CN114213603B - Mud-resistant slow-release polycarboxylate superplasticizer and preparation method and application thereof - Google Patents
Mud-resistant slow-release polycarboxylate superplasticizer and preparation method and application thereof Download PDFInfo
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- CN114213603B CN114213603B CN202111641862.9A CN202111641862A CN114213603B CN 114213603 B CN114213603 B CN 114213603B CN 202111641862 A CN202111641862 A CN 202111641862A CN 114213603 B CN114213603 B CN 114213603B
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- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000008030 superplasticizer Substances 0.000 title claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 101
- 239000000178 monomer Substances 0.000 claims abstract description 81
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 78
- 239000004567 concrete Substances 0.000 claims abstract description 40
- 239000002994 raw material Substances 0.000 claims abstract description 23
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000004568 cement Substances 0.000 claims abstract description 16
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 12
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims abstract description 11
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229930003268 Vitamin C Natural products 0.000 claims abstract description 11
- SXQFCVDSOLSHOQ-UHFFFAOYSA-N lactamide Chemical compound CC(O)C(N)=O SXQFCVDSOLSHOQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 11
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000019154 vitamin C Nutrition 0.000 claims abstract description 11
- 239000011718 vitamin C Substances 0.000 claims abstract description 11
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 claims abstract description 10
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims abstract description 10
- 235000004279 alanine Nutrition 0.000 claims abstract description 10
- WCASXYBKJHWFMY-UHFFFAOYSA-N crotyl alcohol Chemical compound CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 claims abstract description 5
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical group [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 8
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 claims description 6
- KUQWZSZYIQGTHT-UHFFFAOYSA-N hexa-1,5-diene-3,4-diol Chemical compound C=CC(O)C(O)C=C KUQWZSZYIQGTHT-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 238000010276 construction Methods 0.000 claims description 5
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 5
- UCGQKUWLZIMXSV-UHFFFAOYSA-N cyclohex-3-ene-1,1,2,2-tetrol Chemical compound OC1(O)CCC=CC1(O)O UCGQKUWLZIMXSV-UHFFFAOYSA-N 0.000 claims description 4
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 4
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 239000000654 additive Substances 0.000 abstract description 5
- 230000009467 reduction Effects 0.000 abstract description 5
- 230000014759 maintenance of location Effects 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000203 mixture Substances 0.000 description 13
- 238000013268 sustained release Methods 0.000 description 9
- 239000012730 sustained-release form Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 238000009472 formulation Methods 0.000 description 6
- 238000011534 incubation Methods 0.000 description 6
- 239000004615 ingredient Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 description 5
- 239000004576 sand Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229920000858 Cyclodextrin Polymers 0.000 description 3
- 239000001116 FEMA 4028 Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229960004853 betadex Drugs 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- -1 polyoxyethylene methacrylate Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011150 reinforced concrete Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 1
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004574 high-performance concrete Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000728 polyester Chemical group 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 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
- 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
-
- 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)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention belongs to the field of concrete additives, and particularly relates to an anti-mud slow-release type polycarboxylate superplasticizer, a preparation method and application thereof. The mud-resistant slow-release polycarboxylate water reducer is prepared from the following raw materials in parts by mass: 280-330 parts of methyl allyl alcohol polyoxyethylene ether, 35-45 parts of acrylic acid, 1-3 parts of hydroxypropyl acrylate, 0.5-1.5 parts of modified functional monomer, 0.05-0.30 part of slow-release functional monomer, 0.5-1.0 part of vitamin C, 1-5 parts of hydrogen peroxide and 1-5 parts of chain transfer agent; wherein the modified functional monomer is prepared from dimethylaminoethyl acrylate, unsaturated polyhydroxy monomers and alanine; the slow release functional monomer is prepared from maleic anhydride, lactoyl ammonia and concentrated sulfuric acid. The mud-resistant slow-release polycarboxylate water reducer has the functions of high water reduction, high slump retention, good mud resistance effect and the like, can slowly release active water reducer molecules, continuously plays a role in dispersing cement particles, and keeps the slump of concrete.
Description
Technical Field
The invention belongs to the field of concrete additives, and particularly relates to an anti-mud slow-release type polycarboxylate superplasticizer, a preparation method and application thereof.
Background
The reinforced concrete urban forest is placed in the reinforced concrete urban forest, the urban forest which is erected by the high-rise building is not separated from the concrete, the concrete and products thereof make great contribution to the urban development, and along with the continuous progress of the age, the concrete plays a significant role in the urban development. However, in concrete transportation and construction, the condition that the slump loss of fresh concrete is too fast is frequently encountered, so that a lot of inconvenience is brought to engineering construction and concrete engineering quality control, and a great demand is brought to the slump retaining capacity of the concrete.
Meanwhile, as the national importance of ecological environment protection is increased, machine-made sand gradually enters the market, so that the mud content in concrete is higher and higher, and the slump retaining performance requirement of the concrete additive is more severe. The polycarboxylate water reducer is a high-performance concrete additive, and has been widely applied to the middle-low grade ready-mixed concrete industry due to the advantages of low mixing, high water reduction, green environment protection, strong functionality and the like. However, polycarboxylate water reducers are particularly sensitive to the mud content in the aggregate, because clay in the soil can adsorb a large amount of polycarboxylic acid molecules, resulting in a reduction of the effective water reducer molecules in the cement paste, thereby greatly reducing the workability of the concrete. At present, the method of washing aggregate, super-doping water reducer, adding anti-mud sacrificial agent and the like is generally adopted for aggregate with higher mud content in engineering to reduce the influence of clay on the working performance of concrete, but the measures increase the manufacturing cost of concrete or possibly increase the risk of engineering problems.
Patent application CN107090062A discloses a slow-release polycarboxylate superplasticizer and a preparation method thereof, and the specific operation is as follows: and (3) mixing and stirring the polyether macromonomer solution and an initiator to obtain a first mixed solution, dropwise adding a second mixed solution (150-200 min) consisting of a reducing agent, a chain transfer agent and water and a third mixed solution (120-180 min) consisting of unsaturated carboxylic acid, a carboxylic acid protecting monomer and water into the mixed solution in a batch feeding mode, continuing to react for 40-120min after the dripping is finished, and supplementing water to adjust the concentration. The slow-release polycarboxylate water reducer prepared by the process has relatively long slow-release time, can maintain high slump for a long time, and still has the problems of complicated process steps, long production period and the like.
Patent CN104861127B discloses a preparation method and application of an anti-mud type polycarboxylate superplasticizer. Is prepared by copolymerization of the polyoxyethylene methacrylate, maleic anhydride-beta-cyclodextrin, acrylic acid and styryl formate in aqueous solution. The method introduces the beta-cyclodextrin into the polycarboxylic acid product, has a cup-shaped molecular structure, has good mud resistance and time-lapse plastic retention, and is environment-friendly in production process. However, the synthesis conversion rate of the maleic anhydride-beta cyclodextrin monomer in the reaction is low, the polymerization activity is poor, and the styryl formate monomer is difficult to dissolve into a water phase system, so that the polymerization controllability is poor, and the precipitation is easy.
The slow-release type or anti-mud type polycarboxylate superplasticizer is prepared by different methods, but the comprehensive effect is not ideal, and the problems of complex process steps, high cost, harsh synthesis conditions and the like exist, so that the preparation method is not beneficial to large-scale production and application.
Disclosure of Invention
Aiming at the problems of the existing polycarboxylate water reducer, the invention aims to provide the mud-resistant slow-release polycarboxylate water reducer with better comprehensive performance, as well as the preparation method and application thereof, and the synthesized mud-resistant slow-release polycarboxylate water reducer has the functions of high water reduction, high slump loss resistance, good mud resistance effect and the like, can slowly release active water reducer molecules, continuously plays a role in dispersing cement particles, keeps concrete slump, and has the advantages of simple preparation method and low industrial popularization cost.
In order to achieve the above purpose, the main technical scheme adopted by the invention comprises the following steps:
in a first aspect, the invention provides an anti-mud slow-release polycarboxylate water reducer, which is prepared from the following raw materials in parts by mass: 280-330 parts of methyl allyl alcohol polyoxyethylene ether, 35-45 parts of acrylic acid, 1-3 parts of hydroxypropyl acrylate, 0.5-1.5 parts of modified functional monomer, 0.05-0.30 part of slow-release functional monomer, 0.5-1.0 part of vitamin C, 1-5 parts of hydrogen peroxide and 1-5 parts of chain transfer agent; wherein,,
the modified functional monomer is prepared from dimethylaminoethyl acrylate, unsaturated polyhydroxy monomers and alanine;
the slow-release functional monomer is prepared from maleic anhydride, lactoyl ammonia and concentrated sulfuric acid.
As a further embodiment of the present invention, the preparation method of the modified functional monomer comprises the following steps:
taking the dimethylaminoethyl acrylate, the unsaturated polyhydroxy monomer and the alanine as raw materials according to the mol ratio of 1-1.5: 1.5 to 2.5: 8-10, distilling under reduced pressure for 6-8 h at 120-130 ℃, crystallizing with acetone, and drying to obtain an intermediate;
adding the intermediate into 50-60 wt% isopropanol solution, adding 0.5-1.5 times of bromoethane with the molar weight of unsaturated polyhydroxy monomer, stirring for reaction for 3-6 h, decompressing, distilling, washing, suction filtering, cooling filtrate to separate out crystals, and then vacuum drying to obtain the modified functional monomer.
As a further embodiment of the present invention, the unsaturated polyhydroxy monomer is one or more of butenediol, 1, 5-hexadiene-3, 4-diol, and cyclohexene tetraol.
As a further embodiment of the present invention, the preparation method of the slow release functional monomer comprises the following steps:
the molar ratio is 10:10: and 3, weighing the maleic anhydride, the lactoyl ammonia and the concentrated sulfuric acid, mixing, carrying out constant-temperature reaction for 3-4 hours at 80-100 ℃ under the protection of nitrogen, and cooling to 40-50 ℃ after the reaction is finished to obtain the slow-release functional monomer.
In the above steps, maleic anhydride, the lactoyl ammonia and the concentrated sulfuric acid are subjected to a constant temperature reaction in a reactor equipped with a condensing device (the reaction temperature is controlled to 40 ℃ C. To 50 ℃ C.).
As a further embodiment of the present invention, the chain transfer agent is one or more of thioglycolic acid, mercaptopropionic acid, and mercaptoethanol.
In a second aspect, the invention provides a preparation method of the mud-resistant slow-release polycarboxylate superplasticizer, which comprises the following steps:
s1, weighing the raw material components according to the parts by weight;
s2, adding the methallyl alcohol polyoxyethylene ether and the hydrogen peroxide into water, stirring and dissolving to prepare a solution A;
s3, adding the acrylic acid and the hydroxypropyl acrylate into water, and stirring and dissolving to prepare a solution B;
s4, adding the modified functional monomer and the slow-release functional monomer into water, and stirring and dissolving to prepare a solution C;
s5, adding the chain transfer agent and the vitamin C into water, and stirring and dissolving to obtain a solution D;
s6, simultaneously dropwise adding the solution B, the solution C and the solution D into the solution A at normal temperature, after the dropwise adding is finished, preserving heat for 1-2 h, adding alkali to adjust the pH value to 6-8 after the preserving heat is finished, and adding water to adjust the solid content of the solution to 50%, thereby obtaining the mud-resistant slow-release polycarboxylate water reducer.
In the above step, the alkali is sodium hydroxide solution.
In a third aspect, the invention provides an application of the mud-resistant slow-release polycarboxylate superplasticizer of the first aspect in cement/concrete engineering construction.
The mud-resistant slow-release type polycarboxylate water reducer provided by the invention is used as an additive in cement and concrete construction, effectively improves the working performance of cement and concrete, can achieve better mud-resistant and slow-release effects under low doping amount, has higher water-reducing rate, and can maintain excellent slump retention, so that the mud-resistant slow-release type polycarboxylate water reducer provided by the invention has excellent comprehensive performance, is convenient to manufacture and has low cost.
The application method of the mud-resistant slow-release polycarboxylate water reducer is the same as that of a commercial water reducer product, the folding and solidifying mixing amount is 0.05-0.25% of the total cementing material mass, and the optimal dosage can be determined by carrying out a concrete pre-mixing experiment according to actual engineering requirements.
According to the requirement of maintaining the workability of concrete, the mud-resistant slow-release type polycarboxylate water reducer can be used singly or after being compounded with other water reducers (such as polycarboxylate water reducer, lignosulfonate water reducer, naphthalene high-efficiency water reducer and the like) and small materials (such as air entraining agents, expanding agents, early strength agents, tackifiers, viscosity reducers, shrinkage reducers, defoamers and other functional additives), and can play a role in good performance superposition.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the modified functional monomer is introduced into the mud-resistant slow-release type polycarboxylate water reducer, and the unsaturated polyhydroxy monomer is modified to obtain the quaternary ammonium salt functional group, so that a better mud-resistant function is obtained, the ineffective adsorption of a mud-containing material to the water reducer can be effectively reduced, the doping amount of the water reducer is reduced, the working performance of concrete is improved, and the engineering cost is reduced;
(2) According to the invention, the slow-release functional monomer with amide groups and polyester groups is introduced into the mud-resistant slow-release polycarboxylate water reducer, so that the effective adsorbed groups can be continuously released under alkaline conditions, thereby improving the slow-release capacity and simultaneously improving the stability and fluidity of cement paste;
(3) According to the preparation method, the mud-resistant slow-release polycarboxylate water reducer is synthesized by carrying out free radical polymerization reaction on methyl allyl alcohol polyoxyethylene ether, acrylic acid, hydroxypropyl acrylate, a modified functional monomer and a slow-release functional monomer under the action of a redox system of hydrogen peroxide and vitamin C and chain transfer. The preparation method is simple in process and low in industrialized popularization cost, and the synthesized mud-resistant slow-release polycarboxylate water reducer has the functions of high water reduction, high slump loss resistance, good mud resistance effect and the like, can slowly release active water reducer molecules, continuously plays a role in dispersing cement particles, and keeps the slump of concrete.
The foregoing summary is an overview of the present application and is provided to enable one of ordinary skill in the art to make and use the present application and other objects, features and advantages thereof as described in the written description.
Detailed Description
In order to describe the technical content, constructional features, achieved objects and effects of the technical solution in detail, the following description is made in detail with reference to specific embodiments. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are provided, but the protection scope of the present invention is not limited to the following embodiments.
The test materials, reagents and the like used in the examples described below are commercially available unless otherwise specified. The experimental methods in the following examples are conventional methods unless otherwise specified.
Example 1 mud-resistant slow-release polycarboxylate superplasticizer 1
1. Raw materials
The formulation table of the mud-resistant slow-release polycarboxylate superplasticizer of this example is shown in table 1.
Table 1 dosing table for mud-resistant slow-release polycarboxylate water reducer 1
| Raw materials | Parts by weight |
| Methallyl alcohol polyoxyethylene ether | 280 |
| Acrylic acid | 38 |
| Hydroxypropyl acrylate | 1.5 |
| Modified functional monomer | 0.8 |
| Sustained release functional monomer | 0.15 |
| Vitamin C | 0.6 |
| Hydrogen peroxide | 2 |
| Thioglycollic acid (chain transfer agent) | 2 |
2. The preparation method comprises the following steps:
(1) Preparation of modified functional monomer: taking dimethylaminoethyl acrylate, butenediol and alanine as raw materials according to a mole ratio of 1:2:10, distilling for 6 hours under reduced pressure at 120 ℃, crystallizing with acetone, drying to obtain an intermediate, adding the intermediate into 50wt% isopropanol solution, adding bromoethane with 0.7 times of the molar quantity of butenediol, stirring and reacting for 3 hours, distilling under reduced pressure, washing and filtering, cooling filtrate to separate out crystals, and then drying in vacuum to obtain the modified functional monomer.
(2) The preparation method of the slow-release functional monomer comprises the following steps: the molar ratio is 10:10: and 3, weighing maleic anhydride, lactoyl ammonia and concentrated sulfuric acid, mixing, adding the mixture into a reactor provided with a condensing device, carrying out constant-temperature reaction for 3 hours at 100 ℃ under the protection of nitrogen, and cooling to 45 ℃ after the reaction is finished to prepare the slow-release functional monomer.
(3) And (3) preparing the mud-resistant slow-release polycarboxylate water reducer:
s1, weighing the raw material components according to the parts by weight;
s2, adding methyl allyl alcohol polyoxyethylene ether and hydrogen peroxide into water, stirring and dissolving to prepare a solution A;
s3, adding acrylic acid and hydroxypropyl acrylate into water, stirring and dissolving to prepare a solution B;
s4, adding the modified functional monomer and the sustained-release functional monomer into water, stirring and dissolving to prepare a solution C;
s5, adding a chain transfer agent and vitamin C into water, stirring and dissolving to prepare a solution D;
s6, dropwise adding the solution B, the solution C and the solution D into the solution A at normal temperature, keeping the temperature for 1.5h after the dropwise adding is finished, adding alkali to adjust the pH value to 6 after the heat preservation is finished, and adding water to adjust the solid content of the solution to 50%, thus obtaining the mud-resistant slow-release polycarboxylate superplasticizer 1.
Example 2 mud-resistant slow-release polycarboxylate superplasticizer 2
1. Raw materials
The formulation table of the mud-resistant slow-release polycarboxylate superplasticizer of this example is shown in table 2.
Table 2 compounding table of mud-resistant slow-release type polycarboxylate water reducer 2
| Raw materials | Parts by weight |
| Methallyl alcohol polyoxyethylene ether | 290 |
| Acrylic acid | 39 |
| Hydroxypropyl acrylate | 1.5 |
| Modified functional monomer | 0.8 |
| Sustained release functional monomer | 0.1 |
| Vitamin C | 0.6 |
| Hydrogen peroxide | 2.5 |
| Thioglycollic acid (chain transfer agent) | 2 |
2. The preparation method comprises the following steps:
(1) Preparation of modified functional monomer: taking dimethylaminoethyl acrylate, 1, 5-hexadiene-3, 4-diol and alanine as raw materials according to the mole ratio of 1:2:10, distilling for 6 hours under reduced pressure at 120 ℃, crystallizing with acetone, drying to obtain an intermediate, adding the intermediate into 50wt% isopropanol solution, adding bromoethane with the molar quantity of 0.7 times of 1, 5-hexadiene-3, 4-diol, stirring for reacting for 3 hours, distilling under reduced pressure, washing and filtering, cooling filtrate to separate out crystals, and then drying in vacuum to obtain the modified functional monomer.
(2) The preparation method of the slow-release functional monomer comprises the following steps: the molar ratio is 10:10: and 3, weighing maleic anhydride, lactoyl ammonia and concentrated sulfuric acid, mixing, adding the mixture into a reactor provided with a condensing device, carrying out constant-temperature reaction for 3 hours at 100 ℃ under the protection of nitrogen, and cooling to 45 ℃ after the reaction is finished to prepare the slow-release functional monomer.
(3) And (3) preparing the mud-resistant slow-release polycarboxylate water reducer: the procedure was as in example 1.
Example 3 mud-resistant slow-release polycarboxylate superplasticizer 3
1. Raw materials
The formulation table of the mud-resistant slow-release polycarboxylate superplasticizer of this example is shown in table 3.
Table 3 dosing table for mud-resistant slow release polycarboxylate water reducer 3
2. The preparation method comprises the following steps:
(1) Preparation of modified functional monomer: taking dimethylaminoethyl acrylate, cyclohexene tetraol and alanine as raw materials according to a mole ratio of 1:2:10, distilling for 8 hours under reduced pressure at 130 ℃, crystallizing with acetone, drying to obtain an intermediate, adding the intermediate into 60wt% isopropanol solution, adding bromoethane with the molar quantity of 1.5 times of cyclohexene tetraol, stirring and reacting for 6 hours, distilling under reduced pressure, washing and suction filtering, cooling and separating out crystals from filtrate, and then drying in vacuum to obtain the modified functional monomer.
(2) The preparation method of the slow-release functional monomer comprises the following steps: the molar ratio is 10:10: and 3, weighing maleic anhydride, lactoyl ammonia and concentrated sulfuric acid, mixing, adding the mixture into a reactor provided with a condensing device, carrying out constant-temperature reaction for 4 hours at 80 ℃ under the protection of nitrogen, and cooling to 45 ℃ after the reaction is finished to prepare the slow-release functional monomer.
(3) And (3) preparing the mud-resistant slow-release polycarboxylate water reducer: the procedure was as in example 1, except that the incubation time was 2h and the pH was adjusted to 7 by the addition of alkali after the incubation was completed.
Example 4 mud-resistant slow-release polycarboxylate water reducer 4
1. Raw materials
The formulation table of the mud-resistant slow-release polycarboxylate superplasticizer of this example is shown in table 4.
Table 4 dosing table for mud-resistant slow release polycarboxylate water reducer 4
| Raw materials | Parts by weight |
| Methallyl alcohol polyoxyethylene ether | 310 |
| Acrylic acid | 41 |
| Hydroxypropyl acrylate | 2 |
| Modified functional monomer | 0.9 |
| Sustained release functional monomer | 0.2 |
| Vitamin C | 0.7 |
| Hydrogen peroxide | 3.5 |
| Mercaptoethanol (chain transfer agent) | 3 |
2. The preparation method comprises the following steps:
(1) Preparation of modified functional monomer: taking dimethylaminoethyl acrylate, 1, 5-hexadiene-3, 4-diol and alanine as raw materials according to the mole ratio of 1:2:10, distilling for 7h under reduced pressure at 125 ℃, crystallizing with acetone, drying to obtain an intermediate, adding the intermediate into 55wt% isopropanol solution, adding 1.0 times of bromoethane with the molar quantity of 1, 5-hexadiene-3, 4-diol, stirring for reacting for 4.5h, distilling under reduced pressure, washing and filtering, cooling the filtrate to separate out crystals, and then drying in vacuum to obtain the modified functional monomer.
(2) The preparation method of the slow-release functional monomer comprises the following steps: the molar ratio is 10:10: and 3, weighing maleic anhydride, lactoyl ammonia and concentrated sulfuric acid, mixing, adding the mixture into a reactor provided with a condensing device, carrying out constant-temperature reaction for 3.5 hours at 90 ℃ under the protection of nitrogen, and cooling to 45 ℃ after the reaction is finished to prepare the slow-release functional monomer.
(3) And (3) preparing the mud-resistant slow-release polycarboxylate water reducer: the procedure was as in example 1, except that the incubation time was 2h and the pH was adjusted to 8 by the addition of base after the incubation was completed.
Example 5 mud-resistant slow-release polycarboxylate superplasticizer 5
1. Raw materials
The formulation table of the mud-resistant slow-release polycarboxylate superplasticizer of this example is shown in table 4.
Table 4 dosing table for mud-resistant slow release polycarboxylate water reducer 4
| Raw materials | Parts by weight |
| Methallyl alcohol polyoxyethylene ether | 320 |
| Acrylic acid | 42 |
| Hydroxypropyl acrylate | 2 |
| Modified functional monomer | 0.9 |
| Sustained release functional monomer | 0.3 |
| Vitamin C | 0.7 |
| Hydrogen peroxide | 4 |
| Mercaptoethanol (chain transfer agent) | 3 |
2. The preparation method comprises the following steps:
(1) Preparation of modified functional monomer: taking dimethylaminoethyl acrylate, butenediol and alanine as raw materials according to a mole ratio of 1:2:10, distilling for 8 hours under reduced pressure at 130 ℃, crystallizing with acetone, drying to obtain an intermediate, adding the intermediate into 60wt% isopropanol solution, adding bromoethane with 1.5 times of the molar quantity of butenediol, stirring and reacting for 6 hours, distilling under reduced pressure, washing and filtering, cooling filtrate to separate out crystals, and drying in vacuum to obtain the modified functional monomer.
(2) The preparation method of the slow-release functional monomer comprises the following steps: the molar ratio is 10:10: and 3, weighing maleic anhydride, lactoyl ammonia and concentrated sulfuric acid, mixing, adding the mixture into a reactor provided with a condensing device, carrying out constant-temperature reaction for 3.5 hours at 90 ℃ under the protection of nitrogen, and cooling to 45 ℃ after the reaction is finished to prepare the slow-release functional monomer.
(3) And (3) preparing the mud-resistant slow-release polycarboxylate water reducer: the procedure was as in example 1, except that the incubation time was 2h and the pH was adjusted to 7.5 by the addition of base after the incubation was completed.
Comparative example 1
Compared with the example 1, the water reducer in the comparative example does not contain a modified functional monomer and a slow release functional monomer in the ingredients; the other ingredients and the addition amounts were the same as in example 1. The preparation method of the water reducer in this comparative example is the same as the method step of example 1, except that the preparation and dropping of the solution C are omitted. The prepared water reducer sample is marked as water reducer A.
Comparative example 2
Compared with the example 1, the water reducer in the comparative example does not contain a modified functional monomer in the ingredients; the other ingredients and the addition amounts were the same as in example 1. The preparation method of the water reducer in this comparative example was the same as the method step of example 1, except that no modifying functional monomer was added. The prepared water reducer sample is marked as water reducer B.
Comparative example 3
Compared with the example 1, the water reducer in the comparative example does not contain slow-release functional monomers in the ingredients; the other ingredients and the addition amounts were the same as in example 1. The preparation method of the water reducer in this comparative example is the same as the method step of example 1, except that no slow-release functional monomer is added. The prepared water reducer sample is marked as water reducer C.
Comparative example 4
A commercial anti-mud polycarboxylate water reducer sample, point-T.
Comparative example 5
A commercial slow-release polycarboxylate water reducer sample, point-S.
Experimental example 1 net pulp fluidity test
In order to examine the dispersion performance and dispersion retention performance of the mud-resistant slow-release polycarboxylate water reducer prepared by the invention, cement paste fluidity test is carried out on the mud-resistant slow-release polycarboxylate water reducer samples synthesized in examples 1 to 5 and the samples of comparative examples 1 to 5 by referring to the regulations in GB/T8077-2012 "concrete admixture homogeneity test method", 300g of P.I 42.5.5 standard cement (GB-8076-2008 standard) is adopted, 87g of water is added, the cement paste fluidity is tested after stirring uniformly for 30s on a glass plate, the paste fluidity is tested for 60min, 120min and 180min, the fixed cement/water ratio is 0.29, the refraction and fixation mixing amount of the water reducer is 0.10%, and the test results are shown in Table 6.
TABLE 6 Cement paste fluidity test results
As can be seen from the comparison of Table 6, the mud-resistant slow-release polycarboxylate water reducer prepared in accordance with the above examples 1 to 5 is advantageous in slow-release property as compared with the commercially available water reducer products. Meanwhile, compared with comparative examples 1 to 3, in the water reducer samples prepared in examples 1 to 5, the addition of the modified functional monomer and the sustained-release functional monomer can obviously improve the mud resistance effect and the sustained-release effect of the water reducer.
Experimental example 2 concrete Performance test
The concrete performance test is carried out on the samples of the mud-resistant slow-release polycarboxylate water reducer synthesized in examples 1-5 and the samples of comparative examples 1-5, wherein P.O42.5R cement, machine-made sand with fineness modulus of 2.60, crushed stone with particle size of 5-20mm, class II fly ash, class S95 mineral powder are adopted, and the experimental temperature is 10 ℃ -40 ℃ (35 ℃ in the test). Concrete performance tests were conducted according to GB8076-2008 concrete admixture according to the concrete mix ratios shown in Table 7 using sand S1 (mud content 4.2%) and sand S2 (mud content 8.6%), respectively, and the test results are shown in tables 8 and 9.
TABLE 7 concrete test mix (kg/cm) 3 )
| Cement and its preparation method | Sand | Broken stone | Fly ash | Mineral powder | Water and its preparation method | Water reducing agent |
| 200 | 880 | 960 | 80 | 70 | 155 | 0.17 |
(1) Determination of concrete slump and expansion
Table 8 comparative table of slump loss resistance of concrete
As can be seen from the comparison of Table 8, the concrete water reducer prepared by using the different component formulations according to the above examples 1 to 5 has good slump retaining performance compared with the water reducer product purchased in the market, and can effectively reduce the slump/expansion loss of concrete with time. In addition, when the mud content is increased to 8.6 percent (S2), the concrete of the sample of the embodiment of the invention has no obvious change in the expansion degree and the slump and has good mud resistance effect. In addition, the addition of the modified functional monomer and the sustained-release functional monomer is beneficial to the mud resistance effect and the sustained-release effect.
(2) Determination of the strength of a concrete Structure
Table 9 comparison table of concrete structural strength
As can be seen from the comparison of Table 9, the concrete prepared by using the water reducer samples prepared in examples 1 to 5 and the water reducer products purchased in the market can meet the strength requirements.
In the present invention, when an equivalent, molar amount, or other value or parameter is expressed as a range, preferred range, or a range bounded by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when ranges of "1 to 5" are disclosed, the described ranges should be construed to include ranges of "1 to 4", "1 to 3", "1 to 2", "4 to 5", "3 to 5", and the like. When a numerical range is described herein, unless otherwise indicated, the range is intended to include its endpoints and all integers and fractions within the range.
It should be understood that the technical solution of the above embodiment, in which the amount of the raw materials or the reagents used in the above embodiment is expanded or reduced in equal proportion, is substantially the same as that of the above embodiment, and falls within the protection scope of the present invention.
It should be noted that, although the foregoing embodiments have been described herein, the scope of the invention is not limited thereto, and technical parameters that are not described in detail may still be the same as or similar to the above embodiments when they are changed within the scope of the invention, and still fall within the scope of the invention. Therefore, changes and modifications to the embodiments described herein, or equivalent structures or equivalent flow transformations by employing the principles of the present invention, based on the innovative concepts of the present invention, will be apparent to those skilled in the art and will be encompassed by the present invention as described herein.
Claims (7)
1. The mud-resistant slow-release polycarboxylate water reducer is characterized by being prepared from the following raw materials in parts by mass: 280-330 parts of methyl allyl alcohol polyoxyethylene ether, 35-45 parts of acrylic acid, 1-3 parts of hydroxypropyl acrylate, 0.5-1.5 parts of modified functional monomer, 0.05-0.30 part of slow-release functional monomer, 0.5-1.0 part of vitamin C, 1-5 parts of hydrogen peroxide and 1-5 parts of chain transfer agent; wherein,,
the modified functional monomer is prepared from dimethylaminoethyl acrylate, unsaturated polyhydroxy monomers and alanine;
the slow-release functional monomer is prepared from maleic anhydride, lactoyl ammonia and concentrated sulfuric acid.
2. The mud-resistant slow-release polycarboxylate water reducer as claimed in claim 1, wherein the preparation method of the modified functional monomer comprises the following steps:
taking the dimethylaminoethyl acrylate, the unsaturated polyhydroxy monomer and the alanine as raw materials according to the mol ratio of 1-1.5: 1.5 to 2.5: 8-10, distilling under reduced pressure for 6-8 h at 120-130 ℃, crystallizing with acetone, and drying to obtain an intermediate;
adding the intermediate into 50-60 wt% isopropanol solution, adding 0.5-1.5 times of bromoethane with the molar weight of unsaturated polyhydroxy monomer, stirring for reaction for 3-6 h, decompressing, distilling, washing, suction filtering, cooling filtrate to separate out crystals, and then vacuum drying to obtain the modified functional monomer.
3. The mud-resistant slow-release polycarboxylate water reducer as claimed in claim 2, wherein the unsaturated polyhydroxy monomer is one or more of butylene glycol, 1, 5-hexadiene-3, 4-diol and cyclohexene tetraol.
4. The mud-resistant slow-release polycarboxylate water reducer as claimed in claim 1, wherein the preparation method of the slow-release functional monomer comprises the following steps:
the molar ratio is 10:10: and 3, weighing the maleic anhydride, the lactoyl ammonia and the concentrated sulfuric acid, mixing, carrying out constant-temperature reaction for 3-4 hours at 80-100 ℃ under the protection of nitrogen, and cooling to 40-50 ℃ after the reaction is finished to obtain the slow-release functional monomer.
5. The mud-resistant slow-release polycarboxylate water reducer as claimed in claim 1, wherein the chain transfer agent is one or more of thioglycollic acid, mercaptopropionic acid and mercaptoethanol.
6. A method for preparing the mud-resistant slow-release polycarboxylate superplasticizer as described in any one of claims 1 to 5, characterized by comprising the steps of:
s1, weighing the raw material components according to the parts by weight;
s2, adding the methallyl alcohol polyoxyethylene ether and the hydrogen peroxide into water, stirring and dissolving to prepare a solution A;
s3, adding the acrylic acid and the hydroxypropyl acrylate into water, and stirring and dissolving to prepare a solution B;
s4, adding the modified functional monomer and the slow-release functional monomer into water, and stirring and dissolving to prepare a solution C;
s5, adding the chain transfer agent and the vitamin C into water, and stirring and dissolving to obtain a solution D;
s6, dropwise adding the solution B, the solution C and the solution D into the solution A at normal temperature, keeping the temperature for 1-2 h after the dropwise adding is finished, adding alkali to adjust the pH value to 6-8 after the heat preservation is finished, and adding water to adjust the solid content of the solution to 40% -50% to obtain the mud-resistant slow-release polycarboxylate water reducer.
7. Use of the mud-resistant slow-release polycarboxylate water reducer according to any one of claims 1 to 5 in cement/concrete engineering construction.
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