CN117343014A - Preparation method and application of rosin thiourea imidazole quaternary ammonium salt - Google Patents
Preparation method and application of rosin thiourea imidazole quaternary ammonium salt Download PDFInfo
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- CN117343014A CN117343014A CN202311648811.8A CN202311648811A CN117343014A CN 117343014 A CN117343014 A CN 117343014A CN 202311648811 A CN202311648811 A CN 202311648811A CN 117343014 A CN117343014 A CN 117343014A
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- quaternary ammonium
- rosin
- ammonium salt
- thiourea
- imidazole
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- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 title claims abstract description 87
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 title claims abstract description 87
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 title claims abstract description 87
- -1 thiourea imidazole quaternary ammonium salt Chemical class 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000005260 corrosion Methods 0.000 claims abstract description 90
- 230000007797 corrosion Effects 0.000 claims abstract description 88
- 230000000813 microbial effect Effects 0.000 claims abstract description 24
- 230000002401 inhibitory effect Effects 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 19
- 239000003112 inhibitor Substances 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 14
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 14
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000012043 crude product Substances 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- 230000001580 bacterial effect Effects 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- JVVXZOOGOGPDRZ-SLFFLAALSA-N [(1R,4aS,10aR)-1,4a-dimethyl-7-propan-2-yl-2,3,4,9,10,10a-hexahydrophenanthren-1-yl]methanamine Chemical compound NC[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 JVVXZOOGOGPDRZ-SLFFLAALSA-N 0.000 claims description 7
- 239000007769 metal material Substances 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 6
- 238000003818 flash chromatography Methods 0.000 claims description 5
- 238000010898 silica gel chromatography Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000012258 culturing Methods 0.000 claims description 3
- 238000010828 elution Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 claims description 2
- 239000003480 eluent Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 241000894006 Bacteria Species 0.000 abstract description 15
- 230000005764 inhibitory process Effects 0.000 abstract description 15
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 10
- 238000000840 electrochemical analysis Methods 0.000 abstract description 9
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 abstract description 8
- 238000004458 analytical method Methods 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 238000012512 characterization method Methods 0.000 abstract description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 abstract description 4
- 241000192125 Firmicutes Species 0.000 abstract description 3
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 3
- 230000002209 hydrophobic effect Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000001228 spectrum Methods 0.000 abstract description 2
- 230000001954 sterilising effect Effects 0.000 abstract description 2
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 25
- 239000010962 carbon steel Substances 0.000 description 25
- 239000010935 stainless steel Substances 0.000 description 20
- 229910001220 stainless steel Inorganic materials 0.000 description 20
- 238000002474 experimental method Methods 0.000 description 18
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 14
- 239000001963 growth medium Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 241000607598 Vibrio Species 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 230000010287 polarization Effects 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 241000194108 Bacillus licheniformis Species 0.000 description 7
- 238000002791 soaking Methods 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 230000006378 damage Effects 0.000 description 5
- 239000002609 medium Substances 0.000 description 5
- 244000005700 microbiome Species 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229940126062 Compound A Drugs 0.000 description 4
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 229940041514 candida albicans extract Drugs 0.000 description 4
- 150000002540 isothiocyanates Chemical class 0.000 description 4
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- 239000012138 yeast extract Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000006278 bromobenzyl group Chemical group 0.000 description 3
- 230000003203 everyday effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CYDQOEWLBCCFJZ-UHFFFAOYSA-N 4-(4-fluorophenyl)oxane-4-carboxylic acid Chemical compound C=1C=C(F)C=CC=1C1(C(=O)O)CCOCC1 CYDQOEWLBCCFJZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- MQLVWQSVRZVNIP-UHFFFAOYSA-L ferrous ammonium sulfate hexahydrate Chemical compound [NH4+].[NH4+].O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MQLVWQSVRZVNIP-UHFFFAOYSA-L 0.000 description 2
- 150000004687 hexahydrates Chemical class 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 description 2
- 235000011009 potassium phosphates Nutrition 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- 239000001540 sodium lactate Substances 0.000 description 2
- 235000011088 sodium lactate Nutrition 0.000 description 2
- 229940005581 sodium lactate Drugs 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000012137 tryptone Substances 0.000 description 2
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960002233 benzalkonium bromide Drugs 0.000 description 1
- KHSLHYAUZSPBIU-UHFFFAOYSA-M benzododecinium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 KHSLHYAUZSPBIU-UHFFFAOYSA-M 0.000 description 1
- 230000032770 biofilm formation Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/61—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with hydrocarbon radicals, substituted by nitrogen atoms not forming part of a nitro radical, attached to ring nitrogen atoms
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
A preparation method and application of rosin thiourea imidazole quaternary ammonium salt belong to the technical field of microbial corrosion and protection. In order to find the environment-friendly quaternary ammonium salt with sterilization and corrosion resistance, the invention utilizes the natural chiral environment (hydrophobic) of rosin, and the rosin-based thiourea imidazole quaternary ammonium salt with environment-friendly effect is further prepared by connecting a fatty chain containing a thiourea unit with an imidazole quaternary ammonium salt unit (hydrophilic). The rosin thiourea imidazole quaternary ammonium salt obtained through electrochemical analysis, corrosion morphology characterization, corrosion weightlessness analysis and living dead cell characterization can reduce the metal corrosion current density, reduce the thickness of a biological film and realize the effect of inhibiting microbial corrosion. The rosin-based thiourea imidazole quaternary ammonium salt has wide antibacterial spectrum, has obvious inhibition effect on gram-negative bacteria and gram-positive bacteria under the condition of mass concentration of 0.05g/L, and is simple in preparation method, economical, efficient, low in cost, easy to obtain and suitable for large-scale production.
Description
Technical Field
The invention belongs to the field of metal microorganism corrosion and protection, and particularly relates to a preparation method of rosin thiourea imidazole quaternary ammonium salt and application of the rosin thiourea imidazole quaternary ammonium salt as a microorganism corrosion inhibitor.
Background
Microbial corrosion (Microbiologically influenced corrosion, MIC) refers to a phenomenon in which the life metabolic activity of microorganisms directly or indirectly causes corrosion degradation of metallic materials. It is reported that the economic loss caused by microbial corrosion in China exceeds 4000 hundred million yuan each year, accounting for 20% of the total corrosion loss. Sulfate reducing bacteria are one of the most dominant microorganisms responsible for microbial corrosion. The problems of petroleum pipeline leakage, ocean platform equipment failure and the like caused by sulfate reducing bacteria corrosion are urgent to be solved in the field of national industry. The first step of microbial corrosion is to form a biofilm on the surface of a metal material, so inhibition of biofilm formation is an effective means of microbial corrosion and control.
In recent years, green and environment-friendly corrosion inhibitors have been attracting more attention because of their good biodegradability and bio-friendliness. The quaternary ammonium salt is taken as an ionic salt, and is mainly N-containing heterocyclic compound to carry out quaternization reaction to obtain a corrosion inhibitor active molecule, and the corrosion inhibitor active molecule has excellent high temperature resistance, no special pungent smell and low toxicity when being used as a microbial corrosion inhibitor. However, the currently used quaternary ammonium salt corrosion-resistant material has some defects and damages, such as narrow antibacterial spectrum, is used as a low-efficiency corrosion-resistant material, has no killing effect on microorganisms such as fungi, tubercle bacillus, hydrophilic viruses and the like, is easily influenced by environment, and is easily influenced by factors such as pH value, water quality, temperature and the like. Part of the quaternary ammonium salt agent (such as quaternary ammonium benzalkonium bromide) can react with metal ions in the high-hardness water to reduce the effective concentration of the quaternary ammonium salt, so that the corresponding effect cannot be achieved. Meanwhile, certain damage is caused to the environment and organisms, so researchers are continually striving to find and synthesize the environment-friendly quaternary ammonium salt with sterilization and corrosion resistance.
Rosin is widely used as a main forest chemical source and has wide application in industry. Earlier studies show that the rosin quaternary ammonium salt has metal corrosion inhibition effect, but the problems of few structural types, single functionality and the like of the rosin quaternary ammonium salt exist. The invention is based on the diversity synthesis of rosin quaternary ammonium salt as a guide, and finds out the anti-microbial corrosion performance of the rosin quaternary ammonium salt. The natural chiral environment (hydrophobic) of rosin is utilized, the natural chiral environment is connected with an imidazole quaternary ammonium salt unit (hydrophilic) through a fatty chain containing a thiourea unit, and the corrosion inhibition effect is achieved through physical adsorption and chemical adsorption.
Disclosure of Invention
In order to overcome the defects of bacterial drug resistance, environmental harm, biological damage and the like in the use of the conventional quaternary ammonium salt as an anti-corrosion material, the invention provides a preparation method of the rosin thiourea imidazole quaternary ammonium salt as a microbial anti-corrosion material and application thereof. In order to solve the technical problems, the invention adopts the following technical scheme:
the preparation method of the rosin thiourea imidazole quaternary ammonium salt comprises the following steps:
step 1: n, N' -dicyclohexylcarbodiimide, carbon disulfide and dehydroabietylamine (compound A) dissolved in diethyl ether solution are mixed, stirred for reaction, thiourea is separated, and then solid isothiocyanate (compound B) is obtained through elution and separation.
Step 2: compound B and 3- (1H-imidazole) -1-propylamine (compound C) were added to dichloromethane and reacted with stirring to give crude product D without purification.
Step 3: and adding the crude product D and benzyl bromide into toluene solution, stirring for reaction, eluting and separating to obtain a white solid product, namely the rosin thiourea imidazole quaternary ammonium salt.
Said step ofIn step 1, the stirring reaction temperature was 0 o And C, the reaction time is 6-18 h.
In the step 1, the molar ratio of N, N' -dicyclohexylcarbodiimide to dehydroabietylamine=1:1-1:4.
In the step 1, the separation method is silica gel column chromatography, and the eluent comprises 25% of ethyl acetate by mass ratio: n-hexane=1:1 to 1:5.
In the step 2 and the step 3, stirring is carried out for 6-18 h in a nitrogen atmosphere.
In the step 3, the separation method is flash chromatography.
The application of the rosin thiourea imidazole quaternary ammonium salt as a microbial corrosion-resistant material comprises the following steps:
step 1: mixing the rosin thiourea imidazole quaternary ammonium salt with an ethanol solution to prepare an ethanol solution of the rosin thiourea imidazole quaternary ammonium salt as a corrosion inhibitor for standby.
Step 2: and adding a corrosion inhibitor of a rosin thiourea imidazole quaternary ammonium salt ethanol solution into the gram-negative sulfate reducing bacteria vibrio desulfur bacteria liquid under anaerobic conditions and the gram-positive bacillus licheniformis bacteria liquid under aerobic conditions containing the metal materials for culturing, and completing a corrosion inhibition experiment.
In the step 1, the mass concentration of the ethanol solution is 10-20%, and the mass concentration of the rosin thiourea imidazole quaternary ammonium salt ethanol solution is 1.0-2.0 g/L. In the step 2, the metal material is selected from carbon steel material and stainless steel material, more preferably X80 carbon steel material and 316L stainless steel material.
In the step 2, the gram-negative bacteria are sulfate reducing bacteria, namely vibrio desulfur, and the gram-positive bacteria are bacillus licheniformis.
The rosin thiourea imidazole quaternary ammonium salt prepared by the invention uses the same metal material as an experimental group by adding the corrosion inhibitor of the rosin thiourea imidazole quaternary ammonium salt ethanol solution and is used as a blank control group under the condition of not adding any microbial corrosion inhibitor, and the experimental group and the blank control group are simultaneously cultured.
The invention has the beneficial effects that: the preparation method is simple, economical and efficient. The preparation process of the rosin thiourea imidazole quaternary ammonium salt is 0 o And C, the reaction is carried out under the condition of mild reaction conditions, the synthesis steps are few and simple, the raw materials are cheap and easy to obtain, and the method is suitable for large-scale production.
The method is environment-friendly and is environment-friendly. The rosin radical is a natural compound extracted from plants, has little harm to human bodies and environment, and the prepared rosin radical thiourea imidazole quaternary ammonium salt can be used as an environment-friendly microbial inhibitor.
The metal corrosion current density is reduced, and the microbial corrosion is inhibited. Compared with water, the rosin thiourea imidazole quaternary ammonium salt prepared by the invention is easier to adsorb on the surface of metal to form a physical protective layer, and reduces the current density of metal corrosion, thereby playing a role in inhibiting microbial corrosion.
Reduce the film thickness and inhibit the microbial corrosion. The rosin thiourea imidazole quaternary ammonium salt prepared by the invention can kill bacteria and reduce the thickness of a biological film formed on the surface of metal, thereby playing a role in inhibiting microbial corrosion.
Strong antibacterial effect. The rosin-based thiourea imidazole quaternary ammonium salt prepared by the invention has extremely strong corrosion inhibition capability under the condition of the mass concentration of 0.05g/L, and has obvious inhibition effect on gram-negative bacteria and gram-positive bacteria and the effect of inhibiting the formation of a biofilm.
Detailed Description
The present invention will be described in further detail with reference to examples. The experimental reagents used in the following examples, unless otherwise specified, were all conventional biochemical reagents, and the experimental methods without specifying specific conditions were generally carried out according to conventional conditions. The quantitative experiments in the examples were all set up with more than three repeated experiments to avoid experimental errors.
The following examples were followed using the microbial corrosion inhibitor rosin thiourea imidazole quaternary ammonium salt ethanol solution configuration procedure: the rosin thiourea imidazole quaternary ammonium salt is prepared, mixed with 10-20% ethanol solution, filtered and prepared into the rosin thiourea imidazole quaternary ammonium salt ethanol solution with the mass concentration of 1.0-2.0 g/L.
The corrosion materials adopted in the embodiment are X80 carbon steel and 316L stainless steel, and the mass percentages of all components of the X80 carbon steel are as follows: 0.07% C,1.82% Mn,0.19% Si,0.045% S,0.045% P,0.17% Ni,0.01% Mo,0.026% Cr, fe the balance; the 316L stainless steel comprises the following components in percentage by mass: 0.019% of C,1.18% of Mn,0.43% of Si,10.5% of Ni,16.78% of Cr,2.09% of Mo,0.032% of P,0.0006% of S and Fe are the rest. The sizes of the metal materials used were 10mm ×10× 10mm ×5× 5 mm.
Example 1
At 0 o N, N' -dicyclohexylcarbodiimide (20 mmol,4.13 g), carbon disulfide (4.0 mL) and dehydroabietylamine (20 mmol,5.70g, compound A) in diethyl ether solution were mixed, and after 3h reaction was allowed to slowly warm to room temperature, stirring was continued for 12h. After separation of the precipitated thiourea by filtration, the solvent is removed at low pressure. After silica gel column chromatography, eluting with 25% ethyl acetate/n-hexane at a ratio of 1:3 to give isothiocyanate (compound B) as a white solid in 92% yield (6.0 g);
compound B (3.0 g) was reacted with 3- (1H-imidazole) -1-propylamine (10 mmol,1.25g, compound C) in dichloromethane (80 mL) under stirring for 12H under nitrogen atmosphere, and after refluxing, the solvent was removed at low pressure to give crude product D without purification;
the crude product D and bromobenzyl (1.0 equivalent) are added into toluene (10 mL) solution and stirred for 12h under nitrogen atmosphere for reaction, the solvent is removed under reduced pressure after refluxing, and the white solid product rosin-based thiourea imidazole quaternary ammonium salt is obtained after elution through flash column chromatography.
Example 2
At 0 o N, N' -dicyclohexylcarbodiimide (20 mmol,4.13 g), carbon disulphide (4.0 mL) and dehydroabietylamine (40 mmol,11.40g, compound A) in diethyl ether solution were mixed and allowed to slowly warm to room temperature over 3h before stirring for a further 6h. Filtering the sulfur to be precipitatedAfter urea separation, the solvent is removed at low pressure. After silica gel column chromatography, eluting with 25% ethyl acetate/n-hexane at a ratio of 1:1 to give isothiocyanate (compound B) as a white solid in a yield of 90% (5.87, g);
compound B (3.0 g) was reacted with 3- (1H-imidazole) -1-propylamine (10 mmol,1.25g, compound C) in dichloromethane (80 mL) under stirring for 12H under nitrogen atmosphere, and after refluxing, the solvent was removed at low pressure to give crude product D without purification;
the crude product D and bromobenzyl (1.0 equivalent) were added to a toluene (10 mL) solution and stirred under nitrogen for 6h to react, the solvent was removed under reduced pressure after refluxing, and the white solid product rosin-based thiourea imidazole quaternary ammonium salt was obtained by eluting after flash column chromatography.
Example 3
At 0 o N, N' -dicyclohexylcarbodiimide (20 mmol,4.13 g), carbon disulphide (4.0 mL) and dehydroabietylamine (80 mmol,22.84g, compound A) in diethyl ether solution were mixed and allowed to slowly warm to room temperature over 3h before stirring for a further 18h. After separation of the precipitated thiourea by filtration, the solvent is removed at low pressure. After silica gel column chromatography, eluting with 25% ethyl acetate/n-hexane at a ratio of 1:5 to give isothiocyanate (compound B) as a white solid in 89% yield (5.80 g);
compound B (3.0 g) was reacted with 3- (1H-imidazole) -1-propylamine (10 mmol,1.25g, compound C) in dichloromethane (80 mL) under stirring for 18H under nitrogen atmosphere, and after refluxing, the solvent was removed at low pressure to give crude product D without purification;
the crude product D and bromobenzyl (1.0 equivalent) were added to a toluene (10 mL) solution and stirred under nitrogen for 18h to react, the solvent was removed under reduced pressure after refluxing, and the white solid product rosin-based thiourea imidazole quaternary ammonium salt was obtained by eluting after flash column chromatography.
Example 4
The culture medium used in this example was ATCC1249 medium, which contains 1.0g/L of yeast extract, 5.0g/L of sodium citrate, 3.5g/L of sodium lactate, 1.0g/L of calcium sulfate, 1.0g/L of ammonium chloride, 2.0g/L of magnesium sulfate, 1.0g/L of hexahydrate and ferrous ammonium sulfate, and 0.5g/L of potassium phosphate.
1) Electrochemical analysis of corrosion resistance of rosin thiourea imidazole quaternary ammonium salt:
x80 steel is taken as a sample, a sample is inserted as an electrode, under anaerobic condition, a rosin thiourea imidazole quaternary ammonium salt ethanol solution is added into an ATCC1249 culture medium to 0.05g/L to be taken as an experiment group, the ATCC1249 culture medium without the rosin thiourea imidazole quaternary ammonium salt ethanol solution is taken as a blank control group, the same kind of X80 carbon steel working electrode is placed into the experiment group and the blank control group to be soaked for 7 days, and a three-electrode system is used, and the data such as open circuit potential, linear polarization resistance, electrochemical impedance and the like of the blank control group and the X80 carbon steel in the experiment group are tested every day by using an electrochemical workstation. After 7 days of soaking experiments, obtaining corrosion current density of the X80 carbon steel working electrode through Tafel analysis and fitting). Compared with the blank control group, the corrosion current density of the X80 carbon steel of the experimental group is 7.6 mu A/cm 2 （) Down to 1.6. Mu.A/cm 2 （) The corrosion inhibition rate is 79% (calculated by using a formula 1), and through electrochemical tests, the linear polarization resistance of the experimental group is found to be increased along with the addition of the rosin thiourea imidazole quaternary ammonium salt, so that the rosin thiourea imidazole quaternary ammonium salt has the effect of inhibiting microbial corrosion in a sterile state.
Equation 1: corrosion inhibition rate =。
: corrosion current density of the X80 carbon steel working electrode without rosin thiourea imidazole quaternary ammonium salt.
: corrosion current density of X80 carbon steel working electrode with rosin thiourea imidazole quaternary ammonium salt.
Example 5
The culture medium used in this example was ATCC1249 medium, which contains 1.0g/L of yeast extract, 5.0g/L of sodium citrate, 3.5g/L of sodium lactate, 1.0g/L of calcium sulfate, 1.0g/L of ammonium chloride, 2.0g/L of magnesium sulfate, 1.0g/L of hexahydrate and ferrous ammonium sulfate, and 0.5g/L of potassium phosphate. And adding 1% of sulfate reducing bacteria vibrio desulfur bacteria liquid into the prepared ATCC1249 culture medium for standby.
The confocal microscope used in this example was Zeiss LSM 900.
1) Electrochemical analysis of corrosion resistance of rosin thiourea imidazole quaternary ammonium salt.
X80 steel is used as a sample, a sample is inserted as an electrode, 0.05g/L of rosin thiourea imidazole quaternary ammonium salt ethanol solution is added into ATCC1249 culture medium of 1% sulfate reducing bacteria vibrio desulphurisation bacterial liquid under anaerobic condition to be used as an experimental group, and ATCC1249 culture medium of 1% sulfate reducing bacteria vibrio desulphurisation bacterial liquid without the rosin thiourea imidazole quaternary ammonium salt ethanol solution is used as a blank control group. The same kind of X80 carbon steel working electrode is put into an experiment group and a blank control group for 7 days to be cultured, and the data such as corrosion performance, open circuit potential, linear polarization resistance, electrochemical impedance and the like of the blank control group and the experiment group are tested every day by utilizing an electrochemical workstation. After 7 days of soaking experiments, obtaining corrosion current density of the X80 carbon steel working electrode through Tafel analysis and fitting). Compared with the blank control group, the corrosion current density of the X80 carbon steel of the experimental group is from 91.7 mu A/cm 2 （) Down to 5.5. Mu.A/cm 2 （) The corrosion inhibition rate was 94% (calculated using equation 1). Through electrochemical tests, the linear polarization resistance of the experimental group is found to be increased along with the addition of the rosin thiourea imidazole quaternary ammonium salt.
2) Corrosion weight loss analysis of corrosion resistance of rosin thiourea imidazole quaternary ammonium salt.
X80 carbon steel samples are put into 1% sulfate reducing bacteria vibrio desulphurizing bacteria bacterial liquid containing 0.05g/L of rosin thiourea imidazole quaternary ammonium salt ethanol solution to be used as an experimental group, the same X80 carbon steel samples as the experimental group are put into 1% sulfate reducing bacteria vibrio desulphurizing bacteria bacterial liquid without the rosin thiourea imidazole quaternary ammonium salt ethanol solution to be used as a blank control group, the experimental group and the blank control group are cultured for 7 days, and after corrosion products and biological films are removed, the weights W1 and W2 of samples before and after soaking experiments are measured by a balance. The X80 carbon steel sample immersed in ATCC1249 medium containing 1% of the sulfate reducing bacteria Vibrio desulfur liquid showed that the corrosion inhibition rate was 95% after 0.05g/L of the ethanol solution of the rosin-based thiomethylimidazole quaternary ammonium salt was added (calculated by using the formula 2).
Equation 2: corrosion inhibition rate =。
W 1 : mass of X80 carbon steel sample before soaking experiment.
W 2 : mass of X80 carbon steel sample after soaking experiment.
3) Corrosion morphology characterization of rosin thiourea imidazole quaternary ammonium salt corrosion resistance.
And (3) placing the X80 carbon steel sample into 1% sulfate reducing bacteria vibrio desulphurisation bacteria liquid containing 0.05g/L of rosin thiourea imidazole quaternary ammonium salt ethanol solution to serve as an experimental group, placing the same X80 carbon steel sample as the experimental group into 1% sulfate reducing bacteria vibrio desulphurisation bacteria liquid without the rosin thiourea imidazole quaternary ammonium salt ethanol solution to serve as a blank control group, culturing the experimental group and the blank control group for 7 days, removing corrosion products and biological films, and then using a scanning electron microscope to characterize the corrosion morphology. The X80 carbon steel samples of the experimental group were found to be smooth and free of significant corrosion pits, and the X80 carbon steel samples of the blank group had corrosion pits as deep as 20 microns.
4) Analysis of corrosion products of corrosion resistance of rosin thiourea imidazole quaternary ammonium salt:
x80 carbon steel samples are put into 1% sulfate reducing bacteria vibrio desulphurizing bacteria bacterial liquid containing 0.05g/L of rosin thiourea imidazole quaternary ammonium salt ethanol solution to be used as an experimental group, the same X80 carbon steel samples as the experimental group are put into 1% sulfate reducing bacteria vibrio desulphurizing bacteria bacterial liquid without the rosin thiourea imidazole quaternary ammonium salt ethanol solution to be used as a blank control group, and the experimental group and the blank control group are cultured for 7 days. The corrosion products formed on the surface of the X80 carbon steel pattern of the experimental group and the blank group were analyzed using the X-ray photoelectron spectroscopy technique. It was detected that the corrosion products under both conditions were predominantly FeS, and the addition of the rosin-based thiourea imidazole quaternary ammonium salt reduced the production of corrosion products without altering the nature of the corrosion products.
Example 6
The culture medium used in this example was LB (Lurica-Bertani) medium containing 5.0g/L of yeast extract, 10g/L of tryptone and 10g/L of sodium chloride.
1) Electrochemical analysis of corrosion resistance of rosin thiourea imidazole quaternary ammonium salt:
316L stainless steel is used as a sample, a sample is inserted as an electrode, 0.05g/L of rosin thiourea imidazole quaternary ammonium salt ethanol solution is added into LB culture medium under the aerobic condition to be used as an experiment group, the LB culture medium without the rosin thiourea imidazole quaternary ammonium salt ethanol solution is used as a blank control group, the same 316L stainless steel working electrode is placed into the experiment group and the blank control group to be soaked for 7 days, and the three-electrode system is used, so that the electrochemical workstation is used for testing data such as open circuit potential, linear polarization resistance, electrochemical impedance and the like of the 316L stainless steel of the experiment group and the blank control group every day. After 7 days of soaking experiments, obtaining corrosion current density of the 316L stainless steel working electrode through Tafel analysis fitting). Compared with the blank control group, the corrosion current density of the 316L stainless steel of the experimental group is 185nA/cm 2 （) Down to 16.3nA/cm 2 （) The corrosion inhibition rate was 91% (calculated using equation 1). Through electrochemical tests, the linear polarization resistance of the experimental group is found to be increased along with the addition of the rosin thiourea imidazole quaternary ammonium salt. The rosin thiourea imidazole quaternary ammonium salt has the effect of inhibiting microbial corrosion under the aseptic condition.
Example 7
The LB medium comprises the following components: yeast extract 5.0g/L, tryptone 10g/L, sodium chloride 10g/L. And adding 1% of bacillus licheniformis bacteria liquid into the prepared LB culture medium for standby.
The confocal microscope used in this example was Zeiss LSM 900.
1) Electrochemical analysis of corrosion resistance of rosin thiourea imidazole quaternary ammonium salt:
316L stainless steel is used as a sample, a sample is inserted as an electrode, 0.05g/L of rosin thiourea imidazole quaternary ammonium salt ethanol solution is added into LB culture medium containing 1% bacillus licheniformis bacteria liquid under the aerobic condition to be used as an experimental group, and the same 316L stainless steel working electrode as the experimental group is placed into LB culture medium containing 1% bacillus licheniformis bacteria liquid without rosin thiourea imidazole quaternary ammonium salt ethanol solution to be used as a blank control group. The experimental group and the control group were cultured for 7 days, and data such as open circuit potential, linear polarization resistance, electrochemical impedance, etc. of the 316L stainless steel in the experimental group and the blank control group were tested using an electrochemical workstation using a three-electrode system. After 7 days of electrochemical test, the polarization resistance values of the experimental groups are higher than those of the blank control group. After 7 days of culture, performing electrokinetic polarization test on the 316L stainless steel working electrode, and obtaining corrosion current density of the 316L stainless steel working electrode through Tafel analysis fitting). Compared with the blank control group, the corrosion current density of the 316L stainless steel of the experimental group is 55.4nA/cm 2 （) Down to 3.3 nA/cm 2 （) The corrosion inhibition rate was 94% (calculated using equation 1). The rosin thiourea imidazole quaternary ammonium salt has an inhibition effect on microbial corrosion.
2) Live and dead cell characterization of the preservative properties of the rosin-based thiourea imidazole quaternary ammonium salt:
the 316L stainless steel sample is put into 1% bacillus licheniformis bacteria liquid containing 0.05g/L of rosin thiourea imidazole quaternary ammonium salt ethanol solution to be used as an experimental group, the same 316L stainless steel sample as the experimental group is put into 1% bacillus licheniformis bacteria liquid without rosin thiourea imidazole quaternary ammonium salt ethanol solution to be used as a blank control group, the experimental group and the blank control group are cultured for 7 days, and a confocal microscope is utilized to characterize the biological film on the surface of the 316L stainless steel. The results showed that the 316L stainless steel of the experimental group showed a large number of dead cells, while the 316L stainless steel of the blank group did not show a large number of dead cells.
Claims (10)
1. The preparation method of the rosin thiourea imidazole quaternary ammonium salt is characterized by comprising the following steps of:
step 1: n, N' -dicyclohexylcarbodiimide, carbon disulfide and dehydroabietylamine dissolved in diethyl ether solution are mixed, stirred and reacted, and separated to obtain a solid isothiocyanate compound B;
step 2: adding the compound B and 3- (1H-imidazole) -1-propylamine into methylene dichloride, stirring, and carrying out reflux reaction to obtain a crude product D;
step 3: the crude product D reacts with benzyl bromide, and after the reaction is finished, the product rosin thiourea imidazole quaternary ammonium salt is obtained through elution and separation;
。
2. the method according to claim 1The preparation method of the rosin thiourea imidazole quaternary ammonium salt is characterized in that in the step 1, the stirring reaction temperature is 0 o And C, the reaction time is 6-18 h.
3. The method for preparing the rosin-based thiourea imidazole quaternary ammonium salt according to claim 1, wherein in the step 1, the molar ratio of N, N' -dicyclohexylcarbodiimide to dehydroabietylamine=1:1 to 1:4.
4. The preparation method of the rosin-based thiourea imidazole quaternary ammonium salt according to claim 1, wherein in the step 1, the separation method is a silica gel column chromatography, the eluent is 25% ethyl acetate and n-hexane, and the mass ratio is 1:1-1:5.
5. The preparation method of the rosin-based thiourea imidazole quaternary ammonium salt according to claim 1, wherein in the step 2 and the step 3, the stirring reaction time is 6-18 hours in a nitrogen atmosphere.
6. The method for preparing the rosin-based thiourea imidazole quaternary ammonium salt according to claim 1, wherein in the step 3, the separation method is flash chromatography.
7. A rosin-based thiourea imidazole quaternary ammonium salt which is characterized in that the rosin-based thiourea imidazole quaternary ammonium salt is prepared by the preparation method of any one of claims 1-6 and has a molecular formula of C 21 H 57 SN 4 Br。
8. The use of the rosin-based thiomethylimidazole quaternary ammonium salt as claimed in claim 7 as a microbial corrosion inhibitor, wherein the method of use comprises the steps of:
step 1: mixing the rosin thiourea imidazole quaternary ammonium salt with an ethanol solution to prepare a rosin thiourea imidazole quaternary ammonium salt ethanol solution serving as a corrosion inhibitor for standby;
step 2: and adding a rosin thiourea imidazole quaternary ammonium salt corrosion inhibitor into the gram-negative bacterial liquid and the gram-positive bacterial liquid containing the metal materials for culturing to fulfill the aim of inhibiting microbial corrosion.
9. The application of the rosin-based thiourea imidazole quaternary ammonium salt as a microbial corrosion inhibitor according to claim 8, wherein in the step 1, the mass concentration of the ethanol solution is 10-20%.
10. The application of the rosin thiourea imidazole quaternary ammonium salt as a microbial corrosion inhibitor according to claim 8, wherein in the step 1, the mass concentration of the rosin thiourea imidazole quaternary ammonium salt ethanol solution is 1.0-2.0 g/L.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1196373A (en) * | 1997-04-11 | 1998-10-21 | 中国林业科学研究院林产化学工业研究所 | Abietyl quaternary ammonium salt kind compound and preparation methd thereof |
| CN103881697A (en) * | 2014-03-14 | 2014-06-25 | 杭州央力科技有限公司 | Imidazoline compound corrosion inhibitor and preparation method thereof |
| US20140274688A1 (en) * | 2013-03-14 | 2014-09-18 | Dow Agrosciences Llc | Molecules having certain pesticidal utilities, and intermediates, compositions, and processes related thereto |
| CN105085402A (en) * | 2015-09-11 | 2015-11-25 | 陕西科技大学 | Rosin-based imidazoline quaternary ammonium salt compound and preparation method thereof |
| CN105859627A (en) * | 2016-04-27 | 2016-08-17 | 陕西科技大学 | Thiourea based rosin imidazoline quaternary ammonium salt compound and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1196373A (en) * | 1997-04-11 | 1998-10-21 | 中国林业科学研究院林产化学工业研究所 | Abietyl quaternary ammonium salt kind compound and preparation methd thereof |
| US20140274688A1 (en) * | 2013-03-14 | 2014-09-18 | Dow Agrosciences Llc | Molecules having certain pesticidal utilities, and intermediates, compositions, and processes related thereto |
| CN103881697A (en) * | 2014-03-14 | 2014-06-25 | 杭州央力科技有限公司 | Imidazoline compound corrosion inhibitor and preparation method thereof |
| CN105085402A (en) * | 2015-09-11 | 2015-11-25 | 陕西科技大学 | Rosin-based imidazoline quaternary ammonium salt compound and preparation method thereof |
| CN105859627A (en) * | 2016-04-27 | 2016-08-17 | 陕西科技大学 | Thiourea based rosin imidazoline quaternary ammonium salt compound and preparation method thereof |
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