直链烷基苯为C9-C14的直链烷基苯。
优选的,所述抗磨剂为磷酸酯类抗磨剂。
优选的,所述稳定剂为酚类或胺类抗氧剂。
优选的,所述抗泡剂为含氟硅油和二甲基硅油的混合物。
优选的,所述含氟硅油和二甲基硅油的重量比为1:4。
优选的,所述含氟硅油为甲基氟硅油,所述甲基氟硅油的粘度与二甲基硅油的粘度相差小于50cs,所述甲基氟硅油的粘度为100-200cs。
优选的,所述酸捕获剂为新戊二醇二缩水甘油醚和辛基缩水甘油醚中的一种;所述缓蚀剂为苯并三氮唑。
优选的,所述含氟苯甲酸酯的制备方法如下:在氮气气氛下,将C2-C14直链烷基醇和三乙胺加入到二氯甲烷中,于0-20℃下搅拌5-10min,然后加入含氟苯甲酰氯,于0-20℃下反应2-4h,萃取,洗涤,纯化,得到含氟苯甲酸酯。
优选的,所述C8-C14直链烷基醇、含氟苯甲酰氯、三乙胺和二氯甲烷的摩尔比为1:0.8-0.9:1:5-10。
优选的,所述含氟苯甲酰氯为4-氟苯甲酰氯和3-氟苯甲酰氯中的一种。
进一步的,本发明还提供了上述氢氟烃用冷冻机油组合物的制备方法,包括如下步骤:
(1)在氮气气氛下,将直链烷基苯和含氟苯甲酸酯混合,于室温、150-300rpm下搅拌10-20min,得到基础油;
(2)在氮气气氛下,将含氟硅油和二甲基硅油混合,于室温、100-150rpm下搅拌5-10min,得到抗泡剂;
(3)在氮气气氛下,将抗磨剂、稳定剂、抗泡剂、酸捕获剂和缓蚀剂加入到基础油中,于50-80℃、300-450rpm下搅拌10-20min,得到氢氟烃用冷冻机油组合物。
本发明的有益效果:
改善烷基苯与氢氟烃的相容性:传统的基础油烷基苯与氢氟烃的相容性较差,容易形成沉淀或相分离的问题,而本发明中使用直链烷基苯和含氟苯甲酸酯作为基础油,与氢氟烃更具亲和性,能够有效改善相容性。
提高润滑性能:抗磨剂的添加可以降低摩擦表面的磨损,增加机械部件的使用寿命,稳定剂的加入可以抑制油品在高温条件下的氧化分解,防止油品变质,抗泡剂的使用可以防止气泡的生成,保持油品的润滑性能,这些添加剂的综合作用可以提高冷冻机油的润滑性能。
抗腐蚀能力:酸捕获剂的加入可以中和油品中的酸性物质,防止酸腐蚀和腐蚀性气体的生成,缓蚀剂的使用可以形成保护性膜,减少机械部件表面的腐蚀和磨损。
总的来说,本发明提供的氢氟烃用冷冻机油组合物在改善烷基苯与氢氟烃的相容性、提高润滑性能、抗腐蚀和酸中和能力具有显著优势,这些特点使得该组合物和制备方法在冷冻机油领域具有广泛的应用前景。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明白,以下结合具体实施例,对本发明进一步详细说明。
本发明所用原料的来源或性质如下:
直链烷基苯购买于中国石化集团金陵石油化工有限公司烷基苯厂,平均相对分子质量为241.6,密度为0.8562g/cm3,包括C9-C14直链烷基苯,产品批号为WJB20220612-301-2-02;甲基氟硅油购买于浙江环新氟材料股份有限公司,粘度为120cs;二甲基硅油购买于广州市畅宏化工有限公司,粘度为100cs。
实施例1:一种氢氟烃用冷冻机油组合物,具体制备步骤如下:
(1)在氮气气氛下,将13gC8直链烷基醇和10.1g三乙胺加入到60g二氯甲烷中,于10℃下搅拌5min,然后加入12.7g4-氟苯甲酰氯,于10℃下反应2h,萃取,洗涤,经层析柱(1:9,乙酸乙酯/己烷)纯化,得到含氟苯甲酸酯;
(2)在氮气气氛下,将80g直链烷基苯和10g含氟苯甲酸酯混合,于室温、200rpm下搅拌15min,得到基础油;
(3)在氮气气氛下,将0.02g甲基氟硅油和0.08g二甲基硅油混合,于室温、120rpm下搅拌8min,得到抗泡剂;
(4)在氮气气氛下,将1g磷酸三甲酚酯、0.5g2,6-二叔丁基对甲基苯酚、0.1g抗泡剂、0.05g新戊二醇二缩水甘油醚和0.01g苯并三氮唑加入到90g基础油中,于50℃、300rpm下搅拌10min,得到氢氟烃用冷冻机油组合物。
实施例2:一种氢氟烃用冷冻机油组合物,具体制备步骤如下:
(1)在氮气气氛下,将21.6gC9直链烷基醇和15.2g三乙胺加入到90g二氯甲烷中,于10℃下搅拌8min,然后加入19.1g4-氟苯甲酰氯,于10℃下反应3h,萃取,洗涤,经层析柱(1:9,乙酸乙酯/己烷)纯化,得到含氟苯甲酸酯;
(2)在氮气气氛下,将90g直链烷基苯和20g含氟苯甲酸酯混合,于室温、200rpm下搅拌15min,得到基础油;
(3)在氮气气氛下,将0.05g甲基氟硅油和0.2g二甲基硅油混合,于室温、120rpm下搅拌8min,得到抗泡剂;
(4)在氮气气氛下,将1.5g磷酸三甲酚酯、0.7g2,6-二叔丁基对甲基苯酚、0.25g抗泡剂、0.07g新戊二醇二缩水甘油醚和0.015g苯并三氮唑加入到110g基础油中,于60℃、350rpm下搅拌15min,得到氢氟烃用冷冻机油组合物。
实施例3:一种氢氟烃用冷冻机油组合物,具体制备步骤如下:
(1)在氮气气氛下,将47.4gC14直链烷基醇和30.3g三乙胺加入到180g二氯甲烷中,于10℃下搅拌10min,然后加入38.1g4-氟苯甲酰氯,于10℃下反应4h,萃取,洗涤,经层析柱(1:9,乙酸乙酯/己烷)纯化,得到含氟苯甲酸酯;
(2)在氮气气氛下,将100g直链烷基苯和80g含氟苯甲酸酯混合,于室温、300rpm下搅拌20min,得到基础油;
(3)在氮气气氛下,将0.1g甲基氟硅油和0.4g二甲基硅油混合,于室温、150rpm下搅拌10min,得到抗泡剂;
(4)在氮气气氛下,将2g磷酸三甲酚酯、1g2,6-二叔丁基对甲基苯酚、0.5g抗泡剂、0.1g新戊二醇二缩水甘油醚和0.02g苯并三氮唑加入到180g基础油中,于80℃、450rpm下搅拌20min,得到氢氟烃用冷冻机油组合物。
对比例1:
对比例1与实施例2的区别在于:对比例1中基础油为110g直链烷基苯。
对比例2:
对比例2与实施例2的区别在于:对比例2中抗泡剂为0.25g二甲基硅油。
对比例3:
对比例3与实施例2的区别在于:对比例3中基础油为110g直链烷基苯,抗泡剂为0.25g二甲基硅油。
对比例4:
对比例4与实施例2的区别在于:对比例4中含氟苯甲酸酯为4-氟苯甲酸乙酯。
对比例5
对比例5与实施例2的区别在于:对比例4中基础油为90g直链烷基苯和20g苯甲酸壬酯。
性能测试:对上述实施例和对比例进行应用性能测试,结果如表1和表2所示。
表1实施例和对比例制备的冷冻机油组合物的性能测试结果
表2实施例和对比例制备的冷冻机油组合物的性能测试结果
其中,与制冷剂的相容性参照《SH/T0699-2000冷冻机油与制冷剂相溶性试验法》,具体的测试过程为:将一定质量的试验油和制冷剂充入试管中,在室温或水浴中升温,使试验油和制冷剂成为均一、透明的溶液,然后在冷浴中冷却试管,测试含油率5%-50%的冷冻机油与制冷剂混合物缓慢从25℃冷却至-40℃,将混合物产生相分离或白色浑浊的温度作为测定含油率下的两相分离温度,将各不同含油率相对应的两相分离温度绘制两相分离曲线,曲线上最高测定温度即为测试油品与制冷剂的两相分离温度,两相分离温度越低,表明冷冻机油与制冷剂的相溶性越好,低于和等于-40℃基判定为相容性好,高于-40℃及判定为相容性差。
由表1的实施例1-3可以看出,本发明制备的冷冻机油的40℃运动粘度范围宽广,且与新型的氢氟烃类制冷剂、传统的烷基制冷剂均具有优异的相容性;从实施例2和对比例1-3可以看出,本发明中的含氟苯甲酸酯和甲基氟硅油共同调节了冷冻机油的40℃运动粘度,使其具有更宽的应用范围,并且含氟苯甲酸酯大大提高了冷冻机油与氢氟烃类制冷剂的相容性;从实施例2和对比例4、5可以看出,含氟苯甲酸酯中的氟和碳链的长度对于冷冻机油与氢氟烃类制冷剂的相容性具有至关重要的影响。
所属领域的普通技术人员应当理解:以上任何实施例的讨论仅为示例性的,并非旨在暗示本发明的范围(包括权利要求)被限于这些例子;在本发明的思路下,以上实施例或者不同实施例中的技术特征之间也可以进行组合,步骤可以以任意顺序实现,并存在如上所述的本发明的不同方面的许多其它变化,为了简明它们没有在细节中提供。
本发明旨在涵盖落入所附权利要求的宽泛范围之内的所有这样的替换、修改和变型。因此,凡在本发明的精神和原则之内,所做的任何省略、修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种氢氟烃用冷冻机油组合物,其特征在于,按重量份数包括如下组分:90-180份基础油、1-2份抗磨剂、0.5-1份稳定剂、0.1-0.5份抗泡剂、0.05-0.1份酸捕获剂和0.01-0.02份缓蚀剂;
所述基础油按重量份数包括如下组分:80-100份直链烷基苯、10-80份含氟苯甲酸酯;
所述含氟苯甲酸酯的结构式如下:
其中,R选自C8-C14直链烷基中的一种。
2.根据权利要求1所述的氢氟烃用冷冻机油组合物,其特征在于,所述直链烷基苯为C9-C14的直链烷基苯。
3.根据权利要求1所述的氢氟烃用冷冻机油组合物,其特征在于,所述抗磨剂为磷酸酯类抗磨剂;所述稳定剂为酚类或胺类抗氧剂。
4.根据权利要求1所述的氢氟烃用冷冻机油组合物,其特征在于,所述抗泡剂为含氟硅油和二甲基硅油的混合物,所述含氟硅油和二甲基硅油的重量比为1:4。
5.根据权利要求4所述的氢氟烃用冷冻机油组合物,其特征在于,所述含氟硅油为甲基氟硅油,所述甲基氟硅油的粘度与二甲基硅油的粘度相差小于50cs,所述甲基氟硅油的粘度为100-200cs。
6.根据权利要求1所述的氢氟烃用冷冻机油组合物,其特征在于,所述酸捕获剂为新戊二醇二缩水甘油醚和辛基缩水甘油醚中的一种;所述缓蚀剂为苯并三氮唑。
7.根据权利要求1所述的氢氟烃用冷冻机油组合物,其特征在于,所述含氟苯甲酸酯的制备方法如下:在氮气气氛下,将C2-C14直链烷基醇和三乙胺加入到二氯甲烷中,于0-20℃下搅拌5-10min,然后加入含氟苯甲酰氯,于0-20℃下反应2-4h,萃取,洗涤,纯化,得到含氟苯甲酸酯。
8.根据权利要求7所述的氢氟烃用冷冻机油组合物,其特征在于,所述C8-C14直链烷基醇、含氟苯甲酰氯、三乙胺和二氯甲烷的摩尔比为1:0.8-0.9:1:5-10。
9.根据权利要求7所述的氢氟烃用冷冻机油组合物,其特征在于,所述含氟苯甲酰氯为4-氟苯甲酰氯和3-氟苯甲酰氯中的一种。
10.一种根据权利要求1-8任一项所述的氢氟烃用冷冻机油组合物的制备方法,其特征在于,包括如下步骤:
(1)在氮气气氛下,将直链烷基苯和含氟苯甲酸酯混合,于室温、150-300rpm下搅拌10-20min,得到基础油;
(2)在氮气气氛下,将含氟硅油和二甲基硅油混合,于室温、100-150rpm下搅拌5-10min,得到抗泡剂;
(3)在氮气气氛下,将抗磨剂、稳定剂、抗泡剂、酸捕获剂和缓蚀剂加入到基础油中,于50-80℃、300-450rpm下搅拌10-20min,得到氢氟烃用冷冻机油组合物。
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