CN105622471A - Preparation method of methionine derivative corrosion inhibitor - Google Patents

Preparation method of methionine derivative corrosion inhibitor Download PDF

Info

Publication number
CN105622471A
CN105622471A CN201610057222.6A CN201610057222A CN105622471A CN 105622471 A CN105622471 A CN 105622471A CN 201610057222 A CN201610057222 A CN 201610057222A CN 105622471 A CN105622471 A CN 105622471A
Authority
CN
China
Prior art keywords
methionine
fmoc
preparation
synthesis
derivant
Prior art date
Legal status (The legal status 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 status listed.)
Granted
Application number
CN201610057222.6A
Other languages
Chinese (zh)
Other versions
CN105622471B (en
Inventor
何毅
杨冉冉
周艳秋
范毅
卿大咏
马兰
詹迎青
陈钊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chengdu Heng Gu new Mstar Technology Ltd
Original Assignee
Southwest Petroleum University
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
Application filed by Southwest Petroleum University filed Critical Southwest Petroleum University
Priority to CN201610057222.6A priority Critical patent/CN105622471B/en
Publication of CN105622471A publication Critical patent/CN105622471A/en
Application granted granted Critical
Publication of CN105622471B publication Critical patent/CN105622471B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
    • 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
    • C23F11/16—Sulfur-containing compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)

Abstract

The invention discloses a preparation method of a methionine derivative corrosion inhibitor. The method comprises the following steps: synthesis of Fmoc-methionine: adding methionine and Fmoc-OSu into a DMF (N,N-dimethylformamide) solvent to react, and adding NaHCO3 to remove the solvent and residual amine compounds, thereby obtaining the product, wherein the yield is 78%; synthesis of Fmoc-methionine acyl chloride: adding the Fmoc-methionine into 25ml of CH2Cl2, and refluxing to react for 4 hours; and synthesis of Fmoc-methionine amide: after the acyl-chlorination reaction, directly adding into an equal mole of octadecylamine CH2Cl2 solution to obtain a yellow solid, and purifying the product by a chromatographic column separation process, wherein the eluting solution is composed of dichloromethane and methanol in a volume ratio of 20:1. According to the preparation method, the Fmoc- protective group is connected to the methionine molecule by amidation, and the adsorption site formed by the pi-electron-containing benzene ring enhances the adsorptivity of the corrosion inhibitor molecule. The hydrophobic long chain is connected to the methionine molecule to resist the attack of water molecules, so that a protective film is formed on the steel surface, thereby achieving the goal of corrosion inhibition.

Description

A kind of preparation method of methionine derivant corrosion inhibiter
Technical field
The invention belongs to chemical technology field, the preparation method particularly relating to a kind of methionine derivant corrosion inhibiter.
Background technology
Present stage many direct methionine are as corrosion inhibiter or are oxidized as methionine sulfoxide, therefore adopt hydrogen peroxide as oxidant, take 1.492g methionine 51ml deionized water dissolving, 30% hydrogen peroxide is diluted five times, it is slowly added dropwise the hydrogen peroxide 5.1ml after dilution again, there-necked flask is placed in constant temperature water bath 50 DEG C reaction 30min, reaction terminates rear 45 DEG C of backspins and steams major part water, stop rotation when remaining general three milliliters of water to steam, pour into and bottle is put into 45 DEG C of dry 12h in air dry oven, scrape white powder. Although by technique scheme it follows that be naturally easy to get as corrosion inhibiter methionine with methionine or methionine sulfoxide, but its molecular structure is very simple, not strong in steel surface adsorptivity, cause that corrosion mitigating effect is not very good, can be seen that interpolation 250mg L by polarizing-1The corrosion inhibition rate of N80 be can only achieve 72.08% as inhibition by methionine in 3%NaCl solution, and SEM and EDS finds out at interpolation methionine as corrosion inhibiter, and steel disc surface is corroded seriously, creates many corrosion products. These defects make application be restricted.
Summary of the invention
The preparation method that it is an object of the invention to provide a kind of methionine derivant corrosion inhibiter, it is intended to solve methionine molecular structure very simple, not strong in steel surface adsorptivity, cause the problem that corrosion mitigating effect is undesirable.
The preparation method that the present invention is achieved in that a kind of methionine derivant corrosion inhibiter, the preparation method of this methionine derivant corrosion inhibiter comprises the following steps:
Step one: synthesis Fmoc-methionine; 6mmol methionine and 6.3mmolFmoc-OSu are added reaction in 20mlDMF (DMF) solvent, is subsequently added 6.3mmolNaHCO3Remove solvent and remaining aminated compounds, be dried overnight in 50 DEG C of vacuum drying ovens, obtain products collection efficiency to 78%;
Step 2: synthesis Fmoc-methionine acyl chlorides; 4.42mmolFmoc-methionine is added 25mlCH2Cl2In, N2Protection, adds 4.42mmolSOCl2, heating to temperature reaches 50 DEG C, back flow reaction 4h;
Step 3: synthesis Fmoc-methionine amide; After acyl chloride reaction, the 18-amine. CH of amount of substance 4.42mmol such as it is directly added into2Cl2In solution, adding 0.5g natrium carbonicum calcinatum as acid binding agent, react 24h, obtain yellow solid, utilize chromatographic column partition method purified product at 50 DEG C, the volume ratio of eluent dichloromethane and methanol, dichloromethane and methanol is 20:1.
The chemical equation of synthesis Fmoc-methionine is as follows:
The chemical equation of synthesis Fmoc-methionine acyl chlorides is as follows:
The chemical equation of synthesis Fmoc-methionine amide is as follows:
The present invention has the advantage that and has the benefit effect that the preparation method of this methionine derivant corrosion inhibiter accesses Fmoc-blocking group, the adsorption site that the phenyl ring containing pi-electron is formed by amidation method on methionine molecule, increases the adsorptivity of inhibitor molecular; Methionine molecule accessing hydrophobic long-chain and stops the attack of hydrone so that it is forming protecting film thus reaching inhibition purpose at steel surface. By EIS impedance spectrogram it can be seen that add this methionine derivant corrosion inhibiter simply change the shape of resistance value not change impedance diagram, it was demonstrated that this kind of corrosion inhibiter is mainly by being adsorbed on metal surface effect. Tested by EDS it is recognized that, after adding methionine relative to blank sample, the atomic percent of oxygen element somewhat reduces to some extent, but surface carbon element ratio substantially increases after adding methionine derivant, almost without oxygen element, therefore may certify that methionine derivant can well suppress steel disc to corrode as corrosion inhibiter, and effect is substantially better than methionine, so methionine molecular structure being modified synthetic methionine derivant corrosion inhibiter, relative to methionine, there is better corrosion mitigating effect.
Accompanying drawing explanation
Fig. 1 is the flow chart of the preparation method of the methionine derivant corrosion inhibiter that the embodiment of the present invention provides;
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearly understand, below in conjunction with embodiment, the present invention is further elaborated. Should be appreciated that specific embodiment described herein is only in order to explain the present invention, is not intended to limit the present invention.
Below in conjunction with drawings and the specific embodiments, the application principle of the present invention is further described.
The preparation method of this methionine derivant corrosion inhibiter comprises the following steps:
S101: synthesis Fmoc-methionine; 6mmol methionine and 6.3mmolFmoc-OSu are added reaction in 20mlDMF (DMF) solvent, is subsequently added 6.3mmolNaHCO3Remove solvent and remaining aminated compounds, be dried overnight in 50 DEG C of vacuum drying ovens, obtain products collection efficiency to 78%; The chemical equation of synthesis Fmoc-methionine is as follows:
S102: synthesis Fmoc-methionine acyl chlorides; 4.42mmolFmoc-methionine is added 25mlCH2Cl2In, N2Protection, adds 4.42mmolSOCl2, heating to temperature reaches 50 DEG C, back flow reaction 4h; The chemical equation of synthesis Fmoc-methionine acyl chlorides is as follows:
S103: synthesis Fmoc-methionine amide; After acyl chloride reaction, the 18-amine. CH of amount of substance 4.42mmol such as it is directly added into2Cl2In solution, add 0.5g natrium carbonicum calcinatum as acid binding agent, at 50 DEG C, react 24h, obtain yellow solid. Utilizing chromatographic column partition method purified product, the volume ratio of eluent dichloromethane and methanol, dichloromethane and methanol is 20:1.
The chemical equation of synthesis Fmoc-methionine amide is as follows:
Use aminoacid based on methionine, on methionine molecule, access Fmoc-by amidation process and protect base and chain hydrophobic alkane, synthesize a kind of novel methionine derivant corrosion inhibiter. Synthesize the corrosion inhibiter of a kind of asepsis environment-protecting, add adsorption site and hydrophobic long-chain compared to methionine, improve corrosion mitigating effect. On methionine, connect Fmoc-blocking group and hydrophobic long-chain by the method success, and carried out corrosion mitigating effect evaluation and SEM observation steel disc surface corrosion pattern by electrochemistry experiment. Show to add 250mg L by electrochemistry experiment result-1The corrosion inhibition rate of N80 can be reached 86.94% by methionine derivant in 3%NaCl solution; By in the SEM figure after steel disc is soaked 72h in corrosive medium it appeared that add this hatching egg threonine derivative can substantially suppress corrosion.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all any amendment, equivalent replacement and improvement etc. made within the spirit and principles in the present invention, should be included within protection scope of the present invention.

Claims (4)

1. the preparation method of a methionine derivant corrosion inhibiter, it is characterised in that the preparation method of this methionine derivant corrosion inhibiter comprises the following steps:
Step one: synthesis Fmoc-methionine; 6mmol methionine and 6.3mmolFmoc-OSu are added reaction in 20mlDMF (DMF) solvent, is subsequently added 6.3mmolNaHCO3Remove solvent and remaining aminated compounds, be dried overnight in 50 DEG C of vacuum drying ovens, obtain products collection efficiency to 78%;
Step 2: synthesis Fmoc-methionine acyl chlorides; 4.42mmolFmoc-methionine is added 25mlCH2Cl2In, N2Protection, adds 4.42mmolSOCl2, heating to temperature reaches 50 DEG C, back flow reaction 4h;
Step 3: synthesis Fmoc-methionine amide; After acyl chloride reaction, the 18-amine. CH of amount of substance 4.42mmol such as it is directly added into2Cl2In solution, adding 0.5g natrium carbonicum calcinatum as acid binding agent, react 24h, obtain yellow solid, utilize chromatographic column partition method purified product at 50 DEG C, the volume ratio of eluent dichloromethane and methanol, dichloromethane and methanol is 20:1.
2. the preparation method of methionine derivant corrosion inhibiter as claimed in claim 1, it is characterised in that the chemical equation of synthesis Fmoc-methionine is as follows:
3. the preparation method of methionine derivant corrosion inhibiter as claimed in claim 1, it is characterised in that the chemical equation of synthesis Fmoc-methionine acyl chlorides is as follows:
4. the preparation method of methionine derivant corrosion inhibiter as claimed in claim 1, it is characterised in that the chemical equation of synthesis Fmoc-methionine amide is as follows:
CN201610057222.6A 2016-01-27 2016-01-27 A kind of preparation method of methionine derivative corrosion inhibiter Active CN105622471B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610057222.6A CN105622471B (en) 2016-01-27 2016-01-27 A kind of preparation method of methionine derivative corrosion inhibiter

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610057222.6A CN105622471B (en) 2016-01-27 2016-01-27 A kind of preparation method of methionine derivative corrosion inhibiter

Publications (2)

Publication Number Publication Date
CN105622471A true CN105622471A (en) 2016-06-01
CN105622471B CN105622471B (en) 2017-07-25

Family

ID=56037857

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610057222.6A Active CN105622471B (en) 2016-01-27 2016-01-27 A kind of preparation method of methionine derivative corrosion inhibiter

Country Status (1)

Country Link
CN (1) CN105622471B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107459473A (en) * 2017-09-26 2017-12-12 唐山学院 A kind of methionine derivative corrosion inhibiter and its synthetic method for pickling iron and steel
CN108754510A (en) * 2018-06-22 2018-11-06 重庆工业职业技术学院 A kind of compound restrainer and preparation method thereof containing Schiff

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0442585A1 (en) * 1990-02-16 1991-08-21 Dsm N.V. Process for racemization of an optically active amino acid amide
JP4847732B2 (en) * 2005-10-25 2011-12-28 協和発酵バイオ株式会社 Cold remedy
CN104211619A (en) * 2014-08-19 2014-12-17 苏州维泰生物技术有限公司 Synthetic method for N-(2-Fmoc-aminoethyl)glycine methyl ester hydrochloride
CN104775123A (en) * 2015-04-13 2015-07-15 成都石大力盾科技有限公司 Preparation method of thiosemicarbazide imidazoline derivative corrosion inhibitor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0442585A1 (en) * 1990-02-16 1991-08-21 Dsm N.V. Process for racemization of an optically active amino acid amide
JP4847732B2 (en) * 2005-10-25 2011-12-28 協和発酵バイオ株式会社 Cold remedy
CN104211619A (en) * 2014-08-19 2014-12-17 苏州维泰生物技术有限公司 Synthetic method for N-(2-Fmoc-aminoethyl)glycine methyl ester hydrochloride
CN104775123A (en) * 2015-04-13 2015-07-15 成都石大力盾科技有限公司 Preparation method of thiosemicarbazide imidazoline derivative corrosion inhibitor

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
曹艺等: "含硫氨基酸及其衍生物酸洗缓蚀性能的研究", 《河北联合大学硕士学位论文》 *
程明焱等: "氨基酸类绿色缓蚀剂研究进展", 《清洗世界》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107459473A (en) * 2017-09-26 2017-12-12 唐山学院 A kind of methionine derivative corrosion inhibiter and its synthetic method for pickling iron and steel
CN108754510A (en) * 2018-06-22 2018-11-06 重庆工业职业技术学院 A kind of compound restrainer and preparation method thereof containing Schiff

Also Published As

Publication number Publication date
CN105622471B (en) 2017-07-25

Similar Documents

Publication Publication Date Title
Mobin et al. Boswellia serrata gum as highly efficient and sustainable corrosion inhibitor for low carbon steel in 1 M HCl solution: experimental and DFT studies
Kanehashi et al. Preparation and characterization of cardanol‐based epoxy resin for coating at room temperature curing
Umoren et al. Effect of halide ions on the corrosion inhibition of aluminium in alkaline medium using polyvinyl alcohol
CN102549001B (en) Carbon-dioxide absorbent and using method thereof
CN103555313B (en) A kind of imidazolium ionic liquid acidification corrosion inhibitor and preparation method thereof and application
Tebbji et al. The effect of 1′, 3, 5, 5′-tetramethyl-1′ H-1, 3′-bipyrazole on the corrosion of steel in 1.0 M hydrochloric acid
CN105622471A (en) Preparation method of methionine derivative corrosion inhibitor
Gowrani et al. Thermodynamical Analysis of MBTA on The Corrosion Inhibition of Brass In 3% NaCl Medium
Li et al. Rheological properties and enhanced oil recovery performance of a novel sulfonate polyacrylamide
CN103469211B (en) A kind of Polymeric imidazoline corrosion inhibitor and preparation method thereof
Li et al. Inhibition action and adsorption behavior of green inhibitor sodium carboxymethyl cellulose on copper
Musa et al. Inhibition of aluminum alloy corrosion in 0.5 M nitric acid solution by 4-4-dimethyloxazolidine-2-thione
Abdallah et al. Inhibition of zinc corrosion by some benzaldehyde derivatives in HCl solution
KR20120029377A (en) Method of dehydrating an ionic liquid
CN108642500B (en) Water-soluble bipyridyl gemini quaternary ammonium salt corrosion inhibitor and preparation method and application thereof
CN104774180A (en) Preparation method of dendriform imidazoline corrosion inhibitor containing amide bonds
Ameh et al. Characterization of Acacia sieberiana (AS) gum and their corrosion inhibition potentials for zinc in sulphuric acid medium
Ontiveros-Rosales et al. Use of the ionic liquid trioctylmethyl ammonium dodecanedioate as a corrosion inhibitor of steel in production water
AI-Mayouf et al. Inhibition of Type 304 Stainless Steel Corrosion in 2 M Sulfuric Acid by Some Benzoazoles Time and Temperature Effects
CN112694544B (en) Glycan derivative and preparation method and application thereof
CN104562039B (en) Corrosion inhibitor composition and preparation method thereof
Aly et al. New polymer syntheses, Part 44: Synthesis, characterization, and corrosion inhibition behavior of new polyurea derivatives based on diaryl ether in the polymers backbone
CN108165995B (en) Schiff base corrosion inhibitor for iron cultural relics and preparation and application thereof
Al-Sammarraie et al. Synthesis and characterization of benzothiazol derivative as a corrosion inhibitor for carbon steel in seawater
CA2490363A1 (en) Non-corrosive amphoteric surfactants and method of well treatment

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20190613

Address after: 611730 Runcheng Garden, 217 Shengli North Street, Deyuan Town, Pidu District, Chengdu City, Sichuan Province, 4 buildings and 2 units

Patentee after: Chengdu Heng Gu new Mstar Technology Ltd

Address before: 610500 Xindu Road, Xindu District, Chengdu, Sichuan Province, No. 8

Patentee before: Southwest Petroleum University

TR01 Transfer of patent right