CN111171245B - Preparation method and application of acrylate compound for slump-retaining type polycarboxylate superplasticizer - Google Patents
Preparation method and application of acrylate compound for slump-retaining type polycarboxylate superplasticizer Download PDFInfo
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- CN111171245B CN111171245B CN201911377435.7A CN201911377435A CN111171245B CN 111171245 B CN111171245 B CN 111171245B CN 201911377435 A CN201911377435 A CN 201911377435A CN 111171245 B CN111171245 B CN 111171245B
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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
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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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
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
- C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/12—Radicals substituted by oxygen atoms
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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
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Abstract
The invention discloses a preparation method and application of an acrylate compound for a slump-retaining type polycarboxylate water reducer, and relates to the technical field of preparation of hydroxy acrylate. The functional small monomer is synthesized by reacting acrylic acid with an organosilicon silane coupling agent KH560 byproduct epoxy compound at a certain temperature in the presence of a catalyst and a polymerization inhibitor for 2-3 hours, and then performing reduced pressure rectification to obtain a mixture of two long-chain acrylates. The functional slump-retaining small monomer used as the slump-retaining polycarboxylic acid water reducing agent has the characteristics of low cost, lasting slump retaining capacity and good workability with concrete, the prepared acrylate compound is used as a slump-retaining component of the polycarboxylic acid water reducing agent, the beneficial effect of lasting slump retaining can be brought to the polycarboxylic acid water reducing agent, and meanwhile, the acrylate compound is low in preparation cost, safer in preparation process and good in application prospect.
Description
Technical Field
The invention relates to the technical field of preparation of hydroxyl acrylate, and particularly relates to two novel acrylate compounds prepared from a byproduct epoxy compound in the production process of an organosilicon silane coupling agent KH 560.
Background
The polycarboxylic acid water reducing agent plays a great role in modern concrete, and one of the important problems to be solved is that the slump loss of the concrete is large during long-time and long-distance transportation, and the working performance of the concrete is seriously influenced. On the basis of solving the problem of fast slump loss of concrete, a plurality of admixture companies often compound retarders such as sodium gluconate, cane sugar and sodium citrate with water reducing agents. However, this does not completely solve the problem, and thus the slump-retaining type polycarboxylic acid water reducing agent is produced at the same time. The slump-retaining polycarboxylic acid water reducing agent generally introduces long-chain acrylic ester compounds with the slump-retaining function of concrete, such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate and the like, carboxylic acid bonds are stored in polycarboxylic acid molecules in an ester bond mode, the ester bonds can be hydrolyzed into carboxylic acid and corresponding alcohol under the condition of cement hydration, and the newly hydrolyzed carboxylic acid can continue to generate a dispersion effect on cement paste to play a role in slowly releasing the carboxylic acid, so that the slump-retaining performance is improved.
The hydroxyacrylate compound is usually produced by subjecting acrylic acid and a raw material such as ethylene oxide, propylene oxide, chlorohydrin, 1, 4-butanediol to a ring-opening addition reaction or an esterification reaction. In an industrialized synthetic route, ethylene oxide and propylene oxide are mainly used as raw materials, and the prepared acrylate compound has the advantages of high purity and high activity. The reaction of acrylic acid and epoxy compounds such as ethylene oxide or propylene oxide belongs to cation ring-opening addition reaction, has high reaction speed and large heat release, and is usually obtained by adding a catalyst and a polymerization inhibitor at a lower temperature for reaction. The acrylate compound prepared from ethylene oxide or propylene oxide is a common slump retaining agent for the polycarboxylic acid water reducing agent, but because the carbon chain length is short, and the ethylene oxide or propylene oxide is flammable and explosive and is expensive, a slump retaining agent with lower cost and better slump retaining performance needs to be provided, so that the water reducing agent product can stand out in the market with strong competition.
The silane coupling agent KH560, the chemical name of which is gamma- (2, 3-epoxypropoxy) -propyl trimethoxy silane, is an important silane coupling agent product in the organosilane industry and is also a silane compound in the widest application fields at home and abroad at present, and the chemical structural formula is as follows:
the compound is prepared by taking allyl glycidyl ether and hydrogen-containing alkoxy silane as raw materials and carrying out hydrosilylation reaction under the catalysis of a platinum complex:
in fact, both synthetic raw materials used for preparing the target product have side reactions under the action of the catalyst, so that more or less by-products and secondary reaction products thereof are generated. When the hydrosilylation reaction is adopted to synthesize gamma- (2, 3-epoxypropoxy) -propyl trimethoxy silane, allyl glycidyl ether is easy to isomerize to generate propenyl glycidyl ether and 3, 8-dioxa-bicyclo [3,2,1] octane with two different configurations, namely boat type and chair type, wherein the two compounds are common byproducts in light fractions obtained by distillation and purification of synthetic materials.
Meanwhile, trimethoxy silane is easy to generate redistribution reaction in the presence of some catalysts and impurities of compounds of the catalysts, so that polyhydrosilane compounds and tetraalkoxysilane can be generated, and then catalytic dehydrogenation, hydrogenation reduction and the like are carried out, so that another type of byproducts are generated due to hydrogenation reduction:
in the actual industrial production, when the target product gamma- (2, 3-epoxypropoxy) -propyltrimethoxysilane is generally obtained, the yield of the target product is about 85%, and two epoxy compounds of propyl glycidyl ether and 3, 8-dioxa-bicyclo [3,2,1] octane generated by side reaction account for about 5% of the mass of the raw materials.
The invention provides a preparation method of two types of acrylate compounds by taking two epoxy compounds of propyl glycidyl ether and 3, 8-dioxa-bicyclo [3,2,1] octane and acrylic acid as raw materials by referring to a synthesis method of a hydroxyl acrylate compound, and the preparation method is used for further reducing the production cost of a water reducer on the basis of improving the slump persistence of the polycarboxylic acid water reducer in the preparation process of a slump-retaining polycarboxylic acid water reducer.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a preparation method and application of acrylate compounds for a slump-retaining polycarboxylic acid water reducing agent, wherein two byproduct epoxy compounds in the production process of an organosilicon silane coupling agent KH560 are reacted with acrylic acid to prepare two types of acrylate compounds, the two types of acrylate compounds have longer carbon chains of esterified groups and are influenced by steric hindrance, ester groups are slowly hydrolyzed in the process of maintaining the slump of concrete, and carboxyl groups are continuously supplemented, so that a better slump-retaining effect is achieved.
(II) technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme: a preparation method and application of an acrylate compound for a slump-retaining polycarboxylic acid water reducing agent are disclosed, wherein an acrylate small monomer synthesized by taking an epoxy compound byproduct of an organosilicon silane coupling agent KH560 and acrylic acid as raw materials is applied to the slump-retaining polycarboxylic acid water reducing agent, and the specific preparation method comprises the following steps:
s1, rectification: adding the raw material byproduct epoxy compound into a distillation flask with a glass rectification device, controlling the temperature of a reactor to be 115-120 ℃, and rectifying low-boiling-point substances in the byproduct epoxy compound at normal pressure to obtain a refined byproduct epoxy compound, wherein the low-boiling-point substances comprise methanol and methyl orthosilicate;
s2, synthesis: placing a four-neck flask provided with a stirrer, a condenser and a reflux condenser in a constant-temperature water bath kettle, adding an iron-based catalyst, a polymerization inhibitor and acrylic acid into the flask, replacing air in a reaction bottle with nitrogen, heating the flask to 80-85 ℃ in a water bath, replacing the air in the flask with the nitrogen, dropping a refined byproduct epoxy compound into the four-neck flask for 2-3 hours after the iron-based catalyst and the acrylic acid completely react to form a light yellow clear liquid, continuing to react for 1 hour after the dropping is finished, and finishing the reaction;
s3, rectification under reduced pressure: transferring the materials in the reaction flask into a distillation flask, adding a polymerization inhibitor, distilling under reduced pressure, controlling the pressure at 0.005-0.015MPa to distill out acrylic acid and unreacted KH560 byproduct epoxy compound to obtain light yellow liquid in the distillation flask;
s4, washing and separating liquid: transferring the high-boiling-point liquid in the distillation flask to a separating funnel, adding 10% potassium hydroxide solution, washing the obtained acrylate liquid for three times, and separating to obtain an acrylate small monomer containing 2% of water and capable of being used for the slump-retaining polycarboxylic acid water reducer;
wherein, the used by-product epoxy compound mainly comes from a by-product in the process of producing the silane coupling agent KH560, and the components are mainly as follows through gas chromatographic analysis: methanol content 1.05%, methyl orthosilicate content 6.56%, propyl glycidyl ether content 44.00%, 3, 8-dioxa-bicyclo [3,2,1] octane content 48.40%.
The reaction of acrylic acid and epoxy compound to prepare acrylate compound has the following specific equation:
according to the activity characteristics of the two epoxy compounds, experiments prove that the feeding molar ratio of the epoxy compounds to acrylic acid is 1: 1.05-1.15, the proper reaction temperature is controlled at 80-85 ℃, and after the reaction is finished, excessive hydroquinone and soluble ferric acrylate are removed by washing with KOH solution for three times to obtain two colorless to faint yellow acrylate compounds containing a small amount of water.
Two acrylate compounds which are different from the byproduct epoxy compound are obtained through chromatographic analysis, and the effective contents are respectively as follows:
S5, preparation of the slump-retaining type polycarboxylate superplasticizer: respectively adding unsaturated macromonomer, hydrogen peroxide and water into a four-neck flask, dropping acrylic acid at a certain speed through a peristaltic pump 1, preparing acrylate small monomer, thioglycollic acid and water, dropping a mixture of vitamin C and water at a certain speed through another peristaltic pump 2, reacting for 2 hours at room temperature of 24-26 ℃, keeping the temperature for one hour after the reaction is finished, adding 40% liquid alkali for neutralization, and discharging to obtain the slump-retaining polycarboxylic acid water reducer. (0.6-12): (0.8-14): (0.01-0.10): (0.03-0.35): (0.01-0.15).
Preferably, the byproduct epoxy compound is derived from a byproduct in a front cut fraction in the production process of the silane coupling agent KH560, the raw material source is not limited to gamma- (2, 3-epoxypropoxy) alkyl silane coupling agent including KH560, and the silane coupling agent product also comprises gamma- (2, 3-epoxypropoxy) -propyltriethoxysilane, gamma- (2, 3-epoxypropoxy) -propylmethyldimethoxysilane or gamma- (2, 3-epoxypropoxy) -propylmethyldiethoxysilane.
Preferably, the components thereof comprise: 1.05% of methanol, 6.56% of methyl orthosilicate, 44.00% of propyl glycidyl ether and 48.40% of 3, 8-dioxa-bicyclo [3,2,1] octane, wherein the epoxy components of propyl glycidyl ether (I) and 3, 8-dioxa-bicyclo [3,2,1] octane (II) have boiling points of up to 145-150 ℃ and the structural formulas of the two are respectively (I), (II):
preferably, the iron-based catalyst used in the synthesis reaction is one or a combination of two or more of iron formate, iron acetate, iron acrylate, iron benzoate, iron phthalate, iron oxide, iron sulfate, iron powder, iron hydroxide or an iron-containing composite metal inorganic salt, and preferably, iron acrylate or iron oxide is added.
Preferably, the polymerization inhibitor used in the synthesis reaction comprises one or more of Hydroquinone (HQ), p-tert-butyl benzene diphenol, p-hydroxymethyl anisole or phenothiazine, and Hydroquinone (HQ) is preferably added.
Preferably, the unsaturated macromonomer used in the preparation process of the slump-retaining polycarboxylate water reducer is one or more of commercially available methyl allyl alcohol polyoxyethylene ether, isopentenol polyoxyethylene ether, vinyl ether Ethyl Polyoxyethylene Ether (EPEG) or vinyl ether butyl polyoxyethylene ether (VPEG) ether macromonomer and methoxy polyethylene glycol acrylate, methoxy polyethylene glycol monomethyl ether (methyl) acrylate, fumaric acid polyethylene glycol monomethyl ether ester, maleic acid polyethylene glycol monomethyl ether ester, polyethylene glycol methacrylate or polyethylene glycol acrylate macromonomer, and the isopentenol polyoxyethylene ether is preferably added.
(III) advantageous effects
The invention provides a preparation method and application of an acrylate compound for a slump-retaining type polycarboxylate water reducer. Compared with the prior art, the method has the following beneficial effects: the preparation method and the application of the acrylate compound for the slump-retaining type polycarboxylate water reducer are characterized in that two epoxy compounds of propyl glycidyl ether and 3, 8-dioxa-bicyclo [3,2,1] octane and acrylic acid are used as raw materials, the preparation method is used for preparing two types of acrylate compounds in the preparation process of the slump-retaining type polycarboxylate water reducer, the production cost of the water reducer is further reduced on the basis of improving the slump persistence of the polycarboxylate water reducer, meanwhile, two epoxy compounds as by-products in the production process of an organosilicon silane coupling agent KH560 are used for preparing the two types of acrylate compounds by reacting with the acrylic acid, and the two types of epoxy compounds can play a role in keeping the slump of the polycarboxylate water reducer for a long term when being applied to the preparation process of the polycarboxylate water reducer. Compared with the acrylate small monomers with slump retaining functions such as hydroxyethyl acrylate, hydroxypropyl acrylate or hydroxybutyl acrylate and the like, the two acrylate compounds have longer carbon chains of esterified groups and are influenced by steric hindrance, ester groups are slowly hydrolyzed in the process of maintaining the slump of concrete, and carboxyl groups are continuously supplemented, so that a better slump retaining effect is achieved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention provides a technical scheme that: the preparation method and the application of the acrylate compound for the slump-retaining type polycarboxylate superplasticizer specifically comprise the following embodiments:
example 1
(1) Preparation of acrylate compounds: 230.24g of the rectified, separated and purified organosilicon byproduct epoxy compound is dripped into a 1L four-neck flask which is arranged in a constant-temperature water bath kettle and is provided with a stirrer, a condenser and a reflux condenser tube, 3.0g of ferric oxide, 0.076g of hydroquinone and 158.53g of acrylic acid are added into the flask, air in the reaction flask is replaced by nitrogen, the nitrogen replaces the air in the reaction flask, the water bath is heated to 80 ℃, the dripping time is 3 hours, and the temperature is kept for 1 hour after the dripping is finished, so that the reaction is finished. Then, the reaction product was transferred to a distillation flask of a vacuum distillation apparatus, and acrylic acid and by-product epoxy compounds which were not completely reacted were removed therefrom under reduced pressure at 80 ℃ and 0.01 MPa. Then, the distillation product was transferred to a separatory funnel and washed three times with 60g of 10% sodium hydroxide solution, and the acrylic acid ester compound was successfully produced, totaling 376.6 g. The product contained, by gas chromatography analysis:
(2) preparing a slump-retaining polycarboxylic acid water reducing agent: A1L four-neck flask is added with 183.5g of unsaturated macromonomer (OxaB 501), 0.65g of hydrogen peroxide and 110.0g of water in a certain amount, 8.80g of acrylic acid, 37.7g of prepared acrylate small monomer, 0.50g of thioglycollic acid and 29.2g of water are dripped in by a peristaltic pump 1 at a certain speed, a mixture of 0.30g of vitamin C and 65.2g of water is dripped in by another peristaltic pump 2 at a certain speed, the mixture is dripped in from room temperature to about 25 ℃ for reaction for 2 hours, after the reaction is finished, the temperature is continuously kept for 1 hour, 9.0g of 30% NaOH solution is added to adjust the pH value to 5-6, then the discharging is carried out, and 127.9g of water is added, thus obtaining 536.9g of slump-retaining polycarboxylic acid water reducing agent with the solid content of 40%.
Example 2
(1) Preparation of acrylate compounds: 230.24g of the rectified, separated and purified organosilicon byproduct epoxy compound is dripped into a 1L four-neck flask which is arranged in a constant-temperature water bath kettle and is provided with a stirrer, a condenser and a reflux condenser tube, 5.05g of ferric acrylate, 0.085g of p-methylol anisole and 165.74g of acrylic acid are added into the flask, the air in the reaction flask is replaced by nitrogen, the nitrogen replaces the air in the reaction flask, the water bath is heated to 85 ℃, the dripping time is 4 hours, and the temperature is kept for one hour after the dripping is finished, so that the reaction is finished. Then, the reaction product was transferred to a distillation flask of a vacuum distillation apparatus, and acrylic acid and by-product epoxy compounds which were not completely reacted were removed therefrom under reduced pressure at 80 ℃ and 0.01 MPa. Then, the distillate was transferred to a separatory funnel and washed three times with 70g of 10% sodium hydroxide solution, and a total of 378.6g of an acrylate compound was successfully prepared. The product contained, by gas chromatography analysis:
(2) preparing a slump-retaining polycarboxylic acid water reducing agent: A1L four-neck flask is added with 183.5g of unsaturated macromonomer (OxaB 501), 0.65g of hydrogen peroxide and 110.0g of water in a certain amount, 7.60g of acrylic acid, 37.7g of prepared acrylate small monomer, 0.50g of thioglycollic acid and 29.2g of water are dripped in at a certain speed through a peristaltic pump 1, a mixture of 0.35g of vitamin C and 65.2g of water is dripped in at a certain speed through another peristaltic pump 2, the mixture is dripped in at room temperature of 25 ℃ for reaction for 2 hours, after the reaction is finished, the temperature is continuously kept for 1 hour, 9.0g of 40% NaOH solution is added to adjust the pH value to 5-6, discharging is carried out, and 128.2g of water in a certain amount is added, thus obtaining the slump-retaining type polycarboxylic acid water reducing agent with the solid content of 40%.
Comparative example 1
Preparing a slump-retaining polycarboxylic acid water reducing agent: A1L four-neck flask is added with 183.5g of unsaturated macromonomer (OxAB 501), 0.65g of hydrogen peroxide and 110.0g of water in a certain amount, 6.30g of acrylic acid, 23.22g of hydroxyethyl acrylate, 0.60g of thioglycollic acid and 29.2g of water are dripped in by a peristaltic pump 1 at a certain speed, a mixture of 0.40g of vitamin and 65.2g of water is dripped in by another peristaltic pump 2 at a certain speed, the mixture is dripped from room temperature to about 25 ℃ for reaction for 2 hours, after the reaction is finished, heat preservation is continued for 1 hour, 9.0g of 40% NaOH solution is added to adjust the pH value to 5-6, discharging is carried out, and 104.4g of water in a certain amount is added, thus 532.5g of slump-retaining polycarboxylic acid water reducing agent with the solid content of 40% is obtained.
Comparative example 2
Preparing a slump-retaining polycarboxylic acid water reducing agent: A1L four-neck flask is added with 183.5g of unsaturated macromonomer (OxAB 501), 0.65g of hydrogen peroxide and 110.0g of water in a certain amount, 6.30g of acrylic acid, 26.03g of hydroxypropyl acrylate, 0.50g of thioglycollic acid and 29.2g of water are dripped in by a peristaltic pump 1 at a certain speed, a mixture of 0.35g of vitamin C and 65.2g of water is dripped in by another peristaltic pump 2 at a certain speed, the mixture is dripped in for reaction for 2 hours from room temperature to about 25 ℃, after the reaction is finished, heat preservation is continued for 1 hour, 9.0g of 40% NaOH solution is added to adjust the pH value to 5-6, discharging is carried out, and 108.8g of water in a certain amount is added to obtain 539.5g of slump-retaining polycarboxylic acid water reducing agent with the solid content of 40%.
And (3) testing the net slurry fluidity: the samples obtained in example 1, example 2 and comparative example 1 were tested for net slurry fluidity by referring to GB8077-2000, Experimental method for homogeneity of concrete admixture, W/C is 0.29, and the folded solid content of the admixture is 0.09% of the cement content.
Testing the mortar expansion degree: referring to the standard QC-J-304 'mortar expansion degree test method' of Sichuan Xin Union group enterprise, the concrete mortar mixing proportion is as follows: 600g of cement, 1350g of ISO standard sand, 240g of water and an additive are recommended mixing amount, and the mass ratio of the additive, namely Xin leading trade mark standard water reducing type PC250, to the prepared plastic-retaining water reducing agent (containing the above examples and comparative examples) is 5: 5.
TABLE 1 Net mortar fluidity and Sand extensibility for different samples
Testing the performance of the concrete: slump loss and concrete strength tests were carried out on examples 1 to 4 and comparative examples 1 and 2 with reference to GB8076-2008 "concrete admixture". The additive is the recommended mixing amount, the weight ratio of the additive to the prepared plastic-retaining water reducer (containing the above examples and comparative examples) is 5:5, and the additive is Xin lead trade mark standard water-reducing PC 250.
TABLE 2 concrete testing of different samples
Wherein, the slump-retaining water reducer taking hydroxyethyl acrylate and hydroxypropyl acrylate as functional monomers in the comparative examples 1 and 2 is a common method for slump-retaining water reducers in the market. The comparison results show that: the two tables show that the two acrylate compounds prepared from the epoxy compound byproduct of the silane coupling agent KH560 and the acrylic acid serving as raw materials in the embodiment have the advantages of low cost and simple process. The polycarboxylate water reducer taking the two acrylate compounds as the slump-retaining functional monomers as the raw materials has the advantages of improved length and density of side chains, lasting slump-retaining performance, better quality and lower cost than the slump-retaining water reducer taking hydroxyethyl acrylate or hydroxypropyl acrylate as the functional monomers, solves the problem of the out-of-service of the silane KH560 byproduct epoxy compound, and has important application significance.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (4)
1. The preparation method of the slump-retaining type polycarboxylate superplasticizer is characterized by comprising the following steps of: a silane coupling agent KH560 byproduct epoxy compound and acrylic acid are used as raw materials to synthesize an acrylate small monomer and are applied to a slump-retaining type polycarboxylate superplasticizer, and the specific preparation method comprises the following steps:
s1, rectification: adding a raw material KH560 byproduct epoxy compound into a distillation flask with a glass rectification device, controlling the temperature of a reactor to be 115-120 ℃, and rectifying low-boiling-point substances in the byproduct epoxy compound at normal pressure to obtain a refined byproduct epoxy compound;
s2, synthesis: placing a four-neck flask provided with a stirrer, a condenser and a reflux condenser tube in a constant-temperature water bath kettle, adding an iron-based catalyst, a polymerization inhibitor and acrylic acid into the flask, replacing air in a reaction bottle with nitrogen, heating the flask to 80-85 ℃ in a water bath, dropwise adding a refined byproduct epoxy compound into the four-neck flask for 2-3 hours after the iron-based catalyst and the acrylic acid completely react to form a light yellow clear liquid, continuing to react for 1 hour after the dropwise adding is finished, and finishing the reaction;
s3, rectification under reduced pressure: transferring the materials in the reaction flask into a distillation flask, adding a polymerization inhibitor, carrying out reduced pressure distillation under the pressure of 0.005-0.015MPa to distill out acrylic acid and an unreacted KH560 byproduct epoxy compound to obtain a light yellow liquid in the distillation flask;
s4, washing and separating liquid: transferring the high-boiling-point liquid in the distillation flask to a separating funnel, adding 10% potassium hydroxide solution, washing the obtained acrylate liquid for three times, and separating to obtain an acrylate small monomer containing 2% of water and capable of being used for the slump-retaining polycarboxylic acid water reducer;
s5, preparation of the slump-retaining type polycarboxylate superplasticizer: respectively adding unsaturated macromonomer, hydrogen peroxide and water into a four-neck flask, dripping acrylic acid, the prepared acrylate small monomer, thioglycollic acid and water at a certain speed by using a peristaltic pump 1, dripping a mixture of vitamin C and water at a certain speed by using another peristaltic pump 2, dripping into the mixture at room temperature of 24-26 ℃ for reaction for 2 hours, keeping the temperature for one hour after the reaction is finished, adding 40% liquid alkali for neutralization, and discharging to obtain the slump-retaining polycarboxylic acid water reducer;
the KH560 by-product epoxy compound has 1.05% of methanol, 6.56% of methyl orthosilicate, 44.00% of propyl glycidyl ether and 48.40% of 3, 8-dioxa-bicyclo [3,2,1] octane by gas chromatography analysis, wherein the epoxy components of propyl glycidyl ether (I) and 3, 8-dioxa-bicyclo [3,2,1] octane (II) have boiling points as high as 145-150 ℃ and the structural formulas of the two are respectively (I), (II):
2. the method of claim 1, wherein: the iron catalyst used in the synthesis reaction is one or the combination of more than two of ferric formate, ferric acetate, ferric acrylate, ferric benzoate, ferric phthalate, ferric oxide, ferric sulfate, iron powder, ferric hydroxide or composite metal inorganic salt containing iron.
3. The method of claim 1, wherein: the polymerization inhibitor used in the synthesis reaction comprises one or the combination of more than two of Hydroquinone (HQ), p-tert butyl benzene diphenol, p-hydroxymethyl anisole and phenothiazine.
4. The method of claim 1, wherein: the unsaturated macromonomer used in the preparation process of the slump-retaining type polycarboxylate water reducer is one or more of commercially available methallyl alcohol polyoxyethylene ether, isopentenol polyoxyethylene ether, methoxy polyethylene glycol acrylate, fumaric acid polyethylene glycol monomethyl ether ester, maleic acid polyethylene glycol monomethyl ether ester, polyethylene glycol methacrylate or polyethylene glycol acrylate.
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| CN111718148A (en) * | 2020-07-03 | 2020-09-29 | 汤如齐 | Preparation method of cement water reducer with slump retaining performance |
| CN111825373A (en) * | 2020-08-11 | 2020-10-27 | 贵州石博士科技有限公司 | Preparation method for synthesizing high-performance polycarboxylate superplasticizer from novel VPEG polyether |
| CN114426408B (en) * | 2020-10-13 | 2022-12-09 | 中国石油化工股份有限公司 | Oil well cement dispersant, preparation method and application thereof |
| CN113736065B (en) * | 2021-08-27 | 2023-06-02 | 湖北新蓝天新材料股份有限公司 | Treatment method and application of allyl glycidyl ether isomer mixture |
| CN114014989A (en) * | 2021-09-30 | 2022-02-08 | 绵阳麦思威尔科技有限公司 | Hydroxyl acrylic acid aqueous dispersion, preparation method and application thereof |
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| CN109096127A (en) * | 2018-09-27 | 2018-12-28 | 湖北鑫统领万象科技有限公司 | Using silane coupling agent production by-product as the hydramine of raw material and preparation method and application |
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