CN101812693B - 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
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Abstract
The invention discloses a novel pickling corrosion inhibitor O,O'-di-substituted dithiophosphate-N, N-diethyl ammonium. Two substituted groups are separately selected from the following substituted groups: aryl, substituted aryl and aryl substituted alkyl; and the carbon atom number of one of two substituted groups is less than 40. The invention also discloses application of the O,O'-di-substituted dithiophosphate-N, N-diethyl ammonium serving as a metal pickling corrosion inhibitor. The O,O'-di-substituted dithiophosphate-N, N-diethyl ammonium is added into a pickling medium with different concentration to make the concentration be between 40 and 160 mg/L so as to achieve the effective metal corrosion inhibiting effect; and the pickling corrosion inhibitor disclosed by the invention has long lasting effect and wide applicable acidity range.
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, hope through 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 possibly appear in metallic corrosion; Yet impelled the continuous development in inhibiter field just because of these corrosion; Even so, still there are big, the defectives such as production cost is high, narrow in application range of toxicity low like inhibition efficiency, the part organic inhibitor 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.Like amine inhibitor corrosion mitigating effect under the situation of one-component is not fine, so need this type inhibiter carried out being applied after composite; Pyridine derivate and amine inhibitor have irritating smell mostly; This type of imidazolidine derivatives inhibiter 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 one type of compounds with 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 oxidation inhibitor and the anti-wear agent of sterilant and weedicide, lubricating oil and fuel oil, 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; One 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, has the good metal corrosion mitigating effect, and its corrosion inhibition receives the influence of temperature, acidity etc. 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 acidity scope that the time length of N-diethyl ammonium corrosion mitigating effect falls short of, is suitable for is wide inadequately, is necessary further to explore more excellent, as to have more development prospect novel restrainer.
Summary of the invention
Main purpose of the present invention is exactly to improve day by day and can satisfy some problems such as pickle solution shortage of this requirement at present to the requirement to metal pickle liquor corrosion inhibition each side that exists in the above-mentioned prior art; 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 scheme that the present invention adopts is following:
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 following:
In the said structure: R
1And R
2Independently be selected from separately: the substituted alkyl of aryl, substituted aryl or aryl.
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 YLENE again; At 80-130 ℃ of heating 1-3h; Reaction mixture is cold slightly, decolouring, filtered while hot.Filtrating is cooled to room temperature, under cooling and stirring, drips 22-44mL diethylamine (0.2-04mol), hold over night.Filtration under diminished pressure, solvent recrystallization is used in toluene or YLENE 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 through a large amount of experiments, with O, and O '-disubstituted phosphorodithioic acid-N; N-diethyl ammonium adds to according to said 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 receives 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 low in raw material cost, 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 through 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 when lower concentration, just can reach good corrosion inhibiting effect, referring to table 1:
Table 1: compound concentration is to the influence of sulfuric acid pickling solution corrosion inhibition rate
Can know by table 1, O, O '-two (phenmethyl) phosphorodithioic acid-N, N-diethyl ammonium corrosion mitigating effect is better, and when lower concentration, just can reach good corrosion inhibiting effect;
(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 done further to describe in detail as embodiment.
But should this 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 at sulfuric acid concentration identical (5%; Mass percentage concentration, down with) situation under, 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.
In order to investigate the relation of acid concentration and pickle solution corrosion inhibition rate; Present embodiment is with O, and O '-two (phenmethyl) phosphorodithioic acid-N, N-diethyl ammonium join 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, and is 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, and in concentration of hydrochloric acid was the 5-20% scope, the hydrochloric acid pickler corrosion inhibition rate changed 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, and O '-two (phenmethyl) phosphorodithioic acid-N, N-diethyl ammonium join 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, and is 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 received 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, and is 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 graph of a relation as shown in Figure 5.
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, explained 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 receives 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 through 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 investigated density of corrosion inhibitor, acid concentration, sour kind, time to be measured, metal material (aluminium, copper, magnalium) etc., through measuring, learn its part of O; O '-disubstituted phosphorodithioic acid-N; N-diethyl ammonium, promptly substituting group is other compounds except that phenmethyl of aryl, substituted aryl or the substituted alkyl of aryl, has equally than cyclohexyl to replace more good corrosion mitigating effect.
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 aryl, substituted aryl or the substituted alkyl of aryl, is a kind of even more ideal inhibiter.
The mensuration of corrosion inhibition rate IE (%) among above-mentioned each embodiment, 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 is weighed after the drying.According to its corrosion inhibition rate of weight loss data IE%, calculation formula is following:
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 following:
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 YLENE again, at 90 ℃ of heating 1h, reaction mixture is cold slightly, decolouring, filtered while hot.Filtrating is cooled to room temperature, under cooling and stirring, drips 24mL diethylamine (0.2mol), hold over night.Filtration under diminished pressure, solvent recrystallization is used in toluene or YLENE 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 YLENE again, at 100 ℃ of heating 3h, reaction mixture is cold slightly, decolouring, filtered while hot.Filtrating is cooled to room temperature, under cooling and stirring, drips 44mL diethylamine (0.4mol), hold over night.Filtration under diminished pressure, solvent recrystallization is used in toluene or YLENE 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 YLENE again, at 80 ℃ of heating 2h, reaction mixture is cold slightly, decolouring, filtered while hot.Filtrating is cooled to room temperature, under cooling and stirring, drips 33mL diethylamine (0.3mol), hold over night.Filtration under diminished pressure, solvent recrystallization is used in toluene or YLENE 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 ℃.
Embodiment 9
O, O '-two (styroyl) phosphorodithioic acid-N, the preparation of N-diethyl ammonium
Replace the phenol among the embodiment 6 with 2 phenylethyl alcohol, prepared O, O '-two (styroyl) phosphorodithioic acid-N, 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
Replace the phenol among the embodiment 6 with phenylcarbinol, prepared O, O '-two (phenmethyl) phosphorodithioic acid-N, N-diethyl ammonium, productive rate are 89.9%, fusing point is 97-98 ℃.
Claims (4)
1. the application of restrainer in preparation metal acid lotion, it is characterized in that: said restrainer has following structure (I):
In the structure: R
1And R
2Independently be selected from separately: the substituted alkyl of aryl, substituted aryl or aryl.
2. the application of restrainer according to claim 1 in preparation metal acid lotion is characterized in that: R in the said restrainer structure
1Carbonatoms be less than 40.
3. the application of restrainer according to claim 1 in preparation metal acid lotion is characterized in that: R in the said restrainer structure
2Carbonatoms be less than 40.
4. the application of restrainer according to claim 1 in preparation metal acid lotion, it is characterized in that: in the pickling medium of different concns, add restrainer, the concentration that makes restrainer is 40-160mg/L.
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| 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 |
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