CN111825559A - 季铵盐离子液体、合成方法及其作为金属缓蚀剂的应用 - Google Patents
季铵盐离子液体、合成方法及其作为金属缓蚀剂的应用 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/62—Quaternary ammonium compounds
- C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/01—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms
- C07C311/02—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C311/09—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton the carbon skeleton being further substituted by at least two halogen atoms
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/141—Amines; Quaternary ammonium compounds
- C23F11/143—Salts of amines
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/16—Sulfur-containing compounds
- C23F11/164—Sulfur-containing compounds containing a -SO2-N group
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Abstract
本发明公开了一类季铵盐离子液体([N8,8,8,12][NTf2]、[N8,8,8,14][NTf2]和[N8,8,8,Bn][NTf2])的合成方法以及该离子液体作为金属缓蚀剂,尤其是镁合金缓蚀剂的应用。本发明解决了现有金属镁以及镁合金的腐蚀等问题,缓蚀效率均达到了80%以上。本发明的季铵盐离子液体具有成本低、合成路线简单,缓蚀效率高等优点,所制备的季铵盐离子液体的产率均可达到60%以上。
Description
技术领域
本发明属于离子液体技术领域,具体涉及一类季铵盐离子液体、合成方法及其作为金属缓蚀剂的应用,尤其是用于镁合金的缓蚀。
背景技术
镁合金已广泛应用于汽车、计算机、通讯以及航空航天等众多领域,很多国家将其视为21世纪的重要战略物资,并出台了若干开发计划。镁合金以其质轻、结构性能优异、以及易于回收等优点成为制造业轻量化发展的首选材料;而且在储量、特性、应用范围、循环利用、以及节能环保等方面和钢铁相比,均具有非常明显的优势。全球镁合金用量以每年20%的幅度快速增长,大规模开发和利用的时代已经到来,它必将成为未来产业革命与可持续发展资源的核心。镁合金的氧化膜一般都疏松多孔,故镁及镁合金的耐蚀性较差,具有极高的化学和电化学活性;其电化学腐蚀过程主要以析氢为主,以点蚀或全面腐蚀形式迅速溶解直至粉末。
缓蚀剂是一种以适当的浓度和形式存在于环境(介质)中时,可以防止或减缓腐蚀的化学物质或几种化学物质的混合物。与其他防腐技术相比,添加缓蚀剂具有一些明显的优点,例如不需要特殊设备、控制简单、价格低廉、操作简便等。缓蚀剂具有用途广、用量少、成本小、投资低、无毒无臭、操作简单、对金属基体的腐蚀小、保护效果好等优点,因此缓蚀剂的研究与使用已经成为国内外防腐领域的研究热点之一。因为缓蚀剂的这些优点,缓蚀剂已被应用于很多领域。然而,现有的缓蚀剂仍存在缓蚀效果不理想等缺陷。
发明内容
本发明目的在于克服现有缓蚀技术的缺陷,提供一种环保、高效、经济的季铵盐离子液体,该离子液体具有良好的缓蚀效果,可用作金属缓蚀剂。
本发明还提供了上述季铵盐离子液体的合成方法及其作为金属缓蚀剂,尤其是镁合金缓蚀剂的应用。
一类季铵盐离子液体,该季铵盐离子液体为 [N8,8,8,12][NTf2]、[N8,8,8,14][NTf2]和[N8,8,8,Bn][NTf2] 中的一种或两种以上的混合物,所述[N8,8,8,12][NTf2]、[N8,8,8,14][NTf2]和[N8,8,8,Bn][NTf2]的分子结构式分别如下所示:
本发明提供了上述季铵盐离子液体的合成方法,当所述季铵盐离子液体包含[N8,8,8,12][NTf2]、[N8,8,8,14][NTf2]时,其经下述步骤合成获得:
1)将三辛胺与十二烷基溴或十四烷基溴、以及DMF混合后,于N2保护下回流反应9-14h,反应结束后,冷却至室温,加入石油醚,超声,静置分层,固液分离,固体相经重结晶得到白色固体产物三辛基十二烷基溴化铵 [N8,8,8,12]Br或三辛基十四烷基溴化铵 [N8,8,8,14]Br;
2)将[N8,8,8,12]Br或者[N8,8,8,14]Br与双三氟甲烷磺酰亚胺锂和甲醇混合后于35-45℃搅拌反应3-5h,反应结束后,冷却至室温,分液,干燥有机相,浓缩溶剂;然后加入二氯甲烷,去离子水洗涤,再次浓缩溶剂,得到无色粘稠液体,真空干燥,即获得季铵盐离子液体[N8,8,8,12][NTf2]或[N8,8,8,14][NTf2]。
具体的,步骤1)中,三辛胺与十二烷基溴或十四烷基溴的摩尔比为(1-4):2,优选为1:2;步骤2)中,[N8,8,8,12]Br或者[N8,8,8,14]Br与双三氟甲烷磺酰亚胺锂的摩尔比为1:(1-4),优选为1:1.2。
本发明提供了上述季铵盐离子液体的合成方法,当所述季铵盐离子液体为[N8,8,8,Bn][NTf2]时,其经下述步骤合成获得:
1)将三辛胺、氯化苄和氯仿混合后,搅拌回流反应70-75h,反应结束后,冷却至室温,浓缩溶剂;加入环己烷,有白色固体生成,再加入石油醚,静置过夜,过滤;固体相洗涤后得到白色固体产物三辛基苄基氯化铵([N8,8,8,Bn]Cl);
2)将[N8,8,8,Bn]Cl、双三氟甲烷磺酰亚胺锂和甲醇混合后于35-45℃搅拌反应3-5h,反应结束后,冷却至室温,浓缩溶剂;然后加入二氯甲烷,去离子水洗涤,再次浓缩溶剂,得到无色透明的粘稠液体,真空干燥,即获得季铵盐离子液体[N8,8,8,Bn][NTf2]。
具体的,步骤1)中,三辛胺与氯化苄的摩尔比为(1-4):1,优选为1:1;步骤2)中,[N8,8,8,Bn]Cl与双三氟甲烷磺酰亚胺锂的摩尔比为1:(1-3),优选为1:1.2。
本发明还提供了上述季铵盐离子液体作为金属缓蚀剂的应用,尤其是作为镁合金缓蚀剂的应用。
和现有技术相比,本发明具有如下有益效果:
1)本发明离子液体是将三辛胺与十二烷基溴/十四烷基溴/氯化苄通过N烷基化反应合成[N8,8,8,12]Br、[N8,8,8,14]Br和[N8,8,8,Bn]Cl,再通过离子交换反应得到;具有合成路线简单、生产成本低、后处理简便等优点;
2)本发明离子液体含有N、O、S杂原子,杂原子有孤电子对,易与金属发生相互作用,在镁合金表面与腐蚀介质之间形成保护膜,以此降低镁合金的腐蚀速度,从而减缓镁合金的腐蚀。经试验发现:本发明离子液体在0.05 wt.% NaCl溶液中对AZ31B镁合金均具有良好的缓蚀作用,因此可以作为金属缓蚀剂,尤其是镁合金缓蚀剂。
附图说明
图1为本发明离子液体[N8,8,8,14][NTf2]在0.5 wt.% NaCl溶液中对AZ31镁合金缓蚀的结果。图中,a为抛光后AZ31B镁合金的SEM图,b为AZ31B镁合金在0.5 wt.% NaCl中浸泡24 h后的SEM图,c为AZ31B镁合金在含有5 ppm [N8,8,8,14][NTf2]的0.5 wt.% NaCl中浸泡24h后的SEM图;
图2为AZ31B镁合金在无水乙醇稀释的50 ppm [N8,8,8,Bn][NTf2]中浸泡不同时间成膜后,在0.05 wt.% NaCl溶液中电化学实验得到的Nyquist图。
具体实施方法
以下结合实施例对本发明的技术方案作进一步的详细介绍,但本发明的保护范围并不局限于此。
实施例1:
一类季铵盐离子液体,该季铵盐离子液体包括 [N8,8,8,12][NTf2]、[N8,8,8,14][NTf2]和[N8,8,8,Bn][NTf2],所述[N8,8,8,12][NTf2]、[N8,8,8,14][NTf2]和[N8,8,8,Bn][NTf2]的分子结构式分别如下所示:
1、季铵盐离子液体[N8,8,8,12][NTf2]的合成方法,包括如下步骤:
1)在100 mL三口烧瓶中加入10.6 g(30 mmol)三辛胺,14.94 g(60 mmol)十二烷基溴和30 mL DMF,在N2保护下回流反应10 h。反应结束后,溶液由无色液体变为黄色胶状固体,冷却至室温。在三口烧瓶中加入30 mL石油醚,超声,静置,体系出现分层,上层是淡黄色液体,下层为白色固体;固液分离。在固体相中再加入30 mL石油醚,重复上述超声、静置、固液分离步骤;得到白色固体。在固体相中再加入30 mL乙酸乙酯重结晶,重复三次,得到白色固体三辛基十二烷基溴化铵 [N8,8,8,12]Br,产率为62.3%;
2)取上述步骤1)所得产物[N8,8,8,12]Br 2.532 g(4.2 mmoL)、双三氟甲烷磺酰亚胺锂(LiNTf2)1.205 g(4.2 mmoL)和20 mL甲醇加入到100 mL单口烧瓶中。在40℃下搅拌反应4h。反应结束后,冷却至室温,分液,干燥有机相,浓缩溶剂。然后向单口烧瓶中加入20 mL二氯甲烷,用去离子水洗涤(20 mL × 3),浓缩溶剂。得到无色粘稠液体,真空干燥48 h,即得到离子液体[N8,8,8,12][NTf2],产率为90.8%。
季铵盐离子液体[N8,8,8,12][NTf2]的图谱数据如下:
1H NMR (400 MHz, CDCl3) δ: 2.98-2.89(m, -CH2-, 8H), 1.93(t, -CH2-, 8H),1.43-1.22 (m, -CH2-, 48H), 0.88 (t, -CH3, 12H)。经核磁共振谱检验与目标产物结构吻合。
2、季铵盐离子液体[N8,8,8,14][NTf2]的合成方法参照[N8,8,8,12][NTf2],其中,不同之处在于,用十四烷基溴替换十二烷基溴;两步的产率分别为50.4%和89.3%。
季铵盐离子液体[N8,8,8,14][NTf2]的图谱数据如下:
1H NMR (400 MHz, CDCl3) δ: 2.97-2.91(m, -CH2-, 8H), 1.91(d, -CH2-, 8H),1.43-1.17(m, -CH2-, 52H), 0.91-0.83(m, -CH3, 12H)。经核磁共振谱检验与目标产物结构吻合。
3、季铵盐离子液体[N8,8,8,Bn][NTf2]的合成方法,包括如下步骤:
1)在150 mL三口烧瓶中加入7.06 g(20 mmol)三辛胺、2.530 g(20 mmol)氯化苄和30mL氯仿,搅拌回流反应72 h。反应结束后,溶液为无色透明液体,冷却至室温。浓缩溶剂,加入20 mL环己烷,有白色固体生成,再加入20 mL石油醚,在4℃条件下静置过夜,过滤。环己烷洗涤(20 mL × 3),得到白色固体三辛基苄基氯化铵([N8,8,8,Bn]Cl),产率约为82.3%;
2)取上述步骤1)所得产物[N8,8,8,Bn]Cl 4.607 g(9.61 mmoL)、双三氟甲烷磺酰亚胺锂(LiNTf2) 2.757 g(9.61 mmoL)和30 mL甲醇加入到50 mL单口烧瓶中。在40℃下搅拌反应3h。反应结束后,冷却至室温,浓缩溶剂。然后加入20 mL二氯甲烷,去离子水洗涤(15 mL ×5),浓缩溶剂,得到无色透明的粘稠液体。真空干燥24 h,即得到离子液体[N8,8,8,Bn]+[NTf2]-,产率约为92.4%。
季铵盐离子液体[N8,8,8,Bn][NTf2]的图谱数据如下:
1H NMR (300 MHz, CDCl3) δ: 7.54-7.42(dd, -Ph, 5H), 4.98-5.0(s, -CH2-, 2H),3.36-3.30(m, -CH2-, 6H), 1.76-1.74(t, -CH2-, 6H), 1.36-1.21(m, -CH2-, 30H),0.90-0.82(m, -CH3, 9H)。经核磁共振谱检验与目标产物结构吻合。
实施例2:
本发明离子液体缓蚀剂[N8,8,8,12][NTf2]、[N8,8,8,14][NTf2]和[N8,8,8,Bn][NTf2]在0.05wt.% NaCl溶液中对AZ31B镁合金的缓蚀作用。
电化学试验是用上海辰华CHI650E电化学工作站进行测试。电化学试验在三电极系统下进行,饱和甘汞电极为参比电极(SCE),铂电极为对电极(CE),AZ31B镁合金为工作电极(WE)。AZ31B镁合金的大小为1 cm × 1 cm × 0.5 cm。AZ31B镁合金的成分:铝2.5~3.5wt.%、锌0.6~1.4 wt.%、锰0.2~1.0 wt.%、硅0.08 wt.%、钙0.04 wt.%、铜0.01 wt.%、铁0.003 wt.%、镍0.001 wt.%、其他元素0.30 wt.%,余量为镁。
在进行试验之前,先用不同型号的砂纸打磨抛光AZ31B镁合金,然后在每次试验之前用无水乙醇脱脂并用去离子水清洗,在空气中自然风干备用。进行电化学测试时,将铜线嵌入到AZ31B镁合金样品中,用硅橡胶密封AZ31B镁合金样品及与铜线的连接处,仅暴露1cm2 AZ31B镁合金表面用于电化学测试。电化学实验开始之前为了使体系达到一个稳定的状态,将准备好的工作电极浸入不含有或含有不同浓度缓蚀剂的0.05 wt.% NaCl 溶液中4000 s。
表1 Mg合金在含不同浓度离子液体的0.05 wt.% NaCl溶液中的缓蚀效率(%)
表1给出了AZ31B镁合金在含有不同浓度[N8,8,8,12][NTf2]、[N8,8,8,14][NTf2]和[N8,8,8,Bn][NTf2]的0.05 wt.% NaCl溶液中所测得的电化学阻抗得到的缓蚀效率。由表1可以看出[N8,8,8,12][NTf2]和[N8,8,8,14][NTf2]的浓度为10 ppm时有最高的缓蚀效率,分别为83%和90%。而[N8,8,8,Bn][NTf2]的浓度为50 ppm时有最高的缓蚀效率92%。[N8,8,8,12][NTf2]和[N8,8,8,14][NTf2]的缓蚀效率相比,烷基链长越长缓蚀效率越高。而[N8,8,8,14][NTf2]和[N8,8,8,Bn][NTf2]的缓蚀效率相比,芳香环有更高的缓蚀效率。
图1给出了本发明离子液体[N8,8,8,14][NTf2]在0.5 wt.% NaCl溶液中对AZ31镁合金缓蚀的结果。图中,a为抛光后AZ31B镁合金的SEM图,b为AZ31B镁合金在0.5 wt.% NaCl中浸泡24 h后的SEM图,c为AZ31B镁合金在含有5 ppm [N8,8,8,14][NTf2]的0.5 wt.% NaCl中浸泡24 h后的SEM图。由图1可以看出:没有和含有5 ppm [N8,8,8,14][NTf2]的0.5 wt.% NaCl溶液中浸泡24 h的AZ31B镁合金与抛光后的AZ31B镁合金相比,在[N8,8,8,14][NTf2]存在下AZ31B 镁合金表面光滑,能看到明显的金属光泽;而没有[N8,8,8,14][NTf2]时,AZ31B镁合金表面腐蚀严重。说明[N8,8,8,14][NTf2]对Z31B镁合金在0.5 wt.% NaCl溶液中有良好的缓蚀效果。
本发明给出了AZ31B镁合金在无水乙醇稀释的50 ppm [N8,8,8,Bn][NTf2]溶液中浸泡不同时间成膜后,在0.05 wt.% NaCl溶液中的缓蚀结果。图2是AZ31B镁合金在无水乙醇稀释的50 ppm [N8,8,8,Bn][NTf2]中浸泡不同时间成膜后,在0.05 wt.% NaCl溶液中电化学实验得到的Nyquist图。Nyquist图的半圆直径越大说明对AZ31B镁合金的缓蚀效果越好,Nyquist图并不是一个完美的半圆弧,这可能是由于AZ31B镁合金表面粗糙以及缓蚀剂的吸附引起的。由图2可以看出:随着AZ31B镁合金浸泡时间越长半圆的直径越大,在浸泡时间为96 h时,半圆弧的直径达到最大,说明有最好的缓蚀效率。随着浸泡时间的继续增加,半圆弧直径略有降低,说明浸泡时间并不是越长越好。
Claims (7)
2.权利要求1所述季铵盐离子液体的合成方法,其特征在于,所述季铵盐离子液体包含[N8,8,8,12][NTf2]、[N8,8,8,14][NTf2]时,经下述步骤合成获得:
1)将三辛胺与十二烷基溴或十四烷基溴、以及DMF混合后,于N2保护下回流反应9-14h,反应结束后,冷却至室温,加入石油醚,超声,静置分层,固液分离,固体相经重结晶得到三辛基十二烷基溴化铵 [N8,8,8,12]Br或三辛基十四烷基溴化铵 [N8,8,8,14]Br;
2)将[N8,8,8,12]Br或 [N8,8,8,14]Br与双三氟甲烷磺酰亚胺锂和甲醇混合后于35-45℃搅拌反应3-5h,反应结束后,冷却至室温,分液,干燥有机相,浓缩溶剂;然后加入二氯甲烷,去离子水洗涤,再次浓缩溶剂,得到无色粘稠液体,真空干燥,即获得季铵盐离子液体[N8,8,8,12][NTf2]或[N8,8,8,14][NTf2]。
3.如权利要求2所述季铵盐离子液体的合成方法,其特征在于,步骤1)中,三辛胺与十二烷基溴或十四烷基溴的摩尔比为(1-4):2;步骤2)中,[N8,8,8,12]Br或 [N8,8,8,14]Br与双三氟甲烷磺酰亚胺锂的摩尔比为1:(1-4)。
4.权利要求1所述季铵盐离子液体的合成方法,其特征在于,所述季铵盐离子液体包含[N8,8,8,Bn][NTf2]时,经下述步骤合成获得:
1)将三辛胺、氯化苄和氯仿混合后,搅拌回流反应70-75h,反应结束后,冷却至室温,浓缩溶剂;加入环己烷,有白色固体生成,再加入石油醚,静置过夜,过滤;固体相洗涤后得到三辛基苄基氯化铵 [N8,8,8,Bn]Cl;
2)将[N8,8,8,Bn]Cl、双三氟甲烷磺酰亚胺锂和甲醇混合后于35-45℃搅拌反应3-5h,反应结束后,冷却至室温,浓缩溶剂;然后加入二氯甲烷,去离子水洗涤,再次浓缩溶剂,得到无色透明的粘稠液体,真空干燥,即获得季铵盐离子液体[N8,8,8,Bn][NTf2]。
5.如权利要求4所述季铵盐离子液体的合成方法,其特征在于,步骤1)中,三辛胺与氯化苄的摩尔比为(1-4):1;步骤2)中,[N8,8,8,Bn]Cl与双三氟甲烷磺酰亚胺锂的摩尔比为1:(1-3)。
6.权利要求1所述季铵盐离子液体作为金属缓蚀剂的应用。
7.权利要求1所述季铵盐离子液体作为镁合金缓蚀剂的应用。
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