CN111995717A - High-performance polycarboxylate superplasticizer, preparation method thereof and concrete - Google Patents
High-performance polycarboxylate superplasticizer, preparation method thereof and concrete Download PDFInfo
- Publication number
- CN111995717A CN111995717A CN202010843723.3A CN202010843723A CN111995717A CN 111995717 A CN111995717 A CN 111995717A CN 202010843723 A CN202010843723 A CN 202010843723A CN 111995717 A CN111995717 A CN 111995717A
- Authority
- CN
- China
- Prior art keywords
- parts
- solution
- weight
- polycarboxylate superplasticizer
- dripping
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 33
- 239000008030 superplasticizer Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000004567 concrete Substances 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000007800 oxidant agent Substances 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 11
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 8
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 229920000151 polyglycol Polymers 0.000 claims description 3
- 239000010695 polyglycol Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 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 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 abstract description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 abstract description 9
- 229920001223 polyethylene glycol Polymers 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 7
- 230000001603 reducing effect Effects 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000035484 reaction time Effects 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 70
- 238000006243 chemical reaction Methods 0.000 description 14
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 229960005070 ascorbic acid Drugs 0.000 description 6
- 235000010323 ascorbic acid Nutrition 0.000 description 6
- 239000011668 ascorbic acid Substances 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000004574 high-performance concrete Substances 0.000 description 1
- QVDTXNVYSHVCGW-ONEGZZNKSA-N isopentenol Chemical compound CC(C)\C=C\O QVDTXNVYSHVCGW-ONEGZZNKSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000002351 wastewater Substances 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
- 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
-
- 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
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/06—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen
- C08F4/26—Metallic compounds other than hydrides and other than metallo-organic compounds; Boron halide or aluminium halide complexes with organic compounds containing oxygen of manganese, iron group metals or platinum group metals
-
- 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 provides a high-performance polycarboxylate superplasticizer and a preparation method thereof, and concrete, wherein the superplasticizer comprises the following components: ethylene glycol monovinyl polyethylene glycol ether macromonomer, unsaturated carboxylic acid small monomer, alkali, oxidant, reducing agent, chain transfer agent and catalyst. Compared with the prior art, the method realizes the synthesis of the polycarboxylic acid water reducing agent at normal temperature, and has the advantages of short reaction time, simple synthesis process, low investment and better economic benefit. The polycarboxylate superplasticizer prepared by the method has good water reducing effect and excellent collapse protection performance.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a high-performance polycarboxylate superplasticizer, a preparation method thereof and concrete.
Background
Along with the rapid development of economy and the improvement of building level in China, the requirements on the quality of concrete are higher and higher, the polycarboxylate superplasticizer is a concrete admixture of the latest generation, has the characteristics of excellent water reducing rate, good cement adaptability and the like, meanwhile, no process wastewater is generated in the production process of the polycarboxylate superplasticizer, and the polycarboxylate superplasticizer belongs to an environment-friendly material and is widely applied to high-performance concrete.
In recent years, ether polycarboxylic acid water reducing agents have become a hot spot of research in recent years because they have the advantages of simple production process, high cost performance, high water reducing rate and collapse retention capacity, compared with ester polycarboxylic acids. The ether water reducing agent generally uses unsaturated polyether as a macromonomer, and has the advantages of simple operation process, environmental protection, stable product performance and the like, so the ether water reducing agent gradually becomes a great trend for the development of polycarboxylic acid water reducing agents.
In ether macromonomers, prenyl polyoxyethylene ether or methallyl polyoxyethylene ether with wide raw material sources is mostly adopted at home and abroad, the polyether macromonomers and the functional small monomers are polymerized for 3-5 hours at the temperature of 40-80 ℃, and the obtained polycarboxylic acid water reducing agent has stable performance, low doping amount, high water reducing rate and good slump retaining property. However, the synthesis of the water reducing agent usually requires heating to react, so that the synthesis and sale cost of the synthetic polycarboxylic acid water reducing agent is increased unintentionally during the synthesis and transportation process, so that part of consumers are forced to use the water reducing agent such as naphthalene series which has great environmental pollution, and the water reducing agent is limited in part of Europe and may be limited in China in the near future.
Disclosure of Invention
The invention aims to provide a high-performance polycarboxylate superplasticizer which is high in water reducing rate, good in collapse protection performance and strong in adaptability.
The invention also aims to provide a preparation method of the high-performance polycarboxylate superplasticizer, which can be used for preparing the polycarboxylate superplasticizer at normal temperature, and solves the problems of relatively complex production process, high investment, poor economic benefit and the like of the polycarboxylate superplasticizer in the prior art of heating synthesis.
The last object of the invention is to provide concrete containing the high-performance polycarboxylate superplasticizer.
The specific technical scheme of the invention is as follows:
a high-performance polycarboxylate superplasticizer comprises a material A, a material B, a bottom material, an oxidant and a catalyst;
the material A comprises unsaturated carboxylic acid small monomers, a chain transfer agent and softened water; according to the weight portion, the unsaturated carboxylic acid small monomer is 15-45, the chain transfer agent is 0.5-5, and the softened water is 50-150.
The material B comprises 20-80 parts by weight of softened water and 0.5-4.0 parts by weight of reducing agent;
the primer comprises a macromonomer and softened water, wherein the macromonomer is 200-300 parts by weight, and the softened water is 120-250 parts by weight.
1-6 parts of oxidant and 2-10 parts of catalyst according to parts by weight.
The unsaturated carboxylic acid small monomer is one or a combination of more of maleic anhydride and acrylic acid, methacrylic acid or itaconic acid;
the chain transfer agent is at least one of mercaptoethanol or mercaptopropionic acid;
the reducing agent is at least one of ascorbic acid and sodium formaldehyde sulfoxylate;
the macromonomer is ethylene glycol monovinyl polyethylene glycol ether (EPEG);
the number average molecular weight of the ethylene glycol monovinyl polyglycol ether is 1000-4000;
the oxidant is at least one of hydrogen peroxide, ammonium persulfate or potassium persulfate; the hydrogen peroxide solution with the mass fraction of 30% is preferred.
The catalyst is inorganicFe2+Salt, preferably FeSO with mass fraction of 0.5% -2.0%4And (3) solution.
The preparation method of the high-performance polycarboxylate superplasticizer comprises the following steps:
1) adding 15-45 parts of unsaturated carboxylic acid small monomer and 0.5-5 parts of chain transfer agent into 50-150 parts by weight of softened water, and uniformly mixing to prepare solution A;
2) adding 0.5-4 parts of reducing agent into 20-80 parts of softened water by weight, and fully and uniformly mixing to prepare a solution B;
3) adding 200-300 parts of macromonomer into 120-250 parts of softened water by weight under the stirring state, and fully stirring and dissolving to obtain a primer;
4) under the stirring state, dripping 1-6 parts of oxidant into the base material obtained in the step 3), stirring, then dripping 2-10 parts of catalyst solution by weight, and stirring;
5) simultaneously dripping the solution A prepared in the step 2 and the solution B prepared in the step 3) into the system obtained in the step 4); after the dropwise addition is completed, the mixture is cured, and finally, a sodium hydroxide solution is added to adjust the pH.
Dripping 1-6 parts of oxidant in the step 4), stirring for 3-5min, and dripping 2-10 parts of catalyst solution by weight;
further, in the step 4), 2-10 parts by weight of catalyst solution is dripped and stirred for 3-5 min.
In the step 5), the solution A is dripped in 30-45min, and the dripping time of the solution B is 5-15min longer than that of the solution A.
Further, in the step 5), after the solution B is dropwise added, curing is carried out for 10-20 min.
Further, the reaction process of the step 5) does not need heating, and the temperature does not exceed 35 ℃, and preferably, the reaction process is carried out under the condition of room temperature.
And 5) the mass fraction of the sodium hydroxide solution is 20%.
Adjusting the pH value to 6.0-6.5 in the step 5).
The concrete provided by the invention contains the high-performance polycarboxylate superplasticizer.
The beneficial technical effects of the invention are as follows: the invention utilizes the uniqueness of ethylene glycol monovinyl polyglycol etherThe molecular structure of (A) and the inorganic Fe catalyst is introduced during the reaction process2+The salt can greatly shorten the reaction time, excite the activity of the monomer, only needs 1-1.5h in the whole reaction process, does not need heating, not only reduces the energy consumption, but also reduces the side reaction, improves the performance of the polycarboxylic acid mother liquor, and the product has the advantages of high water reducing rate, good collapse-keeping performance and the like. The preparation method of the invention belongs to an environment-friendly process, and has no pollution to reaction raw materials and safe and environment-friendly reaction process.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the preparation methods described in the examples are only for illustrating the present invention and are not to be construed as limiting the present invention, and that the simple modifications of the preparation methods of the present invention based on the concept of the present invention are within the scope of the present invention as claimed.
Example 1
A preparation method of a high-performance polycarboxylate superplasticizer comprises the following steps:
1) preparation of solution A: dissolving 15g of acrylic acid, 5g of maleic anhydride and 1g of mercaptopropionic acid in 80g of softened water, and uniformly mixing to obtain a solution A for later use;
2) preparing a solution B: dissolving 1g of ascorbic acid in 40g of softened water, and uniformly mixing to obtain a solution B for later use;
3) adding 150g of softened water into a four-neck flask, adding 240g of ethylene glycol monovinyl polyethylene glycol ether macromonomer with the molecular weight of 2400 under a stirring state, and obtaining a bottom material after complete dissolution;
4) dripping 2g of 30% by mass hydrogen peroxide solution into the base material obtained in step 3) under stirring, stirring for 5min, and dripping 3g of 0.5% by mass FeSO4Continuously stirring the aqueous solution for 5 min;
5) and (3) simultaneously dripping the solution A and the solution B into the system obtained in the step 4), finishing dripping the solution A within 40min, finishing dripping the solution B within 50min (the dripping time is 10min longer than that of the solution A), carrying out the whole reaction process at normal temperature, curing for 15min after finishing dripping, then adding a sodium hydroxide solution with the mass fraction of 20%, and adjusting the pH value to 6.0 to obtain the high-performance polycarboxylate superplasticizer solution.
Example 2
A preparation method of a high-performance polycarboxylate superplasticizer comprises the following steps:
1) preparation of solution A: 20g of acrylic acid, 3g of maleic anhydride and 2g of mercaptopropionic acid are dissolved in 60g of softened water and uniformly mixed to obtain a solution A for later use;
2) preparing a solution B: 2.5g of ascorbic acid is dissolved in 50g of softened water and uniformly mixed to obtain a solution B for later use;
3) adding 180g of softened water into a four-neck flask, adding 220g of ethylene glycol monovinyl polyethylene glycol ether macromonomer with the molecular weight of 2400 under a stirring state, and obtaining a bottom material after complete dissolution;
4) dripping 4g of 30% by mass hydrogen peroxide solution into the base material obtained in the step 3) under stirring, stirring for 5min, and dripping 5g of 1.0% by mass FeSO4Continuously stirring the aqueous solution for 5 min;
5) and (3) simultaneously dripping the solution A and the solution B into the system obtained in the step 4), finishing dripping the solution A within 45min, finishing dripping the solution B within 60min (15 min longer than the dripping time of the solution A), carrying out the whole reaction process at normal temperature, curing for 10min after finishing dripping, then adding a sodium hydroxide solution with the mass fraction of 20%, and adjusting the pH value to 6.0 to obtain the high-performance polycarboxylate superplasticizer solution.
Example 3
A preparation method of a high-performance polycarboxylate superplasticizer comprises the following steps:
1) preparation of solution A: dissolving 30g of acrylic acid, 8g of maleic anhydride and 3g of mercaptopropionic acid in 100g of softened water, and uniformly mixing to obtain a solution A for later use;
2) preparing a solution B: dissolving 3.5g of ascorbic acid in 60g of softened water, and uniformly mixing to obtain a solution B for later use;
3) adding 200g of softened water into a four-neck flask, adding 280g of ethylene glycol monovinyl polyethylene glycol ether macromonomer with the molecular weight of 2400 under a stirring state, and obtaining a bottom material after complete dissolution;
4) under the stirring state, the following steps3) 5g of hydrogen peroxide solution with the mass fraction of 30 percent is dropped into the obtained backing material, 7g of FeSO with the mass fraction of 1.2 percent is dropped after stirring for 5min4Continuously stirring the aqueous solution for 5 min;
5) and (3) simultaneously dripping the solution A and the solution B into the system obtained in the step 4), finishing dripping the solution A within 30min, finishing dripping the solution B within 40min (the dripping time is 10min longer than that of the solution A), carrying out the whole reaction process at normal temperature, curing for 20min after finishing dripping, then adding a sodium hydroxide solution with the mass fraction of 20%, and adjusting the pH value to 6.0 to obtain the high-performance polycarboxylate superplasticizer solution.
Example 4
A preparation method of a high-performance polycarboxylate superplasticizer comprises the following steps:
1) preparation of solution A: 28g of acrylic acid, 5g of maleic anhydride and 4.5g of mercaptopropionic acid are dissolved in 120g of softened water and uniformly mixed to obtain a solution A for later use;
2) preparing a solution B: dissolving 2g of ascorbic acid in 70g of softened water, and uniformly mixing to obtain a solution B for later use;
3) adding 220g of softened water into a four-neck flask, adding 220g of ethylene glycol monovinyl polyethylene glycol ether macromonomer with the molecular weight of 2400 under a stirring state, and obtaining a bottom material after complete dissolution;
4) dripping 1g of 30% hydrogen peroxide solution into the base material obtained in the step 3) under stirring, stirring for 5min, and dripping 9g of 0.8% FeSO4Continuously stirring the aqueous solution for 5 min;
5) and (3) simultaneously dripping the solution A and the solution B into the system obtained in the step 4), finishing dripping the solution A within 45min, finishing dripping the solution B within 50min (the dripping time is 5min longer than that of the solution A), carrying out the whole reaction process at normal temperature, curing for 15min after finishing dripping, then adding a sodium hydroxide solution with the mass fraction of 20%, and adjusting the pH value to 6.0 to obtain the high-performance polycarboxylate superplasticizer solution.
Example 5
A preparation method of a high-performance polycarboxylate superplasticizer comprises the following steps:
1) preparation of solution A: dissolving 25g of acrylic acid, 6g of maleic anhydride and 3.5g of mercaptopropionic acid in 100g of softened water, and uniformly mixing to obtain a solution A for later use;
2) preparing a solution B: dissolving 0.5g ascorbic acid in 30g softened water, and mixing uniformly to obtain solution B for later use;
3) adding 250g of softened water into a four-neck flask, adding 250g of ethylene glycol monovinyl polyethylene glycol ether macromonomer with the molecular weight of 2400 under a stirring state, and obtaining a bottom material after complete dissolution;
4) dripping 3.5g of 30% hydrogen peroxide solution into the base material obtained in the step 3) under stirring, stirring for 5min, and dripping 2.5g of 1.8% FeSO4Continuously stirring the aqueous solution for 5 min;
5) and (3) simultaneously dripping the solution A and the solution B into the system obtained in the step 4), finishing dripping the solution A within 35min, finishing dripping the solution B within 45min (the dripping time is 10min longer than that of the solution A), carrying out the whole reaction process at normal temperature, curing for 10min after finishing dripping, then adding a sodium hydroxide solution with the mass fraction of 20%, and adjusting the pH value to 6.0 to obtain the high-performance polycarboxylate superplasticizer solution.
Comparative example 1
In the comparative example 1, the macromonomer ethylene glycol monovinyl polyethylene glycol ether in the example 3 is replaced by methallyl alcohol polyoxyethylene ether, and other conditions are not changed.
Comparative example 2
In the comparative example 2, the macromonomer ethylene glycol monovinyl polyethylene glycol ether in the example 3 is replaced by isopentenol polyoxyethylene ether, and other conditions are not changed.
Comparative example 3
Comparative example 3 No catalyst FeSO was added during the reaction in example 34Aqueous solution, other conditions were unchanged.
Comparative example 4
Comparative example 4 No catalyst FeSO was added during the reaction in example 34And (3) adding the material A dropwise and the material B dropwise for 3.5 hours to obtain an aqueous solution, wherein other conditions are unchanged.
Comparative example 5
Comparative example 5 in this example 3, 38g of acrylic acid was added to the primer during the reaction, and maleic anhydride was not added thereto, and the other conditions were not changed.
The clear paste and concrete comparison experiments are respectively carried out on the above examples 1-5 and comparative examples 1-5, wherein the clear paste experiment is in accordance with the GB/T8077 and 2012 'method for testing homogeneity of concrete admixture'; the concrete experiments were in accordance with the Standard test methods for the Performance of ordinary concrete mixtures. Specific test data are shown in tables 1 and 2 below.
TABLE 1 test results of the neat paste test
Table 2C 30 test results of concrete experiments
It is seen from tables 1 and 2 that the polycarboxylic acid water reducing agent of the present invention has excellent water reducing and slump retaining effects.
The technical contents of the invention are further described by the examples, but the invention is not limited by the examples, and any technical extension or re-creation based on the invention is protected by the invention.
Claims (10)
1. The high-performance polycarboxylate superplasticizer is characterized by comprising a material A, a material B, a bottom material, an oxidant and a catalyst;
the material A comprises 15-45 parts by weight of unsaturated carboxylic acid small monomer, 0.5-5 parts by weight of chain transfer agent and 50-150 parts by weight of softened water;
the material B comprises 20-80 parts by weight of softened water and 0.5-4.0 parts by weight of reducing agent;
the primer comprises 300 parts by weight of a macromonomer and 250 parts by weight of softened water;
1-6 parts of oxidant and 2-10 parts of catalyst according to parts by weight.
2. The high-performance polycarboxylate superplasticizer according to claim 1, wherein said unsaturated carboxylic small monomer is a combination of maleic anhydride and one or more of acrylic acid, methacrylic acid or itaconic acid; .
3. The high-performance polycarboxylate water reducer according to claim 1, wherein said chain transfer agent is at least one of mercaptoethanol or mercaptopropionic acid.
4. The high-performance polycarboxylate superplasticizer according to claim 1, wherein said macromonomer is ethylene glycol monovinyl polyglycol ether.
5. The high-performance polycarboxylate superplasticizer according to claim 1, wherein said catalyst is inorganic Fe2+And (3) salt.
6. The high-performance polycarboxylate superplasticizer according to claim 5, wherein the catalyst is FeSO with a mass fraction of 0.5-2.0%4And (3) solution.
7. A preparation method of the high-performance polycarboxylate superplasticizer according to any one of claims 1 to 6, characterized by comprising the following steps:
1) adding 15-45 parts of unsaturated carboxylic acid small monomer and 0.5-5 parts of chain transfer agent into 50-150 parts by weight of softened water, and uniformly mixing to prepare solution A;
2) adding 0.5-4 parts of reducing agent into 20-80 parts of softened water by weight, and fully and uniformly mixing to prepare a solution B;
3) adding 200-300 parts of macromonomer into 120-250 parts of softened water by weight under the stirring state, and fully stirring and dissolving to obtain a primer;
4) under the stirring state, dripping 1-6 parts of oxidant into the base material obtained in the step 3), stirring, then dripping 2-10 parts of catalyst solution by weight, and stirring;
5) simultaneously dripping the solution A prepared in the step 2 and the solution B prepared in the step 3) into the system obtained in the step 4); after the dropwise addition is completed, the mixture is cured, and finally, a sodium hydroxide solution is added to adjust the pH.
8. The method according to claim 7, wherein the solution A is dripped in the step 5) within 30 to 45min, and the dripping time of the solution B is 5 to 15min longer than that of the solution A.
9. The production method according to claim 7 or 8, wherein in the step 5), the solution B is aged for 10 to 20min after completion of the dropwise addition.
10. A concrete comprising the high-performance polycarboxylic acid water reducing agent according to any one of claims 1 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010843723.3A CN111995717A (en) | 2020-08-20 | 2020-08-20 | High-performance polycarboxylate superplasticizer, preparation method thereof and concrete |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010843723.3A CN111995717A (en) | 2020-08-20 | 2020-08-20 | High-performance polycarboxylate superplasticizer, preparation method thereof and concrete |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111995717A true CN111995717A (en) | 2020-11-27 |
Family
ID=73472814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010843723.3A Pending CN111995717A (en) | 2020-08-20 | 2020-08-20 | High-performance polycarboxylate superplasticizer, preparation method thereof and concrete |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111995717A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112625191A (en) * | 2020-12-22 | 2021-04-09 | 湖南中岩建材科技有限公司 | Polycarboxylate superplasticizer and preparation method and application thereof |
| CN113150220A (en) * | 2021-04-26 | 2021-07-23 | 武汉中彭化学科技有限公司 | Preparation method for synthesizing high slump loss resistant water reducer by adopting six-carbon monomer |
| CN113754841A (en) * | 2021-10-21 | 2021-12-07 | 上海三瑞高分子材料股份有限公司 | Method for synthesizing polycarboxylate superplasticizer from vinyl ether monomer at normal temperature |
| CN114249866A (en) * | 2021-12-31 | 2022-03-29 | 安徽海螺新材料科技有限公司 | High-efficiency polycarboxylic acid water reducing agent and preparation method and application thereof |
| CN114478946A (en) * | 2022-03-21 | 2022-05-13 | 砼牛（上海）智能科技有限公司 | Polycarboxylic acid series concrete water reducing agent and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1997679A (en) * | 2004-02-04 | 2007-07-11 | 建筑研究和科技有限公司 | Copolymers based on unsaturated mono- or dicarboxylic acid derivatives and oxyalkyleneglycol-alkenyl ethers, method for the production and use thereof |
| CN109705282A (en) * | 2019-01-08 | 2019-05-03 | 山西佳维新材料股份有限公司 | A kind of preparation method of novel polyether synthesis superelevation water reducing type polycarboxylate water-reducer |
| CN109824836A (en) * | 2019-01-29 | 2019-05-31 | 广东瑞安科技实业有限公司 | Workability is good, wide adaptability polycarboxylate water-reducer and preparation method thereof |
| CN110642995A (en) * | 2019-09-27 | 2020-01-03 | 贵州石博士科技有限公司 | Preparation method of polycarboxylic acid water reducer for low-slump concrete |
-
2020
- 2020-08-20 CN CN202010843723.3A patent/CN111995717A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1997679A (en) * | 2004-02-04 | 2007-07-11 | 建筑研究和科技有限公司 | Copolymers based on unsaturated mono- or dicarboxylic acid derivatives and oxyalkyleneglycol-alkenyl ethers, method for the production and use thereof |
| CN109705282A (en) * | 2019-01-08 | 2019-05-03 | 山西佳维新材料股份有限公司 | A kind of preparation method of novel polyether synthesis superelevation water reducing type polycarboxylate water-reducer |
| CN109824836A (en) * | 2019-01-29 | 2019-05-31 | 广东瑞安科技实业有限公司 | Workability is good, wide adaptability polycarboxylate water-reducer and preparation method thereof |
| CN110642995A (en) * | 2019-09-27 | 2020-01-03 | 贵州石博士科技有限公司 | Preparation method of polycarboxylic acid water reducer for low-slump concrete |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112625191A (en) * | 2020-12-22 | 2021-04-09 | 湖南中岩建材科技有限公司 | Polycarboxylate superplasticizer and preparation method and application thereof |
| CN113150220A (en) * | 2021-04-26 | 2021-07-23 | 武汉中彭化学科技有限公司 | Preparation method for synthesizing high slump loss resistant water reducer by adopting six-carbon monomer |
| CN113754841A (en) * | 2021-10-21 | 2021-12-07 | 上海三瑞高分子材料股份有限公司 | Method for synthesizing polycarboxylate superplasticizer from vinyl ether monomer at normal temperature |
| CN114249866A (en) * | 2021-12-31 | 2022-03-29 | 安徽海螺新材料科技有限公司 | High-efficiency polycarboxylic acid water reducing agent and preparation method and application thereof |
| CN114478946A (en) * | 2022-03-21 | 2022-05-13 | 砼牛（上海）智能科技有限公司 | Polycarboxylic acid series concrete water reducing agent and preparation method thereof |
| CN114478946B (en) * | 2022-03-21 | 2023-08-11 | 山西方兴建材股份有限公司 | Polycarboxylic acid concrete water reducer and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111995717A (en) | High-performance polycarboxylate superplasticizer, preparation method thereof and concrete | |
| CN105367720B (en) | A kind of diminishing collapse protective poly-carboxylic acid water reducing agent and preparation method thereof | |
| CN110128603B (en) | Method for stably synthesizing polycarboxylate superplasticizer under low-temperature condition | |
| CN110845672B (en) | Polycarboxylic acid type concrete glue reducing agent and preparation method thereof | |
| CN109705282A (en) | A kind of preparation method of novel polyether synthesis superelevation water reducing type polycarboxylate water-reducer | |
| CN108794700A (en) | A kind of carboxylic acid group polymer and preparation method thereof and sustained-release polycarboxylic water reducer | |
| CN104788605B (en) | A kind of preparation method of the concrete inner curing agent with nucleocapsid structure | |
| CN109337024B (en) | Preparation method of retarding polycarboxylate superplasticizer | |
| CN110066135A (en) | A kind of high performance water reducing agent of polyocarboxy acid and preparation method thereof | |
| CN102951866A (en) | Ascorbic acid modified carboxylic water reducer and preparation method thereof | |
| WO2020001008A1 (en) | Preparation method for micro-crosslinked powder polycarboxylate water reducing agent | |
| CN106632881A (en) | Low water-reducing and high slump loss resistant type polycarboxylate superplasticizer master batch | |
| CN110358024B (en) | Low-surface-tension hyperbranched shrinkage-reducing polycarboxylate superplasticizer and preparation method thereof | |
| CN101530760A (en) | Polyether-based polycarboxylic acid series hyper-dispersant and synthetizing method | |
| CN106916292B (en) | A kind of polyoxyalkyl ether and preparation method thereof, by its resulting polycarboxylate water-reducer and preparation method | |
| CN104861124A (en) | Polycarboxylic acid water reducing agent and preparation method thereof | |
| CN108948285B (en) | High-water-reduction high-slump-retaining type polycarboxylate superplasticizer and preparation method thereof | |
| CN112625191A (en) | Polycarboxylate superplasticizer and preparation method and application thereof | |
| CN109880022B (en) | High-adaptability polycarboxylate superplasticizer and synthesis method thereof | |
| CN109721271B (en) | Polycarboxylate water reducing agent composition for self-compacting high-workability concrete | |
| CN115368517A (en) | Preparation method of siloxane modified polyether and solid polycarboxylic acid water reducing agent | |
| CN107200819B (en) | Synthetic method of silicon-containing polycarboxylic acid water reducing agent and product thereof | |
| CN111362613A (en) | Cardanol polyoxyethylene maleic anhydride ester and preparation method thereof, solid polycarboxylic acid slump retaining agent and preparation method thereof | |
| CN112011050B (en) | Ultrahigh-performance water reducing agent and preparation method thereof | |
| CN106496446B (en) | A kind of method of expired HEA Material synthesis polycarboxylic acid slump retaining agent masterbatch |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 241000 room 208, building 1, No.9, Wanjiang Avenue, Jiangbei industrial concentration area, Jiujiang District, Wuhu City, Anhui Province Applicant after: Anhui Conch Material Technology Co.,Ltd. Address before: 241000 room 208, building 1, No.9, Wanjiang Avenue, Jiangbei industrial concentration area, Jiujiang District, Wuhu City, Anhui Province Applicant before: Anhui Conch New Materials Technology Co.,Ltd. |
|
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201127 |