CN106244310A - 一种防锈双纳米乳液及其制备方法 - Google Patents
一种防锈双纳米乳液及其制备方法 Download PDFInfo
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- CN106244310A CN106244310A CN201610619142.5A CN201610619142A CN106244310A CN 106244310 A CN106244310 A CN 106244310A CN 201610619142 A CN201610619142 A CN 201610619142A CN 106244310 A CN106244310 A CN 106244310A
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- antirust
- emulsion
- agent
- calcium carbonate
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 54
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 239000008187 granular material Substances 0.000 claims abstract description 19
- 238000004945 emulsification Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 14
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- NWGKJDSIEKMTRX-MDZDMXLPSA-N Sorbitan oleate Chemical compound CCCCCCCC\C=C\CCCCCCCC(=O)OCC(O)C1OCC(O)C1O NWGKJDSIEKMTRX-MDZDMXLPSA-N 0.000 claims abstract description 10
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- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims abstract 5
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- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical group OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 3
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- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 3
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- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims 2
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- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 238000001016 Ostwald ripening Methods 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
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- UDHMTPILEWBIQI-UHFFFAOYSA-N butyl naphthalene-1-sulfonate;sodium Chemical compound [Na].C1=CC=C2C(S(=O)(=O)OCCCC)=CC=CC2=C1 UDHMTPILEWBIQI-UHFFFAOYSA-N 0.000 description 1
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- 239000000176 sodium gluconate Substances 0.000 description 1
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- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
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- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 1
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
- C10M173/00—Lubricating compositions containing more than 10% water
-
- 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
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/08—Inorganic acids or salts thereof
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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
- 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
-
- 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
- C10M2207/126—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 monocarboxylic
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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
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
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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
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2215/042—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Alkoxylated derivatives thereof
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/08—Amides
- C10M2215/082—Amides containing hydroxyl groups; Alkoxylated derivatives
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/221—Six-membered rings containing nitrogen and carbon only
- C10M2215/222—Triazines
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Abstract
本发明提供一种防锈双纳米乳液及其制备方法，包括如下重量份的成分：重烷基苯磺酸钠：10~15份、磷酸酯：1~5份、矿物油：1~5份、低泡渗透剂：5~10份、防团聚剂：1~5份、纳米碳酸钙：5~10份、醇胺：1~5份、单分子羧酸：1~5份、防锈剂：15~20份、司盘80：1~5份、植物油酸：1~5份、杀菌剂：3~5份、树脂：1~5份、水余量。所述双纳米乳液采用固体纳米碳酸钙颗粒低能乳化法改性纳米乳化液，得到了一种相对简单、性能优良的防锈双纳米乳液，具有自消泡性能，有机碱用量少，变滑动摩擦为滚动摩擦，润滑效率成倍提高。
Description
技术领域
本发明属于金属加工防锈技术领域，用于金属加工制件在加工、储存、运输过程中的防锈，具体地，涉及一种防锈双纳米乳液及其制备方法。
背景技术
在金属加工过程中，工件要与环境介质及切削液组分分解或氧化变质而产生的油泥等腐蚀性介质接触而腐蚀，与切削液接触的机床部件表面也会因此而腐蚀。
此外，在工件加工后或工序之间流转过程中暂时存放时，也要求切削液有一定的防锈能力，防止环境介质及残存切削液中的油泥等腐蚀性物质对金属产生侵蚀。特别是在我国南方地区潮湿多雨季节，更应注意工序间防锈措施。
按照不同的介质，切削液可以分为油基切削液和水基切削液。
使用时不需要用水进行稀释的切削液称作油基切削液，油基切削液一般润滑性良好，但冷却性能相较于水基切削液稍差，在高速切削加工过程中，由于发热量大，导致切削油产生烟雾、起火等现象，污染加工环境。用动物油作为原料的油基切削液稳定性差且价格昂贵。现在则多以矿物油为原料辅以各种添加剂制成切削液。
水基切削液在使用前要用大量的水，按一定比例对原液进行稀释。由于其使用过程中不会产生易燃的危险，且价格相对便宜并同样满足加工要求，在国内逐渐获得广泛的应用。尤其是随着全球石油资源紧缺，水基切削液的研究有了更为广阔的应用前景。
纳米乳液在金属磨削、切削、钻孔等过程中能起到润滑、冷却、除锈和清洗等作用，大大降低了乳化剂的用量，节约成本，对人体毒害作用小，是环境友好型加工液。由于以上的诸多优越性能，近年来其在金属加工方面的应用受到广泛关注。
纳米乳液其分散相液滴粒径在50～200nm之间，粒径介于微乳液(5～100nm)与普通乳状液(1～10μm)之间，集微乳液与普通乳液的优点于一身，具体表现在以下几个方面：与普通乳状液相比，液滴粒径小，且分布均匀，粘度低，具有动力学稳定性，长期贮存无明显的絮凝和分层；与微乳液相比，乳化剂用量显著降低，一般不需要助乳化剂，在稀释和温度变化这两方面则表现出较好的稳定性。
纳米乳液是动力学稳定体系，其性质和稳定性主要依赖于制备方法，原料的加序和乳化过程中产生的相态变化；然而纳米乳液在热力学上是不稳定的，且液滴粒径越小，所具有的界面能越高，越有利于奥氏熟化的发生，小液滴中的液体越容易转移到大液滴中，最终导致乳液的粗化，因而，稳定性问题是限制纳米乳液广泛使用的最重要因素之一。
对于防锈切削液，目前国内主要存在如下文献：
专利公开号：CN105623823A，公开了一种乳液型环保切削液，由以下重量份数的原料组成：十二烷基磺酸钠3-5份、蓖麻油1-3份、癸二酸0.5-1份、月桂醇硫酸钠2-4份、油酸丁酯1-3份、三乙醇胺1-3份、石油磺酸钠0.4-0.8份、硼酸钾1-3份、硼砂1-3份、硅酸钠0.5-1份、钨酸钠0.05-0.1份、葡萄糖酸钠8-15份、聚乙烯吡咯烷酮0.01-0.04份、丁基萘磺酸钠0.5-1份、羟基硬脂酸2-5份、去离子水8-15份。本发明安全环保，冷却性能好，具有很好的润滑性和防锈效果。然而，该专利提供的切削液为普通乳液，动力学稳定性差，长期储存容易出现分层、絮凝，影响使用效果。
发明内容
为解决上述存在的问题，本发明的目的在于提供一种防锈双纳米乳液及其制备方法，所述双纳米乳液采用固体纳米碳酸钙颗粒低能乳化法改性纳米乳化液，得到了一种相对简单、性能优良的防锈双纳米乳液，具有自消泡性能，有机碱用量少，变滑动摩擦为滚动摩擦，润滑效率成倍提高。
为达到上述目的，本发明的技术方案是：
一种防锈双纳米乳液，其特征在于，包括如下重量份的成分：重烷基苯磺酸钠：10～15份、磷酸酯：1～5份、矿物油：1～5份、低泡渗透剂：5～10份、防团聚剂：1～5份、纳米碳酸钙：5～10份、醇胺：1～5份、单分子羧酸：1～5份、防锈剂：15～20份、司盘80：1～5份、植物油酸：1～5份、杀菌剂：3～5份、树脂：1～5份、水余量。
进一步，所述低泡渗透剂为脂肪醇聚氧烷基醚或椰子油酸二乙醇酰胺。
另，所述防团聚剂包括1～5份的水处理剂和1～5份的硅烷偶合剂，所述水处理剂为羟基乙叉二膦酸四钠或EDTA二钠。
另有，所述纳米碳酸钙为颗粒状，粒径10～100mm，通过重烷基苯磺酸钠和低泡渗透剂的组成配比调节所述纳米碳酸钙颗粒粒径大小或通过调节醇胺添加量调节pH值，进而调节所述固体纳米颗粒粒径大小；纳米碳酸钙颗粒浓度为3～5wt％。
再，所述纳米碳酸钙颗粒浓度为3.5～4wt％。
其中，在较低的颗粒浓度下，纳米碳酸钙颗粒浓度每增加10倍，液滴大小降低为原来的1/8左右。假设所有被吸附的纳米碳酸钙颗粒都形成与液滴相切的六边形形状，那么根据液滴直径就可以估算出被吸附纳米碳酸钙颗粒数(在界面上)与总纳米碳酸钙颗粒数(界面上的+连续相中的)比值R。计算表明：在颗粒质量分数低于3.0％时，比值均在1左右，表明大部份颗粒都吸附于油/水界面稳定乳滴，并且随着纳米碳酸钙颗粒浓度的提高，乳滴粒径减小；当纳米碳酸钙颗粒质量分数提高到5.6％时，R降到0.5，即吸附的颗粒量仍接近于3％，并未随颗粒浓度的提高而显著增大。这表明，当颗粒浓度大于3％时，继续加入的粒子不再吸附于界面稳定乳滴，而是进入连续相中，乳液粒径也基本保持不变。进入连续相的固体颗粒浓度较高时，可以促进连续相胶凝，大大提高乳液的稳定性，从而阻止油滴分层或者水滴沉降，但这不是本行业所能接受的，因此，本发明将纳米碳酸钙颗粒浓度限定为3～5wt％，优选3.5～4wt％的颗粒浓度。
再有，所述矿物油为矿物油N32、煤油或白油。
且，所述醇胺为三乙醇胺或二乙醇胺；所述单分子羧酸为异壬酸或辛酸。
另，所述杀菌剂为三嗪类或吗啉衍生物类杀菌剂；所述防锈剂为硼酸酯或磺酸钙盐；所述树脂为萜烯树脂，熔点为80～100℃。
同时，本发明还提供一种防锈双纳米乳液制备工艺，所述工艺包括如下步骤：
1)制备纳米乳液浓缩液
按配比取重烷基苯磺酸钠、磷酸酯、醇胺、单分子羧酸、防锈剂、低泡渗透剂、杀菌剂、树脂和水，采用自乳化法，在50～60℃下，搅拌0.5～1.5h，冷却，制备得纳米乳液浓缩液；
2)制备双纳米乳液浓缩液
取司盘80和植物油酸混合形成的第一亲油表面活性剂在50～60℃下对所述纳米碳酸钙进行搅拌修饰，50～70min后，取司盘80和硅烷偶合剂混合形成的第二亲油表面活性剂对所述纳米碳酸钙进行搅拌修饰，将修饰后的纳米碳酸钙颗粒加入步骤1)所得纳米乳液浓缩液中，采用低能乳化法，在50～60℃下搅拌，冷却至35℃以下，制得双纳米乳液浓缩液；
3)制备40～70％双纳米母液
采用反向乳化法，向步骤2)所得双纳米乳液浓缩液中加矿物油搅匀，加水，对所述双纳米乳液浓缩液进行稀释，制得40～70％双纳米母液；
4)制备双纳米乳液
将所述第一亲油表面活性剂加入到步骤3)所得40～70％双纳米母液，采用自乳化法，在常温下，搅拌0.5～1.5h，制得工作液，即为所述双纳米乳液。
本发明的有益效果在于：
现有制备方法中，影响纳米乳液不稳定的主要因素是奥氏熟化和液滴聚合，引入固体纳米颗粒虽然对纳米乳液的稳定性提高有帮助，但同时也增加了固体粒子聚合变大的风险，固体颗粒粒径越小，越有利于稳定，但太小不利于亲油表面活性剂修饰，反而因为固体颗粒不溶于水而沉淀，为此，本发明对双纳米乳液对其进行了如下改进：
1)发出纳米颗粒粒径大小调节技术，固体纳米粒粒径在10～100mm任意调整；
2)改变双纳米颗粒界面膜带电电荷量增加静电斥力，防止发生团聚；
应用库仑定律，在距离达到一定时，分子间的分子轨道发生错位重叠，电子之间的相互作用力超出分子间所允许的临界力，造成分子间能量分布不均，因而形成静电斥力现象。调节温度和第一、第二亲油表面活性剂活性剂用量，改变颗粒界面膜带电电荷量达到效果。
3)对于不同的稀释比(40～70％)，使用不同浓度的第一、第二亲友表面活性剂修饰固体纳米颗粒表面，确保贮存过程中，表面活性剂不被水溶解而发生沉淀；
4)由双纳米乳液浓缩液→40～70％浓度双纳米母液是反相乳化法，浓缩液本身是油包水型，当向油相中逐步滴加水时，先形成W/O微乳液。随着水含量的增加，表面活性剂的水合作用逐渐增强，表面活性剂自发改变其曲率，由原来的负值增加到零。在反相乳化组成点时，表面活性剂的亲水亲油性能达到平衡，同样也形成双连续相和层状液晶相结构。继续滴加水，液滴曲率由零到正值，形成O/W纳米乳液。调整不同的油水比，防止纳米颗粒絮凝漂浮，使之密度适配。
采用固体纳米碳酸钙颗粒低能乳化法改性纳米乳化液，得到了一种相对简单、性能优良的防锈双纳米乳液。双纳米乳液，因纳米乳液引入固体颗粒，表面活性剂用量少，具有自消泡性能。由于碳酸钙含有碱性，有机碱的使用量减少，对有色金属、钴析出有较好帮助。纳米颗粒本身是一种润滑材料变滑动摩擦为滚动摩擦，润滑效率成倍提高。现达到的水平为1.5％使用浓度，Pb值80Kg以上。双纳米乳液干燥后，固体纳米粒子成为吸附中心。与金属间的吸附更牢靠，能阻止水气、盐份对金属的腐蚀。将纳米粒径调节技术应用于油相，纳米粒子的进入促进吸附中心的形成，使油品与金属结合力好，且其为惰性吸附，长期使用也不产生腐蚀点。细小的纳米粒子充填于防锈添加剂分子间隙间，能阻止盐份透过，使油性防锈剂获得理想的抗盐雾性能。目前水平，30％浓度，湿热性能达到336小时，抗盐雾性能也能达到24小时。
具体实施方式
以下实施例用于说明本发明，但不能用来限制本发明的范围。实施例中采用的实施条件可以根据厂家的条件作进一步调整，未说明的实施条件通常为常规实验条件。
本发明所提供的一种防锈双纳米乳液，其特征在于，包括如下重量份的成分：重烷基苯磺酸钠：10～15份、磷酸酯：1～5份、矿物油：1～5份、低泡渗透剂：5～10份、防团聚剂：1～5份、纳米碳酸钙：5～10份、醇胺：1～5份、单分子羧酸：1～5份、防锈剂：15～20份、司盘80：1～5份、植物油酸：1～5份、杀菌剂：3～5份、树脂：1～5份、水余量。
进一步，所述低泡渗透剂为脂肪醇聚氧烷基醚或椰子油酸二乙醇酰胺。
另，所述防团聚剂包括1～5份的水处理剂和1～5份的硅烷偶合剂，所述水处理剂为羟基乙叉二膦酸四钠或EDTA二钠。
另有，所述纳米碳酸钙为颗粒状，粒径10～100mm，通过重烷基苯磺酸钠和低泡渗透剂的组成配比调节所述纳米碳酸钙颗粒粒径大小或通过调节醇胺添加量调节pH值，进而调节所述固体纳米颗粒粒径大小；纳米碳酸钙颗粒浓度为3～5wt％。
再，所述纳米碳酸钙颗粒浓度为3.5～4wt％。
其中，在较低的颗粒浓度下，纳米碳酸钙颗粒浓度每增加10倍，液滴大小降低为原来的1/8左右。假设所有被吸附的纳米碳酸钙颗粒都形成与液滴相切的六边形形状，那么根据液滴直径就可以估算出被吸附纳米碳酸钙颗粒数(在界面上)与总纳米碳酸钙颗粒数(界面上的+连续相中的)比值R。计算表明：在颗粒质量分数低于3.0％时，比值均在1左右，表明大部份颗粒都吸附于油/水界面稳定乳滴，并且随着纳米碳酸钙颗粒浓度的提高，乳滴粒径减小；当纳米碳酸钙颗粒质量分数提高到5.6％时，R降到0.5，即吸附的颗粒量仍接近于3％，并未随颗粒浓度的提高而显著增大。这表明，当颗粒浓度大于3％时，继续加入的粒子不再吸附于界面稳定乳滴，而是进入连续相中，乳液粒径也基本保持不变。进入连续相的固体颗粒浓度较高时，可以促进连续相胶凝，大大提高乳液的稳定性，从而阻止油滴分层或者水滴沉降，但这不是本行业所能接受的，因此，本发明将纳米碳酸钙颗粒浓度限定为3～5wt％，优选3.5～4wt％的颗粒浓度。
再有，所述矿物油为矿物油N32、煤油或白油。
且，所述醇胺为三乙醇胺或二乙醇胺；所述单分子羧酸为异壬酸或辛酸。
另，所述杀菌剂为三嗪类或吗啉衍生物类杀菌剂；所述防锈剂为硼酸酯或磺酸钙盐；所述树脂为萜烯树脂，熔点为80～100℃。
同时，本发明还提供一种防锈双纳米乳液制备工艺，所述工艺包括如下步骤：
1)制备纳米乳液浓缩液
按配比取重烷基苯磺酸钠、磷酸酯、醇胺、单分子羧酸、防锈剂、低泡渗透剂、杀菌剂、树脂和水，采用自乳化法，在50～60℃下，搅拌0.5～1.5h，冷却，制备得纳米乳液浓缩液；
2)制备双纳米乳液浓缩液
取司盘80和植物油酸混合形成的第一亲油表面活性剂在50～60℃下对所述纳米碳酸钙进行搅拌修饰，50～70min后，取司盘80和硅烷偶合剂混合形成的第二亲油表面活性剂对所述纳米碳酸钙进行搅拌修饰，将修饰后的纳米碳酸钙颗粒加入步骤1)所得纳米乳液浓缩液中，采用低能乳化法，在50～60℃下搅拌，冷却至35℃以下，制得双纳米乳液浓缩液；
3)制备40～70％双纳米母液
采用反向乳化法，向步骤2)所得双纳米乳液浓缩液中加矿物油搅匀，加水，对所述双纳米乳液浓缩液进行稀释，制得40～70％双纳米母液；
4)制备双纳米乳液
将所述第一亲油表面活性剂加入到步骤3)所得40～70％双纳米母液，采用自乳化法，在50～60℃下，搅拌0.5～1.5h，冷却，制得工作液，即为所述双纳米乳液。
其中，表1本发明各实施例所提供的一种防锈双纳米乳液成分列表，余量为水。
表1(单位：重量份)
| 实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | |
| 重烷基苯磺酸钠 | 13 | 12 | 11 | 15 | 10 |
| 磷酸酯 | 3 | 2 | 4 | 1 | 5 |
| 矿物油 | 2 | 5 | 4 | 3 | 1 |
| 低泡渗透剂 | 7 | 6 | 8 | 5 | 10 |
| 防团聚剂 | 4 | 2 | 3 | 1 | 5 |
| 纳米碳酸钙 | 8 | 7 | 5 | 6 | 10 |
| 醇胺 | 3 | 1 | 2 | 5 | 4 |
| 单分子羧酸 | 3 | 5 | 2 | 1 | 4 |
| 防锈剂 | 17 | 15 | 20 | 18 | 16 |
| 司盘80 | 4 | 3 | 5 | 2 | 1 |
| 植物油酸 | 3 | 4 | 2 | 5 | 1 |
| 杀菌剂 | 3 | 4 | 3.5 | 5 | 4.5 |
| 树脂 | 3 | 4 | 2 | 5 | 1 |
本发明所提供的一种防锈双纳米乳液，采用固体纳米碳酸钙颗粒低能乳化法改性纳米乳化液，得到了一种相对简单、性能优良的防锈双纳米乳液。双纳米乳液，因纳米乳液引入固体颗粒，表面活性剂用量少，具有自消泡性能。由于碳酸钙含有碱性，有机碱的使用量减少，对有色金属、钴析出有较好帮助。纳米颗粒本身是一种润滑材料变滑动摩擦为滚动摩擦，润滑效率成倍提高。现达到的水平为1.5％使用浓度，Pb值80Kg以上。双纳米乳液干燥后，固体纳米粒子成为吸附中心。与金属间的吸附更牢靠，能阻止水气、盐份对金属的腐蚀。将纳米粒径调节技术应用于油相，纳米粒子的进入促进吸附中心的形成，使油品与金属结合力好，且其为惰性吸附，长期使用也不产生腐蚀点。细小的纳米粒子充填于防锈添加剂分子间隙间，能阻止盐份透过，使油性防锈剂获得理想的抗盐雾性能。目前水平，30％浓度，湿热性能达到336小时，抗盐雾性能也能达到24小时。
所制得双纳米乳液浓缩液颜色为深红色，放置稳定；5％工作液为乳白色，放置稳定，无沉淀，无析出。
需要说明的是，以上实施例仅用以说明本发明的技术方案而非限制。尽管参照较佳实施例对本发明进行了详细说明，本领域的普通技术人员应当理解，可以对发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的范围，其均应涵盖在本发明的权利要求范围中。
Claims (9)
1.一种防锈双纳米乳液，其特征在于，包括如下重量份的成分：重烷基苯磺酸钠：10~15份、磷酸酯：1~5份、矿物油：1~5份、低泡渗透剂：5~10份、防团聚剂：1~5份、纳米碳酸钙：5~10份、醇胺：1~5份、单分子羧酸：1~5份、防锈剂：15~20份、司盘80：1~5份、植物油酸：1~5份、杀菌剂：3~5份、树脂：1~5份、水余量。
2.根据权利要求1所述的一种防锈双纳米乳液，其特征在于，所述低泡渗透剂为脂肪醇聚氧烷基醚或椰子油酸二乙醇酰胺。
3.根据权利要求1所述的一种防锈双纳米乳液，其特征在于，所述防团聚剂包括1~5份的水处理剂和1~5份的硅烷偶合剂，所述水处理剂为羟基乙叉二膦酸四钠或EDTA二钠。
4.根据权利要求1所述的一种防锈双纳米乳液，其特征在于，所述纳米碳酸钙为颗粒状，粒径10~100mm，通过重烷基苯磺酸钠和低泡渗透剂的组成配比调节所述纳米碳酸钙颗粒粒径大小或通过调节醇胺添加量调节pH值，进而调节所述固体纳米颗粒粒径大小；纳米碳酸钙颗粒浓度为3~5wt%。
5.根据权利要求4所述的一种防锈双纳米乳液，其特征在于，所述纳米碳酸钙颗粒浓度为3.5~4wt%。
6.根据权利要求1所述的一种防锈双纳米乳液，其特征在于，所述矿物油为矿物油N32、煤油或白油。
7.根据权利要求1所述的一种防锈双纳米乳液，其特征在于，所述醇胺为三乙醇胺或二乙醇胺；所述单分子羧酸为异壬酸或辛酸。
8.根据权利要求1所述的一种防锈双纳米乳液，其特征在于，所述杀菌剂为三嗪类或吗啉衍生物类杀菌剂；所述防锈剂为硼酸酯或磺酸钙盐；所述树脂为萜烯树脂，熔点为80~100℃。
9.一种如权利要求1~8中任一项所述的防锈双纳米乳液制备工艺，其特征在于，所述工艺包括如下步骤：
1)制备纳米乳液浓缩液
按配比取重烷基苯磺酸钠、磷酸酯、醇胺、单分子羧酸、防锈剂、低泡渗透剂、杀菌剂、树脂和水，采用自乳化法，在50~60℃下，搅拌0.5~1.5h，冷却，制备得纳米乳液浓缩液；
2)制备双纳米乳液浓缩液
取司盘80和植物油酸混合形成的第一亲油表面活性剂在50~60℃下对所述纳米碳酸钙进行搅拌修饰，50~70min后，取司盘80和硅烷偶合剂混合形成的第二亲油表面活性剂对所述纳米碳酸钙进行搅拌修饰，将修饰后的纳米碳酸钙颗粒加入步骤1)所得纳米乳液浓缩液中，采用低能乳化法，在50~60℃下搅拌，冷却至35℃以下，制得双纳米乳液浓缩液；
3)制备40~70%双纳米母液
采用反向乳化法，向步骤2)所得双纳米乳液浓缩液中加矿物油搅匀，加水，对所述双纳米乳液浓缩液进行稀释，制得40~70%双纳米母液；
4)制备双纳米乳液
将所述第一亲油表面活性剂加入到步骤3)所得40~70%双纳米母液，采用自乳化法，在常温下，搅拌0.5~1.5h，制得工作液，即为所述双纳米乳液。
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