CN108912279B - High-adaptability multi-branched-chain amide imine polycarboxylic water reducer and preparation method thereof - Google Patents
High-adaptability multi-branched-chain amide imine polycarboxylic water reducer and preparation method thereof Download PDFInfo
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- CN108912279B CN108912279B CN201810915919.1A CN201810915919A CN108912279B CN 108912279 B CN108912279 B CN 108912279B CN 201810915919 A CN201810915919 A CN 201810915919A CN 108912279 B CN108912279 B CN 108912279B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 57
- -1 amide imine Chemical class 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 56
- 239000002253 acid Substances 0.000 claims abstract description 49
- 239000003999 initiator Substances 0.000 claims abstract description 26
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 15
- 229920000570 polyether Polymers 0.000 claims abstract description 15
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 10
- CWERGRDVMFNCDR-UHFFFAOYSA-M thioglycolate(1-) Chemical compound [O-]C(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-M 0.000 claims abstract description 8
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims abstract description 7
- 229940071127 thioglycolate Drugs 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 18
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 8
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 7
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- 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 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 6
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 6
- 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 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
- 229930003268 Vitamin C Natural products 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 3
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 235000019154 vitamin C Nutrition 0.000 claims description 3
- 239000011718 vitamin C Substances 0.000 claims description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Natural products OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 2
- 125000006353 oxyethylene group Chemical group 0.000 claims description 2
- 239000004568 cement Substances 0.000 abstract description 18
- 230000001603 reducing effect Effects 0.000 abstract description 11
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 20
- 239000007864 aqueous solution Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 10
- 150000001408 amides Chemical class 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000012986 chain transfer agent Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 230000000977 initiatory effect Effects 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical compound [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229920002614 Polyether block amide Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- DGVVJWXRCWCCOD-UHFFFAOYSA-N naphthalene;hydrate Chemical compound O.C1=CC=CC2=CC=CC=C21 DGVVJWXRCWCCOD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention relates to a high-adaptability multi-branched-chain amide imine type polycarboxylic water reducer and a preparation method thereof, belonging to the technical field of concrete admixtures. The polycarboxylic acid water reducing agent consists of the following substances: polyether macromonomer, unsaturated acid monomer, branched chain type functional monomer methoxy polyethylene glycol thioglycolate, amide imine type functional monomer diethylenetriamine maleic acid ester, initiator, reducing agent and deionized water; wherein the molar ratio of the polyether macromonomer, the unsaturated acid monomer, the branched chain type monomer and the amide imine type monomer is 1: 2-5: 0.3-0.6: 0.5-1.0. The prepared water reducing agent has higher water reducing rate and excellent slump retaining performance, and solves the adaptability problem between cement concrete and the polycarboxylic acid water reducing agent. The invention also provides a preparation method of the composition, which comprises four steps, is scientific, reasonable, simple and feasible.
Description
Technical Field
The invention relates to a high-adaptability multi-branched-chain amide imine type polycarboxylic water reducer and a preparation method thereof, belonging to the technical field of concrete admixtures.
Background
During the production process of cement, mineral admixtures such as fly ash, mineral powder and the like with different qualities are used as mixed materials to be mixed. Due to the difference between the fly ash and the mineral powder, the adaptability problem of cement concrete and polycarboxylic acid water reducing agent can be caused to a certain extent, and the problem is further aggravated by numerous domestic cement brands. The poor adaptability is mainly shown by the phenomena of no water reducing plasticizing effect, quick concrete slump loss, shrinkage increase, easy cracking and the like.
The polycarboxylic acid water reducing agent is a third generation water reducing agent after lignin and naphthalene water reducing agents, and is widely applied at present due to a plurality of advantages. The molecular structure of the polycarboxylic acid water reducing agent has designability, and the functionalization including the performances of slow release, early strength, shrinkage reduction and the like can be realized by adjusting the polymerization degree of a main chain, the length of a branched chain and the proportion of carboxyl. The development of polycarboxylic acid water reducers can be divided into first-generation polyester type, second-generation polyether type and third-generation amide type water reducers. The third-generation amide polycarboxylic acid water reducing agent has more excellent performance, and is highlighted in the aspects of high water reducing rate, good plasticity retention property and adaptability to cement concrete, but few domestic research reports on the third-generation amide polycarboxylic acid water reducing agent exist.
The patent with the application number of CN201610824083.5 selects a methacrylic acid monomer, a sodium methallyl sulfonate monomer and polyethylene glycol monomethyl ether methacrylamide as raw materials, and prepares a novel amide polycarboxylic acid water reducer with low mixing amount, high water reducing rate, good slump retention and high early strength through free radical copolymerization, but the used polyethylene glycol monomethyl ether methacrylamide has higher cost and restricts the popularization of the novel amide polycarboxylic acid water reducer.
Patent CN201710934295.3 describes a polycarboxylic acid water reducing agent with an amide/imide structure and a preparation method thereof. The polycarboxylic acid water reducer is prepared by obtaining polymerizable polyether amine through amino-terminated polyether amide/imidization and then carrying out copolymerization reaction with active monomers, and has the advantages of high water reducing rate, good slump retaining performance and the like. However, this method has problems that the raw materials are not easily available and the yield of polyether amine is low.
Patent CN201510463669.9 reports that an amide type polycarboxylic acid water reducing agent is synthesized by using polyethylene glycol acrylate, maleic anhydride, acrylamide and sodium methallyl sulfonate under the action of microwaves. Although the method has low energy consumption, industrialization still needs a current day.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a highly-adaptive multi-branched amide imine type polycarboxylic acid water reducing agent which has higher water reducing rate and excellent slump retaining performance and solves the adaptability problem between cement concrete and the polycarboxylic acid water reducing agent.
Meanwhile, the invention also provides a preparation method of the composition, which is scientific, reasonable, simple and feasible.
The highly-adaptive multi-branched amidoimine type polycarboxylic acid water reducing agent consists of the following substances: polyether macromonomer, unsaturated acid monomer, branched chain type functional monomer methoxy polyethylene glycol thioglycolate, amide imine type functional monomer diethylenetriamine maleic acid ester, initiator, reducing agent and deionized water;
wherein the molar ratio of the polyether macromonomer, the unsaturated acid monomer, the branched chain type monomer and the amide imine type monomer is 1: 2-5: 0.3-0.6: 0.5-1.0.
The polyether macromonomer is one or two of isopentenyl polyoxyethylene ether or methyl allyl polyoxyethylene ether, and is represented by the following general formula
The unsaturated acid monomer is one or more of acrylic acid, methacrylic acid or itaconic acid.
The branched chain type functional monomer methoxy polyethylene glycol thioglycollate has the following molecular formula:
the preparation method comprises the following steps:
adding a certain amount of methoxypolyethylene glycol MPEG400 with the molecular weight of 400 and thioglycolic acid MTA into a reaction kettle, heating to 40 ℃, adding a catalyst concentrated sulfuric acid, slowly heating to 105-115 ℃, keeping the temperature for 6.0h, cooling, adding part of water to obtain a branched chain type functional monomer methoxypolyethylene glycol thioglycolic acid ester JYQ with the solid content of 50%, wherein the molar ratio of methoxypolyethylene glycol to thioglycolic acid is 1:1.2, and the dosage of the catalyst is 0.7% of the total mass of methoxypolyethylene glycol and thioglycolic acid.
The amide imine type functional monomer diethylenetriamine maleic acid ester has the following molecular formula:
the preparation method comprises the following steps:
adding a certain amount of diethylenetriamine DEA and maleic anhydride MAL into a reaction kettle, heating to 50 ℃, adding a catalyst p-toluenesulfonic acid, slowly heating to 100-110 ℃, keeping the temperature for 5.0h, cooling, and adding part of water to obtain an amidoimine functional monomer diethylenetriamine maleic acid ester XAY with 50% of solid content; the molar ratio of the maleic anhydride to the diethylenetriamine is 1.05:1, and the dosage of the catalyst is 1.5 percent of the total mass of the diethylenetriamine and the maleic anhydride.
The initiator is one of hydrogen peroxide, sodium peroxide or ammonium persulfate; the adding amount is 0.5-2.0% of the total mass of the reaction monomers.
The reducing agent is vitamin C or sodium bisulfite; the mass ratio of the initiator to the initiator is 0.1:1-1.0: 1.0.
The preparation method of the high-adaptability multi-branched-chain amide imine polycarboxylic water reducer comprises the following steps:
1) firstly, adding a certain amount of polyether macromonomer and deionized water into a reaction kettle to prepare a solution with the concentration of 40-70 wt%, and heating to 40-60 ℃ to obtain a base solution;
2) preparing an unsaturated acid monomer, a branched chain monomer, an amide imine monomer, a reducing agent and deionized water into a solution A; preparing an initiator and deionized water into a solution B; dripping the solution A and the solution B into the base solution at the reaction temperature of 40-60 ℃;
3) after the dropwise addition is finished, continuously preserving the heat and reacting for 1.0-2.0h at the temperature of 40-60 ℃;
4) cooling to below 30 ℃, adjusting the pH value to 7.0-8.0 by using sodium hydroxide, and adding deionized water to dilute the total solid content of the reaction system to 30-40% to obtain the product.
In the step 2, the mass concentration of the solution A is 40-60%, and the mass concentration of the solution B is 2-8%.
In the step 2, the dropping time of the solution A is 1.0-4.0h, and the dropping time of the solution B is 1.5-4.5 h.
The branched monomer methoxy polyethylene glycol mercaptoacetate can provide a branched functional group, has a chain transfer effect, adjusts the free radical reaction rate of acrylic acid AA, and does not need to additionally add a chain transfer agent.
The combination of the long chain branch provided by the polyether macromonomer and the short chain branch provided by the branched chain type functional monomer in the water reducer molecule can generate excellent steric hindrance combination effect, so that the water reducer molecule shows higher water reducing property and better slump retaining property after being adsorbed by cement particles.
The amide imine functional monomer contains nitrogen atoms with lone pair electrons, which can complex calcium ions to form a calcium-rich protective layer, and delays the hydration of cement, so that the polycarboxylic acid water reducer molecule has excellent slump retaining performance, wide adaptability, better physical and mechanical properties and better durability.
Compared with the prior art, the invention has the following beneficial effects:
1. by introducing a branched functional monomer into the polycarboxylic acid water reducer molecule and forming a structure combining a long branch and a short branch together with a polyether macromonomer, the polycarboxylic acid water reducer has high water reducing rate and good slump retaining performance; the amide imine monomer contains lone pair electrons to form a calcium-rich protective layer, and simultaneously, the rigidity and flexibility of the molecular chain of the polycarboxylic acid water reducing agent are improved, so that the concrete has higher water reducing rate, excellent slump retentivity, better concrete easiness and mechanical durability, and wide adaptability;
2. in the polymerization reaction, a redox initiation system is adopted, so that the initiation temperature of the reaction can be reduced, the controllability is strong, the initiation efficiency is high, and the yield of the product is increased;
3. the branched chain type monomer contains sulfydryl, so that the effect of chain transfer can be achieved, no additional chain transfer agent is added, and the cost of the product can be reduced.
Detailed Description
The present invention will be further described with reference to the following examples.
For simplicity, the following methallyl polyoxyethylene ether is referred to as HPEG; TPEG represents isopentenyl polyoxyethylene ether; DEA represents diethylenetriamine; XAY represents an amide imine type functional monomer diethylenetriamine maleic acid ester; JYQ represents methoxypolyethylene glycol thioglycolate; AA represents acrylic acid; MAL represents maleic anhydride; MAA represents methacrylic acid; h2O2Represents hydrogen peroxide; na (Na)2O2Represents sodium peroxide; VC represents vitamin C; NaHSO3Represents sodium bisulfite; APS represents ammonium persulfate; MPC represents mercaptopropionic acid; MTA represents thioglycolic acid.
Into a four-necked flask equipped with a thermometer, mechanical stirring, reflux condenser and dropping funnel were charged 192g of MPEG400(0.5 mol), 55.2g of MTA (0.6mol), 1.73g of concentrated sulfuric acid as a catalyst (0.7 wt%), and the mixture was stirred up to 110 ℃. Nitrogen with water was introduced and the distillate was analyzed at regular intervals. When the water content in the distillate is close to the theoretical water yield, the reaction time is about 6.0h, and the reaction is stopped. 142.0g of distilled water was added, and when the ester was completely dissolved, the stirring was stopped, and the product had a solid content of 60% JYQ.
51.6g of DEA (0.5 mol), 51.4g of MAL (0.53mol) and 1.55g (1.5 wt%) of a catalyst (p-toluenesulfonic acid) were put into a four-necked flask equipped with a thermometer, a mechanical stirrer, a reflux condenser and a dropping funnel, and stirred up to 105 ℃ for 5.0 hours at a constant temperature. The temperature was reduced to 80 ℃ and 104.5g of distilled water were added, and when the polymer had dissolved completely, the stirring was stopped and the product was XAY with a 50% solids content.
Example 1
HPEG molecular weight 3000, the HPEG macromonomer: AA: XAY: the molar ratio of JYQ is 1:3.0:0.3:0.6, the initiator is H2O2The amount of which is 1.3% by weight, based on the total mass of the monomers, of H2O2And VC in a mass ratio of 1: 0.3.
Adding HPEG into a reaction bottle, adding quantitative deionized water to prepare 50% aqueous solution, opening the stirring, and heating to 60 ℃. AA. XAY, JYQ, VC and a certain amount of water are mixed to obtain 40% aqueous solution A, initiator H2O22.0% aqueous solution B was prepared and added dropwise to the base solution at 60 ℃. Wherein the material A is dripped at a constant speed for 2.0h, and the material B is dripped at a constant speed for 2.5 h. After the material B is added, continuously keeping the temperature at 60 ℃ for 2.0 h. And (3) cooling to below 30 ℃, adjusting the pH to 7.0 by using sodium hydroxide, and then adding water to adjust the solid content to 30%, thus obtaining the product S1 of the multi-branched amide imine polycarboxylic acid water reducing agent.
Example 2
TPEG molecular weight 1200, TPEG macromonomer: AA: XAY: the molar ratio of JYQ is 1:5.0:0.5:0.8, the initiator is APS, the amount of the initiator is 1.0 wt% of the total mass of the monomers, and the mass ratio of APS to VC is 1: 0.5.
Adding TPEG into a reaction bottle, adding quantitative deionized water to prepare a 60% aqueous solution, stirring, and heating to 50 ℃. AA, XAY, JYQ, VC and a certain amount of water are prepared into a 50% aqueous solution A, an initiator APS is prepared into a 3.0% aqueous solution B by adding water, and the aqueous solution B is dripped into a base solution at 50 ℃. Wherein the material A is dripped at a constant speed for 1.5h, and the material B is dripped at a constant speed for 2.0 h. After the material B is added, the temperature is kept for 1.0h at 50 ℃. And (3) cooling to below 30 ℃, adjusting the pH to 7.0 by using sodium hydroxide, and then adding water to adjust the solid content to 40%, thus obtaining the multi-branched amide imine polycarboxylic acid water reducing agent product S2.
Example 3
TPEG molecular weight 2400, HPEG molecular weight 3000, the TPEG and HPEG macromonomers: MAA: XAY: the molar ratio of JYQ is 1:4.0:0.6:1.0, the initiator is Na2O2The amount of N is 0.8 wt% based on the total mass of the monomers2O2And VC in a mass ratio of 1: 0.5.
Adding TPEG and HPEG into a reaction bottle, adding quantitative deionized water to prepare 65% aqueous solution, stirring, and heating to 40 ℃. Preparing AA, XAY, JYQ, VC and a certain amount of water into a 60% aqueous solution A, and adding an initiator Na2O2Adding water to prepare a 5% aqueous solution B, and dripping into the base solution at 40 ℃. Wherein the material A is dripped at a constant speed for 2.5h, and the material B is dripped at a constant speed for 3.0 h. After the material B is added, the temperature is kept for 2.0h at 40 ℃. And (3) cooling to below 30 ℃, adjusting the pH to 8.0 by using sodium hydroxide, and then adding water to adjust the solid content to 35%, thus obtaining the multi-branched amide imine polycarboxylic acid water reducing agent product S3.
Comparative example 1
HPEG molecular weight 1200, HPEG: the molar ratio of AA is 1:3, the initiator is APS, and the dosage of the initiator is 1.2 percent of the total mass of the monomers; the chain transfer agent was MPC and its amount used was 0.5% of the total mass of the monomers.
Adding HPEG1200 into a reaction bottle, adding a certain amount of deionized water to prepare a 50% aqueous solution, stirring, and heating to 70 ℃. AA, a chain transfer agent and a certain amount of water are prepared into a 40% aqueous solution A, an initiator APS is prepared into a 5.0% solution B by adding water, and the solution B is dripped into a base solution at the temperature of 70 ℃ at the same time, and the dripping is finished within 3.0 h. A. And after the material B is added, continuing to preserve heat for 1.5h, cooling to below 30 ℃, adjusting the pH to 7.0-8.0 by using sodium hydroxide, and adding water to adjust the solid content to about 35% to obtain a comparative product C1.
Comparative example 2
TPEG molecular weight 2400, HPEG: the AA molar ratio is 1:3, the initiator is H2O2In an amount of2.0% of the total mass; the chain transfer agent was MTA and was used in an amount of 0.3% of the total mass of the monomers.
Adding TPEG2400 in the amount, adding a certain amount of deionized water to prepare 55% aqueous solution, stirring, and heating to 60 ℃. Preparing AA, MTA and a certain amount of water into 35% aqueous solution A and initiating agent H2O23.0% solution B was prepared and added dropwise to 60 ℃ bottom water. Wherein the material A is dripped at a constant speed for 3.0h, and the material B is dripped at a constant speed for 3.5 h. After the material B is added, the temperature is kept for 1.5h at 60 ℃. And then cooling to below 30 ℃, adjusting the pH to 7.0-8.0 by using sodium hydroxide, and then adding water to adjust the solid content to 40% to obtain a comparative product C2.
Comparative example 3
HPEG molecular weight 3000, HPEG: the AA molar ratio is 1:4, the initiator is APS, and the dosage of the initiator is 1.0 percent of the total mass of the monomers; the chain transfer agent was MTA and was used in an amount of 1.0% of the total mass of the monomers.
Adding HPEG3000 into a reaction bottle, adding a certain amount of deionized water to prepare a 60% aqueous solution, preparing AA, MTA and a certain amount of water into a 40% aqueous solution A, preparing a 3.5% solution B with an initiator APS, and simultaneously dripping into a base solution at 70 ℃, wherein the material A is added after 4.0h, and the material B is added after 4.5 h. After the material A is added, the temperature is kept for 2.0h at 70 ℃. And (3) cooling to below 30 ℃, adjusting the pH to 7.0-8.0 by using sodium hydroxide, and adding water to adjust the solid content to about 35% to obtain a comparative product C3.
Effects of the implementation
The effects of the use of the above 3 examples and 3 comparative examples are specifically described below: the samples obtained in the 3 examples are numbered as S1, S2 and S3 in sequence; the samples obtained in the 3 comparative examples are numbered C1, C2 and C3 in sequence.
The net paste fluidity was measured according to GB/T8077-2012 standard, using a hill aluminum P.O42.5 cement, a water cement ratio of 0.29, and the net paste fluidity results are shown in Table 1.
TABLE 1 Net Performance test for examples S1-S3 and comparative examples C1-C3
Note: net pulp fluidity retention (%) of 1h net pulp fluidity/initial net pulp fluidity
As can be seen from Table 1, the initial net slurry fluidity of comparative example samples C1-C3 is about 220mm, the net slurry fluidity after 1h is about 170mm, and the net slurry fluidity retention rate is 75-80%. The initial net slurry fluidity of the samples S1-S3 is about 240mm, the net slurry fluidity after 1h is about 210mm, and the net slurry fluidity retention rate is 88-90%. The multi-branched amide imine type polycarboxylic acid water reducing agent has better net slurry fluidity and fluidity retention performance for 1h, wherein the performance of the example S3 is the best.
Detecting concrete according to GB8076, and selecting landscape brand P.O 42.5.5 cement, landscape aluminum brand P.O 42.5.5 cement and reference cement; the sand is the sand in the area II, the fineness modulus is 2.8, and the mud content is 1.3%; the pebbles are crushed stones with the nominal grain diameter of 5 mm-20 mm, and are graded in a second grade, wherein 5 mm-10 mm accounts for 40%, 10 mm-20 mm accounts for 60%, and the continuous grading requirement is met.
The reference concrete mixing proportion is cement: sand: stone: water 360: 855: 965: 230, the mixing amount of the detected polycarboxylic acid water reducer is 0.2 percent (calculated by bending solid).
And (3) detecting the water reducing rate, the air content, the change of the slump with time, and the compressive strengths of 3d, 7d and 28d of the concrete. The adaptability of the multi-branched amidoimine-type polycarboxylic acid water-reducing agent obtained in example S3 was tested, and the results are shown in Table 2.
TABLE 2 adaptability of multi-branched-chain amide imine polycarboxylic acid water reducing agent to different cements
Table 2 shows that compared with the common polycarboxylic acid water reducing agent C2, the concrete mixed by the multi-branched-chain amide imine polycarboxylic acid water reducing agent S3 and the standard cement, the Shanshui brand cement and the Shanai brand cement has high water reducing rate, small change of slump with the lapse of time, better and high compressive strength of 3d, 7d and 28d, good concrete workability and better adaptability.
Claims (10)
1. A highly-adaptive multi-branched-chain amide imine type polycarboxylic acid water reducing agent is characterized in that: prepared from the following materials: polyether macromonomer, unsaturated acid monomer, branched chain type functional monomer methoxy polyethylene glycol thioglycolate, amide imine type functional monomer diethylenetriamine maleic acid ester, initiator, reducing agent and deionized water;
wherein the molar ratio of the polyether macromonomer, the unsaturated acid monomer, the branched chain type monomer and the amide imine type monomer is 1: 2-5: 0.3-0.6: 0.5-1.0;
the branched chain type functional monomer methoxy polyethylene glycol thioglycollate has the following molecular formula:
the amide imine type functional monomer diethylenetriamine maleic acid ester has the following molecular formula:
2. the highly adaptable multi-branched amide imine type polycarboxylic acid water reducing agent according to claim 1, characterized in that: the polyether macromonomer is one or two of isopentenyl polyoxyethylene ether or methyl allyl polyoxyethylene ether, and is represented by the following general formula
Wherein R is1Is CH3Or H, EO is an oxyethylene group, and n is an average addition mole number of the oxyalkylene group and is 25 to 120.
3. The highly adaptable multi-branched amide imine type polycarboxylic acid water reducing agent according to claim 1, characterized in that: the unsaturated acid monomer is one or more of acrylic acid, methacrylic acid or itaconic acid.
4. The highly adaptable multi-branched amide imine type polycarboxylic acid water reducing agent according to claim 1, characterized in that: the preparation method of the branched functional monomer methoxy polyethylene glycol thioglycollate comprises the following steps:
adding a certain amount of methoxypolyethylene glycol with the molecular weight of 400 and thioglycolic acid MTA into a reaction kettle, heating to 40 ℃, adding a catalyst concentrated sulfuric acid, slowly heating to 105-115 ℃, keeping the temperature for 6.0h, cooling, adding part of water to obtain a branched chain type functional monomer methoxypolyethylene glycol thioglycolic acid ester with the solid content of 50%, wherein the molar ratio of methoxypolyethylene glycol to thioglycolic acid is 1:1.2, and the dosage of the catalyst is 0.7% of the total mass of methoxypolyethylene glycol and thioglycolic acid.
5. The highly adaptable multi-branched amide imine type polycarboxylic acid water reducing agent according to claim 1, characterized in that:
the preparation method of the amide imine functional monomer diethylenetriamine maleic acid ester comprises the following steps:
adding a certain amount of diethylenetriamine and maleic anhydride into a reaction kettle, heating to 50 ℃, adding a catalyst of p-toluenesulfonic acid, slowly heating to 100-110 ℃, keeping the temperature for 5.0h, cooling, and adding part of water to obtain an imido type functional monomer diethylenetriamine maleic acid ester with 50% of solid content; the molar ratio of the maleic anhydride to the diethylenetriamine is 1.05:1, and the dosage of the catalyst is 1.5 percent of the total mass of the diethylenetriamine and the maleic anhydride.
6. The highly adaptable multi-branched amide imine type polycarboxylic acid water reducing agent according to claim 1, characterized in that: the initiator is one of hydrogen peroxide, sodium peroxide or ammonium persulfate, and the addition amount of the initiator is 0.5-2.0% of the total mass of the reaction monomers.
7. The highly adaptable multi-branched amide imine type polycarboxylic acid water reducing agent according to claim 1, characterized in that: the reducing agent is vitamin C or sodium bisulfite; the mass ratio of the initiator to the initiator is 0.1:1-1.0: 1.0.
8. A preparation method of the highly adaptable multi-branched amide imine type polycarboxylic acid water reducing agent according to claim 1, characterized by comprising: the method comprises the following steps:
1) firstly, adding a certain amount of polyether macromonomer and deionized water into a reaction kettle to prepare a solution with the concentration of 40-70 wt%, and heating to 40-60 ℃ to obtain a base solution;
2) preparing an unsaturated acid monomer, a branched chain monomer, an amide imine monomer, a reducing agent and deionized water into a solution A; preparing an initiator and deionized water into a solution B; dripping the solution A and the solution B into the base solution at the reaction temperature of 40-60 ℃;
3) after the dropwise addition is finished, continuously preserving the heat and reacting for 1.0-2.0h at the temperature of 40-60 ℃;
4) cooling to below 30 ℃, adjusting the pH value to 7.0-8.0 by using sodium hydroxide, and adding deionized water to dilute the total solid content of the reaction system to 30-40% to obtain the product.
9. The preparation method of the highly adaptable multi-branched amide imine type polycarboxylic acid water reducing agent according to claim 8, characterized in that: in the step 2, the mass concentration of the solution A is 40-60%, and the mass concentration of the solution B is 2-8%.
10. The preparation method of the highly adaptable multi-branched amide imine type polycarboxylic acid water reducing agent according to claim 8, characterized in that: in the step 2, the dropping time of the solution A is 1.0-4.0h, and the dropping time of the solution B is 1.5-4.5 h.
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