CN103408324B - A kind of preparation method of curing compound - Google Patents

A kind of preparation method of curing compound Download PDF

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Publication number
CN103408324B
CN103408324B CN201310369533.2A CN201310369533A CN103408324B CN 103408324 B CN103408324 B CN 103408324B CN 201310369533 A CN201310369533 A CN 201310369533A CN 103408324 B CN103408324 B CN 103408324B
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preparation
curing compound
monomer
emulsion
curing
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CN103408324A (en
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王瑞
李磊
刘加平
田倩
王洪松
王文彬
王倩
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Sobute New Materials Co Ltd
Taizhou Jiangyan Bote New Materials Co Ltd
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Sobute New Materials Co Ltd
Taizhou Jiangyan Bote New Materials Co Ltd
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Abstract

The present invention relates to a kind of preparation method of curing compound, (methyl) acrylate, (methyl) acrylate monomer of vinylbenzene and hydroxyl, macromolecule emulsion is obtained through letex polymerization, then with film coalescence aid, defoamer, flow agent and water carry out composite, obtain curing compound.The present invention is simple to operate, easily-controlled reaction conditions; In macromolecular chain, introduce oh group by the method for letex polymerization, oh group can with the Siliciumatom generation chemical bonding effect of concrete surface, enhance the bonding force of curing agent and concrete surface.After being sprayed at concrete surface, along with the volatilization of moisture in curing agent, macromolecule emulsion particular aggregation over time also finally forms curing film; Because hydroxyl and Siliciumatom form covalent linkage, fine and close curing film effectively prevents the evaporation of concrete surface moisture, improves maintenance effect.

Description

A kind of preparation method of curing compound
Technical field
The present invention relates to a kind of preparation method of curing compound.
Background technology
Concrete pouring is an important step of concrete construction, after concrete depositing, must carry out maintenance in the process of initial set, and namely keep necessary humidity and temperature, hydration reaction carries out to make it have suff water to ensure; Suitable maintenance can increase substantially the performances such as concrete weather resistance, intensity, wear resistance, volume stability.Traditional maintenance process litters a bag maintenance, plastics film maintenance and watering maintenance, and these methods are time-consuming, take a lot of work and serious waste water resources.Use the method for film forming curing agent curing concrete long-standing, but its maintenance effect cannot meet actual needs, film forming curing agent is as emulsion type concrete curing agent, mainly prepared by benzene emulsion, after benzene emulsion curing agent is sprayed at concrete surface, in atmosphere along with the volatilization of solvent in curing agent, form fine and close polymer curing film, thus hinder the evaporation of concrete surface moisture.But the surface bonding power of traditional benzene emulsion and green concrete humidity is poor, cause its Water-saving effect unsatisfactory, product performance are difficult to the requirement reaching practical application.
Patent CN102010230 provides a kind of preparation method of curing compound, use (methyl) acrylate, vinylbenzene and organic fluorine unsaturated monomer and/or organosilicon unsaturated monomer, macromolecule emulsion is obtained through letex polymerization, carry out composite with membrane-forming agent, softening agent, defoamer and water afterwards, obtain curing compound.This invent organic fluorine unsaturated monomer used and organosilicon unsaturated monomer expensive, cost is high; And the organic fluorine formed and organosilicon polymer hydrophobicity strong, be unfavorable for that curing agent is to the even coating at concrete surface of the wetting of green concrete surface and curing agent.
Patent CN102976652 provides a kind of preparation method of curing compound of high water retention, comprises the steps: vinylbenzene and acrylic ester monomer to be prepared as emulsion, in emulsion, drip initiator solution; Vinylbenzene, acrylic ester monomer, vinylformic acid and initiator are added drop-wise in reactant and are obtained by reacting polymer emulsion, then it is mixed with film coalescence aid, softening agent, defoamer, flow agent and water, obtain curing compound.This invention is traditional benzene emulsion, and the introducing of nucleocapsid structure can only reduce the minimum film-forming temperature of emulsion, fundamentally can not improve the curing film of formation to the restraining effect of green concrete surface-moisture.
Patent ZL02111497.8 provides a kind of water-base liquid film-type concrete curing agent, this curing agent is made up of acrylate polymer emulsion, wax emulsion, film coalescence aid, wetting agent, softening agent and flow agent, when being coated on concrete and the sand-cement slurry surface of initial set, form the colourless fluid-tight efficient curing film of continuous print, can penetrate into again in concrete pore simultaneously, sealed hair pore, prevents the generation of moisture evaporation and cement concrete surface excreting water phenomenon.This invention is the curing agent that acrylate polymer emulsion and wax latex composite compounding are formed, the composite not positive synergy of physical action, and the consistency of the two is bad.
Above-mentioned curing agent invention is all only considered from curing agent self, does not consider the keying action of curing agent and concrete surface.
Summary of the invention
The object of the invention is to overcome defect that above-mentioned film forming curing agent exists and a kind of preparation method of curing compound is provided.
The object of the invention is to overcome defect that above-mentioned film forming curing agent exists and a kind of preparation method of curing compound is provided.The present invention introduces oh group by the method for letex polymerization in macromolecular chain, oh group can with the Siliciumatom generation chemical bonding effect of concrete surface, enhance the bonding force of curing agent and concrete surface.After being sprayed at concrete surface, along with the volatilization of moisture in curing agent, macromolecule emulsion particular aggregation over time also finally forms curing film; Because hydroxyl and Siliciumatom form covalent linkage, fine and close curing film effectively prevents the evaporation of concrete surface moisture, improves maintenance effect.
The preparation method of curing compound of the present invention comprises the steps:
1) macromolecule emulsion is obtained by following monomer through letex polymerization: 1-20wt% general formula is hydroxyl (methyl) acrylate monomer of a, and the vinylbenzene of 0-75wt% and surplus are the monomer of general formula b;
Wherein R 1for H or CH 3; R 2for CH 2cH 2or CH 2cH 2cH 2; R 3for the alkyl containing 1-20 carbon atom;
2) curing compound is composite: the above-mentioned macromolecule emulsion of 30-90wt% and the film coalescence aid of 0-5wt%, the defoamer of 0-5wt%, and the flow agent of 0-5wt% and the water of surplus mix, obtained curing compound.
In described curing compound, high molecular solid content is 15-55wt%.
(methyl) acrylate monomer a of described hydroxyl is Propylene glycol monoacrylate, Rocryl 410, the mixture of more than one arbitrary proportions in Hydroxyethyl acrylate and hydroxyethyl methylacrylate.Its effect is the keying action in order to the curing agent and concrete surface improving formation.
The monomer of described general formula b is more than one (methyl) vinylformic acid C 1-C 20the mixture of alkyl ester arbitrary proportion.
Described macromolecule emulsion is prepared through letex polymerization by above-mentioned monomer, and letex polymerization is ordinary method, under water soluble starter and emulsifying agent exist, is that solvent or dispersion medium carry out at 40-90 DEG C with water.
Prepared macromolecule emulsion has the solids content of 10-65wt%.
Described film coalescence aid is the mixture of more than one arbitrary proportions in following composition: alcohol ester 12, butyl glycol ether, propylene glycol monomethyl ether, propandiol butyl ether, propylene glycol phenylate, diethylene glycol monoethyl ether and dipropylene glycol methyl ether.
Described defoamer is the mixture of the higher alcohols of C7-C22, more than one arbitrary proportions of polyethers and silicone based defoamer.
Described flow agent is silicone based flow agent, the mixture of more than one arbitrary proportions of acrylic acid or the like flow agent and fluorine class flow agent.
The preparation method of curing compound provided by the invention is simple, easy control of reaction conditions, and obtained macromolecule emulsion is without the need to purification & isolation, and direct and film coalescence aid, defoamer, flow agent and water carry out composite, simple to operate.Compared with existing styrene-acrylate emulsion type curing compound, the present invention is by the method for letex polymerization, oh group is introduced in macromolecular chain, improve the bonding force of emulsion and concrete surface, after being sprayed at concrete surface, along with the volatilization of moisture in curing agent, macromolecule emulsion particular aggregation over time also finally forms curing film; Because hydroxyl and Siliciumatom form covalent linkage, fine and close curing film effectively prevents the evaporation of concrete surface moisture, improves maintenance effect.The curing compound water retention that the present invention obtains is up to 95%.
Embodiment
In following embodiment, the water retention of curing compound is tested according to building material industry standard (JC901-2002).
Embodiment 1
1) preparation of macromolecule emulsion:
The Hydroxyethyl acrylate of proportioning raw materials: 1g, the vinylbenzene of 50g, the methyl methacrylate of 49g, the ammonium persulphate of 0.5g, the emulsifier sodium lauryl sulfate of 0.5g, the emulsifying agent alkylphenol polyoxyethylene (op-10) of 1.5g and appropriate water.
Preparation Hydroxyethyl acrylate/styrene/methacrylic acid methyl ester emulsions, ammonium persulfate aqueous solution.Under agitation, temperature is 75 DEG C, in reactor, add deionized water, then drips Hydroxyethyl acrylate/styrene/methacrylic acid methyl ester emulsions and ammonium persulfate aqueous solution simultaneously.Control rate of addition and add all emulsions and ammonium persulfate aqueous solution simultaneously, after dropwising, reaction solution is warming up to 85 DEG C to be continued to stir 2h, cooling, discharging.
2) mix according to following ingredients and ratio, the macromolecule emulsion of obtained high performance concrete curing agent: 30wt%, film coalescence aid alcohol ester 12, the 1wt% fluorine carbon flow agent of 0.5wt%, the water of 0.5wt% defoamer n-Octanol and 68wt%, testing its water retention is 85%.
Embodiment 2
1) preparation of macromolecule emulsion:
The Propylene glycol monoacrylate of proportioning raw materials: 5g, the vinylbenzene of 45g, the methyl methacrylate of 30g, the methyl acrylate of 20g, the ammonium persulphate of 0.5g, the emulsifier sodium lauryl sulfate of 0.5g, the emulsifying agent alkylphenol polyoxyethylene (op-10) of 1.5g and appropriate water.
Preparation Propylene glycol monoacrylate/styrene/methacrylic acid methyl esters/methyl acrylate emulsion, ammonium persulfate aqueous solution.Under agitation, temperature is 75 DEG C, in reactor, add deionized water, then drips Propylene glycol monoacrylate/styrene/methacrylic acid methyl esters/methyl acrylate emulsion and ammonium persulfate aqueous solution simultaneously.Control rate of addition and add all emulsions and ammonium persulfate aqueous solution simultaneously, after dropwising, reaction solution is warming up to 85 DEG C to be continued to stir 2h, cooling, discharging.
2) mix according to following ingredients and ratio, the macromolecule emulsion of obtained high performance concrete curing agent: 45wt%, the film coalescence aid alcohol ester 12 of 1wt% and the propylene glycol monomethyl ether of 1wt%, 1wt% fluorine carbon flow agent, the water of 1wt% defoamer n-Octanol and 51wt%, testing its water retention is 83%.
Embodiment 3
1) preparation of macromolecule emulsion:
The hydroxyethyl methylacrylate of proportioning raw materials: 3g, the vinylbenzene of 75g, the butyl acrylate of 10g, the lauryl acrylate of 12g, the ammonium persulphate of 0.5g, the emulsifier sodium lauryl sulfate of 0.5g, the emulsifying agent alkylphenol polyoxyethylene (op-10) of 1.5g and appropriate water.
Preparation hydroxyethyl methylacrylate/styrene/acrylic butyl ester/lauryl acrylate emulsion, ammonium persulfate aqueous solution.Under agitation, temperature is 75 DEG C, in reactor, add deionized water, then drips hydroxyethyl methylacrylate/styrene/acrylic butyl ester/lauryl acrylate emulsion and ammonium persulfate aqueous solution simultaneously.Control rate of addition and add all emulsions and ammonium persulfate aqueous solution simultaneously, after dropwising, reaction solution is warming up to 85 DEG C to be continued to stir 2h, cooling, discharging.
2) mix according to following ingredients and ratio, the macromolecule emulsion of obtained high performance concrete curing agent: 80wt%, the film coalescence aid diethylene glycol monoethyl ether of 3wt% and the propylene glycol monomethyl ether of 2wt%, the silicone based flow agent of 5wt%, the water of 3.5wt% polyethers defoamer and 6.5wt%, testing its water retention is 90%.
Embodiment 4
1) preparation of macromolecule emulsion:
The Rocryl 410 of proportioning raw materials: 15g, the butyl methacrylate of 30g, the Isooctyl acrylate monomer of 55g, the ammonium persulphate of 0.5g, the emulsifier sodium lauryl sulfate of 0.5g, the emulsifying agent alkylphenol polyoxyethylene (op-10) of 1.5g and appropriate water.
Preparation Rocryl 410/butyl methacrylate/Isooctyl acrylate monomer emulsion, ammonium persulfate aqueous solution.Under agitation, temperature is 75 DEG C, in reactor, add deionized water, then drips Rocryl 410/butyl methacrylate/Isooctyl acrylate monomer emulsion and ammonium persulfate aqueous solution simultaneously.Control rate of addition and add all emulsions and ammonium persulfate aqueous solution simultaneously, after dropwising, reaction solution is warming up to 85 DEG C to be continued to stir 2h, cooling, discharging.
2) mix according to following ingredients and ratio, the macromolecule emulsion of obtained high performance concrete curing agent: 75wt%, the film coalescence aid dipropylene glycol methyl ether of 2wt%, 0.5wt% organosilicon flow agent, 0.5wt% fluorine class flow agent, the water of the silicone based defoamer of 2wt% and 20wt%, testing its water retention is 87%.
Embodiment 5
1) preparation of macromolecule emulsion:
The Hydroxyethyl acrylate of proportioning raw materials: 20g, the vinylbenzene of 25g, the methyl methacrylate of 10g, the Octyl acrylate of 25g, the methacrylic acid 18 carbon ester of 20g, the ammonium persulphate of 0.5g, the emulsifier sodium lauryl sulfate of 0.5g, the emulsifying agent alkylphenol polyoxyethylene (op-10) of 1.5g and appropriate water.
Preparation Hydroxyethyl acrylate/styrene/methacrylic acid methyl esters/Octyl acrylate/methacrylic acid 18 carbon ester emulsion, ammonium persulfate aqueous solution.Under agitation, temperature is 75 DEG C, in reactor, add deionized water, then drips Hydroxyethyl acrylate/styrene/methacrylic acid methyl esters/Octyl acrylate/methacrylic acid 18 carbon ester emulsion and ammonium persulfate aqueous solution simultaneously.Control rate of addition and add all emulsions and ammonium persulfate aqueous solution simultaneously, after dropwising, reaction solution is warming up to 85 DEG C to be continued to stir 2h, cooling, discharging.
2) mix according to following ingredients and ratio, the macromolecule emulsion of obtained high performance concrete curing agent: 65wt%, the film coalescence aid alcohol ester 12 of 1.5wt%, 0.5wt% acrylic acid or the like flow agent, 0.5wt% defoamer n-Octanol, the water of the silicone based defoamer of 0.5wt% and 32wt%, testing its water retention is 86.5%.
Embodiment 6
1) preparation of macromolecule emulsion:
The Hydroxyethyl acrylate of proportioning raw materials: 2g, the hydroxyethyl methylacrylate of 2g, the vinylbenzene of 50g, the methyl methacrylate of 10g, the butyl acrylate of 26g, the methacrylic acid 20 carbon ester of 10g, the ammonium persulphate of 0.5g, the emulsifier sodium lauryl sulfate of 0.5g, the emulsifying agent alkylphenol polyoxyethylene (op-10) of 1.5g and appropriate water.
Preparation Hydroxyethyl acrylate/hydroxyethyl methylacrylate/styrene/methacrylic acid methyl esters/butyl acrylate/methacrylic acid 20 carbon ester emulsion, ammonium persulfate aqueous solution.Under agitation, temperature is 75 DEG C, in reactor, add deionized water, then drip Hydroxyethyl acrylate/hydroxyethyl methylacrylate/styrene/methacrylic acid methyl esters/butyl acrylate/methacrylic acid 20 carbon ester emulsion and ammonium persulfate aqueous solution simultaneously.Control rate of addition and add all emulsions and ammonium persulfate aqueous solution simultaneously, after dropwising, reaction solution is warming up to 85 DEG C to be continued to stir 2h, cooling, discharging.
2) mix according to following ingredients and ratio, the macromolecule emulsion of obtained high performance concrete curing agent: 75wt%, the film coalescence aid alcohol ester 12 of 0.5wt%, the film coalescence aid butyl glycol ether of 0.5wt%, 1wt% fluorine carbon flow agent, the positive stearyl alcohol of 0.5wt% defoamer, the water of 0.5wt% polyethers defoamer and 22wt%, testing its water retention is 95%.
Embodiment 7
1) preparation of macromolecule emulsion:
The Hydroxyethyl acrylate of proportioning raw materials: 2g, the Rocryl 410 of 7g, the vinylbenzene of 60g, the ethyl propenoate of 31g, the ammonium persulphate of 0.5g, the emulsifier sodium lauryl sulfate of 0.5g, the emulsifying agent alkylphenol polyoxyethylene (op-10) of 1.5g and appropriate water.
Preparation Hydroxyethyl acrylate/Rocryl 410/styrene/acrylic ethyl ester emulsion, ammonium persulfate aqueous solution.Under agitation, temperature is 75 DEG C, in reactor, add deionized water, then drips Hydroxyethyl acrylate/Rocryl 410/styrene/acrylic ethyl ester emulsion and ammonium persulfate aqueous solution simultaneously.Control rate of addition and add all emulsions and ammonium persulfate aqueous solution simultaneously, after dropwising, reaction solution is warming up to 85 DEG C to be continued to stir 2h, cooling, discharging.
2) mix according to following ingredients and ratio, the macromolecule emulsion of obtained high performance concrete curing agent: 45wt%, film coalescence aid alcohol ester 12, the 1wt% fluorine carbon flow agent positive behenyl alcohol of 0.5wt% defoamer of 0.5wt% and the water of 53wt%, testing its water retention is 89%.
Embodiment 8
1) preparation of macromolecule emulsion:
The Hydroxyethyl acrylate of proportioning raw materials: 1g, the hydroxyethyl methylacrylate of 2g, the Propylene glycol monoacrylate of 1g, the vinylbenzene of 50g, the n octyl methacrylate of 46g, the ammonium persulphate of 0.5g, the emulsifier sodium lauryl sulfate of 0.5g, the emulsifying agent alkylphenol polyoxyethylene (op-10) of 1.5g and appropriate water.
Preparation Hydroxyethyl acrylate/hydroxyethyl methylacrylate/Propylene glycol monoacrylate/styrene/methacrylic acid n-octyl emulsion, ammonium persulfate aqueous solution.Under agitation, temperature is 75 DEG C, in reactor, add deionized water, then drips Hydroxyethyl acrylate/hydroxyethyl methylacrylate/Propylene glycol monoacrylate/styrene/methacrylic acid n-octyl emulsion and ammonium persulfate aqueous solution simultaneously.Control rate of addition and add all emulsions and ammonium persulfate aqueous solution simultaneously, after dropwising, reaction solution is warming up to 85 DEG C to be continued to stir 2h, cooling, discharging.
2) mix according to following ingredients and ratio, the macromolecule emulsion of obtained high performance concrete curing agent: 55wt%, the film coalescence aid propandiol butyl ether of 1.5wt%, the PPH of 0.5wt%, the film coalescence aid diethylene glycol monoethyl ether of 0.5wt%, the water of 1wt% fluorine carbon flow agent 0.5wt% defoamer lauryl alcohol and 31wt%, testing its water retention is 92%.

Claims (7)

1. a preparation method for curing compound, is characterized in that comprising the following steps:
1) macromolecule emulsion is obtained by following monomer through letex polymerization: the general formula of 1-20wt% is (methyl) acrylate monomer of the hydroxyl of a, and the vinylbenzene of 0-75wt% and surplus are the monomer of general formula b;
Wherein R 1for H or CH 3; R 2for CH 2cH 2or CH 2cH 2cH 2; R 3for the alkyl containing 1-20 carbon atom;
Described macromolecule emulsion is prepared through letex polymerization by above-mentioned monomer, and letex polymerization is ordinary method, under water soluble starter and emulsifying agent exist, is that solvent or dispersion medium carry out at 40-90 DEG C with water;
The concrete synthesis technique of the obtained macromolecule emulsion of polymerization is:
By aforementioned monomer proportioning raw materials, be mixed with monomer emulsion; And prepared initiator solution;
Under agitation, temperature is 75 DEG C, in reactor, add deionized water, then drips monomer emulsion and initiator solution simultaneously; After dropwising, reaction solution is warming up to 85 DEG C to be continued to stir 2h, cooling, discharging;
2) curing compound is composite: the above-mentioned macromolecule emulsion of 30-90wt% and the film coalescence aid of 0-5wt%, the defoamer of 0-5wt%, and the flow agent of 0-5wt% and the water of surplus mix, obtained curing compound.
2., by the preparation method of curing compound according to claim 1, it is characterized in that: in described curing compound, high molecular solid content is 15-55wt%.
3. by the preparation method of the curing compound described in claim 1 or 2, it is characterized in that (methyl) acrylate monomer a of described hydroxyl is Propylene glycol monoacrylate, Rocryl 410, the mixture of more than one arbitrary proportions in Hydroxyethyl acrylate and hydroxyethyl methylacrylate.
4., by the preparation method of the curing compound described in claim 1 or 2, it is characterized in that the monomer of described general formula b is more than one (methyl) vinylformic acid C 1-C 20the mixture of alkyl ester arbitrary proportion.
5. by the preparation method of the curing compound described in claim 1 or 2, it is characterized in that described film coalescence aid is the mixture of more than one arbitrary proportions in following composition: alcohol ester 12, butyl glycol ether, propylene glycol monomethyl ether, propandiol butyl ether, propylene glycol phenylate, diethylene glycol monoethyl ether and dipropylene glycol methyl ether.
6., by the preparation method of the curing compound described in claim 1 or 2, it is characterized in that described defoamer is the mixture of the higher alcohols of C7-C22, more than one arbitrary proportions of polyethers and silicone based defoamer.
7., by the preparation method of the curing compound described in claim 1 or 2, it is characterized in that described flow agent is silicone based flow agent, the mixture of more than one arbitrary proportions of acrylic acid or the like flow agent and fluorine class flow agent.
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Cited By (1)

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CN104529526B (en) * 2014-12-02 2016-08-17 科之杰新材料集团有限公司 A kind of emulsion type concrete curing agent and preparation method thereof
CN105175009B (en) * 2015-10-01 2017-04-26 王凯 Preparation method of concrete curing agent
CN105218735A (en) * 2015-11-02 2016-01-06 宋介珍 A kind of preparation method of modified polyacrylic acid curing compound
CN109180049A (en) * 2018-09-17 2019-01-11 佛山朝鸿新材料科技有限公司 A kind of preparation method of cement moisturizing material
CN109987966B (en) * 2019-04-24 2021-11-09 中国路桥工程有限责任公司 Concrete curing agent
CN110607098A (en) * 2019-10-12 2019-12-24 苏州市兴邦化学建材有限公司 Surface durability agent applied to silicate building materials and preparation method thereof
CN114230231B (en) * 2022-02-24 2022-05-03 天津冶建特种材料有限公司 Hybrid concrete curing-protecting agent and preparation method thereof

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