CN104005035A - Polymer corrosion inhibitor and preparation method thereof - Google Patents
Polymer corrosion inhibitor and preparation method thereof Download PDFInfo
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- CN104005035A CN104005035A CN201410193126.5A CN201410193126A CN104005035A CN 104005035 A CN104005035 A CN 104005035A CN 201410193126 A CN201410193126 A CN 201410193126A CN 104005035 A CN104005035 A CN 104005035A
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Abstract
The invention provides a high-efficiency, environment-friendly, cheap and easily available cationic polymer corrosion inhibitor and preparation and application of a coating material of the cationic polymer corrosion inhibitor. The polymer corrosion inhibitor has a structural formula as described in the specification and can be prepared through solution polymerization. In situ polymerization can be further carried out on the surface of a metal material so as to obtain a compact anticorrosion coating. The corrosion inhibitor coating and the polymer thereof have the advantages of simple synthesis steps and cheap and easily available raw materials and are green and environment-friendly corrosion inhibitors. Compared with a common inorganic corrosion inhibitor in the prior art, the corrosion inhibitor provided by the invention has the advantages of no toxicity, no harm, no incurrence of environmental problems after usage and accordance with the development trend of green corrosion inhibitors. Experiments prove that the corrosion inhibitor provided by the invention can endure changes of various conditions and has good and stable corrosion inhibition performance; when used in surface pickling of a metal material, harmful corrosion of the metal material can be effectively inhibited by adding a small amount of the corrosion inhibitor, and the corrosion inhibitor has protruding advantages of a small application amount, high corrosion inhibition efficiency, good sustained action and the like compared with common corrosion inhibitors.
Description
Technical field
The invention belongs to chemosynthesis and applied technical field, particularly a kind of polymerization inhibiter and preparation method thereof.
Background technology
The corrosion of strong acid clean surface, dirt are the important cleaning means of pretreatment of metal surface, pipeline and boiler systems cleaning and descaling.Because strong acid all has corrosive nature to hardware, in acid cleaning process, often there is " crossing erosion " phenomenon, in acid cleaning process, not only removed dirt and the corrosion of metallic surface, also in the lump metal base has been disposed simultaneously.Therefore in acid cleaning process, both can cause the corrosion of metallic substance, produce a large amount of acid solutions simultaneously, environment was done great damage.At present, to the guard technology of hardware, be: 1) utilize alloying process to manufacture the non-corrosive metal of various uses; 2) coating protective system is to stop corrosive medium to arrive metallic surface; 3) in the residing corrosive medium of metal, add inhibiter to slow down corrosion of metal.When pickling, adding inhibiter, is to suppress the corrosion of metal in acidic medium, reduces sour usage quantity, improves sour service efficiency, the effective way in extension device work-ing life.
Therefore various metallic substance all have a wide range of applications in the every field of national economy, with inhibiter, hardware are carried out to metal protection significant.Wherein organic inhibitor occupies an important position.Anodic Type organic inhibitor mostly is inorganic strong oxidizer, between positive column, metallic surface and metal ion, interacts, and generates oxide compound or oxyhydroxide oxide film and covers and on anode, form protective membrane.So just suppressed metal dissolves in water.Anodic reaction is controlled, and anode is passivated.But Anodic Type organic inhibitor requires to have higher concentration, so that all anode is all passivated, once underdosage will cause spot corrosion at the position not being passivated.And cathode type organic inhibitor can react with the aqueous solution or with the cathodic area of metallic surface, its reaction product is in cathodic deposition film forming, and along with thickening of film, the reaction that negative electrode discharges electronics is blocked.In actual applications, because calcium ion, carbanion and hydroxide ion are naturally occurring in the aqueous solution, so the application of negatively charged ion organic inhibitor is restricted.
The inhibiter using at present mainly comprises the inorganic inhibitors such as chromic salt, nitrite, poly-phosphate chromic salt, and because it has toxic side effect, environment friendly is poor, and its application is just being restricted and is progressively eliminating.And some heterogeneous ring compound organic inhibitor and the POCA containing oxynitrides such as coloured glaze base benzothiazole, benzotriazole, sulfonated lignin, the polymer chemistry thing polymer class inhibiter of some oligopolymer such as poly aspartic acid is when application, generally the pH value of water is controlled for subacidity, working conditions requires also comparatively harsh.
Organic inhibitor is by reaching the object of inhibition in metal material surface film forming.Conventional organic inhibitor at normal temperatures corrosion mitigating effect is good, but this class inhibiter mostly is adsorption corrosion inhibitor, take often physical adsorption as main, very responsive to corrosive medium and temperature, when high temperature, very easily from metal material surface, come off, decompose, thereby lose its corrosion inhibitive function.At present domestic also do not have a kind of inhibiter or inhibition system can in high temperature or high acidity situation, effectively suppress metal material surface corrosion.Yet most of organic inhibitor, to environment and the toxic effect of life system, is therefore found novel corrosion inhibitor very urgent.Green corrosion inhibitor is not only in use nontoxic to environment, in manufacturing process, also can not cause detrimentally affect to environment.Therefore develop new efficient, environmental protection, cheapness, the organic inhibitor being easy to get has higher productive value and wide market outlook.
In-situ polymerization is a kind of reactive monomer (or its solubility performed polymer) and catalyzer all to be added in disperse phase (or external phase), because monomer (or performed polymer) is soluble in single-phase, and its polymkeric substance is soluble or sl. sol. in whole system, so polyreaction occurs on base material.Reaction starts, monomer pre-polymerization, and performed polymer polymerization, after performed polymer polymerization size progressively increases, is deposited on substrate material surface.The concern that in-situ polymerization is subject to is also more and more, because barrier, mechanical property and the antiseptic property of the material of producing by this technology are stronger, so the constantly expansion of global material market enjoys various circles of society to attract attention.
Chinese patent ZL201010541986.5 discloses a kind of propargyl alcohol type quaternary ammonium salt surfactant and preparation method thereof, this series propargyl alcohol type quaternary ammonium salt surfactant has good surfactivity, this tensio-active agent has better corrosion inhibition as inhibiter with respect to general inhibiter, high temperature resistance and high acidity performance.
The present invention prepares polymerization bromination-N-alkyl pyridine propiolic alcohol by solution polymerization process, simultaneously at metal material surface in-situ polymerization bromination-N-alkyl pyridine propiolic alcohol, obtains fine and close corrosion protection coating, obtains having the new polymers of corrosion inhibitive function.Polymerization has further improved the high temperature resistance of inhibiter and the ability of high acidity, and the anti-peracid high-temperature behavior of the inhibiter coating that obtains of this in-situ polymerization is better.
Summary of the invention
The object of the present invention is to provide a kind of efficient, environmental protection, cation type polymer inhibiter cheap and easy to get and preparation and the application thereof of coated material thereof.
The present invention is achieved through the following technical solutions.
Polymerization inhibiter has following general formula:
Wherein, o represent polymerization substituting group position at ortho position, m represents that polymerization substituting group is in a position, p represents that polymerization substituting group is in contraposition, X represents Br
-or Cl
-, n is carbon atom number in side chain alkyl, k is the number of the monomer in polymkeric substance, i.e. chain number.
Take adjacent,, p-bromination-N-alkyl pyridine propiolic alcohol is raw material, the synthetic or in-situ polymerization of applying soln polymerization process is in the cation type polymer coating of the synthetic series of new of metal material surface, its chemical reaction process is shown below.Wherein, o, m, p represent respectively substituting group position adjacent,, contraposition; N is carbon atom number in side chain alkyl, is respectively 6,8,10,12,14,16.The code name of polymkeric substance is Po-6 respectively, Po-8, Po-10, Po-12, Po-14, Po-16, Pm-6, Pm-8, Pm-10, Pm-12, Pm-14, Pm-16, Pp-6, Pp-8, Pp-10, Pp-12, Pp-14, Pp-16.As Pp-16 representative poly-(bromination 4-(4-hydroxyl fourth-2-alkynyl)-1-cetyl pyridinium); The number of the monomer in k representation polymer, k is greater than 1 integer;
Preparation method
The present invention adopts solution polymerization process to prepare polymerization bromination-N-alkyl pyridine propiolic alcohol, and the present invention also further adopts at metal material surface in-situ polymerization bromination-N-alkyl pyridine propiolic alcohol, obtains fine and close corrosion protection coating.
Solution polymerization process:
(1) preparation of catalyzer
In reactor, add bi triphenyl phosphorus palladium chloride 0.3-0.5mmol and cuprous iodide 0.1-0.2mmol, after vacuumizing, be filled with nitrogen protection, the diethylamine 5-15ml of the new distillation of injection makes solvent, and then slowly inject propiolic alcohol 1-3mmol, under room temperature, stir 10-30 minute, then with 5ml diethylamine, dilute suction filtration, use respectively diethylamine and washing with alcohol, vacuum-drying;
(2) polyreaction
To the catalyzer 0.01-0.1mmol that adds bromination-N-alkyl pyridine propiolic alcohol 0.02mmol and step (1) to prepare in reactor; after vacuumizing, be filled with nitrogen protection; injection trichloromethane/methyl alcohol 1:3-4:1 mixed solvent; at 50-80 ℃, slow stirring and refluxing is 48 hours; reaction solution is dropwise added drop-wise in acetone or ethyl acetate; the cotton-shaped solid of Precipitation, the dry polymerization inhibiter that obtains of suction filtration.
In above-mentioned steps, each material consumption can change by identical multiple.
Polymerization inhibiter obtained above can be directly used in the inhibiter of cleaning metal surface.
In-situ polymerization:
(1) metallic substance is prepared
Metal material surface is smooth rear clean with distilled water flushing with sand papering, then use acetone and dehydrated alcohol oil removing degreasing, be placed in vacuum drying oven and save backup;
(2) catalyzer preparation
In reactor, add bi triphenyl phosphorus palladium chloride 0.3-0.5mmol and cuprous iodide 0.1-0.2mmol, after vacuumizing, be filled with nitrogen protection, the diethylamine 5-15ml of the new distillation of injection makes solvent, and then slowly inject propiolic alcohol 1-3mmol, under room temperature, stir 10-30 minute, then with 5ml diethylamine, dilute suction filtration, use respectively diethylamine and washing with alcohol, vacuum-drying;
(3) home position polymerization reaction
To the catalyzer 0.01-0.1mmol that adds bromination-N-alkyl pyridine propiolic alcohol 0.02mmol and step (2) to prepare in reactor, put into metallic substance prepared by step (1), after vacuumizing, be filled with nitrogen protection, injection trichloromethane/methyl alcohol 1:3-4:1 mixed solvent, at 50-80 ℃, slow stirring and refluxing is 48 hours, after reaction finishes, metallic substance is taken out and hung, vacuum-drying is to constant weight; Reaction solution is dropwise added drop-wise in acetone or ethyl acetate to the cotton-shaped solid of Precipitation, the dry polymerization inhibiter that further obtains of suction filtration.
In above-mentioned steps, each material consumption can change by identical multiple.
Above-mentioned steps realizes at the in-situ polymerization of metallic surface and synthesizes and obtain polymerization inhibiter simultaneously.
Helpfulness of the present invention:
1. cost is low.Inhibiter effective constituent of the present invention is poly-(bromination-N-alkyl pyridine propiolic alcohol) coating and polymkeric substance thereof that polymkeric substance or situ aggregation method obtain, and synthesis step is simple, and raw material is cheap and easy to get, belongs to green type inhibiter.
2. environmental friendliness.Organic inhibitor of the present invention is compared with at present conventional inorganic inhibitor, nontoxic, does not have the environmental problem after use, meets the trend of green corrosion inhibitor development.
3. corrosion inhibition is high and stable.Experimental results show that inhibiter of the present invention can bear the variation of various conditions, example hydrochloric acid concentration (1-5M), temperature (30-90 ℃) and soak time (1-5 days) etc., corrosion inhibition is good and stable.
4. consumption is low, and result of use is good.Experimental results show that the present invention is for metal material surface pickling, add harmful corrosion that a small amount of inhibiter can effectively suppress metallic substance, to compare consumption low with conventional inhibiter, has inhibition efficiency high, and continuous action ability waits by force outstanding advantages.
Accompanying drawing explanation
Fig. 1 is the IR trace analysis of monomer o-16 and polymer P o-16;
Fig. 2 to Fig. 8 is each section of mass spectrum of polymer P o-16;
Fig. 9 is the IR trace analysis of monomer m-16 and polymer P m-16;
Figure 10 to Figure 12 is each section of mass spectrum of polymer P m-16;
Figure 13 is the IR trace analysis of monomer p-16 and polymer P p-16;
Figure 14 to Figure 16 is each section of mass spectrum of polymer P p-16;
Figure 17 is that in-situ polymerization coating is to X
70the corrosion inhibition rate of steel is with the variation relation figure of alkyl chain carbon atom number;
What Figure 18 was concentration of hydrochloric acid on corrosion inhibition rate affects variation relation figure;
Figure 19 is that temperature and soak time are to in-situ polymerization Po-8 coating X
70steel corrosion inhibition rate affect graph of a relation;
Figure 20 and Figure 21 are respectively thermogravimetric analysis and the difference quotient thermogravimetric analysis comparison diagrams of in-situ polymerization Pp-12 coating and monomer p-12;
Figure 22 to Figure 24 be respectively corrosion inhibition rate with density of corrosion inhibitor the variation relation figure under condition of different temperatures;
Figure 25 is non-polymer inhibiter condition X
70steel soaks the scanning electron microscope (SEM) photograph after 3 hours in 60 ℃, 5MHCl;
Figure 26 is containing 50ppmPp-16 polymkeric substance inhibiter condition X
70steel soaks the scanning electron microscope (SEM) photograph after 3 hours in 60 ℃, 5MHCl;
Figure 27 and Figure 28 are that acid concentration and soak time are to X in Pm-16 solution
70steel corrosion speed affect comparison diagram;
Figure 29 is that acid concentration and soak time are to X in Pm-16 solution
70steel corrosion inhibition rate affect graph of a relation.
Embodiment
Below by embodiment, the present invention is specifically described; the present embodiment is only for being further detailed the present invention; but can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art makes according to the content of the invention described above and adjustment also belong to the scope of protection of the invention.
Catalyzer preparation
In reactor, add bi triphenyl phosphorus palladium chloride 0.3-0.5mmol and cuprous iodide 0.1-0.2mmol; after vacuumizing, be filled with nitrogen protection; the diethylamine 5-15ml of the new distillation of injection makes solvent; and then slowly inject propiolic alcohol 1-3mmol; under room temperature, stir 10-30 minute, then with 5ml diethylamine, dilute suction filtration; use respectively diethylamine and washing with alcohol, standby after vacuum-drying.
Metallic substance is prepared
By the about 10cm of surface-area
2metal material surface smooth rear clean with distilled water flushing with sand papering, then use acetone and dehydrated alcohol oil removing degreasing, be placed in vacuum drying oven and save backup, this example employing X
70carbon steel coupon, is of a size of 3cm * 1.5cm * 0.3cm, and the same method of other metallic substance is processed.
Embodiment 1
Synthetic poly-(bromination-2-(4-hydroxyl-2-butyne base)-N-cetyl pyridinium propiolic alcohol) and at X
70corrosion protection coating on steel disc
In two mouthfuls of round-bottomed flasks of 25ml, add bromination-2-(4-hydroxyl-2-butyne base)-N-cetyl pyridinium propiolic alcohol 0.02mmol and catalyzer 0.04mmol, 29.6mg, and put into standby X
70steel disc, is filled with nitrogen protection after vacuumizing, and injection trichloromethane/methyl alcohol (volume ratio: 3/1) mixed solvent 10ml, slow stirring and refluxing 48 hours at 60 ℃, reaction finishes carefully steel disc to be taken out and hung afterwards, and vacuum-drying is to constant weight; Reaction solution is dropwise added drop-wise in acetone or ethyl acetate, the cotton-shaped solid of Precipitation, and suction filtration is dry can further obtain polymerization inhibiter.
In aforesaid method, in reaction solution, do not put into standby X
70steel disc, directly synthesized polymer inhibiter.
Polymerization inhibitor structure formula obtained above is as follows:
Infrared, mass spectrometry results.
Fig. 1 is the IR trace analysis of monomer o-16 and polymer P o-16, and in figure, top curve is monomer o-16 collection of illustrative plates, and lower curve is polymer P o-16 collection of illustrative plates; Ordinate zou is transmitance, and X-coordinate is wave number, and polymer P o-16 result is as following table 1;
Table 1, the infrared spectrum of Po-16 is resolved
| cm -1. | Ownership | cm -1. | Ownership |
| 3427.71, | H 2O | 3032.36 | OH |
| 2920.77，2851.56 | CH 3，CH 2 | 1509.97 | Pyridine ring |
| 1165.55，1100.98， | Pyridine ring | 1625.79 | C＝N，C＝C |
| 1469.34，1372.21 | CH 3，CH 2 | ? | ? |
The infrared spectrum of contrast Po-16 and O-16 is not difficult to find, P-16 has the characteristic infrared of acetylene bond to absorb: 2102.05cm
-1, and in corresponding polymer P o-16, there is no this peak; In Po-16, show the peak 1625.79cm that C=N or C=C absorb
-1significantly strengthen.
Fig. 2 to Fig. 8 is each section of mass spectrum of polymer P o-16, the relative intensity of fragment ion wherein, and X-coordinate is the position of molecular ion peak, i.e. molecular weight.From figure, analyze knownly, record molecular weight 745.5197,786.4078 for dimer; And 1068.5262,1319.8930,1089.4592,1216.0536,1244.0851 be tripolymer.
According to spectroscopic data analytical results, the compound that synthesized is described is target product.
Embodiment 2
Synthetic poly-(bromination-3-(4-hydroxyl-2-butyne base)-N-cetyl pyridinium propiolic alcohol) and at X
70corrosion protection coating on steel disc
In two mouthfuls of round-bottomed flasks of 25ml, add bromination-3-(4-hydroxyl-2-butyne base)-N-cetyl pyridinium propiolic alcohol 0.02mmol and catalyzer 0.04mmol, 29.6mg), and put into standby X
70steel disc, is filled with nitrogen protection after vacuumizing, and injection trichloromethane/methyl alcohol (volume ratio: 3/1) mixed solvent 10ml, slow stirring and refluxing 48 hours at 60 ℃, reaction finishes carefully steel disc to be taken out and hung afterwards, and vacuum-drying is to constant weight; Reaction solution is dropwise added drop-wise in acetone or ethyl acetate, the cotton-shaped solid of Precipitation, and suction filtration is dry can obtain polymerization inhibiter.
In aforesaid method, in reaction solution, do not put into standby X
70steel disc, directly synthesized polymer inhibiter.
Polymerization inhibitor structure formula obtained above is as follows:
Infrared, mass spectrometry results.
Table 2, FT-IR (KBr, cm
-1)
| cm -1. | Ownership | cm -1. | Ownership |
| 3396.05 | H 2O | 3045.33 | OH |
| 2923.57，2852.80 | CH 3，CH 2 | 1509.74 | Pyridine ring |
| 1164.87,1100.74 | Pyridine ring | 1627.50，1582.31 | C＝N，C＝C |
| 1461.08，1373.40 | CH 3，CH 2 | ? | ? |
Fig. 9 is the IR trace analysis of monomer m-16 and polymer P m-16, and in figure, top curve is monomer m-16 collection of illustrative plates, and lower curve is polymer P m-16 collection of illustrative plates; Ordinate zou is transmitance, and X-coordinate is wave number.
Figure 10 to Figure 12 is each section of mass spectrum of polymer P m-16, the relative intensity of fragment ion wherein, and X-coordinate is the position of molecular ion peak, i.e. molecular weight.From figure, analyze knownly, record molecular weight 823.5600 for dimer; 1216.0574 and 1244.0871 be tripolymer.
Above-mentioned spectroscopic data analysis and ortho position polymers analysis results are similar, and the compound that synthesized is described is target product.
Embodiment 3
Synthetic poly-(bromination-4-(4-hydroxyl-2-butyne base)-N-cetyl pyridinium propiolic alcohol) and the corrosion protection coating on X70 steel disc thereof
In two mouthfuls of round-bottomed flasks of 25ml, add bromination-4-(4-hydroxyl-2-butyne base)-N-cetyl pyridinium propiolic alcohol 0.02mmol and catalyzer 0.04mmol, 29.6mg, and put into standby X
70steel disc, is filled with nitrogen protection after vacuumizing, and injection trichloromethane/methyl alcohol (volume ratio: 3/1) mixed solvent 10ml, slow stirring and refluxing 48 hours at 60 ℃, reaction finishes carefully steel disc to be taken out and hung afterwards, and vacuum-drying is to constant weight; Reaction solution is dropwise added drop-wise in acetone or ethyl acetate, the cotton-shaped solid of Precipitation, and suction filtration is dry can obtain polymerization inhibiter.
In aforesaid method, in reaction solution, do not put into standby X
70steel disc, directly synthesized polymer inhibiter.
Polymerization inhibitor structure formula obtained above is as follows:
Infrared, mass spectrometry results.
Table 3, FT-IR (KBr, cm
-1)
| cm -1. | Ownership | cm -1. | Ownership |
| 3397.98 | H 2O | 2969.57 | OH |
| 2925.60，2855.58 | CH 3，CH 2 | 1509.13 | Pyridine ring |
| 1089.12 | Pyridine ring | 1640.70 | C＝N，C＝C |
| 1463.55，1378.57 | CH 3，CH 2 | ? | ? |
Figure 13 is the IR trace analysis of monomer p-16 and polymer P p-16, and in figure, top curve is monomer p-16 collection of illustrative plates, and lower curve is polymer P p-16 collection of illustrative plates; Ordinate zou is transmitance, and X-coordinate is wave number.
Figure 14 to Figure 16 is each section of mass spectrum of polymer P p-16, and wherein ordinate zou is the relative intensity of fragment ion, and X-coordinate is the position of molecular ion peak, i.e. molecular weight.From figure, analyze knownly, record molecular weight 745.5234 for dimer; And 1094.7981 and 1319.8986 be tripolymer.
Above-mentioned spectroscopic data analysis and ortho position polymers analysis results are similar, and the compound that synthesized is described is target product.
Test example
The present invention, according to GB10124-88 < < Uniform Corrosion Method of Laboratory Immersion Test method > >, adopts static steel weight-loss method method to detect the corrosion inhibition of in-situ polymerization coating steel disc.
Raw material required for the present invention is synthetic according to method described in (propargyl alcohol type quaternary ammonium salt surfactant and preparation method thereof ZL201010541986.5).
The present invention's etchant solution used is respectively the hydrochloric acid soln of 1,3,5mol/L, and the concentrated hydrochloric acid by 37% is prepared with three distilled water dilutings.
One, weight-loss method experiment
1) in-situ polymerization coating steel disc corrosion inhibition detects
By 100mL1, the hydrochloric acid soln of 3,5mol/L is placed in 100mL ground Erlenmeyer flask respectively, uses the cord of carrying out mark by the X of in-situ polymerization coating
70steel disc hangs in Erlenmeyer flask, and blank assay (blank X is in solution submergence simultaneously
70steel disc is respectively the hydrochloric acid soln of 1,3,5mol/L).Erlenmeyer flask is placed in to water bath with thermostatic control (be respectively 30 ℃, 60 ℃, 90 ℃), without stirring, soak a couple of days (be respectively 1 day, 3 days, 5 days).
Experiment is taken out carbon steel coupon after finishing from solution, and distilled water flushing, then with the soaked in absolute ethyl alcohol cleaning of dewatering for 5 minutes.Carbon steel coupon after dehydration is put into acetone oil removing, remove surface corrosion product and polymeric coating, then with cold wind, dry up, under room temperature, be dried and weigh.According to X
70the weight loss of steel calculates its corrosion speed V (g/cm in hydrochloric acid
2d) and inhibition efficiency IE%.Carry out three groups of parallel tests, getting its mean value is test result simultaneously.
2) polymers soln corrosion inhibition is evaluated
The hydrochloric acid soln of 100mL5mol/L is placed in to 100mL ground Erlenmeyer flask, and in bottle, adds respectively the polymkeric substance inhibiter (10-60ppm) of different concns, then with vernier callipers, measure X
70the size of carbon steel coupon, calculates its area.Electronic balance weighs up its weight.With the fine rule of carrying out mark by this X
70steel disc hangs in Erlenmeyer flask, and blank assay (the not blank 5mol/L hydrochloric acid soln of addition polymerization compound inhibiter) is done in solution submergence simultaneously.Erlenmeyer flask is placed in to water bath with thermostatic control (be respectively 30 ℃, 60 ℃, 90 ℃), without stirring, soaks 3h.
Experiment is taken out carbon steel coupon after finishing from solution, and distilled water flushing, then with the soaked in absolute ethyl alcohol cleaning of dewatering for 5 minutes.Carbon steel coupon after dehydration is put into acetone oil removing, remove surface corrosion product, then with cold wind, dry up, under room temperature, be dried and weigh.According to X
70the weight loss of steel calculates its corrosion speed V (g/cm in hydrochloric acid
2h) and inhibition efficiency IE%.Carry out three groups of parallel tests, getting its mean value is test result simultaneously.
Two, the calculating of erosion rate:
According to the weightlessness of steel disc, can calculate the inhibition efficiency of absolute erosion rate and coating steel disc:
V＝(W
0－W)/St
W in formula
0, the weight (g) before and after the experiment of W-steel disc;
Surface-area (the cm of S-steel disc
2);
T-inhibition experimental period (d);
V-erosion rate (g/cm
2d)
The calculating of corrosion inhibition rate:
V in formula
0-blank X
70absolute erosion rate (the g/cm of carbon steel
2d)
Absolute erosion rate (the g/cm of V-in-situ polymerization coating X70 carbon steel
2d)
IE%-inhibition efficiency
IE％＝(V
0－V)/V
0×100％
Three, experimental result
1), according to previous experiments method, measured the corrosion inhibition of in-situ polymerization coating steel disc.
Figure 17 is that in-situ polymerization coating is to X
70the corrosion inhibition rate of steel is with the variation relation figure of alkyl chain carbon atom number, and in figure, ordinate zou is corrosion inhibition rate (IE%), and X-coordinate is alkyl chain carbon atom number n; In figure o, m, p represent respectively substituting group position adjacent,, contraposition.By Figure 17, analyzed known: this series in-situ polymerization coating steel disc soaks and within 5 days, all has good corrosion inhibition in 30 ℃ of 5MHCl; With carbonatoms object in polymer side alkyl group, increase, inhibition efficiency slightly reduces.
Figure 18 be concentration of hydrochloric acid on corrosion inhibition rate affect variation relation figure, in figure, ordinate zou is corrosion inhibition rate (IE%), X-coordinate is concentration of hydrochloric acid (C
hCl), the mol/L of unit; Pp-6, Pm-6, Po-6 represent respectively Pp-6 coating, Pm-6 coating, the Po-6 coating of in-situ polymerization, by Figure 18, analyzed known: polymer coated steel disc soaks and within 1 day, all presents good corrosion inhibition in 30 ℃ of 5MHCl, and corrosion inhibition rate increases with the increase of concentration of hydrochloric acid; Pp-6 in-situ polymerization X
70steel soaked after one day in 5mol/L solution, and corrosion inhibition rate can reach 96.99%.
In addition, also investigated the impact on in-situ polymerization coating steel disc corrosion inhibition of temperature and soak time, take Po-8 as example, Figure 19 is that temperature and soak time are to in-situ polymerization Po-8 coating X
70the impact of steel corrosion inhibition rate (IE%), in figure, ordinate zou is corrosion inhibition rate (IE%), and X-coordinate is temperature (T), and 1d, 3d, 5d represent respectively 1 day, 3 days, 5 days.As can be seen from Fig. 19, in-situ polymerization Po-8 coating X
70steel soaks different time in 1MHCl solution, with temperature, is elevated to 90 ℃ from 30 ℃, and corrosion inhibition rate changes very unobvious, has shown that this inhibiter has the ability of good resistance to high temperature corrosion; When along with soak time extended to 5 days from 1 day, gather Po-8 coating the corrosion inhibition rate of X70 steel is not only declined, raise on the contrary.Illustrate that in-situ polymerization coating is to X
70steel has good corrosion inhibition, can effectively suppress high concentration of hydrochloric acid and high temperature resistance to X
70the corrosion of steel.
Figure 20 and Figure 21 are respectively thermogravimetric analysis and the difference quotient thermogravimetric analysis comparison diagrams of in-situ polymerization Pp-12 coating and monomer p-12, the percentage composition that in figure, TG is surplus materials; DTG is that TG curve is to the temperature first order derivative of (or time).
From thermogravimetric analysis result, P-12, when 242.21 ℃ of 232 ℃ and in-situ polymerization Pp-12 coatings, starts to decompose.At 450 ℃ of P-12, decompose completely, and still have 30% quality residual at 600 ℃ of Pp-12.Thermogravimetric analysis test result explanation P-12 and Pp-12 are at 200 ℃ with interior very stable, and the stability of in-situ polymerization thing film is more better.In-situ polymerization coating is expected as high-temperature corrosion inhibitor.
2), according to previous experiments method, evaluated the polymers soln of synthesized to X in 5MHCl
70the corrosion inhibition of carbon steel.
Figure 22 to Figure 24 be respectively corrosion inhibition rate (IE%) with density of corrosion inhibitor the variation relation under condition of different temperatures, Figure 22 is 30 ℃ of temperature condition, Figure 23 is 60 ℃ of temperature condition, Figure 24 is 90 ℃ of temperature condition, in figure, ordinate zou is corrosion inhibition rate (IE%), and X-coordinate is density of corrosion inhibitor (C), the ppm of unit.
From Figure 22 to Figure 24, analyzed, this series polymer under differing temps, in 5mol/L hydrochloric acid to X
70carbon steel all has good corrosion inhibition; Inhibition efficiency is along with density of corrosion inhibitor increases and increases, along with alkyl chain in molecule increases and slightly increases.For O-series polymer, X
70steel is in 60 ℃ of 5mol/L solution, and when its concentration surpasses 20ppm, corrosion inhibition rate reaches more than 90%, reaches as high as 96.67%.
Table 2 is Po-16 corrosion inhibition rates (5MHCl, 3h) under differing temps
From table 2 Data Comparison, inhibition efficiency is along with polymkeric substance density of corrosion inhibitor increases and increases; When temperature is lower, inhibition efficiency raises and increases with temperature; And during high temperature, corrosion inhibition rate is still higher.Illustrate that this polymkeric substance inhibiter has good high temperature resistant property.
Figure 25 is non-polymer inhibiter condition X
70steel soaks the scanning electron microscope (SEM) photograph after 3 hours in 60 ℃, 5MHCl, and Figure 26 is containing 50ppmPp-16 polymkeric substance inhibiter condition X
70steel soaks the scanning electron microscope (SEM) photograph after 3 hours in 60 ℃, 5MHCl.As can be seen from the figure, while there is no polymkeric substance inhibiter, X
70steel is subject to the heavy corrosion of HCl, and the corrosion product that steel surface coverage is a large amount of has many corrosion holes.And add after Pp-16, surface ratio is more smooth, and extent of corrosion declines greatly.
In addition, also investigated the impact on polymkeric substance corrosion inhibition of acidity and soak time, take Pm-16 as example, result is as shown in Figure 27 to Figure 29.
Figure 27 and Figure 28 are that acid concentration and soak time are to X in Pm-16 solution
70steel corrosion speed (V) affect comparison, Figure 28 is the blank solution that there is no inhibiter, Figure 29 is that acid concentration and soak time are to X in Pm-16 solution
70the impact of steel corrosion inhibition rate (IE%).In Figure 27 and Figure 28, ordinate zou is erosion rate (V), and X-coordinate is time (t); In Figure 29, ordinate zou is corrosion inhibition rate (IE%), and X-coordinate is time (t).
As can be seen from Fig. 27, in Pm-16 concentration, be 40ppm, 30 ℃ time, along with acidity strengthens, the erosion rate of X70 steel increases, but does not have in the blank solution of inhibiter (Figure 28), along with time lengthening and acidity increase, X
70the erosion rate of steel improves faster, by contrast, adds after Pm-16, and along with time lengthening and acidity increase, corrosion inhibition rate also increases (Figure 29); Illustrate that this polymkeric substance inhibiter has good corrosion inhibition, there is high temperature resistance, resistance to strong acid and persistence rot-resistant function.
Claims (6)
1. polymerization inhibiter, is characterized in that: have following general formula
Wherein, polymerization substituting group position be adjacent, or contraposition, X is Br
-or Cl
-, n is carbon atom number in side chain alkyl, k is the number of the monomer in polymkeric substance.
2. polymerization inhibiter according to claim 1, is characterized in that: wherein X is Br
-.
3. polymerization inhibiter according to claim 1, is characterized in that: wherein in side chain alkyl carbon atom number n be 6,8,10,12,14 or 16.
4. polymerization inhibiter according to claim 1, is characterized in that: wherein k is the number of the monomer in polymkeric substance, and k is greater than 1 integer.
5. according to the preparation method of the polymerization inhibiter described in claim 1 to 4 any one,
It is characterized in that comprising the following steps:
(1) preparation of catalyzer
In reactor, add bi triphenyl phosphorus palladium chloride 0.3-0.5mmol and cuprous iodide 0.1-0.2mmol, after vacuumizing, be filled with nitrogen protection, the diethylamine 5-15ml of the new distillation of injection makes solvent, and then slowly inject propiolic alcohol 1-3mmol, under room temperature, stir 10-30 minute, then with 5ml diethylamine, dilute suction filtration, use respectively diethylamine and washing with alcohol, vacuum-drying;
(2) polyreaction
To the catalyzer 0.01-0.1mmol that adds bromination-N-alkyl pyridine propiolic alcohol 0.02mmol and step (1) to prepare in reactor, after vacuumizing, be filled with nitrogen protection, injection trichloromethane/methyl alcohol 1:3-4:1 mixed solvent, at 50-80 ℃, slow stirring and refluxing is 48 hours, reaction solution is dropwise added drop-wise in acetone or ethyl acetate, the cotton-shaped solid of Precipitation, the dry polymerization inhibiter that obtains of suction filtration;
In above-mentioned steps, each material consumption can change by identical multiple.
6. according to the preparation method of the polymerization inhibiter described in claim 1 to 4 any one,
It is characterized in that comprising the following steps:
(1) metallic substance is prepared
By surface-area 10 ± 1cm
2metal material surface with sand papering smooth rear clean with distilled water flushing, then use acetone and dehydrated alcohol oil removing degreasing, be placed in vacuum drying oven and save backup;
(2) catalyzer preparation
In reactor, add bi triphenyl phosphorus palladium chloride 0.3-0.5mmol and cuprous iodide 0.1-0.2mmol, after vacuumizing, be filled with nitrogen protection, the diethylamine 5-15ml of the new distillation of injection makes solvent, and then slowly inject propiolic alcohol 1-3mmol, under room temperature, stir 10-30 minute, then with 5ml diethylamine, dilute suction filtration, use respectively diethylamine and washing with alcohol, vacuum-drying;
(3) home position polymerization reaction
To the catalyzer 0.01-0.1mmol that adds bromination-N-alkyl pyridine propiolic alcohol 0.02mmol and step (2) to prepare in reactor, put into metallic substance prepared by step (1), after vacuumizing, be filled with nitrogen protection, injection trichloromethane/methyl alcohol 1:3-4:1 mixed solvent, at 50-80 ℃, slow stirring and refluxing is 48 hours, after reaction finishes, metallic substance is taken out and hung, vacuum-drying is to constant weight; Reaction solution is dropwise added drop-wise in acetone or ethyl acetate to the cotton-shaped solid of Precipitation, the dry polymerization inhibiter that further obtains of suction filtration;
In above-mentioned steps, each material consumption can change by identical multiple.
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Cited By (3)
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| CN104649913A (en) * | 2014-11-19 | 2015-05-27 | 西华师范大学 | N-alkyl aminomethyl aniline as well as synthesis and polymer thereof and application of N-alkyl aminomethyl aniline in metal surface anticorrosion |
| CN113122031A (en) * | 2019-12-31 | 2021-07-16 | 江苏苏博特新材料股份有限公司 | In-situ polymerization type metal corrosion inhibitor and application thereof |
| CN115466960A (en) * | 2022-09-15 | 2022-12-13 | 河北工业大学 | Preparation method and application of benzothiazole group-containing modified polyaspartic acid fluorescent corrosion inhibitor |
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| CN102049213A (en) * | 2010-11-12 | 2011-05-11 | 西华师范大学 | Propargyl alcohol type quaternary ammonium salt surfactant and preparation method thereof |
| CN102382638A (en) * | 2011-09-20 | 2012-03-21 | 南京华洲新材料有限公司 | Application of pyridine compound for preparing acidization corrosion inhibitors |
| CN102796502A (en) * | 2012-09-11 | 2012-11-28 | 西华师范大学 | Corrosion inhibitor bromide-N-alkyl pyridine-acrylate and method for preparing same |
| CN103289670A (en) * | 2013-05-24 | 2013-09-11 | 华中科技大学 | Polymer corrosion inhibitor and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102049213A (en) * | 2010-11-12 | 2011-05-11 | 西华师范大学 | Propargyl alcohol type quaternary ammonium salt surfactant and preparation method thereof |
| CN102382638A (en) * | 2011-09-20 | 2012-03-21 | 南京华洲新材料有限公司 | Application of pyridine compound for preparing acidization corrosion inhibitors |
| CN102796502A (en) * | 2012-09-11 | 2012-11-28 | 西华师范大学 | Corrosion inhibitor bromide-N-alkyl pyridine-acrylate and method for preparing same |
| CN103289670A (en) * | 2013-05-24 | 2013-09-11 | 华中科技大学 | Polymer corrosion inhibitor and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104649913A (en) * | 2014-11-19 | 2015-05-27 | 西华师范大学 | N-alkyl aminomethyl aniline as well as synthesis and polymer thereof and application of N-alkyl aminomethyl aniline in metal surface anticorrosion |
| CN113122031A (en) * | 2019-12-31 | 2021-07-16 | 江苏苏博特新材料股份有限公司 | In-situ polymerization type metal corrosion inhibitor and application thereof |
| CN115466960A (en) * | 2022-09-15 | 2022-12-13 | 河北工业大学 | Preparation method and application of benzothiazole group-containing modified polyaspartic acid fluorescent corrosion inhibitor |
| CN115466960B (en) * | 2022-09-15 | 2023-05-26 | 河北工业大学 | Preparation method and application of benzothiazole group-containing modified polyaspartic acid fluorescent corrosion inhibitor |
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