CN105712658B - A kind of concrete admixture for being used under marine environment suppress etching medium transmission - Google Patents
A kind of concrete admixture for being used under marine environment suppress etching medium transmission Download PDFInfo
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- CN105712658B CN105712658B CN201511009958.8A CN201511009958A CN105712658B CN 105712658 B CN105712658 B CN 105712658B CN 201511009958 A CN201511009958 A CN 201511009958A CN 105712658 B CN105712658 B CN 105712658B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/40—Compounds containing silicon, titanium or zirconium or other organo-metallic compounds; Organo-clays; Organo-inorganic complexes
- C04B24/42—Organo-silicon compounds
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/61—Corrosion inhibitors
Abstract
The invention discloses a kind of concrete admixture for being used under marine environment suppress etching medium transmission, the concrete admixture includes amino modified polyether polysiloxane, poly- hydroxypropyl methyl silsesquioxane, alkoxy silane, stearic acid, stearate, nano silicon, nano titanium oxide, aliphatic amine polyoxyethylene base ether and aliphatic acid polyethenoxy base ester.The concrete admixture can reduce etching medium under concrete charge pass, the resistance to chloride erosion performance of raising concrete, suppression marine environment and corrode so as to significantly improve the durability of concrete.
Description
Technical field
The present invention relates to concrete admixture field, and in particular to one kind is used to suppress etching medium transmission under marine environment
Concrete admixture.
Background technology
Concrete admixture is mixed during ready-mixed concrete, is accounted for cement quality below 5%, can be significantly improved mixed
The chemical substance of solidifying soil nature energy, mixes additive in concrete, has small investment, quick, technical economic benefit is significant
Feature.With the continuous progress of science and technology, additive has been increasingly being application, and commonly using additive in engineering can be divided into
Four classes：
1st, the additive of concrete mix rheological property is improved.Including water reducer, air entraining agent and pumping admixture.
2nd, concrete coagulating time, the additive of hardening capacity are adjusted.Including retarder, early strength agent and accelerator.
3rd, the additive of concrete durability is improved.Including air entraining agent, waterproofing agent and corrosion inhibitor etc..
4th, the additive of other performances of concrete is improved.Including air-entrainment, swelling agent, antifreezing agent, colouring agent, waterproofing agent and
Pumping admixture.
These additives have the characteristics of improving concrete a certain performance.But there is presently no a kind of additive to be developed
For solving concrete in marine environment corrosion-resistant property.Under marine environment, due to the chlorion or coagulation in surrounding medium
Chlorion in native raw material is penetrated into around reinforcing bar, is reached the passivating film of destruction reinforcing bar after finite concentration, is caused steel bar corrosion,
Its effective cross-section is cut down, reduces the stress performances such as its adhesion strength, it is to influence extra large work coagulation along muscle spalling to make concrete cover
The Major Diseases of soil structure durability, most attention both domestic and external is caused.
At present during marine engineering design to prevent the resistance to chloride erosion of concrete from using method to be improved concrete strength etc.
Level, increase thickness of concrete cover or in concrete surface brushing resistant to corrosion coating, but these methods have obvious disadvantage
End, without fundamentally suppression etching medium in the transmission of inside concrete.Such as the approach of Chloride Attack concrete is usual
There are two kinds：One is " being mixed into ", such as mix chloride ion-containing additive, using sea sand, construction water chloride ion-containing, in saline environment
Middle mixing cast concrete etc.；The second is " infiltration ", the chlorion in environment is penetrated into by macroscopic view, the microdefect of concrete
In concrete, and reach rebar surface.The problem of " being mixed into " phenomenon is mostly construction management；And " infiltration " phenomenon is then comprehensive skill
The problem of art, with concrete material porous, density, construction quality, many factors such as rebar surface concrete layer thickness have
Close.
The content of the invention
The purpose of the present invention is to overcome shortcoming in the prior art, fundamentally suppresses biography of the etching medium in inside concrete
It is defeated, there is provided it is a kind of be used for marine environment under suppress etching medium transmission concrete admixture, can reduce concrete charge pass,
Etching medium under the resistance to chloride erosion performance of concrete, suppression marine environment is improved to corrode so as to significantly improve the durable of concrete
Property.
The concrete admixture of the present invention for being used under marine environment suppress etching medium transmission uses multiple elements design skill
Art, first by amino modified polyether polysiloxane, poly- hydroxypropyl methyl silsesquioxane, alkoxy silane, stearic acid, stearic acid
Salt, nano silicon, nano titanium oxide, aliphatic amine polyoxyethylene base ether, aliphatic acid polyethenoxy base ester effectively combine, profit
It is anti-with alkaline concrete with amino modified polyether polysiloxane, alkoxy silane, nano silicon, nano titanium oxide
Should be active, increase additional agent material cement reaction site quantity during mix, utilize nano silicon, nano-silica
Change titanium, the nano-filled Pinhole closure of poly- hydroxypropyl methyl silsesquioxane, reduce concrete pore rate so as to improve compactness, profit
With the unique diffusion activity of aliphatic acid polyethenoxy base ether, aliphatic acid polyethenoxy base ester and stearic acid, stearate it is efficient
Surface-active, it is dispersed during concrete mixing to be advantageous to the additional agent material, avoids reuniting.Each component effectively combines
And cooperative effect is produced, the shortcomings that overcoming its each, efficiently suppress etching medium transmission under marine environment, reduce concrete electric
Flux, the resistance to chloride erosion performance of concrete is improved so as to significantly improve the durability of concrete.
The concrete admixture for being used under marine environment suppress etching medium transmission includes consisting of, with parts by weight
Number meter：
The amino modified polyether polysiloxane is gathered with silicon oil of low hydrogen content and α-alkenyl epoxide and α-alkenyl
The hydrosilylation addition reaction of ether obtains polyether/epoxy resin silicone oil intermediate, the amino modified polyethers then obtained with organic amine open loop
Type polysiloxane.
The preparation method of the amino modified polyether polysiloxane：There are agitator, reflux condensing tube, thermometer in device
Reaction vessel in, sequentially add containing hydrogen silicone oil, α-alkenyl epoxide and α-alkenyl polyether, lead to N2Stir 10min, heating
To 90 DEG C, platinum catalyst reaction 4h is added dropwise to, obtains polyether/epoxy resin silicone oil intermediate；
Then ethylenediamine is put into as 1.05: 1.00 ratio using amine and polyether/epoxy resin silicone oil intermediate epoxy radicals mol ratio,
Continue to react 4h, after decompression removes low-boiling-point substance, be down to room temperature, with mixed solvent washing impurity-removing, obtain viscous liquid, as described ammonia
Base modified polyether polysiloxanes.
The mixed solvent is thiacyclohexane and chloroform；Hexamethylene：The weight ratio of chloroform is 8: 2.
The poly- hydroxypropyl methyl silsesquioxane be with MTES, propyl-triethoxysilicane after hydrolysis
It is condensed to yield.
The preparation method of the poly- hydroxypropyl methyl silsesquioxane：There are agitator, reflux condensing tube, thermometer in device
In reaction vessel, MTES, propyl-triethoxysilicane, 0.0lmol/L hydrochloric acid, isopropanol are added；At 60 DEG C
Magnetic agitation adds 28% ammoniacal liquor after reaction l hours, 80 DEG C of heating continues reaction 1 hour, is neutralized with hydrochloric acid, obtains poly- propyl group first
Base silsesquioxane.
Described oxyalkylsiloxane contains following components：MTES, butyl trimethoxy silane, butyl
Triethoxysilane, octyl group trimethoxy silane, octyltri-ethoxysilane, isooctyltrimethoxysi,ane, dodecyl three
Methoxy silane and/or dodecyl triethoxysilane.
Described aliphatic amine polyoxyethylene base ether is in lauryl amine polyoxyethylene ether, octadecylamine polyoxyethylene ether
More than one arbitrary proportions mix.
The aliphatic acid polyethenoxy base ester is selected from stearic stearic acid polyoxyethylene base ester, laurate polyoxyethylene groups
Ester, more than one arbitrary proportions mixing of oleic acid polyoxyethylene base ester.
It is described be used for marine environment under suppress etching medium transmission concrete admixture have reduce concrete charge pass,
Etching medium under the resistance to chloride erosion performance of concrete, suppression marine environment is improved to corrode so as to significantly improve the durability of concrete
Effect.
It is of the present invention be used under marine environment suppress etching medium transmission the preparation method of concrete admixture be：Will
Each component is well mixed produces at 60 c.
It is of the present invention be used under marine environment suppress etching medium transmission the application method of concrete admixture be：
The additive is added during concrete mixing, recommends dosage 1-5kg per square concrete, it is equal with the mix such as adhesive material, aggregate
Even after-pouring uses.
The concrete admixture for being used under marine environment suppress etching medium transmission suppresses to corrode under marine environment
Medium has a unique and obvious action in inside concrete transmission, the material can reduce concrete carbonization speed, electric flux,
Chloride permeability coefficient, there is provided concrete impervious grade.The material has high stable based on the Si-O-Si structures of uniqueness
Property and corrosion resistance, feature is amino modified and the microporous structure of the effect improved concrete of nano-scale, and plays each component
Cooperative effect realize suppress etching medium transmission purpose, when with the similar material composition phase without component disclosed by the invention
Than when, material feed composition of the invention can show dramatically increase suppress etching medium transmission performance.
Embodiment
The present invention is further illustrated with embodiment below, but the present invention is not intended to be limited thereto.
Embodiment 1
1) prepared by amino modified polyether polysiloxane：Hold in the reaction that device has agitator, reflux condensing tube, thermometer
In device, 75g containing hydrogen silicone oils, 3g allyl glycidyl ethers, 220g allyl polyethenoxy polyethenoxy ethers are sequentially added, leads to N2
10min is stirred, is warming up to 90 DEG C, platinum catalyst reaction 4h is added dropwise to, obtains polyether/epoxy resin silicone oil intermediate.Then with amine with gathering
The ratio that ether/epoxy silicon oil intermediate epoxy radicals mol ratio is 1.05: 1.00 puts into ethylenediamine and continues to react 4h, and decompression removes low boiling
After thing, room temperature is down to, with hexamethylene/chloroform (weight ratio is 8: 2) mixed solvent washing impurity-removing, obtains viscous liquid.
2) preparation of poly- hydroxypropyl methyl silsesquioxane：Hold in the reaction that device has agitator, reflux condensing tube, thermometer
In device, MTES 140ml, propyl-triethoxysilicane 60ml, 0.0lmol/L hydrochloric acid 20mL, isopropanol are added
Magnetic agitation adds 28% ammoniacal liquor 4.0mL at 100.0mL60 DEG C after reaction l hours, and 80 DEG C of heating continues reaction 1 hour, uses salt
Acid neutralizes, and obtains poly- hydroxypropyl methyl silsesquioxane.
3) preparation of the concrete admixture of etching medium transmission is suppressed：There are agitator, reflux condensing tube, temperature in device
In the reaction vessel of meter, amino modified polyether polysiloxane, poly- hydroxypropyl methyl silsesquioxane, alkane are sequentially added at 25 DEG C
Epoxide siloxanes, stearic acid, stearate, aliphatic amine polyoxyethylene base ether, aliphatic acid polyethenoxy base ester are warming up to 60 DEG C of machines
After tool stirs 2 hours, addition nano silicon, nano titanium oxide continue after stirring 30min, are cooled to normal temperature discharging, obtain
Transmitted to etching medium and suppress concrete admixture.
Embodiment 2
1) prepared by amino modified polyether polysiloxane：Hold in the reaction that device has agitator, reflux condensing tube, thermometer
In device, 85g containing hydrogen silicone oils, 3.5g allyl glycidyl ethers, 240g allyl polyethenoxy polyethenoxy ethers are sequentially added, is led to
N2 stirs 10min, is warming up to 90 DEG C, is added dropwise to platinum catalyst reaction 4h, obtains polyether/epoxy resin silicone oil intermediate.Then with amine with
The ratio that polyether/epoxy resin silicone oil intermediate epoxy radicals mol ratio is 1.05: 1.00 puts into ethylenediamine and continues to react 4h, and decompression is except low
After boiling thing, room temperature is down to, with hexamethylene/chloroform (weight ratio is 9: 1) mixed solvent washing impurity-removing, obtains viscous liquid.
2) preparation of poly- hydroxypropyl methyl silsesquioxane：Hold in the reaction that device has agitator, reflux condensing tube, thermometer
In device, MTES 140ml, propyl-triethoxysilicane 65ml, 0.0lmol/L hydrochloric acid 20mL, isopropanol are added
Magnetic agitation adds 28% ammoniacal liquor 4.0mL at 100.0mL60 DEG C after reaction l hours, and 80 DEG C of heating continues reaction 1 hour, uses salt
Acid neutralizes, and obtains poly- hydroxypropyl methyl silsesquioxane.
3) preparation of the concrete admixture of etching medium transmission is suppressed：There are agitator, reflux condensing tube, temperature in device
In the reaction vessel of meter, amino modified polyether polysiloxane, poly- hydroxypropyl methyl silsesquioxane, alkane are sequentially added at 25 DEG C
Epoxide siloxanes, stearic acid, stearate, aliphatic amine polyoxyethylene base ether, aliphatic acid polyethenoxy base ester are warming up to 60 DEG C of machines
After tool stirs 2 hours, addition nano silicon, nano titanium oxide continue after stirring 30min, are cooled to normal temperature discharging, obtain
Transmitted to etching medium and suppress concrete admixture.
Embodiment 3
1) prepared by amino modified polyether polysiloxane：Hold in the reaction that device has agitator, reflux condensing tube, thermometer
In device, 100g containing hydrogen silicone oils, 4g allyl glycidyl ethers, 225g allyl polyethenoxy polyethenoxy ethers are sequentially added, is led to
N2 stirs 10min, is warming up to 90 DEG C, is added dropwise to platinum catalyst reaction 4h, obtains polyether/epoxy resin silicone oil intermediate.Then with amine with
The ratio that polyether/epoxy resin silicone oil intermediate epoxy radicals mol ratio is 1.05: 1.00 puts into ethylenediamine and continues to react 4h, and decompression is except low
After boiling thing, room temperature is down to, (weight ratio is 9: 1 mixed solvent washing impurity-removings, obtains viscous liquid with hexamethylene/chloroform.
2) preparation of poly- hydroxypropyl methyl silsesquioxane：Hold in the reaction that device has agitator, reflux condensing tube, thermometer
In device, MTES 140ml, propyl-triethoxysilicane 60ml, 0.0lmol/L hydrochloric acid 20mL, isopropanol are added
Magnetic agitation adds 28% ammoniacal liquor 4.0mL at 100.0mL60 DEG C after reaction l hours, and 80 DEG C of heating continues reaction 1 hour, uses salt
Acid neutralizes, and obtains poly- hydroxypropyl methyl silsesquioxane.
3) preparation of the concrete admixture of etching medium transmission is suppressed：There are agitator, reflux condensing tube, temperature in device
In the reaction vessel of meter, amino modified polyether polysiloxane, poly- hydroxypropyl methyl silsesquioxane, alkane are sequentially added at 25 DEG C
Epoxide siloxanes, stearic acid, stearate, aliphatic amine polyoxyethylene base ether, aliphatic acid polyethenoxy base ester are warming up to 60 DEG C of machines
After tool stirs 2 hours, addition nano silicon, nano titanium oxide continue after stirring 30min, are cooled to normal temperature discharging, obtain
Transmitted to etching medium and suppress concrete admixture.
Embodiment 5
1) prepared by amino modified polyether polysiloxane：Hold in the reaction that device has agitator, reflux condensing tube, thermometer
In device, 70g containing hydrogen silicone oils, 3g allyl glycidyl ethers, 200g allyl polyethenoxy polyethenoxy ethers are sequentially added, leads to N2
10min is stirred, is warming up to 90 DEG C, platinum catalyst reaction 4h is added dropwise to, obtains polyether/epoxy resin silicone oil intermediate.Then with amine with gathering
The ratio that ether/epoxy silicon oil intermediate epoxy radicals mol ratio is 1.05: 1.00 puts into N, and N- dimethylated propyl diethylenetriamines continue to react 4h,
After decompression removes low-boiling-point substance, room temperature is down to, with hexamethylene/chloroform (weight ratio is 9: 1) mixed solvent washing impurity-removing, obtains thick liquid
Body.
2) preparation of poly- hydroxypropyl methyl silsesquioxane：Hold in the reaction that device has agitator, reflux condensing tube, thermometer
In device, MTES 160ml, propyl-triethoxysilicane 50ml, 0.0lmol/L hydrochloric acid 20mL, isopropanol are added
Magnetic agitation adds 28% ammoniacal liquor 4.0mL at 80.0mL60 DEG C after reaction l hours, and 80 DEG C of heating continues reaction 1 hour, uses hydrochloric acid
Neutralize, obtain poly- hydroxypropyl methyl silsesquioxane.
3) preparation of the concrete admixture of etching medium transmission is suppressed：There are agitator, reflux condensing tube, temperature in device
In the reaction vessel of meter, amino modified polyether polysiloxane, poly- hydroxypropyl methyl silsesquioxane, alkane are sequentially added at 25 DEG C
Epoxide siloxanes, stearic acid, stearate, aliphatic amine polyoxyethylene base ether, aliphatic acid polyethenoxy base ester are warming up to 60 DEG C of machines
After tool stirs 2 hours, addition nano silicon, nano titanium oxide continue after stirring 30min, are cooled to normal temperature discharging, obtain
Transmitted to etching medium and suppress concrete admixture.
Embodiment 6
1) prepared by amino modified polyether polysiloxane：Hold in the reaction that device has agitator, reflux condensing tube, thermometer
In device, 85g containing hydrogen silicone oils, 2.5g allyl glycidyl ethers, 210g allyl polyethenoxy polyethenoxy ethers are sequentially added, is led to
N2 stirs 10min, is warming up to 90 DEG C, is added dropwise to platinum catalyst reaction 4h, obtains polyether/epoxy resin silicone oil intermediate.Then with amine with
The ratio that polyether/epoxy resin silicone oil intermediate epoxy radicals mol ratio is 1.05: 1.00 puts into N, and N- dimethylated propyl diethylenetriamines continue to react
4h, after decompression removes low-boiling-point substance, room temperature is down to, with hexamethylene/chloroform (weight ratio is 8: 2) mixed solvent washing impurity-removing, obtained sticky
Shape liquid.
2) preparation of poly- hydroxypropyl methyl silsesquioxane：Hold in the reaction that device has agitator, reflux condensing tube, thermometer
In device, MTES 110ml, propyl-triethoxysilicane 160ml, 0.0lmol/L hydrochloric acid 20mL, isopropanol are added
Magnetic agitation adds 28% ammoniacal liquor 15mL at 100.0mL60 DEG C after reaction l hours, and 80 DEG C of heating continues reaction 1 hour, uses hydrochloric acid
Neutralize, obtain poly- hydroxypropyl methyl silsesquioxane.
3) preparation of the concrete admixture of etching medium transmission is suppressed：There are agitator, reflux condensing tube, temperature in device
In the reaction vessel of meter, amino modified polyether polysiloxane, poly- hydroxypropyl methyl silsesquioxane, alkane are sequentially added at 25 DEG C
Epoxide siloxanes, stearic acid, stearate, aliphatic amine polyoxyethylene base ether, aliphatic acid polyethenoxy base ester are warming up to 60 DEG C of machines
After tool stirs 2 hours, addition nano silicon, nano titanium oxide continue after stirring 30min, are cooled to normal temperature discharging, obtain
Transmitted to etching medium and suppress concrete admixture.
Embodiment 7
1) prepared by amino modified polyether polysiloxane：Hold in the reaction that device has agitator, reflux condensing tube, thermometer
In device, 65g containing hydrogen silicone oils, 5g allyl glycidyl ethers, 175g allyl polyethenoxy polyethenoxy ethers are sequentially added, leads to N2
10min is stirred, is warming up to 90 DEG C, platinum catalyst reaction 4h is added dropwise to, obtains polyether/epoxy resin silicone oil intermediate.Then with amine with gathering
The ratio that ether/epoxy silicon oil intermediate epoxy radicals mol ratio is 1.05: 1.00 puts into piperazine and continues to react 4h, and decompression removes low-boiling-point substance
Afterwards, room temperature is down to, with hexamethylene/chloroform (weight ratio is 9: 1) mixed solvent washing impurity-removing, obtains viscous liquid.
2) preparation of poly- hydroxypropyl methyl silsesquioxane：Hold in the reaction that device has agitator, reflux condensing tube, thermometer
In device, MTES 150ml, propyl-triethoxysilicane 50ml, 0.0lmol/L hydrochloric acid 20mL, isopropanol are added
Magnetic agitation adds 28% ammoniacal liquor 15mL at 100.0mL60 DEG C after reaction l hours, and 80 DEG C of heating continues reaction 1 hour, uses hydrochloric acid
Neutralize, obtain poly- hydroxypropyl methyl silsesquioxane.
3) preparation of the concrete admixture of etching medium transmission is suppressed：There are agitator, reflux condensing tube, temperature in device
In the reaction vessel of meter, amino modified polyether polysiloxane, poly- hydroxypropyl methyl silsesquioxane, alkane are sequentially added at 25 DEG C
Epoxide siloxanes, stearic acid, stearate, aliphatic amine polyoxyethylene base ether, aliphatic acid polyethenoxy base ester are warming up to 60 DEG C of machines
After tool stirs 2 hours, addition nano silicon, nano titanium oxide continue after stirring 30min, are cooled to normal temperature discharging, obtain
Transmitted to etching medium and suppress concrete admixture.
Embodiment 8
1) prepared by amino modified polyether polysiloxane：Hold in the reaction that device has agitator, reflux condensing tube, thermometer
In device, 90g containing hydrogen silicone oils, 2g allyl glycidyl ethers, 180g allyl polyethenoxy polyethenoxy ethers are sequentially added, leads to N2
10min is stirred, is warming up to 90 DEG C, platinum catalyst reaction 4h is added dropwise to, obtains polyether/epoxy resin silicone oil intermediate.Then with amine with gathering
The ratio that ether/epoxy silicon oil intermediate epoxy radicals mol ratio is 1.05: 1.00 puts into piperazine and continues to react 4h, and decompression removes low-boiling-point substance
Afterwards, room temperature is down to, with hexamethylene/chloroform (weight ratio is 8: 2) mixed solvent washing impurity-removing, obtains viscous liquid.
2) preparation of poly- hydroxypropyl methyl silsesquioxane：Hold in the reaction that device has agitator, reflux condensing tube, thermometer
In device, MTES 140ml, propyl-triethoxysilicane 60ml, 0.0lmol/L hydrochloric acid 20mL, isopropanol are added
Magnetic agitation adds 28% ammoniacal liquor 4.0mL at 100.0mL60 DEG C after reaction l hours, and 80 DEG C of heating continues reaction 1 hour, uses salt
Acid neutralizes, and obtains poly- hydroxypropyl methyl silsesquioxane.
3) preparation of the concrete admixture of etching medium transmission is suppressed：There are agitator, reflux condensing tube, temperature in device
In the reaction vessel of meter, amino modified polyether polysiloxane, poly- hydroxypropyl methyl silsesquioxane, alkane are sequentially added at 25 DEG C
Epoxide siloxanes, stearic acid, stearate, aliphatic amine polyoxyethylene base ether, aliphatic acid polyethenoxy base ester are warming up to 60 DEG C of machines
After tool stirs 2 hours, addition nano silicon, nano titanium oxide continue after stirring 30min, are cooled to normal temperature discharging, obtain
Transmitted to etching medium and suppress concrete admixture.
Embodiment 9
1) prepared by amino modified polyether polysiloxane：Hold in the reaction that device has agitator, reflux condensing tube, thermometer
In device, 80g containing hydrogen silicone oils, 3g allyl glycidyl ethers, 125g allyl polyethenoxy polyethenoxy ethers are sequentially added, leads to N2
10min is stirred, is warming up to 90 DEG C, platinum catalyst reaction 4h is added dropwise to, obtains polyether/epoxy resin silicone oil intermediate.Then with amine with gathering
The ratio that ether/epoxy silicon oil intermediate epoxy radicals mol ratio is 1.05: 1.00 puts into N- aminoethyl piperazines and continues to react 4h, decompression
After low-boiling-point substance, room temperature is down to, with hexamethylene/chloroform (weight ratio is 9: 1) mixed solvent washing impurity-removing, obtains viscous liquid.
2) preparation of polymethyl-benzene base silsesquioxane and poly- hydroxypropyl methyl silsesquioxane：Device have agitator, return
In the reaction vessel for flowing condenser pipe, thermometer, MTES 140ml, propyl-triethoxysilicane 60ml are added,
0.0lmol/L hydrochloric acid 20mL, magnetic agitation adds 28% ammoniacal liquor 4.0mL after reaction l hours at 100.0mL60 DEG C of isopropanol, rises
80 DEG C of temperature continues reaction 1 hour, is neutralized with hydrochloric acid, obtains poly- hydroxypropyl methyl silsesquioxane.
3) preparation of the concrete admixture of etching medium transmission is suppressed：There are agitator, reflux condensing tube, temperature in device
In the reaction vessel of meter, amino modified polyether polysiloxane, poly- hydroxypropyl methyl silsesquioxane, alkane are sequentially added at 25 DEG C
Epoxide siloxanes, stearic acid, stearate, aliphatic amine polyoxyethylene base ether, aliphatic acid polyethenoxy base ester are warming up to 60 DEG C of machines
After tool stirs 2 hours, addition nano silicon, nano titanium oxide continue after stirring 30min, are cooled to normal temperature discharging, obtain
Transmitted to etching medium and suppress concrete admixture.
Embodiment 10
1) prepared by amino modified polyether polysiloxane：Hold in the reaction that device has agitator, reflux condensing tube, thermometer
In device, 75g containing hydrogen silicone oils, 4g allyl glycidyl ethers, 160g allyl polyethenoxy polyethenoxy ethers are sequentially added, leads to N2
10min is stirred, is warming up to 90 DEG C, platinum catalyst reaction 4h is added dropwise to, obtains polyether/epoxy resin silicone oil intermediate.Then with amine with gathering
The ratio that ether/epoxy silicon oil intermediate epoxy radicals mol ratio is 1.05: 1.00 puts into N- aminoethyl piperazines and continues to react 4h, decompression
After low-boiling-point substance, room temperature is down to, with hexamethylene/chloroform (weight ratio is 9: 1) mixed solvent washing impurity-removing, obtains viscous liquid.
2) preparation of poly- hydroxypropyl methyl silsesquioxane：Hold in the reaction that device has agitator, reflux condensing tube, thermometer
In device, MTES 165ml, propyl-triethoxysilicane 55ml, 0.0lmol/L hydrochloric acid 20mL, isopropanol are added
Magnetic agitation adds 28% ammoniacal liquor 8mL at 100.0mL60 DEG C after reaction l hours, and 80 DEG C of heating continues reaction 1 hour, uses hydrochloric acid
Neutralize, obtain poly- hydroxypropyl methyl silsesquioxane.
3) preparation of the concrete admixture of etching medium transmission is suppressed：There are agitator, reflux condensing tube, temperature in device
In the reaction vessel of meter, amino modified polyether polysiloxane, poly- hydroxypropyl methyl silsesquioxane, alkane are sequentially added at 25 DEG C
Epoxide siloxanes, stearic acid, stearate, aliphatic amine polyoxyethylene base ether, aliphatic acid polyethenoxy base ester are warming up to 60 DEG C of machines
After tool stirs 2 hours, addition nano silicon, nano titanium oxide continue after stirring 30min, are cooled to normal temperature discharging, obtain
Transmitted to etching medium and suppress concrete admixture.
Application examples
Fill after the concrete admixture carries out extra large work C40 concrete formations experiment and carry out contrast experiment, evaluate material
Erosion medium resistance rejection, as a result as shown in table 1.Concrete sample dry cleansing after being conserved by 28d is handled, Suo Youshi
Part is carried out under same experimental conditions.Wherein seepage-resistant grade normative reference GB/T50082-2009 is tested, water absorption rate reference
Standard BS1881：part122：1983 are tested, and chlorine ion binding capacity water suction is tested with reference to JTG/TB 07-01-2006,
Electric flux normative reference JTJ 275-2000 are tested.
Table 1 fills the maritime concrete corrosion-resistant property contrast of the concrete admixture
Blank test specimen is the concrete performance for being not spiked with feature additive involved in the present invention in upper table, contrast 1,2,3,
4 be to be not spiked with amino modified polyether polysiloxane, be not spiked with poly- hydroxypropyl methyl silsesquioxane and alkoxy silane, no respectively
Admixture stearate and stearate, concrete performance obtained by nano silicon and nano titanium oxide is not spiked with, passed through
Data can see in upper table：When using blank sample or lacking the material of constituent part, anti-carbonation properties, the chlorine of concrete
The performances such as ionic diffusion coefficient, electric flux, water absorption rate are substantially deteriorated, and after using feature additive involved in the present invention,
Concrete rate of water absorption is significantly reduced, concrete hydrophobicity is improved and suppresses etching medium particularly chlorion in concrete
Holetransport acts on.So as to greatly improve the corrosion-resistant property of concrete, so as to significantly improve the durability of concrete.
Claims (4)
1. a kind of concrete admixture for being used under marine environment suppress etching medium transmission, it is characterised in that comprising with the following group
Into in terms of parts by weight：
The amino modified polyether polysiloxane is with silicon oil of low hydrogen content and α-alkenyl epoxide and α-alkenyl polyether
Hydrosilylation addition reaction obtains polyether/epoxy resin silicone oil intermediate, and the amino modified polyether-type then obtained with organic amine open loop gathers
Siloxanes；
The poly- hydroxypropyl methyl silsesquioxane is through hydrolyzing after-condensation with MTES, propyl-triethoxysilicane
Obtain；
Described alkoxy silane contains following components：MTES, butyl trimethoxy silane, the ethoxy of butyl three
Base silane, octyl group trimethoxy silane, octyltri-ethoxysilane, isooctyltrimethoxysi,ane, dodecyl trimethoxy
Silane and/or dodecyl triethoxysilane；
The one kind of described aliphatic amine polyoxyethylene base ether in lauryl amine polyoxyethylene ether, octadecylamine polyoxyethylene ether
Any of the above ratio mixes；
The aliphatic acid polyethenoxy base ester be selected from stearic stearic acid polyoxyethylene base ester, laurate polyoxyethylene base ester,
More than one arbitrary proportions mixing of oleic acid polyoxyethylene base ester.
2. being used under marine environment suppress the concrete admixture of etching medium transmission according to claim 1, its feature exists
In the preparation method of the amino modified polyether polysiloxane：
In the reaction vessel that device has agitator, reflux condensing tube, thermometer, containing hydrogen silicone oil, α-alkenyl epoxy are sequentially added
Compound and α-alkenyl polyether, lead to N210min is stirred, is warming up to 90 DEG C, platinum catalyst reaction 4h is added dropwise to, obtains polyether/epoxy resin
Silicone oil intermediate；
Then ethylenediamine is put into as 1.05: 1.00 ratio using amine and polyether/epoxy resin silicone oil intermediate epoxy radicals mol ratio, continued
4h is reacted, after decompression removes low-boiling-point substance, room temperature is down to, with mixed solvent washing impurity-removing, obtains viscous liquid, as described amino changes
Property polyether type polysiloxane；
The mixed solvent is thiacyclohexane and chloroform；Hexamethylene：The weight ratio of chloroform is 8: 2.
3. being used under marine environment suppress the concrete admixture of etching medium transmission according to claim 1, its feature exists
In the preparation method of the poly- hydroxypropyl methyl silsesquioxane：There is the reaction of agitator, reflux condensing tube, thermometer in device
In container, MTES, propyl-triethoxysilicane, 0.0lmol/L hydrochloric acid, isopropanol are added；Magnetic force at 60 DEG C
Stirring reaction adds 28% ammoniacal liquor after l hours, 80 DEG C of heating continues reaction 1 hour, is neutralized with hydrochloric acid, and obtains poly- hydroxypropyl methyl times
Half siloxanes.
4. it is used under marine environment suppress the system of the concrete admixture of etching medium transmission described in any one of claim 1-3
Preparation Method, it is characterised in that be well mixed at 60 DEG C to produce each component and described be used to suppress etching medium under marine environment
The concrete admixture of transmission.
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