CN104829539A - Adipic acid bis-imidazoline derivative and preparation method thereof, and applications of adipic acid bis-imidazoline derivative as corrosion inhibitor - Google Patents

Adipic acid bis-imidazoline derivative and preparation method thereof, and applications of adipic acid bis-imidazoline derivative as corrosion inhibitor Download PDF

Info

Publication number
CN104829539A
CN104829539A CN 201510172494 CN201510172494A CN104829539A CN 104829539 A CN104829539 A CN 104829539A CN 201510172494 CN201510172494 CN 201510172494 CN 201510172494 A CN201510172494 A CN 201510172494A CN 104829539 A CN104829539 A CN 104829539A
Authority
CN
Grant status
Application
Patent type
Prior art keywords
adipic acid
step
reaction
added
method
Prior art date
Application number
CN 201510172494
Other languages
Chinese (zh)
Other versions
CN104829539B (en )
Inventor
何毅
马兰
陈丽
郭睿
Original Assignee
成都石大力盾科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D233/00Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04Heterocyclic 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
    • C07D233/06Heterocyclic 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
    • C07D233/08Heterocyclic 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
    • C07D233/12Heterocyclic 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
    • C07D233/16Radicals substituted by nitrogen atoms
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/54Compositions for in situ inhibition of corrosion in boreholes or wells
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; MISCELLANEOUS COMPOSITIONS; MISCELLANEOUS APPLICATIONS OF MATERIALS
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/32Anticorrosion additives

Abstract

The present invention discloses an adipic acid bis-imidazoline derivative and a preparation method thereof, and applications of the adipic acid bis-imidazoline derivative as a corrosion inhibitor. According to the present invention, the preparation method comprises that: adipic acid and triethylenetetramine react to generate an imidazoline intermediate, the imidazoline intermediate and benzyl chloride react to obtain a quaternization product, and the quaternization product and thiourea react to generate a target compound. According to the present invention, when the adipic acid bis-imidazoline derivative prepared by the method is adopted as the corrosion inhibitor, the excellent anti-CO2 corrosion performance is provided at the low temperature.

Description

-种己二酸双咪睡嘟衍生物、其制备方法和该衍生物作为缓蚀剂的应用 - Species microphone bis- sleep beep derivatives, their preparation and use as inhibitors of the derivatives

技术领域 FIELD

[0001] 本发明设及一种己二酸双咪挫咐衍生物、其制备方法和该衍生物作为缓蚀剂的应用。 [0001] The present invention is provided adipate and bis imidazole derivative commanded setback, their preparation and use as inhibitors of the derivatives.

背景技术 Background technique

[0002] 在油气田开采工业中,C〇2腐蚀由于酸化增产措施的使用,酸液对金属产生了强烈的腐蚀,对油田开采造成巨大经济损失。 [0002] In the oil and gas extraction industry, C〇2 corrosion due to the use of acid stimulation measures, generated a strong acid to metal corrosion, resulting in huge economic losses to oil exploration. 目前油田中常用缓蚀剂W酷胺、咪挫咐类缓蚀剂为主,但大多数咪挫咐缓蚀剂均为单咪挫咐环结构,在金属表面的吸附点较少,引入了双咪挫环结构W增加缓蚀剂的吸附中屯、。 Oilfield corrosion inhibitor used currently W cool amines, imidazole-based corrosion inhibitor commanded setback, but most are single microphone setback commanded inhibitor microphone setback commanded ring structure, small in the metal surface adsorption sites, is introduced bis imidazole ring structure W increase of inhibitor fell in the village adsorption. 双咪挫环缓蚀剂在酸化方面的应用较多,但在抗二氧化碳腐蚀方面的研究较少。 Bis imidazole ring inhibitor fell more applications in terms of the acidification, but few studies in terms of anti-corrosion of carbon dioxide. 现有技术中的双咪挫咐季锭盐缓蚀剂的制备方法是;由己二酸和二己締=胺为原料在二甲苯溶剂中反应一定时间后得到栋褐色的双咪挫咐缓蚀剂,并加入氯化节反应生成双咪挫咐季锭盐。 Preparing an ingot dual microphone salt corrosion inhibitor prior art quaternary setback is commanded; of adipic acid and amine starting material = dihexyl association in xylene solvent to give a brown double ridge microphone setback commanded a certain time after the reaction inhibition agent, and chlorination reaction was added bis microphone section setback spindles commanded quaternary salt. 现有技术中的缓蚀剂在抗C〇2腐蚀性能上都还不够理想, 尤其是在低温的环境下,缓蚀效率较低。 The prior art corrosion inhibitor are not ideal anti C〇2 on corrosion, especially at a low temperature environment, the inhibition efficiency is low. 为了有效地控制C〇2腐蚀,减轻C0 2腐蚀在油田开采过程中所带来的巨大经济损失,研究者一直在致力研制一种抗C〇2腐蚀的缓蚀剂,达到进一步提高缓蚀效率的目的。 In order to effectively control the C〇2 corrosion, reduce C0 2 corrosion in oil mining process enormous economic losses, researchers have been committed to the development of an anti-C〇2 corrosion inhibitor, to further improve the inhibition efficiency the goal of.

发明内容 SUMMARY

[0003] 本发明的目的是提供一种己二酸双咪挫咐衍生物、其制备方法和该衍生物作为缓蚀剂的应用,该方法制备出的己二酸双咪挫咐衍生物作为缓蚀剂来使用时,在低温下同样具有优良的抗C〇2腐蚀性能。 [0003] The object of the present invention is to provide a microphone setback commanded bis- derivative, its preparation and the adipic acid derivatives, to the preparation of a corrosion inhibitor as an application bis imidazole derivative as a setback commanded when the inhibitor is used at a low temperature also has excellent resistance to corrosion C〇2.

[0004] 为实现上述发明目的,本发明所采用的技术方案是: [0004] In order to achieve the above object, the technical solution employed in the present invention:

[0005] 下述结构式的化合物: [0005] The compound of the following structural formula:

[0006] [0006]

Figure CN104829539AD00031

[0007] 上述化合物的制备方法,该方法包括先将己二酸与=己締四胺进行反应生成咪挫咐中间体,再将咪挫咐中间体与氯化节进行反应得季锭化产物,最后将季锭化产物与硫脈进行反应生成目标化合物。 Preparation [0007] The method of the above compounds, the process comprising first reacting adipic acid with = cyclohexyl tetraamine associated microphone to generate intermediate setback commanded, then imidazole intermediate with a setback commanded section chlorination reaction product obtained ingot quaternary Finally, the product ingot quaternary reaction with thiourea of ​​the title compound.

[0008] 进一步的,该方法具体包括下述步骤: [0008] Further, the method comprises the steps of:

[0009] (1)将己二酸在溶剂中溶解; [0009] (1) adipic acid is dissolved in a solvent;

[0010] (2)将步骤(1)中的溶液升温至105-115°c后,按己二酸与S己締四胺摩尔比为1:1. 4-1.6向步骤(1)的溶液中滴加S己締四胺,待S己締四胺滴加完成后,再升温至140-160°C下反应1. 5-2.化; After [0010] (2) The solution of step (1) was warmed to 105-115 ° c, S molar ratio of adipic acid with cyclohexyl tetraamine association of 1: 4-1.6 to 1 in step (1) was was added dropwise S-hexyl associated tetramine, S hexyl after completion of the dropwise associated tetramine, then heated to 140-160 ° C under the reaction of 1. 5-2.;

[0011] (3)再将温度升至220-230°C,进行成环反应,待反应1. 5-2.化后,成环反应结束, 然后在高温下蒸去溶剂W及过量的=己締四胺,得咪挫咐中间体; [0011] (3) then the temperature was raised to 220-230 ° C, for cyclization reaction, the reaction until 1. 5-2. Of the end of the reaction ring, and then the solvent was distilled off at elevated temperature and the excess of W = hexyl association tetraamine, imidazole fell to give intermediate commanded;

[0012] (4)按己二酸与氯化节摩尔比为1:2-2. 5的量将氯化节加至上述步骤(3)中所得的咪挫咐中间体中,在90-110°C下反应3-3.化,得到季锭化产物; [0012] (4) by the molar ratio of adipic acid chloride of section 1: the amount of 2-25 sections will be added to the above chloride in step (3) obtained in the intermediate commanded microphone setback, the 90- the reaction at 110 ° C 3-3, thereby obtaining an ingot quaternary product.;

[0013] (5)再向步骤(4)所得的季锭化产物中加入硫脈,加入的硫脈与步骤(4)中加入的氯化节的摩尔比为1:1-1. 5,在90-110°C下反应1. 2-1.她,得到目标化合物。 [0013] (5) again in step (4) with thiourea in step (4) was added in a molar ratio of chloride quaternary section ingot product resulting thiourea is added, is added 1: 1-15, the reaction 1. 2-1 at 90-110 ° C. she, to give the title compound.

[0014] 进一步的,所述步骤(1)中的溶剂为二甲苯。 [0014] Further, the solvent in step (a) is xylene.

[0015] 进一步的,所述步骤(2)中滴加S己締四胺采用恒压滴液漏斗,滴液速度控制在每8-12S-滴。 [0015] Further, the step (2) was added dropwise S cyclohexyl tetraamine association constant pressure dropping funnel, dropping the speed control in each 8-12S- drop.

[0016] 进一步的,所述步骤(3)中,是通过减压蒸馈方法蒸除溶剂及过量的=己締四胺, 采用油累,真空度控制在0.09-0.IMPa,温度控制在145-155°C。 [0016] Further, the step (3), is associated tetraamine = hexyl distilled off under reduced pressure by distilling off the solvent and method of feeding excess of oil tired employed, the degree of vacuum in 0.09-0.IMPa, temperature control 145-155 ° C.

[0017] 上述的化合物的合成过程为: [0017] The synthesis of the compound is:

[0018] [0018]

Figure CN104829539AD00041

[0019] 上述化合物可W在抗二氧化碳腐蚀中作为缓蚀剂应用。 [0019] W above compounds may be anti-dioxide etching applications as corrosion inhibitors.

[0020] 本发明具有W下有益效果: [0020] The present invention has the beneficial effects W:

[0021] 此种缓蚀剂在低温下的缓蚀性能表现优异,缓蚀剂的双季锭盐结构进一步提高了缓蚀剂的水溶性,能在低温下溶解在腐蚀溶液中,进而易于在钢铁表面吸附,此种缓蚀剂在低温下具有优良的抗C〇2腐蚀性能。 [0021] Such excellent corrosion inhibition performance at low temperatures, corrosion inhibitors diquaternary salt ingot structure further improves the corrosion inhibitor a water-soluble, can be dissolved in the etching solution at a low temperature, and thus liable to steel surface adsorption inhibitor such C〇2 having excellent resistance to corrosion at a low temperature.

具体实施方式 detailed description

[0022] -、制备实施例; [0022] - Preparation Example;

[002引制备实施例1 : [Preparation Example 1 002 primer:

[0024] 下述结构式的化合物; [0024] The compounds of the following formula;

[00巧] [00 clever]

Figure CN104829539AD00051

[0026] 上述化合物的制备方法,该方法包括先将己二酸与=己締四胺进行反应生成咪挫咐中间体,再将咪挫咐中间体与氯化节进行反应得季锭化产物,最后将季锭化产物与硫脈进行反应生成目标化合物。 Preparation [0026] The method of the above compounds, the process comprising first reacting adipic acid with = cyclohexyl tetraamine associated microphone to generate intermediate setback commanded, then imidazole intermediate with a setback commanded section chlorination reaction product obtained ingot quaternary Finally, the product ingot quaternary reaction with thiourea of ​​the title compound.

[0027] 进一步的,该方法具体包括下述步骤: [0027] Further, the method comprises the steps of:

[002引(1)将5. 85g己二酸(0. 04mol)在20ml二甲苯中溶解,己二酸与二甲苯的体积比为1:1 (通过己二酸的相对密度计算其体积,然后按照体积比加二甲苯); [002 Primer (1) 5. 85g of adipic acid (0. 04mol) was dissolved in 20ml of xylene, xylene and the volume ratio of adipic acid is 1: 1 (volume calculated by the relative density of adipic acid, xylene was then added in a volume ratio);

[002引似将步骤(1)中的溶液升温至ll0°C后,按己二酸与;己締四胺摩尔比为1:3向步骤(1)的溶液中滴加S己締四胺,S己締四胺的具体用量为17. 55g,S己締四胺采用恒压滴液漏斗滴加,滴液速度控制在每10s-滴,待=己締四胺滴加完成后,再升温至150°C 下反应化; [002 primer solution like after the step (1) is heated to ll0 ° C, according to adipic acid; molar ratio of cyclohexyl tetraamine association of 1: 3 solution of step (1) was added dropwise S-hexyl associated tetramine , the specific amount S is already associated tetraamine 17. 55g, S cyclohexyl tetraamine association constant pressure dropping funnel, dropping the speed control 10s- after each drop, until the association = cyclohexyl tetraamine addition was complete, then temperature was raised to 150 ° C for the reaction of;

[0030] (3)再将温度升至220°C,进行成环反应,待反应化后,成环反应结束,然后在高温下蒸去二甲苯W及过量的=己締四胺,具体是通过减压蒸馈方法蒸除二甲苯及过量的S己締四胺,采用油,累,真空度控制在0.095MPa,温度控制在150°C,最后得咪挫咐中间体12. 76g,收率87%; [0030] (3) then the temperature was raised to 220 ° C, for cyclization reaction, until the reaction of the end ring of the reaction, xylene was distilled off and the excess of W = cyclohexyl tetraamine association at high temperatures, in particular distilled off under reduced pressure by feeding method associated S hexyl tetraamine and the excess of xylene was distilled off, the use of oil, tired, the degree of vacuum controlled to 0.095MPa, a temperature controlled at 150 ° C, to give the final intermediate commanded setback microphone 12. 76g, yield 87%;

[0031] (4)按己二酸与氯化节摩尔比为1:2的量将氯化节加至上述步骤(3)中所得的咪挫咐中间体中,氯化节具体的加入量为10. 13g,然后在100°C下反应化,得到季锭化产物17. 28g,收率91%; [0031] (4) by the molar ratio of adipic acid chloride as Section 1: 2, the amount of chloride added to the above step section (3) obtained in the intermediate commanded microphone setback, the added amount of the specific section chloride of 10. 13g, followed by reaction of at 100 ° C, to obtain an ingot quaternary product 17. 28g, yield 91%;

[0032] (5)再向步骤(4)所得的季锭化产物中加入硫脈,加入的硫脈与步骤(4)中加入的氯化节的摩尔比为1:1,硫脈具体的加入量为6. 09g,然后在100°C下反应1.化,得到目标化合物16. 82g,收率80%。 [0032] (4) The resulting ingot quaternary product (5) was added again in step thiourea, thiourea is added in step (4) the molar ratio of the added section chloride 1: 1, in particular thiourea was added in an amount of 6. 09g, followed by reaction of 1 at 100 ° C, to give the title compound 16. 82g, 80% yield.

[003引制备实施例2 ; [Preparation Example 2 003 primer;

[0034] 下述结构式的化合物: [0034] The compound of the following structural formula:

[00巧] [00 clever]

Figure CN104829539AD00061

[0036] 上述化合物的制备方法,该方法包括先将己二酸与=己締四胺进行反应生成咪挫咐中间体,再将咪挫咐中间体与氯化节进行反应得季锭化产物,最后将季锭化产物与硫脈进行反应生成目标化合物。 Preparation [0036] The method of the above compounds, the process comprising first reacting adipic acid with = cyclohexyl tetraamine associated microphone to generate intermediate setback commanded, then imidazole intermediate with a setback commanded section chlorination reaction product obtained ingot quaternary Finally, the product ingot quaternary reaction with thiourea of ​​the title compound.

[0037] 进一步的,该方法具体包括下述步骤: [0037] Further, the method comprises the steps of:

[003引(1)将5. 85g己二酸在20ml二甲苯中溶解,己二酸与二甲苯的体积比为1:1 (通过己二酸的相对密度计算其体积,然后按照体积比加二甲苯); [003 Primer (1) 5. 85g of adipic acid were dissolved in 20ml of xylene, xylene and the volume ratio of adipic acid is 1: 1 (volume calculated by the relative density of adipic acid, and then added at a volume ratio of xylene);

[003引似将步骤(1)中的溶液升温至115°C后,按己二酸与;己締四胺摩尔比为1:2. 5 向步骤(1)的溶液中滴加S己締四胺,S己締四胺的具体用量为14. 62g,S己締四胺采用恒压滴液漏斗滴加,滴液速度控制在每8s-滴,待=己締四胺滴加完成后,再升温至140°C下反应2.化; [003 primer solution like after the step (1) is warmed to 115 ° C, according to adipic acid; molar ratio of cyclohexyl tetraamine association of 1: 25 to step (1) was added dropwise S hexyl associated after tetraamine, the specific amount S is already associated tetraamine 14. 62g, S cyclohexyl tetraamine association constant pressure dropping funnel, dropping speed control 8s- each drop, until the association = cyclohexyl tetraamine completion of the dropwise , then heated to 140 ° C 2. reaction of;

[0040] (3)再将温度升至230°C,进行成环反应,待反应2.化后,成环反应结束,然后在高温下蒸去二甲苯W及过量的=己締四胺,具体是通过减压蒸馈方法蒸除二甲苯及过量的S己締四胺,采用油累,真空度控制在0.09MPa,温度控制在155°C,最后得咪挫咐中间体12. 17g,收率:83% ; [0040] (3) then the temperature was raised to 230 ° C, for cyclization reaction, until the reaction of 2, the end of the cyclization reaction, and then xylene was distilled off at elevated temperature and the excess of W = cyclohexyl tetraamine association, in particular by evaporation under reduced pressure the xylene was distilled off and the feeding method of an excess of S-hexyl association tetramine, tired by oil, the degree of vacuum at 0.09MPa, temperature controlled at 155 ° C, to give the final intermediate commanded setback microphone 12. 17g, yield: 83%;

[0041] (4)按己二酸与氯化节摩尔比为1:2. 5的量将氯化节加至上述步骤(3)中所得的咪挫咐中间体中,氯化节具体的加入量为12. 66g,在90°C下反应3.化,得到季锭化产物16. 12g,收率:89% ; [0041] (4) by the molar ratio of adipic acid chloride of section 1: the amount of the 25 sections of the chloride added to the above step (3) obtained in the intermediate commanded microphone setback, the specific section chloride was added in an amount of 12. 66g, reaction of 3 at 90 ° C, to obtain an ingot quaternary product 16. 12g, yield: 89%;

[0042] (5)再向步骤(4)所得的季锭化产物中加入硫脈,加入的硫脈与步骤(4)中加入的氯化节的摩尔比为1:1. 5,硫脈具体的加入量为18. 99g,在90°C下反应1.化,得到目标化合物14.91g,收率;76%。 (4) the molar ratio of quaternary ingot product obtained [0042] (5) again in step (4) was added thiourea, and thiourea is added to the step section chloride is added to 1: 1 5, thiourea the specific amount added 18. 99g, reaction of 1 at 90 ° C, to give the title compound 14.91g, yield; 76%.

[004引制备实施例3 ; [Preparation Example 3 004 primer;

[0044] 下述结构式的化合物: [0044] The compound of the following structural formula:

[00451 [00451

Figure CN104829539AD00062

[0046] 上述化合物的制备方法,该方法包括先将己二酸与=己締四胺进行反应生成咪挫咐中间体,再将咪挫咐中间体与氯化节进行反应得季锭化产物,最后将季锭化产物与硫脈进行反应生成目标化合物。 Preparation [0046] The method of the above compounds, the process comprising first reacting adipic acid with = cyclohexyl tetraamine associated microphone to generate intermediate setback commanded, then imidazole intermediate with a setback commanded section chlorination reaction product obtained ingot quaternary Finally, the product ingot quaternary reaction with thiourea of ​​the title compound.

[0047] 进一步的,该方法具体包括下述步骤: [0047] Further, the method comprises the steps of:

[004引(1)将5. 86g己二酸在20ml二甲苯中溶解,己二酸与二甲苯的体积比为1:1 (通过己二酸的相对密度计算其体积,然后按照体积比加二甲苯); [004 Primer (1) 5. 86g of adipic acid were dissolved in 20ml of xylene, xylene and the volume ratio of adipic acid is 1: 1 (volume calculated by the relative density of adipic acid, and then added at a volume ratio of xylene);

[0049] (2)将步骤(1)中的溶液升温至105°C后,按己二酸与S己締四胺摩尔比为1:2. 2 向步骤(1)的溶液中滴加S己締四胺,S己締四胺的具体用量为12. 86g,S己締四胺采用恒压滴液漏斗滴加,滴液速度控制在每12s-滴,待=己締四胺滴加完成后,再升温至160°C下反应1.化; After [0049] (2) The step (1) was warmed to 105 ° C, and the molar ratio of S-hexyl adipate association tetraamine is 1: 2 to 2 in step (1) was added dropwise S hexyl association tetraamine, the specific amount S is already associated tetraamine 12. 86g, S cyclohexyl tetraamine association constant pressure dropping funnel, dropping the speed control in each 12s- dropwise until solution of tetraamine = hexyl associative after completion, the reaction was then heated to 160 ° C 1. technology;

[0050] (3)再将温度升至225°C,进行成环反应,待反应1.化后,成环反应结束,然后在高温下蒸去二甲苯W及过量的=己締四胺,具体是通过减压蒸馈方法蒸除二甲苯及过量的S己締四胺,采用油累,真空度控制在0.IMPa,温度控制在145°C,最后得咪挫咐中间体13. 05g,收率;89%; [0050] (3) then the temperature was raised to 225 ° C, for cyclization reaction, of 1. After the reaction, the end of the cyclization reaction, and then xylene was distilled off at elevated temperature and the excess of W = cyclohexyl tetraamine association, specifically S cyclohexyl tetraamine associative method by feeding distilled off under reduced pressure and the excess of xylene was distilled off, the oil accumulated employed, the degree of vacuum in 0.IMPa, temperature controlled at 145 ° C, and finally fell commanded to give intermediate 13. 05g microphone yield; 89%;

[0051] (4)按己二酸与氯化节摩尔比为1:2. 2的量将氯化节加至上述步骤(3)中所得的咪挫咐中间体中,氯化节具体的加入量为11. 14g,在90°C下反应3.化,得到季锭化产物16. 70g,收率;86%; [0051] (4) by the molar ratio of adipic acid chloride of section 1: the amount of the 22 sections of the chloride added to the above step (3) obtained in the intermediate commanded microphone setback, the specific section chloride was added in an amount of 11. 14g, reaction of 3 at 90 ° C, to obtain an ingot quaternary product 16. 70g, yield; 86%;

[0052] (5)再向步骤(4)所得的季锭化产物中加入硫脈,加入的硫脈与步骤(4)中加入的氯化节的摩尔比为1:1. 3,硫脈具体的加入量为5. 15g,在110°C下反应1.她,得到目标化合物16.66g,收率;82%。 (4) the molar ratio of quaternary ingot product obtained [0052] (5) again in step (4) was added thiourea, and thiourea is added to the step section chloride is added to 1: 13, thiourea the specific amount added 5. 15g, reaction at 110 ° C for 1 her, to give the title compound 16.66 g, yield; 82%.

[005引二、实验例; [005 cited two, experimental examples;

[0054] 通过失重法对本发明制备实施例1所合成的己二酸双咪挫咐衍生物缓蚀剂在抗C02腐蚀方面进行评价: Inhibitor was evaluated in an anti-corrosion synthesized C02 bis- imidazole derivative setback commanded Example [0054] embodiment of the present invention are prepared by a weight loss method:

[00巧]1、实验准备; [00 Qiao] 1, experimental preparation;

[0056] ①通过失重法对本发明所合成的己二酸双咪挫咐衍生物缓蚀剂在抗C02腐蚀方面进行评价,参照标准SY-T5273-2000《油田采出水用缓蚀剂性能评价方法》,试样采用P110钢,将P110钢加工成15mmX30mmX2mm大小的钢片,试验前将钢片用400,600,800, 1200目的金相砂子依次打磨,用丙酬、无水己醇依次清洗后将其放置干燥箱中W备使用。 [0056] ① by weight loss of the inhibitor of the present invention synthesized bis- imidazole derivative setback commanded C02 evaluated in the anti-corrosion, the reference standard SY-T5273-2000 "Corrosion Inhibitor Performance Evaluation Method oilfield produced water "steel sample using P110, P110 will be processed into steel 15mmX30mmX2mm size steel, steel with 400,600,800 prior to testing, the purpose of metallurgical sand 1200 sequentially polished with propan pay anhydrous hexanol placed sequentially after washing dried W box ready for use.

[0057] ②配置3%化C1溶液作为腐蚀介质溶液。 [0057] ② arranged as a 3% solution of C1 corrosive solution.

[0058] 2、实验过程及结果; [0058] 2, and the results of the experiment;

[0059] 在温度为333K,饱和二氧化碳条件下评价72h。 [0059] at a temperature of 333K, saturated with carbon dioxide under the conditions evaluated 72h. 失重法评价结果得出缓蚀剂在lOOmg/L时,缓蚀剂效率为97. 06%。 The evaluation results in weight loss corrosion inhibitor obtained lOOmg / L, the corrosion inhibitor efficiency was 97.06%.

[0060] 在低温313K下,饱和二氧化碳条件下评价72h。 [0060] at low temperatures 313K, saturated with carbon dioxide under the conditions evaluated 72h. 失重法评价结果得出缓蚀剂在lOOmg/L时,缓蚀剂效率可达到99%。 The evaluation results are obtained corrosion weight loss method at lOOmg / L, corrosion inhibitor efficiency can reach 99%.

[0061] 实验得出,此种缓蚀剂在低温下的缓蚀性能表现优异,说明缓蚀剂的双季锭盐结构进一步提高了缓蚀剂的水溶性,能在低温下溶解在腐蚀溶液中,进而易于在钢铁表面吸附,研究表明,此种缓蚀剂在低温下具有优良的抗C〇2腐蚀性能。 [0061] Experimental results, such corrosion inhibition performance is excellent at low temperatures, the ingot described diquaternary salt structure further improves the corrosion inhibitor is a water-soluble, can be dissolved in the etching solution at a low temperature in further easily adsorbed on the steel surface, studies show that this inhibitor has excellent corrosion resistance at low temperatures C〇2. 然而针对C02腐蚀,目前的研究中,效果较好的缓蚀剂,其缓蚀率基本可达到80 % -98. 5 %左右,且基本是经过复配之后得到。 However, for C02 corrosion, the present study, the better the corrosion inhibitor, the inhibition rate basically can reach 80% -98 5%, and basically get through after complex. 而本发明所合成的缓蚀剂能在未经复配的情况下,其抗C〇2腐蚀的缓蚀率最高可达到99 %,在低温下尤其具有优良的抗C〇2腐蚀性能。 The present invention is synthesized and corrosion inhibitors without the compound, which is an anti-corrosion C〇2 inhibition could be up to 99%, in particular, has excellent resistance to corrosion at a low temperature C〇2.

[0062]=、通过失重法对本发明制备实施例2和制备实施例3所合成的己二酸双咪挫咐衍生物缓蚀剂继续进行抗C〇2腐蚀方面评价,所得结果与上述实验例中制备实施例1的缓蚀效果一致。 [0062] =, and Synthesis Example 3 Preparation of bis- imidazole derivative setback commanded continued corrosion inhibitors embodiment aspect evaluation, experimental results obtained with the above-described embodiments by weight loss anti C〇2 embodiment of the present invention prepared in Example 2 prepared in the Example 1 inhibition embodiments consistent results.

Claims (7)

1. 下述结构式的化合物: 1. The compound of the following structural formula:
Figure CN104829539AC00021
2. 根据权利要求1化合物的制备方法,其特征在于:该方法包括先将己二酸与三乙烯四胺进行反应生成咪唑啉中间体,再将咪唑啉中间体与氯化苄进行反应得季铵化产物,最后将季铵化产物与硫脲进行反应生成目标化合物。 The method of preparing a compound as claimed in claim 1, wherein: the first method comprises adipic acid and triethylene tetramine imidazoline intermediate for reaction, and then imidazoline intermediate obtained is reacted with benzyl chloride quaternary quaternized product finally quaternized reaction product with thiourea to generate the title compound.
3. 根据权利要求2化合物的制备方法,其特征在于:该方法包括下述步骤: (1) 将己二酸在溶剂中溶解; (2) 将步骤(1)中的溶液升温至105-115 °C后,按己二酸与三乙烯四胺摩尔比为1:1.4-1.6向步骤(1)的溶液中滴加三乙烯四胺,待三乙烯四胺滴加完成后,再升温至140-160°C下反应I. 5-2. 5h ; (3) 再将温度升至220-230°C,进行成环反应,待反应I. 5-2. 5h后,成环反应结束,然后在高温下蒸去溶剂以及过量的三乙烯四胺,得咪唑啉中间体; (4) 按己二酸与氯化苄摩尔比为1:2-2. 5的量将氯化苄加至上述步骤(3)中所得的咪唑啉中间体中,在90-110°C下反应3-3. 5h,得到季铵化产物; (5) 再向步骤⑷所得的季铵化产物中加入硫脲,加入的硫脲与步骤⑷中加入的氯化苄的摩尔比为1:1-1. 5,在90-110°C下反应I. 2-1. 8h,得到目标化合物。 3. A method for preparing a compound according to claim 2, characterized in that: the method comprising the steps of: (1) dissolving the adipic acid in a solvent; (2) the solution of step (1) is heated to 105-115 after ° C, according to a molar ratio of adipic acid with triethylenetetramine of 1: 1.4-1.6 after step (1) was added dropwise triethylenetetramine, triethylenetetramine dropwise until complete, then heated to 140 reaction at -160 ° C I. 5-2 5h; (3) the temperature was raised to 220-230 ° C, for cyclization reaction, be reacted I. after 5-2 5h, the end of the cyclization reaction, then. the solvent was evaporated at an elevated temperature and an excess of triethylene tetramine to give intermediate imidazoline; (4) by the molar ratio of adipic acid with benzyl chloride is 1: 2-25 quantity will benzyl chloride added to the above. step (3) in the resulting imidazoline intermediate, 3-3 5h the reaction at 90-110 ° C, to obtain quaternized product;. (5) step ⑷ again resulting quaternized product was added thiourea the molar ratio of thiourea was added ⑷ step was added benzyl chloride is 1: 1-15, I. 2-1 8h the reaction at 90-110 ° C, to give the title compound.
4. 根据权利要求3化合物的制备方法,其特征在于:所述步骤(1)中的溶剂为二甲苯。 4. A method of preparing a compound according to claim 3, wherein: said solvent in step (a) is xylene.
5. 根据权利要求3化合物的制备方法,其特征在于:所述步骤⑵中滴加三乙烯四胺采用恒压滴液漏斗,滴液速度控制在每8-12s -滴。 The method for preparing a compound according to claim 3, wherein: said step ⑵ triethylenetetramine was added dropwise using a constant pressure funnel, dropping the speed control in each 8-12s - drop.
6. 根据权利要求3化合物的制备方法,其特征在于:所述步骤(3)中,是通过减压蒸馏方法蒸除溶剂及过量的三乙烯四胺,采用油泵,真空度控制在0.09-0.1 MPa,温度控制在145-155°C。 6. A method of preparing a compound according to claim 3, wherein: said step (3), is triethylenetetramine by distillation under reduced pressure and excess solvent was distilled off using an oil pump, the degree of vacuum in the 0.09-0.1 MPa, temperature controlled at 145-155 ° C.
7. 权利要求1中的化合物在抗二氧化碳腐蚀中作为缓蚀剂的应用。 7. The compound of claim 1 in use as an anti-etching the carbon dioxide corrosion inhibitor.
CN 201510172494 2015-04-13 2015-04-13 Bis- imidazoline derivatives, their preparation and use as inhibitors of the derivatives CN104829539B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 201510172494 CN104829539B (en) 2015-04-13 2015-04-13 Bis- imidazoline derivatives, their preparation and use as inhibitors of the derivatives

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN 201510172494 CN104829539B (en) 2015-04-13 2015-04-13 Bis- imidazoline derivatives, their preparation and use as inhibitors of the derivatives

Publications (2)

Publication Number Publication Date
CN104829539A true true CN104829539A (en) 2015-08-12
CN104829539B CN104829539B (en) 2018-02-27

Family

ID=53807782

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 201510172494 CN104829539B (en) 2015-04-13 2015-04-13 Bis- imidazoline derivatives, their preparation and use as inhibitors of the derivatives

Country Status (1)

Country Link
CN (1) CN104829539B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105237479A (en) * 2015-10-19 2016-01-13 西安石油大学 Preparation method of octaacetate amphoteric imidazoline iron ion stabilizer
CN105542737A (en) * 2015-12-10 2016-05-04 深圳市创智材料科技有限公司 Preparation method and application of high-temperature high-pressure corrosion inhibitor capable of resisting corrosion by H2S and CO2
CN106543083A (en) * 2016-11-04 2017-03-29 中海油天津化工研究设计院有限公司 Adsorbed film type imidazoline corrosion inhibitor and preparing method thereof

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008096272A (en) * 2006-10-12 2008-04-24 Jeol Ltd Gas chromatography system
CN101230260A (en) * 2007-11-01 2008-07-30 新疆德蓝科技有限公司 Compound inhibitor for exploitation of oil-gas field and preparation method thereof
CN101280222A (en) * 2008-06-02 2008-10-08 中国石油化工集团公司;中国石化集团洛阳石油化工工程公司 Water-soluble corrosion inhibitor, preparation and application thereof
CN101613622A (en) * 2009-07-29 2009-12-30 中国石油化工集团公司;中国石化集团洛阳石油化工工程公司;洛阳高新龙浦石油化工开发公司 Composite inhibiter and preparation method and application thereof
CN102071427A (en) * 2010-12-14 2011-05-25 中国石油天然气股份有限公司吉林油田分公司采油工艺研究院 Corrosion inhibitor for inhibiting corrosion of high-temperature high-pressure carbon dioxide and preparation method thereof
CN102321463A (en) * 2011-06-14 2012-01-18 北京科技大学 Sulfur-containing bis-imidazoline type carbon dioxide corrosion inhibitor and preparation method thereof
CN103059825A (en) * 2011-10-18 2013-04-24 中国石油化工股份有限公司 Corrosion inhibitor for oil wells and preparation method
CN103668215A (en) * 2013-11-26 2014-03-26 中国海洋石油总公司 Composite corrosion inhibitor resisting to corrosion CO2/H2S/HCl corrosion

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008096272A (en) * 2006-10-12 2008-04-24 Jeol Ltd Gas chromatography system
CN101230260A (en) * 2007-11-01 2008-07-30 新疆德蓝科技有限公司 Compound inhibitor for exploitation of oil-gas field and preparation method thereof
CN101280222A (en) * 2008-06-02 2008-10-08 中国石油化工集团公司;中国石化集团洛阳石油化工工程公司 Water-soluble corrosion inhibitor, preparation and application thereof
CN101613622A (en) * 2009-07-29 2009-12-30 中国石油化工集团公司;中国石化集团洛阳石油化工工程公司;洛阳高新龙浦石油化工开发公司 Composite inhibiter and preparation method and application thereof
CN102071427A (en) * 2010-12-14 2011-05-25 中国石油天然气股份有限公司吉林油田分公司采油工艺研究院 Corrosion inhibitor for inhibiting corrosion of high-temperature high-pressure carbon dioxide and preparation method thereof
CN102321463A (en) * 2011-06-14 2012-01-18 北京科技大学 Sulfur-containing bis-imidazoline type carbon dioxide corrosion inhibitor and preparation method thereof
CN103059825A (en) * 2011-10-18 2013-04-24 中国石油化工股份有限公司 Corrosion inhibitor for oil wells and preparation method
CN103668215A (en) * 2013-11-26 2014-03-26 中国海洋石油总公司 Composite corrosion inhibitor resisting to corrosion CO2/H2S/HCl corrosion

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
张光华,等: "硫脲基烷基咪唑啉季铵盐缓蚀剂在油水两相中的传质性能", 《化工进展》 *
张光华,等: "硫脲基烷基咪唑啉类缓蚀剂的制备、缓蚀性能及其机理", 《材料保护》 *
李志远,等: "双咪唑啉季铵盐的合成与缓蚀性能研究", 《腐蚀与防护》 *
梅平,等: "酸化用双环咪唑啉延安眼缓蚀剂的合成与性能评价试验", 《石油天然气学报(江汉石油学院学报)》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105237479A (en) * 2015-10-19 2016-01-13 西安石油大学 Preparation method of octaacetate amphoteric imidazoline iron ion stabilizer
CN105237479B (en) * 2015-10-19 2017-12-12 西安石油大学 Preparation eight amphoteric imidazoline acetate ferric ion stabilizer
CN105542737A (en) * 2015-12-10 2016-05-04 深圳市创智材料科技有限公司 Preparation method and application of high-temperature high-pressure corrosion inhibitor capable of resisting corrosion by H2S and CO2
CN106543083A (en) * 2016-11-04 2017-03-29 中海油天津化工研究设计院有限公司 Adsorbed film type imidazoline corrosion inhibitor and preparing method thereof

Also Published As

Publication number Publication date Type
CN104829539B (en) 2018-02-27 grant

Similar Documents

Publication Publication Date Title
Zhang et al. Molecular modeling of the inhibition mechanism of 1-(2-aminoethyl)-2-alkyl-imidazoline
CN104677778A (en) Device and method for evaluating temporarily freezing plugging properties of coalbed methane in process of fracturing
CN101613598A (en) Inhibitor restraining H2S/CO2 corrosion and preparation method thereof
CN103521697A (en) Graphite casting coating
CN101928309A (en) Synthesis method of 3,2',6'-tri-N-acetyl gentamicin Cla
CN102071005A (en) High-temperature acidification corrosion inhibitor and preparation method thereof
CN103820795A (en) Efficient compounded corrosion inhibitor and preparation method and application thereof
CN103436247A (en) Retarded-acid acidizing fluid
CN103059825A (en) Corrosion inhibitor for oil wells and preparation method
CN102051622A (en) Carbon steel acidizing corrosion inhibitor
CN104787736A (en) Method for large-scale preparation of black phosphorus with bilayer structure
CN103074050A (en) Anti-scaling multi-hydrogen retarded acid for highly argillaceous sandstone reservoir
CN103055539A (en) Method for extracting lithium salts in lithium-containing brine
CN102382638A (en) Application of pyridine compound for preparing acidization corrosion inhibitors
CN104830291A (en) Compound low dosage natural gas hydrate inhibitor
James et al. Adsorption behaviour of pyrazolo [3, 4-b] pyridine on corrosion of stainless steel in HCl solutions
Zhu et al. Imidazolineson's Corrosion Inhibition in Acide Solution for A3 Steel
CN103289671A (en) Inhibitor and preparation method
CN101629072A (en) Oil field acidification high temperature inhibiter and preparation method thereof
CN105295886A (en) Composite retarded acid
CN102586782A (en) Corrosion inhibitor and preparation and application thereof
CN105482802A (en) On-line injection acidification acid fluid system for water injection well and preparation method of on-line injection acidification acid fluid system
CN102108515A (en) Application of environment-friendly corrosion inhibitor to copper in seawater
CN102504199A (en) Preparation method of room-temperature self-crosslinking water-based epoxy resin
US8707720B2 (en) Hybrid vapor compression-absorption cycle

Legal Events

Date Code Title Description
C06 Publication
EXSB Decision made by sipo to initiate substantive examination
GR01
TR01