CN115340640A - Preparation method of viscosity-reduction type solid polycarboxylate superplasticizer - Google Patents
Preparation method of viscosity-reduction type solid polycarboxylate superplasticizer Download PDFInfo
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- CN115340640A CN115340640A CN202110513990.9A CN202110513990A CN115340640A CN 115340640 A CN115340640 A CN 115340640A CN 202110513990 A CN202110513990 A CN 202110513990A CN 115340640 A CN115340640 A CN 115340640A
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- 239000007787 solid Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 229920005646 polycarboxylate Polymers 0.000 title claims description 39
- 239000008030 superplasticizer Substances 0.000 title claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 63
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 52
- 239000002253 acid Substances 0.000 claims abstract description 51
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 49
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 48
- 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 19
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 13
- 238000007259 addition reaction Methods 0.000 claims abstract description 7
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 7
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims description 53
- 239000002585 base Substances 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 22
- 239000003999 initiator Substances 0.000 claims description 20
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 20
- 239000012986 chain transfer agent Substances 0.000 claims description 19
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 10
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 10
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 10
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 8
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 7
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 7
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 7
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 5
- -1 diisocyanate compound Chemical class 0.000 claims description 5
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical class COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- IEVADDDOVGMCSI-UHFFFAOYSA-N 2-hydroxybutyl 2-methylprop-2-enoate Chemical compound CCC(O)COC(=O)C(C)=C IEVADDDOVGMCSI-UHFFFAOYSA-N 0.000 claims description 3
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004705 High-molecular-weight polyethylene Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 26
- 230000008569 process Effects 0.000 abstract description 14
- 230000008901 benefit Effects 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 5
- 238000001308 synthesis method Methods 0.000 abstract description 5
- 239000011259 mixed solution Substances 0.000 description 41
- 239000000243 solution Substances 0.000 description 30
- 239000004567 concrete Substances 0.000 description 26
- 229920000570 polyether Polymers 0.000 description 19
- 239000004721 Polyphenylene oxide Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 13
- 238000010276 construction Methods 0.000 description 10
- 230000009467 reduction Effects 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 230000001603 reducing effect Effects 0.000 description 8
- 238000012662 bulk polymerization Methods 0.000 description 6
- 239000004568 cement Substances 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 238000006053 organic reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- OSMSIOKMMFKNIL-UHFFFAOYSA-N calcium;silicon Chemical compound [Ca]=[Si] OSMSIOKMMFKNIL-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method 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
-
- 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
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
- C08G65/33348—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group
- C08G65/33355—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group cyclic
- C08G65/33358—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group cyclic aromatic
-
- 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
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)
- General Chemical & Material Sciences (AREA)
- Polyethers (AREA)
Abstract
The invention discloses a preparation method of a viscosity-reducing solid polycarboxylic acid water reducer, wherein the viscosity-reducing solid polycarboxylic acid water reducer is obtained by the steps of respectively carrying out addition reaction on small molecular weight polyethylene glycol monomethyl ether and large molecular weight polyethylene glycol monomethyl ether with diisocyanate compounds, and respectively polymerizing the obtained products with acrylic acid and hydroxyl-containing unsaturated monomers; the molecular weight of the small molecular weight polyethylene glycol monomethyl ether is 600-2000, and the molecular weight of the large molecular weight polyethylene glycol monomethyl ether is 2000-6000. Compared with the traditional method, the synthesis method has the advantages that the raw materials required by the reaction are common and easy to obtain, the whole synthesis process is simple, controllable, efficient and convenient, the steps used in the reaction are common operation processes, special operation or expensive auxiliaries are not needed, the reaction conditions are mild, and the process is green and environment-friendly, so that the industrial production is easy to realize; the synthesis process has no special requirements on equipment, has the advantages of strong molecular designability, controllable molecular weight, good performance and the like, and has good popularization potential and application value.
Description
Technical Field
The invention relates to the technical field of concrete admixtures, in particular to a preparation method of a viscosity-reducing solid polycarboxylic acid water reducer.
Background
The polycarboxylic acid water reducer (PC) serving as a fourth-generation high-performance water reducer has the advantages of high water reducing rate, low slump loss, low environmental load and the like, and is widely applied to key construction projects in some countries. The excellent performance of PC is mainly determined by the special molecular structure, the main chain, the branched chain and the anionic group of the PC can be adjusted by changing reaction raw materials, the molecular structure of the polycarboxylic acid high-performance water reducing agent is comb-shaped, the main chain is shorter, the side chain is longer, the main chain is generally a polyethylene chain, the side chain generally contains alkyl, carboxyl, sulfonic group, polyoxyalkyl, amide group and the like, the molecular structure has large spatial freedom degree, and each chain segment has strong designability. The polycarboxylate superplasticizer is used as a third-generation superplasticizer, is widely applied to the field of buildings due to the advantages of high water reduction, diversified performance, easy preparation and the like, is generally liquid with solid content of 10-60%, causes the increase of logistics cost due to long-distance transportation, and cannot be applied to special fields such as grouting materials; in addition, the viscosity of the existing polycarboxylic acid water reducing agent is high, so that the viscosity of the whole concrete is high in the preparation of high-admixture and low-cement-ratio concrete after the existing polycarboxylic acid water reducing agent is used, the construction process is troublesome, and the construction is not facilitated.
In order to solve the problem, researchers develop solid polycarboxylic acids, and at present, two main concepts of solid polycarboxylic acids are spray drying and free radical bulk polymerization, and the spray drying is a common method for preparing powder or solid polycarboxylic acid products at present. Patent CN 1095340A discloses a powdery early strength type polycarboxylate superplasticizer and a preparation method thereof, the invention introduces rigid groups and high molecular weight polyether chains into a polymerization system, and the rigid groups and the high molecular weight polyether chains are hybridized with calcium-silicon composite oxides to prepare polymers, and then the powdery early strength type polycarboxylate superplasticizer is prepared by a spray drying method. But the spray drying cost is low, and the traditional high-temperature powder spraying process for preparing the solid polycarboxylate superplasticizer has high energy consumption and is easy to agglomerate; the addition of other components prevents caking and enhances flow, but reduces the amount of active ingredient in the powder.
The free radical bulk polymerization method is another main solid polycarboxylic acid synthesis method, compared with an aqueous polycarboxylic acid product, the solid content is higher, even no solvent is added, and the reaction mechanism is similar to that of a liquid polycarboxylic acid product. The patent CN109928661A prepares a viscosity reduction type solid polycarboxylic acid water reducer by free radical bulk polymerization, and the viscosity reduction type solid polycarboxylic acid water reducer is prepared by carrying out free radical polymerization on an unsaturated polyoxyethylene ether macromonomer, an unsaturated small monomer, an initiator, a reducing agent and a chain transfer agent at 60-90 ℃, and has the advantage that solid polycarboxylic acid can be directly prepared without adding other components; patent CN109694446A discloses a method for synthesizing a solid polycarboxylic acid water reducing agent, which comprises the steps of preparing a phthalic acid mono-polyether ester from liquid polyether a and phthalic anhydride, mixing a part of the phthalic acid mono-polyether ester with an unsaturated polyether macromonomer to obtain a base solution, and dripping an initiator and a carboxylic acid monomer into the base solution respectively to obtain the solid polycarboxylic acid water reducing agent. The solid polycarboxylate superplasticizers are prepared by free radical bulk polymerization, the free radical bulk polymerization has the condition that the performance is inferior to that of a water reducer water aqua, the viscosity of a reaction system of the type is high, great test is provided for reaction transmission equipment, the problem that the molecular weight of a polymer is not easy to control due to the rise of the viscosity, and the like, and the quality of the polycarboxylate superplasticizers is adversely affected.
Disclosure of Invention
The invention overcomes the defects that in the prior art, the viscosity of the whole concrete is high due to high viscosity of a polycarboxylate superplasticizer, the whole concrete is prepared from a high admixture and low cement-to-cement ratio concrete after the polycarboxylate superplasticizer is used, so that the construction process is troublesome, the construction is not facilitated, and the structure and the functionality can not be adjusted according to actual requirements, and the like, and provides a preparation method of a viscosity-reducing solid polycarboxylate superplasticizer, which has the following specific technical scheme: a preparation method of a viscosity-reducing solid polycarboxylate superplasticizer comprises the following steps: the viscosity-reducing solid polycarboxylate superplasticizer is prepared by respectively carrying out addition reaction on two polyethylene glycol monomethyl ethers with different molecular weights and diisocyanate compounds, and polymerizing the obtained product with acrylic acid and hydroxyl-containing unsaturated monomers respectively; the polyethylene glycol monomethyl ethers with different molecular weights are respectively small molecular weight polyethylene glycol monomethyl ether and large molecular weight polyethylene glycol monomethyl ether, the molecular weight of the small molecular weight polyethylene glycol monomethyl ether is 600-2000, and the molecular weight of the large molecular weight polyethylene glycol monomethyl ether is 2000-6000.
The diisocyanate compound is any one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate, and the molar ratio of the diisocyanate compound to the polyethylene glycol monomethyl ether is (1 +/-0.05): 1.
The hydroxyl-containing unsaturated monomer is any one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate.
A preparation method of a viscosity-reducing solid polycarboxylic acid water reducer comprises the following specific process steps: (1) Carrying out addition reaction on diisocyanate compounds and small molecular weight polyethylene glycol monomethyl ether to obtain a component A1; (2) Carrying out addition reaction on diisocyanate compounds and high molecular weight polyethylene glycol monomethyl ether to obtain a component A2; (3) Adding a chain transfer agent and an initiator into a solvent, uniformly stirring to form a base solution, then mixing acrylic acid and a hydroxyl-containing unsaturated monomer, dropwise adding the mixture into the base solution, and vacuumizing the solvent after the reaction is finished to remove the solvent to obtain a component B; (4) And (3) uniformly mixing the component A1 prepared in the step (1) and the component A2 prepared in the step (2), adding the mixture into the component B obtained in the step (3), uniformly mixing and stirring, and condensing and slicing after the reaction is finished to obtain the viscosity-reducing solid polycarboxylic acid water reducer.
The reaction conditions in the step (1) and the step (2) are both reaction temperature of 50-120 ℃ and reaction time of 4-10 h.
In the reaction processes of the step (1) and the step (2), a catalyst is used, the catalyst is any one of triethylamine, triethylene diamine, dibutyltin dilaurate and tetraisobutyl titanate, and the dosage of the catalyst is 0.1-5% of the mole number of the small molecular weight polyethylene glycol monomethyl ether or the large molecular weight polyethylene glycol monomethyl ether.
The initiator in the step (3) is any one of azobisisobutyronitrile, ammonium persulfate and azobisisobutyramidine hydrochloride.
The chain transfer agent in the step (3) is mercaptoethanol or mercaptopropionic acid.
In the step (3), the molar ratio of acrylic acid to the hydroxyl group-containing unsaturated monomer is (3-8): 1.
The molar ratio of the initiator to the hydroxyl-containing unsaturated monomer in the step (3) is (0.02-0.04): 1.
The molar ratio of the chain transfer agent to the hydroxyl group-containing unsaturated monomer in the step (3) is (0.01-0.06): 1.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, a main chain molecule (component B) and a side chain molecule (component A1 and component A2) are respectively synthesized, and then the main chain and the side chain are combined through a simple and efficient organic reaction to prepare the polycarboxylic acid water reducer; the component A1 and the component A2 both adopt the same preparation method, two polyether molecules with different lengths are adopted to prepare the polycarboxylic acid water reducing agent, and the long-chain polyether and the short-chain polyether are matched on the main chain, so that the water reducing effect of the water reducing agent is ensured, and the viscosity of the water reducing agent molecules is reduced; the polycarboxylate superplasticizer prepared by the method has the advantages of easily-adjusted structure, easily-performed reaction and higher reaction yield; compared with free radical polymerization, the preparation method is not influenced by the polymerization activity of the monomers, the selection range of polyether molecules is expanded, and the synthesis method in the field of solid polycarboxylic acid is enriched;
2. according to the invention, two polyether molecules with different lengths are selected to prepare the polycarboxylic acid water reducer, so that the viscosity reduction performance and the water reduction effect of the water reducer can be enhanced; the water reducer prepared by singly using the large-molecular-weight polyethylene glycol monomethyl ether as a raw material has a good water reducing effect, but the viscosity of the water reducer is too poor, so that the construction of commercial concrete is not facilitated; the water reducer prepared by singly using the small-molecular-weight polyethylene glycol monomethyl ether as the raw material has a good viscosity reduction effect, but the water reducer has a poor water reduction effect and is not beneficial to the construction of commercial concrete; according to the invention, through the matching of long-chain polyether and short-chain polyether, the water reducer has a good water reducing effect and can effectively reduce the viscosity of concrete.
3. According to the invention, the polycarboxylic acid water reducer is prepared by adopting an organic reaction, so that the problems that the molecular weight of the bulk free radical polymerization is not easy to control and the like are avoided under the condition of ensuring environmental protection and no pollution, the performance of the prepared water reducer is superior to that of the water reducer prepared by bulk polymerization, and the structural property and the functionality can be adjusted according to actual needs; meanwhile, the preparation process is green and environment-friendly, and is obviously beneficial to large-scale industrial production.
Compared with the traditional method, the synthesis method has the advantages that the raw materials required by the reaction are common and easy to obtain, the whole synthesis process is simple, controllable, efficient and convenient, the steps used in the reaction are common operation processes, special operation or expensive auxiliaries are not needed, the reaction conditions are mild, and the process is green and environment-friendly, so that the industrial production is easy to realize; the synthesis process has no special requirements on equipment, has the advantages of strong molecular designability, controllable molecular weight, good performance and the like, and has good popularization potential and application value.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
a preparation method of a viscosity-reducing solid polycarboxylic acid water reducer comprises the following steps:
(1) Uniformly mixing 87g of toluene diisocyanate and 6g of dibutyltin dilaurate to obtain a mixed solution, then adding 300g of polyethylene glycol monomethyl ether with the molecular weight of 600 into the mixed solution, and reacting for 4 hours at the temperature of 50 ℃ until the reaction is finished to obtain a component A1;
(2) Uniformly mixing 87g of toluene diisocyanate and 12g of dibutyltin dilaurate to obtain a mixed solution, then adding 3000g of polyethylene glycol monomethyl ether with the molecular weight of 6000 into the mixed solution, and reacting for 4 hours at the temperature of 50 ℃ until the reaction is finished to obtain a component A2;
(3) Adding 4.68g of chain transfer agent mercaptoethanol and 3.28g of initiator azobisisobutyronitrile into 332g of tetrahydrofuran, uniformly stirring to form a base solution, then mixing 216g of acrylic acid and 116g of hydroxyethyl acrylate, slowly dropwise adding into the base solution, controlling the dropwise adding time to be 2h, reacting for 1h at 65 ℃ and stopping the reaction, and vacuumizing and removing the solvent to prepare a component B;
(4) And (3) uniformly mixing the component A1 prepared in the step (1) and the component A2 prepared in the step (2), adding the mixture into the component B obtained in the step (3), reacting for 4 hours at the temperature of 100 ℃, and condensing and slicing after the reaction is finished to obtain the viscosity-reducing solid polycarboxylic acid water reducer.
Example 2:
a preparation method of a viscosity-reducing solid polycarboxylate superplasticizer comprises the following steps:
(1) Uniformly mixing 111g of isophorone diisocyanate and 3g of dibutyltin dilaurate to obtain a mixed solution, then adding 500g of polyethylene glycol monomethyl ether with the molecular weight of 1000 into the mixed solution, and reacting at 70 ℃ for 6 hours until the reaction is finished to obtain a component A1;
(2) Uniformly mixing 111g of isophorone diisocyanate and 6g of dibutyltin dilaurate to obtain a mixed solution, then adding 1000g of polyethylene glycol monomethyl ether with the molecular weight of 2000 into the mixed solution, and reacting for 6 hours at 70 ℃ until the reaction is finished to obtain a component A2;
(3) Adding 2.34g of chain transfer agent mercaptoethanol and 4.92g of initiator azobisisobutyronitrile into 332g of tetrahydrofuran, uniformly stirring to form a base solution, then mixing 288g of acrylic acid with 130g of hydroxypropyl acrylate, slowly dropwise adding into the base solution, controlling the dropwise adding time to be 2h, reacting for 2h at 70 ℃, stopping the reaction, and removing the solvent by vacuumizing to prepare a component B;
(4) And (3) uniformly mixing the component A1 prepared in the step (1) and the component A2 prepared in the step (2), adding the mixture into the component B obtained in the step (3), reacting for 6 hours at the temperature of 80 ℃, and condensing and slicing after the reaction is finished to obtain the viscosity-reducing solid polycarboxylic acid water reducer.
Example 3:
a preparation method of a viscosity-reducing solid polycarboxylate superplasticizer comprises the following steps:
(1) Uniformly mixing 125g of diphenylmethane diisocyanate and 0.19g of triethylamine to obtain a mixed solution, then adding 500g of polyethylene glycol monomethyl ether with the molecular weight of 1000 into the mixed solution, and reacting for 8 hours at the temperature of 90 ℃ until the reaction is finished to obtain a component A1;
(2) Uniformly mixing 125g of diphenylmethane diisocyanate and 0.48g of triethylamine to obtain a mixed solution, then adding 2000g of polyethylene glycol monomethyl ether with the molecular weight of 4000 into the mixed solution, and reacting for 8 hours at the temperature of 90 ℃ until the reaction is finished to obtain a component A2;
(3) Adding 1.75g of chain transfer agent mercaptoethanol and 9.12g of initiator ammonium persulfate into 332gN, and uniformly stirring to form a base solution, then mixing 360g of acrylic acid with 144g of hydroxybutyl acrylate, slowly dropwise adding the mixture into the base solution, controlling the dropwise adding time to be 3h, reacting for 1h at 90 ℃, stopping the reaction, and vacuumizing to remove the solvent to prepare a component B;
(4) And (3) uniformly mixing the component A1 prepared in the step (1) and the component A2 prepared in the step (2), adding the mixture into the component B obtained in the step (3), reacting for 8 hours at 70 ℃, and condensing and slicing after the reaction is finished to obtain the viscosity-reducing solid polycarboxylic acid water reducer.
Example 4:
a preparation method of a viscosity-reducing solid polycarboxylic acid water reducer comprises the following steps:
(1) 131g of dicyclohexylmethane diisocyanate and 0.05g of triethylene diamine are uniformly mixed to obtain a mixed solution, then 1000g of polyethylene glycol monomethyl ether with the molecular weight of 2000 is added into the mixed solution, and the mixed solution is reacted for 7 hours at the temperature of 120 ℃ until the reaction is finished to obtain a component A1;
(2) Uniformly mixing 131g of dicyclohexylmethane diisocyanate and 0.53g of triethylene diamine to obtain a mixed solution, then adding 1500g of polyethylene glycol monomethyl ether with the molecular weight of 3000 into the mixed solution, and reacting at 120 ℃ for 7 hours until the reaction is finished to obtain a component A2;
(3) Adding 1.9g of chain transfer agent mercaptopropionic acid and 4.56g of initiator ammonium persulfate into 332gN, stirring uniformly to form a base solution, then mixing 432g of acrylic acid with 130g of hydroxyethyl methacrylate, slowly dropwise adding the mixture into the base solution, controlling the dropwise adding time to be 3h, reacting for 2h at 70 ℃, stopping the reaction, vacuumizing the solvent, and removing the solvent to prepare a component B;
(4) And (3) uniformly mixing the component A1 prepared in the step (1) and the component A2 prepared in the step (2), adding the mixture into the component B obtained in the step (3), reacting for 7 hours at the temperature of 50 ℃, and condensing and slicing after the reaction is finished to obtain the viscosity-reducing solid polycarboxylic acid water reducer.
Example 5:
a preparation method of a viscosity-reducing solid polycarboxylic acid water reducer comprises the following steps:
(1) Uniformly mixing 84g of hexamethylene diisocyanate and 1.29g of tetraisobutyl titanate to obtain a mixed solution, then adding 1000g of polyethylene glycol monomethyl ether with the molecular weight of 2000 into the mixed solution, and reacting for 9 hours at the temperature of 80 ℃ until the reaction is finished to obtain a component A1;
(2) Uniformly mixing 84g of hexamethylene diisocyanate and 3.23g of tetraisobutyl titanate to obtain a mixed solution, then adding 2000g of polyethylene glycol monomethyl ether with the molecular weight of 4000 into the mixed solution, and reacting for 9 hours at the temperature of 80 ℃ until the reaction is finished to obtain a component A2;
(3) Adding 1.59g of chain transfer agent mercaptopropionic acid and 8.1g of initiator azobisisobutyramidine hydrochloride into 332g of water, uniformly stirring to form a base solution, then mixing 504g of acrylic acid with 144g of hydroxypropyl methacrylate, slowly dropwise adding into the base solution, controlling the dropwise adding time to be 4h, reacting for 1h at 60 ℃ and stopping the reaction, and vacuumizing to remove the solvent to prepare a component B;
(4) And (3) uniformly mixing the component A1 prepared in the step (1) and the component A2 prepared in the step (2), adding the mixture into the component B obtained in the step (3), reacting for 9 hours at the temperature of 80 ℃, and condensing and slicing after the reaction is finished to obtain the viscosity-reducing solid polycarboxylic acid water reducer.
Example 6:
a preparation method of a viscosity-reducing solid polycarboxylic acid water reducer comprises the following steps:
(1) Uniformly mixing 87g of toluene diisocyanate and 1.2g of dibutyltin dilaurate to obtain a mixed solution, then adding 500g of polyethylene glycol monomethyl ether with the molecular weight of 1000 into the mixed solution, and reacting for 6 hours at the temperature of 90 ℃ until the reaction is finished to obtain a component A1;
(2) Uniformly mixing 87g of toluene diisocyanate and 3.0g of dibutyltin dilaurate to obtain a mixed solution, then adding 2500g of polyethylene glycol monomethyl ether with the molecular weight of 5000 into the mixed solution, and reacting for 6 hours at the temperature of 90 ℃ until the reaction is finished to obtain a component A2;
(3) Adding 1.26g of chain transfer agent mercaptopropionic acid and 10.8g of initiator azobisisobutyramidine hydrochloride into 332g of water, uniformly stirring to form a base solution, then mixing 576g of acrylic acid and 160g of hydroxybutyl methacrylate, slowly dropwise adding the mixture into the base solution, controlling the dropwise adding time to be 4h, reacting for 2h at 50 ℃ for 2h, stopping the reaction, and removing the solvent by vacuumizing to prepare a component B;
(4) And (3) uniformly mixing the component A1 prepared in the step (1) and the component A2 prepared in the step (2), adding the mixture into the component B obtained in the step (3), reacting for 6 hours at the temperature of 80 ℃, and condensing and slicing after the reaction is finished to obtain the viscosity-reducing solid polycarboxylic acid water reducer.
Comparative example 1:
a preparation method of a viscosity-reducing solid polycarboxylic acid water reducer comprises the following steps:
(1) The preparation method comprises the following steps of uniformly mixing 87g of toluene diisocyanate and 6g of dibutyltin dilaurate to obtain a mixed solution, adding 300g of polyethylene glycol monomethyl ether with the molecular weight of 600 into the mixed solution, and reacting at 50 ℃ for 4 hours until the reaction is finished to obtain a component A1 and a component A2;
(2) Adding 4.68g of chain transfer agent mercaptoethanol and 3.28g of initiator azobisisobutyronitrile into 332g of tetrahydrofuran, uniformly stirring to form a base solution, then mixing 216g of acrylic acid and 116g of hydroxyethyl acrylate, slowly dropwise adding into the base solution, controlling the dropwise adding time to be 2h, reacting for 1h under the reaction condition of 65 ℃, stopping the reaction, and removing the solvent by vacuum pumping to prepare a component B;
(4) And (2) uniformly mixing the components A1 and A2 prepared in the step (1), adding the mixture into the component B obtained in the step (3), reacting for 4 hours at the temperature of 100 ℃, and condensing and slicing after the reaction is finished to obtain the viscosity-reducing solid polycarboxylic acid water reducer.
Comparative example 2:
a preparation method of a viscosity-reducing solid polycarboxylate superplasticizer comprises the following steps:
(1) When the component A1 and the component A2 are prepared, polyethylene glycol monomethyl ether with molecular weight of 6000 is used as a raw material, and the preparation method comprises the following steps of uniformly mixing 87g of toluene diisocyanate and 12g of dibutyltin dilaurate to obtain a mixed solution, then adding 3000g of polyethylene glycol monomethyl ether with molecular weight of 6000 into the mixed solution, and reacting at 50 ℃ for 4 hours until the reaction is finished to obtain the component A1 and the component A2;
(3) Adding 4.68g of chain transfer agent mercaptoethanol and 3.28g of initiator azobisisobutyronitrile into 332g of tetrahydrofuran, uniformly stirring to form a base solution, then mixing 216g of acrylic acid and 116g of hydroxyethyl acrylate, slowly dropwise adding into the base solution, controlling the dropwise adding time to be 2h, reacting for 1h at 65 ℃ and stopping the reaction, and vacuumizing and removing the solvent to prepare a component B;
(4) And (2) uniformly mixing the components A1 and A2 prepared in the step (1), adding the mixture into the component B obtained in the step (3), reacting for 4 hours at the temperature of 100 ℃, and condensing and slicing after the reaction is finished to prepare the viscosity-reducing solid polycarboxylic acid water reducer.
Comparative example 3:
a preparation method of a viscosity-reducing solid polycarboxylic acid water reducer comprises the following steps:
(1) Polyethylene glycol monomethyl ether with molecular weight of 2000 is adopted as a raw material when the component A1 and the component A2 are prepared, the preparation method comprises the following steps of uniformly mixing 131g of dicyclohexylmethane diisocyanate and 0.05g of triethylene diamine to obtain a mixed solution, then adding 1000g of polyethylene glycol monomethyl ether with molecular weight of 2000 into the mixed solution, and reacting for 7 hours at 120 ℃ until the reaction is finished to obtain the component A1 and the component A2;
(3) Adding 1.9g of chain transfer agent mercaptopropionic acid and 4.56g of initiator ammonium persulfate into 332gN, stirring uniformly to form a base solution, then mixing 432g of acrylic acid with 130g of hydroxyethyl methacrylate, slowly dropwise adding the mixture into the base solution, controlling the dropwise adding time to be 3h, reacting for 2h at 70 ℃, stopping the reaction, vacuumizing the solvent, and removing the solvent to prepare a component B;
(4) And (2) uniformly mixing the component A1 and the component A2 prepared in the step (1), adding the mixture into the component B obtained in the step (3), reacting for 7 hours at the temperature of 50 ℃, and condensing and slicing after the reaction is finished to prepare the viscosity-reduction type solid polycarboxylic acid water reducer.
Comparative example 4:
a preparation method of a viscosity-reducing solid polycarboxylate superplasticizer comprises the following steps:
(1) The preparation method comprises the following steps of uniformly mixing 131g of dicyclohexylmethane diisocyanate and 0.05g of triethylenediamine to obtain a mixed solution, adding 1500g of polyethylene glycol monomethyl ether with the molecular weight of 3000 into the mixed solution, and reacting at 120 ℃ for 7 hours until the reaction is finished to obtain a component A1 and a component A2;
(3) Adding 1.9g of chain transfer agent mercaptopropionic acid and 4.56g of initiator ammonium persulfate into 332gN, stirring uniformly to form a base solution, then mixing 432g of acrylic acid with 130g of hydroxyethyl methacrylate, slowly dropwise adding the mixture into the base solution, controlling the dropwise adding time to be 3h, reacting for 2h at 70 ℃, stopping the reaction, vacuumizing the solvent, and removing the solvent to prepare a component B;
(4) Uniformly mixing the component A1 and the component A2 prepared in the step (1), adding the mixture into the component B obtained in the step (3), reacting for 7 hours at 50 ℃, and condensing and slicing after the reaction is finished to prepare the viscosity-reduction type solid polycarboxylic acid water reducer
Comparative example 5:
a preparation method of a viscosity-reducing solid polycarboxylic acid water reducer comprises the following steps:
(1) Uniformly mixing 131g of dicyclohexylmethane diisocyanate and 0.05g of triethylene diamine to obtain a mixed solution, then adding 250g of polyethylene glycol monomethyl ether with the molecular weight of 500 into the mixed solution, and reacting at 120 ℃ for 7 hours until the reaction is finished to obtain a component A1;
(2) Uniformly mixing 131g of dicyclohexylmethane diisocyanate and 0.53g of triethylene diamine to obtain a mixed solution, then adding 1500g of polyethylene glycol monomethyl ether with the molecular weight of 3000 into the mixed solution, and reacting for 7 hours at the temperature of 120 ℃ until the reaction is finished to obtain a component A2;
(3) Adding 1.9g of chain transfer agent mercaptopropionic acid and 4.56g of initiator ammonium persulfate into 332gN, N-dimethylformamide, uniformly stirring to form a base solution, then mixing 432g of acrylic acid and 130g of hydroxyethyl methacrylate, slowly dropwise adding into the base solution, controlling the dropwise adding time to be 3h, reacting for 2h at 70 ℃, stopping the reaction, vacuumizing and removing the solvent to prepare a component B;
(4) And (3) uniformly mixing the component A1 prepared in the step (1) and the component A2 prepared in the step (2), adding the mixture into the component B obtained in the step (3), reacting for 7 hours at the temperature of 50 ℃, and condensing and slicing after the reaction is finished to obtain the viscosity-reducing solid polycarboxylic acid water reducer.
Comparative example 6:
a preparation method of a viscosity-reducing solid polycarboxylate superplasticizer comprises the following steps:
(1) Uniformly mixing 131g of dicyclohexylmethane diisocyanate and 0.05g of triethylene diamine to obtain a mixed solution, then adding 1000g of polyethylene glycol monomethyl ether with the molecular weight of 2000 into the mixed solution, and reacting at 120 ℃ for 7 hours until the reaction is finished to obtain a component A1;
(2) 131g of dicyclohexylmethane diisocyanate and 0.53g of triethylene diamine are uniformly mixed to obtain a mixed solution, then 3500g of polyethylene glycol monomethyl ether with the molecular weight of 7000 is added into the mixed solution, and the mixture reacts for 7 hours at the temperature of 120 ℃ until the reaction is finished to obtain a component A2;
(3) Adding 1.9g of chain transfer agent mercaptopropionic acid and 4.56g of initiator ammonium persulfate into 332gN, stirring uniformly to form a base solution, then mixing 432g of acrylic acid with 130g of hydroxyethyl methacrylate, slowly dropwise adding the mixture into the base solution, controlling the dropwise adding time to be 3h, reacting for 2h at 70 ℃, stopping the reaction, vacuumizing the solvent, and removing the solvent to prepare a component B;
(4) And (3) uniformly mixing the component A1 prepared in the step (1) and the component A2 prepared in the step (2), adding the mixture into the component B obtained in the step (3), reacting for 7 hours at the temperature of 50 ℃, and condensing and slicing after the reaction is finished to obtain the viscosity-reducing solid polycarboxylic acid water reducer.
The viscosity-reducing solid polycarboxylate superplasticizers prepared in examples 1-6 and comparative examples 1-6 are prepared into a 50% solid content solution, and compared with a commercially available polycarboxylate superplasticizer with 50% solid content in terms of mortar fluidity and concrete fresh mixing performance. The fluidity test of the cement mortar refers to GB/T8077-2012 'homogeneity test method for concrete admixture', and the results are shown in Table 1. The method adopts the P.O42.5R grade common portland cement with the water-cement mass ratio W/C =0.33 and the water reducing agent mixing amount (based on the cement mass) as the folded mixing amount (added according to the amount after the solid content is converted). The concrete fresh mixing performance refers to GB/T50080-2016 standard of common concrete mixture performance test method, the result is shown in Table 2, the concrete slump is controlled to be 200-220mm, the viscosity of the concrete is tested by an inverted slump cone method test, and the smaller the time for the concrete to flow out of the inverted slump cone is, the smaller the viscosity of the concrete is. The concrete foundation comprises the following components in proportion: 220kg/m cement 3 80kg/m of fly ash 3 90kg/m of mineral powder 3 780kg/m of sand 3 1080kg/m of pebbles 3 170kg/m of water 3 The cement is conch cement P.O42.5R.
Table 1 mortar dispersing properties:
table 2 fresh mix properties of the concrete:
and (4) conclusion: as can be seen from the test results in tables 1 and 2, the comparison between the solid polycarboxylic acid water reducing agent prepared in examples 1 to 6 and the commercially available water reducing agent shows that the solid polycarboxylic acid water reducing agent synthesized by the invention has larger initial water reducing, viscosity and slump retaining properties than the commercially available water reducing agent; under the condition of controlling the initial performance of the concrete to be equivalent, compared with a commercial water reducing agent, the polycarboxylic acid water reducing agent synthesized by the invention can effectively reduce the viscosity of the concrete, obviously improve the workability of the concrete and is beneficial to the construction of commercial concrete. Meanwhile, the determination results of the embodiment 1, the comparative example 1 and the comparative example 2 show that the solid polycarboxylate water reducer prepared by selecting long-chain polyether molecules in the comparative example 2 has enough water reducing performance, but the viscosity of the solid polycarboxylate water reducer is lower than that of the solid polycarboxylate water reducer prepared by matching long and short polyethers in the embodiment 1, and the construction of commercial concrete is not facilitated; comparative example 1 the solid polycarboxylate superplasticizer prepared by using short-chain polyether molecules has good viscosity but insufficient water reducing performance; therefore, the polyether molecules with two different lengths are selected to prepare the polycarboxylate superplasticizer, the viscosity reduction performance of the polycarboxylate superplasticizer molecules can be enhanced through the matching of the long polyether and the short polyether, the adaptability of the polycarboxylate superplasticizer is improved, and the water reduction performance of the polycarboxylate superplasticizer is ensured. From the comparison of the results between example 4 and comparative examples 3 and 6, it can be seen that the selection of the molecular weight of the raw polyethylene glycol monomethyl ether in the A2 component is reasonable; a comparison of the results of example 4 with those of comparative examples 4 and 5 shows that the molecular weight of the starting polyethylene glycol monomethyl ether in component A1 is selected to be between 600 and 2000, which is relatively effective. The results of the examples 1 to 6 show that the invention can be adjusted in structure and functionality according to actual needs, the obtained solid polycarboxylic acid water reducing agent has excellent water reducing and slump retaining properties, the viscosity of concrete can be effectively reduced, the construction of concrete is facilitated, and meanwhile, the preparation process is green and environment-friendly, and is obviously beneficial to large-scale industrial production. Compared with the traditional method, the synthesis method has the advantages that the raw materials required by the reaction are common and easy to obtain, the whole synthesis process is simple, controllable, efficient and convenient, the steps used in the reaction are common operation processes, special operation or expensive auxiliaries are not needed, the reaction conditions are mild, and the process is green and environment-friendly, so that the industrial production is easy to realize; the synthesis process has no special requirements on equipment, has the advantages of strong molecular designability, controllable molecular weight, good performance and the like, and has good popularization potential and application value.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (11)
1. The preparation method of the viscosity-reducing solid polycarboxylate superplasticizer is characterized by comprising the following steps: the viscosity-reducing solid polycarboxylate superplasticizer is prepared by respectively carrying out addition reaction on two polyethylene glycol monomethyl ethers with different molecular weights and diisocyanate compounds, and polymerizing the obtained product with acrylic acid and hydroxyl-containing unsaturated monomers respectively; the polyethylene glycol monomethyl ethers with different molecular weights are respectively small molecular weight polyethylene glycol monomethyl ether and large molecular weight polyethylene glycol monomethyl ether, the molecular weight of the small molecular weight polyethylene glycol monomethyl ether is 600-2000, and the molecular weight of the large molecular weight polyethylene glycol monomethyl ether is 2000-6000.
2. The preparation method of the viscosity-reducing solid polycarboxylate superplasticizer according to claim 1, which is characterized by comprising the following steps: the diisocyanate compound is any one of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate and hexamethylene diisocyanate, and the molar ratio of the diisocyanate compound to the polyethylene glycol monomethyl ether is (1 +/-0.05): 1.
3. The preparation method of the viscosity-reducing solid polycarboxylate superplasticizer according to claim 1, which is characterized by comprising the following steps: the hydroxyl-containing unsaturated monomer is any one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and hydroxybutyl methacrylate.
4. The preparation method of the viscosity-reducing solid polycarboxylate superplasticizer according to claim 1, which is characterized by comprising the following specific steps: (1) Carrying out addition reaction on diisocyanate compounds and small molecular weight polyethylene glycol monomethyl ether to obtain a component A1; (2) Carrying out addition reaction on diisocyanate compounds and high molecular weight polyethylene glycol monomethyl ether to obtain a component A2; (3) Adding a chain transfer agent and an initiator into a solvent, uniformly stirring to form a base solution, then mixing acrylic acid and a hydroxyl-containing unsaturated monomer, dropwise adding the mixture into the base solution, and removing the solvent after the reaction is finished by vacuumizing to obtain a component B; (4) And (3) uniformly mixing the component A1 prepared in the step (1) and the component A2 prepared in the step (2), adding the mixture into the component B obtained in the step (3), uniformly mixing and stirring, and condensing and slicing after the reaction is finished to obtain the viscosity-reducing solid polycarboxylic acid water reducer.
5. The preparation method of the viscosity-reducing solid polycarboxylate superplasticizer according to claim 4, characterized by comprising the following steps: the reaction conditions in the step (1) and the step (2) are both reaction temperature of 50-120 ℃ and reaction time of 4-10 h.
6. The preparation method of the viscosity-reducing solid polycarboxylate superplasticizer according to claim 5, characterized by comprising the following steps: catalysts are used in the reaction processes of the step (1) and the step (2), the catalysts are any one of triethylamine, triethylenediamine, dibutyltin dilaurate and tetraisobutyl titanate, and the dosage of the catalysts is 0.1-5% of the mole number of the low molecular weight polyethylene glycol monomethyl ether or the high molecular weight polyethylene glycol monomethyl ether.
7. The preparation method of the viscosity-reducing solid polycarboxylic acid water reducer according to claim 6, characterized by comprising the following steps: the initiator in the step (3) is any one of azobisisobutyronitrile, ammonium persulfate and azobisisobutyramidine hydrochloride.
8. The preparation method of the viscosity-reducing solid polycarboxylic acid water reducer according to claim 7, characterized by comprising the following steps: the chain transfer agent in the step (3) is mercaptoethanol or mercaptopropionic acid.
9. The preparation method of the viscosity-reducing solid polycarboxylate superplasticizer according to claim 8, characterized by comprising the following steps: the molar ratio of the acrylic acid to the hydroxyl-containing unsaturated monomer in the step (3) is (3-8): 1.
10. The preparation method of the viscosity-reducing solid polycarboxylate superplasticizer according to claim 9, characterized by comprising the following steps: the molar ratio of the initiator to the hydroxyl-containing unsaturated monomer in the step (3) is (0.02-0.04): 1.
11. The preparation method of the viscosity-reducing solid polycarboxylate superplasticizer according to claim 10, characterized by comprising the following steps: the molar ratio of the chain transfer agent to the hydroxyl-containing unsaturated monomer in the step (3) is (0.01-0.06): 1.
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