CN105271907B - A kind of organic corrosion inhibitor of hud typed armored concrete and preparation method thereof - Google Patents
A kind of organic corrosion inhibitor of hud typed armored concrete and preparation method thereof Download PDFInfo
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- CN105271907B CN105271907B CN201510867968.9A CN201510867968A CN105271907B CN 105271907 B CN105271907 B CN 105271907B CN 201510867968 A CN201510867968 A CN 201510867968A CN 105271907 B CN105271907 B CN 105271907B
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- corrosion inhibitor
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Abstract
The invention discloses a kind of hud typed organic corrosion inhibitor of armored concrete, organic corrosion inhibitor is contained by the polyethylene glycol b polystyrene block copolymers of narrow ditribution and constituted.The invention also discloses the preparation method of above-mentioned organic corrosion inhibitor, comprise the following steps：(1) preparation of sheathing material：Styrene polymerization is triggered using Transfer Radical Polymerization, the polyethylene glycol b polystyrene block copolymers of narrow ditribution are obtained；(2) hud typed organic corrosion inhibitor is prepared：The method dialysed using solution is combined the polyethylene glycol b polystyrene block copolymers that step (1) is synthesized with organic corrosion inhibitor, obtains the organic corrosion inhibitor of hud typed armored concrete.The organic corrosion inhibitor of hud typed armored concrete of the present invention possesses good dispersive property and compatibility in aqueous, and possesses certain sensitiveness to environment pH changes, it is possible to achieve the release of resistance rust composition under specific pH environment.
Description
Technical field
The present invention relates to organic corrosion inhibitor of armored concrete, more particularly to a kind of organic resistance rust of hud typed armored concrete
Agent and preparation method thereof.
Background technology
Reinforcement corrosion is to cause armored concrete destruction to influence one of major reason of its durability.Reinforcement corrosion band
The endurance issues come can influence the service life of reinforced concrete constructional work, and maintenance, repair are costly, and economic loss is serious.
The chlorion for containing a large amount of highly corrosives in the reinforced concrete constructional work of coastal region is because of residing marine environment is built, it is general
All over by corrosion failure, endurance issues are protruded.China coastline is long, and coastal area is populous, economically developed, has repaiied
Build and a large amount of reinforced concrete constructional works will be built.Therefore, the preventing and treating of coastal region reinforced concrete constructional work corrosion and guarantor
Shield is the major issue of urgent need to resolve.
Typically, the pH value of hole solution is between 12.6-13.5 in concrete, under this high alkalinity environment, rebar surface
One layer of stable passivating film can be formed, protects reinforcing bar not to be corroded.But, when carbon dioxide and chlorion etc. penetrate into concrete
In and reach rebar surface, the corrosion of reinforcing bar may be induced.On the one hand, the carbonization of concrete can cause concrete mesopore
The pH value of solution drops to 8-9, causes the homogeneous corrosion of reinforcing bar；On the other hand, when the chlorine ion concentration in rebar surface somewhere reaches
To after critical value, the local corrosion of reinforcing bar can be induced, the pH value of corrosion area even drops to less than 6.
In order to prevent and treat the corrosion of reinforcement in concrete, people have developed various methods for a long time, can be divided mainly into early stage
Prevention repairs two major classes with the later stage.In reinforced concrete structure, corrosion inhibitor is by being directly incorporated into energy in concrete mostly
Enough to slow down or prevent the material of steel bar corrosion and reach resistance rust purpose, this method is easy to operate, economical and practical, is current preventing and treating
One of important method of reinforcement corrosion.Although corrosion of the corrosion inhibitor to reinforcing bar can play a part of protection, there is also permitted
Many shortcomings：(1) because bio-toxicity is larger, with carcinogenesis, the inorganic corrosion inhibitor such as nitrite, chromate is by gradually
Limit and prohibit the use of；(2) organic corrosion inhibitor imidazoline system, alkanolamine, amine and amino acid etc., it hinders rust effect and corrosion inhibitor
Species, the environment acted on have contact, but the still comprehensive explanation of neither one system up to now.Therefore, have at present
The research for closing corrosion inhibitor agent starts to develop towards the direction of green, environmental protection, non-hazardous.
Research shows, although corrosion inhibitor can reduce the corrosion rate of reinforcing bar, plays resistance rust effect, but effect respectively has
It is different.Corrosion inhibiter is directly incorporated into medium transport in meeting concrete surface hole obstruction, influence concrete in reinforced concrete structure
And change hydrolysis product of cement, the performance of armored concrete can so be affected.
Existing frequently-used corrosion inhibitor generally existing bad dispersibility, concrete substrate is had a negative impact, environment it is not friendly
The problems such as good.
The content of the invention
It is mixed it is an object of the invention to provide a kind of nucleocapsid steel bar in order to overcome the disadvantages mentioned above and deficiency of prior art
Coagulate native organic corrosion inhibitor, the sensitiveness with the pH to environment, can avoid corrosion inhibitor be directly incorporated into concrete to environment and
The negative effect of concrete material performance, while corrosion inhibitor discharges when pH declines when corroding generation and plays more preferable resistance
Rust is acted on.
Another object of the present invention is to provide the preparation method of the above-mentioned organic corrosion inhibitor of hud typed armored concrete.
The purpose of the present invention is achieved through the following technical solutions：
A kind of organic corrosion inhibitor of hud typed armored concrete, by the polyethylene glycol-b- polystyrene block copolymerization of narrow ditribution
Thing contains organic corrosion inhibitor and constituted.
The molecular formula of the polyethylene glycol-b- polystyrene is PEO114-b-PS1171。
The molecular weight of the polyethylene glycol-b- polystyrene block copolymers is 93,561, molecular weight distribution Mw/Mn=
1.25。
Organic corrosion inhibitor is BTA.
The preparation method of the described organic corrosion inhibitor of hud typed armored concrete, comprises the following steps：
(1) preparation of sheathing material：Styrene polymerization is triggered using Transfer Radical Polymerization, narrow ditribution is obtained
Polyethylene glycol-b- polystyrene block copolymers；
(2) hud typed organic corrosion inhibitor is prepared：Polyethylene glycol-the b- that the method dialysed using solution is synthesized step (1)
Polystyrene block copolymer is combined with organic corrosion inhibitor, obtains the organic corrosion inhibitor of hud typed armored concrete.
The preparation of step (1) described sheathing material, specifically includes following steps：
(11) macromole evocating agent PEO-Br is prepared：By the poly glycol monomethyl ether and alpha-brominated isobutyl by drying water removal
Base acylbromide reacts, and obtains the macromole evocating agent PEO-Br of bromine end-blocking；The poly glycol monomethyl ether and alpha-brominated isobutyl group acyl
The mol ratio of bromine is 1:(2.5~3.5)；
(12) polyethylene glycol-b- polystyrene block copolymers are prepared：By Transfer Radical Polymerization, with CuBr
For catalyst, styrene polymerization is triggered using PEO-Br macromole evocating agents, reaction temperature is 105~115 DEG C, in course of reaction
Remove water；The mass ratio of wherein CuBr and PEO-Br macromole evocating agents is (25~30):1000；The PEO-Br macromoleculars
The mass volume ratio of initiator and styrene is 1:(60~70) g/mL.
Step (2) is described to prepare hud typed organic corrosion inhibitor, is specially：
The BTA aqueous solution is added drop-wise to the polyethylene glycol-b- polystyrene being stirred vigorously with 8~10 drops/minute embedding
In Duan Gongju thing dioxane solvents, and after some minutes are stirred, it is loaded into bag filter, and bag filter is sealed；Will be close
The bag filter sealed is put into BTA solution and dialysed, and obtains hud typed organic corrosion inhibitor；
Polyethylene glycol-b- the polystyrene block copolymers and the mass ratio of organic corrosion inhibitor are less than 1：10.
Compared with prior art, the present invention has advantages below and beneficial effect：
(1) shell of the organic corrosion inhibitor of hud typed armored concrete of the invention is hydrophilic PEO, therefore
Shell can be dissolved in mixing water, mix and be wherein stirred in concrete preparation process, with good dispersiveness, to mixed
Solidifying soil material performance will not have a negative impact.
(2) the organic corrosion inhibitor of hud typed armored concrete of the invention utilizes PEO base in shell block copolymer
The characteristics of group is to pH sensitive, after steel reinforced concrete erosion induction, the reduction of hole solution pH value, which can be triggered, is stored in capsule
The release of interior organic corrosion inhibitor, can produce self-repair function to reinforcement corrosion.
Brief description of the drawings
Fig. 1 is the nuclear magnetic resonance map of PEO-Br macromole evocating agents prepared by embodiments of the invention.
Fig. 2 is the nuclear magnetic resonance map of PEO-b-PS block copolymers prepared by embodiments of the invention.
Fig. 3 is PEO prepared by embodiments of the invention114-b-PS1171Gel chromatography.
Fig. 4 is the grain size distribution of the organic corrosion inhibitor of hud typed armored concrete prepared by embodiments of the invention.
The release profiles of the organic corrosion inhibitor of hud typed armored concrete prepared by Fig. 5 embodiments of the invention.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Embodiment 1
The preparation method of the organic corrosion inhibitor of hud typed armored concrete of the present embodiment comprises the following steps：
(1) preparation of PEO-Br macromole evocating agents：
(a) by 5g (1mmol) by drying the mPEO removed water114Add in the 250ml three-necked flasks with stirrer；Take out true
Sky, then leads to nitrogen toward three-necked bottle, constant pressure funnel, circulates three times, three minutes every time, plug sealing kept logical nitrogen；Note
Emitter first cleaned with nitrogen three times it is standby.
(b) extract the injection of 50mL dichloromethane in five times with 10mL syringes, open magnetic stirring apparatus, bath on the rocks, cooling
To 0 DEG C；The triethylamine for extracting 0.42mL (3mmol) with 1mL syringes injects；With 1ml syringes extract 0.37mL (3mmol) α-
Bromo isobutyl group acylbromide, extracts 30mL dichloromethane with 10mL syringes and is added to constant pressure funnel, be added dropwise, acutely stir dropwise
Mix about 1 hour；Ice bath is removed, system is warmed to room temperature；
(c) after reaction 24h, then evaporation removing dichloromethane adds tetrahydrofuran and dissolves again, filter off in solution and produce
White amine salt, filter desalination, this step is repeated twice, rotary evaporation is concentrated into after 10mL, and solution is slowly poured into high-speed stirring
Precipitate, be dried in vacuum overnight after product suction filtration at 40 DEG C in the cold methanol (- 40 DEG C) mixed.
(2) preparation of PEO-b-PS block copolymers：
(a) by PEO114- Br macromole evocating agents (0.2g), methyl phenyl ethers anisole (1.3mL) adds the mono- branch pipes of dry 25mL together
In round-bottomed flask, vacuumized under stirring, water removal deoxygenation three times；Catalyst CuBr is added under logical drying nitrogen state
Deoxygenation three times is vacuumized under (5.6mg), stirring；Then the new styrene (13mL) and the first of N, N five for distilling and deaerating is added
Base diethylenetriamine part (8.1uL), sealing, liquid nitrogen frozen-vacuumizing-thaws, circulation three deoxygenations closing.
(b) after stirring is warmed to room temperature for 10 minutes, oil bath is reacted 3 hours at 110 DEG C；Frozen water is freezed, and is opened plug, is poured into
Precipitated in methanol, what is obtained is precipitated as PEO-b-PS crude products；Crude product is dissolved into tetrahydrofuran, neutral alumina column is crossed
Son, removes insoluble mantoquita, and obtained purified solution rotation rotary evaporation concentration, in methyl alcohol secondary precipitation obtains white powder,
After white powder is dried in vacuo, PEO is finally given114- b-PS block copolymers.
(3) preparation of hud typed organic corrosion inhibitor：
Weighing 100mg PEO-b-PS block copolymers and 119mg (1mmol) BTA (can also select other
Organic resistance rust composition of type) it is dissolved in 100mL dioxane solvents (sealing of beaker preservative film prevents the volatilization of solvent), and
Dissolve 4 hours under intense agitation；The solution dissolved is fitted into bag filter, and bag filter is sealed.By good seal
Bag filter be put into 0.2mol/L BTA solution (about 2L) and dialysed, BTA solution was every 1 hour
Change 1 time；After being dialysed 8 times with BTA solution, second day is used ultra-pure water instead and dialysed again 8 times, and ultra-pure water is equally every 1
Hour is changed 1 time.
The PEO-Br macromole evocating agents of the present embodiment and nuclear magnetic resonance map such as Fig. 1 of PEO-b-PS block copolymers and
Shown in Fig. 2.The purity of PEO-Br macromole evocating agents is 99%, available for atom transferred free radical reaction；PEO-b-PS blocks
The molecular formula of the block copolymer synthesized in copolymer in the chain of polystyrene a length of 1171, the present embodiment is PEO114-b-
PS1171；The PEO-b-PS block copolymers amount of gel chromatography (GPC, Fig. 3) display synthesis is 93,561, molecular weight distribution
Mw/Mn=1.25.It has been generally acknowledged that molecular weight distribution Mw/Mn＜ 1.3 is the polymer of narrow ditribution, therefore gel chromatography experimental result
Show that the reaction product in the present embodiment can be used for the preparation of follow-up hud typed organic corrosion inhibitor.The bag prepared using dialysis
The particle diameter about 250nm of hud typed organic corrosion inhibitor of BTA is wrapped up in, as shown in Figure 4.
The organic corrosion inhibitor release process of hud typed armored concrete manufactured in the present embodiment as shown in figure 5, in 0~4h,
The burst size of BTA is larger, after 50%, the 4h for having exceeded final burst size, due to rate of release reduction, corrosion inhibiter
Burst size is increasesd slowly, and the 70%~80% of final burst size is just reached after 16h even 20h；In addition, in high ph-values
Rate of release is slower in the solution of (pH=11,13), rate of release is slower in pH value lower (pH=7,9) solution, and after 20h
Accumulative release rate of the BTA in low ph solution is big by 10% or so than in high ph-values, illustrates the release of BTA
Process has certain pH sensitiveness.The present embodiment is successfully prepared hud typed organic corrosion inhibitor of BTA, benzo three
The release process of nitrogen azoles has certain pH sensitiveness, therefore possesses the potentiality repaired to reinforcement corrosion.
Embodiment 2
The present embodiment is in addition to following characteristics, and remaining feature and embodiment 1 are same：
In the preparation process of PEO-Br macromole evocating agents, mole of poly glycol monomethyl ether and alpha-brominated isobutyl group acylbromide
Than for 1:3.5；
In the preparation process for preparing polyethylene glycol-b- polystyrene block copolymers, CuBr triggers with PEO-Br macromoleculars
The mass ratio of agent is 25:1000；The mass volume ratio of the PEO-Br macromole evocating agents and styrene is 1:60g/mL.
The test result of the present embodiment is similar to Example 1.
Embodiment 3
The present embodiment is in addition to following characteristics, and remaining feature and embodiment 1 are same：
In the preparation process of PEO-Br macromole evocating agents, mole of poly glycol monomethyl ether and alpha-brominated isobutyl group acylbromide
Than for 1:2.5；
In the preparation process for preparing polyethylene glycol-b- polystyrene block copolymers, CuBr triggers with PEO-Br macromoleculars
The mass ratio of agent is -30:1000；The mass volume ratio of the PEO-Br macromole evocating agents and styrene is 1:70g/mL.
The test result of the present embodiment is similar to Example 1.
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by the embodiment of the invention
Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (6)
1. a kind of preparation method of the organic corrosion inhibitor of hud typed armored concrete, it is characterised in that comprise the following steps：
(1) preparation of sheathing material：Styrene polymerization is triggered using Transfer Radical Polymerization, the poly- second of narrow ditribution is obtained
Glycol-b- polystyrene block copolymers；
(2) hud typed organic corrosion inhibitor is prepared：Polyethylene glycol-b- the polyphenyl that the method dialysed using solution is synthesized step (1)
Ethylene block copolymer is combined with organic corrosion inhibitor, obtains the organic corrosion inhibitor of hud typed armored concrete；The nucleocapsid steel bar
The organic corrosion inhibitor of concrete contains organic corrosion inhibitor by the polyethylene glycol-b- polystyrene block copolymers of narrow ditribution and constituted.
2. the preparation method of the organic corrosion inhibitor of hud typed armored concrete according to claim 1, it is characterised in that step
(1) preparation of the sheathing material, specifically includes following steps：
(11) macromole evocating agent PEO-Br is prepared：By the poly glycol monomethyl ether and alpha-brominated isobutyl group acyl by drying water removal
Bromine reaction, obtains the macromole evocating agent PEO-Br of bromine end-blocking；The poly glycol monomethyl ether and alpha-brominated isobutyl group acylbromide
Mol ratio is 1:(2.5~3.5)；
(12) polyethylene glycol-b- polystyrene block copolymers are prepared：By Transfer Radical Polymerization, using CuBr to urge
Agent, styrene polymerization is triggered using PEO-Br macromole evocating agents, and reaction temperature is 105~115 DEG C, is deoxygenated in course of reaction
Remove water；The mass ratio of wherein CuBr and PEO-Br macromole evocating agents is (25~30):1000；The PEO-Br macromoleculars trigger
The mass volume ratio of agent and styrene is 1：(60~70) g/mL.
3. the preparation method of the organic corrosion inhibitor of hud typed armored concrete according to claim 1, it is characterised in that step
(2) it is described to prepare hud typed organic corrosion inhibitor, be specially：
The BTA aqueous solution is added drop-wise to the polyethylene glycol-b- polystyrene blocks being stirred vigorously with 8~10 drops/minute to be total to
In poly- Wu dioxanes solvent, and after some minutes are stirred, it is loaded into bag filter, and bag filter is sealed；By good seal
Bag filter be put into BTA solution and dialysed, obtain hud typed organic corrosion inhibitor；
Polyethylene glycol-b- the polystyrene block copolymers and the mass ratio of organic corrosion inhibitor are less than 1：10.
4. the preparation method of the organic corrosion inhibitor of hud typed armored concrete according to claim 1, it is characterised in that described
The molecular formula of polyethylene glycol-b- polystyrene is PEO114-b-PS1171。
5. the preparation method of the organic corrosion inhibitor of hud typed armored concrete according to claim 1, it is characterised in that described
The molecular weight of polyethylene glycol-b- polystyrene block copolymers is 93,561, molecular weight distribution Mw/Mn=1.25.
6. the preparation method of the organic corrosion inhibitor of hud typed armored concrete according to claim 1, it is characterised in that described
Organic corrosion inhibitor is BTA.
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