CN108103544B - A kind of resistance rust means of defence of armored concrete - Google Patents
A kind of resistance rust means of defence of armored concrete Download PDFInfo
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- CN108103544B CN108103544B CN201711170646.4A CN201711170646A CN108103544B CN 108103544 B CN108103544 B CN 108103544B CN 201711170646 A CN201711170646 A CN 201711170646A CN 108103544 B CN108103544 B CN 108103544B
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/02—Electrolytic coating other than with metals with organic materials
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/06—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
- C07D233/08—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms with alkyl radicals, containing more than four carbon atoms, directly attached to ring carbon atoms
- C07D233/10—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms with alkyl radicals, containing more than four carbon atoms, directly attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring nitrogen atoms
Abstract
The present patent application discloses a kind of resistance rust means of defence of armored concrete; uniformly closed protective film can be formed in rebar surface; inside concrete consolidation resistance to compression is without gap;, the following steps are included: triethylene tetramine and phthalic anhydride 1) are put into dimethylbenzene, reaction obtains compound 1 for it；2) compound 1 and lauric acid are put into dimethylbenzene, acylation reaction obtains compound 2；3) compound 2 and hydrazine hydrate are put into dehydrated alcohol, stirs to get compound 3；4) compound 3 is put into dimethylbenzene, reaction obtains bis-imdazoline；5) bis-imdazoline is activated, obtains cationic bis-imdazoline；6) using the aqueous solution of cationic bis-imdazoline as electrolyte, using reinforcing bar as cathode, power supply connects cathode and anode, energization.
Description
Technical field
The present invention relates to reinforced concrete technology field, in particular to the resistance rust means of defence of a kind of armored concrete.
Background technique
In sea port dock, strand facility, hydraulic engineering, armored concrete is under bar in chlorine salt solution, causes steel bar corrosion,
Corrosion failure reinforced concrete structure reduces the durability of concrete structure, causes economic loss heavy.It is asked for reinforcement corrosion
Patch reparation can be used, using the methods of special reinforcing steel in topic, when engineering control, prevention then using incorporation corrosion inhibitor, surface covering,
The methods of cathodic protection.In the resistance rust measure of numerous reinforcing bars, reinforcing steel bar corrosion inhibitor is due to environment-friendly and low-toxicity, economical and practical, operation letter
Just the attention of industry is received.Domestic and international reinforcing steel bar corrosion inhibitor mainly uses doped in application process at present, to migration-type
The research of reinforcing steel bar corrosion inhibitor is still in infancy, and many problems do not solve.
Existing concrete electrical mobility corrosion inhibitor is mainly amine or hydramine type organic, and to other species compounds
It studies less, although hydramine type organic is very mature, can buy on the market, the purity of synthesis is low, uses resistance
Become rusty less effective.Main reason is that the cation ratio that alcamines dissociates in aqueous solution is less, so electromigration ability compared with
It is weak, quick, fully penetrated it cannot arrive rebar surface.It can be seen that carrying out the study on prevention of reinforcement corrosion, especially to service phase
Between and by the armored concrete that bar in chlorine salt solution is encroached on, take economical rationality, technical feasibility, excellent resistance rust against corrosion and reparation side
Method has great society and economic value.
Summary of the invention
The technical problem to be solved by the invention is to provide a kind of economical rationality, technical feasibility, excellent reinforcing bar against corrosion are mixed
The resistance rust means of defence for coagulating soil, can form uniformly closed protective film in rebar surface.
The present invention is as follows to the technical solution of above-mentioned technical problem: a kind of resistance rust means of defence of armored concrete,
It the following steps are included:
1) by molar ratio be 1:1.5~1:2.5 triethylene tetramine and phthalic anhydride put into dimethylbenzene, 130~
150 DEG C of 10~15h of reaction remove excess of solvent, obtain compound 1；
2) compound 1 and lauric acid that molar ratio is 1:1.5~1:2.5 are put into dimethylbenzene, 130~150 DEG C of progress
6~10h of acylation reaction removes excess of solvent, obtains compound 2；
3) compound 2 and hydrazine hydrate that molar ratio is 1:0.5~1:1.5 are put into dehydrated alcohol, stirring 2 under room temperature~
4h removes excess of solvent, obtains compound 3；
4) compound 3 is put into dimethylbenzene, 130~150 DEG C of 6~10h of reaction remove excess of solvent, obtain bicyclic imidazo
Quinoline；
5) bis-imdazoline is activated, obtains cationic bis-imdazoline；
6) using the aqueous solution of cationic bis-imdazoline as electrolyte, using the reinforcing bar of armored concrete as cathode, power supply
Connect cathode and anode, energization.
A kind of resistance rust means of defence of armored concrete of the present invention compared with prior art, has the advantages that and shows
The progress of work:
Step 1)~step 4) uses commercially available cheap solvent drug, and reaction condition is not necessarily to remove oxygen, and the reaction time is short, instead
Solvent is removed after answering, processing is easy, and purer bis-imdazoline can be obtained.After step 5) activates bis-imdazoline,
The cationic bis-imdazoline of formation is a kind of imidazoline quaternary ammonium salt, soluble easily in water, there is apparent surface-active, can be in water
It will be completely dissociated out cation in solution, electromigration ability significantly increases under electric field action, quick, fully penetrated to arrive bar list
Face has excellent technical effect applied to the resistance rust of armored concrete and reparation；Step 6) is under electric field action, in concrete
Anode direction flowing of the anion such as chloride ion into electrolyte solution and be discharged, and the bicyclic miaow of cationic in solution
As corrosion inhibitor cation, the reinforcing bar into concrete flows oxazoline, and is attached to rebar surface, forms film layer, i.e., " forms a film "
Effect prevents chloride ion, hydrogen etc. from entering reinforcing bar, and then prevents corrosion, prevents hydrogen embrittlement.Meanwhile cationic bis-imdazoline
It in transition process, when adjourning the hole in concrete, can be filled in hole, i.e. " consent " effect, and then increase concrete
Intensity extends the service life of armored concrete.To in the resistance rust protection process of armored concrete, rebar surface is formed the present invention
Uniformly closed protective film, inside concrete consolidation resistance to compression is without gap.The resistance rust means of defence warp of above-mentioned armored concrete
Ji rationally, it is technical feasibility, against corrosion excellent.
Preferably, the activation method of the step 5) are as follows: introduce cationic quaternary amine reagent into bis-imdazoline, be dissolved in
Toluene removes solvent after completion of the reaction, obtains cationic bis-imdazoline in 60~90 DEG C of at a temperature of 10~20h of reaction.
It is further preferred that concentration of the bis-imdazoline in toluene is 0.04~0.06mol/L；The cationic quaternary amineization examination
The ratio between amount of substance of agent and the bis-imdazoline is 2:0.5~2:1.5.
Preferably, the cationic quaternary amine reagent is one of sodium chloroacetate, bromoacetic acid sodium, sodium iodoacetate.
Preferably, the anode is one of graphite, stainless (steel) wire, titanium net, wire netting.It is further preferred that anode
Partly or entirely it is immersed in electrolyte.Anode is close to armored concrete.
Preferably, the concentration of the electrolyte is 0.01~2mol/L.
Preferably, after energization the current density of reinforcing bar in 0.1~10A/m2。
Preferably, the molecular structure of the bis-imdazoline is as follows:
The bis-imdazoline includes two imidazoline heterocycles and two lauric long alkyl chains, two imidazoline heterocycles
Outer end connects lauric long alkyl chain, connects two carbon atoms among two imidazoline heterocycles.On the one hand, imidazoline heterocycle contains
There are two N atoms, and two N atoms more individual to the adsorption capacity of transition metal are strong, and the supplied for electronic of the entire heterocycle of N atom pair
Effect significantly increases cloud density on imidazoline heterocycle, and imidazoline heterocycle is made to be capable of providing enough electronics and transition gold
Belong to the empty d track firm connection that atom does not occupy.Two carbon atoms are only connected among two five-ring heterocycles of bis-imdazoline,
Away from small, two five-ring heterocycles integrally have certain conjugation, further increase cloud density on imidazolyl heterocycle, make miaow
Oxazoline heterocycle is capable of providing the d rail in enough electronics and transition metal atoms not being occupied by an electron or do not fully taken up by electronics
Road firm connection.On the other hand, lauric long alkyl chain is linked by 11 carbon atom straight chains, has good hydrophobicity, by
Its hydrophobic membrane formed can guarantee to cover in the omnidirection of metal surface, region-wide height, and this film layer quite securely with
Densification has very efficient physical barrier ability to the diffusion of metal surface to corrosive medium in solution.Above-mentioned bicyclic imidazo
Quinoline stable chemical performance, is unlikely to deteriorate, and is very beneficial for applying the resistance rust dimension being particularly suitable in corrosion inhibitor field to reinforcing bar
Shield.
Preferably, the molecular structure of the cationic bis-imdazoline is as follows:
The cationic bis-imdazoline is a kind of imidazoline quaternary ammonium salt, soluble easily in water, there is apparent surface-active, energy
Enough to will be completely dissociated out cation in aqueous solution, electromigration ability significantly increases under electric field action, quick, fully penetrated to arrive steel
Muscle surface can be used for newly-built concrete structure and be used for the resistance rust of armored concrete and repair, promote built concrete
The durability of structure.
Preferably, the step 1)~step 4) bis-imdazoline synthesis path is as follows:
Rationally, strong operability, processing is easy, and product is pure, and yield is high for the synthesis path design of above-mentioned bis-imdazoline.System
The bis-imdazoline stable chemical performance obtained, is unlikely to deteriorate.In addition, using commercially available cheap solvent drug, reaction condition is not necessarily to
Except oxygen, the reaction time is short, and processing is easy after reaction, and reaction yield is high, is conducive to industrialized production.
Preferably, in step 1), the amount of the substance of the phthalic anhydride is not less than the substance of the triethylene tetramine
Amount.The theoretical molar of the triethylene tetramine and phthalic anhydride ratio is 1:2, and dimethylbenzene, will be anti-as azeotropic agent
The water and xylenes that should be generated are discharged after condensing, and reaction generates compound 1.
Preferably, in step 2), the amount of the lauric substance is not less than the amount of the substance of the compound 1.Step
It 2) is acylation reaction, the theoretical molar ratio that compound 1 and lauric acid react is 1:2；Use dimethylbenzene as azeotropic agent, more favorably
It reacts, water and xylenes that reaction generates is discharged after condensing, yield is higher in compound 1 and lauric acid.
Preferably, in step 3), the amount of the substance of the hydrazine hydrate is not less than the amount of the substance of the compound 2.Into one
Preferably, the ratio between amount of substance of the amount of the substance of the hydrazine hydrate and the compound 2 is greater than 3 to step.Use hydrazine hydrate and nothing
Water-ethanol can slough the cyclisation object on 2 both sides of compound under room temperature.
Preferably, in step 4), use dimethylbenzene as azeotropic agent, further cyclodehydration, product bis-imdazoline exists
Temperature is faint yellow flowing oily liquids when higher (being higher than 50 DEG C), in compared with strong basicity (pH is 10~11).Product bicyclic imidazo
Quinoline is cooling to be frozen into faint yellow solid by liquid retrogradation.
Detailed description of the invention
Fig. 1 is the synthesis path of bis-imdazoline of the present invention.
Fig. 2 is that the hydrogen of bis-imdazoline of the present invention is composed.
Fig. 3 is the schematic device of the resistance rust means of defence of armored concrete of the present invention.
Specific embodiment
The present invention is described in further details in the following with reference to the drawings and specific embodiments, but the present invention be not only limited to
Lower specific embodiment.
The molecular structure of bis-imdazoline is as follows:
Fig. 2 is that the hydrogen of bis-imdazoline is composed, and abscissa is chemical shift, and specific chemical shift and peak area are as follows,1H-
NMR(400MHz,CDCl3): 0.88 (t, 6H, CH3C),1.29(t,32H,C(CH2)8C),1.62(m,4H,CH2(CH2)8CH3),
2.19(t,4H,CH2), C=N 2.52 (t, 8H, CH2), NC 3.32 (t, 4H, C=NCH2)。
Fig. 3 is the schematic device of the resistance rust means of defence of armored concrete, and electrolyte is cationic bis-imdazoline
Aqueous solution, reinforcing bar is cathode, and graphite, stainless (steel) wire or titanium net are anode；The anode of power supply is connect with external anode, power supply
The connection of the reinforcing bar of cathode and armored concrete, the bottom surface of concrete are equipped with arrangement graphite, stainless (steel) wire or titanium net (i.e. external sun
Pole, external anode are contacted with the bottom surface of concrete or are not contacted), supporting plate is equipped with below external anode, in concrete
Anode direction of the anion such as chloride ion into electrolyte solution is flowed and is discharged, and the cationic bicyclic imidazo in solution
As corrosion inhibitor cation, the reinforcing bar into concrete flows quinoline, and is attached to rebar surface, forms film layer；Meanwhile cation
Type bis-imdazoline is in transition process, when adjourning the hole in concrete, can be filled in hole.
Multiple compounds involved in the present invention, wherein triethylene tetramine, phthalic anhydride, dimethylbenzene, lauric acid, hydration
Hydrazine, toluene, sodium chloroacetate, bromoacetic acid sodium, sodium iodoacetate are commercially available, and compound 1, compound 2, compound 3, bicyclic imidazo
Quinoline, cationic bis-imdazoline are the compound of present invention design synthesis, have embodiment in synthesis path, can refer to synthesis
The molecular structure in path is understood.
The parameter occurred in synthetic method of the present invention and activation method, such as temperature, time, weight percent, there are also answered
Parameters, the expression ways of these parameters such as concentration of electrolyte, the current density that the used time uses are one section of models that the upper limit is limited to from down
Enclose, unit (as DEG C, h, wt%, mol/L, A/m2) be unified in the upper limit after mark, such as 130~150 DEG C, 10~15h, 26~
30wt%, 0.01~2mol/L, 0.1~10A/m2.It is, of course, also possible to using unit is marked after upper limit value and lower limit value, such as
130 DEG C~150 DEG C, 10h~15h, 26wt%~30wt%, 0.01mol/L~2mol/L, 0.1A/m2~10A/m2.Both
The expression way of parameter area all can band after numerical value in embodiment to the upper limit, two endpoint values of lower limit and intermediate value
Unit.In addition, the reactant, raw material used in synthesizing in synthetic method of the invention have some preferred proportions, such as triethylene four
The molar ratio (i.e. the ratio between the amount of substance) of amine and phthalic anhydride is 1:1.5~1:2.5, compound 1 and lauric rubs
Your ratio is 1:1.5~1:2.5, and the representation method of these proportions is the range from lower limit ratio to upper limit ratio.Certainly, may be used also
To use than preceding paragraph as a numerical value, than it is consequent be a segment limit representation method, such as triethylene tetramine and phthalic anhydride
Molar ratio is 1:(1.5~2.5), compound 1 and lauric molar ratio be 1:(1.5~2.5).
The organic compound of synthesis is applied to reinforced concrete by present invention combination organic synthesis and armored concrete field
Soil, thus it is related to two fields of organic synthesis field and armored concrete.
For the technical staff of organic synthesis field, explanation belongs to basic theories and experimental technique below, but in order to
It helps armored concrete field or other references to be understood using the personnel of the content of present invention, makes as described below: 1) synthesizing
Raw material, product have specific molecular structure, these molecular structures are clearly expressed in synthesis path, pass through nucleus magnetic hydrogen spectrum
Mode identified.2) in reactant, (reactant herein refers to triethylene tetramine, compound 1, compound 2, change to reaction process
Close object 3) in use additive (commercially available), solvent (commercially available), the raw material used according to the theoretical molar of chemical equation match come
Addition, the addition proportion of reactant is then different because of situation in practice, commercially available to add generally for obtaining the principal product of higher yields
Add object (substance on synthesis path arrow, such as phthalic anhydride, lauric acid, hydrazine hydrate) and solvent (such as dimethylbenzene, first
Benzene) it is generally excessive, the material cost that these are bought is low, facilitates processing after reaction；In industrial production, to commercially available addition
Object, the additive amount of solvent are then more；It is sometimes not high to productivity requirements and in scientific research, at this time reactant very high to purity requirement
It may be excessive.So the addition of various raw materials matches not absolute range in synthetic method, after adding necessary raw material,
The stoichiometric reacted can be realized；So the proportion of raw material is not limited in the claims, certainly, this
Invention has preferred scope in summary of the invention, lists preferred proportion in embodiment.3) reaction condition (temperature, time) is then
It is got by repeatedly probing into, for the parameter of these reaction conditions in the present invention with Range Representation, claim limits these ranges
It is scheduled within the scope of call parameter, summary of the invention, embodiment are related to further preferred embodiment.4) use dimethylbenzene as taking water
The water of generation and xylenes are discharged after condensing for agent, that is, indicate to react successfully.
For the technical staff in armored concrete field, explanation belongs to basic theories and experimental technique below, but is
Help organic synthesis field or other with reference to being understood using the personnel of the content of present invention, make as described below.It is general next
It says, electrical mobility corrosion inhibitor need to meet following 3 conditions: 1) corrosion inhibitor must have preferable water solubility, and being dissolved in after water being capable of ion
Change；2) the resistance rust group formed after ionizing must be cation group；3) after being powered under certain current density, corrosion inhibitor should
Rebar surface is reached in short period (three weeks was to one month) interior fast transferring, infiltration, and accumulates enough concentration to mixed
Solidifying soil reinforcing bar forms effective corrosion protection.It is that the aqueous solution of corrosion inhibitor is made into electrolyte, steel when using electrical mobility corrosion inhibitor
Muscle makees cathode, and anode is sacrificial electrode, is powered and forms an electric field, cation transport to reinforcing bar, forms protective film in rebar surface；
Anion transport leaves reinforcing bar to anode, and then reinforcing bar is prevented to be rusted.
Embodiment provided below is not intended to limit the invention covered range, and described step is also not use
Sequence is executed to limit its.Those skilled in the art combine existing common knowledge to do conspicuous improvement to the present invention, also fall
Enter the present invention claims protection scope within.
Embodiment one
A kind of resistance of armored concrete is become rusty means of defence, it the following steps are included:
1) 4mol triethylene tetramine and 6mol phthalic anhydride are put into 200ml dimethylbenzene, 130 DEG C of reaction 15h are removed
Excess of solvent generates compound 1；
2) 2mol compound 1 and 3mol lauric acid are put into 100ml dimethylbenzene, 130 DEG C of progress acylation reaction 10h are removed
Excess of solvent generates compound 2；
3) 1mol compound 2 and 0.5mol hydrazine hydrate are put into 100ml dehydrated alcohol, 2h is stirred under room temperature, it is extra to remove
Solvent obtains compound 3；
4) 0.5mol compound 3 is put into 100ml dimethylbenzene, 130 DEG C of reaction 10h remove excess of solvent, obtain bicyclic miaow
Oxazoline；
5) 0.1mol sodium chloroacetate is added into 0.05mol bis-imdazoline, is dissolved in 100ml toluene, is reacted at 80 DEG C
15h removes solvent after completion of the reaction, obtains cationic bis-imdazoline；
6) using concentration for the cationic bis-imdazoline of 0.01mol/L aqueous solution as electrolyte, in concrete surface
Arrangement wire netting makees anode, and wire netting is close to armored concrete, is all immersed in electrolyte；It is yin with the reinforcing bar of armored concrete
Pole, power supply connect cathode and anode, are powered 25 days；The current density of reinforcing bar is in 0.1A/m after energization2。
The molecular structure of the bis-imdazoline is as follows:
The step 1)~step 4) bis-imdazoline synthesis path is as follows:
The molecular structure of the cationic bis-imdazoline is as follows:
Embodiment two
A kind of resistance rust means of defence of armored concrete, comprising the following steps:
1) 4mol triethylene tetramine and 10mol phthalic anhydride are put into 100ml dimethylbenzene, 150 DEG C of reaction 10h are removed
Excess of solvent is removed, compound 1 is generated；
2) 2mol compound 1 and 5mol lauric acid are put into 100ml dimethylbenzene, 150 DEG C of progress acylation reaction 6h are removed more
Remaining solvent generates compound 2；
3) 1mol compound 2 and 1.5mol hydrazine hydrate are put into 100ml dehydrated alcohol, 4h is stirred under room temperature, it is extra to remove
Solvent obtains compound 3；
4) 0.5mol compound 3 is put into 100ml dimethylbenzene, 150 DEG C of reaction 6h remove excess of solvent, obtain bicyclic miaow
Oxazoline；
5) 0.1mol bromoacetic acid sodium is added into 0.05mol bis-imdazoline, is dissolved in 100ml toluene, is reacted at 90 DEG C
10h removes solvent after completion of the reaction, obtains cationic bis-imdazoline；
6) using concentration for the cationic bis-imdazoline of 2mol/L aqueous solution as electrolyte, concrete surface arrange
Wire netting makees anode, and wire netting is close to armored concrete, is all immersed in electrolyte；Using the reinforcing bar of armored concrete as cathode,
Power supply connects cathode and anode, is powered 20 days；The current density of reinforcing bar is in 10A/m after energization2。
Embodiment three
A kind of resistance rust means of defence of armored concrete, comprising the following steps:
1) 4mol triethylene tetramine and 8mol phthalic anhydride are put into 100ml dimethylbenzene, 140 DEG C of reaction 12h are removed
Excess of solvent generates compound 1；
2) 2mol compound 1 and 4mol lauric acid are put into 100ml dimethylbenzene, 140 DEG C of progress acylation reaction 8h are removed more
Remaining solvent generates compound 2；
3) 1mol compound 2 and 1mol hydrazine hydrate are put into 100ml dehydrated alcohol, 3h is stirred under room temperature, removed extra molten
Agent obtains compound 3；
4) 0.5mol compound 3 is put into 100ml dimethylbenzene, 140 DEG C of reaction 8h remove excess of solvent, obtain bicyclic miaow
Oxazoline；
5) 0.1mol sodium iodoacetate is added into 0.05mol bis-imdazoline, is dissolved in 100ml toluene, is reacted at 60 DEG C
20h removes solvent after completion of the reaction, obtains cationic bis-imdazoline；
6) using concentration for the cationic bis-imdazoline of 1mol/L aqueous solution as electrolyte, concrete surface arrange
Wire netting makees anode, and wire netting is close to armored concrete, is all immersed in electrolyte；Using the reinforcing bar of armored concrete as cathode,
Power supply connects cathode and anode, is powered 15 days；The current density of reinforcing bar is in 1A/m after energization2。
Product test
One, cationic bis-imdazoline corrosion inhibitor is tested
Weight-loss method is a kind of method of resistance to corrosion of the research metal in corrosion inhibitor solution, and principle is to pass through measurement
Metal impregnates mass loss after a certain period of time in aggressive solutions, finds out its corrosion rate.Weight-loss method measuring method is simple
Easy, to equipment without particular/special requirement, and measurement result is accurate, reliable, is widely used in metal erosion field.
With saturated calcium hydroxide solution simulated concrete pore solution, in order to accelerate corrosion rate, in simulation concrete hole
The sodium chloride of 3% (mass fraction) is added in liquid.Used in experiment 10 × 100mm of Φ common plain bar (work area for
25πmm2≈0.785cm2), it is successively polished step by step derusting with the water-proof abrasive paper of 600 mesh, 1000 mesh, 2000 mesh before experiment, use
The hydrochloric acid of 0.1mol/L washes away the corrosion product of rebar surface.Washes of absolute alcohol is used again, removes degreasing, the steel handled well
Muscle weighs after dry and records every steel bar quality.Using triethylene tetramine, cationic bis-imdazoline prepared by the present invention
The corrosion inhibitor solution of two kinds of corrosion inhibitor sample preparations 1L, 2wt% is put into reinforcing bar 6 handled well in every kind of corrosion inhibitor solution, soaks
After steeping 7d, 14d, temporally every kind of match ratio solution takes out 3 respectively, washes away surface corrosion product, claims after being dried in vacuo constant weight
Quality calculates mass loss and corrosion inhibition rate that different corrosion inhibitor samples respectively impregnate age.Calculation formula is as follows:
Corrosion rate V=(m0-m1)/St
Corrosion inhibition rate η=(V1-V2)/V1
In formula: m0,m1--- the quality before and after reinforcement corrosion, g；
S --- reinforcing work area, cm2；
T --- reinforcement corrosion age, d；
V1--- reinforcement corrosion rate, g/ (cm not plus when corrosion inhibitor sample2·d)；
V2--- reinforcement corrosion rate when adding corrosion inhibitor sample, g/ (cm2·d)。
Experiment condition is reinforcing steel
Weightless test of the different corrosion inhibitor samples of table 1 in simulated concrete pore solution
As seen from the above table, in concrete simulation hole solution, the resistance rust effect of cationic bis-imdazoline corrosion inhibitor is excellent
In triethylene tetramine.And the resistance rust effect of cationic bis-imdazoline (acidity) is than cationic bis-imdazoline (alkalinity)
Advantageously, this is related to the building stone of imidazoline itself.Corrosion inhibition rate the result shows that, the positive ion imidazoline electromigration of development
Type corrosion inhibitor has better rebar surface protective action, needs further to be verified cation transport type corrosion inhibitor in reinforced concrete
Resistance rust effect in soil structure.
Two, the resistance rust protection test of armored concrete
Concrete sample is made, specific concrete mix is cement: sand: stone: water=1:2.58:3.17:
0.53, sodium chloride volume is the 3% of cement quality.Wherein, cement is P.O.42.5 class g cement, sand natural river sand, stone 5
The rubble of~20mm continuous grading, sodium chloride are that analysis is pure.
Using the cationic bis-imdazoline of preparation, it is applied to above-mentioned concrete sample, tests its resistance rust effect.Chlorine from
Sub- content is lower, and resistance rust effect in surface is better.
Referring to Fig.1, by 2 reinforcing bar landfills in concrete, reinforcing bar is away from concrete bottom surface 30mm；On concrete bottom surface
It arranges stainless (steel) wire, then concrete is placed on supporting plate, stainless (steel) wire is located at the top of armored concrete bottom surface and supporting plate
Between surface.Reinforcing bar is cathode, using the aqueous solution of 1mol/L cationic bis-imdazoline as electrolyte, is powered 15 days, electric current
Density domination is 3A/m3, make experimental group.The aqueous solution for not adding cationic bis-imdazoline compares group, compares control group
With experimental group inside concrete chloride ion content, table 2 is as a result seen below:
The Chloride Ion in Concrete content of 2 different experiments of table
As can be seen from Table 2, compared with the initial chloride ion content of concrete, chloride ion content is decreased obviously.Show
Under the action of extra electric field, nearby chloride ion declines reinforcing bar to external migration, internal chloride ion content.
Since, comprising 2 nitrogenous five-ring heterocycles, nitrogen element content represents sun in cationic bis-imdazoline corrosion inhibitor
Ionic bis-imdazoline.Reinforcing bar is cathode, using the aqueous solution of 1mol/L cationic bis-imdazoline as electrolyte, energization 15
It, current density control is 3A/m3, nitrogen element content in the concrete of different depth is tested, table 3 is as a result seen below:
Nitrogen element content in the concrete of 3 different depth of table
As shown in Table 3, with increasing of the test away from concrete surface depth, nitrogen element content increases, reaches at 30mm
Peak value, the herein exactly position of embedded steel.This shows that cationic bis-imdazoline sufficiently moves under electric field action
Rebar surface forms film layer in rebar surface, to play a protective role to reinforcing bar.
Reinforcing bar is cathode, using the aqueous solution of 1mol/L cationic bis-imdazoline as electrolyte, is powered 15 days, electric current is close
Degree control is 3A/m3, the dynamic potential polarization curve of electrolyte is tested, table 4 is as a result seen below:
The measurement of 4 dynamic potential polarization curve of table
As shown in Table 4, cationic bis-imdazoline corrosion inhibitor keeps the corrosion potential of reinforcing bar mobile to forward direction, illustrates use
After cationic bis-imdazoline corrosion inhibitor, protective film layer is formed in rebar surface, reinforcing bar is made to have wider array of passivation region, thus
Improve the durability of concrete structure.
It is learnt by reinforcing bar corrosion inhibition rate and two-way electric osmose electrochemical test result, imidazoline quaternary ammonium salt cation resistance rust group packet
Polar portion and nonpolar moiety are included, after polar portion is adsorbed on rebar surface, changes state of charge and the boundary of rebar surface
Surface properties reduce solution-reinforcing bar interfacial electric double layer capacitor, increase rebar surface charge transfer resistance, and nonpolar moiety
One layer of barrier protective film is formed in rebar surface, substance transfer related with corrosion reaction is hindered, reduces O2It is anti-to cathode
The Depolarization rate answered, so that reinforcement corrosion rate be made to reduce.
Claims (8)
- The means of defence 1. resistance of armored concrete a kind of is become rusty, which is characterized in that it the following steps are included:1) by molar ratio be 1:1.5~1:2.5 triethylene tetramine and phthalic anhydride put into dimethylbenzene, 130~150 DEG C 10~15h is reacted, excess of solvent is removed, obtains compound 1；2) compound 1 and lauric acid that molar ratio is 1:1.5~1:2.5 are put into dimethylbenzene, 130~150 DEG C are acylated 6~10h is reacted, excess of solvent is removed, obtains compound 2；3) compound 2 and hydrazine hydrate that molar ratio is 1:0.5~1:1.5 are put into dehydrated alcohol, stir 2~4h under room temperature, Excess of solvent is removed, compound 3 is obtained；4) compound 3 is put into dimethylbenzene, 130~150 DEG C of 6~10h of reaction remove excess of solvent, obtain bis-imdazoline；5) bis-imdazoline is activated, obtains cationic bis-imdazoline；6) using the aqueous solution of cationic bis-imdazoline as electrolyte, using the reinforcing bar of armored concrete as cathode, power supply connection Cathode and anode, energization；The molecular structure of the cationic bis-imdazoline is as follows:Step 1)~step 4) reaction condition is not necessarily to remove oxygen；For step 6) under electric field action, cationic bis-imdazoline is attached Form film layer in rebar surface, while adjourning the hole in concrete, be filled in hole.
- The means of defence 2. resistance of armored concrete according to claim 1 is become rusty, which is characterized in that the activation of the step 5) Method are as follows: introduce cationic quaternary amine reagent into bis-imdazoline, obtain cationic bis-imdazoline.
- The means of defence 3. resistance of armored concrete according to claim 2 is become rusty, which is characterized in that the cationic quaternary amine Reagent is one of sodium chloroacetate, bromoacetic acid sodium, sodium iodoacetate.
- The means of defence 4. resistance of armored concrete according to claim 1 is become rusty, which is characterized in that the anode be graphite, One of stainless (steel) wire, titanium net.
- The means of defence 5. resistance of armored concrete according to claim 1 is become rusty, which is characterized in that the concentration of the electrolyte For 0.01~2mol/L.
- The means of defence 6. resistance of armored concrete according to claim 1 is become rusty, which is characterized in that the electric current of reinforcing bar after energization Density is in 0.1~10A/m2。
- The means of defence 7. resistance of armored concrete according to claim 1 is become rusty, which is characterized in that the bis-imdazoline Molecular structure is as follows:
- The means of defence 8. resistance of armored concrete according to claim 1 is become rusty, which is characterized in that the step 1)~step 4) synthesis path of bis-imdazoline is as follows:
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| CN110467912B (en) * | 2019-09-10 | 2021-06-25 | 肯特催化材料股份有限公司 | High-temperature triggered wetting reversal agent and preparation method and application thereof |
| CN111763028A (en) * | 2020-06-17 | 2020-10-13 | 东南大学 | Application of imidazole derivative as anticorrosive material for newly-built reinforced concrete |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845019A (en) * | 2009-03-24 | 2010-09-29 | 苗俊良 | Method for synthesizing imidazoline intermediate and cationic derivative thereof |
| CN102162101A (en) * | 2010-12-23 | 2011-08-24 | 大庆高新区华龙祥化工有限公司 | Preparation method of metal corrosion inhibitor |
| CN102924379A (en) * | 2012-10-30 | 2013-02-13 | 华南理工大学 | Cationic electromigration imidazoline quaternary ammonium salt and application thereof |
| CN102924378A (en) * | 2012-10-30 | 2013-02-13 | 华南理工大学 | Preparation method and preparation device of cationic electromigration imidazoline concrete reinforcing bar corrosion inhibitor |
| CN102964306A (en) * | 2012-07-26 | 2013-03-13 | 新疆科力新技术发展有限公司 | Preparation method of imidazoline corrosion inhibitor |
| CN105585530A (en) * | 2014-10-21 | 2016-05-18 | 中国石油化工股份有限公司 | Preparation method of imidazoline |
| CN106007469A (en) * | 2016-05-18 | 2016-10-12 | 山东华安铁塔有限公司 | Efficient permeating reinforced concrete preservative |
-
2017
- 2017-11-22 CN CN201711170646.4A patent/CN108103544B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845019A (en) * | 2009-03-24 | 2010-09-29 | 苗俊良 | Method for synthesizing imidazoline intermediate and cationic derivative thereof |
| CN102162101A (en) * | 2010-12-23 | 2011-08-24 | 大庆高新区华龙祥化工有限公司 | Preparation method of metal corrosion inhibitor |
| CN102964306A (en) * | 2012-07-26 | 2013-03-13 | 新疆科力新技术发展有限公司 | Preparation method of imidazoline corrosion inhibitor |
| CN102924379A (en) * | 2012-10-30 | 2013-02-13 | 华南理工大学 | Cationic electromigration imidazoline quaternary ammonium salt and application thereof |
| CN102924378A (en) * | 2012-10-30 | 2013-02-13 | 华南理工大学 | Preparation method and preparation device of cationic electromigration imidazoline concrete reinforcing bar corrosion inhibitor |
| CN105585530A (en) * | 2014-10-21 | 2016-05-18 | 中国石油化工股份有限公司 | Preparation method of imidazoline |
| CN106007469A (en) * | 2016-05-18 | 2016-10-12 | 山东华安铁塔有限公司 | Efficient permeating reinforced concrete preservative |
Non-Patent Citations (3)
| Title |
|---|
| "新型电迁移性阻锈剂的设计、合成及其对钢筋混凝土组成、结构与性能的影响";艾志勇;《中国优秀硕士学位论文全文数据库 工程科技II辑》;20131215(第S2期);第3.2小节，第3.2.1、3.2.1.2、3.2.2小节，第41页最后一段，第5.1-5.2小节 * |
| "迁移性阻锈剂在钢筋混凝土中的研究进展";潘崇根 等;《材料导报》;20160710;第30卷(第7期);第145-151页 * |
| "阳离子型咪唑啉阻锈剂的合成及防腐蚀性能";余其俊 等;《华南理工大学学报》;20121031;第40卷(第10期);第134-141页 * |
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