CN101812693A - Novel pickling corrosion inhibitor and application thereof in preparing metal pickling agent - Google Patents
Novel pickling corrosion inhibitor and application thereof in preparing metal pickling agent Download PDFInfo
- Publication number
- CN101812693A CN101812693A CN 201010166782 CN201010166782A CN101812693A CN 101812693 A CN101812693 A CN 101812693A CN 201010166782 CN201010166782 CN 201010166782 CN 201010166782 A CN201010166782 A CN 201010166782A CN 101812693 A CN101812693 A CN 101812693A
- Authority
- CN
- China
- Prior art keywords
- diethyl ammonium
- corrosion
- pickling
- concentration
- acid
- 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
Links
- 238000005554 pickling Methods 0.000 title claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 25
- 239000002184 metal Substances 0.000 title claims abstract description 25
- 230000007797 corrosion Effects 0.000 title abstract description 103
- 238000005260 corrosion Methods 0.000 title abstract description 103
- 239000003112 inhibitor Substances 0.000 title abstract description 13
- 239000003795 chemical substances by application Substances 0.000 title description 2
- 125000003118 aryl group Chemical group 0.000 claims abstract description 9
- 125000003107 substituted aryl group Chemical group 0.000 claims abstract description 5
- 239000000837 restrainer Substances 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000006210 lotion Substances 0.000 claims description 3
- 230000005764 inhibitory process Effects 0.000 abstract description 66
- 230000000694 effects Effects 0.000 abstract description 4
- 125000001424 substituent group Chemical group 0.000 abstract 3
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 42
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 40
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 33
- VJYLDRLVRFWDLE-UHFFFAOYSA-N CCNCC.OP(O)(S)=S Chemical class CCNCC.OP(O)(S)=S VJYLDRLVRFWDLE-UHFFFAOYSA-N 0.000 description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 235000021110 pickles Nutrition 0.000 description 21
- TWPJXAJXJTXPSO-UHFFFAOYSA-N CCNCC.OP(OCC1=CC=CC=C1)(S)=S Chemical compound CCNCC.OP(OCC1=CC=CC=C1)(S)=S TWPJXAJXJTXPSO-UHFFFAOYSA-N 0.000 description 17
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 16
- 230000000116 mitigating effect Effects 0.000 description 15
- 238000000034 method Methods 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 230000009471 action Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 4
- 230000003292 diminished effect Effects 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 208000016261 weight loss Diseases 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 239000012490 blank solution Substances 0.000 description 3
- 238000002848 electrochemical method Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910001051 Magnalium Inorganic materials 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 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 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- -1 (phenyl) phosphorodithioic acid-N, N-diethyl ammonium Chemical compound 0.000 description 1
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical group Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002461 imidazolidines Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Abstract
本发明公开了一种新型酸洗缓蚀剂O，O’-二取代基二硫代磷酸-N，N-二乙铵，其中两个取代基各自独立的选自取代基：芳基、取代芳基、芳基取代的烷基，且两个取代基各自的碳原子数均少于40；并公开了O，O’-二取代基二硫代磷酸-N，N-二乙铵作为金属酸洗缓蚀剂的应用，向不同浓度的酸洗介质中加入O，O’-二取代基二硫代磷酸-N，N-二乙铵，使其浓度为40-160mg/L，即可获得有效的金属缓蚀效果，本发明公开的酸洗缓蚀剂缓蚀效果持续时间长、适用酸度范围宽。
The invention discloses a novel pickling corrosion inhibitor O, O'-disubstituent dithiophosphoric acid-N, N-diethylammonium, wherein two substituents are independently selected from substituents: aryl, substituted Aryl, aryl-substituted alkyl, and both substituents have less than 40 carbon atoms each; and O,O'-disubstituted dithiophosphoric acid-N,N-diethylammonium is disclosed as metal For the application of pickling corrosion inhibitor, add O, O'-disubstituted dithiophosphoric acid-N, N-diethylammonium to the pickling medium with different concentrations to make the concentration 40-160mg/L. An effective metal corrosion inhibition effect is obtained, and the corrosion inhibition effect of the pickling corrosion inhibitor disclosed by the invention lasts for a long time and is applicable to a wide range of acidity.
Description
Technical field
The invention belongs to metal pickling corrosion and protection technical field, particularly a kind of O, O '-disubstituted phosphorodithioic acid-N, N-diethyl ammonium is as the application of metal pickling corrosion inhibitor.
Background technology
Corrosion is one of universe's challenge that need face, and well-known metallic corrosion is again one of most important aspect in the corrosion, and metallic corrosion not only brings enormous economic loss to society, and brings very big harm to people's life and production.So people are constantly carrying out the research of metal pickling corrosion and protection, wish by making great efforts and dropping to the bite degree of metal minimum.Just in acid cleaning process, add inhibiter if reduce at present one of most important, effective means of metal pickling corrosion in actual life and the production process.In recent years, Research on Corrosion Inhibitor has obtained major progress in the metal pickle liquor, progressively from function singleness, inhibition efficiency is low, toxicity is big, production cost is high, range of application narrow to have special construction, multi-functional, efficient, cheap, be easy to get, the direction of applied range develops.
The pickle solution that is applied to acid cleaning process is more, comprises the most frequently used sulfuric acid and hydrochloric acid.The mass concentration of pickle solution generally is no more than 20% in the acid cleaning process.Corrosion such as uniform corrosion, spot corrosion, crevice corrosion, stress corrosion, galvanic corrosion may appear in metallic corrosion, yet impelled the continuous development in inhibiter field just because of these corrosion, even so, still there are defectives such as toxicity low as inhibition efficiency, the part organic inhibitor is big, production cost is high, range of application is narrow in the development of inhibiter.
Present stage is applied to the inhibiter numerous types of pickle solution, and still there are some defectives separately in dissimilar inhibiter.As amine inhibitor corrosion mitigating effect under the situation of one-component is not fine, so this class inhibiter need be carried out being applied after composite; Pyridine derivate and amine inhibitor have irritating smell mostly; This class inhibiter of imidazolidine derivatives does not have special irritating smell, Heat stability is good, toxicity is low but this compounds needs multistep to synthesize; The inhibition efficiency of thiourea derivative is influenced greatly by substituting group, and there is optimized scope in the concentration of inhibiter; Rosin derivative, the application performance of natural rosin is relatively poor, needs usually just can be used widely through after the different methods modification.
Therefore development of new inhibiter and the acid cleaning process that is applied to metal then have immeasurable realistic meaning.
O; O '-dialkyl dithiophosphate and title complex thereof are the compounds that a class has extensive use; the recovery of Materials science, life science, agricultural, Industrial Catalysis, petroleum industry, rubber industry, mining industry, heavy metal with separate, field such as environment protection all plays a part very importantly, is widely used as the oxidation inhibitor of sterilant and weedicide, lubricating oil and fuel oil and anti-wear agent, the additive of fuel oil, the stablizer of macromolecular material, vulcanization accelerator, mineral flotation agent and the noble metal extractant etc. of synthetic chloroprene rubber.
The applicant is with regard to O, O '-dicyclohexyl phosphorodithioic acid-N, N-diethyl ammonium as the restrainer application patent of invention, Chinese patent application number is 201010114594.0, though O, O '-dicyclohexyl phosphorodithioic acid-N, N-diethyl ammonium has overcome the shortcoming of above-mentioned existing restrainer to a certain extent, have the good metal corrosion mitigating effect, and its corrosion inhibition is subjected to temperature, the influence of acidity etc. is less, can be used for multiple metal pickling, applied range, with low cost, be suitable for industry and advantage such as apply, still, O, O '-dicyclohexyl phosphorodithioic acid-N, the time length of N-diethyl ammonium corrosion mitigating effect falls short of, the acidity scope that is suitable for is wide inadequately, is necessary further to explore more excellent, have more the novel restrainer of development prospect.
Summary of the invention
Main purpose of the present invention is exactly to improve day by day at the requirement to metal pickle liquor corrosion inhibition each side that exists in the above-mentioned prior art and can satisfy some problems such as pickle solution shortage of this requirement at present, provide a kind of corrosion mitigating effect time length longer, be suitable for the wideer novel restrainer of acidity scope.
In order to realize the foregoing invention purpose, the technical solution used in the present invention is as follows:
The contriver finds in a large amount of experimental study processes, with O, and O '-disubstituted phosphorodithioic acid-N, N-diethyl ammonium joins in the pickling mediums such as hydrochloric acid or sulfuric acid by finite concentration, can obtain more efficiently corrosion inhibition for metal effect.
Above-mentioned O, O '-disubstituted phosphorodithioic acid-N, the structural formula of N-diethyl ammonium is as follows:
In the said structure: R
1And R
2Independently be selected from separately: the alkyl that aryl, substituted aryl or aryl replace.
As preferably: R
1Carbonatoms be less than 40.
As preferably: R
2Carbonatoms be less than 40.
The application of above-mentioned metal pickling corrosion inhibitor in preparation metal acid lotion, the O that in the pickling medium (pickle solutions such as the hydrochloric acid of different concns, sulfuric acid) of different concns, adds different concns, O '-disubstituted phosphorodithioic acid-N, N-diethyl ammonium, the concentration that makes inhibiter is 40-160mg/L, be part of O, O '-disubstituted phosphorodithioic acid-N, N-diethyl ammonium has corrosion inhibition for metal effect efficiently.
With O, O '-phenylbenzene phosphorodithioic acid-N, N-diethyl ammonium is an example, the preparation method of the restrainer among the application is: under the normal pressure, 22.2g thiophosphoric anhydride (0.1mol) and 30.1-45.1g phenol (0.32-0.48mol) are joined in the there-necked flask, add 50-80mL toluene or dimethylbenzene again, at 80-130 ℃ of heating 1-3h, reaction mixture is cold slightly, decolouring, filtered while hot.Filtrate is cooled to room temperature, under cooling and stirring, drips 22-44mL diethylamine (0.2-04mol), standing over night.Filtration under diminished pressure, solvent recrystallization is used in toluene or dimethylbenzene washing, and vacuum-drying gets white crystal O, O '-phenylbenzene phosphorodithioic acid-N, N-diethyl ammonium, productive rate is 81.6%, records fusing point to be: 125-127 ℃
Compared with prior art, the invention has the beneficial effects as follows:
The contriver shows by a large amount of experiments, with O, O '-disubstituted phosphorodithioic acid-N, N-diethyl ammonium adds to according to described concentration in the metal pickling medium of various different concns, and the result shows the O of part, O '-disubstituted phosphorodithioic acid-N, N-diethyl ammonium has good metal pickling corrosion mitigating effect, its corrosion mitigating effect is subjected to the influence of temperature, acidity etc. less and the corrosion mitigating effect time length is longer, can be used for multiple metal pickling, applied range; In addition, part of O, O '-disubstituted phosphorodithioic acid-N, N-diethyl ammonium raw material cheapness, product is easy to get when synthetic, thereby it is with low cost to be used for metal pickle liquor, is suitable for industry and applies.Simultaneously, the present invention also is O, and O '-disubstituted dithiophosphates has been widened Application Areas.
Learn by test: the restrainer that the application provided is a kind of than O, O '-dicyclohexyl phosphorodithioic acid-N, the ideal type restrainer that N-diethyl ammonium is more excellent, have more development prospect.With O, O '-dicyclohexyl phosphorodithioic acid-N, N-diethyl ammonium is compared, and the application's restrainer has the following advantages:
(1) the application's restrainer, such as O, O '-two (phenmethyl) phosphorodithioic acid-N, productive rate was higher when N-diethyl ammonium was synthetic, can reach 89.9%; And O, O '-dicyclohexyl phosphorodithioic acid-N, productive rate was 80.7% when N-diethyl ammonium was synthetic, concrete data are referring to the application's embodiment part;
(2) during equal in quality concentration, the application's restrainer, such as O, O '-two (phenmethyl) phosphorodithioic acid-N, the corrosion mitigating effect of N-diethyl ammonium is better, and just can reach good corrosion inhibiting effect when lower concentration, referring to table 1:
Table 1: compound concentration is to the influence of sulfuric acid pickling solution corrosion inhibition rate
As shown in Table 1, O, O '-two (phenmethyl) phosphorodithioic acid-N, N-diethyl ammonium corrosion mitigating effect is better, and just can reach good corrosion inhibiting effect when lower concentration;
(3) the application's restrainer, such as O, O '-two (phenmethyl) phosphorodithioic acid-N, N-diethyl ammonium when concentration is 100mg/L, 5%H
2SO
4In the solution, its corrosion mitigating effect can be continuously 144h, and O, O '-dicyclohexyl phosphorodithioic acid-N, N-diethyl ammonium corrosion mitigating effect under the same conditions can only continue 120h; O, O '-two (phenmethyl) phosphorodithioic acid-N, N-diethyl ammonium is when concentration is 100mg/L, in 20% the HCl solution, it is 91.46% that its inhibition is imitated, and O, O '-dicyclohexyl phosphorodithioic acid-N, N-diethyl ammonium inhibition is under the same conditions imitated but has only 48.6%.
So, the application's restrainer and O, O '-dicyclohexyl phosphorodithioic acid-N, N-diethyl ammonium is compared, and that the application's restrainer is that a kind of corrosion mitigating effect continues is longer, be suitable for the wideer restrainer of acidity scope.The application's that hence one can see that restrainer is a kind of more excellent, ideal type restrainer of having more development prospect.
Description of drawings
Fig. 1 is that temperature is 25 ± 1 ℃, at 5%H
2SO
4In the solution, O, O '-two (phenmethyl) phosphorodithioic acid-N, N-diethyl ammonium concentration and corrosion inhibition rate graph of a relation;
Fig. 2 is that temperature is 25 ± 1 ℃, O, and O '-two (phenmethyl) phosphorodithioic acid-N, when N-diethyl ammonium concentration is 100mg/L, the graph of a relation of corrosion inhibition rate and HCl concentration;
Fig. 3 is in the 5%HCl pickle solution, O, and O '-two (phenmethyl) phosphorodithioic acid-N, when N-diethyl ammonium concentration is 100mg/L, the graph of a relation of corrosion inhibition rate and temperature;
Fig. 4 is that temperature is 25 ± 1 ℃, 5%H
2SO
4In the solution, O, O '-two (phenmethyl) phosphorodithioic acid-N, corrosion inhibition rate when N-diethyl ammonium concentration is 100mg/L and the graph of a relation of inhibiter time length;
Fig. 5 is that temperature is 25 ± 1 ℃, at 5%H
2SO
4In the solution, O, O '-two (phenyl) phosphorodithioic acid-N, N-diethyl ammonium concentration and corrosion inhibition rate graph of a relation;
Fig. 6 is that temperature is 25 ± 1 ℃, in 5%HCl solution, and O, O '-two (phenmethyl) phosphorodithioic acid-N, N-diethyl ammonium concentration and corrosion inhibition rate graph of a relation;
Fig. 7 is that temperature is 25 ± 1 ℃, in the 5%HCl solution, and O, O '-two (phenmethyl) phosphorodithioic acid-N, corrosion inhibition rate when N-diethyl ammonium concentration is 100mg/L and the graph of a relation of action time;
Fig. 8 is that temperature is 25 ± 1 ℃, O, and O '-two (phenmethyl) phosphorodithioic acid-N, when N-diethyl ammonium concentration is 100mg/L, corrosion inhibition rate and H
2SO
4The graph of a relation of concentration.
Embodiment
Below in conjunction with O, O '-disubstituted phosphorodithioic acid-N, N-diethyl ammonium is chosen O, O '-two (phenmethyl) phosphorodithioic acid-N, N-diethyl ammonium and O, O '-phenylbenzene phosphorodithioic acid-N, N-diethyl ammonium comes foregoing invention content of the present invention is described in further detail as embodiment.
But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment.Not breaking away under the above-mentioned technological thought situation of the present invention, according to ordinary skill knowledge and customary means, make various replacements and change, all should comprise within the scope of the invention.
In order to investigate O, O '-two (phenmethyl) phosphorodithioic acid-N, the relation of N-diethyl ammonium concentration and sulfuric acid pickling solution corrosion inhibition rate, present embodiment is under the situation of sulfuric acid concentration identical (5%, mass percentage concentration is descended together), add O, O '-two (phenmethyl) phosphorodithioic acid-N, N-diethyl ammonium, making it concentration is 40-160mg/L (seeing Table 1), under 25 ± 1 ℃ of temperature condition, be used for the pickling of Q235 steel, measure its corrosion inhibition rate respectively, the result is as shown in table 1.And with O, O '-two (phenmethyl) phosphorodithioic acid-N, N-diethyl ammonium concentration C (mg/L) is an X-coordinate, corrosion inhibition rate IE (%) is an ordinate zou, obtains in 5% sulfuric acid pickling solution O, O '-two (phenmethyl) phosphorodithioic acid-N, the graph of a relation of N-diethyl ammonium concentration and corrosion inhibition rate, as shown in Figure 1.
According to The above results, in the 40-160mg/L concentration range, the sulfuric acid pickling solution corrosion inhibition rate is basically along with O, O '-two (phenmethyl) phosphorodithioic acid-N, the increase of N-diethyl ammonium concentration and increasing, corrosion inhibition rate is at O, O '-two (phenmethyl) phosphorodithioic acid-N, all reached 97.98% when N-diethyl ammonium concentration is 40mg/L, contrast table 1 and table 1 ' then explanation, this inhibiter is a kind of more excellent, more rising efficient ideal type restrainer.
Embodiment 2 present embodiments are that the acid concentration of hydrochloric acid is not simultaneously to the influence of corrosion inhibition rate
In order to investigate the relation of acid concentration and pickle solution corrosion inhibition rate, present embodiment is with O, O '-two (phenmethyl) phosphorodithioic acid-N, N-diethyl ammonium joins in the HCl solution (seeing Table 2) of different mass concentration according to same concentrations (100mg/L), under 25 ± 1 ℃ of temperature condition, be used for the pickling of Q235 steel, measure the corrosion inhibition rate of each pickle solution respectively, the result is as shown in table 2.And with concentration of hydrochloric acid (C
HClMass concentration) be X-coordinate, corrosion inhibition rate IE (%) is an ordinate zou, obtains in hydrochloric acid pickler, the graph of a relation of concentration of hydrochloric acid and corrosion inhibition rate, as shown in Figure 2.
When table 2 compound concentration was 100mg/L, acid concentration was to the influence of hydrochloric acid pickler corrosion inhibition rate
According to The above results, O, O '-two (phenmethyl) phosphorodithioic acid-N, N-diethyl ammonium concentration is 100mg/L, in concentration of hydrochloric acid is the 5-20% scope, the hydrochloric acid pickler corrosion inhibition rate changes little, O is described, O '-two (phenmethyl) phosphorodithioic acid-N, N-diethyl ammonium compares O, O '-dicyclohexyl phosphorodithioic acid-N, the acidity acidity scope that N-diethyl ammonium uses is wideer.
Embodiment 3 present embodiments are the influence of temperature difference to the hydrochloric acid pickler corrosion inhibition rate
In order to investigate the relation of temperature and pickle solution corrosion inhibition rate, present embodiment is with O, O '-two (phenmethyl) phosphorodithioic acid-N, N-diethyl ammonium joins in the HCl solution (5%) of same concentrations according to same concentrations (100mg/L), under condition of different temperatures, be respectively applied for the pickling of Q235 steel, the corrosion inhibition rate of pickle solution when measuring differing temps, the result is as shown in table 3.And with the pickle solution temperature T (℃) be X-coordinate, corrosion inhibition rate IE (%) is an ordinate zou, obtains in 5% hydrochloric acid pickler, the graph of a relation of temperature and pickle solution corrosion inhibition rate, as shown in Figure 3.
Table 3 temperature is to the influence of hydrochloric acid pickler corrosion inhibition rate
| Temperature (℃) | ??25 | ??30 | ??40 | ??50 | ??60 | ??70 |
| Inhibition efficiency (%) | ??94.38 | ??93.56 | ??94.62 | ??94.39 | ??94.73 | ??94.78 |
According to The above results, in the pickle solution temperature was 25-70 ℃ of scope, the sulfuric acid pickling solution corrosion inhibition rate changed little.
Embodiment 4 present embodiments are O, O '-two (phenmethyl) phosphorodithioic acid-N, and when N-diethyl ammonium concentration was 100mg/L, corrosion inhibition rate was subjected to the influence of inhibiter continuous action time
The contriver has also investigated O, O '-two (phenmethyl) phosphorodithioic acid-N, the relation of N-diethyl ammonium time length and sulfuric acid pickling solution corrosion inhibition rate, under the situation of sulfuric acid concentration identical (5%), add O, O '-two (phenmethyl) phosphorodithioic acid-N, N-diethyl ammonium, concentration 100mg/L examines or check in 144 hours the variation of corrosion inhibition rate (seeing Table 4).Under 25 ± 1 ℃ of temperature condition, be respectively applied for Q235 steel sulfuric acid washing, the corrosion inhibition rate of each pickle solution of electrochemical method determining, the result is as shown in table 4.And with action time (Time/h) be X-coordinate, corrosion inhibition rate IE (%) is an ordinate zou, obtains in 5% sulfuric acid pickling solution, the graph of a relation of action time and corrosion inhibition rate, as shown in Figure 4.
The table 4 inhibiter time length is to the influence of sulfuric acid pickling solution corrosion inhibition rate
| Time (Time/h) | ??0 | ??24 | ??48 | ??72 | ??96 | ??120 | ??144 |
| Corrosion inhibition rate (%) | ??94.40 | ??94.40 | ??93.38 | ??92.03 | ??93.20 | ??94.30 | ??94.53 |
According to The above results, in the 0-144h scope, the fluctuation of pickle solution corrosion inhibition rate is less, constant basically.
Table 4 ' the inhibiter time length is to the influence of sulfuric acid pickling solution corrosion inhibition rate
| Time (Time/h) | ??0 | ??24 | ??48 | ??72 | ??96 | ??120 | ??144 |
| Corrosion inhibition rate (%) | ??93.8 | ??89.79 | ??89.41 | ??90.13 | ??91.57 | ??91.26 | ??38.2 |
Contrast table 4 and table 4 ' result, O is described, O '-two (phenmethyl) phosphorodithioic acid-N, N-diethyl ammonium be than O, O '-dicyclohexyl phosphorodithioic acid-N, the corrosion mitigating effect time length of N-diethyl ammonium is longer.
Present embodiment adds O, O '-phenylbenzene phosphorodithioic acid-N under the situation of sulfuric acid concentration identical (5%), N-diethyl ammonium, making it concentration is 40-160mg/L (seeing Table 5), under 25 ± 1 ℃ of temperature condition, be used for the pickling of Q235 steel, measure its corrosion inhibition rate respectively, the result is as shown in table 5.And with O, O '-phenylbenzene phosphorodithioic acid-N, N-diethyl ammonium concentration C (mg/L) is an X-coordinate, corrosion inhibition rate IE (%) is an ordinate zou, obtains, as shown in Figure 5 graph of a relation.
Table 5O, O '-phenylbenzene phosphorodithioic acid-N, N-diethyl ammonium concentration is to the influence of sulfuric acid pickling solution corrosion inhibition rate
| O, O '-phenylbenzene phosphorodithioic acid-N, N-diethyl ammonium concentration (mg/L) | ??40 | ??60 | ??80 | ??100 | ??120 | ??160 |
| Corrosion inhibition rate (%) | ??54 | ??80.4 | ??88.2 | ??90.9 | ??92.9 | ??92.9 |
According to The above results, in the 40-120mg/L concentration range, the sulfuric acid pickling solution corrosion inhibition rate is basically along with O, O '-diphenyl-methyl phosphorodithioic acid-N, the increase of N-diethyl ammonium concentration and increasing, corrosion inhibition rate be at O, O '-phenylbenzene phosphorodithioic acid-N, all reached 92.9% when N-diethyl ammonium concentration is 120mg/L, illustrated that then this inhibiter is a kind of good inhibiter.
The contriver has investigated the influence to corrosion inhibition rate of sour kind, acid concentration, pickle solution temperature and time equally, its result is referring to Fig. 6 and Fig. 7 and Fig. 8, as can be seen from the figure: O, O '-two (phenmethyl) phosphorodithioic acid-N, N-diethyl ammonium is subjected to the influence of acid concentration and temperature and action time all less.The contriver also will add the O of different concns, and O '-two (phenmethyl) phosphorodithioic acid-N, N-diethyl ammonium are used for other metal of pickling such as aluminium, copper, magnalium etc., and by measuring, its corrosion mitigating effect is good equally.
In addition, the contriver is also with different O, O '-disubstituted phosphorodithioic acid-N, N-diethyl ammonium is used for metal pickling, and density of corrosion inhibitor, acid concentration, sour kind, time to be measured, metal material (aluminium, copper, magnalium) etc. have been investigated, by measuring, learn its part of O, O '-disubstituted phosphorodithioic acid-N, N-diethyl ammonium, be that substituting group is other compounds except that phenmethyl of the alkyl of aryl, substituted aryl or aryl replacement, have equally than the more good corrosion mitigating effect of cyclohexyl replacement.
At last, the contriver is also with different O, O '-disubstituted phosphorodithioic acid-N, the corrosion inhibition of N-diethyl ammonium has carried out comparative study with the various factors that influences corrosion inhibition, learn part of O, O '-disubstituted phosphorodithioic acid-N, N-diethyl ammonium, being that substituting group is the compound of the alkyl of aryl, substituted aryl or aryl replacement, is a kind of even more ideal inhibiter.
The mensuration of corrosion inhibition rate IE (%) in the various embodiments described above, adopt static suspension weight-loss method and electrochemical method commonly used in the industry to carry out:
1) static suspension weight-loss method has been considered under differing temps, with the different metal materials prints such as Q235 steel after weighing respectively static suspension be soaked in blank solution (water) and the pickle solution, take out behind the 48h, wipe corrosion product, deionized water rinsing with vulcanite, acetone cleans, and weighs after the drying.According to its corrosion inhibition rate of weight loss data IE%, calculation formula is as follows:
In the formula, W
0And W
CorrThe weight loss rate of representing print in blank solution and the pickle solution respectively, unit are mg/cm
2.h.
2) electrochemical method, classical three-electrode system is adopted in research, and working electrode is cylindric Q235 steel, and reference electrode is saturated calomel (SCE) electrode, and supporting electrode is a Graphite Electrodes.The CHI440A electrochemical workstation is adopted in the scanning of electrokinetic potential polarization curve, sweep velocity 0.5mV/s, and the polarization scope is E
Corr± 250mV.Calculate its corrosion inhibition rate IE% according to electrochemical parameter, calculation formula is as follows:
In the formula, I
CorrAnd I '
CorrRepresent blank solution and the corrosion electric current density that is added with corrosion inhibitor solution, μ A/cm respectively
2
Embodiment 6
O, O '-phenylbenzene phosphorodithioic acid-N, the preparation of N-diethyl ammonium
Under the normal pressure, 22.2g thiophosphoric anhydride (0.1mol) and 30.1g phenol (0.32mol) are joined in the there-necked flask, add 50mL toluene or dimethylbenzene again, at 90 ℃ of heating 1h, reaction mixture is cold slightly, decolouring, filtered while hot.Filtrate is cooled to room temperature, under cooling and stirring, drips 24mL diethylamine (0.2mol), standing over night.Filtration under diminished pressure, solvent recrystallization is used in toluene or dimethylbenzene washing, and vacuum-drying gets white crystal O, O '-phenylbenzene phosphorodithioic acid-N, N-diethyl ammonium, productive rate is 81.6%, records fusing point to be: 125-127 ℃.
Embodiment 7
O, O '-phenylbenzene phosphorodithioic acid-N, the preparation of N-diethyl ammonium
Under the normal pressure, 22.2g thiophosphoric anhydride (0.1mol) and 45.1g phenol (0.48mol) are joined in the there-necked flask, add 80mL toluene or dimethylbenzene again, at 100 ℃ of heating 3h, reaction mixture is cold slightly, decolouring, filtered while hot.Filtrate is cooled to room temperature, under cooling and stirring, drips 44mL diethylamine (0.4mol), standing over night.Filtration under diminished pressure, solvent recrystallization is used in toluene or dimethylbenzene washing, and vacuum-drying gets white crystal O, O '-phenylbenzene phosphorodithioic acid-N, N-diethyl ammonium, productive rate is 82.3%, records fusing point to be: 125-127 ℃.
Embodiment 8
O, O '-phenylbenzene phosphorodithioic acid-N, the preparation of N-diethyl ammonium
Under the normal pressure, 22.2g thiophosphoric anhydride (0.1mol) and 30.1-45.1g phenol (0.4mol) are joined in the there-necked flask, add 50-80mL toluene or dimethylbenzene again, at 80 ℃ of heating 2h, reaction mixture is cold slightly, decolouring, filtered while hot.Filtrate is cooled to room temperature, under cooling and stirring, drips 33mL diethylamine (0.3mol), standing over night.Filtration under diminished pressure, solvent recrystallization is used in toluene or dimethylbenzene washing, and vacuum-drying gets white crystal O, O '-phenylbenzene phosphorodithioic acid-N, N-diethyl ammonium, productive rate is 81.2%, records fusing point to be: 125-127 ℃.
O, O '-two (styroyl) phosphorodithioic acid-N, the preparation of N-diethyl ammonium
Phenol with among the 2 phenylethyl alcohol replacement embodiment 6 has prepared O, O '-two (styroyl) phosphorodithioic acid-N, and N-diethyl ammonium, productive rate are 78.6%, fusing point is 84-85.5 ℃.
O, O '-two (phenmethyl) phosphorodithioic acid-N, the preparation of N-diethyl ammonium
Phenol with among the phenylcarbinol replacement embodiment 6 has prepared O, O '-two (phenmethyl) phosphorodithioic acid-N, and N-diethyl ammonium, productive rate are 89.9%, fusing point is 97-98 ℃.
Claims (4)
1. novel restrainer is characterized in that: have following structure (I):
In the structure: R
1And R
2Independently be selected from separately: the alkyl that aryl, substituted aryl or aryl replace.
2. novel restrainer according to claim 1 is characterized in that: R
1Carbonatoms be less than 40.
3. novel restrainer according to claim 1 is characterized in that: R
2Carbonatoms be less than 40.
4. the application of the described novel restrainer of claim 1 in preparation metal acid lotion, it is characterized in that: add restrainer in the pickling medium of different concns, the concentration that makes restrainer is 40-160mg/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010166782 CN101812693B (en) | 2010-05-10 | 2010-05-10 | A Novel Pickling Corrosion Inhibitor and Its Application in Preparation of Metal Pickling Agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010166782 CN101812693B (en) | 2010-05-10 | 2010-05-10 | A Novel Pickling Corrosion Inhibitor and Its Application in Preparation of Metal Pickling Agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101812693A true CN101812693A (en) | 2010-08-25 |
| CN101812693B CN101812693B (en) | 2012-04-25 |
Family
ID=42620056
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010166782 Expired - Fee Related CN101812693B (en) | 2010-05-10 | 2010-05-10 | A Novel Pickling Corrosion Inhibitor and Its Application in Preparation of Metal Pickling Agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101812693B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265573A (en) * | 2013-05-30 | 2013-08-28 | 四川理工学院 | Preparation method of O,O'-bis(phenylmethyl)dithiophosphoric acid benzyl ester and application of O,O'-bis(phenylmethyl)dithiophosphoric acid benzyl ester in metal pickling solution |
| CN103275353A (en) * | 2013-05-31 | 2013-09-04 | 四川理工学院 | Nitrogen and phosphorus halogen ternary flame retardant, preparation method of flame retardant and flame retardant material for preparing flame retardant |
| CN110016047A (en) * | 2019-05-21 | 2019-07-16 | 四川文理学院 | A kind of preparation method of new and effective antisludging agent DDTPA |
| CN110028170A (en) * | 2019-05-21 | 2019-07-19 | 四川文理学院 | A kind of efficient scale inhibitor and its application |
| CN110127871A (en) * | 2019-05-21 | 2019-08-16 | 四川文理学院 | A kind of Novel scale inhibitor and its application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1123316A (en) * | 1995-06-22 | 1996-05-29 | 中国石油化工总公司 | A kind of antiwear additive and preparation method thereof |
| CN1804125A (en) * | 2006-01-19 | 2006-07-19 | 重庆大学 | Metal pickling inhibitor and method for preparing the same |
| CN101146898A (en) * | 2005-03-21 | 2008-03-19 | 西巴特殊化学品控股有限公司 | Antiwear lubricant compositions for use in combustion engines |
-
2010
- 2010-05-10 CN CN 201010166782 patent/CN101812693B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1123316A (en) * | 1995-06-22 | 1996-05-29 | 中国石油化工总公司 | A kind of antiwear additive and preparation method thereof |
| CN101146898A (en) * | 2005-03-21 | 2008-03-19 | 西巴特殊化学品控股有限公司 | Antiwear lubricant compositions for use in combustion engines |
| CN1804125A (en) * | 2006-01-19 | 2006-07-19 | 重庆大学 | Metal pickling inhibitor and method for preparing the same |
Non-Patent Citations (1)
| Title |
|---|
| 《化工技术与开发》 20081031 李园等 钢铁及铁质文物有机缓蚀剂的研究进展 17-19 1-3 第37卷, 第10期 2 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265573A (en) * | 2013-05-30 | 2013-08-28 | 四川理工学院 | Preparation method of O,O'-bis(phenylmethyl)dithiophosphoric acid benzyl ester and application of O,O'-bis(phenylmethyl)dithiophosphoric acid benzyl ester in metal pickling solution |
| CN103265573B (en) * | 2013-05-30 | 2015-08-05 | 四川理工学院 | The preparation method of O, O '-two (phenmethyl) phosphorodithioic acid benzyl ester and the application in metal pickle liquor thereof |
| CN103275353A (en) * | 2013-05-31 | 2013-09-04 | 四川理工学院 | Nitrogen and phosphorus halogen ternary flame retardant, preparation method of flame retardant and flame retardant material for preparing flame retardant |
| CN110016047A (en) * | 2019-05-21 | 2019-07-16 | 四川文理学院 | A kind of preparation method of new and effective antisludging agent DDTPA |
| CN110028170A (en) * | 2019-05-21 | 2019-07-19 | 四川文理学院 | A kind of efficient scale inhibitor and its application |
| CN110127871A (en) * | 2019-05-21 | 2019-08-16 | 四川文理学院 | A kind of Novel scale inhibitor and its application |
| CN110016047B (en) * | 2019-05-21 | 2021-10-01 | 四川文理学院 | Preparation method of novel efficient scale inhibitor DDTPA |
| CN110028170B (en) * | 2019-05-21 | 2022-01-25 | 四川文理学院 | Efficient scale inhibitor and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101812693B (en) | 2012-04-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101812693A (en) | Novel pickling corrosion inhibitor and application thereof in preparing metal pickling agent | |
| Benbouguerra et al. | Synthesis, spectroscopic characterization and a comparative study of the corrosion inhibitive efficiency of an α-aminophosphonate and Schiff base derivatives: experimental and theoretical investigations | |
| Fawzy et al. | Thermodynamic, kinetic and mechanistic approach to the corrosion inhibition of carbon steel by new synthesized amino acids-based surfactants as green inhibitors in neutral and alkaline aqueous media | |
| Atta et al. | Corrosion inhibition, hydrogen evolution and antibacterial properties of newly synthesized organic inhibitors on 316L stainless steel alloy in acid medium | |
| Bentiss et al. | The substituted 1, 3, 4-oxadiazoles: a new class of corrosion inhibitors of mild steel in acidic media | |
| El-Naggar | Corrosion inhibition of mild steel in acidic medium by some sulfa drugs compounds | |
| El Ouafi et al. | New bipyrazole derivatives as effective inhibitors for the corrosion of mild steel in 1M HCI medium | |
| Hegazy et al. | Inhibition effect of novel nonionic surfactants on the corrosion of carbon steel in acidic medium | |
| Shaban et al. | Evaluation of some cationic surfactants based on dimethylaminopropylamine as corrosion inhibitors | |
| Deyab | Hydrogen evolution inhibition by L-serine at the negative electrode of a lead–acid battery | |
| Yaro et al. | Peach juice as an anti‐corrosion inhibitor of mild steel | |
| Aiad et al. | Enhancing of corrosion inhibition and the biocidal effect of phosphonium surfactant compounds for oil field equipment | |
| Chebabe et al. | Corrosion inhibition of Armco iron in 1 M HCl solution by alkyltriazoles | |
| CN100379717C (en) | Polyamine-Based Corrosion Inhibitors | |
| CN101531635B (en) | A kind of imidazoline unsymmetrical diquaternary ammonium salt and its preparation method and application | |
| CN102690702A (en) | Extreme-pressure abrasion-resistant open gear oil | |
| El Faydy et al. | Synthesis and application of new quinoline as hydrochloric acid corrosion inhibitor of carbon steel | |
| Yao et al. | Corrosion inhibition of iron in 20% hydrochloric acid by 1, 4/1, 6-bis (α-octylpyridinium) butane/hexane dibromide | |
| Kharchouf et al. | Effect of three 2-allyl-p-mentha-6, 8-dien-2-ols on inhibition of mild steel corrosion in 1 M HCl | |
| CN102586782B (en) | Corrosion inhibitor and preparation and application thereof | |
| CN101818349B (en) | Application of 1-myristyl-3-methylimidazolium chloride ionic liquid serving as steel corrosion inhibitor | |
| Shahi et al. | Comparison of dodecyl trimethyl ammonium bromide (DTAB) and cetylpyridinium chloride (CPC) as corrosion inhibitors for mild steel in sulphuric acid solution | |
| CN104342257A (en) | Precise copper strip rolling oil composition and application thereof | |
| Juan et al. | The Preparation of a Novel Corrosion Inhibitor and Its Corrosion Inhibition Behavior on 2024 Al‐Cu‐Mg Alloy in Acid Solution | |
| CN105755485A (en) | Novel water soluble metal pickling corrosion inhibitor and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120425 Termination date: 20200510 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |