CN113698551A - Phosphonate modified polycarboxylate superplasticizer and preparation method thereof - Google Patents
Phosphonate modified polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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- CN113698551A CN113698551A CN202111111354.XA CN202111111354A CN113698551A CN 113698551 A CN113698551 A CN 113698551A CN 202111111354 A CN202111111354 A CN 202111111354A CN 113698551 A CN113698551 A CN 113698551A
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- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 44
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000008030 superplasticizer Substances 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 57
- 239000000178 monomer Substances 0.000 claims abstract description 57
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 18
- 229920000570 polyether Polymers 0.000 claims abstract description 18
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 12
- XQRLCLUYWUNEEH-UHFFFAOYSA-N diphosphonic acid Chemical compound OP(=O)OP(O)=O XQRLCLUYWUNEEH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 14
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- -1 4-hydroxybutyl vinyl Chemical group 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 229930003268 Vitamin C Natural products 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- 235000019154 vitamin C Nutrition 0.000 claims description 4
- 239000011718 vitamin C Substances 0.000 claims description 4
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 3
- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 3
- WRUUGTRCQOWXEG-UHFFFAOYSA-N pamidronate Chemical compound NCCC(O)(P(O)(O)=O)P(O)(O)=O WRUUGTRCQOWXEG-UHFFFAOYSA-N 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 3
- 235000019252 potassium sulphite Nutrition 0.000 claims description 3
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 3
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 125000002962 imidazol-1-yl group Chemical group [*]N1C([H])=NC([H])=C1[H] 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- 229920000151 polyglycol Polymers 0.000 claims description 2
- 239000010695 polyglycol Substances 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000004927 clay Substances 0.000 abstract description 12
- 230000001603 reducing effect Effects 0.000 abstract description 6
- 239000004566 building material Substances 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 31
- 239000004567 concrete Substances 0.000 description 17
- 239000004568 cement Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000011056 performance test Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/243—Phosphorus-containing polymers
- C04B24/246—Phosphorus-containing polymers 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention relates to the field of building materials, and particularly relates to a phosphonate modified polycarboxylate superplasticizer and a preparation method thereof. The polycarboxylate superplasticizer is mainly prepared from the following raw materials in parts by weight: 90-120 parts of unsaturated polyether macromonomer, 4-6 parts of phosphonate monomer, 7-10 parts of unsaturated carboxylic small monomer, 0.7-1.3 parts of initiator, 0.1-0.5 part of reducing agent and 0.4-0.6 part of chain transfer agent; the phosphonate monomer is mainly prepared from the following raw materials in parts by weight: 0.1-0.15 part of catalyst, 3-5 parts of unsaturated anhydride and 5-7 parts of diphosphonic acid. The polycarboxylate superplasticizer has excellent water reducing performance and slump retaining performance, strong adaptability and certain resistance to clay.
Description
Technical Field
The invention relates to the field of building materials, and particularly relates to a phosphonate modified polycarboxylate superplasticizer and a preparation method thereof.
Background
In recent years, with the continuous development of economy, the building industries such as houses, bridges, railways and highways develop rapidly, and the demand of the water reducing agent as an indispensable part of concrete admixtures is gradually increased. The main function of the water reducer is that the water consumption of the concrete mixture in the mixing process is reduced under the condition that the slump constant is kept, the rheological property of the concrete mixture is improved, and the strength of hardened concrete is increased.
With the rise of the building industry, capital construction projects are increased sharply, the consumption of gravel aggregates is huge, high-quality gravel resources are increasingly in short supply, the problems of large mud content of aggregates, high impurity content and the like can be met by adopting inferior gravel, the mud content of the aggregates is very sensitive to the polycarboxylate superplasticizer, and the polycarboxylate superplasticizer is greatly adsorbed by clay when being used along with the increase of the mud content of the gravel, so that the dispersity and the retentivity of the polycarboxylate superplasticizer are reduced, and the flowability of concrete is greatly reduced. Therefore, how to effectively solve the increasingly serious problems of compatibility and adaptability between the polycarboxylate superplasticizer and cement and sandstone, the polycarboxylate superplasticizer with high adaptability under the complex environment with high mud content is developed, and the polycarboxylate superplasticizer has important significance for the development of concrete admixtures and the concrete industry.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention relates to a polycarboxylic acid water reducing agent, which is mainly prepared from the following raw materials in parts by weight:
90-120 parts of unsaturated polyether macromonomer, 4-6 parts of phosphonate monomer, 7-10 parts of unsaturated carboxylic small monomer, 0.7-1.3 parts of initiator, 0.1-0.5 part of reducing agent and 0.4-0.6 part of chain transfer agent;
the phosphonate monomer is mainly prepared from the following raw materials in parts by weight:
0.1-0.15 part of catalyst, 3-5 parts of unsaturated anhydride and 5-7 parts of diphosphonic acid.
The polycarboxylate superplasticizer has excellent water reducing property and slump retaining property, strong adaptability and certain resistance to clay.
According to another aspect of the invention, the invention also relates to a preparation method of the polycarboxylate superplasticizer, which comprises the following steps:
mixing the unsaturated polyether macromonomer, the phosphonate monomer, the unsaturated carboxylic acid small monomer, the initiator, the reducing agent, the chain transfer agent and water, and carrying out a first reaction;
the preparation method of the phosphonate monomer comprises the following steps: and (3) carrying out a second reaction on the mixture of the catalyst, the unsaturated anhydride and the diphosphonic acid under the heating condition.
The preparation method of the polycarboxylate superplasticizer is simple and easy to operate, and the prepared polycarboxylate superplasticizer has excellent performance and can adapt to various scenes.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the polycarboxylate water reducer provided by the invention, the unsaturated polyether macromonomer, the phosphonate monomer and the unsaturated carboxylic acid small monomer are added, so that the obtained polycarboxylate water reducer shows better slump retaining performance, the cement dispersing performance of the polycarboxylate water reducer is improved, the cement hydration can be delayed, clay adsorption can be resisted for a clay-containing sandstone material, the concrete workability is improved, and the polycarboxylate water reducer has wider adaptability to the sandstone material.
(2) The phosphonate monomer prepared by the invention can gradually hydrolyze to diphosphonic acid groups, phosphonic acid groups and Ca on the surface of cement in the alkaline environment of cement paste2+The complex can delay cement hydration and show better slump retaining performance, and the phosphonic acid group is preferentially adsorbed on the surface of cement or montmorillonite compared with carboxylic acid group, so that more carboxyl groups are adsorbed on the surface of cement, and the dispersing performance of the polycarboxylic acid water reducing agent on the cement is improved.
(3) The preparation method of the polycarboxylate superplasticizer provided by the invention is safe and reliable, simple in process, easy to operate, green and pollution-free, and beneficial to industrial production, and the prepared polycarboxylate superplasticizer has excellent performance, is beneficial to smooth actual construction, reduces the using amount of cement, and saves cost.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following detailed description, but those skilled in the art will understand that the following described examples are some, not all, of the examples of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. 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. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
According to one aspect of the invention, the invention relates to a polycarboxylic acid water reducing agent which is mainly prepared from the following raw materials in parts by weight:
90-120 parts of unsaturated polyether macromonomer, 4-6 parts of phosphonate monomer, 7-10 parts of unsaturated carboxylic small monomer, 0.7-1.3 parts of initiator, 0.1-0.5 part of reducing agent and 0.4-0.6 part of chain transfer agent;
the phosphonate monomer is mainly prepared from the following raw materials in parts by weight:
0.1-0.15 part of catalyst, 3-5 parts of unsaturated anhydride and 5-7 parts of diphosphonic acid.
Wherein, the unsaturated polyether macromonomer can be, for example, but not limited to, 90 parts, 95 parts, 100 parts, 105 parts, 110 parts, 115 parts or 120 parts by weight; the phosphonate monomer can be, for example, but is not limited to, 4 parts, 4.5 parts, 5 parts, 5.5 parts, or 6 parts; the unsaturated carboxylic small monomer can be, for example, but not limited to, 7 parts, 7.5 parts, 8 parts, 8.5 parts, 9 parts, or 10 parts; the initiator may be, for example, but is not limited to, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts, 1.1 parts, 1.2 parts, or 1.3 parts; the reducing agent may be, for example, but is not limited to, 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, or 0.5 parts; the chain transfer agent may be, for example, but is not limited to, 0.4 parts, 0.45 parts, 0.5 parts, 0.55 parts, or 0.6 parts; the catalyst may be, for example, but is not limited to, 0.1 part, 0.11 part, 0.12 part, 0.13 part, 0.14 part, or 0.15 part; the unsaturated anhydride can be, for example, but is not limited to, 3 parts, 3.5 parts, 4 parts, 4.5 parts, or 5 parts; bisphosphonic acids may be, for example, but are not limited to, 5 parts, 5.5 parts, 6 parts, 6.5 parts, or 7 parts.
According to the polycarboxylic acid water reducer provided by the invention, the unsaturated polyether macromonomer, the phosphonate monomer and the unsaturated carboxylic acid small monomer are added, so that the polycarboxylic acid water reducer has excellent water reducing performance and slump retaining performance, is strong in adaptability and has certain resistance to clay.
The unsaturated acid anhydride and the diphosphonic acid react under the action of the catalyst to obtain the phosphonate monomer, and the polycarboxylate water reducer is modified by the phosphonate monomer, so that the obtained polycarboxylate water reducer has more excellent water reducing performance and slump retaining performance. For the higher grit material that contains clay, can resist clay and adsorb, promote concrete workability, have more extensive adaptability to the grit material.
Preferably, the unsaturated polyether macromonomer comprises at least one of ethylene glycol monovinyl polyethylene glycol ether and 4-hydroxybutyl vinyl polyoxyethylene ether.
The unsaturated polyether macromonomer used in the invention comprises ethylene glycol monovinyl polyglycol ether (EPEG) and 4-hydroxybutyl Vinyl Polyoxyethylene Ether (VPEG), and the monomer has high reactivity, can react at normal temperature, has safe and reliable preparation process, simple process, no pollution and is beneficial to industrial production.
Preferably, the bisphosphonic acid comprises at least one of 1-hydroxy-2- (imidazol-1-yl) -ethylene-1, 1-bisphosphonic acid, 3-amino-1-hydroxypropane-1, 1-diphosphonic acid, and 1-hydroxy-3- (methyl-n-pentylamino) -propylidene-1, 1-diphosphonic acid.
Preferably, the unsaturated anhydride comprises at least one of maleic anhydride and itaconic anhydride.
Preferably, the unsaturated carboxylic small monomer comprises at least one of maleic anhydride, acrylic acid and methacrylic acid.
Preferably, the initiator comprises at least one of hydrogen peroxide, sodium persulfate, ammonium persulfate and potassium persulfate.
Preferably, the catalyst comprises at least one of p-toluenesulfonic acid, zinc acetate and manganese acetate.
Preferably, the reducing agent includes at least one of sodium sulfite, potassium sulfite, sodium bisulfite, vitamin C, and sodium formaldehyde sulfoxylate.
Preferably, the chain transfer agent comprises at least one of sodium hypophosphite, mercaptoethanol, thioglycolic acid and mercaptopropionic acid.
Preferably, the raw material of the polycarboxylate superplasticizer further comprises a neutralizing agent.
Preferably, the neutralizing agent is an alkali solution.
Preferably, the alkali solution is selected from at least one of a potassium hydroxide solution and a sodium hydroxide solution.
Preferably, the alkali concentration in the alkali solution is 25% to 30% by mass (e.g. 25%, 26%, 27%, 29% or 30%).
According to another aspect of the invention, the invention relates to a preparation method of a polycarboxylate superplasticizer, which comprises the following steps:
mixing the unsaturated polyether macromonomer, the phosphonate monomer, the unsaturated carboxylic acid small monomer, the initiator, the reducing agent, the chain transfer agent and water, and carrying out a first reaction;
the preparation method of the phosphonate monomer comprises the following steps: and (3) carrying out a second reaction on the mixture of the catalyst, the unsaturated anhydride and the diphosphonic acid under the heating condition.
The preparation method of the polycarboxylate superplasticizer is simple and easy to operate, and the prepared polycarboxylate superplasticizer has strong adaptability, good quality and good performance.
Compared with the common polycarboxylate superplasticizer, the phosphonate monomer disclosed by the invention has more excellent water reducing performance and slump retaining performance. For the higher grit material that contains clay, can resist clay and adsorb, promote concrete workability, have more extensive adaptability to the grit material.
Preferably, the first reaction comprises in particular the following steps:
dropwise adding a material A and a material B into a first mixed system of the unsaturated polyether macromonomer, the initiator and first water to obtain a second mixed system; and carrying out heat preservation treatment on the second mixed system.
Preferably, the material A is a mixture of the phosphonate monomer, the unsaturated carboxylic acid small monomer, the chain transfer agent and second water.
Preferably, the material B is a mixture of a reducing agent and third water.
Preferably, the dropping time is 1-2 h (e.g., 1h, 1.2h, 1.4h, 1.6h, 1.8h or 2 h).
According to the invention, the feed liquid A and the feed liquid B are dripped in a certain time, so that the reaction can be ensured to be slow and sufficient, and the obtained polycarboxylic acid water reducing agent has excellent water reducing performance and slump retaining performance, strong adaptability and certain resistance to clay.
Preferably, the heat preservation time is 1-2 h (for example, 1h, 1.2h, 1.4h, 1.6h, 1.8h or 2 h).
The heat preservation time can ensure that the reaction is fully completed, and can not cause waste of time and resources.
Preferably, after the first mixed system is kept still for 5-10 min (for example, 5min, 6min, 7min, 8min, 9min or 10min), the material A and the material B are dripped.
Preferably, the mass ratio of the unsaturated polyether macromonomer to the first water is (90-120): (100-120);
and/or the mass ratio of the unsaturated carboxylic acid small monomer to the phosphonate monomer to the chain transfer agent to the second water is (7-10): (4-6): (0.4-0.6): (20-23);
and/or the mass ratio of the reducing agent to the third water is (0.1-0.5): (20-23).
Preferably, the mass ratio of the unsaturated polyether macromonomer to the first water can be, for example, but not limited to, 90: 100. 90: 120. 120: 100. 120: 120. 100, and (2) a step of: 110. 110: 115 or 115: 105.
preferably, the mass ratio of the unsaturated carboxylic small monomer, the phosphonate monomer, the chain transfer agent and the second water may be, for example, but not limited to 7: 4: 0.4: 20. 10: 6: 0.6: 23. 8: 5: 0.5: 21. 9: 4: 0.6: 22 or 10: 5: 0.6: 20.
preferably, the mass ratio of the reducing agent to the third water may be, but is not limited to, 0.1: 20. 0.1: 23. 0.5: 20. 0.5: 23. 0.3: 22 or 0.4: 21.
preferably, the preparation method of the phosphonate monomer specifically comprises the following steps: and (3) carrying out heat treatment on the mixture of the catalyst and the unsaturated acid anhydride, and then adding the diphosphonic acid for heating.
Preferably, the heat treatment temperature is 55 to 65 ℃ (e.g., 55 ℃, 57 ℃, 59 ℃, 61 ℃, 63 ℃ or 65 ℃).
Preferably, the heating temperature is 95-105 ℃ (such as 95 ℃, 97 ℃, 99 ℃, 101 ℃, 103 ℃ or 105 ℃), and the heating time is 2.5-3.5 h (such as 2.5h, 2.7h, 2.9h, 3.1h, 3.3h or 3.5 h).
Preferably, a neutralizing agent is added into the mixed system obtained after the first reaction until the pH value of the mixed system is 7.0.
The present invention will be further explained with reference to specific examples and comparative examples.
Example 1
The preparation method of the polycarboxylic acid water reducing agent provided by the embodiment comprises the following steps:
(1) placing 0.14 part of p-toluenesulfonic acid and 4 parts of maleic anhydride into a dry three-neck flask, stirring, heating to 65 ℃, slowly adding 6 parts of 1-hydroxy-2- (imidazole-1-yl) -ethylene-1, 1-diphosphonic acid, stirring at 95 ℃ for reaction for 2.5 hours, and obtaining a phosphonate monomer after the reaction is finished;
(2) preparing 90 parts of EPEG, 0.4 part of sodium hypophosphite and 120 parts of deionized water into kettle bottom liquid for later use;
(3) dissolving 7 parts of methacrylic acid and 4 parts of phosphonate monomer in 23 parts of water to prepare a feed liquid A for later use;
(4) dissolving 0.4 part of potassium sulfite in 20 parts of water to prepare a feed liquid B for later use;
(5) and (3) at normal temperature, adding 0.7 part of hydrogen peroxide into the kettle bottom liquid, dropwise adding the material liquid A and the material liquid B at a constant speed after 7min, wherein the dropwise adding time is 2h, preserving heat for 1h after the dropwise adding is finished, ending the reaction, and adjusting the pH value to be neutral by using alkali to obtain the polycarboxylic acid water reducer.
Example 2
The preparation method of the polycarboxylic acid water reducing agent provided by the embodiment comprises the following steps:
(1) placing 0.12 part of p-toluenesulfonic acid and 3.5 parts of maleic anhydride into a dry three-neck flask, stirring, heating to 55 ℃, slowly adding 5.5 parts of 3-amino-1-hydroxypropane-1, 1-diphosphonic acid, stirring at 105 ℃ for reaction for 3.5 hours, and obtaining phosphonate monomer after the reaction is finished;
(2) dissolving 120 parts of VPEG in 100 parts of deionized water to prepare kettle bottom liquid for later use;
(3) dissolving 10 parts of acrylic acid, 6 parts of phosphonate monomer and 0.6 part of thioglycolic acid in 20 parts of water to prepare a feed liquid A for later use;
(4) dissolving 0.5 part of sodium bisulfite in 23 parts of water to prepare a feed liquid B for later use;
(5) and (3) at normal temperature, adding 1.3 parts of hydrogen peroxide into the kettle bottom liquid, dropwise adding the material liquid A and the material liquid B at a constant speed after 8min, wherein the dropwise adding time is 1h, preserving heat for 1.5h after the dropwise adding is finished, ending the reaction, and adjusting the pH value to be neutral by using alkali to obtain the polycarboxylic acid water reducer.
Example 3
The preparation method of the polycarboxylic acid water reducing agent provided by the embodiment comprises the following steps:
(1) placing 0.1 part of p-toluenesulfonic acid and 3 parts of maleic anhydride into a dry three-neck flask, stirring, heating to 60 ℃, slowly adding 5 parts of 1-hydroxy-3- (methyl n-pentylamino) -propylidene-1, 1-diphosphonic acid, stirring at 100 ℃ for reaction for 3 hours, and obtaining a phosphonate monomer after the reaction is finished;
(2) dissolving 100 parts of EPEG in 100 parts of deionized water to prepare a kettle bottom solution for later use;
(3) dissolving 8 parts of acrylic acid, 4 parts of phosphonate monomer and 0.4 part of mercaptopropionic acid in 22 parts of water to prepare a feed liquid A for later use;
(4) dissolving 0.1 part of vitamin C in 22 parts of water to prepare a feed liquid B for later use;
(5) and (3) at normal temperature, adding 0.7 part of hydrogen peroxide into the kettle bottom liquid, dropwise adding the material liquid A and the material liquid B at a constant speed after 5min, wherein the dropwise adding time is 1.5h, preserving heat for 1h after the dropwise adding is finished, finishing the reaction, and adjusting the pH value to be neutral by using alkali to obtain the polycarboxylic acid water reducer.
Example 4
The preparation method of the polycarboxylic acid water reducing agent provided by the embodiment comprises the following steps:
(1) placing 0.15 part of p-toluenesulfonic acid and 5 parts of maleic anhydride into a dry three-neck flask, stirring, heating to 60 ℃, slowly adding 7 parts of 1-hydroxy-2- (imidazole-1-yl) -ethylidene-1, 1-diphosphonic acid, stirring at 100 ℃ for reaction for 3 hours, and obtaining a phosphonate monomer after the reaction is finished;
(2) dissolving 110 parts of EPEG in 100 parts of deionized water to prepare kettle bottom liquid for later use;
(3) dissolving 10 parts of acrylic acid, 5 parts of phosphonate monomer and 0.4 part of thioglycolic acid in 20 parts of water to prepare a feed liquid A for later use;
(4) dissolving 0.2 part of vitamin C in 20 parts of water to prepare a feed liquid B for later use;
(5) and (3) at normal temperature, adding 0.8 part of hydrogen peroxide into the kettle bottom liquid, dropwise adding the material liquid A and the material liquid B at a constant speed after 10min, wherein the dropwise adding time is 1.5h, preserving heat for 1h after the dropwise adding is finished, finishing the reaction, and adjusting the pH value to be neutral by using alkali to obtain the polycarboxylic acid water reducer.
Example 5
The preparation method of the polycarboxylic acid water reducing agent provided by the embodiment comprises the following steps:
(1) placing 0.13 part of p-toluenesulfonic acid and 3 parts of maleic anhydride into a dry three-neck flask, stirring, heating to 60 ℃, slowly adding 5 parts of 1-hydroxy-2- (imidazole-1-yl) -ethylidene-1, 1-diphosphonic acid, stirring at 100 ℃ for reaction for 3 hours, and obtaining a phosphonate monomer after the reaction is finished;
(2) dissolving 120 parts of VPEG in 120 parts of deionized water to prepare kettle bottom liquid for later use;
(3) dissolving 10 parts of methacrylic acid, 4 parts of phosphonate monomer and 0.6 part of mercaptoethanol in 23 parts of water to prepare a feed liquid A for later use;
(4) dissolving 0.5 part of sodium formaldehyde sulfoxylate in 23 parts of water to prepare a feed liquid B for later use;
(5) and (3) at normal temperature, adding 1.1 parts of ammonium persulfate into the bottom liquid of the kettle, dropwise adding the feed liquid A and the feed liquid B at a constant speed after 8min, wherein the dropwise adding time is 1.5h, preserving heat for 1h after the dropwise adding is finished, finishing the reaction, and adjusting the pH value to be neutral by using alkali to obtain the polycarboxylic acid water reducer.
Comparative example 1
The common polycarboxylic acid water reducing agent is sold on the market.
Comparative example 2
Comparative example 2 differs from example 3 only in that the polycarboxylate water reducer does not contain a phosphonate monomer.
Test examples
Concrete performance tests were carried out on the polycarboxylic acid water-reducing agents prepared in examples 1 to 5 and comparative examples 1 to 2 and a commercially available ordinary polycarboxylic acid water-reducing agent.
Adopting conch P.O 42.5.5 cement; class II fly ash; machine-made sand with fineness modulus of 2.60 (mud content of 5%); crushed stone with the particle size of 5-30 mm; the folding and solid content of the polycarboxylic acid water reducing agent is 0.15 percent. Concrete performance tests were performed according to the concrete mix ratios of table 1.
TABLE 1C 30 concrete test mix proportion (kg cm)-3)
The working performance and slump change of the freshly mixed concrete were measured according to GB/T-50080-2016 ordinary concrete mixture Performance test method, as shown in Table 2.
TABLE 2 Effect of different polycarboxylic acid water reducing agents on concrete slump/extension
As can be seen from the test results in Table 2, the water-reducing rate and slump retaining property of the polycarboxylate water reducers prepared in examples 1 to 5 are superior to those of the common polycarboxylate water reducers on the market and the polycarboxylate water reducers prepared in proportion. The polycarboxylate superplasticizer prepared by the method has excellent raw material adaptability and can resist clay adsorption to a certain extent.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The polycarboxylate superplasticizer is characterized by being mainly prepared from the following raw materials in parts by weight:
90-120 parts of unsaturated polyether macromonomer, 4-6 parts of phosphonate monomer, 7-10 parts of unsaturated carboxylic small monomer, 0.7-1.3 parts of initiator, 0.1-0.5 part of reducing agent and 0.4-0.6 part of chain transfer agent;
the phosphonate monomer is mainly prepared from the following raw materials in parts by weight:
0.1-0.15 part of catalyst, 3-5 parts of unsaturated anhydride and 5-7 parts of diphosphonic acid.
2. The polycarboxylate superplasticizer according to claim 1, wherein said unsaturated polyether macromonomer comprises at least one of ethylene glycol monovinyl polyglycol ether and 4-hydroxybutyl vinyl polyoxyethylene ether;
and/or the bisphosphonic acid comprises at least one of 1-hydroxy-2- (imidazol-1-yl) -ethylene-1, 1-bisphosphonic acid, 3-amino-1-hydroxypropane-1, 1-bisphosphonic acid, and 1-hydroxy-3- (methyl-n-pentylamino) -propylidene-1, 1-bisphosphonic acid;
and/or the unsaturated anhydride comprises at least one of maleic anhydride and itaconic anhydride;
and/or the unsaturated carboxylic small monomer comprises at least one of maleic anhydride, acrylic acid and methacrylic acid.
3. The polycarboxylate water reducer according to claim 1, characterized in that the initiator comprises at least one of hydrogen peroxide, sodium persulfate, ammonium persulfate and potassium persulfate;
and/or, the catalyst comprises at least one of p-toluenesulfonic acid, zinc acetate and manganese acetate;
and/or the reducing agent comprises at least one of sodium sulfite, potassium sulfite, sodium bisulfite, vitamin C and sodium formaldehyde sulfoxylate;
and/or the chain transfer agent comprises at least one of sodium hypophosphite, mercaptoethanol, mercaptoacetic acid and mercaptopropionic acid.
4. The polycarboxylate water reducer according to claim 1, characterized in that the raw materials of the polycarboxylate water reducer further comprise a neutralizer;
preferably, the neutralizing agent is an alkali solution;
preferably, the alkali solution is selected from at least one of a potassium hydroxide solution and a sodium hydroxide solution;
preferably, the mass concentration of the alkali in the alkali solution is 25-30%.
5. The preparation method of the polycarboxylic acid water reducer according to any one of claims 1 to 4, characterized by comprising the steps of:
mixing the unsaturated polyether macromonomer, the phosphonate monomer, the unsaturated carboxylic acid small monomer, the initiator, the reducing agent, the chain transfer agent and water, and carrying out a first reaction;
the preparation method of the phosphonate monomer comprises the following steps: and (3) carrying out a second reaction on the mixture of the catalyst, the unsaturated anhydride and the diphosphonic acid under the heating condition.
6. The preparation method of the polycarboxylate water reducer according to claim 5, characterized in that the first reaction specifically comprises the following steps:
dropwise adding a material A and a material B into a first mixed system of the unsaturated polyether macromonomer, the initiator and first water to obtain a second mixed system; carrying out heat preservation treatment on the second mixed system;
the material A is a mixture of the phosphonate monomer, the unsaturated carboxylic acid small monomer, the chain transfer agent and second water;
the material B is a mixture of a reducing agent and third water;
preferably, the dripping time is 1-2 h;
preferably, the heat preservation time is 1-2 h;
preferably, after the first mixed system is kept stand for 5-10 min, the material A and the material B are dripped.
7. The preparation method of the polycarboxylate water reducer as claimed in claim 6, wherein the mass ratio of the unsaturated polyether macromonomer to the first water is (90-120): (100-120);
and/or the mass ratio of the unsaturated carboxylic acid small monomer to the phosphonate monomer to the chain transfer agent to the second water is (7-10): (4-6): (0.4-0.6): (20-23);
and/or the mass ratio of the reducing agent to the third water is (0.1-0.5): (20-23).
8. The preparation method of the polycarboxylate water reducer according to claim 5, wherein the preparation method of the phosphonate monomer specifically comprises the following steps: and (3) carrying out heat treatment on the mixture of the catalyst and the unsaturated acid anhydride, and then adding the diphosphonic acid for heating.
9. The preparation method of the polycarboxylate water reducer according to claim 8, characterized in that the temperature of the heat treatment is 55-65 ℃;
preferably, the heating temperature is 95-105 ℃, and the heating time is 2.5-3.5 h.
10. The preparation method of the polycarboxylate water reducer as claimed in claim 5, characterized in that a neutralizing agent is added to the mixed system obtained after the first reaction until the pH of the mixed system is 7.0.
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