CN108130158B - 一种可生物降解环保润滑油 - Google Patents
一种可生物降解环保润滑油 Download PDFInfo
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- CN108130158B CN108130158B CN201810046367.5A CN201810046367A CN108130158B CN 108130158 B CN108130158 B CN 108130158B CN 201810046367 A CN201810046367 A CN 201810046367A CN 108130158 B CN108130158 B CN 108130158B
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- 239000010687 lubricating oil Substances 0.000 title claims abstract description 42
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 claims abstract description 43
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229920002472 Starch Polymers 0.000 claims abstract description 24
- 235000019698 starch Nutrition 0.000 claims abstract description 24
- 239000008107 starch Substances 0.000 claims abstract description 24
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- 150000002148 esters Chemical class 0.000 claims abstract description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001718 carbodiimides Chemical class 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 9
- 239000008158 vegetable oil Substances 0.000 claims abstract description 9
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000007865 diluting Methods 0.000 claims abstract description 8
- 239000005457 ice water Substances 0.000 claims abstract description 8
- 238000010992 reflux Methods 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 5
- 239000013556 antirust agent Substances 0.000 claims abstract description 3
- 229920001577 copolymer Polymers 0.000 claims abstract description 3
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- QDCPNGVVOWVKJG-VAWYXSNFSA-N 2-[(e)-dodec-1-enyl]butanedioic acid Chemical compound CCCCCCCCCC\C=C\C(C(O)=O)CC(O)=O QDCPNGVVOWVKJG-VAWYXSNFSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 235000019482 Palm oil Nutrition 0.000 claims description 2
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000004359 castor oil Substances 0.000 claims description 2
- 235000019438 castor oil Nutrition 0.000 claims description 2
- 239000003240 coconut oil Substances 0.000 claims description 2
- 235000019864 coconut oil Nutrition 0.000 claims description 2
- 235000012343 cottonseed oil Nutrition 0.000 claims description 2
- 239000002385 cottonseed oil Substances 0.000 claims description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 2
- 239000003921 oil Substances 0.000 claims description 2
- 235000019198 oils Nutrition 0.000 claims description 2
- 239000002540 palm oil Substances 0.000 claims description 2
- 239000008159 sesame oil Substances 0.000 claims description 2
- 235000011803 sesame oil Nutrition 0.000 claims description 2
- 239000003549 soybean oil Substances 0.000 claims description 2
- 235000012424 soybean oil Nutrition 0.000 claims description 2
- 235000020238 sunflower seed Nutrition 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims 1
- 239000003112 inhibitor Substances 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 11
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000001050 lubricating effect Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 2
- 238000006065 biodegradation reaction Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 231100000241 scar Toxicity 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- -1 dodecenylsuccinic acid ester Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012208 gear oil Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010722 industrial gear oil Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
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- C10M145/40—Polysaccharides, e.g. cellulose
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- C08B31/00—Preparation of derivatives of starch
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Abstract
本发明公开了一种可生物降解环保润滑油，包括如下重量份的原料：2,5‑呋喃二甲酸淀粉酯30‑40份、乙烯‑醋酸乙烯‑一氧化碳共聚物1‑3份、植物油40‑50份、极压抗磨剂1‑3份、防锈剂0.1‑0.5份、抗氧剂0.1‑0.5份；所述2,5‑呋喃二甲酸淀粉酯的制备方法，包括如下步骤：将2,5‑呋喃二甲酸溶于四氢呋喃中，然后加入淀粉、碳二亚胺、4‑二甲胺基吡啶，在冰水浴中搅拌2‑3小时，后在40‑50℃下回流搅拌18‑24小时，后依次经过过滤、用有机溶剂稀释、水洗3‑5次、饱和食盐水洗4‑6次、无水硫酸镁吸水，过滤，再在50‑60℃下旋蒸除去溶剂；该发明公开的可生物降解环保润滑油可生物降解环保，且还具有良好的热稳定性、低温性能和氧化稳定性，粘度指数较低，通用性较高的优点。
Description
技术领域
本发明涉及润滑油技术领域，更具体地说，涉及一种可生物降解环保润滑油。
背景技术
润滑油在航空、汽车、机械加工、交通运输、冶金、煤炭、建筑、轻工等行业有着广泛应用，它能减少摩擦磨损、节约能源、延长机械寿命。然而，在其被大量使用的同时，不可避免地会通过运输、泄露、溅射、溢出或不恰当的排放等各种途径进入环境，严重污染着土壤、陆地、江河和湖泊，影响甚至破坏生态环境和生态平衡。在此背景下，世界各国纷纷研究可生物降解环保润滑油，这种润滑油既能满足机械零部件润滑要求，其耗损产物又对环境不造成危害。
植物油天然的可再生和可生物降解性能使它和传统润滑油相比提供明显的环境和经济可持续发展的好处。除了这些好处，植物油还具有挥发性低、闪点高、润滑性能优异、资源丰富、价格较低的优点。因此，以植物油为来源的生物基润滑油就成为了现有技术中环保润滑油的主要力量。但植物油氧化稳定性差、粘度指数较低、低温性能不佳，因而通用性较差，成为了制约其发展的主要障碍。
作为改进，中国专利公开号为CN 102041148A公开了一种风力发电合成齿轮油，该方法用95～98％的二元酸季戊四醇C5～C18复合酯合成基础油，5～2％的工业齿轮油复合添加剂以及适量的抗泡剂制得风力发电齿轮油，该方法制制得的风力发电齿轮油具有提高风力发电齿轮油的寿命，改善齿轮油与密封材料的相容性，可生物降解，使用安全、环保的特点，但是粘度较低，应用领域较小。
因此，开发一种环境友好、易生物降解，而且高质量的润滑油来弥补现有技术中以植物油为代表的润滑油的不足，对促进工业生产的发展具有重要意义。
发明内容
本发明的主要目的在于提供一种可生物降解环保润滑油，该润滑油原料易得，价格低廉，环境友好，既符合润滑油油品性能规格的要求，又能在较短时间内被微生物分解成CO2和H2O，不会对环境造成危害；另外其还具有良好的热稳定性、低温性能和氧化稳定性，粘度指数较低，通用性较高的优点。
为达到以上目的，本发明采用的技术方案为：一种可生物降解环保润滑油，包括如下重量份的原料：
其中，所述2,5-呋喃二甲酸淀粉酯的制备方法，包括如下步骤：将2,5-呋喃二甲酸溶于四氢呋喃中，然后加入淀粉、碳二亚胺、4-二甲胺基吡啶，在冰水浴中搅拌2-3小时，后在40-50℃下回流搅拌18-24小时，后依次经过过滤、用有机溶剂稀释、水洗3-5次、饱和食盐水洗4-6次、无水硫酸镁吸水，过滤，再在50-60℃下旋蒸除去溶剂；
所述2,5-呋喃二甲酸、四氢呋喃、淀粉、碳二亚胺、4-二甲胺基吡啶的质量比为2：(18-24)：(1-1.3)：(3-4)：(1.5-3)；
所述有机溶剂选自四氢呋喃、二氯甲烷、乙酸乙酯中的一种或几种；
所述的植物油为蓖麻油、菜籽油、棕榈油、大豆油、椰子油、葵花籽油、棉籽油或者芝麻油中的一种或几种；
所述防锈剂为十二烯基丁二酸、十二烯基丁二酸酯或十二烯基丁二酸半酯中的一种或者几种的混合；
所述极压抗磨剂为磷酸酯类化合物、亚磷酸酯类化合物、硫磷复合剂或含硫极压剂中的一种或者几种；
所述抗氧剂为烷基酚衍生物和/或烷基胺衍生物；优选的，所述抗氧剂为T501抗氧剂、T521抗氧剂、成分为N-苯基-α-萘胺的T531抗氧剂中的一种或几种。
由于上述技术方案运用，本发明与现有技术相比具有下列优点：
(1)本发明设计的可生物降解环保润滑油，原料易得，价格较低廉，各组分制备方法简单易行，对设备要求不高。
(2)本发明设计的可生物降解环保润滑油，自主合成的2,5-呋喃二甲酸淀粉酯具有良好的生物降解性、热稳定性和低温性能，并且，还具有粘度稳定的特性和调节粘度的作用，使得润滑油生物降解性良好，同时粘度指数较高，低温性能良好。
(3)本发明设计的可生物降解环保润滑油，添加乙烯-醋酸乙烯-一氧化碳共聚物，不仅具有可生物降解性，还可以改善润滑油粘温性能，提高耐磨润滑性，另一方面，还具有粘度改进作用。
(4)本发明设计的可生物降解环保润滑油，合成2,5-呋喃二甲酸淀粉酯时，采用EDC/DMAP催化体系，加快了化学反应速率，不使用浓硫酸等有毒有害物质，减少了反应对环境的污染；只需在常温下进行，不需要加热，节约了资源和成本。
(5)本发明设计的可生物降解环保润滑油，选用淀粉与2,5-呋喃二甲酸这两种可生物降解的物质作为酯化反应物，淀粉上含有较多是羟基，酯化后形成三维网状结构，有利于提高润滑油的润滑性、抗氧化性和耐热性，且能改善分散性。
具体实施方式
以下描述用于揭露本发明以使本领域技术人员能够实现本发明。以下描述中的优选实施例只作为举例，本领域技术人员可以想到其他显而易见的变型。
本实施例中所述原料购自国药集团化学试剂有限公司。
实施例1
一种可生物降解环保润滑油，包括如下重量份的原料：
其中，所述2,5-呋喃二甲酸淀粉酯的制备方法，包括如下步骤：将2,5-呋喃二甲酸20g溶于四氢呋喃180g中，然后加入淀粉10g、碳二亚胺30g、4-二甲胺基吡啶15g，在冰水浴中搅拌2小时，后在40℃下回流搅拌18小时，后依次经过过滤、用四氢呋喃稀释、水洗3次、饱和食盐水洗4次、无水硫酸镁吸水，过滤，再在50℃下旋蒸除去溶剂；
实施例2
一种可生物降解环保润滑油，包括如下重量份的原料：
其中，所述2,5-呋喃二甲酸淀粉酯的制备方法，包括如下步骤：将2,5-呋喃二甲酸20g溶于四氢呋喃200g中，然后加入淀粉11g、碳二亚胺30g、4-二甲胺基吡啶20g，在冰水浴中搅拌2.3小时，后在43℃下回流搅拌20小时，后依次经过过滤、用二氯甲烷稀释、水洗4次、饱和食盐水洗5次、无水硫酸镁吸水，过滤，再在53℃下旋蒸除去溶剂；
实施例3
一种可生物降解环保润滑油，包括如下重量份的原料：
其中，所述2,5-呋喃二甲酸淀粉酯的制备方法，包括如下步骤：将2,5-呋喃二甲酸20g溶于四氢呋喃220g中，然后加入淀粉12g、碳二亚胺36g、4-二甲胺基吡啶22g，在冰水浴中搅拌2.5小时，后在45℃下回流搅拌22小时，后依次经过过滤、用乙酸乙酯稀释、水洗5次、饱和食盐水洗6次、无水硫酸镁吸水，过滤，再在56℃下旋蒸除去溶剂；
实施例4
一种可生物降解环保润滑油，包括如下重量份的原料：
其中，所述2,5-呋喃二甲酸淀粉酯的制备方法，包括如下步骤：将2,5-呋喃二甲酸20g溶于四氢呋喃230g中，然后加入淀粉13g、碳二亚胺38g、4-二甲胺基吡啶27g，在冰水浴中搅拌3小时，后在49℃下回流搅拌23小时，后依次经过过滤、用四氢呋喃稀释、水洗5次、饱和食盐水洗6次、无水硫酸镁吸水，过滤，再在58℃下旋蒸除去溶剂；
实施例5
一种可生物降解环保润滑油，包括如下重量份的原料：
其中，所述2,5-呋喃二甲酸淀粉酯的制备方法，包括如下步骤：将2,5-呋喃二甲酸20g溶于四氢呋喃240g中，然后加入淀粉13g、碳二亚胺40g、4-二甲胺基吡啶30g，在冰水浴中搅拌3小时，后在50℃下回流搅拌24小时，后依次经过过滤、用二氯甲烷稀释、水洗5次、饱和食盐水洗6次、无水硫酸镁吸水，过滤，再在60℃下旋蒸除去溶剂；
对比例
国内常用润滑油脂，购自无锡普润科技有限公司。
上述实施例1-5以及对比例所得样品进行相应的性能测试，测试结果如表1所示。测试方法如下：
(1)四球实验：按照ASTMD-2783进行测试；在四球实验测试结果中，在一定温度、转速下，最大无卡咬负荷PB值，表示的是钢球在润滑状态不发生卡咬的最大负荷，PB值越高，说明润滑油的润滑性能越好。烧结负荷PD值，表示的是逐级增大负荷，上方钢球和下方钢球因负荷过重而发生高温烧结，设备不得不停止运转的负荷，PD值越高，说明润滑油的极压润滑性能越好。磨斑直径d值，表示的是承重钢球面因摩擦导致磨损斑痕直径的大小，d值越小，说明润滑油的抗磨能力润滑性越好。
(2)倾点：按照GB/T3535进行测试。
(3)粘度指数：按照GB/T1995-88进行测试。
(4)生物降解性：根据欧共体的CEC L-33-A-93(前身为CEC L-33-T-82)的实验方法进行测试。
表1实施例和对比例样品性能
从上表可以看出，本发明实施例公开的润滑油组合物最大无卡咬负荷72-97N(kg)，烧结负荷150-170N(kg)，倾点-23～-29℃，磨斑直径0.30-0.18mm，粘度指数182-191，生物降解率93-99％；而国内常用润滑油脂最大无卡咬负荷60N(kg)，烧结负荷130N(kg)，倾点-21℃，磨斑直径0.4mm，生物降解率65％，粘度指数135；可见，本发明实施例公开的润滑油组合物具有较好的具有较好的极压性能和润滑性能。且粘温性能和生物降解性能优异。
以上显示和描述了本发明的基本原理、主要特征和本发明的优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是本发明的原理，在不脱离本发明精神和范围的前提下本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明的范围内。本发明要求的保护范围由所附的权利要求书及其等同物界定。
Claims (5)
1.一种可生物降解环保润滑油，其特征在于，包括如下重量份的原料：
2,5-呋喃二甲酸淀粉酯 30-40份；
乙烯-醋酸乙烯-一氧化碳共聚物 1-3份；
植物油 40-50份；
极压抗磨剂 1-3份；
防锈剂 0.1-0.5份；
抗氧剂 0.1-0.5份；
所述2,5-呋喃二甲酸淀粉酯的制备方法，包括如下步骤：将2,5-呋喃二甲酸溶于四氢呋喃中，然后加入淀粉、碳二亚胺、4-二甲胺基吡啶，在冰水浴中搅拌2-3小时，后在40-50℃下回流搅拌18-24小时，后依次经过过滤、用有机溶剂稀释、水洗3-5次、饱和食盐水洗4-6次、无水硫酸镁吸水，过滤，再在50-60℃下旋蒸除去溶剂。
2.根据权利要求1 所述的一种可生物降解环保润滑油，其特征在于，所述2,5-呋喃二甲酸、四氢呋喃、淀粉、碳二亚胺、4-二甲胺基吡啶的质量比为2：（18-24）：（1-1.3）：（3-4）：（1.5-3）。
3.根据权利要求2所述的一种可生物降解环保润滑油，其特征在于，所述有机溶剂选自四氢呋喃、二氯甲烷、乙酸乙酯中的一种或几种。
4.根据权利要求1所述的一种可生物降解环保润滑油，其特征在于，所述植物油为蓖麻油、菜籽油、棕榈油、大豆油、椰子油、葵花籽油、棉籽油或者芝麻油中的一种或几种。
5.根据权利要求1所述的一种可生物降解环保润滑油，其特征在于，所述防锈剂为十二烯基丁二酸、十二烯基丁二酸酯或十二烯基丁二酸半酯中的一种或者几种的混合。
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