CN113549486A - 一种组合物的应用及其制备方法 - Google Patents
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Abstract
本发明属于金属加工液技术领域,特别涉及一种组合物在制备用于金属加工液的缓释型pH调节剂的应用,所述组合物包括至少一种化合物A和至少一种化合物B;所述组合物的制备方法,所述组合物由干冰或二氧化碳气体通入乙醇胺和/或二乙醇胺溶液制备得到,所述组合物包括至少一种氨基甲酸盐离子,和至少一种乙醇胺盐离子。本发明所提供的组合物可有效解决传统胺类化合物作为金属加工液pH调节剂在加工过程中被快速消耗的问题,以及大剂量添加胺类化合物导致金属加工液pH过高的问题。
Description
技术领域
本发明属于金属加工液技术领域,特别涉及一种组合物在制备用于金属加工液的缓释型pH调节剂的应用及其制备方法。
背景技术
金属加工液是金属加工过程中起到润滑、降温、防腐蚀、抗菌作用的一类必备工业化学品。金属加工液的pH值对于金属加工液的性能起到至关重要的作用。这些作用包括:中和加工液中的脂肪酸类防锈剂,中和加工液中的磷酸酯型防腐蚀剂,抑制细菌生长,延长加工液使用寿命等。
在现有技术中,金属加工液的配制都会选用乙醇胺、二乙醇胺、三乙醇胺中的一种或几种胺进行混合,添加至加工液体系中,从而获得理想的pH。这种方案可以立竿见影的将加工液体系的pH调整至应用场景所需状态。
但是这种方案的缺点也是显而易见的,即随着加工液在金属加工过程中的不断使用,整个体系的pH会因为胺的消耗(蒸发,与空气中的氧气和二氧化碳反应,被细菌代谢等)而快速下降。当pH下降至8以下时,加工液就会出现油水分离、细菌滋生等问题,严重时导致加工液彻底失效。相对应的,为了保证胺不会被过快的消耗掉,就需要在加工液中加入更大剂量的胺,而这将导致加工液体系pH过高,从而导致加工液对金属腐蚀性变强,灼烧工人皮肤等新的问题。
另外,错误的加工液维护方法(如错误的加入过量的酸)也会导致pH的陡然下降。这个过程一旦发生,就会导致加工液油水分离,难以挽回。
发明内容
为了克服上述现有技术的缺陷,本发明所要解决的技术问题是:解决传统胺类化合物作为金属加工液pH调节剂在加工过程中被快速消耗的问题。
为了解决上述技术问题,本发明提出的技术方案为:一种组合物在制备用于金属加工液的缓释型pH调节剂的应用,其特征在于,所述组合物包括至少一种化合物A和至少一种化合物B;
所述化合物A由下式(Ⅰ)表示,所述化合物B由下式(Ⅱ)表示;
其中,所述R1选自羧基,所述R2选自氢或羧基。
进一步提出一种组合物的制备方法,所述组合物由干冰或二氧化碳气体通入乙醇胺和/或二乙醇胺溶液制备得到,所述组合物包括至少一种氨基甲酸盐离子,和至少一种乙醇胺盐离子。
本发明的有益效果在于:该组合物可在高温作业过程中,通过释放二氧化碳和胺,使得金属加工液的pH适当上升,同时通过释放胺而抵消因为蒸发、变质引起的胺类物质的消耗;并且在非作业过程中,该化合物能够保持稳定,不会对金属加工液的pH产生明显的影响;即通过在金属加工液中加入该组合物可对金属加工液产生动态而精细的pH再调节。并且,该组合物不仅对高温敏感,同时也可在pH降低过程中通过释放二氧化碳和胺,以抵消金属加工液pH降低幅度,起到pH缓冲的作用,同时也进一步提升金属加工液的使用寿命。
具体实施方式
为详细说明本发明的技术内容、所实现目的及效果,以下结合实施方式予以说明。
一种组合物在制备用于金属加工液的缓释型pH调节剂的应用,所述组合物包括至少一种化合物A和至少一种化合物B;
所述化合物A由下式(Ⅰ)表示,所述化合物B由下式(Ⅱ)表示;
其中,所述R1选自羧基,所述R2选自氢或羧基。
所述组合物可适用于半合成或全合成的金属加工液的调配,优选的,由所述组合物所构成的缓释型pH调节剂占金属加工液的总配方质量的3%~8%。
虽然上述组合物已经可以满足对金属加工液的pH调节和缓冲的作用,但是在常规的金属加工液中引入了大量的无机盐,而大量的无机盐会降低金属加工液的体系的稳定性,如导致金属加工液油水分离、产生固体沉淀,以及被引入的大量的磷元素存在污染环境的问题。因此,可选的,所述组合物还包括磷酸二氢钠/磷酸氢二钠,或碳酸钠/碳酸氢钠,即通过进一步添加磷酸二氢钠/磷酸氢二钠缓冲体系或碳酸钠/碳酸氢钠缓冲体系,以进一步提高金属加工液的稳定性。
一种组合物的制备方法,所述组合物由干冰或二氧化碳气体通入乙醇胺和/或二乙醇胺溶液制备得到,所述组合物包括至少一种氨基甲酸盐离子,和至少一种乙醇胺盐离子。
其中,所述氨基钾酸盐离子和乙醇胺盐离子均为基于两性离子反应和去质子化反应的产物。
优选的,所述干冰的添加量为30~1000g。
需要说明的是,所述乙醇胺和/或二乙醇胺溶液中水的添加量是灵活的,可以不加,或无限添加,具体的添加量应根据实际的需求进行调整。具体而言,当选用干冰反应时,由于干冰密度较小,在于乙醇胺或二乙醇胺反应时倾向于悬浮在乙醇胺或二乙醇胺液体表面,反应效率相对较低,因此在实际的加工过程中水的添加量为0~8000mL,而当选用二氧化碳气体通入时,二氧化碳气体可与乙醇胺或二乙醇胺高效反应,因此在实际的加工过程中水的添加量可以不加,也可以无限添加。
进一步的,所述组合物由干冰或二氧化碳气体通入乙醇胺或二乙醇胺的水溶液中,至所述水溶液终点pH为8.0~9.6时制备得到。
进一步的,所述组合物由干冰或二氧化碳气体通入乙醇胺和二乙醇胺的混合水溶液中,至所述混合水溶液终点pH为8.0~9.6时制备得到,所述乙醇胺和二乙醇胺的质量比为1:20至20:1。
需要说明的是,水溶液或混合水溶液的终点pH是灵活的。具体而言,当终点pH在8.0~9.6时,组合物在溶液中的浓度已达到使用标准。
进一步的,所述制备的温度为40~60℃。
一种金属加工液,包括缓释型pH调节剂,所述缓释型pH调节剂由干冰或二氧化碳气体通入乙醇胺和/或二乙醇胺溶液制备得到,所述缓释型pH调节剂包括至少一种氨基甲酸盐离子和至少一种乙醇胺盐离子;
所述金属加工液由如下按质量百分比计的组分构成:
5%缓释型pH调节剂、10%三乙醇胺、6%乙醇胺、3.5%新癸酸、2.5%癸二酸、0.6%苯并三氮唑、7.5%聚醚、0.6%阳离子和64%水。
一种金属加工液,包括缓释型pH调节剂,所述缓释型pH调节剂由干冰或二氧化碳气体通入乙醇胺和/或二乙醇胺溶液制备得到,所述缓释型pH调节剂包括至少一种氨基甲酸盐离子和至少一种乙醇胺盐离子;
所述金属加工液由如下按质量百分比计的组分构成:
5%缓释型pH调节剂、5%三乙醇胺、2%乙醇胺、35%棕榈酸异辛酯、3%蓖麻油酸、2%妥尔油酸、1.5%十二烷二酸、1.5%己内酰胺、1%苯氧乙醇、0.8%苯并异噻唑啉酮、7%蓖麻油、7%油酸甘油酯、8%聚醚、2%消泡剂、19.7%水。
实施例1
一种组合物的制备方法,在一个1000mL的圆底烧瓶中,加入850g乙醇胺和150g水,搅拌至乙醇胺完全溶解;向乙醇胺水溶液中缓慢加入630g干冰;期间,保持反应温度在60℃以下,40℃以上,反应体系排气通畅。干冰添加完毕后,出料即为产品,不必进行进一步提纯。
实施例2
一种组合物的制备方法,在一个1000mL的圆底烧瓶中,加入850g乙醇胺和150g水,搅拌至乙醇胺完全溶解;向乙醇胺水溶液中缓慢通入二氧化碳气体,二氧化碳气体流速为200mL/min,直至反应体系pH降低至8.3时停止反应,出料即为产品,不必进行进一步提纯。期间,保持反应温度在60℃以下,40℃以上,反应体系排气通畅。
实施例3
在一个1000mL的圆底烧瓶中,加入850g二乙醇胺和150g水,搅拌至二乙醇胺完全溶解;向二乙醇胺水溶液中缓慢加入360g干冰。期间,保持反应温度在60℃以下,40℃以上,反应体系排气通畅。干冰添加完毕后,出料即为产品,不必进行进一步提纯。
实施例4
在一个1000mL的圆底烧瓶中,加入850g二乙醇胺和150g水,搅拌至二乙醇胺完全溶解,缓慢通入二氧化碳气体,二氧化碳气体流速为200mL/min,直至反应体系pH降低至8.3时停止反应,出料即为产品,不必进行进一步提纯。期间,保持反应温度在60℃以下,40℃以上,反应体系排气通畅。
实施例5
在一个1000mL的圆底烧瓶中,加入540g二乙醇胺、315g乙醇胺和150g水,搅拌至二乙醇胺和乙醇胺完全溶解;向乙醇胺和二乙醇胺的混合水溶液中缓慢加入450g干冰。期间,保持反应温度在60℃以下,40℃以上,反应体系排气通畅。干冰添加完毕后,出料即为产品,不必进行进一步提纯。
实施例6
在一个1000mL的圆底烧瓶中,加入540g二乙醇胺、315g乙醇胺和150g水,搅拌至二乙醇胺和乙醇胺完全溶解;向乙醇胺和二乙醇胺的混合水溶液中缓慢通入二氧化碳气体,二氧化碳气体流速为200mL/min,直至反应体系pH降低至8.3时停止反应,出料即为产品,不必进行进一步提纯。期间,保持反应温度在60℃以下,40℃以上,反应体系排气通畅。
对比例1
将实施例5所制备得到的产品(简称AD)用以制备全合成金属加工液C和D,具体金属加工液C和D的配方分别为表1和表2所示。
表1
AD | 5% |
三乙醇胺 | 10% |
乙醇胺 | 6% |
新癸酸 | 3.5% |
癸二酸 | 2.5% |
苯并三氮唑 | 0.6% |
聚醚 | 7.5% |
聚塞氯铵 | 0.6% |
水 | 64% |
表2
分别对金属加工液C和D进行30天的模拟循环实验,实验条件为:分别取50mL金属加工液C和D,用水稀释20倍,即在两组水溶液(实验组和对比组)中金属加工液的浓度为5%;然后将两组水溶液分别加入两个金属加工液循环测试箱中,实验参数为:循环测试箱暴露在空气中,水溶液流速为10mL/s,水溶液温度保持在30℃,期间不对加工液做任何维护。实验30天,得到如表3数据。
表3
从表3可以看出,对比组的pH在30天循环过程中快速下降,由9.4下降至8.3,并且对比组出现液体浑浊且有油滴的现象;而实验组的pH在30天循环过程中pH并未下降,由9.2上升至9.4,并且实验组依然保持液体透明。
对比例2
将实施例5所制备得到的产品(简称AD)用以制备半合成金属加工液E和F,具体金属加工液E和F的配方分别为表4和表5所示,其中AFE-1267购自道康宁。
表4
AD | 5% |
三乙醇胺 | 5% |
乙醇胺 | 2% |
棕榈酸异辛酯 | 35% |
蓖麻油酸 | 3% |
妥尔油酸 | 2% |
十二烷二酸 | 1.5% |
己内酰胺 | 1.5% |
苯氧乙醇 | 1% |
苯并异噻唑啉酮 | 0.8% |
蓖麻油 | 7% |
油酸甘油酯 | 7% |
聚醚 | 8% |
AFE-1267 | 2% |
水 | 19.7% |
表5
分别对金属加工液E和F进行30天的模拟循环实验,实验条件为:分别取50mL金属加工液E和F,用水稀释20倍,即在两组水溶液(实验组和对比组)中金属加工液的浓度为5%;然后将两组水溶液分别加入两个金属加工液循环测试箱中,实验参数为:循环测试箱暴露在空气中,水溶液流速为10mL/s,水溶液温度保持在30℃,期间不对加工液做任何维护。实验30天,得到如表6数据。
表6
从表6可以看出,对比组的pH在30天循环过程中快速下降,由8.6下降至7.8,并且对比组出现油水分离和油层透明的现象;而实验组的pH在30天循环过程中pH并未下降,由8.4上升至8.8,并且实验组表现处液体为乳白且不透明的均匀液体。
综上所述,本发明提供一种组合物在制备用于金属加工液的缓释型pH调节剂的应用及其制备方法,该组合物可在高温作业过程中,通过释放二氧化碳和胺,使得金属加工液的pH适当上升,同时通过释放胺而抵消因为蒸发、变质引起的胺类物质的消耗;并且在非作业过程中,该化合物能够保持稳定,不会对金属加工液的pH产生明显的影响;即通过在金属加工液中加入该组合物可对金属加工液产生动态而精细的pH再调节。并且,该组合物不仅对高温敏感,同时也可在pH降低过程中通过释放二氧化碳和胺,以抵消金属加工液pH降低幅度,起到pH缓冲的作用,同时也进一步提升金属加工液的使用寿命。
以上所述仅为本发明的实施例,并非因此限制本发明的专利范围,凡是利用本发明说明书内容所作的等同变换,或直接或间接运用在相关的技术领域,均同理包括在本发明的专利保护范围内。
Claims (8)
2.根据权利要求1所述组合物在制备用于金属加工液的缓释型pH调节剂的应用,其特征在于,所述组合物还包括磷酸二氢钠/磷酸氢二钠,或碳酸钠/碳酸氢钠。
3.一种组合物的制备方法,其特征在于,所述组合物由干冰或二氧化碳气体通入乙醇胺和/或二乙醇胺溶液制备得到,所述组合物包括至少一种氨基甲酸盐离子,和至少一种乙醇胺盐离子。
4.根据权利要求3所述组合物的制备方法,其特征在于,所述组合物由干冰或二氧化碳气体通入乙醇胺或二乙醇胺的水溶液中,至所述水溶液终点pH为8.0~9.6时制备得到。
5.根据权利要求3所述组合物的制备方法,其特征在于,所述组合物由干冰或二氧化碳气体通入乙醇胺和二乙醇胺的混合水溶液中,至所述混合水溶液终点pH为8.0~9.6时制备得到,所述乙醇胺和二乙醇胺的质量比为1:20至20:1。
6.根据权利要求3至5任一项所述组合物的制备方法,其特征在于,所述制备的温度为40~60℃。
7.一种金属加工液,其特征在于,包括缓释型pH调节剂,所述缓释型pH调节剂由干冰或二氧化碳气体通入乙醇胺和/或二乙醇胺溶液制备得到,所述缓释型pH调节剂包括至少一种氨基甲酸盐离子和至少一种乙醇胺盐离子;
所述金属加工液由如下按质量百分比计的组分构成:
5%缓释型pH调节剂、10%三乙醇胺、6%乙醇胺、3.5%新癸酸、2.5%癸二酸、0.6%苯并三氮唑、7.5%聚醚、0.6%阳离子和64%水。
8.一种金属加工液,其特征在于,包括缓释型pH调节剂,所述缓释型pH调节剂由干冰或二氧化碳气体通入乙醇胺和/或二乙醇胺溶液制备得到,所述缓释型pH调节剂包括至少一种氨基甲酸盐离子和至少一种乙醇胺盐离子;
所述金属加工液由如下按质量百分比计的组分构成:
5%缓释型pH调节剂、5%三乙醇胺、2%乙醇胺、35%棕榈酸异辛酯、3%蓖麻油酸、2%妥尔油酸、1.5%十二烷二酸、1.5%己内酰胺、1%苯氧乙醇、0.8%苯并异噻唑啉酮、7%蓖麻油、7%油酸甘油酯、8%聚醚、2%消泡剂、19.7%水。
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