CN114106248A - Slow-release polycarboxylate superplasticizer and preparation method thereof - Google Patents
Slow-release polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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- CN114106248A CN114106248A CN202111481856.1A CN202111481856A CN114106248A CN 114106248 A CN114106248 A CN 114106248A CN 202111481856 A CN202111481856 A CN 202111481856A CN 114106248 A CN114106248 A CN 114106248A
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- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 39
- 239000008030 superplasticizer Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229920000881 Modified starch Polymers 0.000 claims abstract description 43
- 239000004368 Modified starch Substances 0.000 claims abstract description 43
- 235000019426 modified starch Nutrition 0.000 claims abstract description 43
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 35
- 229920002472 Starch Polymers 0.000 claims abstract description 34
- 239000008107 starch Substances 0.000 claims abstract description 33
- 235000019698 starch Nutrition 0.000 claims abstract description 33
- 239000000178 monomer Substances 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 26
- 150000002148 esters Chemical class 0.000 claims abstract description 14
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 13
- 229920000570 polyether Polymers 0.000 claims abstract description 13
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 12
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- HCLJOFJIQIJXHS-UHFFFAOYSA-N 2-[2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOCCOC(=O)C=C HCLJOFJIQIJXHS-UHFFFAOYSA-N 0.000 claims description 10
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 10
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 claims description 9
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 9
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 8
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical group OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 8
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 6
- 229920000151 polyglycol Polymers 0.000 claims description 6
- 239000010695 polyglycol Substances 0.000 claims description 6
- 150000008064 anhydrides Chemical class 0.000 claims description 5
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 5
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 3
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 3
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- 229940014800 succinic anhydride Drugs 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 136
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 32
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 10
- 239000003513 alkali Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 235000010323 ascorbic acid Nutrition 0.000 description 5
- 229960005070 ascorbic acid Drugs 0.000 description 5
- 239000011668 ascorbic acid Substances 0.000 description 5
- 238000010276 construction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000004568 cement Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000002262 irrigation Effects 0.000 description 2
- 238000003973 irrigation Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229920002261 Corn starch Polymers 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001592 potato starch Polymers 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
Classifications
-
- 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
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- 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
-
- 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 slow-release polycarboxylate water reducer and a preparation method thereof, wherein the slow-release polycarboxylate water reducer comprises, by weight, 200-375 parts of modified starch solution, 100-180 parts of polyether macromonomer, 57-70 parts of a first mixture and 39-44 parts of a second mixture, wherein the first mixture comprises unsaturated ester small monomers and unsaturated acid small monomers, and the second mixture comprises a reducing agent and a chain transfer agent. The slow-release polycarboxylate superplasticizer has the characteristics of high slump loss resistance and good material adaptability. The main raw material of the slow-release polycarboxylic acid water reducing agent is a modified starch solution, the modified starch solution is obtained by modifying starch, the starch is renewable, the source is wide, the price is low, petroleum is not required to be used as the raw material, and the using amount of the petroleum is greatly reduced.
Description
Technical Field
The invention relates to the technical field of concrete admixtures, in particular to a slow-release type polycarboxylate superplasticizer and a preparation method thereof.
Background
The water reducing agent is a concrete admixture capable of reducing the water consumption for mixing under the condition of maintaining the slump constant of concrete basically. Most of modern concrete irrigation projects use premixed concrete, and a mixing station of the premixed concrete is often far away from a construction position, so that the concrete is required to have certain slump after being transported for a long time to meet the requirements of site construction. Therefore, it is necessary to develop a polycarboxylate superplasticizer with a good slump loss prevention effect, so that the hazards of incapability of discharging, pump blockage and the like can be avoided, and the waste of raw materials is reduced.
Disclosure of Invention
Based on the above, a slow-release polycarboxylate superplasticizer and a preparation method thereof are needed to solve the technical problems that the slump loss prevention effect of the polycarboxylate superplasticizer in the prior art is poor, so that the discharging and pump plugging cannot be realized.
The invention provides a slow-release polycarboxylate superplasticizer which comprises the following components in parts by weight:
wherein the first mixture comprises unsaturated ester small monomers and unsaturated acid small monomers;
the second mixture includes a reducing agent and a chain transfer agent.
Further, the modified starch solution comprises the following components in parts by weight:
further, the unsaturated anhydride includes one or more of maleic anhydride, itaconic anhydride, and succinic anhydride.
Further, the polyether macromonomer comprises ethylene glycol monovinyl polyglycol ether and/or methallyl alcohol polyoxyethylene ether.
Further, the molecular weight of the polyether macromonomer is 2000-4000.
Further, the unsaturated acid small monomer comprises one or more of acrylic acid, methacrylic acid, maleic anhydride, itaconic acid and fumaric acid.
Further, the unsaturated ester monomer comprises one or more of triethylene glycol diacrylate, tetraethylene glycol diacrylate and methacrylate.
Further, the reducing agent comprises one or more of sodium formaldehyde sulfoxylate, sodium thiosulfate, sodium hypophosphite and sodium phosphite.
Further, the chain transfer agent is mercaptoethanol and/or mercaptoacetic acid.
The invention also provides a preparation method of the polycarboxylic acid, which comprises the following steps:
gelatinizing starch, and adding an initiator, unsaturated acid anhydride and water into the gelatinized starch to obtain a modified starch solution;
dissolving a polyether macromonomer in water to obtain a first solution;
dissolving unsaturated ester small monomers and unsaturated acid small monomers in water to obtain a second solution;
dissolving a reducing agent and a chain transfer agent in water to obtain a third solution;
and adding an initiator and the first solution into the modified starch solution, uniformly stirring, and then, dripping the second solution and the third solution into the modified starch solution to react to obtain the polycarboxylate superplasticizer.
According to the slow-release polycarboxylate water reducer provided by the invention, the unsaturated ester small monomer, the reducing agent and the chain transfer agent are added, so that the slump retaining effect of the slow-release polycarboxylate water reducer is improved, and the material adaptability of the slow-release polycarboxylate water reducer is good.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the embodiments.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.
It should be noted that all the directional indicators (such as up, down, left, right, front, and rear … …) in the embodiment of the present invention are only used to explain the relative position relationship between the components, the motion situation, and the like in a specific posture, and if the specific posture is changed, the directional indicator is changed accordingly.
In addition, the descriptions related to "first", "second", etc. in the present invention are for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In addition, "and/or" in the whole text includes three schemes, taking a and/or B as an example, including a technical scheme, and a technical scheme that a and B meet simultaneously; in addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
The invention provides a slow-release polycarboxylate superplasticizer which comprises, by weight, 200-375 parts of modified starch solution, 100-180 parts of polyether macromonomer, 57-70 parts of a first mixture and 39-44 parts of a second mixture, wherein the first mixture comprises unsaturated ester small monomers and unsaturated acid small monomers, and the second mixture comprises a reducing agent and a chain transfer agent. The slow-release polycarboxylate superplasticizer has the characteristics of high slump loss resistance and good material adaptability.
The main raw material of the slow-release polycarboxylic acid water reducing agent is a modified starch solution, the modified starch solution is obtained by modifying starch, the starch is renewable, the source is wide, the price is low, petroleum is not required to be used as the raw material, and the using amount of the petroleum is greatly reduced.
In addition, most of modern concrete irrigation projects use premixed concrete, and a mixing station of the premixed concrete is often far away from a construction position, so that the concrete is required to have certain slump after being transported for a long time to meet the requirements of site construction. The slow-release polycarboxylate superplasticizer has the characteristics of good slump retaining effect, good cement paste fluidity, capability of improving the workability of concrete and the like, so that the hazards of incapability of discharging, pump blockage and the like can be avoided, and the waste of raw materials is reduced.
Specifically, the modified starch solution comprises, by weight, 100-120 parts of starch, 120-240 parts of water, 5-12 parts of unsaturated anhydride and 1-2.4 parts of an initiator. More specifically, the initiator is an aqueous solution of persulfate.
Further, the unsaturated anhydride includes one or more of maleic anhydride, itaconic anhydride, and succinic anhydride. The unsaturated anhydride is preferably maleic anhydride.
Specifically, the polyether macromonomer includes ethylene glycol monovinyl polyglycol ether and/or methallyl alcohol polyoxyethylene ether. Further, the molecular weight of the polyether macromonomer is 2000-4000.
Specifically, the unsaturated acid small monomer comprises one or more of acrylic acid, methacrylic acid, maleic anhydride, itaconic acid and fumaric acid. The unsaturated acid small monomer is preferably acrylic acid. Furthermore, the molecular weight of the unsaturated acid small monomer is 50-200.
Specifically, the unsaturated ester monomer comprises one or more of triethylene glycol diacrylate, tetraethylene glycol diacrylate and methacrylate. The unsaturated ester small monomer is preferably triethylene glycol diacrylate.
Furthermore, the molecular weight of the unsaturated ester small monomer is 50-1000.
Specifically, the reducing agent comprises one or more of sodium formaldehyde sulfoxylate, sodium thiosulfate, sodium hypophosphite and sodium phosphite.
Specifically, the chain transfer agent is mercaptoethanol and/or mercaptoacetic acid.
The invention also provides a preparation method of the slow-release polycarboxylate superplasticizer, which comprises the following steps:
s1: and (3) carrying out gelatinization treatment on the starch, and then adding an initiator, unsaturated acid anhydride and water into the gelatinized starch to obtain a modified starch solution.
S2: the polyether macromonomer is dissolved in water to obtain a first solution.
S3: and dissolving the unsaturated ester small monomer and the unsaturated acid small monomer in water to obtain a second solution.
S4: and (3) dissolving a reducing agent and a chain transfer agent in water to obtain a third solution.
S5: and adding an initiator and the first solution into the modified starch solution, uniformly stirring, dripping the second solution and the third solution into the modified starch solution, and reacting to obtain the slow-release polycarboxylate superplasticizer.
Specifically, the polycarboxylate superplasticizer can be a slow-release starch-based carboxylate superplasticizer, and is a starch-based carboxylate superplasticizer solution. The preparation method and the production process of the polycarboxylate superplasticizer are simple, and an aqueous solution free copolymerization process is adopted, so that no organic solvent is used, and no waste water, waste gas and waste residue are discharged, thereby solving the environmental problem caused by the application of petroleum.
The preparation method is described in detail for a clearer understanding of the preparation method. And S1, mixing starch and water to prepare a starch solution, heating to 60-65 ℃ while stirring to gelatinize the starch, adding a maleic anhydride aqueous solution and an ammonium persulfate aqueous solution (serving as an initiator) once again, heating to 90-92 ℃, reacting, and keeping the temperature for 0.5-1 hour to obtain the modified starch solution. More specifically, the starch comprises one or more of potato starch, tapioca starch, wheat starch, and corn starch.
In the step of S2, the polyether macromonomer and ammonium persulfate are added to water and stirred to be melted to obtain a first solution. The reaction temperature of the S2 step may be carried out at 35 ℃. Wherein, the polyether macromonomer accounts for 90-140 parts by weight, the water accounts for 90-120 parts by weight, and the initiator accounts for 1.0-1.8 parts by weight. The first solution may be an aqueous solution of ethylene glycol monovinyl polyglycol ether or methallyl alcohol polyoxyethylene ether.
In the step of S3, the second solution includes 7 to 10 parts by weight of unsaturated acid small monomers, 25 to 30 parts by weight of unsaturated ester small monomers, and 25 to 30 parts by weight of water.
In the step of S4, the third solution includes 0.7 to 1.5 parts by weight of a chain transfer agent, 0.3 to 0.5 parts by weight of a reducing agent, and 38 to 42 parts by weight of water.
In the step S5, the initiator and the first solution are added to the modified starch solution and uniformly stirred for 10 minutes, then the second solution and the third solution are dropped at a temperature of 35 ℃, the temperature is maintained for 1 hour after the second solution and the third solution are dropped, and polymerization reaction occurs by the initiator.
The following is a detailed description of specific examples.
Example 1
Modified starch solution: adding 120g of water and 100g of starch into a reaction kettle to prepare 45% starch suspension, heating to 65 ℃ while stirring, adding 10g of maleic anhydride and 1g of ammonium persulfate, heating to 92 ℃, preserving the temperature for 1 hour, and cooling to normal temperature after the reaction is finished to obtain the modified starch solution.
A first solution: in a 250ml beaker, 100g of methallyl alcohol polyoxyethylene ether, 1.6g of ammonium persulfate and 120g of water were added to prepare a first solution.
A second solution: in a 100ml beaker, 8g of acrylic acid, 25g of triethylene glycol diacrylate and 25g of water were added to prepare a second solution.
A third solution: in a 100ml beaker, 0.75g of mercaptoethanol, 0.4g of ascorbic acid and 38g of water were added to prepare a solution, i.e., a third solution.
And adding the first solution into the modified starch solution, uniformly stirring for 10min, then beginning to dropwise add the third solution and the fourth solution for 90min, and adding liquid alkali to adjust the pH value to 7 after dropwise addition is finished, thus obtaining the slow-release polycarboxylic acid water reducer.
Example 2
The embodiment of the invention provides a method for preparing a polycarboxylate superplasticizer, which comprises the following specific steps:
modified starch solution: adding 120g of water and 100g of starch into a reaction kettle to prepare 45% starch suspension, heating to 65 ℃ while stirring, adding 10g of maleic anhydride and 1g of ammonium persulfate, heating to 92 ℃, preserving the temperature for 1 hour, and cooling to normal temperature after the reaction is finished to obtain the modified starch solution.
A first solution: in a 250ml beaker, 140g of methallyl alcohol polyoxyethylene ether, 1.8g of ammonium persulfate and 90g of water were added to prepare a first solution.
A second solution: in a 100ml beaker, 10.2g of maleic anhydride, 25g of triethylene glycol diacrylate and 25g of water were added to prepare a second solution.
A third solution: in a 100ml beaker, 1.0g of thioglycolic acid, 0.5g of sodium hypophosphite and 38g of water were added to prepare a solution, i.e., a third solution.
And adding the first solution into the modified starch solution, uniformly stirring for 10min, then beginning to dropwise add the second solution and the third solution for 90min, and adding liquid alkali to adjust the pH value to 7 after dropwise addition is finished, thus obtaining the slow-release polycarboxylic acid water reducer.
Example 3
The embodiment of the invention provides a method for preparing a polycarboxylate superplasticizer, which comprises the following specific steps:
modified starch solution: adding 100g of water and 120g of starch into a reaction kettle to prepare 55% starch suspension, heating to 60 ℃ while stirring, adding 12g of maleic anhydride and 2.4g of ammonium persulfate, heating to 90 ℃, preserving the temperature for 0.5 hour, and cooling to normal temperature after the reaction is finished to obtain the modified starch solution.
A first solution: in a 250ml beaker, 100g of ethylene glycol monovinyl polyglycol ether, 1.8g of ammonium persulfate and 100g of water were added to prepare a first solution.
A second solution: 10g of acrylic acid, 30g of triethylene glycol diacrylate and 30g of water are added into a 100ml beaker to prepare a solution, namely a second solution.
A third solution: in a 100ml beaker, 1.5g of mercaptoethanol, 0.5g of ascorbic acid and 42g of water were added to prepare a solution, i.e., a third solution.
And adding the first solution into the modified starch solution, uniformly stirring for 10min, then beginning to dropwise add the second solution and the third solution for 90min, and adding liquid alkali to adjust the pH value to 6.9 after dropwise addition is finished, thus obtaining the slow-release polycarboxylic acid water reducer.
Example 4
The embodiment of the invention provides a method for preparing a polycarboxylate superplasticizer, which comprises the following specific steps:
modified starch solution: adding 240g of water and 100g of starch into a reaction kettle to prepare 29.5% starch suspension, heating to 65 ℃ while stirring, adding 12g of maleic anhydride and 1.5g of ammonium persulfate, heating to 92 ℃, keeping the temperature for 1 hour, and cooling to normal temperature after the reaction is finished to obtain the modified starch solution.
A first solution: in a 250ml beaker, 140g of methallyl alcohol polyoxyethylene ether, 1.0g of ammonium persulfate and 90g of water were added to prepare a first solution.
A second solution: in a 100ml beaker, 7.5g of maleic anhydride, 30g of tetraethyleneglycol diacrylate and 25g of water were added to prepare a second solution.
A third solution: in a 100ml beaker, 0.70g of mercaptoethanol, 0.5g of ascorbic acid and 38g of water were added to prepare a solution, i.e., a third solution.
And adding the first solution into the modified starch solution, uniformly stirring for 10min, then beginning to dropwise add the second solution and the third solution for 90min, and adding liquid alkali to adjust the pH value to 7.0 after dropwise addition is finished, thus obtaining the slow-release polycarboxylic acid water reducer.
Example 5
The embodiment of the invention provides a method for preparing a polycarboxylate superplasticizer, which comprises the following specific steps:
modified starch solution: adding 100g of water and 100g of starch into a reaction kettle to prepare 50% starch suspension, heating to 65 ℃ while stirring, adding 5g of maleic anhydride and 1g of ammonium persulfate, heating to 92 ℃, preserving the temperature for 1 hour, and cooling to normal temperature after the reaction is finished to obtain the modified starch solution.
A first solution: in a 250ml beaker, 120g of methallyl alcohol polyoxyethylene ether, 1.0g of ammonium persulfate and 120g of water were added to prepare a first solution.
A second solution: 10g of acrylic acid, 25g of triethylene glycol diacrylate and 25g of water are added into a 100ml beaker to prepare a solution, namely a second solution.
A third solution: in a 100ml beaker, 1g of mercaptoethanol, 0.5g of ascorbic acid and 40g of water were added to prepare a solution, i.e., a third solution.
And adding the first solution into the modified starch solution, uniformly stirring for 10min, then beginning to dropwise add the second solution and the third solution for 90min, and adding liquid alkali to adjust the pH value to 7 after dropwise addition is finished, thus obtaining the slow-release polycarboxylic acid water reducer.
Example 6
The embodiment of the invention provides a method for preparing a polycarboxylate superplasticizer, which comprises the following specific steps:
modified starch solution: adding 180g of water and 110g of starch into a reaction kettle to prepare 38% starch suspension, heating to 62 ℃ while stirring, adding 8g of maleic anhydride and 1.8g of ammonium persulfate, heating to 90 ℃, keeping the temperature for 1 hour, and cooling to normal temperature after the reaction is finished to obtain the modified starch solution.
A first solution: in a 250ml beaker, 120g of ethylene glycol monovinyl polyglycol ether, 1.8g of ammonium persulfate and 100g of water were added to prepare a first solution.
A second solution: in a 100ml beaker, 7g of acrylic acid, 26g of tetraethyleneglycol diacrylate and 28g of water were added to prepare a second solution.
A third solution: in a 100ml beaker, 1g of mercaptoethanol, 0.3g of ascorbic acid and 40g of water were added to prepare a solution, i.e., a third solution.
And adding the first solution into the modified starch solution, uniformly stirring for 10min, then beginning to dropwise add the second solution and the third solution for 90min, and adding liquid alkali to adjust the pH value to 7 after dropwise addition is finished, thus obtaining the slow-release polycarboxylic acid water reducer.
Example 7
The embodiment of the invention provides a method for preparing a polycarboxylate superplasticizer, which comprises the following specific steps:
modified starch solution: adding 240g of water and 100g of starch into a reaction kettle to prepare 29.5% starch suspension, heating to 65 ℃ while stirring, adding 12g of maleic anhydride and 2g of ammonium persulfate, heating to 92 ℃, preserving the temperature for 0.5 hour, and cooling to normal temperature after the reaction is finished to obtain the modified starch solution.
A first solution: 90g of methallyl alcohol polyoxyethylene ether, 1.0g of ammonium persulfate and 90g of water were added to a 250ml beaker, and the prepared solution was a first solution.
A second solution: in a 100ml beaker, 7.2g of acrylic acid, 27g of triethylene glycol diacrylate and 28g of water were added to prepare a solution, i.e., a second solution.
A third solution: in a 100ml beaker, 1g of thioglycolic acid, 0.3g of sodium formaldehyde sulfoxylate (commonly known as sodium formaldehyde sulfoxylate) and 40g of water are added to prepare a solution, namely a third solution.
And adding the first solution into the modified starch solution, uniformly stirring for 10min, then beginning to dropwise add the second solution and the third solution for 90min, and adding liquid alkali to adjust the pH value to 7 after dropwise addition is finished, thus obtaining the slow-release polycarboxylic acid water reducer.
And (3) performance testing:
the polycarboxylic acid water reducing agents obtained in examples 1 to 7 were compared with commercially available slump-retaining polycarboxylic acid water reducing agents, and a mortar and concrete test was performed. The test method is carried out by referring to the standard regulation of GB 8076 + 2008 concrete admixture. The mixing ratio of the clear paste is as follows: c, W, A is 300:87:0.2 wt%; the C30 concrete mixing ratio is: k, F, G, A, W, 250, 60, 50, 800, 980, 0.50 and 180. The results of the cement paste fluidity test are shown in table 1. The concrete performance test results are shown in table 2.
TABLE 1 Cement paste fluidity test results
TABLE 2 concrete Performance test results
From the above data, one can see: the embodiment of the slow-release polycarboxylate superplasticizer provided by the invention has relatively good dispersibility initially, and as the slow-release monomer is gradually released, the net slurry fluidity at 60min is slightly increased, the net slurry fluidity at 90min is hardly lost, and the slump retaining property is better. In a concrete test, the slump expansion degree can be kept unchanged within 90min, the workability is good, the compressive strength of a concrete test piece 3d is slightly reduced, and the retarding effect is good. The main raw material of the polycarboxylic acid water reducing agent is a modified starch solution, the modified starch solution is obtained by modifying starch, the starch is renewable, the source is wide, the price is low, petroleum is not needed to be used as the raw material, the consumption of the petroleum is greatly reduced, and the environmental problem caused by the application of the petroleum is reduced.
The above description is only a preferred embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the present specification and directly/indirectly applied to other related technical fields within the spirit of the present invention are included in the scope of the present invention.
Claims (10)
1. The slow-release polycarboxylate superplasticizer is characterized by comprising the following components in parts by weight:
wherein the first mixture comprises unsaturated ester small monomers and unsaturated acid small monomers;
the second mixture includes a reducing agent and a chain transfer agent.
2. The slow-release polycarboxylate superplasticizer according to claim 1, wherein said modified starch solution comprises, in parts by weight:
3. the slow release polycarboxylate water reducer according to claim 2, wherein the unsaturated anhydride comprises one or more of maleic anhydride, itaconic anhydride and succinic anhydride.
4. The slow-release polycarboxylate superplasticizer of claim 1, wherein said polyether macromonomer comprises ethylene glycol monovinyl polyglycol ether and/or methallyl alcohol polyoxyethylene ether.
5. The slow-release polycarboxylate superplasticizer according to claim 1, wherein the molecular weight of the polyether macromonomer is 2000-4000.
6. The slow-release polycarboxylate water reducer according to claim 1, wherein the unsaturated acid small monomers comprise one or more of acrylic acid, methacrylic acid, maleic anhydride, itaconic acid and fumaric acid.
7. The slow-release polycarboxylate water reducer according to claim 1, wherein the unsaturated ester monomers comprise one or more of triethylene glycol diacrylate, tetraethylene glycol diacrylate and methacrylate.
8. The slow-release polycarboxylate water reducer according to claim 1, wherein the reducing agent comprises one or more of sodium formaldehyde sulfoxylate, sodium thiosulfate, sodium hypophosphite and sodium phosphite.
9. The slow-release polycarboxylate water reducer according to claim 1, wherein the chain transfer agent is mercaptoethanol and/or mercaptoacetic acid.
10. A preparation method of a slow-release type polycarboxylate superplasticizer is characterized by comprising the following steps:
gelatinizing starch, and adding an initiator, unsaturated acid anhydride and water into the gelatinized starch to obtain a modified starch solution;
dissolving a polyether macromonomer in water to obtain a first solution;
dissolving unsaturated ester small monomers and unsaturated acid small monomers in water to obtain a second solution;
dissolving a reducing agent and a chain transfer agent in water to obtain a third solution;
and adding an initiator and the first solution into the modified starch solution, uniformly stirring, and then, dripping the second solution and the third solution into the modified starch solution to react to obtain the polycarboxylate superplasticizer.
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| CN103864338A (en) * | 2014-03-05 | 2014-06-18 | 济南大学 | Oxydative degradation starch grafted polycarboxylate superplasticizer and preparation method thereof |
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| CN112608067A (en) * | 2021-03-05 | 2021-04-06 | 建研建材有限公司 | Method for preparing starch-based high-performance water reducing agent and product thereof |
| CN112920336A (en) * | 2021-01-29 | 2021-06-08 | 成都博思聚合科技有限公司 | Starch modified polycarboxylate superplasticizer and preparation method thereof |
| CN113636774A (en) * | 2021-08-13 | 2021-11-12 | 科之杰新材料集团有限公司 | Polycarboxylic acid water reducing agent for mass concrete and preparation method thereof |
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