CN113980202B - Polycarboxylate superplasticizer and preparation method thereof - Google Patents
Polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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- CN113980202B CN113980202B CN202111362216.9A CN202111362216A CN113980202B CN 113980202 B CN113980202 B CN 113980202B CN 202111362216 A CN202111362216 A CN 202111362216A CN 113980202 B CN113980202 B CN 113980202B
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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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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The invention relates to a polycarboxylate water reducer and a preparation method thereof, wherein the polycarboxylate water reducer comprises the following components in parts by weight: 100-110 parts of allyl polyether macromonomer; 10-30 parts of ester macromonomer; 10-40 parts of A liquid; 3-5 parts of a photoinitiator; 1-3 parts of chain transfer agent; 10-100 parts of water; the solution A comprises unsaturated acid monomer, crosslinking monomer and water; the molecular formula of the initiator of the allyl polyether macromonomer is CH 2 ＝CH‑CH 2 ‑O‑(CH 2 ‑CH 2 ) c -OH, wherein: c is an integer from 2 to 4. The polycarboxylic acid water reducer provided by the invention introduces-O- (CH 2CH 2) c-, so that the water reducer has more excellent water reducing property.
Description
Technical Field
The invention relates to the technical field of building additives, in particular to a polycarboxylate water reducer and a preparation method thereof.
Background
The current synthesis of the polycarboxylate water reducer mainly comprises the step of carrying out free radical copolymerization on a polyether monomer with unsaturated double bonds, unsaturated acid and unsaturated monomers with amino, sulfonic groups and other functional groups to form a comb-shaped high polymer, wherein the side chain of the polymer is a polyether chain segment, and the proportion of the polyether chain segment in the polycarboxylate water reducer is more than 80%, so that the main component of the polycarboxylate water reducer is polyether. In the existing polycarboxylate water reducer synthesis technology, the starter of polyether for synthesizing the polycarboxylate water reducer is mainly enol ether, polyethylene glycol or (methyl) acrylic ester of methyl polyethylene glycol, and polyether monomers are few in variety and single in structure, so that the water reducing performance of the polycarboxylate water reducer cannot be improved.
Disclosure of Invention
Based on the above, the invention provides a polycarboxylate water reducer with excellent water reducing property and a preparation method thereof.
The polycarboxylate water reducer comprises the following components in parts by weight:
100-110 parts of allyl polyether macromonomer;
10-30 parts of ester macromonomer;
10-40 parts of A liquid;
3-5 parts of a photoinitiator;
1-3 parts of chain transfer agent; and
10-100 parts of water;
the solution A comprises unsaturated acid monomers, crosslinking monomers and water;
the molecular formula of the initiator of the allyl polyether macromonomer is CH 2 ＝CH-CH 2 -O-(CH 2 -CH 2 ) c -OH, wherein: c is an integer from 2 to 4.
Preferably, the polycarboxylate water reducer comprises, in parts by weight:
preferably, the allyl polyether macromonomer has the structural formulaWherein: c is an integer of 2-4, and d is an integer of 30-110.
Preferably, the ester macromer has the structural formulaWherein: e is an integer of 4 to 15.
Preferably, the unsaturated acid monomer has the structural formulaWherein: wherein R is-H or-CH 3 。
Preferably, the photoinitiator comprises any one of 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phosphonate and 2-methyl-1- [ 4-methylthiophenyl ] -2-morpholino-1-propanone.
Preferably, the concentration of the photoinitiator ranges from 0.1 to 1%;
preferably, the mass ratio of the unsaturated acid monomer, the crosslinking monomer and the water in the solution A is 10: (1-5): (10-50).
The invention also provides a preparation method of the polycarboxylate superplasticizer, which comprises the following steps:
adding allyl polyether macromonomer, ester macromonomer and water into a reactor to obtain a first mixed solution;
under the ultraviolet irradiation environment of 15-20 ℃, dropwise adding a photoinitiator, a solution A and a chain transfer agent into the first mixed solution to start reaction, after the dropwise adding is finished, carrying out heat preservation reaction for 0.5-1h to obtain a second mixed solution, and adding a NaOH solution with the mass concentration of 32% into the second mixed solution to adjust the pH value of the second mixed solution to 6.0-7.0 to obtain the polycarboxylate water reducer;
100-110 parts of allyl polyether macromonomer; 10-30 parts of ester macromonomer; 10-40 parts of A liquid; 3-5 parts of a photoinitiator; 1-3 parts of chain transfer agent; 10-100 parts of water;
the solution A comprises unsaturated acid monomers, crosslinking monomers and water;
the molecular formula of the initiator of the allyl polyether macromonomer is CH 2 ＝CH-CH 2 -O-(CH 2 -CH 2 ) c -OH, wherein: c is an integer from 2 to 4.
Preferably, the wavelength of the ultraviolet light is 300-400mm, and the irradiation intensity is 30-100W/m 2 。
Compared with the prior art, the invention has the following beneficial effects:
the polyether macromonomer used in the invention is an allyl polyether macromonomer, and the molecule of the allyl polyether macromonomer introduces-O- (CH) 2 CH 2 )c-，-O-(CH 2 CH 2 ) c The introduction increases the distance between the double bond and the ether bond of the allyl polyether macromonomer molecule, and the electron cloud distribution of the double bond shifts, so that the double bond in the allyl polyether macromonomer has much higher reactivity than that of a general macromonomer and is easier to carry out polymerization reaction. On the other hand, as the double bond connecting alkyl in the allyl polyether macromonomer molecule is longer, the swing of the side chain of the allyl polyether macromonomer is more free, the moving range is larger, the spreadability of the side chain of the allyl polyether macromonomer is improved, and the synthesized polycarboxylate water reducer has outstanding water reducing performance.
Because the double bond reactivity in the allyl polyether macromonomer is much higher than that of a general macromonomer, the polymerization reaction of the allyl polyether macromonomer needs to be carried out at a lower temperature, the photoinitiator used in the invention is a photoinitiator which replaces the existing redox system initiator, and ultraviolet light is utilized to decompose the photoinitiator to generate an initiator free radical at a lower temperature (20 ℃), and the initiator free radical is transferred to the allyl polyether macromonomer and the ester macromonomer to carry out copolymerization reaction to synthesize the polycarboxylate water reducer.
According to the synthetic polycarboxylate water reducer, the allyl polyether macromonomer and the ester macromonomer are subjected to copolymerization reaction, the molecule of the synthetic polycarboxylate water reducer is of a micro-crosslinking structure, and the ester group and the ether group in the molecule of the polycarboxylate water reducer jointly improve the water reducing performance of the polycarboxylate water reducer.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The experimental methods in the following examples are conventional methods unless otherwise specified. The test materials, reagents and the like used in the examples described below are commercially available unless otherwise specified. The quantitative tests in the following examples were all set up with three replicates, and the data are the mean or mean ± standard deviation of the three replicates.
In addition, "and/or" throughout this document includes three schemes, taking a and/or B as an example, including a technical scheme, a technical scheme B, and a technical scheme that both a and B satisfy; in addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present invention.
A polycarboxylic acid water-reducing composition comprising, in weight fractions:
100-110 parts of allyl polyether macromonomer;
10-30 parts of ester macromonomer;
10-40 parts of A liquid;
3-5 parts of a photoinitiator;
1-3 parts of chain transfer agent; and
10-100 parts of water;
the solution A comprises unsaturated acid monomer, crosslinking monomer and water;
the molecular formula of the initiator of the allyl polyether macromonomer is CH 2 ＝CH-CH 2 -O-(CH 2 -CH 2 ) c -OH, wherein: c is an integer from 2 to 4.
The polyether macromonomer used in the invention is an allyl polyether macromonomer, and the introduction of-O- (CH 2CH 2) c-, -O- (CH 2CH 2) c-into the allyl polyether macromonomer molecule increases the distance between double bonds and ether bonds of the allyl polyether macromonomer molecule, and the electron cloud distribution of the double bonds shifts, so that the charge environment of unsaturated double bonds in the allyl polyether macromonomer is improved, the reactivity of the double bonds in the allyl polyether macromonomer is much higher than that of the common macromonomer, and the polymerization reaction is easier to carry out. On the other hand, the double bond structure in the allyl polyether macromonomer reduces the space resistance of the swing of the side chain of the allyl polyether macromonomer, so that the swing of the side chain of the allyl polyether macromonomer is more free, the movable range is larger, the wrapping property and winding property of the side chain of the allyl polyether macromonomer are improved, and the synthesized polycarboxylate water reducer has outstanding water reducing property.
Because the double bond reactivity of the allyl polyether macromonomer is much higher than that of a general macromonomer, the polymerization reaction of the allyl polyether macromonomer needs to be carried out at a lower temperature, the synthesis of the existing polycarboxylate water reducer generally adopts an initiator of a redox initiation system, the temperature required for the decomposition of the initiator is higher, when the reaction initiation temperature is more than 20 ℃, the double bond of the allyl polyether macromonomer is deactivated, and the allyl polyether macromonomer cannot be subjected to copolymerization reaction with other monomers, so that the water reducing performance and slump retaining performance of the polyether water reducer are reduced. Therefore, the initiator used in the invention is a photoinitiator which replaces the existing redox system initiator, and ultraviolet light is utilized to decompose the photoinitiator to generate an initiator free radical at a lower temperature (below 20 ℃), and the initiator free radical is transferred to the allyl polyether macromonomer and the ester macromonomer to carry out copolymerization reaction to synthesize the polycarboxylate superplasticizer.
According to the synthetic polycarboxylate water reducer, the allyl polyether macromonomer and the ester macromonomer are subjected to copolymerization reaction, and meanwhile, the crosslinking monomer is introduced, so that the molecule of the synthetic water reducer is of a micro-crosslinking structure, and the water reducing performance of the polycarboxylate water reducer is jointly improved among the crosslinking structure, the ester group and the ether group.
Specifically, the allyl polyether macromer has a molecular weight in the range of 2400 to 5000;
the molecular weight of the ester macromer ranges from 500 to 2400;
chain transfer agents may be used to control the chain length of the polymer, including thioglycolic acid, mercaptopropionic acid, and the like, which are effective in effecting free radical transfer of chain-extending free radicals;
the concentration of the chain transfer agent ranges from 0.2 to 1.2%.
In some embodiments, the polycarboxylate water reducer comprises, in parts by weight:
in some embodiments, the allyl polyether macromonomer has the formulaWherein: c is an integer of 2-4, and d is an integer of 30-110.
In some embodiments, the ester macromer has the formulaWherein: e is an integer of 4 to 15.
In some embodiments, the unsaturated acid monomer has the formulaWherein: wherein R is-H or-CH 3 。
In some embodiments, the photoinitiator includes any of 2,4,6 (trimethylbenzoyl) diphenyl phosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phosphonate, and 2-methyl-1- [ 4-methylthiophenyl ] -2-morpholino-1-propanone.
In some embodiments, the concentration of photoinitiator ranges from 0.1 to 1%;
in some embodiments, the mass ratio of unsaturated acid monomer, crosslinking monomer, and water in solution a is 10: (1-5): (10-50).
The invention also provides a preparation method of the polycarboxylate superplasticizer, which comprises the following steps:
adding allyl polyether macromonomer, ester macromonomer and water into a reactor to obtain a first mixed solution;
under the ultraviolet irradiation environment of 15-20 ℃, dropwise adding a photoinitiator, a solution A and a chain transfer agent into the first mixed solution to start reaction, after the dropwise adding is finished, carrying out heat preservation reaction for 0.5-1h to obtain a second mixed solution, and adding a NaOH solution with the mass concentration of 32% into the second mixed solution to adjust the pH value of the second mixed solution to 6.0-7.0 to obtain the polycarboxylate water reducer;
100-110 parts of allyl polyether macromonomer; 10-30 parts of ester macromonomer; 10-40 parts of A liquid; 3-5 parts of a photoinitiator; 1-3 parts of chain transfer agent; 10-100 parts of water;
the solution A comprises unsaturated acid monomer, crosslinking monomer and water;
the molecular formula of the initiator of the allyl polyether macromonomer is CH 2 ＝CH-CH 2 -O-(CH 2 -CH 2 ) c -OH, wherein: c is an integer from 2 to 4.
In some embodiments, the ultraviolet light has a wavelength of 300-400mm and an irradiation intensity of 30-100W/m 2 。
Specifically, the second mixed solution was dropwise added with a 32% by mass concentration of NaOH solution to adjust the pH of the second mixed solution to 6.0 to 7.0 in order to terminate the reaction.
In the step of simultaneously dripping the photoinitiator, the solution A and the chain transfer agent into the first mixed solution, dripping at a constant speed for 1-3h, wherein the concentration of the slump type water reducing agent in the second mixed solution is 40-50wt.%;
the solution is continuously stirred in the process of dripping the photoinitiator, the solution A and the chain transfer agent, so that reactants are fully contacted, and the reaction is more complete.
The polycarboxylate water reducer can effectively improve the water reducing performance of concrete in practical application, in particular to machine-made sand concrete. The polycarboxylate water reducer has the advantages of 2-3h of synthesis time, high production efficiency and simple process.
Example 1
Adding 100g of hexanediol monoallyl polyethylene glycol ether, 15g of polyethylene glycol diacrylate and 50g of water into a reaction kettle to obtain a first mixed solution;
dropwise adding 2,4,6 (trimethyl benzoyl) diphenyl phosphine oxide aqueous solution, A solution and 30g of thioglycollic acid solution with the mass concentration of 7.5% into the first mixed solution under the ultraviolet irradiation environment at 15 ℃ while stirring, dropwise adding 1.5h, reacting for 0.5h after the dropwise adding is finished, obtaining a second mixed solution, adding 32% NaOH solution into the second mixed solution, and regulating the pH value of the second mixed solution to 6.0, thus obtaining the polycarboxylic acid water reducer;
wherein, the initiator of the hexanediol monoallyl polyethylene glycol ether is hexanediol allyl ether;
the molecular weight of the hexanediol monoallyl polyethylene glycol ether is 3000, and the molecular weight of the polyethylene glycol diacrylate is 500;
2,4,6 (trimethylbenzoyl) diphenylphosphine oxide aqueous solution was a mixed solution of 2.5g of 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide and 20g of water;
the solution A is a mixed solution of 10g of acrylic acid, 6g of cross-linking monomer diethylene glycol vinyl ether and 180g of water;
the wavelength of the ultraviolet light is 230mm, and the irradiation intensity is 50W/m 2 。
Example 2
Adding 100g of butanediol monoallyl polyethylene glycol ether, 12g of polyethylene glycol diacrylate and 50g of water into a reaction kettle to obtain a first mixed solution;
dropwise adding an aqueous solution of 2,4, 6-trimethylbenzoyl ethyl phosphonate, a solution A and 30g of thioglycollic acid solution with the mass concentration of 7.5% into the first mixed solution under the ultraviolet irradiation environment at 20 ℃ while stirring, dropwise adding for 1.5h, and after the dropwise adding is finished, carrying out heat preservation reaction for 0.5h to obtain a second mixed solution, and adding a NaOH solution with the mass concentration of 32% into the second mixed solution to regulate the pH value of the second mixed solution to 6.5 to obtain the polycarboxylate water reducer;
wherein, the initiator of the butanediol monoallyl polyethylene glycol ether is butanediol allyl ether;
the molecular weight of the butanediol monoallyl polyglycol ether is 4000 and the molecular weight of the polyethylene glycol diacrylate is 600.
The aqueous solution of ethyl 2,4, 6-trimethylbenzoylphosphonate was a mixture of 3g of ethyl 2,4, 6-trimethylbenzoylphosphonate and 20g of water.
The solution A is a mixed solution of 10g of acrylic acid, 5g of cross-linking monomer diethylene glycol vinyl ether and 180g of water;
the wavelength of the ultraviolet light is 250mm, and the irradiation intensity is 60W/m 2 。
Comparative example 1
Strictly comparing example 2, butanediol monoallyl polyethylene glycol ether is changed into isobutylenol polyoxyethylene ether when preparing the water reducer, and the water reducer is used for comparing and researching the performance of the polycarboxylic acid water reducer.
Adding 100g of isobutylether, 12g of polyethylene glycol diacrylate and 50g of water into a reaction kettle to obtain a first mixed solution;
dropwise adding an aqueous solution of 2,4, 6-trimethylbenzoyl ethyl phosphonate, a solution A and 30g of thioglycollic acid solution with the mass concentration of 7.5% into the first mixed solution under the ultraviolet irradiation environment at 20 ℃ while stirring, dropwise adding for 1.5h, and after the dropwise adding is finished, carrying out heat preservation reaction for 0.5h to obtain a second mixed solution, and adding a NaOH solution with the mass concentration of 32% into the second mixed solution to regulate the pH value of the second mixed solution to 6.5 to obtain the polycarboxylate water reducer;
wherein the molecular weight of the isobutylether is 4000, and the molecular weight of the polyethylene glycol diacrylate is 600.
The aqueous solution of ethyl 2,4, 6-trimethylbenzoylphosphonate was a mixture of 3g of ethyl 2,4, 6-trimethylbenzoylphosphonate and 20g of water.
The solution A is a mixed solution of 10g of acrylic acid, 5g of cross-linking monomer diethylene glycol vinyl ether and 180g of water;
the wavelength of the ultraviolet light is 250mm, and the irradiation intensity is 60W/m 2 。
Comparative example 2
Strictly comparative example 2, polyethylene glycol diacrylate was not added in the preparation of the water reducer, and was used in the performance comparison study with the polycarboxylic acid water reducer of the present invention.
100g of butanediol monoallyl polyethylene glycol ether and 50g of water are added into a reaction kettle to obtain a first mixed solution;
dropwise adding an aqueous solution of 2,4, 6-trimethylbenzoyl ethyl phosphonate, a solution A and 30g of thioglycollic acid solution with the mass concentration of 7.5% into the first mixed solution under the ultraviolet irradiation environment at 20 ℃ while stirring, dropwise adding for 1.5h, and after the dropwise adding is finished, carrying out heat preservation reaction for 0.5h to obtain a second mixed solution, and adding a NaOH solution with the mass concentration of 32% into the second mixed solution to regulate the pH value of the second mixed solution to 6.5 to obtain the polycarboxylate water reducer;
wherein, the initiator of the butanediol monoallyl polyethylene glycol ether is butanediol allyl ether;
the molecular weight of the butanediol monoallyl polyglycol ether is 4000 and the molecular weight of the polyethylene glycol diacrylate is 600.
The aqueous solution of ethyl 2,4, 6-trimethylbenzoylphosphonate was a mixture of 3g of ethyl 2,4, 6-trimethylbenzoylphosphonate and 20g of water.
The solution A is a mixed solution of 10g of acrylic acid, 5g of cross-linking monomer diethylene glycol vinyl ether and 180g of water;
the wavelength of the ultraviolet light is 250mm, and the irradiation intensity is 60W/m 2 。
Comparative example 3
Strictly comparative example 2, no crosslinking monomer was added when preparing the water reducer, and was used for performance comparison study with the polycarboxylic acid water reducer of the present invention.
Adding 100g of butanediol monoallyl polyethylene glycol ether, 12g of polyethylene glycol diacrylate and 50g of water into a reaction kettle to obtain a first mixed solution;
dropwise adding an aqueous solution of 2,4, 6-trimethylbenzoyl ethyl phosphonate, a solution A and 30g of thioglycollic acid solution with the mass concentration of 7.5% into the first mixed solution under the ultraviolet irradiation environment at 20 ℃ while stirring, dropwise adding for 1.5h, and after the dropwise adding is finished, carrying out heat preservation reaction for 0.5h to obtain a second mixed solution, and adding a NaOH solution with the mass concentration of 32% into the second mixed solution to regulate the pH value of the second mixed solution to 6.5 to obtain the polycarboxylate water reducer;
wherein, the initiator of the butanediol monoallyl polyethylene glycol ether is butanediol allyl ether;
the molecular weight of the butanediol monoallyl polyglycol ether is 4000 and the molecular weight of the polyethylene glycol diacrylate is 600.
The aqueous solution of ethyl 2,4, 6-trimethylbenzoylphosphonate was a mixture of 3g of ethyl 2,4, 6-trimethylbenzoylphosphonate and 20g of water.
The solution A is a mixed solution of 10g of acrylic acid and 180g of water;
the wavelength of the ultraviolet light is 250mm, and the irradiation intensity is 60W/m 2 。
Comparative example 4
Strictly comparative example 2, a redox initiation system was used in the preparation of the water reducer and was used in the performance comparison study with the polycarboxylate water reducer of the present invention.
Adding 100g of butanediol monoallyl polyethylene glycol ether, 12g of polyethylene glycol diacrylate and 50g of water into a reaction kettle to obtain a first mixed solution;
simultaneously dropwise adding a hydrogen peroxide water solution, an A solution and 30g of thioglycollic acid solution with the mass concentration of 7.5% into the first mixed solution at the temperature of 45 ℃, dropwise adding for 1.5 hours, and after the dropwise adding is finished, carrying out heat preservation reaction for 0.5 hour to obtain a second mixed solution, adding a NaOH solution with the mass concentration of 32% into the second mixed solution, and regulating the pH value of the second mixed solution to 6.5 to obtain the polycarboxylate water reducer;
wherein, the initiator of the butanediol monoallyl polyethylene glycol ether is butanediol allyl ether;
the molecular weight of the butanediol monoallyl polyglycol ether is 4000 and the molecular weight of the polyethylene glycol diacrylate is 600.
The hydrogen peroxide solution is a mixed solution of 2.5g of hydrogen peroxide and 20g of water.
The solution A is a mixed solution of 10g of acrylic acid, 5g of cross-linking monomer diethylene glycol vinyl ether, 0.5g of vitamin C and 180g of water;
the wavelength of the ultraviolet light is 250mm, and the irradiation intensity is 60W/m 2 。
Performance test experiment of polycarboxylate water reducer:
according to GB/T50080-2016 Standard for Performance test of common concrete mixtures, the water reducing agent prepared in the above examples 1-2 and comparative examples 1-4 is added to concrete, and the initial slump, 1h slump and 28d compressive strength of the concrete are measured. The water to ash ratio was fixed at 0.48.
The concrete mixing ratio is as follows: water: 175Kg of cement (southern Cement P.052.5R): 360Kg of machine-made sand (mud content 5%): 790Kg, stone: 1060Kg
The experimental results are shown in table 1.
Table 1 concrete experimental results
As can be seen from Table 1, the polycarboxylic acid water reducer synthesized in examples 1-2 is added into concrete, and the initial slump and 1h slump of the concrete are large, and the folding and solidifying doping amount is small, so that the polycarboxylic acid water reducer prepared by the invention has outstanding water reducing performance, better slump retention performance and improved concrete workability when applied to the concrete;
the polyether macromonomer used in the water reducer of comparative example 1 is isobutylether, the water reducer of comparative example 1 is synthesized into a traditional water reducer, and as can be seen from the table, the initial slump and slump of the water reducer of comparative example 1 are smaller than those of example 2, and the refraction and fixation doping amount of the water reducer of comparative example 1 is obviously larger than those of example 2, therefore, the polycarboxylate water reducer synthesized by the invention has outstanding water reducing performance compared with the traditional water reducer;
the water reducer of comparative example 2 did not incorporate an ester macromer, and comparative example 3 did not incorporate a crosslinking monomer. The water reducing agents synthesized in comparative examples 2 and 3 have higher folding and solidifying amounts, the initial slump and the 1h slump of the concrete are obviously reduced, and the workability of the concrete is also poor. Therefore, the water reducing performance and the slump retaining performance of the slump retaining water reducer prepared in the embodiment 2 are obviously better than those of the polycarboxylic acid water reducer with the ether ester blending structure which is synthesized by the mutual synergy of allyl polyether, ester macromonomer and crosslinking monomer, and the water reducing performance and the slump retaining performance of the polycarboxylic acid water reducer are improved together by the crosslinking structure, the ester group and the ether group;
the polycarboxylate water reducer of comparative example 4 adopts a redox initiation system (the reaction temperature is more than 20 ℃), the folding and solidifying doping amount of the water reducer synthesized in comparative example 4 is higher, the initial slump and the 1h slump of concrete are obviously reduced, and the workability of the concrete is also poor. Therefore, the temperature for preparing the polycarboxylate water reducer is reduced by changing the initiator into photoinitiation, so that the prepared polycarboxylate water reducer has outstanding water reducing performance.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (9)
1. The polycarboxylate water reducer is characterized by comprising the following components in parts by weight:
100-110 parts of allyl polyether macromonomer;
10-30 parts of ester macromonomer;
10-40 parts of A liquid;
3-5 parts of a photoinitiator;
1-3 parts of chain transfer agent; and
10-100 parts of water;
the solution A comprises unsaturated acid monomers, crosslinking monomers and water;
the structural formula of the ester macromonomer is as follows,
wherein: e is an integer from 4 to 15;
the molecular formula of the initiator of the allyl polyether macromonomer is CH 2 ＝CH-CH 2 -O-(CH 2 -CH 2 ) c -OH, wherein: c is an integer from 2 to 4.
2. The polycarboxylate superplasticizer as recited in claim 1, wherein, in parts by weight, it comprises:
100 parts of allyl polyether macromonomer;
15 parts of ester macromonomer;
25 parts of A liquid;
3.5 parts of photoinitiator;
1.5 parts of chain transfer agent; and
50 parts of water.
3. The polycarboxylate superplasticizer as recited in claim 1, wherein the allylpolyether macromonomer has the structural formulaWherein: c is an integer of 2-4, and d is an integer of 30-110.
4. The polycarboxylate superplasticizer as recited in claim 1, wherein the unsaturated acid monomer has a structural formula ofWherein: wherein R is-H or-CH 3 。
5. The polycarboxylate water reducing agent according to claim 1, wherein the photoinitiator comprises any one of 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phosphonate and 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone.
6. The polycarboxylate superplasticizer as recited in claim 1, wherein the concentration of the photoinitiator ranges from 0.1 to 1%.
7. The polycarboxylate water reducer according to claim 1, wherein the mass ratio of unsaturated acid monomer, crosslinking monomer and water in the liquid a is 10: (1-5): (10-50).
8. A method for preparing the polycarboxylate superplasticizer as described in claim 1, comprising the steps of:
adding allyl polyether macromonomer, ester macromonomer and water into a reactor to obtain a first mixed solution;
under the ultraviolet irradiation environment of 15-20 ℃, dropwise adding a photoinitiator, a solution A and a chain transfer agent into the first mixed solution to start reaction, after the dropwise adding is finished, carrying out heat preservation reaction for 0.5-1h to obtain a second mixed solution, and adding a NaOH solution with the mass concentration of 32% into the second mixed solution to adjust the pH value of the second mixed solution to 6.0-7.0 to obtain the polycarboxylate water reducer;
100-110 parts of allyl polyether macromonomer; 10-30 parts of ester macromonomer; 10-40 parts of A liquid; 3-5 parts of a photoinitiator; 1-3 parts of chain transfer agent; 10-100 parts of water;
the solution A comprises unsaturated acid monomers, crosslinking monomers and water;
the molecular formula of the initiator of the allyl polyether macromonomer is CH 2 ＝CH-CH 2 -O-(CH 2 -CH 2 ) c -OH, wherein: c is an integer from 2 to 4.
9. The method for preparing a polycarboxylate superplasticizer according to claim 8, wherein the ultraviolet light has a wavelength of 300-400nm and an irradiation intensity of 30-100W/m 2 。
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| CN110003405A (en) * | 2019-04-24 | 2019-07-12 | 四川同舟化工科技有限公司 | Comprehensive high-performance polycarboxylic acids diminishing |
| CN110105504A (en) * | 2019-05-27 | 2019-08-09 | 马清浩 | A kind of high-thin arch dam slow-setting polycarboxylic acid water reducing agent and its preparation and application |
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| CN108484840A (en) * | 2018-03-26 | 2018-09-04 | 厦门宏发先科新型建材有限公司 | A kind of anti-chamotte mould polycarboxylate water-reducer of ester ether mixed structure and preparation method thereof |
| CN110003405A (en) * | 2019-04-24 | 2019-07-12 | 四川同舟化工科技有限公司 | Comprehensive high-performance polycarboxylic acids diminishing |
| CN110105504A (en) * | 2019-05-27 | 2019-08-09 | 马清浩 | A kind of high-thin arch dam slow-setting polycarboxylic acid water reducing agent and its preparation and application |
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