CN110229281A - A kind of Concrete Protective Agent and preparation method thereof - Google Patents
A kind of Concrete Protective Agent and preparation method thereof Download PDFInfo
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- CN110229281A CN110229281A CN201910537365.0A CN201910537365A CN110229281A CN 110229281 A CN110229281 A CN 110229281A CN 201910537365 A CN201910537365 A CN 201910537365A CN 110229281 A CN110229281 A CN 110229281A
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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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/48—Macromolecular compounds
- C04B41/4857—Other macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6696—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/36 or hydroxylated esters of higher fatty acids of C08G18/38
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
Abstract
The present invention relates to concrete protection technologies, specifically disclose a kind of Concrete Protective Agent and preparation method thereof.The Concrete Protective Agent, including the following raw material components of mass fraction: 18-23 parts of polyaminoester emulsion；30-43 parts of acrylate monomer；0.1-1 parts of carboxyl group-containing monomer；2-10 parts of monomer containing carbonyl；0.2-0.8 parts of initiator；2-9 parts of crosslinking agent；32-38 parts of deionized water.Protective agent provided by the invention is brushed in concrete surface; protective coating is formed, the water obstructed outside concrete penetrates into concrete, and its internal moisture is not interfered to discharge; the Anti-Chloride Ion Penetration and anti-carbonation properties for improving concrete, improve the durability of concrete.
Description
Technical field
The present invention relates to concrete protection technologies more particularly to a kind of Concrete Protective Agent and preparation method thereof.
Background technique
Concrete is most wide as purposes in civil engineering, one of maximum construction material of dosage, in the development of last 100 years,
Its intensity is continuously improved.But concrete is exposed to throughout the year in the use environments such as atmosphere, rainwater, endurance issues are also more come
More of interest by people.
People are always to be very durable material for concrete, until phase late 1970s, developed country just by
Gradually find that premature breakdown occurs in some environments in the infrastructure project originally built up.Investigation shows most of industrial buildings
Object needs overhaul after using 25~30 years, and the building service life under harsh environment only 15~20 years.Civil buildings
It is relatively preferable with the use environment of public building, it can generally maintain 50 years or more, but the outdoor component such as outdoor balcony, canopy
Service life usually only has 30~40 years.The endurance issues of the infrastructure projects such as bridge, harbour are even more serious,
The service life of general concrete engineering is about 50~100 years, but has many engineerings using 10~20 in practice
Year, some is even needed repairing after using several years, and here it is as caused by concrete durability low (deficiency).It influences mixed
The reason of solidifying soil durability, is intricate, and outside removing social factor, human factor, the principal element of technical aspect has following several
Point: carbonization, freeze-thaw damage, burn into steel bar corrosion of corrosive medium of concrete etc..Whether above-mentioned any factor is leading
The deterioration process of concrete, common ground be the intrusion for having sufficient moisture and other harmful substances in concrete.It improves
Concrete durability meets life requirement, it is necessary to reduce the infiltration of moisture and corrosive medium.
Summary of the invention
For the problem of existing concrete durability difference, the present invention provides a kind of Concrete Protective Agent and preparation method thereof.
To achieve the above object of the invention, the embodiment of the present invention uses the following technical solution:
A kind of Concrete Protective Agent, including the following raw material components of mass fraction: 18-23 parts of polyaminoester emulsion；Acrylic acid
30-43 parts of ester monomer；0.1-1 parts of carboxyl group-containing monomer；2-10 parts of monomer containing carbonyl；0.2-0.8 parts of initiator；2-9 parts of crosslinking agent；
32-38 parts of deionized water.
Using the polyaminoester emulsion as pre-polymerization precursor emulsion, carried out with acrylate monomer, carboxyl group-containing monomer and monomer containing carbonyl
Copolymerization prepares aqueous emulsion, and aqueous emulsion has post-crosslinking effect, with cross-linker molecules crosslinking curing, is formed and is had in concrete surface
There is the film coating in appropriate aperture and hydrophobicity capillary channel.Hydrophobic capillary channel has the function of blocking water, breathe freely, to realize
The water obstructed outside concrete penetrates into concrete, while concrete is discharged further through capillary in the vapor in concrete, in turn
Concrete is avoided because the harm that the factors such as carbonization, freeze thawing, ion infiltration generate caused by the infiltration of water, improves coagulation
The durability of soil.
Further, the polyaminoester emulsion includes the following raw material components of mass fraction: polyoxypropyleneglycol 2-8
Part；1-7 parts of castor oil；2-6 parts of methyl diphenylene diisocyanate；0.3-1.5 parts of dihydromethyl propionic acid；20-30 parts of acetone；Two
0.1-0.6 parts of dibutyl tin laurate；0.1-1.5 parts of triethylamine；55-65 parts of deionized water.Polyaminoester emulsion is set to contain insatiable hunger
There is certain plasticity with after double bond (C=C) and hydrophilic radical (amino or its cation, carboxyl or its anion) film forming, and
With autoemulsification, make without adding any surfactant in protective agent, and pass through the selection and its content of hydrophilic radical
Control, improve stability of emulsion and the hydrophobicity at membrane micropore.
Further, the preparation method of the polyaminoester emulsion is by polyoxypropyleneglycol, castor oil and diphenylmethyl
After the mixing of alkane diisocyanate, in 40-50 DEG C of isothermal reaction 10-30min, dihydromethyl propionic acid, acetone and February is then added
Triethylamine is added in dilaurylate, the reaction was continued 5-8h, then after reacting 1-4h, deionized water is added, reacts 0.5-1.5h.
By the regulation in the selection of urethane monomer, feeding sequence and reaction time, polyurethane segment size, and and acrylate are controlled
Monomer, carboxyl group-containing monomer and monomer containing carbonyl are copolymerized, and so that the relative size of copolymer segment is easy regulation, are improved concrete
Protectant filming performance.
Further, the acrylate monomer be methyl methacrylate, ethyl methacrylate, methyl acrylate,
At least one of ethyl acrylate, butyl acrylate or butyl methacrylate, and polyaminoester emulsion, carboxyl group-containing monomer and contain
Carbonyl monomer is copolymerized, and aqueous emulsion is prepared.
Further, the carboxyl group-containing monomer is one of acrylic acid, methacrylic acid, fumaric acid or maleic acid, with
Polyaminoester emulsion, acrylate monomer and monomer containing carbonyl are copolymerized, and aqueous emulsion is prepared.
Further, the monomer containing carbonyl is methacrylaldehyde, methacrolein, Diacetone Acrylamide or Methacrylamide
One of, it is copolymerized with polyaminoester emulsion, acrylate monomer and carboxyl group-containing monomer, preparation aqueous emulsion, aqueous emulsion stabilization,
Environmental protection, is free of any volatile organic solvent at economy.
Further, the initiator is one of ammonium persulfate, sodium peroxydisulfate or potassium peroxydisulfate.
Selected initiator is used cooperatively with monomer, be more advantageous to guarantee copolymerization reaction rate and the degree of polymerization, improve at
Film properties.
Further, the crosslinking agent is adipic dihydrazide, careless acid dihydrazide, two acyl of succinic acid hydrazide ii or decanedioic acid
One of hydrazine, selected crosslinking agent are crosslinked with aqueous emulsion, and crosslink density makes capillary channel proper pore size in coating,
Guarantee that capillary channel has the function of blocking water, breathe freely, improves the durability of concrete.
The present invention also provides the preparation methods of above-mentioned Concrete Protective Agent, comprising the following steps:
(1) after mixing the polyaminoester emulsion with 18-20 parts of deionized waters, it is warming up to 70-90 DEG C, obtains performed polymer cream
Liquid；
(2) acrylate monomer, carboxyl group-containing monomer and monomer containing carbonyl are mixed with 12-14 parts of deionized waters, is obtained
To monomer dispersion liquid, initiator is mixed with 2-4 parts of deionized waters, obtains initiator solution；
(3) initiator solution, monomer dispersion liquid are added sequentially in the pre-polymerization precursor emulsion, react 0.5-
1.5h obtains aqueous emulsion；
(4) after the aqueous emulsion is cooled to room temperature, pH to 7-9 is adjusted, crosslinking agent is added, stirring obtains concrete guarantor
Protect agent.
Specifically, in step (3), after reaction, if there are gels in system, it is filtered processing, obtains water and milk
Liquid.
Above-mentioned Concrete Protective Agent is brushed in substrate, substrate and coating are dried 5-7 days under room temperature natural conditions,
Obtain concrete protective coatings.
Further, in step (3), the addition time of the monomer dispersion liquid is 2-4h, reaction rate is controlled, convenient for altogether
The relative size of copolymer segment is easy regulation, improves the filming performance of Concrete Protective Agent, and facilitate hydrophobic capillary in coating
The formation of pipeline (micropore).
Compared with the existing technology, Concrete Protective Agent provided by the invention, using polyaminoester emulsion as pre-polymerization precursor emulsion, with third
Olefin(e) acid ester monomer, carboxyl group-containing monomer and monomer containing carbonyl are copolymerized, and aqueous emulsion is obtained, and aqueous emulsion has post-crosslinking effect, with
Cross-linker molecules crosslinking curing forms the film coating with appropriate aperture and hydrophobicity capillary channel, tool in concrete surface
There are good water resistance, resistance to acid and alkali and weatherability, while having the function of blocking water, breathe freely, the water obstructed outside concrete penetrates into
Concrete is discharged further through capillary in vapor in concrete, while in concrete, and then avoids infiltration of the concrete because of water
The harm that the factors such as carbonization, freeze thawing, ion infiltration generate caused by entering, improves the durability of concrete.In addition, this hair
The preparation method of the Concrete Protective Agent of bright offer, simple process is easy to operate, economic and environment-friendly with water for main reaction dissolvent,
Green safe, obtained aqueous emulsion is stable, is free of any volatile organic solvent, solidifies to obtain concrete guarantor with cross-linking agents
Protect coating.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
Embodiment 1
A kind of Concrete Protective Agent, including the following raw material components of mass fraction: 22 parts of polyaminoester emulsion；Butyl acrylate
19 parts；15 parts of methyl methacrylate；0.2 part of acrylic acid；3 parts of diacetone propionamide；0.8 part of sodium peroxydisulfate；Two acyl of adipic acid
3 parts of hydrazine；38 parts of deionized water.
Wherein, polyaminoester emulsion includes the following raw material components of mass fraction: 2 parts of polyoxypropyleneglycol；Castor oil 4
Part；3 parts of methyl diphenylene diisocyanate；0.6 part of dihydromethyl propionic acid；25 parts of acetone；0.2 part of dibutyl tin dilaurate；
0.2 part of triethylamine；65 parts of deionized water.
The preparation method of above-mentioned Concrete Protective Agent, includes the following steps:
(1) under nitrogen atmosphere by polyoxypropyleneglycol, castor oil and the methyl diphenylene diisocyanate place of being placed in
After mixing in reactor, after 40 DEG C of isothermal reaction 30min, dihydromethyl propionic acid, acetone and two are successively added into reactor
Dibutyl tin laurate continues isothermal reaction 5h, then triethylamine is added into reactor, then after reacting 1h, deionized water is added,
0.5h is reacted, rotary evaporation removes organic solvent, obtains polyaminoester emulsion；
(2) it will be mixed in the polyaminoester emulsion and 20 parts of deionized water places of being added to reactor under nitrogen atmosphere
Afterwards, 70 DEG C are warming up to, pre-polymerization precursor emulsion is obtained；
(3) by the butyl acrylate, methyl methacrylate, acrylic acid and diacetone propionamide and 14 parts of deionized waters
Mixing, obtains monomer dispersion liquid, sodium peroxydisulfate is mixed with 4 parts of deionized waters, obtains initiator solution；
(4) above-mentioned initiator solution, monomer dispersion liquid are added sequentially in the pre-polymerization precursor emulsion using dropping funel,
The rate of addition of monomer dispersion liquid is controlled, time for adding 2h after monomer dispersion liquid is added dropwise, reacts 0.5h, with 200 mesh Buddhist nuns
Gel filtration is obtained aqueous emulsion by imperial cloth；
(5) after the aqueous emulsion is cooled to room temperature, the ammonia water conditioning system pH to 7 for being 25%-28% with mass fraction,
It is added adipic dihydrazide (mass concentration 10%), stirring obtains Concrete Protective Agent.
Embodiment 2
A kind of Concrete Protective Agent, including the following raw material components of mass fraction: 21 parts of polyaminoester emulsion；Butyl acrylate
20 parts；16 parts of methyl methacrylate；0.3 part of acrylic acid；4 parts of diacetone propionamide；0.7 part of sodium peroxydisulfate；Two acyl of adipic acid
4 parts of hydrazine；35 parts of deionized water.
Wherein, polyaminoester emulsion includes the following raw material components of mass fraction: 4 parts of polyoxypropyleneglycol；Castor oil 5
Part；3 parts of methyl diphenylene diisocyanate；1 part of dihydromethyl propionic acid；28 parts of acetone；0.5 part of dibutyl tin dilaurate；Three
0.5 part of ethamine；58 parts of deionized water.
The preparation method of above-mentioned Concrete Protective Agent, includes the following steps:
(1) under nitrogen atmosphere by polyoxypropyleneglycol, castor oil and the methyl diphenylene diisocyanate place of being placed in
After mixing in reactor, after 45 DEG C of isothermal reaction 20min, dihydromethyl propionic acid, acetone and two are successively added into reactor
Dibutyl tin laurate continues isothermal reaction 6h, then triethylamine is added into reactor, then after reacting 2h, deionized water is added,
1h is reacted, rotary evaporation removes organic solvent, obtains polyaminoester emulsion；
(2) it will be mixed in the polyaminoester emulsion and 19 parts of deionized water places of being added to reactor under nitrogen atmosphere
Afterwards, 80 DEG C are warming up to, pre-polymerization precursor emulsion is obtained；
(3) by the butyl acrylate, methyl methacrylate, acrylic acid and diacetone propionamide and 13 parts of deionized waters
Mixing, obtains monomer dispersion liquid, sodium peroxydisulfate is mixed with 3 parts of deionized waters, obtains initiator solution；
(4) above-mentioned initiator solution, monomer dispersion liquid are added sequentially in the pre-polymerization precursor emulsion using dropping funel,
The rate of addition of monomer dispersion liquid is controlled, time for adding 3h after monomer dispersion liquid is added dropwise, reacts 1h, with 200 mesh nylon
Gel filtration is obtained aqueous emulsion by cloth；
(5) after the aqueous emulsion is cooled to room temperature, the ammonia water conditioning system pH to 9 for being 25%-28% with mass fraction,
It is added adipic dihydrazide (mass concentration 10%), stirring obtains Concrete Protective Agent.
Embodiment 3
A kind of Concrete Protective Agent, including the following raw material components of mass fraction: 20 parts of polyaminoester emulsion；Butyl acrylate
21 parts；17 parts of methyl methacrylate；0.41 part of acrylic acid；4 parts of diacetone propionamide；0.6 part of sodium peroxydisulfate；Two acyl of adipic acid
4 parts of hydrazine；32 parts of deionized water.
Wherein, polyaminoester emulsion includes the following raw material components of mass fraction: 6 parts of polyoxypropyleneglycol；Castor oil 3
Part；4 parts of methyl diphenylene diisocyanate；0.3 part of dihydromethyl propionic acid；30 parts of acetone；0.3 part of dibutyl tin dilaurate；
0.4 part of triethylamine；56 parts of deionized water.
The preparation method of above-mentioned Concrete Protective Agent, includes the following steps:
(1) under nitrogen atmosphere by polyoxypropyleneglycol, castor oil and the methyl diphenylene diisocyanate place of being placed in
After mixing in reactor, after 45 DEG C of isothermal reaction 20min, dihydromethyl propionic acid, acetone and two are successively added into reactor
Dibutyl tin laurate continues isothermal reaction 7h, then triethylamine is added into reactor, then after reacting 3h, deionized water is added,
1h is reacted, rotary evaporation removes organic solvent, obtains polyaminoester emulsion；
(2) it will be mixed in the polyaminoester emulsion and 18 parts of deionized water places of being added to reactor under nitrogen atmosphere
Afterwards, 80 DEG C are warming up to, pre-polymerization precursor emulsion is obtained；
(3) by the butyl acrylate, methyl methacrylate, acrylic acid and diacetone propionamide and 12 parts of deionized waters
Mixing, obtains monomer dispersion liquid, sodium peroxydisulfate is mixed with 2 parts of deionized waters, obtains initiator solution；
(4) above-mentioned initiator solution, monomer dispersion liquid are added sequentially in the pre-polymerization precursor emulsion using dropping funel,
The rate of addition of monomer dispersion liquid is controlled, time for adding 3h after monomer dispersion liquid is added dropwise, reacts 1h, with 200 mesh nylon
Gel filtration is obtained aqueous emulsion by cloth；
(5) after the aqueous emulsion is cooled to room temperature, the ammonia water conditioning system pH to 8 for being 25%-28% with mass fraction,
It is added adipic dihydrazide (mass concentration 10%), stirring obtains Concrete Protective Agent.
Embodiment 4
A kind of Concrete Protective Agent, including the following raw material components of mass fraction: 19 parts of polyaminoester emulsion；Butyl acrylate
19 parts；16 parts of methyl methacrylate；0.5 part of acrylic acid；6 parts of diacetone propionamide；0.5 part of potassium peroxydisulfate；Two acyl of adipic acid
9 parts of hydrazine；32 parts of deionized water.
Wherein, polyaminoester emulsion includes the following raw material components of mass fraction: 5 parts of polyoxypropyleneglycol；Castor oil 4
Part；2 parts of methyl diphenylene diisocyanate；0.4 part of dihydromethyl propionic acid；28 parts of acetone；0.2 part of dibutyl tin dilaurate；
0.4 part of triethylamine；60 parts of deionized water.
The preparation method of above-mentioned Concrete Protective Agent, includes the following steps:
(1) under nitrogen atmosphere by polyoxypropyleneglycol, castor oil and the methyl diphenylene diisocyanate place of being placed in
After mixing in reactor, after 50 DEG C of isothermal reaction 10min, dihydromethyl propionic acid, acetone and two are successively added into reactor
Dibutyl tin laurate continues isothermal reaction 8h, then triethylamine is added into reactor, then after reacting 4h, deionized water is added,
1.5h is reacted, rotary evaporation removes organic solvent, obtains polyaminoester emulsion；
(2) it will be mixed in the polyaminoester emulsion and 18 parts of deionized water places of being added to reactor under nitrogen atmosphere
Afterwards, 90 DEG C are warming up to, pre-polymerization precursor emulsion is obtained；
(3) by the butyl acrylate, methyl methacrylate, acrylic acid and diacetone propionamide and 12 parts of deionized waters
Mixing, obtains monomer dispersion liquid, potassium peroxydisulfate is mixed with 2 parts of deionized waters, obtains initiator solution；
(4) above-mentioned initiator solution, monomer dispersion liquid are added sequentially in the pre-polymerization precursor emulsion using dropping funel,
The rate of addition of monomer dispersion liquid is controlled, time for adding 4h after monomer dispersion liquid is added dropwise, reacts 1.5h, with 200 mesh Buddhist nuns
Gel filtration is obtained aqueous emulsion by imperial cloth；
(5) after the aqueous emulsion is cooled to room temperature, the ammonia water conditioning system pH to 9 for being 25%-28% with mass fraction,
It is added adipic dihydrazide (mass concentration 10%), stirring obtains Concrete Protective Agent.
Embodiment 5
A kind of Concrete Protective Agent, including the following raw material components of mass fraction: 20 parts of polyaminoester emulsion；Ethyl acrylate
8 parts；10 parts of butyl acrylate；12 parts of methyl methacrylate；1 part of methacrylic acid；2 parts of Methacrylamide；Sodium peroxydisulfate
0.2 part；2 parts of careless acid dihydrazide；32 parts of deionized water.
Wherein, polyaminoester emulsion includes the following raw material components of mass fraction: 8 parts of polyoxypropyleneglycol；Castor oil 7
Part；4 parts of methyl diphenylene diisocyanate；0.3 part of dihydromethyl propionic acid；20 parts of acetone；0.6 part of dibutyl tin dilaurate；
1.5 parts of triethylamine；56 parts of deionized water.
The preparation method of above-mentioned Concrete Protective Agent, includes the following steps:
(1) under nitrogen atmosphere by polyoxypropyleneglycol, castor oil and the methyl diphenylene diisocyanate place of being placed in
After mixing in reactor, after 45 DEG C of isothermal reaction 20min, dihydromethyl propionic acid, acetone and two are successively added into reactor
Dibutyl tin laurate continues isothermal reaction 7h, then triethylamine is added into reactor, then after reacting 3h, deionized water is added,
1h is reacted, rotary evaporation removes organic solvent, obtains polyaminoester emulsion；
(2) it will be mixed in the polyaminoester emulsion and 18 parts of deionized water places of being added to reactor under nitrogen atmosphere
Afterwards, 80 DEG C are warming up to, pre-polymerization precursor emulsion is obtained；
(3) by the ethyl acrylate, butyl acrylate, methyl methacrylate, methacrylic acid and methacryl
Amine is mixed with 12 parts of deionized waters, obtains monomer dispersion liquid, and sodium peroxydisulfate is mixed with 2 parts of deionized waters, it is molten to obtain initiator
Liquid；
(4) above-mentioned initiator solution, monomer dispersion liquid are added sequentially in the pre-polymerization precursor emulsion using dropping funel,
The rate of addition of monomer dispersion liquid is controlled, time for adding 2h after monomer dispersion liquid is added dropwise, reacts 0.5h, with 200 mesh Buddhist nuns
Gel filtration is obtained aqueous emulsion by imperial cloth；
(5) after the aqueous emulsion is cooled to room temperature, the ammonia water conditioning system pH to 8 for being 25%-28% with mass fraction,
Careless acid dihydrazide (mass concentration 10%) is added, stirring obtains Concrete Protective Agent.
Embodiment 6
A kind of Concrete Protective Agent, including the following raw material components of mass fraction: 23 parts of polyaminoester emulsion；Butyl acrylate
20 parts；15 parts of methyl methacrylate；8 parts of ethyl methacrylate；0.1 part of acrylic acid；10 parts of methacrolein；Ammonium persulfate
0.6 part；4 parts of succinic acid hydrazide ii；32 parts of deionized water.
Wherein, polyaminoester emulsion includes the following raw material components of mass fraction: 5 parts of polyoxypropyleneglycol；Castor oil 1
Part；6 parts of methyl diphenylene diisocyanate；1.5 parts of dihydromethyl propionic acid；25 parts of acetone；0.1 part of dibutyl tin dilaurate；
0.1 part of triethylamine；56 parts of deionized water.
The preparation method of above-mentioned Concrete Protective Agent, includes the following steps:
(1) under nitrogen atmosphere by polyoxypropyleneglycol, castor oil and the methyl diphenylene diisocyanate place of being placed in
After mixing in reactor, after 45 DEG C of isothermal reaction 20min, dihydromethyl propionic acid, acetone and two are successively added into reactor
Dibutyl tin laurate continues isothermal reaction 7h, then triethylamine is added into reactor, then after reacting 3h, deionized water is added,
1h is reacted, rotary evaporation removes organic solvent, obtains polyaminoester emulsion；
(2) it will be mixed in the polyaminoester emulsion and 18 parts of deionized water places of being added to reactor under nitrogen atmosphere
Afterwards, 80 DEG C are warming up to, pre-polymerization precursor emulsion is obtained；
(3) by the butyl acrylate, methyl methacrylate, ethyl methacrylate, acrylic acid and methacrolein with
12 parts of deionized water mixing, obtain monomer dispersion liquid, ammonium persulfate are mixed with 2 parts of deionized waters, obtains initiator solution；
(4) above-mentioned initiator solution, monomer dispersion liquid are added sequentially in the pre-polymerization precursor emulsion using dropping funel,
The rate of addition of monomer dispersion liquid is controlled, time for adding 4h after monomer dispersion liquid is added dropwise, reacts 1.5h, with 200 mesh Buddhist nuns
Gel filtration is obtained aqueous emulsion by imperial cloth；
(5) after the aqueous emulsion is cooled to room temperature, the ammonia water conditioning system pH to 8 for being 25%-28% with mass fraction,
It is added succinic acid hydrazide ii (mass concentration 10%), stirring obtains Concrete Protective Agent.
The Concrete Protective Agent provided in above-described embodiment is brushed in substrate, by substrate and coating in room temperature nature item
It is 5-7 days dry under part, obtain concrete protective coatings.
The characteristic for the Concrete Protective Agent that embodiment provides in order to better illustrate the present invention, below by embodiment 1-6 system
Standby Concrete Protective Agent and its respective coatings carry out the test of respective performances, and the results are shown in Table 1.
Table 1
Note: it determination of solid content: provides to measure according to GB-1725-79.Gel fraction measurement: it after emulsion polymerization, uses
The nylon cloth of 200 mesh filters lotion, collects in reaction system, the condensation product in bottle wall, thermometer, stirring rod, uses deionized water
It rinses well and is placed on evaporating dish, drying to constant weight at 105 DEG C, measures its gel fraction after cooling.Percentage of water loss and water absorption rate
Measurement: according to ASTM C1585-2013 " standard test method of measurement concrete water absorption rate " measurement.Anti-Chloride Ion Penetration
Measurement: it is measured according to CECS207:2006 high performance concrete application technology regulation.Anti-carbonation properties measurement: according to GB/T
50082-2009 normal concrete chronicity and endurance quality test method standard and test measure.
As seen from the above table, Concrete Protective Agent solid content provided by the invention is high, and stability is good.By guarantor provided by the invention
It protects agent to brush in concrete surface, form one layer of equably protective coating has while the coating assigns concrete water resistance
The good effect for blocking water, breathing freely, the water obstructed outside concrete penetrates into concrete, and does not interfere its internal moisture to outlet
Out, i.e. Unidirectional water permeable effectively avoids concrete because carbonization, freeze thawing, ion such as permeate at the factors caused by the infiltration of water
The harm of generation improves the Anti-Chloride Ion Penetration and anti-carbonation properties of concrete, improves the durability of concrete.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modification, equivalent replacement or improvement etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (10)
1. a kind of Concrete Protective Agent, which is characterized in that including the following raw material components of mass fraction: polyaminoester emulsion 18-23
Part；30-43 parts of acrylate monomer；0.1-1 parts of carboxyl group-containing monomer；2-10 parts of monomer containing carbonyl；0.2-0.8 parts of initiator；It hands over
Agent 2-9 parts of connection；32-38 parts of deionized water.
2. Concrete Protective Agent as described in claim 1, which is characterized in that the polyaminoester emulsion includes that mass fraction is as follows
Raw material components: 2-8 parts of polyoxypropyleneglycol；1-7 parts of castor oil；2-6 parts of methyl diphenylene diisocyanate；Dihydroxymethyl
0.3-1.5 parts of propionic acid；20-30 parts of acetone；0.1-0.6 parts of dibutyl tin dilaurate；0.1-1.5 parts of triethylamine；Deionized water
55-65 parts.
3. Concrete Protective Agent as claimed in claim 2, it is characterised in that: the polyaminoester emulsion the preparation method comprises the following steps: will
After polyoxypropyleneglycol, castor oil and methyl diphenylene diisocyanate mixing, in 40-50 DEG C of isothermal reaction 10-30min,
Then dihydromethyl propionic acid, acetone and dibutyl tin dilaurate is added, triethylamine is added, then reacts 1- in the reaction was continued 5-8h
After 4h, deionized water is added, reacts 0.5-1.5h.
4. Concrete Protective Agent as described in claim 1, it is characterised in that: the acrylate monomer is methyl methacrylate
At least one in ester, ethyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate or butyl methacrylate
Kind.
5. Concrete Protective Agent as described in claim 1, it is characterised in that: the carboxyl group-containing monomer is acrylic acid, methyl-prop
One of olefin(e) acid, fumaric acid or maleic acid.
6. Concrete Protective Agent as described in claim 1, it is characterised in that: the monomer containing carbonyl is methacrylaldehyde, isobutene
One of aldehyde, Diacetone Acrylamide or Methacrylamide.
7. Concrete Protective Agent as described in claim 1, it is characterised in that: the initiator is ammonium persulfate, sodium peroxydisulfate
Or one of potassium peroxydisulfate.
8. Concrete Protective Agent as described in claim 1, it is characterised in that: the crosslinking agent is adipic dihydrazide, oxalic acid
One of two hydrazides, succinic acid hydrazide ii or sebacic dihydrazide.
9. a kind of preparation method of the described in any item Concrete Protective Agents of claim 1 to 8, which is characterized in that including following
Step:
(1) after mixing the polyaminoester emulsion with 18-20 parts of deionized waters, it is warming up to 70-90 DEG C, obtains pre-polymerization precursor emulsion；
(2) acrylate monomer, carboxyl group-containing monomer and monomer containing carbonyl are mixed with 12-14 parts of deionized waters, obtains list
Initiator is mixed with 2-4 parts of deionized waters, obtains initiator solution by dispersion liquid；
(3) initiator solution, monomer dispersion liquid are added sequentially in the pre-polymerization precursor emulsion, react 0.5-1.5h, obtains
To aqueous emulsion；
(4) after the aqueous emulsion is cooled to room temperature, pH to 7-9 is adjusted, crosslinking agent is added, stirring obtains Concrete Protective Agent.
10. the preparation method of Concrete Protective Agent as claimed in claim 9, it is characterised in that: in step (3), the monomer
The addition time of dispersion liquid is 2-4h.
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