CN115806648B - Polycarboxylate superplasticizer prepared from viscosity reducing macromonomer and preparation method thereof - Google Patents
Polycarboxylate superplasticizer prepared from viscosity reducing macromonomer and preparation method thereof Download PDFInfo
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- CN115806648B CN115806648B CN202211696504.2A CN202211696504A CN115806648B CN 115806648 B CN115806648 B CN 115806648B CN 202211696504 A CN202211696504 A CN 202211696504A CN 115806648 B CN115806648 B CN 115806648B
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- 230000001603 reducing effect Effects 0.000 title claims abstract description 31
- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 26
- 239000008030 superplasticizer Substances 0.000 title claims description 10
- 238000002360 preparation method Methods 0.000 title abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 46
- 239000000178 monomer Substances 0.000 claims abstract description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 14
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 239000010703 silicon Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 4
- -1 dimethylaminoethyl (methacrylate) propyltrimethoxysilane Chemical compound 0.000 claims description 17
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 229920001451 polypropylene glycol Polymers 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 6
- 239000012986 chain transfer agent Substances 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- POVITWJTUUJBNK-UHFFFAOYSA-N n-(4-hydroxyphenyl)prop-2-enamide Chemical compound OC1=CC=C(NC(=O)C=C)C=C1 POVITWJTUUJBNK-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-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
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-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
- 238000004321 preservation Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 2
- 150000002148 esters Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 10
- 239000004576 sand Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000004568 cement Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 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
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 125000003827 glycol group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical compound [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
- 230000001105 regulatory effect Effects 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
- 238000005204 segregation Methods 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
-
- 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
- C08F4/40—Redox systems
-
- 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
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention relates to a polycarboxylate water reducer prepared from a viscosity reducing macromonomer and a preparation method thereof, wherein the preparation raw materials of the polycarboxylate water reducer prepared from the viscosity reducing macromonomer comprise: 50-150 parts of viscosity reducing functional macromonomer; 50-150 parts of ether macromonomer; 1-10 parts of nitrogen-containing and silicon-containing functional monomer; 10-30 parts of unsaturated acid; and water; the structural formula of the viscosity reduction functional macromonomer is as follows:wherein R is 1 、R 2 Is H or CH 3 ；n 1 ＝5～32，n 2 =1 to 10. The polycarboxylic acid water reducer prepared from the viscosity reducing macromonomer is environment-friendly in production, can effectively reduce the viscosity of concrete, and improves the strength of the concrete.
Description
Technical Field
The invention relates to the technical field of concrete additives, in particular to a polycarboxylate water reducer prepared from viscosity reducing macromonomers and a preparation method thereof.
Background
In recent years, due to the shortage of river sand resources, for the purpose of environmental protection, a series of policies are put out of the country to encourage the development and application of machine-made sand, the natural sand proportion is reduced year by year, the machine-made sand proportion is improved year by year, and the national machine-made sand proportion is about 80 percent at present. Compared with natural sand, the machine-made sand is coarser in whole, has poorer grain composition, higher mud content and stone powder content, and larger machine-made sand difference in each region, the polycarboxylate water reducer in each region at present can basically meet the requirement of the basic performance of concrete, but the high-grade concrete is easy to have the phenomenon of high viscosity in the region with higher mud content and stone powder content.
The improvement of the grain composition mode of the superfine powder material is optimized, so that the cost is increased on one hand, and the viscosity reduction is not obviously improved on the other hand; through improving the mode of improving the mixing amount of the water reducer, the phenomenon that bleeding, segregation and the like are more unfavorable for pumping construction easily occurs.
In order to reduce the viscosity of high-grade concrete, the development of viscosity-reducing water reducers has been a research hotspot in the field of concrete water reducers in recent years. The viscosity-reducing water reducer generally has lower side chain length, lower molecular weight and lower HLB value, and can enable concrete to release more free water, thereby achieving the viscosity-reducing effect. In the application process of the viscosity-reducing water reducer, the viscosity-reducing water reducer has the advantages that when the mixing amount of the viscosity-reducing water reducer is low, the viscosity-reducing effect is not obvious, and in order to achieve a good viscosity-reducing effect, the mixing amount of the viscosity-reducing water reducer accounts for a large proportion of the total additive, so that the problems of large air content, low strength and the like easily occur.
Therefore, the viscosity-reducing water reducer has an excellent viscosity-reducing effect, can improve the workability of concrete, has small influence on strength, and has important significance for the production and development of high-grade concrete.
Disclosure of Invention
Based on this, it is necessary to provide a polycarboxylate water reducer prepared from a viscosity reducing macromer and a preparation method thereof.
In order to achieve the above object, the present invention provides a technical solution:
the polycarboxylate water reducer prepared from the viscosity reducing macromer comprises the following raw materials in parts by weight:
the structural formula of the viscosity reduction functional macromonomer is as follows:
wherein R is 1 、R 2 Is H or CH 3 ；n 1 ＝5～32，n 2 ＝1～10。
Specifically, the viscosity reduction functional macromonomer is prepared by esterifying hydroxyalkylacrylamide and polypropylene glycol polyethylene glycol, and the mol ratio of unsaturated alkoxybenzoic acid to methoxy polypropylene glycol polyethylene glycol is (1.05-1.1): 1.
Specifically, the hydroxyalkyl acrylamide comprises at least one of 4-hydroxy-2-methylacrylamide and N-p-hydroxyphenyl acrylamide.
Specifically, the molecular weight of the viscosity reduction functional macromonomer is 500-1500.
The ether macromonomer comprises at least one of methyl allyl polyoxyethylene ether and isopentenyl polyoxyethylene ether, and the molecular weight of the ether macromonomer is 2400.
Specifically, the structure of the nitrogen-containing silicon-containing monomer is as follows:
wherein the R is 3 Is H or CH 3 ；R 4 Is (CH) 2 )y，1≤y≤3；R 5 Is (CH) 2 )z，1≤z≤3；R 6 、R 7 、R 8 Is CH 3 Or CH (CH) 2 CH 3 。
Specifically, the nitrogen-containing silicon-containing monomer includes at least one of (dimethylaminoethyl methacrylate) -propyltrimethoxysilane, (dimethylaminoethyl methacrylate) -propyltriethoxysilane, (dimethylaminomethyl methacrylate) -propyltrimethoxysilane, (dimethylaminomethyl methacrylate) -propyltriethoxysilane, (dimethylaminoethyl methacrylate) -propyltrimethoxysilane, (dimethylaminoethyl methacrylate) -ethyltrimethoxysilane and (dimethylaminoethyl methacrylate) -butyltrimethoxysilane.
Specifically, the unsaturated acid includes at least one of acrylic acid, methacrylic acid, maleic anhydride, and itaconic acid.
Specifically, the preparation raw materials of the polycarboxylate water reducer prepared from the viscosity reducing macromer further comprise, in parts by weight:
1-5 parts of oxidant;
0.2 to 1.5 portions of reducing agent; and
0.5 to 1.5 parts of chain transfer agent.
More specifically, the oxidizing agent includes at least one of hydrogen peroxide, sodium persulfate, and ammonium persulfate.
The reducing agent includes at least one of ascorbic acid, sodium formaldehyde sulfoxylate, and Bruggolite FF6 (a boulgeman reducing agent).
The chain transfer agent includes at least one of mercaptoethanol, mercaptopropionic acid, and mercaptoacetic acid.
The invention also provides a preparation method of the polycarboxylate superplasticizer prepared from the viscosity reducing macromonomer, which comprises the following steps:
and stirring and mixing the viscosity reduction functional macromonomer, the ether macromonomer, the nitrogenous and siliceous functional monomer, the unsaturated acid and the water for reaction, and adding an alkali solution to adjust the pH value to 6-8 after the reaction is finished, thus obtaining the polycarboxylate water reducer prepared from the viscosity reduction macromonomer.
Specifically, the method comprises the following specific steps:
and placing the viscosity reduction functional macromonomer, the ether macromonomer and the water into a reactor, dropwise adding the nitrogenous and siliceous functional monomer, the unsaturated acid, the chain transfer agent, the oxidant and the reducing agent into the reactor, continuously carrying out heat preservation reaction after the dropwise addition, and adding alkali solution to adjust the pH value to 6-8 after the reaction is finished, thus obtaining the polycarboxylic acid water reducer prepared from the viscosity reduction macromonomer.
The invention has the beneficial effects that:
1. the viscosity reducing functional macromonomer A has shorter introduced length and has side chains of rigid benzene ring, ester group and methoxy polypropylene glycol polyethylene glycol group, the molecular space configuration of the water reducing agent can be regulated to be more stretched, a water film layer is formed to be thin, compact and firm, the hydrophilicity of the methoxy polypropylene glycol group is weaker, the water film layer has certain hydrophobicity at the outer edge, namely, when the water film layer acts in concrete, free water is released, and simultaneously, the water reducing agent also has lubricating effect, so that the viscosity reducing effect is more remarkable.
2. After the siloxane group introduced by the nitrogen-containing and silicon-containing functional monomer is hydrolyzed under alkaline conditions, the water reducer molecules can be firmly adsorbed on the surfaces of cement particles through the siloxane bond, and meanwhile, the introduced quaternary ammonium salt group and the siloxane group act synergistically, so that the hydration of cement is accelerated, and the strength of concrete is improved.
3. According to the invention, the large monomer A is introduced into the amide and the benzene ring to act synergistically with the nitrogen-containing and silicon-containing functional monomer, so that the strength of the concrete can be further improved.
4. The longer side chain is introduced through the ether monomer, so that the prepared high-workability polycarboxylate superplasticizer prepared from the viscosity-reducing macromonomer has a comb-shaped structure with alternate long and short side chains, the steric hindrance is not lost while the viscosity-reducing effect is ensured, and the polycarboxylate superplasticizer has a higher water-reducing rate while the viscosity-reducing effect is achieved.
5. The polycarboxylic acid water reducer prepared from the viscosity reducing macromonomer is environment-friendly in production, can effectively reduce the viscosity of concrete, and improves the strength of the concrete.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
In the examples, the test methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used are commercially available.
1. Preparation of viscosity-reducing functional macromonomer
In the following examples, the structural formula of the viscosity reducing functional macromonomer is as follows:
wherein R is 1 、R 2 Is H or CH 3 ；n 1 ＝5～32，n 2 ＝1～10。
The viscosity-reducing functional macromonomer is prepared by esterifying hydroxyalkyl acrylamide and polypropylene glycol polyethylene glycol, and is prepared from the hydroxyalkyl acrylamide and n of the viscosity-reducing functional monomer 1 And n 2 As shown in table 1.
TABLE 1
2. Preparation of viscosity-reducing polycarboxylate water reducer
The preparation method comprises the following steps:
placing the viscosity-reducing functional macromonomer A, the ether macromonomer B, the oxidant and the water which are prepared by esterification into a reactor, adding part of liquid alkali to adjust the pH value of the base solution to 8-9, respectively dripping the mixed solution of the unsaturated acid D and the nitrogen silicon-containing monomer C, the chain transfer agent solution and the reducer solution into the reactor within 2-3 hours, after finishing dripping, preserving heat for 1 hour, supplementing water, adding the liquid alkali to adjust the pH value to 7, and obtaining the polycarboxylic acid water reducer prepared by the viscosity-reducing macromonomer with 40% of solid content.
The preparation materials and the amounts of the preparation materials of the respective comparative examples are shown in Table 2 and Table 3.
TABLE 2
TABLE 3 Table 3
When the mixing amount of the water reducer is adjusted by adopting red lion cement to ensure that the expansion degree of the concrete is (600+/-10) mm, the performances of the water reducer prepared in examples 1-4 and comparative examples 1-3, such as initial and 1h slump, initial and 1h expansion degree, 0h inverted slump barrel emptying time, compressive strength of each age and the like, of the concrete are tested according to GB 8076-2008 concrete admixture.
The concrete mixing ratio is as follows: 360kg/m of cement 3 80kg/m of fly ash 3 60kg/m of mineral powder 3 750kg/m of sand 3 980kg/m stone 3 145kg/m of water 3 。
The formula of the additive is as follows: kejie group standard polycarboxylate water reducer Point-S: viscosity reduction type polycarboxylate water reducer=1:1 is compounded to prepare an external solution with the solid content of 15%.
The concrete test results are shown in table 4.
Table 4 results of concrete performance test
Comparative example 1 is a water reducing agent prepared by removing a viscosity reducing macromer and a nitrogen-containing silicon-containing functional monomer simultaneously on the basis of example 1; comparative example 2 is a water reducing agent prepared by removing the functional monomer containing nitrogen and silicon based on the example 1; comparative example 3 is a water reducing agent prepared by removing the viscosity reducing macromer based on example 1;
the test results of the combination of the example 1 and the comparative examples 1 to 3 show that the viscosity reducing macromer has the effect of obviously reducing the emptying time, the nitrogen-containing and silicon-containing functional monomer has the effect of improving the compressive strength, and the example 1 of the combination of the two functional monomers has the effect of synergistically improving the viscosity reducing and the strength.
The results of examples 1-4 show that the viscosity-reducing water reducer prepared by the method can improve the dispersibility and strength of concrete, and the viscosity-reducing effect is obvious.
It should be noted that the specific parameters or some reagents in the above embodiments are specific embodiments or preferred embodiments under the concept of the present invention, and are not limited thereto; and can be adaptively adjusted by those skilled in the art within the concept and the protection scope of the invention.
Claims (8)
1. The polycarboxylate water reducer prepared from the viscosity reducing macromer is characterized by comprising the following raw materials in parts by weight:
the structural formula of the viscosity reduction functional macromonomer is as follows:
wherein R is 1 、R 2 Is H or CH 3 ；n 1 ＝5～32，n 2 ＝1～10；
The structure of the nitrogen-containing and silicon-containing functional monomer is as follows:
wherein the R is 3 Is H or CH 3 ；R 4 Is (CH) 2 )y，1≤y≤3；R 5 Is (CH) 2 )z，1≤z≤3；R 6 、R 7 、R 8 Is CH 3 Or CH (CH) 2 CH 3 。
2. The polycarboxylate water reducer prepared from viscosity reducing macromonomer according to claim 1, wherein the viscosity reducing functional macromonomer is prepared by esterifying at least one of 4-hydroxy-2-methylacrylamide and N-p-hydroxyphenyl acrylamide with at least one of methoxypolypropylene glycol polyethylene glycol and polypropylene glycol polyethylene glycol, and the mole ratio (1.05-1.1) of the at least one of 4-hydroxy-2-methylacrylamide and N-p-hydroxyphenyl acrylamide to the at least one of methoxypolypropylene glycol polyethylene glycol and polypropylene glycol polyethylene glycol ester is 1.
3. The polycarboxylate superplasticizer prepared from a viscosity reducing macromer according to claim 1, wherein the molecular weight of said viscosity reducing functional macromer is 500-1500.
4. The polycarboxylate water reducer prepared from a viscosity reducing macromer according to claim 1, wherein said nitrogen-containing silicon-containing functional monomer comprises at least one of dimethylaminoethyl (methacrylate) propyltrimethoxysilane, (dimethylaminoethyl (methacrylate) propyltriethoxysilane, (dimethylaminomethyl (methacrylate) propyltrimethoxysilane, (dimethylaminomethyl (methacrylate)) propyltriethoxysilane, (dimethylaminoethyl (methacrylate)) ethyltrimethoxysilane and (dimethylaminoethyl) butyltrimethoxysilane.
5. The polycarboxylate water reducer prepared from viscosity reducing macromer according to claim 1, wherein said unsaturated acid comprises at least one of acrylic acid, methacrylic acid, maleic anhydride and itaconic acid.
6. The polycarboxylate superplasticizer prepared from a viscosity reducing macromer according to claim 1, wherein the polycarboxylate superplasticizer prepared from a viscosity reducing macromer further comprises, in parts by weight:
1-5 parts of oxidant;
0.2 to 1.5 portions of reducing agent; and
0.5 to 1.5 parts of chain transfer agent.
7. A method for preparing the polycarboxylate superplasticizer prepared from the viscosity reducing macromonomer according to any one of claims 1 to 6, comprising the steps of:
and stirring and mixing the viscosity reduction functional macromonomer, the ether macromonomer, the nitrogenous and siliceous functional monomer, the unsaturated acid and the water for reaction, and adding an alkali solution to adjust the pH value to 6-8 after the reaction is finished, thus obtaining the polycarboxylate water reducer prepared from the viscosity reduction macromonomer.
8. The method for preparing a polycarboxylate superplasticizer prepared from a viscosity reducing macromonomer according to claim 7, wherein the specific steps comprise:
and placing the viscosity reduction functional macromonomer, the ether macromonomer and the water into a reactor, dropwise adding the nitrogenous and siliceous functional monomer, the unsaturated acid, the chain transfer agent, the oxidant and the reducing agent into the reactor, continuously carrying out heat preservation reaction after the dropwise addition, and adding alkali solution to adjust the pH value to 6-8 after the reaction is finished, thus obtaining the polycarboxylic acid water reducer prepared from the viscosity reduction macromonomer.
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| PCT/CN2023/123950 WO2024139523A1 (en) | 2022-12-28 | 2023-10-11 | Polycarboxylate superplasticizer prepared from viscosity-reducing macromonomer and preparation method therefor |
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| WO2024139523A1 (en) | 2024-07-04 |
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