CN110105499B - Hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducing agent and preparation method thereof - Google Patents
Hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducing agent and preparation method thereof Download PDFInfo
- Publication number
- CN110105499B CN110105499B CN201910485886.6A CN201910485886A CN110105499B CN 110105499 B CN110105499 B CN 110105499B CN 201910485886 A CN201910485886 A CN 201910485886A CN 110105499 B CN110105499 B CN 110105499B
- Authority
- CN
- China
- Prior art keywords
- water reducing
- reducing agent
- hyperbranched polyamine
- ester
- polycarboxylic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 67
- 239000002253 acid Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 31
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 7
- 150000002148 esters Chemical class 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- 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 12
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- SZHIIIPPJJXYRY-UHFFFAOYSA-M sodium;2-methylprop-2-ene-1-sulfonate Chemical group [Na+].CC(=C)CS([O-])(=O)=O SZHIIIPPJJXYRY-UHFFFAOYSA-M 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-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
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- 125000004386 diacrylate group Chemical group 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 239000004568 cement Substances 0.000 abstract description 11
- 230000001603 reducing effect Effects 0.000 abstract description 11
- 239000002245 particle Substances 0.000 abstract description 7
- 229920000587 hyperbranched polymer Polymers 0.000 abstract description 5
- 239000004570 mortar (masonry) Substances 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000006845 Michael addition reaction Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 238000002390 rotary evaporation Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- 229920005646 polycarboxylate Polymers 0.000 description 4
- 125000004185 ester group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000008030 superplasticizer Substances 0.000 description 3
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 2
- 229920000831 ionic polymer Polymers 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- -1 N, N-dihydroxyethyl-3-amino butyl Chemical group 0.000 description 1
- GTTSNKDQDACYLV-UHFFFAOYSA-N Trihydroxybutane Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 150000003138 primary alcohols Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
Images
Classifications
-
- 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
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
-
- 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)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducing agent and a preparation method thereof2Monomer, and then AB2Mixing the monomer, trimethylolpropane and a catalyst to prepare a hyperbranched polyamine-ester polymer, finally mixing an ester macromonomer, the hyperbranched polyamine-ester polymer and an unsaturated acid small monomer to prepare a solution A, and adding the solution A and an initiator solution into a chain transfer agent solution to prepare the hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducing agent. The hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducing agent has a highly branched structure similar to a hyperbranched polymer, provides a new molecular structure, increases the steric hindrance between water reducing agent molecules and cement particles, and enhances the water reducing effect of the water reducing agent.
Description
Technical Field
The invention belongs to the field of water reducing agents, and particularly relates to a hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducing agent and a preparation method thereof.
Background
With the development of economy and society, people have higher and higher requirements on the building industry. The development of the building industry cannot be separated from the development of the concrete technology, and the development of the concrete technology cannot be separated from the development of the concrete admixture. The water reducing agent is used for reducing the dosage of mixing water, changing the setting time and improving the strength of concrete under the condition that the dosage of cement and sand is not changed; the flocculation on the surface of the cement particles is hindered through the surface activity, the electrostatic repulsion or the steric hindrance, and the dispersibility of the cement particles is improved, so that the strength of the concrete is improved while the water consumption is reduced.
The existing water reducing agent is a third-generation high-performance water reducing agent represented by a polycarboxylic acid water reducing agent and is applied to actual engineering construction. The polycarboxylate superplasticizer molecules are in a comb-shaped long-chain structure, the structure of the polycarboxylate superplasticizer molecules comprises ionic polymers, polar groups and the like, electrostatic repulsion is provided through the ionic polymers, steric hindrance is provided through a side chain structure, the contact area of cement particles and water is increased, and the fluidity of cement is improved. However, researches show that the steric hindrance is the main action mechanism, and the comb-shaped long-chain structure of the polycarboxylate superplasticizer greatly limits the improvement of the steric hindrance.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducing agent which can effectively increase the steric hindrance between water reducing agent molecules and cement particles and enhance the water reducing effect;
the second purpose of the invention is to provide a preparation method of the water reducing agent.
The technical scheme is as follows: the hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducing agent has the structure
Wherein,
a＝1-100，b＝1-100，c＝1-100，n＝10-100。
the invention discloses a method for preparing a hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducing agent, which comprises the following steps:
(1) preparation of hyperbranched polyamine-ester polymers: dissolving diethanolamine in anhydrous methanol, dropwise adding organic monoester, and reacting at 30-50 ℃ for 4-6 h to obtain AB2A monomer; will AB2Mixing the monomer, trimethylolpropane and a catalyst, and reacting for 3-5 hours at 100-120 ℃ in a heat preservation manner to obtain a hyperbranched polyamine-ester polymer; wherein, trimethylolpropane and AB2The molar ratio of the monomer to the catalyst is 1: (3-12): (0.1 to 0.8);
(2) preparing the hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducing agent: mixing an ester macromonomer, a hyperbranched polyamine-ester polymer and an unsaturated acid small monomer to prepare a solution A, adding the solution A and an initiator solution into a chain transfer agent solution, adjusting the pH value to 6-8, and reacting at 60-120 ℃ for 3-6 hours to prepare a hyperbranched polyamine-ester polycarboxylic acid high-efficiency water reducing agent; wherein the molar ratio of the ester macromonomer, the hyperbranched polyamine-ester polymer, the unsaturated acid small monomer, the chain transfer agent and the initiator is 1: (0.5-2.5): (3-5): (1-2): (0.2-2).
When the preparation method is used, diethanolamine is firstly added on organic monoester to prepare AB with smaller molecular weight2A type monomer; then, taking trihydroxy methyl propane as a core, carrying out condensation reaction, removing a hydroxyl and H atoms, and forming a hyperbranched polymer with the end group of hydroxyl, wherein the hyperbranched polymer has the advantages of more branched chains, good solubility and a large amount of linear molecules such as end groups and the like which are not possessed by linear molecules; finally, the hyperbranched polymer is adopted to modify the polycarboxylate water reducing agent, a spherical structure is grafted on the original comb-shaped structure, the branching degree of molecules is increased, and further the steric hindrance effect of the water reducing agent molecules and cement is improved, so that the cement has better dispersibility, and the overall fluidity is improved.
Further, in the step (1), the molar ratio of diethanolamine, anhydrous methanol and organic monoester may be 1: (0.2-0.5): (0.5 to 3).
Further, in the step (1), the organic monoester may be methyl methacrylate, methyl acrylate or butyl acrylate. The catalyst is concentrated sulfuric acid, p-toluenesulfonic acid or phosphotungstic acid. In the step (2), the ester macromonomer can be polyethylene glycol monoacrylate, polyethylene glycol diacrylate or polyethylene glycol methacrylate. The unsaturated acid small monomer can be acrylic acid, methacrylic acid or maleic anhydride. The chain transfer agent may be sodium methallylsulfonate or dodecyl mercaptan. The initiator may be ammonium persulfate, potassium persulfate or hydrogen peroxide.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: the hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducing agent has high branch similar to hyperbranched polymerThe chemical structure provides a new molecular structure, increases the steric hindrance between the water reducing agent molecules and cement particles, and enhances the water reducing effect of the water reducing agent; meanwhile, the water reducing agent contains sulfonic acid groups in the branched chain structure, so that on one hand, hydrogen bonds can be formed with water, and the dispersibility of cement particles is improved; on the other hand promote C2S and C3The hydration of S improves the strength of concrete, has the advantages of low mixing amount, excellent slump-retaining performance, high water reducing rate, strong adjustability on molecular structure, capability of improving the strength of concrete, less environmental pollution in the production process and the like, and has wide development prospect in the actual application of concrete.
Drawings
FIG. 1 is an infrared spectrum of a hyperbranched polymer of the invention;
FIG. 2 is an infrared diagram of the hyperbranched polyamine-ester type polycarboxylic acid high efficiency water reducing agent of the invention.
Detailed Description
The technical solution of the present invention is further described in detail with reference to the accompanying drawings and examples.
Example 1
The preparation method of the hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducing agent comprises the following steps:
1) preparation of hyperbranched polyamine-ester polymers: under the protection of nitrogen, 0.6mol of diethanolamine is dissolved in 0.2mol of absolute methanol, 0.6mol of methyl acrylate is dripped, the temperature is kept at 40 ℃ for 6 hours for reaction, and AB is prepared by Michael addition reaction2The monomer (N, N-dihydroxyethyl-3-amino methyl propionate) is subjected to rotary evaporation at 40 ℃ to remove methanol; followed by 0.3mol AB2Mixing a monomer and 0.1mol of trimethylolpropane, adding 0.01mol of p-toluenesulfonic acid as a catalyst, reacting for 3 hours at 120 ℃, placing the mixture in a vacuum drying oven, purifying for 1 hour at-0.1 MPa and 120 ℃, and taking out to prepare a hyperbranched polyamine-ester polymer;
2) preparing a hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducing agent: 0.3mol of acrylic acid, 0.1mol of hyperbranched polyamine-ester polymer and 0.1mol of polyethylene glycol acrylate monoester are dissolved in 180ml of deionized water to prepare solution A, 0.02mol of ammonium persulfate is dissolved in 120ml of deionized water to prepare solution B, 0.1mol of sodium methallyl sulfonate is dissolved in 210ml of water, the solution A and the solution B are simultaneously dripped after the solution A is dissolved by heating to 80 ℃, the solution A is dripped for 1.5h, the solution B is dripped for 2.5h, the heat preservation reaction is carried out for 3h after the dripping is finished to carry out the free radical copolymerization reaction, the pH value is adjusted to be 7 by 30 percent of sodium hydroxide solution, and water is added to prepare the hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducing agent with the mass concentration of 20 percent.
The synthesis of the hyperbranched polyamine-ester polymer is shown as the following formula (I):
meanwhile, infrared spectroscopic analysis was performed on the hyperbranched polyamine-ester type polymer prepared by the present invention, and the obtained results are shown in fig. 1. As can be seen from FIG. 1, 3456cm-1A stretching vibration peak of hydroxyl appears; 2950cm-1And 2881cm-1C-H stretching vibration peaks of methyl and methylene respectively; 1727cm-1Is the absorption peak of carbonyl, and the C ═ O stretching vibration belonging to the ester group; 1600cm-1Is the stretching vibration peak of the tertiary amine group; 1192cm-1Is trimethylolpropane and AB2A stretching vibration peak of transesterification of monomers; 1058cm-1Is the C-O absorption peak in primary alcohols. It follows that hyperbranched polyamine-ester polymers have been successfully synthesized.
The water reducing agent prepared by the invention is subjected to infrared spectroscopic analysis, as shown in figure 2, at 3427cm-1And 2873cm-1The absorption peak appears, which indicates the existence of carboxyl; at 2500-2000 cm-1No absorption peak exists between the two monomers, which indicates that no double bond exists in the molecule and all the monomers are copolymerized; present 1717cm-1And 1643cm-1The absorption peak of (a), indicating the presence of an ester group; 1565cm-1And 1455cm-1Is the vibration absorption peak of carboxylic acid hydrolysis; 1250cm-1And 1104cm-1Is the stretching vibration peak of sulfonic acid; 960cm-1And 865cm-1The absorption peak is the absorption of the carboxyl external variation angle vibration of the trans-double bond. From this, it can be seen that the water reducing agent has groups such as carboxylic acid, ester group, and sulfonic acid group, and the structure thereof is as follows.
Wherein,
a＝1-100，b＝1-100，c＝1-100，n＝10-100。
infrared spectroscopy is sufficient and the core paper is published and also described in infrared spectroscopy.
Performance detection
And adding 0.4% of water reducing agent into the mortar, and detecting the water reducing agent to obtain that the water reducing rate of the mortar reaches 28.2%, the initial fluidity of the mortar is 231mm, and the fluidity after 2 hours is 204 mm.
Example 2
The preparation method of the hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducing agent comprises the following steps:
1) preparation of hyperbranched polyamine-ester polymers: under the protection of nitrogen, 0.6mol of diethanolamine is dissolved in 0.2mol of anhydrous methanol, then 0.6mol of methyl acrylate is dripped, the temperature is kept at 40 ℃ for 6 hours for reaction, and AB is prepared by Michael addition reaction2Performing rotary evaporation on the monomer at 40 ℃ to remove methanol; followed by 0.6mol AB2Mixing a monomer and 0.1mol of trimethylolpropane, adding 0.01mol of p-toluenesulfonic acid as a catalyst, reacting for 3 hours at 120 ℃, placing the mixture in a vacuum drying oven, purifying for 1 hour at-0.1 MPa and 120 ℃, and taking out to prepare a hyperbranched polyamine-ester polymer;
2) preparing a hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducing agent: 0.5mol of acrylic acid, 0.05mol of hyperbranched polyamine-ester polymer and 0.1mol of polyethylene glycol acrylate monoester are dissolved in 150ml of deionized water to prepare solution A, 0.03mol of ammonium persulfate is dissolved in 150ml of deionized water to prepare solution B, 0.2mol of sodium methallyl sulfonate is dissolved in 220ml of water, the solution A and the solution B are simultaneously dripped after the solution A is dissolved by heating to 80 ℃, the solution A is dripped for 2 hours, the solution B is dripped for 3 hours, the heat preservation reaction is carried out for 3 hours after the dripping is finished, the free radical copolymerization reaction is carried out, the pH value is adjusted to be 7 by using 30 percent of sodium hydroxide solution, and water is added to prepare the hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducing agent with the mass concentration of 20 percent.
The structural formula is as follows:
wherein,
a＝1-100，b＝1-100，c＝1-100，n＝10-100。
performance detection
And adding 0.4% of water reducing agent into the mortar, and detecting the water reducing agent to obtain that the water reducing rate of the mortar reaches 31.4%, the initial fluidity of the mortar is 255mm, and the fluidity of the mortar is 218mm after 2 hours.
Example 3
The preparation method of the hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducing agent comprises the following steps:
1) preparation of hyperbranched polyamine-ester polymers: under the protection of nitrogen, 0.6mol of diethanolamine is dissolved in 0.15mol of anhydrous methanol, then 0.3mol of methyl acrylate is dripped, the temperature is kept at 40 ℃ for 6 hours, and AB is prepared by Michael addition reaction2Performing rotary evaporation on the monomer at 40 ℃ to remove methanol; followed by 0.3mol AB2Mixing a monomer and 0.1mol of trimethylolpropane, adding 0.01mol of p-toluenesulfonic acid as a catalyst, reacting for 3 hours at 120 ℃, placing the mixture in a vacuum drying oven, purifying for 1 hour at-0.08 MPa and 120 ℃, and taking out to prepare a hyperbranched polyamine-ester polymer;
2) preparing a hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducing agent: 0.5mol of acrylic acid, 0.05mol of hyperbranched polyamine-ester polymer and 0.1mol of polyethylene glycol monoacrylate are dissolved in 150ml of deionized water to prepare solution A, 0.02mol of ammonium persulfate is dissolved in 120ml of deionized water to prepare solution B, 0.1mol of sodium methallylsulfonate is dissolved in 220ml of water, the solution A and the solution B are simultaneously dripped after the solution A is dissolved by heating to 80 ℃, the solution A is dripped for 2 hours, the solution B is dripped for 3 hours, the heat preservation reaction is carried out for 3 hours after the dripping is finished, the pH value is adjusted to be 7 by using 30% of sodium hydroxide solution, and water is added to prepare the hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducer with the mass concentration of 20%.
The structural formula is as follows:
wherein,
a＝1-100，b＝1-100，c＝1-100，n＝10-100。
performance detection
And adding 0.4% of water reducing agent into the mortar, and detecting the water reducing agent to obtain that the water reducing rate of the mortar reaches 28.8%, the initial fluidity of the mortar is 242mm, and the fluidity of the mortar is 209mm after 2 hours.
Example 4
The preparation method of the hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducing agent comprises the following steps:
1) preparation of hyperbranched polyamine-ester polymers: under the protection of nitrogen, 0.6mol of diethanolamine is dissolved in 0.15mol of anhydrous methanol, then 0.3mol of methyl acrylate is dripped, the temperature is kept at 40 ℃ for 6 hours, and AB is prepared by Michael addition reaction2Performing rotary evaporation on the monomer at 40 ℃ to remove methanol; then 0.6mol AB2Mixing a monomer and 0.1mol of trimethylolpropane, adding 0.01mol of p-toluenesulfonic acid as a catalyst, reacting for 3 hours at 120 ℃, placing the mixture in a vacuum drying oven, purifying for 1 hour at-0.08 MPa and 120 ℃, and taking out to prepare a hyperbranched polyamine-ester polymer;
2) preparing a hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducing agent: 0.3mol of acrylic acid, 0.1mol of hyperbranched polyamine-ester polymer and 0.1mol of polyethylene glycol acrylate monoester are dissolved in 180ml of deionized water to prepare solution A, 0.03mol of ammonium persulfate is dissolved in 150ml of deionized water to prepare solution B, 0.2mol of sodium methallyl sulfonate is dissolved in 210ml of water, the solution A and the solution B are simultaneously dripped after the solution A is dissolved by heating to 80 ℃, the solution A is dripped for 1.5h, the solution B is dripped for 2h, the heat preservation reaction is carried out for 3h after the dripping is finished to carry out the free radical copolymerization reaction, the pH value is adjusted to be 7 by 30 percent of sodium hydroxide solution, and water is added to prepare the hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducing agent with the mass concentration of 20 percent.
The structural formula is as follows:
wherein,
a＝1-100，b＝1-100，c＝1-100，n＝10-100。
performance detection
And adding 0.4% of water reducing agent into the mortar, and detecting the mixture to obtain that the water reducing rate of the mortar reaches 29.1%, the initial fluidity of the mortar is 236mm, and the fluidity of the mortar is 212mm after 2 hours.
Example 5
The preparation method of the hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducing agent comprises the following steps:
1) preparation of hyperbranched polyamine-ester polymers: under the protection of nitrogen, 1mol of diethanolamine is dissolved in 0.2mol of anhydrous methanol, 0.5mol of methyl methacrylate is dripped, the temperature is kept at 30 ℃ for 5 hours for reaction, and AB is prepared by Michael addition reaction2The monomer (N, N-dihydroxyethyl-3-amino-2-methyl propionate) is subjected to rotary evaporation at 40 ℃ to remove methanol; followed by 0.8mol AB2Mixing a monomer and 0.1mol of trimethylolpropane, adding 0.08mol of concentrated sulfuric acid as a catalyst, reacting for 4 hours at the temperature of 110 ℃, placing the mixture in a vacuum drying oven, purifying for 1 hour at the temperature of 120 ℃ and under the pressure of-0.1 MPa, and taking out to prepare a hyperbranched polyamine-ester polymer;
2) preparing a hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducing agent: 0.5mol of methacrylic acid, 0.25mol of hyperbranched polyamine-ester polymer and 0.1mol of polyethylene glycol diacrylate are dissolved in 250ml of deionized water to prepare solution A, 0.02mol of potassium persulfate is dissolved in 220ml of deionized water to prepare solution B, 0.1mol of dodecyl mercaptan is dissolved in 230ml of water, the solution A and the solution B are simultaneously dripped after the solution A is dissolved at the temperature of 120 ℃, the solution A is dripped for 1.5h, the solution B is dripped for 2.5h, the heat preservation reaction is carried out for 5h after the dripping is finished, the free radical copolymerization reaction is carried out, the pH value is adjusted to be 7 by 30 percent of sodium hydroxide solution, and water is added to prepare the hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducing agent with the mass concentration of 20 percent.
The structural formula is as follows:
wherein,
a＝1-100，b＝1-100，c＝1-100，n＝10-100。
performance detection
And adding 0.4% of water reducing agent into the mortar, and detecting the water reducing agent to obtain that the water reducing rate of the mortar reaches 27.3%, the initial fluidity of the mortar is 220mm, and the fluidity of the mortar is 201mm after 2 hours.
Example 6
The preparation method of the hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducing agent comprises the following steps:
1) preparation of hyperbranched polyamine-ester polymers: under the protection of nitrogen, 2mol of diethanolamine is dissolved in 1mol of anhydrous methanol, 6mol of butyl acrylate is dripped, the temperature is kept at 50 ℃ for 4 hours for reaction, and AB is prepared by Michael addition reaction2The monomer (N, N-dihydroxyethyl-3-amino butyl propionate) is subjected to rotary evaporation at 40 ℃ to remove methanol; followed by 1.2mol AB2Mixing the monomer with 0.1mol of trimethylolpropane, adding 0.05mol of phosphotungstic acid as a catalyst, reacting for 5h under the condition of 100 ℃, placing the mixture in a vacuum drying oven, purifying for 1h under the conditions of-0.1 MPa and 120 ℃, and taking out the mixtureTo prepare hyperbranched polyamine-ester polymer;
2) preparing a hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducing agent: 0.5mol of maleic anhydride, 0.25mol of hyperbranched polyamine-ester polymer and 0.1mol of polyethylene glycol methacrylate are dissolved in 250ml of deionized water to prepare solution A, 0.2mol of hydrogen peroxide is dissolved in 220ml of deionized water to prepare solution B, 0.1mol of dodecyl mercaptan is dissolved in 230ml of water, the solution A and the solution B are simultaneously dripped after the solution A is dissolved by heating to 60 ℃, the solution A is dripped for 1.5h, the solution B is dripped for 2.5h, the heat preservation reaction is carried out for 6h after the dripping is finished, the free radical copolymerization reaction is carried out, the pH value is adjusted to be 7 by 30 percent of sodium hydroxide solution, and water is added to prepare the hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducing agent with the mass concentration of 20 percent.
The structural formula is as follows:
wherein,
a＝1-100，b＝1-100，c＝1-100，n＝10-100。
performance detection
And adding 0.4% of water reducing agent into the mortar, and detecting the mixture to obtain that the water reducing rate of the mortar reaches 26.1%, the initial fluidity of the mortar is 224mm, and the fluidity of the mortar is 198mm after 2 hours.
Claims (8)
1. A preparation method of a hyperbranched polyamine-ester type polycarboxylic acid high efficiency water reducing agent is characterized by comprising the following steps:
(1) preparation of hyperbranched polyamine-ester polymers: dissolving diethanolamine in anhydrous methanol, dropwise adding organic monoester, and reacting at 30-50 ℃ for 4-6 h to obtain AB2A monomer; will AB2Mixing the monomer, trimethylolpropane and a catalyst, and reacting for 3-5 hours at 100-120 ℃ in a heat preservation manner to obtain a hyperbranched polyamine-ester polymer; wherein, trimethylolpropane and AB2The molar ratio of the monomer to the catalyst is 1: (3-12): (0.1-0.8), wherein the organic mono-ester is methyl methacrylate, methyl acrylate or butyl acrylate;
(2) preparing the hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducing agent: mixing an ester macromonomer, a hyperbranched polyamine-ester polymer and an unsaturated acid small monomer to prepare a solution A, adding the solution A and an initiator solution into a chain transfer agent solution, and reacting for 3-6 hours at 60-120 ℃ to prepare a hyperbranched polyamine-ester polycarboxylic acid high-efficiency water reducing agent; wherein the molar ratio of the ester macromonomer, the hyperbranched polyamine-ester polymer, the unsaturated acid small monomer, the chain transfer agent and the initiator is 1: (0.5-2.5): (3-5): (1-2): (0.2-2).
2. The method for preparing the hyperbranched polyamine-ester type polycarboxylic acid high efficiency water reducing agent according to claim 1, which is characterized in that: in the step (1), the mol ratio of the diethanolamine to the anhydrous methanol to the organic monoester is 1: (0.2-0.5): (0.5 to 3).
3. The method for preparing the hyperbranched polyamine-ester type polycarboxylic acid high efficiency water reducing agent according to claim 1, which is characterized in that: in the step (1), the catalyst is concentrated sulfuric acid, p-toluenesulfonic acid or phosphotungstic acid.
4. The method for preparing the hyperbranched polyamine-ester type polycarboxylic acid high efficiency water reducing agent according to claim 1, which is characterized in that: in the step (2), the ester macromonomer is polyethylene glycol acrylate monoester, polyethylene glycol diacrylate or polyethylene glycol methacrylate.
5. The method for preparing the hyperbranched polyamine-ester type polycarboxylic acid high efficiency water reducing agent according to claim 1, which is characterized in that: in the step (2), the unsaturated acid small monomer is acrylic acid, methacrylic acid or maleic anhydride.
6. The method for preparing the hyperbranched polyamine-ester type polycarboxylic acid high efficiency water reducing agent according to claim 1, which is characterized in that: in the step (2), the chain transfer agent is sodium methallyl sulfonate or dodecyl mercaptan.
7. The method for preparing the hyperbranched polyamine-ester type polycarboxylic acid high efficiency water reducing agent according to claim 1, which is characterized in that: in the step (2), the initiator is ammonium persulfate, potassium persulfate or hydrogen peroxide.
8. The hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducing agent obtained by the preparation method of any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910485886.6A CN110105499B (en) | 2019-06-05 | 2019-06-05 | Hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducing agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910485886.6A CN110105499B (en) | 2019-06-05 | 2019-06-05 | Hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducing agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110105499A CN110105499A (en) | 2019-08-09 |
| CN110105499B true CN110105499B (en) | 2021-08-31 |
Family
ID=67493924
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910485886.6A Active CN110105499B (en) | 2019-06-05 | 2019-06-05 | Hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducing agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110105499B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113698548A (en) * | 2021-08-31 | 2021-11-26 | 湖北恒利建材科技有限公司 | High-performance polycarboxylate superplasticizer and preparation method thereof |
| CN113716923A (en) * | 2021-09-13 | 2021-11-30 | 湖北恒利建材科技有限公司 | Cement-based grouting material for semi-flexible mixture and preparation method thereof |
| CN114163578A (en) * | 2021-11-11 | 2022-03-11 | 科之杰新材料集团(海南)有限公司 | Viscosity-controlled polycarboxylate superplasticizer and preparation method thereof |
| CN115093487B (en) * | 2021-12-30 | 2023-07-25 | 江苏超力建材科技有限公司 | Hydration heat inhibitor and preparation method thereof |
| CN114890694A (en) * | 2022-04-13 | 2022-08-12 | 安徽永茂泰环保科技有限公司 | Cement material based on aluminum ash recycling and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103613306B (en) * | 2013-11-18 | 2016-09-07 | 济南大学 | A kind of poly carboxylic acid series water reducer containing hyperbranched polyamine-ester structure and preparation method thereof |
| CN107325296A (en) * | 2017-08-02 | 2017-11-07 | 盐城工学院 | Hyperbranched poly carboxylic acid water reducer and preparation method thereof |
-
2019
- 2019-06-05 CN CN201910485886.6A patent/CN110105499B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110105499A (en) | 2019-08-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110105499B (en) | Hyperbranched polyamine-ester type polycarboxylic acid high-efficiency water reducing agent and preparation method thereof | |
| CN103613306B (en) | A kind of poly carboxylic acid series water reducer containing hyperbranched polyamine-ester structure and preparation method thereof | |
| CN102504247B (en) | Hyperbranched polymer, hyperbranched polycarboxylic acid-series super plasticizer and preparation method thereof | |
| CN107474196B (en) | Polycarboxylate superplasticizer for low-slump concrete and preparation method thereof | |
| WO2019129307A2 (en) | Preparation method for polycarboxylate water reducer having regular sequence structure | |
| CN101817657A (en) | Polycarboxylic acid slump retaining agent | |
| CN103467669A (en) | Early-strength polycarboxylate water-reducing agent and preparation method thereof | |
| CN112795022B (en) | Anti-cracking shrinkage-reducing polycarboxylate superplasticizer and preparation method thereof | |
| WO2014059765A1 (en) | Super plasticizer for precast concrete component | |
| CN103265201A (en) | Sorbitol modified polycarboxylate-type water reducing agent and synthetic method thereof | |
| CN104193913A (en) | Early-strength polycarboxylate concrete water reducing agent and preparation method thereof | |
| CN101906193A (en) | Method for synthesizing polycarboxylic acid water reducing agent | |
| CN104628972A (en) | Preparation method of anti-crack shrinkage reducing polycarboxylate based superplasticizer | |
| CN105440276A (en) | Preparation method and application of polymer containing phosphorous acid group | |
| CN110642995A (en) | Preparation method of polycarboxylic acid water reducer for low-slump concrete | |
| WO2022110356A1 (en) | High-early-strength cement dispersion polymer and preparation method therefor | |
| CN111378083A (en) | Polycarboxylic acid dispersant with star structure and preparation method and application thereof | |
| CN111378079A (en) | Star-shaped polycarboxylate superplasticizer with controllable molecular structure and preparation method thereof | |
| CN107163191B (en) | Anti-mud polycarboxylic acid high-efficiency water reducing agent and preparation method thereof | |
| CN107722194B (en) | High-water-reduction polycarboxylic acid cement dispersant and preparation method thereof | |
| CN110078407B (en) | Early-strength hyperbranched polycarboxylate superplasticizer and preparation method thereof | |
| CN112724340A (en) | Viscosity-reducing composite polycarboxylate superplasticizer and preparation method thereof | |
| WO2014059766A1 (en) | Super plasticizer for precast concrete component | |
| CN106957398B (en) | Tree-shaped hyperbranched polycarboxylic acid super-plasticizer of a kind of eight arms and its preparation method and application | |
| CN106188418B (en) | A kind of preparation method of amphoteric polycarboxylate water-reducer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220907 Address after: 230000 Room 203, building 2, phase I, e-commerce Park, Jinggang Road, Shushan Economic Development Zone, Hefei City, Anhui Province Patentee after: Hefei Jiuzhou Longteng scientific and technological achievement transformation Co.,Ltd. Address before: 224051 middle road of hope Avenue, Yancheng City, Jiangsu Province, No. 1 Patentee before: YANCHENG INSTITUTE OF TECHNOLOGY |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221101 Address after: 222000 West Jingyi Road and South Zhongxin Road, Dapu Industrial Zone, Lianyungang Economic and Technological Development Zone, Jiangsu Province Patentee after: JIANGSU LIAN OUTSIDE INDUSTRIAL CO.,LTD. Address before: 230000 Room 203, building 2, phase I, e-commerce Park, Jinggang Road, Shushan Economic Development Zone, Hefei City, Anhui Province Patentee before: Hefei Jiuzhou Longteng scientific and technological achievement transformation Co.,Ltd. |