CN106632277B - 一种防止腐蚀性硫腐蚀的金属钝化剂及其制备方法与应用 - Google Patents
一种防止腐蚀性硫腐蚀的金属钝化剂及其制备方法与应用 Download PDFInfo
- Publication number
- CN106632277B CN106632277B CN201610996910.9A CN201610996910A CN106632277B CN 106632277 B CN106632277 B CN 106632277B CN 201610996910 A CN201610996910 A CN 201610996910A CN 106632277 B CN106632277 B CN 106632277B
- Authority
- CN
- China
- Prior art keywords
- matal deactivator
- benzazoles
- application according
- preparation
- deactivator
- 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.)
- Expired - Fee Related
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 12
- 239000011593 sulfur Substances 0.000 title claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 5
- 230000000996 additive effect Effects 0.000 claims abstract description 5
- -1 benzazoles compound Chemical class 0.000 claims description 30
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 11
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 claims description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical class C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- 125000001976 hemiacetal group Chemical group 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 2
- 229940112669 cuprous oxide Drugs 0.000 claims description 2
- 150000004292 cyclic ethers Chemical class 0.000 claims description 2
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- LULAYUGMBFYYEX-UHFFFAOYSA-N metachloroperbenzoic acid Natural products OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 9
- 238000005260 corrosion Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- SAIKULLUBZKPDA-UHFFFAOYSA-N Bis(2-ethylhexyl) amine Chemical compound CCCCC(CC)CNCC(CC)CCCC SAIKULLUBZKPDA-UHFFFAOYSA-N 0.000 abstract 1
- 231100000614 poison Toxicity 0.000 abstract 1
- 239000003440 toxic substance Substances 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 9
- 238000004440 column chromatography Methods 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 238000000935 solvent evaporation Methods 0.000 description 9
- DKGAVHZHDRPRBM-UHFFFAOYSA-N tert-butyl alcohol Substances CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000009413 insulation Methods 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 5
- 239000012964 benzotriazole Substances 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- WGLUMOCWFMKWIL-UHFFFAOYSA-N dichloromethane;methanol Chemical compound OC.ClCCl WGLUMOCWFMKWIL-UHFFFAOYSA-N 0.000 description 3
- 238000003810 ethyl acetate extraction Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- LJUQGASMPRMWIW-UHFFFAOYSA-N 5,6-dimethylbenzimidazole Chemical compound C1=C(C)C(C)=CC2=C1NC=N2 LJUQGASMPRMWIW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- SKDGWNHUETZZCS-UHFFFAOYSA-N 2,3-ditert-butylphenol Chemical class CC(C)(C)C1=CC=CC(O)=C1C(C)(C)C SKDGWNHUETZZCS-UHFFFAOYSA-N 0.000 description 1
- DHTAIMJOUCYGOL-UHFFFAOYSA-N 2-ethyl-n-(2-ethylhexyl)-n-[(4-methylbenzotriazol-1-yl)methyl]hexan-1-amine Chemical compound C1=CC=C2N(CN(CC(CC)CCCC)CC(CC)CCCC)N=NC2=C1C DHTAIMJOUCYGOL-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- GVPWHKZIJBODOX-UHFFFAOYSA-N dibenzyl disulfide Chemical compound C=1C=CC=CC=1CSSCC1=CC=CC=C1 GVPWHKZIJBODOX-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/38—Heterocyclic nitrogen compounds
- C10M133/44—Five-membered ring containing nitrogen and carbon only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/38—Heterocyclic nitrogen compounds
- C10M133/44—Five-membered ring containing nitrogen and carbon only
- C10M133/46—Imidazoles
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/02—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using non-aqueous solutions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/223—Five-membered rings containing nitrogen and carbon only
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant Compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/223—Five-membered rings containing nitrogen and carbon only
- C10M2215/224—Imidazoles
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/14—Electric or magnetic purposes
- C10N2040/16—Dielectric; Insulating oil or insulators
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Lubricants (AREA)
Abstract
本发明涉及一种防止腐蚀性硫腐蚀的金属钝化剂及其制备方法与应用，所述的金属钝化剂为具有式(I)结构的半缩醛基的苯并唑类，
Description
技术领域
本发明涉及变压器防止腐蚀性硫技术领域，特别是涉及一种防止腐蚀性硫腐蚀的金属钝化剂及其制备方法与应用。
背景技术
绝缘油-固体绝缘纸绝缘体系由于价格低、性能良好，而广泛应用于电力变压器、配电变压器和电抗器，该体系的介电强度强烈依赖于其绝缘特性。
目前部分绝缘油中含有腐蚀性硫，腐蚀性硫与变压器的铜导体发生化学反应，会形成绝缘性能较差的硫化亚铜。硫化亚铜的产生会降低起始局部放电水平，在高场强下或者瞬变电流下，局部放电会使固体绝缘纸降解而导致故障产生。而在极端情况下，硫化亚铜大量产生，受污染的绕组渗透、污染固体绝缘纸，使其绝缘强度下降，最终匝间绝缘击穿，局部放热过高导致事故的发生。
处理腐蚀性硫绝缘油的措施包括绝缘油的再生和在绝缘油中添加金属钝化剂。绝缘油的再生技术是利用吸附剂对极性物质例如腐蚀性硫进行吸附，但由于传统吸附剂处理效果不佳，而新型吸附剂的成本过高，实际利用该方法较少；另一种方法是往绝缘油中添加苯并三氮唑类金属钝化剂，金属钝化剂与导体铜反应，在其表面形成钝化膜，从而阻止腐蚀性硫对铜表面的腐蚀，该方法成本较低，实际操作方便，已经得到广泛的应用。
目前广泛使用的苯并三氮唑类金属钝化剂是商品化的Irgamet39TM，该产品油溶性好，防腐蚀效果佳，但是该产品对水生生物毒性大。究其原因是该产品容易水解生成甲醛和二异辛胺。
发明内容
基于此，有必要提供一种钝化抗腐蚀效果好的苯并唑类金属钝化剂。本发明的技术方案为一种防止腐蚀性硫腐蚀的金属钝化剂，所述的金属钝化剂为具有式(I)结构的半缩醛基的苯并唑类金属钝化剂：
R1、R2分别任选自：H，Me；
A分别任选自：N，CH；
n等于1或者2；
X分别任选自CH2，O。
在其中一个实施例中，任选自如下化合物：
本发明还提供所述的半缩醛基苯并唑类金属钝化剂的制备方法，具体为一种防止腐蚀性硫腐蚀的金属钝化剂的制备方法：n当量的苯并唑类化合物记为原料A和环醚记为B在氧化剂和催化剂的作用下在溶剂中反应发生脱氢偶联反应，得到半缩醛基苯并唑类化合物记为C。
本发明所述的氧化剂是三氯化铁，四丁基碘化铵，氧化亚铜，硝酸银，碘化亚铜，溴化亚铜，碘，碘化钾，氯化亚铁，醋酸铜等。本发明所述的氧化剂是双氧水，氧气，过氧叔丁醇，间氯过氧苯甲酸，过硫酸钾，二叔丁基过氧化物，2，3-二氯-5，6-二氰对苯醌等。本发明所述的溶剂是乙酸乙酯，N，N-二甲基甲酰胺，乙腈，二甲基亚砜，二氯甲烷，1，2-二氯乙烷，甲苯，氯苯等，或上述溶剂的混合物。
本发明还提供所述上述金属钝化剂或上述方法制备的半缩醛基苯并唑类金属钝化剂在绝缘油中的应用。
在其中一个实施例中，以绝缘油为10000重量份计算，所述半缩醛基苯并唑类金属钝化剂的添加量为0.5-2.5重量份。
与现有技术相比，本发明具有以下有益效果：
具有本发明所述结构特征的苯并咪唑类金属钝半缩醛基苯并唑类金属钝化剂化剂，在使用的过程中不会向环境释放出甲醛和二异辛胺等高毒性物质，提高添加剂使用的安全性，可以广泛应用于电力变压器、配电变压器或电抗器等电力设备。
本发明所述半缩醛基苯并唑类金属钝化剂的制备方法简单，成本低，适用于工业应用。
具体实施方式
以下结合具体实施例对本发明的半缩醛基苯并唑类金属钝化剂及其制备方法和应用作进一步详细的说明。
实施例1
本实施例1中半缩醛基苯并唑类金属钝化剂，结构如下：
上述金属钝化剂的制备方法，包括如下步骤：
将苯并三氮唑11.9g，二氧六环132g、过氧叔丁醇31.5g和四丁基碘化铵0.32g溶解在400mL二氯乙烷中，接着混合物加热回流，TLC检测反应结束后。溶剂蒸发后用乙酸乙酯进行萃取，产物经过乙酸乙酯-正己烷体系进行柱层析分离得到。化合物结构经过核磁谱图进行确定。1H NMR(400MHz，CDCl3)δ8.09(d，J＝8.3Hz，1H)，7.76(d，J＝8.3Hz，1H)，7.53(t，J＝7.6Hz，1H)，7.40(t，J＝7.6Hz，1H)，6.10(dd，J＝7.2，2.8Hz，1H)，4.54(dd，J＝11.8，7.3Hz，1H)，4.24(dd，J＝11.9，2.7Hz，1H)，4.03-3.80(m，4H)；13C NMR(100MHz，CDCl3)δ146.0，132.5，127.9，124.4，120.1，110.6，82.0，67.3，65.9，65.3.
实施例2
本实施例2中半缩醛基苯并唑类金属钝化剂，结构如下：
上述金属钝化剂的制备方法，包括如下步骤：
将苯并三氮唑11.9g，四氢呋喃108g、过氧叔丁醇31.5g和四丁基碘化铵0.32g溶解在400mL二氯乙烷中，接着混合物加热回流，TLC检测反应结束，溶剂蒸发后用乙酸乙酯进行萃取，产物经过乙酸乙酯-正己烷体系进行柱层析分离得到。化合物结构经过核磁谱图进行确定。1H NMR(400MHz，CDCl3)δ：7.99(d，J＝8.3Hz，1H)，7.64(d，J＝8.3Hz，lH)，7.43(t，J＝7.6Hz，1H)，7.31(t，J＝7.6Hz，1H)，6.44(dd，J＝6.5，1.6Hz，1H)，4.10-3.88(m，2H)，3.20-3.10(m，1H)，2.57-2.47(m，1H)，2.32-2.43(m，1H)，2.19-2.04(m，1H)；13C NMR(100.61 MHz，CDCl3)δ146.2，132.8，127.5，124.1，119.7，110.4，87.9，69.2，30.8，24.3.
实施例3
本实施例3中半缩醛基苯并唑类金属钝化剂，结构如下：
上述金属钝化剂的制备方法，包括如下步骤：
将苯并三氮唑11.9g，四氢吡喃129g，过氧叔丁醇31.5g和四丁基碘化铵0.32g溶解在400mL二氯乙烷中，接着混合物加热回流，TLC检测反应结束，溶剂蒸发后用乙酸乙酯进行萃取，产物经过乙酸乙酯-正己烷体系进行柱层析分离得到。化合物结构经过核磁谱图进行确定。1H NMR(400MHz，CDCl3)δ8.08(d，J＝8.4Hz，1H)，7.75(d，J＝8.3Hz，1H)，7.50(t，J＝7.6Hz，1H)，7.39(t，J＝7.6Hz，1H)，6.05(dd，J＝8.2，2.8Hz，1H)，3.96(dd，J＝11.6，4.4Hz，1H)，3.86-3.72(m，1H)，2.71-2.56(m，1H)，2.29-2.11(m，2H)，1.87-1.68(m，3H)；13C NMR(100MHz，CDCl3)δ146.2，132.5，127.4，124.1，119.8，111.1，85.6，66.8，29.2，24.9，21.4.
实施例4
本实施例4中半缩醛基苯并唑类金属钝化剂，结构如下：
上述金属钝化剂的制备方法，包括如下步骤：
将5-甲基苯并三氮唑11.9g，二氧六环132g、过氧叔丁醇31.5g和四丁基碘化铵0.32g溶解在400mL二氯乙烷中，接着混合物加热回流，TLC检测反应结束后。溶剂蒸发后用乙酸乙酯进行萃取，产物经过乙酸乙酯-正己烷体系进行柱层析分离得到。化合物结构经过核磁谱图进行确定。1H NMR(400MHz，CDCl3)δ7.78(d，J＝8.0Hz，1H)，7.63(s，1H)，7.22(d，J＝8.0Hz，1H)，6.10(dd，J＝7.2，2.8Hz，1H)，4.54(dd，J＝11.8，7.3Hz，1H)，4.24(dd，J＝11.9，2.7Hz，1H)，4.03-3.80(m，4H)，2，48(s，3H).
实施例5
本实施例5中半缩醛基苯并唑类金属钝化剂，结构如下：
上述金属钝化剂的制备方法，包括如下步骤：
将5-甲基苯并三氮唑11.9g，四氢呋喃108g、过氧叔丁醇31.5g和四丁基碘化铵0.32g溶解在400mL二氯乙烷中，接着混合物加热回流，TLC检测反应结束后。溶剂蒸发后用乙酸乙酯进行萃取，产物经过乙酸乙酯-正己烷体系进行柱层析分离得到。化合物结构经过核磁谱图进行确定。1H(400MHz，CDCl3)δ7.78(d，J＝8.0Hz，1H)，7.63(s，1H)，7.22(d，J＝8.0Hz，1H)，6.44(dd，J＝6.5，1.6Hz，1H)，4.10-3.88(m，2H)，3.20-3.10(m，1H)，2.57-2.47(m，1H)，2.48(s，3H)，2.32-2.43(m，1H)，2.19-2.04(m，1H).
实施例6
本实施例6中半缩醛基苯并唑类金属钝化剂，结构如下：
上述金属钝化剂的制备方法，包括如下步骤：
将苯并咪唑11.8g，二氧六环132g、过氧叔丁醇31.5g和四丁基碘化铵0.32g溶解在400mL二氯乙烷中，接着混合物加热回流，TLC检测反应结束后。溶剂蒸发后用乙酸乙酯进行萃取，产物经过甲醇-二氯甲烷体系进行柱层析分离得到。化合物结构经过核磁谱图进行确定。1H NMR(400MHz，CDCl3)δ8.21(s，1H)，7.75(d，J＝6.0Hz，1H)，7.44(d，J＝5.6Hz，1H)，7.29-7.18(m，2H)，5.63(s，1H)，4.07(d，J＝4.6Hz，2H)，3.88-3.59(m，4H).
实施例7
本实施例7中半缩醛基苯并唑类金属钝化剂，结构如下：
上述金属钝化剂的制备方法，包括如下步骤：
将苯并咪唑11.8g，四氢呋喃108g、过氧叔丁醇31.5g和四丁基碘化铵0.32g溶解在400mL二氯乙烷中，接着混合物加热回流，TLC检测反应结束，溶剂蒸发后用乙酸乙酯进行萃取，产物经过乙酸乙酯-正己烷体系进行柱层析分离得到。化合物结构经过核磁谱图进行确定。1H NMR(400MHz，CDCl3)δ：8.03(s，1H)，7.85-7.75(m，1H)，7.50-7.42(m，1H)，7.36-7.25(m，2H)，6.19(dd，J＝5.6，4.0Hz，1H)，4.23-4.17(m，1H)，4.10-4.04(m，1H)，2.52-2.44(m，2H)，2.19-2.12(m，2H).
实施例8
本实施例八中半缩醛基苯并唑类金属钝化剂，结构如下：
上述金属钝化剂的制备方法，包括如下步骤：
将5，6-二甲基苯并咪唑14.6g，二氧六环132g、过氧叔丁醇31.5g和四丁基碘化铵0.32g溶解在400mL二氯乙烷中，接着混合物加热回流，TLC检测反应结束后。溶剂蒸发后用乙酸乙酯进行萃取，产物经过甲醇-二氯甲烷体系进行柱层析分离得到。化合物结构经过核磁谱图进行确定。1H NMR(400MHz，CDCl3)δ8.16(s，1H)，7.57(s，1H)，7.28(s，1H)，5.65(t，J＝3.6Hz，1H)，4.45(t，J＝6.1Hz，1H)，4.24-4.06(m，1H)，3.97-3.75(m，4H)，2.38(d，J＝7.3Hz，6H).
实施例9
本实施例九中半缩醛基苯并唑类金属钝化剂，结构如下：
上述金属钝化剂的制备方法，包括如下步骤：
将5，6-二甲基苯并咪唑14.6g，四氢呋喃108g、过氧叔丁醇31.5g和四丁基碘化铵0.32g溶解在400mL二氯乙烷中，接着混合物加热回流，TLC检测反应结束后。溶剂蒸发后用乙酸乙酯进行萃取，产物经过甲醇-二氯甲烷体系进行柱层析分离得到。化合物结构经过核磁谱图进行确定。1H NMR(400MHz，CDCl3)δ7.90(s，1H)，7.55(s，1H)，7.23(s，1H)，6.14(t，J＝4.7Hz，1H)，4.17(dd，J＝14.7，7.1Hz，1H)，4.05(dd，J＝15.3，7.7Hz，1H)，2.50-2.30(m，8H)，2.15(dd，J＝14.3，7.1Hz，2H).
实施例10
以绝缘油为10000重量份计算，所述半缩醛基苯并唑类金属钝化剂一种或多种混合物的添加量为0.5-2.5重量份，抗氧化剂2，6-二叔丁基对甲酚或者2，60二叔丁基苯酚或其混合物40重量份，将金属钝化剂、抗氧化剂与绝缘油混合均匀后，通过常规油处理装置加入到变压器、电抗器本体中。
实施例11
实验用油含有半缩醛基的苯并唑类金属钝化剂50mg/kg，二苄基二硫醚150mg/kg。接着将裸铜片浸没在油中，容器经过氩气吹扫3分钟，保证体系在惰性气体气氛中。反应容器盖子拧紧，避免与空气发生交换。实验容器放在老化箱中，维持老化温度150℃，反应时间72小时。老化反应后，实验容器冷却到室温，打开反应容器盖子，用镊子取出铜片，并浸泡在石油醚或者正己烷中去掉油污。每组实验平均进行两次试验。观察铜片表面的颜色变化，没有出现黑色沉淀物，证明添加金属钝化剂可以抑制硫化亚铜的形成。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。
Claims (6)
1.一种防止腐蚀性硫腐蚀的金属钝化剂在绝缘油中的应用，其特征在于，
所述的金属钝化剂为具有式(I)结构的半缩醛基的苯并唑类金属钝化剂，
R1、R2分别任选自：H或Me；
A任选自：N或CH；
n等于1或者2；
X任选自CH2或O；
以绝缘油为10000重量份计算，所述半缩醛基的苯并唑类金属钝化剂的添加量为0.5-2.5重量份。
2.根据权利要求1所述的应用，其特征在于，所述金属钝化剂选自如下化合物：
3.根据权利要求2所述的应用，其特征在于，金属钝化剂的制备包括如下步骤：n当量的苯并唑类化合物和环醚在氧化剂和催化剂的作用下，在溶剂中发生脱氢偶联反应，得到半缩醛基苯并唑类化合物即所述金属钝化剂。
4.根据权利要求3所述的应用，其特征在于，所述的催化剂是三氯化铁，四丁基碘化铵，氧化亚铜，硝酸银，碘化亚铜，溴化亚铜，碘，碘化钾，氯化亚铁，醋酸铜或其混合物。
5.根据权利要求4所述的应用，其特征在于，所述的氧化剂是双氧水，氧气，过氧叔丁醇，间氯过氧苯甲酸，过硫酸钾，二叔丁基过氧化物，2，3-二氯-5-二氰对苯醌，或者，2，3-二氯-6-二氰对苯醌。
6.根据权利要求5所述的应用，其特征在于，所述的溶剂是乙酸乙酯，N，N-二甲基甲酰胺，乙腈，二甲基亚砜，二氯甲烷，1，2-二氯乙烷，甲苯，氯苯，或上述溶剂的混合物。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610996910.9A CN106632277B (zh) | 2016-11-11 | 2016-11-11 | 一种防止腐蚀性硫腐蚀的金属钝化剂及其制备方法与应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610996910.9A CN106632277B (zh) | 2016-11-11 | 2016-11-11 | 一种防止腐蚀性硫腐蚀的金属钝化剂及其制备方法与应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106632277A CN106632277A (zh) | 2017-05-10 |
| CN106632277B true CN106632277B (zh) | 2019-04-16 |
Family
ID=58806248
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610996910.9A Expired - Fee Related CN106632277B (zh) | 2016-11-11 | 2016-11-11 | 一种防止腐蚀性硫腐蚀的金属钝化剂及其制备方法与应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106632277B (zh) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0721979A2 (en) * | 1995-01-13 | 1996-07-17 | Ciba-Geigy Ag | Stabilized lubricant compositions |
| CN1274743A (zh) * | 1999-05-19 | 2000-11-29 | 西巴特殊化学品控股有限公司 | 稳定的氢化处理及氢化脱蜡润滑剂组合物 |
| CN101092583A (zh) * | 2006-06-19 | 2007-12-26 | 西安近代化学研究所 | 酯类润滑油用缓蚀剂 |
| CN104327054A (zh) * | 2014-11-05 | 2015-02-04 | 华东交通大学 | 水溶性苯并三氮唑咪唑啉极压抗磨剂及其制备方法 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8722592B2 (en) * | 2008-07-25 | 2014-05-13 | Wincom, Inc. | Use of triazoles in reducing cobalt leaching from cobalt-containing metal working tools |
-
2016
- 2016-11-11 CN CN201610996910.9A patent/CN106632277B/zh not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0721979A2 (en) * | 1995-01-13 | 1996-07-17 | Ciba-Geigy Ag | Stabilized lubricant compositions |
| CN1274743A (zh) * | 1999-05-19 | 2000-11-29 | 西巴特殊化学品控股有限公司 | 稳定的氢化处理及氢化脱蜡润滑剂组合物 |
| CN101092583A (zh) * | 2006-06-19 | 2007-12-26 | 西安近代化学研究所 | 酯类润滑油用缓蚀剂 |
| CN104327054A (zh) * | 2014-11-05 | 2015-02-04 | 华东交通大学 | 水溶性苯并三氮唑咪唑啉极压抗磨剂及其制备方法 |
Non-Patent Citations (4)
| Title |
|---|
| Chemical Stability of Benzotriazole Copper Surface Passivators in Insulating Oils;Per Wiklund;《Ind. Eng. Chem. Res.》;20070414;第46卷;第3312-3316页 |
| Cross-Dehydrogenative Coupling of Azoles with α-C(sp3)-H of Ethers and Thioethers under Metal-Free Conditions: Functionalization of H-N Azoles via C-H Activation;Hariprasad Aruri et al.;《J. Org. Chem.》;20150114;第80卷;第1929-1936页 |
| Synthesis and biological investigations of 1-(tetrahydropyran-2-yl)- and 1-(tetrahydrofuran-2-yl)benzimidazoles and 1/2-(tetrahydropyran-2-yl)- and 1/2-(tetrahydrofuran-2-yl)benzotriazoles;Anna Sparatore et al.;《IL Farmaco》;19971231;第52卷(第8-9期);第509-521页 |
| 矿物绝缘油中腐蚀性硫问题研究;任双赞 等;《绝缘材料》;20101231;第43卷(第3期);第69-73页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106632277A (zh) | 2017-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Synergism between cerium nitrate and sodium dodecylbenzenesulfonate on corrosion of AA5052 aluminium alloy in 3 wt.% NaCl solution | |
| Sathiya Priya et al. | Development of novel acidizing inhibitors for carbon steel corrosion in 15% boiling hydrochloric acid | |
| Ho et al. | Cerium dibutylphosphate as a corrosion inhibitor for AA2024-T3 aluminum alloys | |
| Legeai et al. | Room-temperature ionic liquid for lanthanum electrodeposition | |
| Chang et al. | Corrosion resistance of tannic acid, d-limonene and nano-ZrO2 modified epoxy coatings in acid corrosion environments | |
| CN101866751A (zh) | 一种耐高温铝电解的电解液及其应用 | |
| Musa et al. | Galvanic corrosion of aluminum alloy (Al2024) and copper in 1.0 M nitric acid | |
| CN113698917B (zh) | 一种氢燃料电池车用冷却液组合物 | |
| Karki et al. | Equisetum hyemale: a new candidate for green corrosion inhibitor family | |
| Zunita et al. | Investigation of corrosion inhibition activity of 3-butyl-2, 4, 5-triphenylimidazole and 3-butyl-2-(2-butoxyphenyl)-4, 5-diphenylimidazole toward carbon steel in 1% NaCl solution | |
| Li et al. | The use of phytic acid conversion coating to enhance the corrosion resistance of AZ91D magnesium alloy | |
| CN106632277B (zh) | 一种防止腐蚀性硫腐蚀的金属钝化剂及其制备方法与应用 | |
| Voina et al. | Study regarding corrosiveness and thermal stability of some insulating oils in contact with red cooper and S235J2G3 carbon steel | |
| Zhao et al. | Inhibition effectiveness and depletion characteristic of Irgamet 39 in transformer oil | |
| Arukalam et al. | Cellulosic polymers for corrosion protection of aluminium | |
| Goel et al. | Synthesis characterization and corrosion inhibition efficiency of N-C2 {(2E)-2-[4-(dimethylamino) benzylidene] hydrazinyl} 2-oxo ethyl benzamide on mild steel | |
| Makarychev et al. | Vapor-phase deposition of polymer siloxane coatings on the surface of copper and low-carbon steel | |
| CN101452768A (zh) | 一种抑制电解电容器铝箔氧化膜和水反应的处理工艺的检验方法 | |
| CN110684196B (zh) | 多羧基改性硅油及其制备方法和应用以及包含其的防锈剂 | |
| Mansri et al. | The synergistic effect of poly (acrylamide-co-4-vinylpyridine) copolymer" AM-4VP-24" and iodide ion on corrosion inhibition | |
| Cai et al. | Influence of alkyl chain length of 1, 3-bis-dialkylamino-2-propanol on the adsorption and corrosion behavior of steel Q235 in simulated concrete pore solution | |
| Aghazada et al. | Characterisation of conservative liquids based on liquid rubber, the salts of the natural petroleum acids and nitro compounds-C14H28 | |
| M'hanni et al. | Comparative study of the copper inhibition of two [H4L] calixarenic molecules in sulfuric acid medium | |
| Munot et al. | Electrochemical investigations on semi-conducting properties of a passive film on conducting polypyrrole coated low carbon steel in a simulated concrete pore solution | |
| Musa et al. | Manufacturing Enamel Resin Using Furancarboxalehyde-3 Compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190416 Termination date: 20211111 |