CN107827926A - 小分子功能化的表面活性剂及其制备方法和应用 - Google Patents

小分子功能化的表面活性剂及其制备方法和应用 Download PDF

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CN107827926A
CN107827926A CN201711050370.6A CN201711050370A CN107827926A CN 107827926 A CN107827926 A CN 107827926A CN 201711050370 A CN201711050370 A CN 201711050370A CN 107827926 A CN107827926 A CN 107827926A
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sodium
surfactant
water
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蔡美荣
王玉荣
周峰
于强亮
刘维民
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Lanzhou Institute of Chemical Physics LICP of CAS
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Abstract

本发明公开了小分子功能化的表面活性剂，该表面活性剂为水溶性功能化的季铵离子液体，其阳离子为不同烷基链长季铵阳离子，阴离子为乙酰磺酸根、邻苯甲酰磺酰亚胺酸根、水杨酸根、甘氨酸根、D‑葡萄糖酸根、柠檬酸根、二羟基丁二酸根。本发明还公开了该表面活性剂的制备方法及其作为水溶润滑添加剂的应用。

Description

小分子功能化的表面活性剂及其制备方法和应用
技术领域
本发明涉及一种小分子功能化的表面活性剂及其制备方法和应用。该表面活性剂制备简单且具有良好的摩擦学性能，是一种优异的水润滑添加剂。
背景技术
目前矿物油基润滑产品以其优异的减摩抗磨性能被广泛地应用在工业领域，其大大减小了机械设备因摩擦造成的能源消耗，延长了其寿命。但在某些特殊领域如煤矿、金属加工等工况，石油基产品因其低闪点、易燃、导热系数小等缺点制约了其应用，且随着人类环保意识的不断增强，人们意识到矿物油基润滑剂造成的环境污染问题越来越严重，逐渐影响到我们的日常生活和身心健康，因此人们开始在润滑领域积极地寻找可替代品。水基润滑剂因具有优异的冷却、难燃、低污染、高导热系数和高比热容等优点，被视为一种新型的绿色润滑剂而不断发展并被广泛应用于抗燃液压液和金属加工液领域。然而，与油基润滑剂相比，现有的水基润滑剂存在润滑性和防锈性差的问题，这在很大程度上限制了水基润滑剂的发展，因此研究开发一种高效的水基润滑添加剂是提高水基润滑剂综合性能进而拓宽其使用范围的关键所在。
离子液体由于其独特的物理化学性能和良好的润滑性能使其作为润滑油、添加剂和润滑薄膜而被广泛研究(M. H. Yao, M. J. Fan, Y. M, Liang, F. Zhou, Y. Q. Xia,Wear 268 (2010) 67–71); X. Q. Liu, M. R. Cai, Z. Zhao, Y. M. Liang, F. Zhou,W. M. Liu, Tribol. Lett. 40 (2010) 215-224.)，故其也有发展成为一种高效水基润滑添加剂的潜能。目前报道的一些作为水润滑添加剂的离子液体仍然存在与水相溶性差、稳定性差、润滑性能不佳及对基底的腐蚀性等问题，它们都极大地限制了其在水基润滑添加剂领域的应用。因此开发高性能的水溶性润滑离子液体添加剂是当前该领域的研究热点之一。申请人所在的课题组在2017年合成了一种新型离子液体类似物N-（3-（二乙氧基磷酰基）丙基）-N，N-二甲基十八烷-1-溴化铵盐，其作为水溶性润滑添加剂有良好的减摩抗磨能力(Y Wang, Q Yu, Z Ma, G Huang, M Cai, F Zhou, W. M. Liu, Tribol. Inter.(2017)112: 86–93.)，但是因为其阴离子为Br-，单独作为水基添加剂会腐蚀金属摩擦副，使用的过程中需添加防腐蚀添加剂。
发明内容
本发明的目的在于提供小分子功能化的表面活性剂及其制备方法和应用。
本发明通过分子设计，在表面活性剂的结构中引入无卤素绿色的阴离子，从而制备可作为绿色环保、无腐蚀水基润滑添加剂的表面活性剂，并通过改变表面活性剂阳离子取代烷基的链长来调节其在水中的溶解性能。通过分子设计，本发明制备了一系列功能化的季铵水溶性离子液体类似物-小分子表面活性剂，作为水溶性润滑添加剂，不仅具有较好的润滑和抗磨性能，还能有效的降低水对金属的腐蚀，有望作为一种水润滑添加剂被应用在水基润滑加工液或切削液行业。
小分子功能化的表面活性剂，其特征在于该表面活性剂为水溶性功能化的季铵离子液体，其阳离子为不同烷基链长季铵阳离子（记作A1、A2、A3），阴离子为乙酰磺酸根（记作B1）、邻苯甲酰磺酰亚胺酸根（记作B2）、水杨酸根（记作B3）、甘氨酸根（记作B4）、D-葡萄糖酸根（记作B5）、柠檬酸根（记作B6）、二羟基丁二酸根（记作B7）；所述阳离子和阴离子的结构式如下：
，
其中R1代表甲基、乙基或丙基，R2代表辛基、十二烷基或十八烷基, n=0、1或2。
本发明所述表面活性剂常温下为白色粉末。
本发明所述表面活性剂的制备反应方程式如下：
，
式中R1代表甲基、乙基或丙基，R2代表辛基、十二烷基或十八烷基,n=0、1或2，Y代表乙酰舒泛钾、邻苯甲酰磺酰亚胺、水杨酸钠、甘氨酸钠、D-葡萄糖酸钠、柠檬酸钠或酒石酸钠；X代表乙酰磺酸根、邻苯甲酰磺酰亚胺酸根、水杨酸根、甘氨酸根、D-葡萄糖酸根、柠檬酸根或二羟基丁二酸根。反应方程式中，3-溴丙(乙)基磷酸二乙酯合成参考文献：(Z. G. Mu, W.M. Liu, S. X. Zhang, F. Zhou. Chemistry Letters 33 (2004) 524-525.)。
所述小分子功能化的表面活性剂的制备方法，其特征在于具体步骤如下：在惰性气氛保护下，将2-溴乙醇、3-溴丙-1-醇、4-溴丁-1-醇、3-溴丙酸、4-溴丁酸、5-溴戊酸、2-溴乙基磷酸二乙酯、3-溴丙基磷酸二乙酯或4-溴丁基磷酸二乙酯分别与三烷基胺混合，乙腈为溶剂，70-82 ℃加热回流15-20个小时后蒸出溶剂得到亮黄色油状粘稠液体，旋转蒸发重结晶后得到白色粉末Ⅰ；取白色粉末Ⅰ溶解于乙醇或乙腈中，加入乙酰舒泛钾、邻苯甲酰磺酰亚胺、水杨酸钠、甘氨酸钠、D-葡萄糖酸钠、柠檬酸钠或酒石酸钠在室温下进行离子交换，23-25小时后抽滤得到白色粉末即为水溶性表面活性剂的粗产品，为了纯化，用无水乙醇反复洗涤除去未完全反应的乙酰舒泛钾、邻苯甲酰磺酰亚胺、水杨酸钠、甘氨酸钠、D-葡萄糖酸钠、柠檬酸钠或酒石酸钠及离子交换产生的盐至乙醇相澄清，有机相用无水硫酸钠干燥过夜，最终旋干溶剂得到目标产物即为小分子功能化的表面活性剂。
所述2-溴乙醇、3-溴丙-1-醇、4-溴丁-1-醇、3-溴丙酸、4-溴丁酸、5-溴戊酸、2-溴乙基磷酸二乙酯、3-溴丙基磷酸二乙酯或4-溴丁基磷酸二乙酯与三烷基胺的摩尔比为1-2:1。
所述白色粉末Ⅰ与乙酰舒泛钾、邻苯甲酰磺酰亚胺、水杨酸钠、甘氨酸钠、D-葡萄糖酸钠、柠檬酸钠或酒石酸钠的摩尔比为1.6-1:1。
本发明所述小分子功能化的表面活性剂具有良好的水溶性，大大减小了水对铜片和铁片的腐蚀，可作为水溶润滑添加剂使用，具有良好的减摩抗磨性能，明显地提高了水的承载能力。
本发明所述功能化水溶性表面活性剂用核磁进行了结构表征。
采用的实验方法如下：
采用德国 optimol 油脂公司生产的SRV-IV微振动摩擦磨损试验机评价所合成的水溶性表面活性剂作为水润滑添加剂的摩擦磨损性能。摩擦副接触形式为球-盘点接触，选用载荷100 N，温度25℃，频率20 Hz，振幅1 mm，实验时间30min，上试球为直径10 mm GCr15(SAE52100)钢球，下试盘为52100轴承钢。实验结果表明：该表面活性剂作为水润滑添加剂具有低且平稳的摩擦系数和小的磨损体积，具有优良的减摩抗磨性能。
具体实施方式
为了更好的理解本发明，通过以下实施例进行说明。
实施例 1：
在250mL三口瓶中加入12.94克十八烷基二甲基叔胺和14.87克3-溴丙基磷酸二乙酯，并加入60mL乙腈做溶剂，在惰性气体保护下于75℃下反应20个小时。反应结束后旋除溶剂，得到24克亮黄色油状粘稠液体，记为C18NPBr，产率为86%。随后，在150mL圆底烧瓶中加入14克C18NPBr和5克乙酰舒泛钾，并加适量无水乙醇完全溶解，溶液在60 ℃下充分搅拌24个小时。抽滤得到白色粉末即为水溶性表面活性剂的粗产品，用无水乙醇反复洗涤除去未完全反应的乙酰舒泛钾及离子交换产生的盐至乙醇相澄清，旋转蒸发溶剂得到白色固体。将白色固体在真空烘箱中在60℃下干燥12小时，即得到14克表面活性剂NPAK粉末，产率为88%。1H NMR (400 MHz, CDCl3) δ: 5.34 (s,1 H), 4.02 (t, J = 7.2 Hz, 4H),3.65 (t, J =8.0Hz, 2H),3.37(t, J = 8.0Hz, 2H),3.30-3.19 (m, 6H), 1.94 (s, 3H), 1.84-1.78(m, 2H), 1.65(s, 2H), 1.41-1.02 (m, 38H), 0.79 (t, J = 6.0Hz, 3H). 13C NMR(100 MHz, CDCl3) δ: 169.55, 160.91, 102.25, 77.48, 77.16, 76.84, 65.92,64.28, 63.16, 63.01 , 62.06, 60.96, 57.86, 53.45, 51.13, 50.74, 31.86, 29.64,29.55, 29.50, 29.44, 29.38, 29.29, 29.17,22.67, 21.07, 19.88, 16.53, 14.05.31PNMR (162 MHz, CDCl3) δ: 29.23(s).
实施例 2：
在250mL三口瓶中加入12.94克十八烷基二甲基叔胺和14.87克3-溴丙基磷酸二乙酯并加入60mL乙腈做溶剂，在惰性气体保护下于75 ℃下反应20个小时。反应后旋除溶剂，得到24克亮黄色油状粘稠液体，记为C18NPBr，产率为86%。随后，在150mL圆底烧瓶中加入14克C18NPBr和5.45克D-葡萄糖酸钠，并加适量无水乙醇完全溶解，溶液在60 ℃下充分搅拌24个小时。抽滤得到白色粉末即为水溶性表面活性剂的粗产品，用无水乙醇反复洗涤除去未完全反应的D-葡萄糖酸钠及离子交换产生的盐至乙醇相澄清，旋转蒸发溶剂得到白色固体。将白色固体在真空烘箱中在60℃下干燥12小时，即得到15克NPGAS粉末，产率为89%。1H NMR(400 MHz, CDCl3) δ: 4.21-3.96 (m, 6H), 3.92-3.82(m, 1H), 3.53-3.42(m, 3H),3.37 (s, 6H), 2.02(t, J = 8.0Hz, 2H), 1.91-1.75(m, 2H), 1.75-1.61 (s, 2H),1.46-1.02(m, 45H), 0.83(t, J = 6.0Hz, 3H). 13C NMR (100 MHz, CDCl3) δ: 66.50,64.40, 63.25, 63.10, 62.20, 62.13, 61.17, 51.33, 51.23, 31.95, 29.73, 29.69,29.63, 29.56, 29.51,29.46,29.39, 29.27, 26.35, 23.02, 22.80, 22.71, 21.25,16.78, 16.74, 16.56, 16.50, 14.14. 31P NMR (162 MHz, CDCl3) δ: 29.15(s).
实施例 3：
在250mL三口瓶中加入15.7克辛烷基二甲基叔胺和20.0克4-溴丁酸并加入50mL乙腈做溶剂，在惰性气体保护下于75 ℃下反应20个小时。反应后旋除溶剂，得到26.9克亮黄色油状粘稠液体，记为C8NOBr，产率为87%。随后，在150mL圆底烧瓶中加入15.6克C8NOBr和12.0克D-葡萄糖酸钠，并加适量无水乙醇完全溶解，溶液在60 ℃下充分搅拌24个小时。抽滤得到白色粉末即为水溶性表面活性剂的粗产品，用无水乙醇反复洗涤除去未完全反应的D-葡萄糖酸钠及离子交换产生的盐至乙醇相澄清，旋转蒸发溶剂得到白色固体。将白色固体在真空烘箱中在60℃下干燥12小时，即得到18.2克NOGAS粉末，产率为86%。1H NMR (400 MHz,CDCl3) δ: 11.26(s, 1 H), 5.09(s, 1 H), 4.28 (t, J = 8.0Hz, 2H), 4.10-3.89(m,3 H), 3.72-3.51(m, 4H), 3.42-3.10(m, 11H), 2.3-1.9(m, 4H), 1.71(m, 2H), 1.61(t, J = 8.0Hz, 2H),1.26-1.20 (m, 6H), 0.81(t, J = 6.0Hz, 3H). 13C NMR (100MHz, CDCl3) δ: 168.42, 161.81, 74.92, 71.61, 70.42, 64.47, 63.72, 52.60,34.20, 31.24, 28.71, 26.41, 24.93, 22.72, 21.31, 14.10.
实施例 4：
在250mL三口瓶中加入21.34克十二烷基二甲基叔胺和15.14克3-溴丙-1-醇，并加入60mL乙腈做溶剂，在惰性气体保护下于75℃下反应20个小时。反应结束后旋除溶剂，得到29.6克亮黄色油状粘稠液体，记为C18NPBr，产率为84%。随后，在150mL圆底烧瓶中加入17.6克C12NOBr和10.1克乙酰舒泛钾，并加适量无水乙醇完全溶解，溶液在60 ℃下充分搅拌24个小时。抽滤得到白色粉末即为水溶性表面活性剂的粗产品，用无水乙醇反复洗涤除去未完全反应的乙酰舒泛钾及离子交换产生的盐至乙醇相澄清，旋转蒸发溶剂得到白色固体。将白色固体在真空烘箱中在60℃下干燥12小时，即得到19.1克表面活性剂NOAK粉末，产率为88%。1H NMR (400 MHz, CDCl3) δ: 6.78 (s,1 H), 4.18 (s,1 H), 3.43 (t, J = 8.0Hz,2H), 3.21 (s, 6 H),3.19 (t, J = 7.2 Hz, 4H),2.26 (s, 3H),1.96-1.70 (m, 4H),1.32-1.21(m, 18H), 0.82 (t, J = 6.0Hz, 3H). 13C NMR (100 MHz, CDCl3) δ:170.49, 96.8, 64.12, 61.20, 60.41, 57.6,31.92, 29.4, 29.1, 26.4, 26.12,25.04, 21.82, 14.08.
实施例 5：
为了进一步说明我们制备的表面活性剂在水基金属切削液体系的溶解性，我们做了简单的溶解性实验。从表1可以看出，该类水溶性离子液体在水-乙二醇和水-二乙二醇体系均表现出优异的溶解性能。
表1表面活性剂的溶解性
实施例 6：
根据表2，我们发现在水-二乙二醇体系中，表面活性剂NPAK和NPGAS的室温运动粘度与商业水溶性润滑添加剂Ops75e水溶性磷酸盐（记作OPS）和Hostagliss L4聚合蓖麻油酸酯（记作HL4）相似。通过铜片腐蚀试验(GB6144-85)可知，本发明的表面活性剂NPAK和NPGAS对水的腐蚀程度与商业水性添加剂相似，都可以大大减少水对金属的腐蚀。
表2不同润滑剂的运动粘度和腐蚀程度
实施例 7 ：
采用SRV-IV 微振动摩擦磨损试验机评价了所发明的表面活性剂NPAK和NPGAS作为水润滑添加剂的摩擦磨损性能。
表3展示了不同浓度的表面活性剂NPAK作为水基润滑添加剂对钢-钢的摩擦磨损实验结果，我们发现：与空白水-二乙二醇相比，添加NPAK的水-二乙二醇体系具有更低、更平稳的摩擦系数和较小的磨损体积，这说明NPAK作为水基润滑添加剂能极大的提高水的减摩抗磨性能。
表3不同浓度的表面活性剂NPAK作为水基润滑剂的平均摩擦系数和平均磨损体积（SRV：载荷 100 N，温度 25 ℃，频率 20 Hz，振幅 1 mm，实验时间 30 min，实验上试球为不锈钢球，下试样为52100轴承钢）
表4展示了不同浓度的表面活性剂NPGAS作为水基润滑添加剂对钢-钢的摩擦磨损实验结果，该数据表明：与空白水-二乙二醇相比，添加NPGAS的水-二乙二醇体系极大地提高了水的减摩抗磨性能。
表4不同浓度的NPGAS作为水基润滑剂的平均摩擦系数和平均磨损体积（SRV：载荷100 N，温度 25 ℃，频率 20 Hz，振幅 1 mm，实验时间 30 min，实验上试球为不锈钢球，下试样为52100轴承钢）
表5展示了不同水溶性润滑剂对钢-钢摩擦副的摩擦磨损实验结果，该数据表明与商业水溶性润滑添加剂HL4和OPS相比，NPAK和NPGAS作为水溶性润滑添加剂具有优异的润滑性能，能明显地改善水的减摩抗磨性能。
表5 不同水溶性润滑剂的平均摩擦系数和平均磨损体积（SRV：载荷 100 N，温度25 ℃，频率 20 Hz，振幅 1 mm，实验时间 30 min，实验上试球为不锈钢球，下试样为52100轴承钢）
表6展示了不同水溶性润滑剂变频的SRV实验结果，该数据表明：在整个变频实验过程中，空白的水-二乙二醇和商业水溶性润滑添加剂HL4的摩擦系数都非常大且不稳定，虽然商业水溶性润滑添加剂OPS的摩擦系数比较稳定，但与所发明的表面活性剂NPAK和NPGAS相比，摩擦系数还是比较大。这说明我们所发明的表面活性剂NPAK和NPGAS作为水溶性润滑添加剂具有很好地耐磨性能。
表6不同水溶性润滑剂的变频平均摩擦系数（SRV：载荷100N，振幅1mm，温度150℃，频率10Hz-35 Hz，每隔5分钟提高5 Hz；实验上试球为直径为10mm钢球，下试样为钢块）
。

Claims (5)

1.小分子功能化的表面活性剂，其特征在于该表面活性剂为水溶性功能化的季铵离子液体，其阳离子为不同烷基链长季铵阳离子，阴离子为乙酰磺酸根、邻苯甲酰磺酰亚胺酸根、水杨酸根、甘氨酸根、D-葡萄糖酸根、柠檬酸根、二羟基丁二酸根；所述阳离子和阴离子的结构式如下：
，
其中R1代表甲基、乙基或丙基，R2代表辛基、十二烷基或十八烷基, n=0、1或2。
2.如权利要求1所述小分子功能化的表面活性剂的制备方法，其特征在于具体步骤如下：
在惰性气氛保护下，将2-溴乙醇、3-溴丙-1-醇、4-溴丁-1-醇、3-溴丙酸、4-溴丁酸、5-溴戊酸、2-溴乙基磷酸二乙酯、3-溴丙基磷酸二乙酯或4-溴丁基磷酸二乙酯分别与三烷基胺混合，乙腈为溶剂，70-82 ℃加热回流15-20个小时后蒸出溶剂得到亮黄色油状粘稠液体，旋转蒸发重结晶后得到白色粉末Ⅰ；取白色粉末Ⅰ溶解于乙醇或乙腈中，加入乙酰舒泛钾、邻苯甲酰磺酰亚胺、水杨酸钠、甘氨酸钠、D-葡萄糖酸钠、柠檬酸钠或酒石酸钠在室温下进行离子交换，23-25小时后抽滤得到白色粉末即为水溶性表面活性剂的粗产品，为了纯化，用无水乙醇反复洗涤除去未完全反应的乙酰舒泛钾、邻苯甲酰磺酰亚胺、水杨酸钠、甘氨酸钠、D-葡萄糖酸钠、柠檬酸钠或酒石酸钠及离子交换产生的盐至乙醇相澄清，有机相用无水硫酸钠干燥过夜，最终旋干溶剂得到目标产物即为小分子功能化的表面活性剂。
3.如权利要求2所述的制备方法，其特征在于所述2-溴乙醇、3-溴丙-1-醇、4-溴丁-1-醇、3-溴丙酸、4-溴丁酸、5-溴戊酸、2-溴乙基磷酸二乙酯、3-溴丙基磷酸二乙酯或4-溴丁基磷酸二乙酯与三烷基胺的摩尔比为1-2:1。
4.如权利要求2所述的制备方法，其特征在于所述白色粉末Ⅰ与乙酰舒泛钾、邻苯甲酰磺酰亚胺、水杨酸钠、甘氨酸钠、D-葡萄糖酸钠、柠檬酸钠或酒石酸钠的摩尔比为1.6-1:1。
5.如权利要求1所述小分子功能化的表面活性剂作为水溶润滑添加剂的应用。
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CN111715137A (zh) * 2020-06-15 2020-09-29 沈阳新意精细助剂有限公司 一种复配型非离子表面活性剂

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