CN104005035B - Polymerization inhibiter and preparation method thereof - Google Patents
Polymerization inhibiter and preparation method thereof Download PDFInfo
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- CN104005035B CN104005035B CN201410193126.5A CN201410193126A CN104005035B CN 104005035 B CN104005035 B CN 104005035B CN 201410193126 A CN201410193126 A CN 201410193126A CN 104005035 B CN104005035 B CN 104005035B
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Abstract
The invention provides a kind of efficient, environmental protection, the preparation of cation type polymer inhibiter cheap and easy to get and coated material thereof and application thereof.Inventive polymers inhibitor structure formula is:
can by solution polymerization process preparation polymerization inhibiter; Can also adopt further and obtain fine and close corrosion protection coating at metal material surface in-situ polymerization.Simply, cheaper starting materials is easy to get for inhibiter coating of the present invention and Macroscopic single crystal step thereof, belongs to environment-friendly corrosion inhibitor; Compared with inorganic inhibitor conventional at present, nontoxic, do not deposit environmental problem after a procedure, meet the trend of green corrosion inhibitor development; Experiment proves that inhibiter of the present invention can bear the change of various condition, and corrosion inhibition is good and stable; For metal material surface pickling, add the unwanted corrosion that a small amount of inhibiter effectively can suppress metallic substance, consumption is low compared with conventional inhibiter, has inhibition efficiency high, and continuous action ability waits outstanding advantages by force.
Description
Technical field
The invention belongs to chemosynthesis and applied technical field, particularly one 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, often there is " crossing erosion " phenomenon in acid cleaning process, namely not only remove dirt and the corrosion of metallic surface in acid cleaning process, also in the lump metal base has been disposed simultaneously.Therefore both can cause the corrosion of metallic substance in acid cleaning process, produce a large amount of acid solutions simultaneously, environment is 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) apply protective system and arrive metallic surface to stop corrosive medium; 3) in the corrosive medium residing for metal, inhibiter is added to slow down corrosion of metal.Add inhibiter when pickling, be suppress the corrosion of metal in acidic medium, reduce the usage quantity of acid, improve the service efficiency of acid, the effective way in extension device work-ing life.
Various metallic substance all has a wide range of applications in the every field of national economy, therefore uses inhibiter to carry out metal protection to hardware significant.Wherein organic inhibitor occupies an important position.Anodic Type organic inhibitor mostly is inorganic strong oxidizer, the interphase interaction of positive column, metallic surface and metal ion, and generation oxide compound or oxyhydroxide oxide film cover on anode and form protective membrane.Metal is so just inhibit to dissolve in water.Anodic reaction is controlled, and anode is passivated.But Anodic Type organic inhibitor requires higher concentration, to make whole anode all be passivated, once underdosage, cause spot corrosion by the position be not 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 of negative electrode release electronics is stopped.In actual applications, because calcium ion, carbanion and hydroxide ion are naturally occurring in aqueous, therefore the application of negatively charged ion organic inhibitor is restricted.
The inhibiter of current use 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 inhibitors containing oxynitrides such as coloured glaze base benzothiazole, benzotriazole, sulfonated lignin and POCA, the polymer chemistry thing polymer class inhibiter of some oligopolymer such as poly aspartic acid is when applying, generally the pH value of water controlled as subacidity, working conditions requires also comparatively harsh.
Organic inhibitor is by reaching the object of inhibition in metal material surface film forming.Corrosion mitigating effect is good at normal temperatures for conventional organic inhibitor, but this kind of inhibiter mostly is adsorption corrosion inhibitor, often based on physical adsorption, to corrosive medium and temperature very responsive, very easily come off from metal material surface when high temperature, decompose, thus lose its corrosion inhibitive function.Domestic at present also do not have a kind of inhibiter or inhibition system under high temperature or highly acidity situation, effectively to suppress metal material surface to corrode.But most of organic inhibitor is to environment and the toxic effect of life system, therefore find 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, cheap, the organic inhibitor be easy to get has higher productive value and wide market outlook.
In-situ polymerization is that one all adds reactive monomer (or its solubility performed polymer) and catalyzer in disperse phase (or external phase), because monomer (or performed polymer) is solvable 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 is polymerized, and after performed polymer aggregate size progressively increases, is deposited on substrate material surface.The concern that in-situ polymerization is subject to also gets more and more, and because the barrier of the material produced by this technology, mechanical property and antiseptic property are stronger, so global material market is constantly expanded, 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 serial propargyl alcohol type quaternary ammonium salt surfactant has excellent surfactivity, this tensio-active agent has better corrosion inhibition as inhibiter relative to general inhibiter, high temperature resistance and highly acidity performance.
The present invention, by solution polymerization process preparation polymerization bromination-N-alkyl pyridine propiolic alcohol, simultaneously at metal material surface in-situ polymerization bromination-N-alkyl pyridine propiolic alcohol, obtains fine and close corrosion protection coating, obtains the new polymers with corrosion inhibitive function.Polymerization further increases the high temperature resistance of inhibiter and the ability of highly acidity, and the anti-peracid high-temperature behavior of inhibiter coating that this in-situ polymerization obtains is better.
Summary of the invention
The object of the present invention is to provide a kind of efficient, environmental protection, the preparation of cation type polymer inhibiter cheap and easy to get and coated material thereof and application thereof.
The present invention is achieved through the following technical solutions.
Polymerization inhibiter has following general formula:
Wherein, o represent polymerizable substituent position at ortho position, m represents that polymerizable substituent is in a position, p represents that polymerizable substituent is in contraposition, and X represents Br
-or Cl
-, n is carbon atom number in pendant alkyl group, and k is the number of the monomer in polymkeric substance, i.e. chain number.
With adjacent, p-bromination-N-alkyl pyridine propiolic alcohol for raw material, the synthesis of applying soln polymerization process or in-situ polymerization are in the cation type polymer coating of metal material surface synthesis series of new, and its chemical reaction process is shown below.Wherein, o, m, p represent respectively substituting group position neighbour, contraposition; N is carbon atom number in pendant alkyl group, is respectively 6,8,10,12,14,16.Code name Po-6, 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, the Pp-16 respectively of polymkeric substance.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 be 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 adopts at metal material surface in-situ polymerization bromination-N-alkyl pyridine propiolic alcohol further, obtains fine and close corrosion protection coating.
Solution polymerization process:
(1) preparation of catalyzer
Bi triphenyl phosphorus palladium chloride 0.3-0.5mmol and cuprous iodide 0.1-0.2mmol is added in reactor, nitrogen protection is filled with after vacuumizing, the diethylamine 5-15ml of the new distillation of injection makes solvent, and then slowly inject propiolic alcohol 1-3mmol, stirred at ambient temperature 10-30 minute, then dilute with 5ml diethylamine, suction filtration, use diethylamine and washing with alcohol respectively, vacuum-drying;
(2) polyreaction
Catalyzer 0.01-0.1mmol prepared by bromination-N-alkyl pyridine propiolic alcohol 0.02mmol and step (1) is added in reactor; nitrogen protection is filled with after vacuumizing; injection trichloromethane/methyl alcohol 1:3-4:1 mixed solvent; slow stirring and refluxing 48 hours at 50-80 DEG C; reaction solution is dropwise added drop-wise in acetone or ethyl acetate; Precipitation fluffy solid, suction filtration drying obtains being polymerized inhibiter.
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 prepares
Smooth for metal material surface sand papering rear distilled water flushing is clean, then use acetone and dehydrated alcohol oil removing degreasing, be placed in vacuum drying oven and save backup;
(2) catalyst preparing
Bi triphenyl phosphorus palladium chloride 0.3-0.5mmol and cuprous iodide 0.1-0.2mmol is added in reactor, nitrogen protection is filled with after vacuumizing, the diethylamine 5-15ml of the new distillation of injection makes solvent, and then slowly inject propiolic alcohol 1-3mmol, stirred at ambient temperature 10-30 minute, then dilute with 5ml diethylamine, suction filtration, use diethylamine and washing with alcohol respectively, vacuum-drying;
(3) home position polymerization reaction
Catalyzer 0.01-0.1mmol prepared by bromination-N-alkyl pyridine propiolic alcohol 0.02mmol and step (2) is added in reactor, put into metallic substance prepared by step (1), nitrogen protection is filled with after vacuumizing, injection trichloromethane/methyl alcohol 1:3-4:1 mixed solvent, slow stirring and refluxing 48 hours at 50-80 DEG C, taken out by metallic substance after reaction terminates and hang, vacuum-drying is to constant weight; Dropwise be added drop-wise to by reaction solution in acetone or ethyl acetate, Precipitation fluffy solid, suction filtration drying obtains being polymerized inhibiter further.
In above-mentioned steps, each material consumption can change by identical multiple.
Above-mentioned steps realizes the in-situ polymerization in metallic surface and synthesizes simultaneously obtaining being polymerized inhibiter.
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 that obtains of polymkeric substance or situ aggregation method and polymkeric substance thereof, and synthesis step is simple, and cheaper starting materials is easy to get, and belongs to green type inhibiter.
2. environmental friendliness.Organic inhibitor of the present invention is compared with inorganic inhibitor conventional at present, nontoxic, does not deposit environmental problem after a procedure, meets the trend of green corrosion inhibitor development.
3. corrosion inhibition is high and stable.Experiment proves that inhibiter of the present invention can bear the change of various condition, example hydrochloric acid concentration (1-5M), temperature (30-90 DEG C) and soak time (1-5 days) etc., and corrosion inhibition is good and stable.
4. consumption is low, and result of use is good.Experiment proves that the present invention is used for metal material surface pickling, adds the unwanted corrosion that a small amount of inhibiter effectively can suppress metallic substance, and consumption is low compared with conventional inhibiter, has inhibition efficiency high, and continuous action ability waits outstanding advantages by force.
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;
Figure 18 is that concentration of hydrochloric acid affects variation relation figure to corrosion inhibition rate;
Figure 19 is that temperature and soak time are to in-situ polymerization Po-8 coating X
70the interact relation figure of steel corrosion inhibition rate;
Figure 20 and Figure 21 is thermogravimetric analysis and the difference quotient thermogravimetric analysis comparison diagram of in-situ polymerization Pp-12 coating and monomer p-12 respectively;
Figure 22 to Figure 24 is that corrosion inhibition rate is with the variation relation figure of density of corrosion inhibitor under condition of different temperatures respectively;
Figure 25 is non-polymer inhibiter condition X
70steel 60 DEG C, soak 3 hours in 5MHCl after scanning electron microscope (SEM) photograph;
Figure 26 is containing 50ppmPp-16 Polymer corrosion inhibitor condition X
70steel 60 DEG C, soak 3 hours in 5MHCl after scanning electron microscope (SEM) photograph;
Figure 27 and Figure 28 is 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
70the interact relation figure of steel corrosion inhibition rate.
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.
Catalyst preparing
Bi triphenyl phosphorus palladium chloride 0.3-0.5mmol and cuprous iodide 0.1-0.2mmol is added in reactor; nitrogen protection is filled with after vacuumizing; the diethylamine 5-15ml of the new distillation of injection makes solvent; and then slowly inject propiolic alcohol 1-3mmol; stirred at ambient temperature 10-30 minute, then dilute with 5ml diethylamine, suction filtration; use diethylamine and washing with alcohol respectively, for subsequent use after vacuum-drying.
Metallic substance prepares
Surface-area is about 10cm
2the smooth rear distilled water flushing of metal material surface sand papering clean, 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, the same method process of other metallic substance.
Embodiment 1
Synthesis poly-(bromination-2-(4-hydroxyl-2-butyne base)-N-cetyl pyridinium propiolic alcohol) and at X
70corrosion protection coating on steel disc
In 25ml two mouthfuls of round-bottomed flasks, add bromination-2-(4-hydroxyl-2-butyne base)-N-cetyl pyridinium propiolic alcohol 0.02mmol and catalyzer 0.04mmol, 29.6mg, and put into X for subsequent use
70steel disc, is filled with nitrogen protection after vacuumizing, and (reaction terminates rear carefully taking-up by steel disc and hangs injection trichloromethane/methyl alcohol, and vacuum-drying is to constant weight for volume ratio: 3/1) mixed solvent 10ml, slow stirring and refluxing 48 hours at 60 DEG C; Reaction solution is dropwise added drop-wise in acetone or ethyl acetate, Precipitation fluffy solid, and suction filtration drying can obtain being polymerized inhibiter further.
In aforesaid method, in reaction solution, do not put into X for subsequent use
70steel disc, can direct 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 through rate, 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 absorption of acetylene bond: 2102.05cm
-1, and in corresponding polymer P o-16, there is no this peak; The peak 1625.79cm that C=N or C=C absorbs is shown in Po-16
-1remarkable enhancing.
Fig. 2 to Fig. 8 is each section of mass spectrum of polymer P o-16, and the wherein relative intensity of fragment ion, X-coordinate is the position of molecular ion peak, i.e. molecular weight.Analyze known from figure, record molecular weight 745.5197,786.4078 for dimer; And 1068.5262,1319.8930,1089.4592,1216.0536,1244.0851 are tripolymer.
According to spectral data analysis result, the compound synthesized by explanation is target product.
Embodiment 2
Synthesis poly-(bromination-3-(4-hydroxyl-2-butyne base)-N-cetyl pyridinium propiolic alcohol) and at X
70corrosion protection coating on steel disc
Bromination-3-(4-hydroxyl-2-butyne base)-N-cetyl pyridinium propiolic alcohol 0.02mmol and catalyzer 0.04mmol, 29.6mg is added in 25ml two mouthfuls of round-bottomed flasks), and put into X for subsequent use
70steel disc, is filled with nitrogen protection after vacuumizing, and (reaction terminates rear carefully taking-up by steel disc and hangs injection trichloromethane/methyl alcohol, and vacuum-drying is to constant weight for volume ratio: 3/1) mixed solvent 10ml, slow stirring and refluxing 48 hours at 60 DEG C; Reaction solution is dropwise added drop-wise in acetone or ethyl acetate, Precipitation fluffy solid, and suction filtration drying can obtain being polymerized inhibiter.
In aforesaid method, in reaction solution, do not put into X for subsequent use
70steel disc, can direct 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 through rate, and X-coordinate is wave number.
Figure 10 to Figure 12 is each section of mass spectrum of polymer P m-16, and the wherein relative intensity of fragment ion, X-coordinate is the position of molecular ion peak, i.e. molecular weight.Analyze known from figure, record molecular weight 823.5600 for dimer; 1216.0574 and 1244.0871 are tripolymer.
Above-mentioned spectral data analysis and ortho position polymers analysis results similar, the compound synthesized by explanation is target product.
Embodiment 3
Synthesis poly-(bromination-4-(4-hydroxyl-2-butyne base)-N-cetyl pyridinium propiolic alcohol) and the corrosion protection coating on X70 steel disc thereof
In 25ml two mouthfuls of round-bottomed flasks, add bromination-4-(4-hydroxyl-2-butyne base)-N-cetyl pyridinium propiolic alcohol 0.02mmol and catalyzer 0.04mmol, 29.6mg, and put into X for subsequent use
70steel disc, is filled with nitrogen protection after vacuumizing, and (reaction terminates rear carefully taking-up by steel disc and hangs injection trichloromethane/methyl alcohol, and vacuum-drying is to constant weight for volume ratio: 3/1) mixed solvent 10ml, slow stirring and refluxing 48 hours at 60 DEG C; Reaction solution is dropwise added drop-wise in acetone or ethyl acetate, Precipitation fluffy solid, and suction filtration drying can obtain being polymerized inhibiter.
In aforesaid method, in reaction solution, do not put into X for subsequent use
70steel disc, can direct 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 through rate, 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.Analyze known from figure, record molecular weight 745.5234 for dimer; And 1094.7981 and 1319.8986 are tripolymer.
Above-mentioned spectral data analysis and ortho position polymers analysis results similar, the compound synthesized by explanation 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 synthesizes 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 three distilled water dilutings of the concentrated hydrochloric acid by 37% are prepared.
One, weight-loss method experiment
1) in-situ polymerization coating steel disc corrosion inhibition detects
Respectively by 100mL1, the hydrochloric acid soln of 3,5mol/L is placed in 100mL ground Erlenmeyer flask, with carrying out the cord of mark by the X of in-situ polymerization coating
70steel disc hangs in Erlenmeyer flask, solution submergence, is blank assay (blank X simultaneously
70steel disc is respectively the hydrochloric acid soln of 1,3,5mol/L).Erlenmeyer flask being placed in water bath with thermostatic control (being respectively 30 DEG C, 60 DEG C, 90 DEG C), soaking a couple of days (being respectively 1 day, 3 days, 5 days) without stirring.
From solution, take out carbon steel coupon, distilled water flushing after experiment terminates, then within 5 minutes, carry out dehydration cleaning by soaked in absolute ethyl alcohol.Carbon steel coupon after dehydration is put into acetone oil removing, removes surface corrosion product and polymeric coating, then dry up with cold wind, drying under room temperature is also weighed.According to X
70the weight loss of steel calculates its corrosion speed V (g/cm in hydrochloric acid
2d) with 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 100mL ground Erlenmeyer flask, and in bottle, adds the Polymer corrosion inhibitor (10-60ppm) of different concns respectively, then measure X with vernier callipers
70the size of carbon steel coupon, calculates its area.Electronic balance weighs up its weight.With carrying out the fine rule of mark by this X
70steel disc hangs in Erlenmeyer flask, solution submergence, does blank assay (the blank 5mol/L hydrochloric acid soln of non-addition polymerization compound inhibiter) simultaneously.Erlenmeyer flask being placed in water bath with thermostatic control (being respectively 30 DEG C, 60 DEG C, 90 DEG C), soaking 3h without stirring.
From solution, take out carbon steel coupon, distilled water flushing after experiment terminates, then within 5 minutes, carry out dehydration cleaning by soaked in absolute ethyl alcohol.Carbon steel coupon after dehydration is put into acetone oil removing, removes surface corrosion product, then dry up with cold wind, drying under room temperature is also weighed.According to X
70the weight loss of steel calculates its corrosion speed V (g/cm in hydrochloric acid
2h) with 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, the inhibition efficiency of absolute erosion rate and coating steel disc can be calculated:
V＝(W
0－W)/St
W in formula
0, the weight (g) before and after W-steel disc experiment;
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, the corrosion inhibition of in-situ polymerization coating steel disc is determined.
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 neighbour, contraposition.Analyzed from Figure 17: this serial in-situ polymerization coating steel disc soaks and all has good corrosion inhibition in 5 days in 30 DEG C of 5MHCl; Increase with carbonatoms object in polymer side alkyl group, inhibition efficiency slightly reduces.
Figure 18 is that concentration of hydrochloric acid affects variation relation figure to corrosion inhibition rate, and in figure, ordinate zou is corrosion inhibition rate (IE%), and X-coordinate is concentration of hydrochloric acid (C
hCl), unit mol/L; Pp-6, Pm-6, Po-6 represent Pp-6 coating, Pm-6 coating, the Po-6 coating of in-situ polymerization respectively, analyzed from Figure 18: polymer coated steel disc soaks and all presents good corrosion inhibition in 1 day in 30 DEG C of 5MHCl, and corrosion inhibition rate increases with the increase of concentration of hydrochloric acid; Pp-6 in-situ polymerization X
70steel soaks after one day in 5mol/L solution, and corrosion inhibition rate can reach 96.99%.
In addition, also having investigated temperature and soak time to the impact of in-situ polymerization coating steel disc corrosion inhibition, is that temperature and soak time are to in-situ polymerization Po-8 coating X for Po-8, Figure 19
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 1 day respectively, 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, is elevated to 90 DEG C with temperature from 30 DEG C, and corrosion inhibition rate change is very unobvious, shows the ability that this inhibiter has good resistance to high temperature corrosion; When extending to 5 days along with soak time from 1 day, the poly-corrosion inhibition rate of Po-8 coating to X70 steel does not only decline, and raises 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 is thermogravimetric analysis and the difference quotient thermogravimetric analysis comparison diagram of in-situ polymerization Pp-12 coating and monomer p-12 respectively, and in figure, TG is the percentage composition of surplus materials; DTG is the first order derivative of TG curve to temperature (or time).
From thermal gravimetric analysis results, P-12, when 232 DEG C and in-situ polymerization Pp-12 coating 242.21 DEG C, starts to decompose.Decompose completely at 450 DEG C of P-12, and still have the quality of 30% to remain at 600 DEG C of Pp-12.Thermogravimetric analysis test result illustrates that P-12 and Pp-12 is very stable within 200 DEG C, and the stability of in-situ polymerization thing film is more better.In-situ polymerization coating is expected to be used as high-temperature corrosion inhibitor.
2) according to previous experiments method, have rated synthesized polymers soln to X in 5MHCl
70the corrosion inhibition of carbon steel.
Figure 22 to Figure 24 is that corrosion inhibition rate (IE%) is with the variation relation of density of corrosion inhibitor under condition of different temperatures respectively, Figure 22 is 30 DEG C of temperature condition, Figure 23 is 60 DEG C of temperature condition, Figure 24 is 90 DEG C of temperature condition, in figure, ordinate zou is corrosion inhibition rate (IE%), and X-coordinate is density of corrosion inhibitor (C), unit ppm.
Analyzed from Figure 22 to Figure 24, this series polymer at different temperatures, to X in 5mol/L hydrochloric acid
70carbon steel all has good corrosion inhibition; Inhibition efficiency increases along with density of corrosion inhibitor and increases, and increases and slightly increase along with alkyl chain in molecule.For O-series polymer, X
70steel is in 60 DEG C of 5mol/L solution, and when its concentration is more than 20ppm, corrosion inhibition rate reaches more than 90%, reaches as high as 96.67%.
Table 2 is Po-16 corrosion inhibition rates (5MHCl, 3h) at different temperatures
From table 2 Data Comparison, inhibition efficiency increases along with Polymer corrosion inhibitor concentration and increases; When temperature is lower, inhibition efficiency raises with temperature and increases; And during high temperature, corrosion inhibition rate is still higher.Illustrate that this Polymer corrosion inhibitor has good high temperature resistant property.
Figure 25 is non-polymer inhibiter condition X
70steel 60 DEG C, soak 3 hours in 5MHCl after scanning electron microscope (SEM) photograph, Figure 26 is containing 50ppmPp-16 Polymer corrosion inhibitor condition X
70steel 60 DEG C, soak 3 hours in 5MHCl after scanning electron microscope (SEM) photograph.As can be seen from the figure, when there is no Polymer corrosion inhibitor, X
70steel is subject to the heavy corrosion of HCl, the corrosion product that steel surface coverage is a large amount of, has many corrosion holes.And after adding Pp-16, surface ratio is more smooth, extent of corrosion declines greatly.
In addition, also investigated acidity and soak time to the impact of polymkeric substance corrosion inhibition, for Pm-16, result is as shown in Figure 27 to Figure 29.
Figure 27 and Figure 28 is that acid concentration and soak time are to X in Pm-16 solution
70the impact of steel corrosion speed (V) is compared, and Figure 28 is the blank solution not having inhibiter, and 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 the time (t); In Figure 29, ordinate zou is corrosion inhibition rate (IE%), and X-coordinate is the time (t).
As can be seen from Fig. 27, Pm-16 concentration be 40ppm, 30 DEG C time, along with acidity strengthens, the erosion rate of X70 steel increases, but does not have (Figure 28) in the blank solution of inhibiter, along with time lengthening and acidity increase, X
70the erosion rate of steel improves faster, and by contrast, after adding Pm-16, along with time lengthening and acidity increase, corrosion inhibition rate also increases (Figure 29); Illustrate that this Polymer corrosion inhibitor has good corrosion inhibition, there is high temperature resistance, resistance to strong acid and persistence rot-resistant function.
Claims (5)
1. be polymerized inhibiter, it is characterized in that: there is following general formula
Wherein, polymerizable substituent position be adjacent, or contraposition, X is Br or Cl, n is carbon atom number in pendant alkyl group, and 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 pendant alkyl group, carbon atom number n is 6,8,10,12,14 or 16.
4. the preparation method of the polymerization inhibiter according to any one of claims 1 to 3,
It is characterized in that comprising the following steps:
(1) preparation of catalyzer
Bi triphenyl phosphorus palladium chloride 0.3-0.5mmol and cuprous iodide 0.1-0.2mmol is added in reactor, nitrogen protection is filled with after vacuumizing, the diethylamine 5-15ml of the new distillation of injection makes solvent, and then slowly inject propiolic alcohol 1-3mmol, stirred at ambient temperature 10-30 minute, then dilute with 5ml diethylamine, suction filtration, use diethylamine and washing with alcohol respectively, vacuum-drying;
(2) polyreaction
Catalyzer 0.01-0.1mmol prepared by bromination-N-alkyl pyridine propiolic alcohol 0.02mmol and step (1) is added in reactor, nitrogen protection is filled with after vacuumizing, injection trichloromethane/methyl alcohol volume ratio 1:3-4:1 mixed solvent, slow stirring and refluxing 48 hours at 50-80 DEG C, reaction solution is dropwise added drop-wise in acetone or ethyl acetate, Precipitation fluffy solid, suction filtration drying obtains being polymerized inhibiter;
In above-mentioned steps, each material consumption can change by identical multiple.
5. the preparation method of the polymerization inhibiter according to any one of claims 1 to 3,
It is characterized in that comprising the following steps:
(1) metallic substance prepares
By surface-area 10 ± 1cm
2the smooth rear distilled water flushing of metal material surface sand papering clean, then use acetone and dehydrated alcohol oil removing degreasing, be placed in vacuum drying oven and save backup;
(2) catalyst preparing
Bi triphenyl phosphorus palladium chloride 0.3-0.5mmol and cuprous iodide 0.1-0.2mmol is added in reactor, nitrogen protection is filled with after vacuumizing, the diethylamine 5-15ml of the new distillation of injection makes solvent, and then slowly inject propiolic alcohol 1-3mmol, stirred at ambient temperature 10-30 minute, then dilute with 5ml diethylamine, suction filtration, use diethylamine and washing with alcohol respectively, vacuum-drying;
(3) home position polymerization reaction
Catalyzer 0.01-0.1mmol prepared by bromination-N-alkyl pyridine propiolic alcohol 0.02mmol and step (2) is added in reactor, put into metallic substance prepared by step (1), nitrogen protection is filled with after vacuumizing, injection trichloromethane/methyl alcohol volume ratio 1:3-4:1 mixed solvent, slow stirring and refluxing 48 hours at 50-80 DEG C, taken out by metallic substance after reaction terminates and hang, vacuum-drying is to constant weight; Dropwise be added drop-wise to by reaction solution in acetone or ethyl acetate, Precipitation fluffy solid, suction filtration drying obtains being polymerized inhibiter further;
In above-mentioned steps, each material consumption can change by identical multiple.
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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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| 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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