CN104926730B - 一种松香基咪唑啉类化合物及其合成方法和应用 - Google Patents
一种松香基咪唑啉类化合物及其合成方法和应用 Download PDFInfo
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- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/06—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
- C07D233/08—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms with alkyl radicals, containing more than four carbon atoms, directly attached to ring carbon atoms
- C07D233/12—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms with alkyl radicals, containing more than four carbon atoms, directly attached to ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
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- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
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- 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
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Abstract
本发明涉及用于金属防腐蚀的化合物合成及应用技术领域,具体公开一种新型松香基咪唑啉类化合物及其合成方法和应用。本发明的松香基咪唑啉类化合物的起始原料为松香酸,原料单一,合成路线操作简单。将合成出的该化合物制备缓蚀剂的方法简单,只需将该化合物溶解于二甲基甲酰胺,溶解完全后再溶解于水中,搅拌均匀即得。同时此缓蚀剂安全环保,具有优异的缓蚀效果。可以用于油气田地面集输和储运管路,防止腐蚀气体对钢铁等金属材料的破坏,降低腐蚀损耗。
Description
技术领域
本发明涉及用于金属防腐蚀的化合物合成及应用技术领域,具体涉及一种新型松香基咪唑啉类化合物及其合成方法和应用,该化合物可以作为缓蚀剂用于油、气井生产,管道运输过程中的金属防腐。
背景技术
近几十年来,含硫化氢、二氧化碳及高矿化度地层水等多种腐蚀介质的油气田相继出现。酸性环境下油气田设备的严重腐蚀,已经越来越引起人们的关注。油气田的腐蚀不仅给油气田的开发、生产造成巨大的经济损失,同时也直接威胁着人类的生存环境和身体健康。可见,加强腐蚀与防护技术研究,实施有效的监测和保护措施对生产工业的开源节流,增产增效具有重大意义。
腐蚀介质中投加缓蚀剂是一种经济有效且实用的防腐方法,在众多缓蚀剂品种中,咪唑啉类缓蚀剂以高效低毒、无特殊刺激性气味、环境污染小等优点而颇受亲睐。咪唑啉类缓蚀剂作为一种制备过程简单的环境友好型缓蚀剂,应用范围十分广泛。用于合成咪唑啉类缓蚀剂的有机酸品种很多,但天然原料比较少,我国作为松香生产和出口大国,天然松香资源丰富,价格低廉,用其合成缓蚀剂并投入生产实践将具有极大社会效益和经济效益。松香基独具的三环二萜分子结构,将使得制取的松香基咪唑啉具有更好的缓蚀效率。现有技术中尚未见相关报道。
发明内容
针对现有技术中存在的不足,本发明的第一个目的在于提供了一种式(5)所示的松香基咪唑啉类化合物:
第二个目的在于提供了一种上述式(5)所示松香基咪唑啉类化合物的合成方法,该化合物系发明人首次合成并确认。
本发明目的通过以下技术方案得以实现。
一种式(5)所示松香基咪唑啉类化合物的合成方法,其步骤如下:
步骤a:将松香酸和K2CO3溶于二甲基甲酰胺中,加入碘甲烷(MeI),搅拌3小时,TLC点板反应完全。减压旋蒸去掉MeI,用乙酸乙酯(EA)萃取,浓缩,水洗除去二甲基甲酰胺,有机层用饱和氯化钠洗涤、干燥、浓缩,剩余组分用1:10的乙酸乙酯(EA)/石油醚(PE)过硅胶柱子纯化后得到式(2)化合物,反应式如下:
步骤b:在0-10℃条件下,往甲苯中加入乙二胺和三甲基铝(AlMe3),混合均匀,再加入步骤a得到的式(2)化合物,充分搅拌回流12小时。冷却到0℃,过滤,滤液用乙酸乙酯萃取,有机层用硫酸钠干燥、浓缩,产品用硅胶柱层析纯化(石油醚/乙酸乙酯=1/1),得到式(3)化合物,为白色固体,反应式如下:
步骤c:式(3)化合物和丙炔酸乙酯在甲苯中加热回流12小时,除去溶剂得到式(4)化合物,反应式如下:
步骤d:在甲醇与水的体积比为25:1的甲醇水溶液中加入式(4)化合物和LiOH,加热到70℃,反应12小时后冷却到室温除去甲醇,剩余部分溶解于水,调pH值到3-4,再用乙酸乙酯萃取,有机层用水清洗后浓缩得到目标产物式(5)化合物,反应式如下:
本发明的第三个目的在于提供了一种含有式(5)化合物的缓蚀剂,该缓蚀剂主要用于油、气井生产,管道运输过程中的金属防腐。新型松香基咪唑啉缓蚀剂无毒,缓蚀效率高,能达到90%以上。本发明的缓蚀剂具体的配方为:
组分 含量
式(5)化合物 10mg/L—100mg/L,
二甲基甲酰胺 5g/L—15g/L,
水 余量。
上述配方的缓蚀剂的制备方法为:先将式(5)化合物溶解于二甲基甲酰胺(DMF),得溶液,再将所得溶液溶解于水中,搅拌均匀即得。
本缓蚀剂可以用于油气田地面集输和储运管路系统,防止腐蚀气体对钢铁等金属材料的破坏,降低腐蚀损耗。
与现有技术相比,本发明的优点和有益效果在于:
1、松香基咪唑啉类化合物用作缓蚀剂不仅具有良好的抗H2S/CO2腐蚀的缓蚀性能,同时具有热稳定性好、毒性低、无特殊刺激气味等优点。松香基独具的三环二萜分子结构,新型松香基咪唑啉缓蚀剂无毒,缓蚀率高,能达到90%。松香基咪唑啉具有更好的缓蚀效率,主要用于油、气井生产,管道运输过程中的金属防腐。
2、本发明的松香基咪唑啉类化合物的合成原料单一,合成路线操作简单。
3、按照本发明配方制备缓蚀剂的方法简单,只需将式(5)化合物溶解于二甲基甲酰胺(DMF),溶解完全后再溶解于水中,搅拌均匀即得。同时此缓蚀剂安全环保,具有优异的缓蚀效果。可以用于油气田地面集输和储运管路,防止腐蚀气体对钢铁等金属材料的破坏,降低腐蚀损耗。
具体实施方式
下面结合具体实施例对本发明做进一步的详细说明。
除非另有说明,本文中出现的百分比都为质量百分比。
实施例1:
一种式(5)化合物的合成方法,其步骤如下:
步骤a:式(2)化合物的合成:
将100g松香酸(0.331mol)和69g K2CO3(0.497mol)溶解于800ml二甲基甲酰胺溶剂中,加入65.87克(0.397mol)MeI,搅拌3小时点板确认反应完全。减压旋蒸去掉MeI,用EA萃取、浓缩,水洗去掉DMF溶剂,有机层用饱和氯化钠洗涤、干燥、浓缩,剩余组分用1:10的EA/PE过硅胶柱子纯化后得到100g式(2)化合物。
1H NMR(CDCl3,400MHz):0.75(m,7H);0.94(m,6H);1.18(m,7H);1.50(m,4H),1.73(m,6H);2.01(m,4H);2.14(m,1H);3.55(s,3H);5.29(d,1H);5.70(s,1H).
步骤b:式(3)化合物的合成:
在0-10℃条件下,往1L甲苯中加入57.0g(0.949mol)乙二胺和0.949molAlMe3,混合均匀,再加入步骤a得到的100g(0.123mol)式(2)化合物,充分搅拌回流12小时。冷却到0℃,过滤,滤液用乙酸乙酯萃取,有机层用硫酸钠干燥、浓缩,产品用硅胶柱层析纯化(石油醚/乙酸乙酯=1/1)得到白色固体17g,为式(3)化合物:
1H NMR:(CDCl3,400MHz):0.88(m,9H);1.00(m,6H);1.28(m,10H);1.66(m,4H),1.80(m,5H);2.08(m,4H);2.20(m,1H);5.38(d,1H);5.77(s,1H).
步骤c:式(4)化合物的合成:
20g式(3)化合物和12g丙炔酸乙酯(0.123mol)在120mL甲苯中加热回流12小时,除去溶剂得到26g式(4)化合物。
1H NMR:(CDCl3,400MHz):0.88(m,9H);1.00(m,6H);1.28(m,10H);1.66(m,4H),1.80(m,5H);2.08(m,4H);2.20(m,1H);4.20(m,2H);4.66(d,1H)5.28(d,1H);5.69(s,1H);8.31(s,1H).
步骤d:目标产物式(5)化合物的合成:
在500mL甲醇和20mL水混合液中加入37g(0.087mol)式(4)化合物和4g(0.175mol)LiOH加热到70℃,反应12小时后却到室温除去甲醇,剩余的溶解于水,调pH值到3-4,再用乙酸乙酯萃取,有机层用水清洗后浓缩得到目标产物式(5)化合物。
1H NMR:(CDCl3,400MHz):0.65(m,3H);0.92(m,6H);1.18(m,2H);1.36(m,3H),1.62(m,2H);1.62(m,2H);2.00(m,8H);3.48(m,2H);3.81(m,2H);4.64(d,1H);5.28(s,1H);5.68(s,1H);8.34(d,1H).
实施例2:
首先,将实施例1制得的式(5)化合物制备成缓蚀剂,所述缓蚀剂由式(5)化合物、二甲基甲酰胺和水组成,具体含量范围如下:
组分 含量
式(5)化合物 10mg/L—100mg/L,
二甲基甲酰胺 5g/L—15g/L,
水 余量。
更具体的,各缓蚀剂配方如下表1所示:
表1缓蚀剂配方试验
编号 | 式(5)化合物(mg/L) | DMF(g/L) | 水 |
配方1 | 10 | 5 | 余量 |
配方2 | 30 | 10 | 余量 |
配方3 | 50 | 15 | 余量 |
配方4 | 70 | 5 | 余量 |
配方5 | 90 | 10 | 余量 |
配方6 | 100 | 15 | 余量 |
以上各配方的缓蚀剂的制备方法均如下:先将式(5)化合物溶解于二甲基甲酰胺(DMF),得溶液,再将所得溶液溶解于水中,搅拌均匀即得缓蚀剂。
酸条件下缓蚀效率测量:
根据SY/T5405-1996《酸化用缓蚀剂性能试验方法及评价指标》,通过试验模拟具体说明本发明制备的式(5)化合物作为缓蚀剂的缓蚀效果,见表2。
表2
表2中各配方的缓蚀剂浓度计量以表1配方制备好的缓蚀剂计。
松香基独具的三环二萜分子结构,新型松香基咪唑啉缓蚀剂无毒,缓蚀率高,能达到90%以上。松香基咪唑啉具有更好的缓蚀效率,主要用于油、气井生产,管道运输过程中的金属防腐。
本说明书中所描述的具体实施例仅仅是对本发明精神作举例说明。本发明所属技术领域的技术人员可以对所描述的具体实施例做各种各样的修改或补充或采用类似的方式替代,但并不会偏离本发明的精神或者超越所附权利要求书所定义的范围。
Claims (4)
1.一种式(5)所示的松香基咪唑啉类化合物:
2.一种权利要求1所述的松香基咪唑啉类化合物的合成方法,其步骤如下:
步骤a:将松香酸和K2CO3溶于二甲基甲酰胺中,加入碘甲烷,反应完全后减压旋蒸去掉碘甲烷,用乙酸乙酯萃取,浓缩,水洗除去二甲基甲酰胺,有机层用饱和氯化钠洗涤、干燥、浓缩,剩余组分用1:10的乙酸乙酯/石油醚过硅胶柱子纯化后得到式(2)化合物,反应式如下:
步骤b:在0-10℃条件下,往甲苯中加入乙二胺和三甲基铝,混合均匀,再加入步骤a得到的式(2)化合物,充分搅拌回流反应,冷却到0℃,过滤,滤液用乙酸乙酯萃取,有机层用硫酸钠干燥、浓缩,硅胶柱层析纯化,得到式(3)化合物,反应式如下:
步骤c:式(3)化合物和丙炔酸乙酯在甲苯中加热回流,反应完全后除去溶剂得到式(4)化合物,反应式如下:
步骤d:在甲醇水溶液中加入式(4)化合物和LiOH,加热反应完全后冷却到室温除去甲醇,剩余部分溶解于水,调pH值到3-4,再用乙酸乙酯萃取,有机层用水清洗后浓缩得到式(5)化合物,反应式如下:
3.一种含有权利要求1所述的松香基咪唑啉类化合物的缓蚀剂。
4.根据权利要求3所述的缓蚀剂,配方如下:
组分 含量
式(5)化合物 10mg/L—100mg/L,
二甲基甲酰胺 5g/L—15g/L,
水 余量。
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