CN108103544A - 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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- CN108103544A CN108103544A CN201711170646.4A CN201711170646A CN108103544A CN 108103544 A CN108103544 A CN 108103544A CN 201711170646 A CN201711170646 A CN 201711170646A CN 108103544 A CN108103544 A CN 108103544A
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- imdazoline
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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, without gap, it comprises the following steps the resistance to compression of inside concrete consolidation：1) triethylene tetramine and phthalic anhydride are put into dimethylbenzene, compound 1 is obtained by the reaction；2) compound 1 and lauric acid are put into dimethylbenzene, acylation reaction obtains compound 2；3) compound 2 and hydrazine hydrate are put into absolute ethyl alcohol, stirs to get compound 3；4) compound 3 is put into dimethylbenzene, bis-imdazoline is obtained by the reaction；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 connection cathode and anode, energization.
Description
Technical field
The present invention relates to reinforced concrete technology field, the resistance rust means of defence of more particularly to a kind of armored concrete.
Background technology
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
Topic, patch reparation can be used in when engineering control, using special reinforcing steel the methods of, prevention then using incorporation corrosion inhibitor, face coat,
The methods of cathodic protection.Among 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 ripe, 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, it is impossible to quick, fully penetrated to rebar surface.It can be seen that carry 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.
The content of the invention
The technical problem to be solved by the invention is to provide a kind of economical rationality, technical feasibility, excellent reinforcing bars against corrosion to mix
The resistance rust means of defence of soil is coagulated, uniformly closed protective film can be formed 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 comprises the following steps：
1) it is 1 by molar ratio:1.5~1:2.5 triethylene tetramine and phthalic anhydride input dimethylbenzene, 130~
150 DEG C of 10~15h of reaction, remove excess of solvent, obtain compound 1；
2) it is 1 by molar ratio:1.5~1:2.5 compound 1 and lauric acid input dimethylbenzene, 130~150 DEG C of progress
6~10h of acylation reaction removes excess of solvent, obtains compound 2；
3) it is 1 by molar ratio:0.5~1:1.5 compound 2 and hydrazine hydrate input absolute ethyl 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 need not be except oxygen, and the reaction time is short, instead
Solvent is removed after answering, processing is easy, you can obtains purer bis-imdazoline.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 bar list
Face has excellent technique 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 chlorion into electrolyte solution and be discharged, and the bicyclic miaow of the cationic in solution
Oxazoline is as corrosion inhibitor cation, the reinforcing bar flowing into concrete, and is attached to rebar surface, forms film layer, i.e., " forms a film "
Effect prevents chlorion, hydrogen etc. into 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.The present invention is in the resistance rust protection process of armored concrete, rebar surface is formed
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) is：Cationic quaternary amine reagent is introduced into bis-imdazoline, is dissolved in
Toluene reacts 10~20h at a temperature of 60~90 DEG C, removes solvent after completion of the reaction, obtain cationic bis-imdazoline.
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 kind in sodium chloroacetate, bromoacetic acid sodium, sodium iodoacetate.
Preferably, the anode is one kind in 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, and two carbon atoms are connected 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 pairs
Effect significantly increases cloud density on imidazoline heterocycle, and imidazoline heterocycle is made to be capable of providing enough electronics and transition gold
It is strong bonded to belong to the empty d tracks 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 rails for not being occupied by an electron in enough electronics and transition metal atoms or not fully taken up by electronics
Road is strong bonded.On the other hand, lauric long alkyl chain is linked by 11 carbon atom straight chains, possesses good hydrophobicity, by
Its hydrophobic membrane formed can ensure 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 diffusion of the corrosive medium in solution to metal surface.Above-mentioned bicyclic imidazo
Quinoline stable chemical performance, is unlikely to deteriorate, and is very beneficial for applying the resistance rust dimension in corrosion inhibitor field, being particularly suitable for 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 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 synthesis path of the step 1)~step 4) bis-imdazoline is as follows：
The synthesis path design of above-mentioned bis-imdazoline is reasonable, and workable, processing is easy, and product is pure, and yield is high.System
The bis-imdazoline stable chemical performance obtained, is unlikely to deteriorate.In addition, using commercially available cheap solvent drug, reaction condition need not
Except oxygen, the reaction time is short, and processing is easy after reaction, and reaction yield is high, beneficial 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, dimethylbenzene, will be anti-as azeotropic agent
The water that should be generated and the condensed rear discharge of xylenes, reaction generation 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
2) it is acylation reaction, the theoretical molar ratio of compound 1 and lauric acid reaction is 1:2；Using dimethylbenzene as azeotropic agent, more favorably
It is reacted in compound 1 and lauric acid, the water generated and the condensed rear discharge of xylenes, yield higher will be reacted.
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 more 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), using dimethylbenzene as azeotropic agent, further cyclodehydration, product bis-imdazoline exists
It is faint yellow flowing oily liquids during temperature higher (being higher than 50 DEG C), in compared with strong basicity (pH is 10~11).Product bicyclic imidazo
Quinoline cooling is frozen into faint yellow solid by liquid retrogradation.
Description of the drawings
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 connected with external anode, power supply
The bar connecting 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 not contacted), support plate is equipped with below external anode, in concrete
Anode direction of the anion such as chlorion into electrolyte solution is flowed and is discharged, and the cationic bicyclic imidazo in solution
Quinoline is as corrosion inhibitor cation, the reinforcing bar flowing into concrete, 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, is also being answered
The parameters such as concentration of electrolyte, the current density that the used time uses, the expression way of these parameters is one section of model 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 limiting 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 being synthesized in the synthetic method of the present invention have some preferably to match, such as triethylene four
The molar ratio of amine and phthalic anhydride (i.e. the ratio between amount of substance) is 1:1.5~1:2.5th, compound 1 and lauric rub
Your ratio is 1:1.5~1:2.5, the method for expressing of these proportionings is the scope 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 method for expressing, such as triethylene tetramine and phthalic anhydride
Molar ratio is 1:(1.5~2.5), compound 1 and lauric molar ratio are 1:(1.5~2.5).
The present invention combines organic synthesis and armored concrete field, and the organic compound of synthesis is applied to reinforced concrete
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
Armored concrete field or other references is helped to be understood using the personnel of present invention, are made as described below：1) synthesize
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 using additive (commercially available), solvent (commercially available), the raw material used according to the theoretical molar of chemical equation match come
Addition, the addition proportioning of reactant is then different due to 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 in synthetic method, the addition of various raw materials matches no absolute scope, after adding necessary raw material,
The stoichiometric reacted can be realized；So the proportioning of raw material is not limited in the claims, certainly, this
Invention has preferred scope in the content of the invention, lists preferred proportioning 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 scopes
It is scheduled in the range of call parameter, the content of the invention, embodiment are related to further preferred embodiment.4) using dimethylbenzene as taking water
Agent by the condensed rear discharge of the water of generation and xylenes, that is, represents 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 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 during using electrical mobility corrosion inhibitor
Muscle makees cathode, and anode is sacrificial electrode, is powered and forms an electric field, and cation transport to reinforcing bar forms protective film in rebar surface；
Anion transport leaves reinforcing bar, and then prevents reinforcing bar by corrosion to anode.
Embodiment provided below be not to limit the scope that is covered of the present invention, described step nor with
To limit its execution sequence.Those skilled in the art are the present invention with reference to existing common knowledge conspicuously improved, also fall
Enter the present invention claims protection domain within.
Embodiment one
A kind of resistance rust means of defence of armored concrete, it comprises the following steps：
1) 4mol triethylene tetramines and 6mol phthalic anhydrides are put into 200ml dimethylbenzene, 130 DEG C of reaction 15h are removed
Excess of solvent generates compound 1；
2) 2mol compounds 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 compounds 2 and 0.5mol hydrazine hydrates are put into 100ml absolute ethyl alcohols, 2h is stirred under room temperature, it is extra to remove
Solvent obtains compound 3；
4) 0.5mol compounds 3 are put into 100ml dimethylbenzene, 130 DEG C of reaction 10h remove excess of solvent, obtain bicyclic miaow
Oxazoline；
5) 0.1mol sodium chloroacetates are added in into 0.05mol bis-imdazolines, 100ml toluene is dissolved in, is reacted at 80 DEG C
15h removes solvent after completion of the reaction, obtains cationic bis-imdazoline；
6) aqueous solution using concentration as the cationic bis-imdazoline of 0.01mol/L is electrolyte, in concrete surface
Arrangement 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 the moon
Pole, power supply connection 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 synthesis path of the step 1)~step 4) bis-imdazoline 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, comprises the following steps：
1) 4mol triethylene tetramines and 10mol phthalic anhydrides are put into 100ml dimethylbenzene, 150 DEG C of reaction 10h are removed
Excess of solvent is removed, generates compound 1；
2) 2mol compounds 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 compounds 2 and 1.5mol hydrazine hydrates are put into 100ml absolute ethyl alcohols, 4h is stirred under room temperature, it is extra to remove
Solvent obtains compound 3；
4) 0.5mol compounds 3 are 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 in into 0.05mol bis-imdazolines, 100ml toluene is dissolved in, is reacted at 90 DEG C
10h removes solvent after completion of the reaction, obtains cationic bis-imdazoline；
6) aqueous solution using concentration as the cationic bis-imdazoline of 2mol/L is electrolyte, is arranged in concrete surface
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, comprises the following steps：
1) 4mol triethylene tetramines and 8mol phthalic anhydrides are put into 100ml dimethylbenzene, 140 DEG C of reaction 12h are removed
Excess of solvent generates compound 1；
2) 2mol compounds 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 compounds 2 and 1mol hydrazine hydrates are put into 100ml absolute ethyl alcohols, 3h is stirred under room temperature, removed extra molten
Agent obtains compound 3；
4) 0.5mol compounds 3 are put into 100ml dimethylbenzene, 140 DEG C of reaction 8h remove excess of solvent, obtain bicyclic miaow
Oxazoline；
5) 0.1mol sodium iodoacetates are added in into 0.05mol bis-imdazolines, 100ml toluene is dissolved in, is reacted at 60 DEG C
20h removes solvent after completion of the reaction, obtains cationic bis-imdazoline；
6) aqueous solution using concentration as the cationic bis-imdazoline of 1mol/L is electrolyte, is arranged in concrete surface
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
First, cationic bis-imdazoline corrosion inhibitor is tested
Weight-loss method is a kind of method of resistance to corrosion of 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, its corrosion rate is obtained.Weight-loss method assay 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 polished step by step derusting with the water-proof abrasive paper of 600 mesh, 1000 mesh, 2000 mesh successively before experiment, use
The hydrochloric acid of 0.1mol/L washes away the corrosion product of rebar surface.Again with washes of absolute alcohol, except degreasing, the steel handled well
Muscle weighs after dry and records every steel bar quality.The cationic bis-imdazoline prepared using triethylene tetramine, the present invention
The corrosion inhibitor solution of two kinds of corrosion inhibitor sample preparations 1L, 2wt% is put into the reinforcing bar 6 handled well in each corrosion inhibitor solution, soaks
After steeping 7d, 14d, temporally each 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 during corrosion inhibitor sample2·d)；
V2--- reinforcement corrosion rate during admixture corrosion inhibitor sample, g/ (cm2·d)。
Experiment condition is reinforcing steel
The different corrosion inhibitor samples of table 1 are in the weightless test of simulated concrete pore solution
As seen from the above table, in concrete simulates hole solution, the resistance rust effect of cationic bis-imdazoline corrosion inhibitor is excellent
In triethylene tetramine.And the resistance of cationic bis-imdazoline (acidity) becomes rusty effect than cationic bis-imdazoline (alkalescence)
Advantageously, this building stone to imidazoline in itself is related.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 verify cation transport type corrosion inhibitor in reinforced concrete
Resistance rust effect in soil structure.
2nd, 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 be P.O.42.5 class g cements, sand natural river sand, stone 5
The rubble of~20mm continuous gradings, sodium chloride are pure to analyze.
Using the cationic bis-imdazoline of preparation, applied to above-mentioned concrete sample, its resistance rust effect is tested.Chlorine from
Sub- content is lower, and resistance rust effect in surface is better.
With reference to Fig. 1, by 2 reinforcing bar landfills and concrete, reinforcing bar is away from concrete bottom surface 30mm；On concrete bottom surface
It arranges stainless (steel) wire, then concrete is positioned on support plate, stainless (steel) wire is located at the top of armored concrete bottom surface and support plate
Between surface.Reinforcing bar is cathode, using the aqueous solution of 1mol/L cationic bis-imdazolines 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, the result is shown in table 2 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 chlorion declines reinforcing bar to external migration, internal chloride ion content.
Due to including 2 nitrogenous five-ring heterocycles in cationic bis-imdazoline corrosion inhibitor, nitrogen element content represents sun
Ionic bis-imdazoline.Reinforcing bar is cathode, using the aqueous solution of 1mol/L cationic bis-imdazolines as electrolyte, energization 15
My god, current density control is 3A/m3, nitrogen element content in the concrete of different depth is tested, the result is shown in table 3 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 fully moves under electric field action
Rebar surface forms film layer, so as to play a protective role to reinforcing bar in rebar surface.
Reinforcing bar is cathode, using the aqueous solution of 1mol/L cationic bis-imdazolines as electrolyte, is powered 15 days, electric current is close
Degree control is 3A/m3, the dynamic potential polarization curve of electrolyte is tested, the result is shown in table 4 below：
4 dynamic potential polarization curve of table measures
As shown in Table 4, cationic bis-imdazoline corrosion inhibitor makes the corrosion potential of reinforcing bar mobile to forward direction, illustrates to use
After cationic bis-imdazoline corrosion inhibitor, protection film layer is formed in rebar surface, reinforcing bar is made to have wider array of passivation region, so as to
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 bag
Polar portion and nonpolar moiety are included, polar portion is adsorbed after rebar surface, changes state of charge and the boundary of rebar surface
Surface properties reduce solution-reinforcing bar interfacial electric double layer capacitance, increase rebar surface charge transfer resistance, and nonpolar moiety
One layer of barrier protective film is formed in rebar surface, the substance transfer related with corrosion reaction is hindered, reduces O2It is anti-to cathode
The Depolarization rate answered, so that reinforcement corrosion rate reduces.
Claims (9)
1. the resistance rust means of defence of a kind of armored concrete, which is characterized in that it comprises the following steps：
1) it is 1 by molar ratio:1.5~1:2.5 triethylene tetramine and phthalic anhydride input dimethylbenzene, 130~150 DEG C
10~15h is reacted, excess of solvent is removed, obtains compound 1；
2) it is 1 by molar ratio:1.5~1:2.5 compound 1 and lauric acid input dimethylbenzene, 130~150 DEG C are acylated
6~10h is reacted, excess of solvent is removed, obtains compound 2；
3) it is 1 by molar ratio:0.5~1:1.5 compound 2 and hydrazine hydrate puts into absolute ethyl alcohol, and 2~4h is stirred under room temperature,
Excess of solvent is removed, obtains compound 3；
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.
2. the resistance rust means of defence of armored concrete according to claim 1, which is characterized in that the activation of the step 5)
Method is：Cationic quaternary amine reagent is introduced into bis-imdazoline, obtains cationic bis-imdazoline.
3. the resistance rust means of defence of armored concrete according to claim 2, which is characterized in that the cationic quaternary amine
Reagent is sodium chloroacetate, one kind in bromoacetic acid sodium, sodium iodoacetate.
4. armored concrete according to claim 1 resistance rust means of defence, which is characterized in that the anode for graphite,
One kind in stainless (steel) wire, titanium net.
5. the resistance rust means of defence of armored concrete according to claim 1, which is characterized in that the concentration of the electrolyte
For 0.01~2mol/L.
6. the resistance rust means of defence of armored concrete according to claim 1, which is characterized in that the electric current of reinforcing bar after energization
Density is in 0.1~10A/m2。
7. the resistance rust means of defence of armored concrete according to claim 1, which is characterized in that the bis-imdazoline
Molecular structure is as follows：
8. the resistance rust means of defence of armored concrete according to claim 1, which is characterized in that the step 1)~step
4) synthesis path of bis-imdazoline is as follows：
9. the resistance rust means of defence of armored concrete according to claim 1, which is characterized in that the cationic is bicyclic
The molecular structure of imidazoline is as follows：
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