CN115010875A - Viscosity-reducing polycarboxylate superplasticizer and preparation method thereof - Google Patents

Viscosity-reducing polycarboxylate superplasticizer and preparation method thereof Download PDF

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CN115010875A
CN115010875A CN202110238896.7A CN202110238896A CN115010875A CN 115010875 A CN115010875 A CN 115010875A CN 202110238896 A CN202110238896 A CN 202110238896A CN 115010875 A CN115010875 A CN 115010875A
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viscosity
reducing
parts
polycarboxylate superplasticizer
monomer
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朱建民
刘兆滨
董振鹏
姜云鹏
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Liaoning Oxiranchem Co ltd
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Liaoning Oxiranchem Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2605—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds 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
    • 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
    • C04B24/2664—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers
    • C04B24/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Abstract

The application provides a viscosity-reducing polycarboxylate superplasticizer and a preparation method thereof, the viscosity-reducing polycarboxylate superplasticizer comprises a unit derived from an unsaturated polyether monomer with a structure shown in formula I and a unit derived from a micromolecule monomer containing unsaturated bonds, and the unsaturated polyether monomer has a structure shown in formula (I): r 1 O(R 2 ) m (R 3 ) n R 4 (I) is provided. The viscosity reduction type polycarboxylate superplasticizer provided by the invention introduces a unit derived from an unsaturated polyether monomer containing a longer C chain, so that the polycarboxylate superplasticizer contains a longer side chain structure, the steric hindrance of the polycarboxylate superplasticizer is increased, and the reduction of the polycarboxylate superplasticizer is realizedThe water aqua has more obvious space stabilizing effect and obvious viscosity reducing effect, can better play the steric hindrance effect when acting with sandstone materials such as cement and the like, and has the advantages of low cost, low energy consumption, easy preparation, no pollution to the environment, easy degradation and huge future market prospect.

Description

Viscosity-reducing polycarboxylate superplasticizer and preparation method thereof
Technical Field
The invention relates to the technical field of concrete admixtures, in particular to a viscosity-reducing polycarboxylic acid water reducer and a preparation method thereof.
Background
Concrete is one of the most widely used and used building materials among civil engineering materials, and is also the largest man-made material so far, and is widely used in various civil engineering fields of building engineering, traffic, municipal, water conservancy, energy, ports, ocean engineering, underground engineering, and other special structural engineering.
Admixtures have been developed as an important component of concrete materials into functional products having various properties. The concrete admixture is mainly composed of an early strength agent, a retarder, an air entraining agent, an expanding agent, an accelerator, a pumping aid and a water reducing agent, and the water reducing agent is one of the necessary components in the cement concrete. The existing polycarboxylic acid water reducing agent synthesis technology has the following problems: (1) the polyether structure is single, and the types are few; (2) the polymerization activity is low, uniform polymerization is difficult to realize, the side chain distribution of the synthesized polycarboxylate superplasticizer is uneven, the molecular structure is not essentially changed, and the performance is difficult to be greatly improved, so that the development of a novel functional polycarboxylate superplasticizer is very important.
With the higher and higher technical requirements of modern concrete, high-speed rail and other heavy-duty engineering on gravels, the quantity of natural gravels capable of meeting the requirements is less and less, in order to meet the rigidity requirement of the gravels market, machine-made sand becomes the first choice of the construction market, and the machine-made sand gradually replaces natural gravels to meet the requirement of market situation development. The quality of the machine-made sand is difficult to guarantee, the mud content and the stone powder content in the machine-made sand are relatively high, the adsorption capacity to the added sand is large, and the workability and the retention performance of concrete are greatly influenced.
Patent CN 109053974B discloses a preparation method of a viscosity-reducing polycarboxylic acid water reducer, which is mainly prepared by carrying out free radical polymerization on an isopentenol polyoxyethylene ether monomer, an unsaturated dibasic acid monomer or a derivative monomer thereof and a viscosity-reducing auxiliary agent under the action of a reducing agent, an oxidizing agent and a chain transfer agent, wherein the viscosity-reducing auxiliary agent is fumaric acid diethanolamide phosphate. The proportion of polar hydrophilic groups on a prenyl polyoxyethylene ether molecular chain can be increased by the aid of ethanol groups, amide groups, phosphate groups and other polar groups contained in the molecular structure of the fumaric acid diethanolamide phosphate ester so as to increase the hydrophilic-lipophilic balance value of the water reducer and improve the viscosity reduction effect of the water reducer.
The patent CN 109180876B discloses a preparation method of a viscosity-reducing polycarboxylate water reducer, which is characterized in that a mixture of a product prepared by esterification reaction of allyl hydroxyethyl ether and 2-butane phosphate-1, 2, 4-tricarboxylic acid and single esterification of carboxyl in the 2-butane phosphate-1, 2, 4-tricarboxylic acid, a small amount of product prepared by double esterification and three esterification of carboxyl in the 2-butane phosphate-1, 2, 4-tricarboxylic acid, VPE (vacuum pressure equipment), 2-methacryloyloxyethyl phosphorylcholine and unsaturated acid is copolymerized to prepare the viscosity-reducing polycarboxylate water reducer. The viscosity reduction type polycarboxylate superplasticizer has viscosity reduction performance, water reduction, slump loss prevention and mud resistance, and solves the problems of high viscosity, poor workability and excessive loss caused by large mud content in the existing concrete raw material.
Patent CN 111377643 a discloses a viscosity-reducing polycarboxylic acid water reducer, the main chain of the polymer contains hydrophobic benzene ring and hydrophilic amine, has strong rigidity and good solubility in aqueous solution, is rich in two adsorption groups of carboxyl group/phosphonic acid group, has strong adaptability to concrete materials, and can effectively reduce the viscosity of high-strength concrete (C50-C100).
Disclosure of Invention
The invention aims to provide a viscosity-reducing polycarboxylic acid water reducer to solve the problems of poor concrete workability and high viscosity caused by high mud content of sand and stone materials in the existing concrete; meanwhile, the technical defects that the existing viscosity reduction type polycarboxylate superplasticizer is not ideal in effect, high in energy consumption in the production process and difficult in ensuring the product stability are overcome.
The application provides a viscosity-reducing polycarboxylate superplasticizer which comprises a unit derived from an unsaturated polyether monomer with a structure shown in a formula I and a unit derived from a micromolecule monomer containing an unsaturated bond,
the unsaturated polyether monomer has a structure shown in a formula (I):
R 1 O(R 2 ) m (R 3 ) n R 4 (Ⅰ)
wherein R is 1 Represents a terminal alkenyl group having 9 to 24 carbon atoms, R 2 Represents an acyloxy group having 1 to 6 carbon atoms, m represents 0 or 1, R 3 Represents an alkoxy group having 2 to 12 carbon atoms, n represents the number of alkylene oxide additions, n is an integer of 1 to 400, R 4 Represents a hydrogen atom or an alkyl group having 6 to 9 carbon atoms.
In one embodiment, the unsaturated bond-containing small molecule monomer is selected from one or more of acrylic acid, methacrylic acid, maleic anhydride, sodium allyl sulfonate, and sodium methallyl sulfonate.
In one embodiment, its weight average molecular weight is 20000-70000.
In one embodiment, the weight ratio of units derived from the unsaturated polyether monomer of the structure of formula I to units derived from the small molecule monomer containing an unsaturated bond is 6 to 20: 1.
On the other hand, the preparation method of the viscosity-reducing polycarboxylate superplasticizer comprises the following steps:
and (2) carrying out polymerization reaction on the unsaturated polyether monomer with the structure shown in the formula I and the micromolecule monomer containing an unsaturated bond in the presence of an initiator and an optional chain transfer agent to obtain the viscosity-reducing polycarboxylate superplasticizer.
In one embodiment, the polymerization system comprises the following raw materials in parts by weight:
Figure BDA0002961401440000031
in one embodiment, the initiator is one or more of hydrogen peroxide, sodium formaldehyde sulfoxylate, vitamin C, ferrous sulfate, ammonium persulfate, sodium sulfite, and sodium bisulfite.
In one embodiment, the chain transfer agent is one or more of mercaptopropionic acid, thioglycolic acid, sodium hypophosphite, and sodium aluminum phosphate.
In one embodiment, performing the polymerization reaction comprises:
a. adding deionized water and an unsaturated polyether monomer with a structure shown in formula I into a reactor;
b. adding an initiator to the reactor;
c. simultaneously adding deionized water and a mixture of small molecule monomers containing unsaturated bonds and an optional chain transfer agent and deionized water into a reactor;
d. reacting the contents of the reactor;
e. adding alkali to adjust the pH value to obtain the viscosity-reducing polycarboxylic acid water reducer.
In one embodiment, the temperature of step d is from 40 to 70 ℃ for 2 to 4 hours.
The viscosity reduction type polycarboxylate superplasticizer provided by the invention introduces a unit derived from an unsaturated polyether monomer containing a longer C chain, so that the polycarboxylate superplasticizer contains a longer side chain structure, the steric hindrance of the polycarboxylate superplasticizer is increased, the steric stabilization effect of the polycarboxylate superplasticizer is more obvious, the polycarboxylate superplasticizer has an obvious viscosity reduction effect, the steric hindrance effect of the polycarboxylate superplasticizer can be better exerted when the polycarboxylate superplasticizer is used with sand and stone materials such as cement, and the polycarboxylate superplasticizer has the advantages of low cost, low energy consumption, easiness in preparation, no pollution to the environment, easiness in degradation and huge market prospect in the future.
Detailed Description
The application provides a viscosity-reducing polycarboxylic acid water reducer which is a copolymerization product of an unsaturated polyether monomer with a structure shown in formula I and a micromolecular monomer containing an unsaturated bond,
the unsaturated polyether monomer has a structure shown in a formula (I):
R 1 O(R 2 ) m (R 3 ) n R 4 (Ⅰ)
wherein R is 1 Represents a terminal alkenyl group having 9 to 24 carbon atoms, R 2 Represents an acyloxy group having 1 to 6 carbon atoms, m represents 0 or 1, R 3 Represents an alkoxy group having 2 to 18 carbon atoms, n represents the number of alkylene oxide additions, n is an integer of 1 to 400, R 4 Represents a hydrogen atom or an alkyl group having 6 to 9 carbon atoms.
The viscosity-reducing polycarboxylate superplasticizer comprises a unit derived from an unsaturated polyether monomer with a structure shown in a formula I and a unit derived from a small-molecule monomer containing an unsaturated bond. These units may be present in the polymer chain in random, block, and combinations thereof. In one embodiment, the weight-average molecular weight of the viscosity-reduction type polycarboxylate superplasticizer is 20000-70000.
In one embodiment, the weight ratio of the unsaturated polyether monomer with the structure shown in formula I to the unsaturated bond-containing small molecular monomer is 6-20:1, so that the weight ratio of the unit derived from the unsaturated polyether monomer with the structure shown in formula I to the unit derived from the unsaturated bond-containing small molecular monomer is 6-20: 1.
In one embodiment, the unsaturated bond-containing small molecule monomer is selected from one or more of acrylic acid, methacrylic acid, maleic anhydride, sodium allyl sulfonate, and sodium methallyl sulfonate.
In one embodiment, the unsaturated polyether monomer has the structure of formula I,
R 1 O(R 2 ) m (R 3 ) n R 4 (Ⅰ)
wherein R is 1 Represents a terminal alkenyl group having 9 to 24 carbon atoms, R 2 Represents an acyloxy group having 1 to 6 carbon atoms, m represents 0 or 1, R 3 Represents an alkoxy group having 2 to 12 carbon atoms, n represents the number of alkylene oxide additions, n is an integer of 1 to 400, R 4 Represents a hydrogen atom or an alkyl group having 6 to 9 carbon atoms.
The unsaturated polyether monomer can be prepared by the addition reaction of corresponding alcohol or carboxylic acid or derivatives thereof and alkylene oxide through alkoxylation. For example, when m is 0, the unsaturated polyether monomer can be obtained by alkoxylation of the corresponding alcohol. When m is 1, the unsaturated polyether monomer can be obtained by esterification reaction of corresponding alcohol and corresponding hydroxycarboxylic acid, and then alkoxylation reaction of the esterification product. Those skilled in the art can select these raw materials and reaction conditions as desired. For example, the esterification reaction can be carried out by adding p-toluenesulfonic acid accounting for 6 percent of the total mass of the alcohol and the acid into raw material alcohol and hydroxy acid at the temperature of 95-120 ℃. Various alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, and the like, and combinations thereof can be used as the alkoxylating agent in the alkoxylation reaction.
The unsaturated polyether monomer containing a longer C chain is added during the synthesis of the viscosity-reducing polycarboxylate superplasticizer provided by the invention, so that the synthesized polycarboxylate superplasticizer contains a longer side chain structure, the steric hindrance of the polycarboxylate superplasticizer is increased, the steric stabilization effect of the polycarboxylate superplasticizer is more remarkable, the viscosity-reducing polycarboxylate superplasticizer has an obvious viscosity-reducing effect, the steric hindrance effect of the polycarboxylate superplasticizer can be better exerted when the polycarboxylate superplasticizer is used with sand and stone materials such as cement, the polycarboxylate superplasticizer is low in cost, low in energy consumption, easy to prepare, free of environmental pollution and easy to degrade, and has a huge future market prospect.
The application also provides a preparation method of the viscosity-reducing polycarboxylic acid water reducer, which comprises the following steps:
and (2) carrying out polymerization reaction on the unsaturated polyether monomer with the structure shown in the formula I and the micromolecule monomer containing an unsaturated bond in the presence of an initiator and an optional chain transfer agent to obtain the viscosity-reducing polycarboxylate superplasticizer.
In one embodiment, the polymerization system comprises the following raw materials in parts by weight:
Figure BDA0002961401440000051
in one embodiment, the initiator is one or more of hydrogen peroxide, sodium formaldehyde sulfoxylate, vitamin C, ferrous sulfate, ammonium persulfate, sodium sulfite, and sodium bisulfite.
In one embodiment, the chain transfer agent is one or more of mercaptopropionic acid, thioglycolic acid, sodium hypophosphite, and sodium aluminum phosphate.
In one embodiment, conducting the polymerization reaction comprises:
a. adding deionized water and an unsaturated polyether monomer with a structure shown in formula I into a reactor;
b. adding an initiator to the reactor;
c. simultaneously adding a mixture of deionized water and a small molecule monomer containing an unsaturated bond and an optional chain transfer agent and deionized water into a reactor;
d. reacting the contents of the reactor;
e. adding alkali to adjust the pH value to obtain the viscosity-reducing polycarboxylic acid water reducer.
In one embodiment, the temperature of step d is from 40 to 70 ℃ for 2 to 4 hours.
Specifically, the viscosity-reducing polycarboxylic acid water reducer can be prepared as follows:
adding a certain amount of deionized water into the reactor, starting a stirrer, adding polyether, and stirring and mixing uniformly; adding an initiator into the flask, and uniformly stirring; simultaneously dripping A, B materials by using a peristaltic pump, controlling the dripping time of the material A for 2-3h, controlling the dripping time of the material B for 2-3h, and keeping the temperature for 1-2h after the dripping is finished; adding liquid caustic soda to adjust the pH value to 6-7 to obtain the finished product of the polycarboxylic acid water reducing agent.
Wherein, the drop feed a can be prepared as follows: at room temperature, 20-50 parts of unsaturated bond-containing micromolecule monomer and 30-100 parts of deionized water are sequentially added into a container, uniformly mixed and sealed by a plastic film for later use.
Drop feed B can be prepared as follows: at room temperature, 0-2.5 parts of chain transfer agent (or other monomers, initiator and the like) and 80-155 parts of deionized water are sequentially added into a container, uniformly mixed and sealed by a plastic film for later use.
In one embodiment, the liquid base used to adjust the pH may be an aqueous NaOH solution.
The technical solution of the present invention is further described below with reference to specific embodiments, but is not limited thereto.
The following unsaturated polyether monomers were used in the examples:
T1：R 1 is C9 alkenyl; r 2 Is an acyloxy group of 1 carbon atom; m is 0; r is 3 Is alkoxy of 2 carbon atoms; n is 65; r 4 ＝H。
T2：R 1 Is C9 alkenyl; r is 2 Is an acyloxy group of 1 carbon atom; m is 0; r is 3 Is alkoxy of 2 carbon atoms; n is 65; r 4 ＝H。
T3：R 1 Is C18 alkenyl; r 2 Is acyloxy with 3 carbon atoms; m is 0; r 3 Alkoxy of 12 carbon atoms; n is 107; r 4 Is an alkyl group of 6 carbon atoms.
T4：R 1 Is C9 alkenyl; r is 2 Is acyloxy of 6 carbon atoms; m is 0; r 3 Is alkoxy of 2 carbon atoms; n is 65; r 4 Is 9C atom alkyl.
T5：R 1 Is C24 alkenyl; r 2 Is acyloxy of 6 carbon atoms; m is 0; r 3 Is alkoxy of 2 carbon atoms; n-133; r 4 ＝H。
T6：R 1 Is C9 alkenyl; r 2 Is an acyloxy group of 1 carbon atom; m is 1; r 3 Is alkoxy of 2 carbon atoms; n is 65; r 4 ＝H。
The materials used in the following examples are commercially available products unless otherwise specified. The weight average molecular weights of the polycarboxylic acid water reducing agents of the examples were measured by means of a Beckmann multiangle laser light scattering apparatus.
Preparation example
T1 preparation process: adding 73.5 parts of nonanol into a 2L reaction kettle, adding 1.13 parts of metallic sodium as a catalyst, closing the reaction kettle to enable the reaction kettle to be in a sealed state, raising the temperature to 100 ℃, slowly introducing 1032 parts of ethylene oxide to enable the ethylene oxide to react for 3.5 hours, controlling the temperature to be between 120 and 130 ℃, and controlling the reaction pressure to be 0.35 to 0.45 MPa. Aging for 1.5h after the reaction is finished, cooling and discharging.
T2 preparation process: adding 70.8 parts of nonanol into a 2L reaction kettle, adding 1.08 parts of metallic sodium as a catalyst, closing the reaction kettle to be in a sealed state, heating to 100 ℃, slowly introducing 986 parts of ethylene oxide to react for 3.5 hours, controlling the temperature to be between 120 and 130 ℃, and controlling the reaction pressure to be 0.35 to 0.45 MPa. And (5) aging for 1h after the reaction is finished, and cooling and discharging.
T3 preparation process: adding 73.5 parts of octadecanol into a 2L reaction kettle, adding 1.13 parts of metallic sodium as a catalyst, closing the reaction kettle to be in a sealed state, heating to 100 ℃, slowly introducing 1651 parts of ethylene oxide to react for 3.5 hours, controlling the temperature to be between 120 and 130 ℃, and controlling the reaction pressure to be 0.35 to 0.45 MPa. And (5) aging for 1h after the reaction is finished, and cooling and discharging.
T4 preparation process: adding 78.2 parts of nonanol into a 2L reaction kettle, adding 1.05 parts of metallic sodium as a catalyst, closing the reaction kettle to enable the reaction kettle to be in a sealed state, raising the temperature to 100 ℃, slowly introducing 1164.5 parts of ethylene oxide to enable the ethylene oxide to react for 3.5 hours, controlling the temperature to be 120-130 ℃, and controlling the reaction pressure to be 0.35-0.45 MPa. And (5) aging for 1h after the reaction is finished, and cooling and discharging.
T5 preparation process: adding 67.8 parts of nonanol into a 2L reaction kettle, adding 1.13 parts of metallic sodium as a catalyst, closing the reaction kettle to enable the reaction kettle to be in a sealed state, raising the temperature to 100 ℃, slowly introducing 1824.5 parts of ethylene oxide to enable the ethylene oxide to react for 3.5 hours, controlling the temperature to be 120-130 ℃, and controlling the reaction pressure to be 0.35-0.45 MPa. And (5) aging for 1h after the reaction is finished, and cooling and discharging.
T6 preparation process: adding 150.6 parts of tetracosanol and 294 parts of hydroxy formic acid into a flask provided with a stirrer, starting the stirrer, heating to 90 ℃, uniformly stirring and mixing, adding 13.8 parts of p-toluenesulfonic acid as a catalyst, and uniformly stirring again; reacting for 3h under the protection of nitrogen, and discharging to obtain A1. Adding 73.5 parts of A1 into a 2L reaction kettle, adding 1.13 parts of metallic sodium as a catalyst, closing the reaction kettle to enable the reaction kettle to be in a sealed state, heating to 100 ℃, slowly introducing 1032 parts of ethylene oxide to enable the ethylene oxide to react for 3.5 hours, controlling the temperature to be between 120 and 130 ℃, and controlling the reaction pressure to be 0.35 to 0.45 MPa. And (5) aging for 1h after the reaction is finished, and cooling and discharging.
T1-T6 characterize data:
Figure BDA0002961401440000071
Figure BDA0002961401440000081
the above characterization data acquisition can be referred to GB/T12008-2010.
Example 1
Adding 200 parts of deionized water and 300 parts of T1 polyether into a four-neck flask with a stirrer, starting the stirrer, heating to 65 ℃, and stirring and mixing uniformly; 5 parts of ammonium persulfate is added into the flask at intervals of 5 minutes and is stirred uniformly; dripping A (30 parts of maleic anhydride and 50 parts of deionized water) and B (100 parts of deionized water) simultaneously by using a peristaltic pump, controlling the dripping time for 2 hours for the A material and 2.5 hours for the B material, and keeping the temperature and aging for 2 hours after dripping; after the aging is finished, 28 parts of caustic soda liquid (30% NaOH aqueous solution, the same applies below) and 160 parts of deionized water are added to the mixture to adjust the pH value to 6-7 (wherein the concentration of the caustic soda liquid is 30%), and the finished product of the polycarboxylic acid water reducer p-1 with the weight-average molecular weight of 30500 is obtained.
Example 2
Adding 200 parts of deionized water and 300 parts of T2 polyether into a four-neck flask with a stirrer, starting the stirrer, heating to 50 ℃, and stirring and mixing uniformly; adding 2.4 parts of ammonium persulfate into the flask at intervals of 5 minutes, and uniformly stirring; simultaneously dripping materials A (22 parts of maleic anhydride, 50 parts of deionized water) and B (0.5 part of chain transfer agent, 0.4 part of vitamin C and 100 parts of deionized water) by using a peristaltic pump, controlling the dripping time for 2 hours for the materials A and 2.5 hours for the materials B, and keeping the temperature and aging for 2 hours after dripping; after the aging is finished, cooling to room temperature, adding 19.7 parts of caustic soda liquid and 132.15 parts of deionized water to adjust the pH value to 6-7 (wherein the concentration of the caustic soda liquid is 30%), and obtaining the finished product of the polycarboxylic acid water reducing agent p-2 with the weight-average molecular weight of 24600.
Example 3
Adding 200 parts of deionized water and 300 parts of T3 polyether into a four-neck flask with a stirrer, starting the stirrer, heating to 70 ℃, and stirring and mixing uniformly; adding 4.5 parts of ammonium persulfate into the flask at intervals of 5 minutes, and uniformly stirring; simultaneously dropwise adding 23.78 parts of acrylic acid and 50 parts of deionized water A and 1 part of sodium hypophosphite and 100 parts of deionized water B by using a peristaltic pump, controlling the dropwise adding time for 2 hours for the material A and 2.5 hours for the material B, and keeping the temperature and aging for 2 hours after dropwise adding; after the aging is finished, the temperature can be reduced to room temperature, 22 parts of liquid caustic soda and 153 parts of deionized water are added to adjust the pH value to 6-7 (wherein the concentration of the liquid caustic soda is 30%), and the finished product of the polycarboxylate superplasticizer p-3 with the weight-average molecular weight of 42300 is obtained.
Example 4
Adding 200 parts of deionized water and 300 parts of T4 polyether into a four-neck flask with a stirrer, starting the stirrer, heating to 65 ℃, and stirring and mixing uniformly; 5 parts of ammonium persulfate is added into the flask at intervals of 5 minutes and is stirred uniformly; dripping A (30 parts of maleic anhydride, 6 parts of sodium methallyl sulfonate and 70 parts of deionized water) and B (100 parts of deionized water) by using a peristaltic pump at the same time, controlling the dripping time for 2 hours for the A material and 2.5 hours for the B material, and preserving heat and aging for 2 hours after dripping; after the aging is finished, cooling to room temperature, adding 30 parts of liquid caustic soda and 189 parts of deionized water to adjust the pH value to 6-7 (wherein the concentration of the liquid caustic soda is 30%), and obtaining the finished product of the polycarboxylic acid water reducing agent p-4 with the weight-average molecular weight of 23000.
Example 5
Adding 200 parts of deionized water and 300 parts of T5 polyether into a four-neck flask with a stirrer, starting the stirrer, heating to 65 ℃, and stirring and mixing uniformly; 5.5 parts of ammonium persulfate is added into the flask at intervals of 5 minutes and is stirred uniformly; dripping A (20 parts of methacrylic acid and 50 parts of deionized water) and B (2 g of mercaptopropionic acid and 100 parts of deionized water) simultaneously by using a peristaltic pump, controlling the dripping time for 2 hours for the material A and 2.5 hours for the material B, and preserving heat and aging for 2 hours after dripping; after the aging is finished, cooling to room temperature, adding 16.5 parts of liquid caustic soda and 152.5 parts of deionized water to adjust the pH value to 6-7 (wherein the concentration of the liquid caustic soda is 30%), and obtaining the finished product of the polycarboxylic acid water reducing agent p-5.
Example 6
Adding 200 parts of deionized water and 300 parts of T6 polyether into a four-neck flask with a stirrer, starting the stirrer, heating to 65 ℃, and stirring and mixing uniformly; 4.5 parts of ammonium persulfate is added into the flask at intervals of 5 minutes and is stirred uniformly; simultaneously dripping materials A (30 parts of maleic anhydride and 50 parts of deionized water) and B (0.6 g of mercaptopropionic acid and 100 parts of deionized water) by using a peristaltic pump, controlling the dripping time for 2 hours for the materials A and 2.5 hours for the materials B, and keeping the temperature and aging for 2 hours after dripping; and after the aging is finished, cooling to room temperature, adding 28 parts of caustic soda liquid and 160 parts of deionized water to adjust the pH value to 6-7 (wherein the concentration of the caustic soda liquid is 30%), and obtaining the finished product of the polycarboxylic acid water reducing agent p-6 with the weight-average molecular weight of 38200.
Comparative example
Adding 200 parts of deionized water and 357 parts of methyl alkene butyl polyoxyethylene polyoxypropylene ether into a four-neck flask with a stirrer, starting the stirrer, heating to 40 ℃, and stirring and mixing uniformly; adding 2 parts of hydrogen peroxide into the flask at an interval of 5 minutes, and uniformly stirring; simultaneously dropwise adding A (38.5 parts of acrylic acid and 12.11 parts of deionized water) and B (1.7 parts of mercaptopropionic acid, 0.5 part of vitamin C and 115.3 parts of deionized water) by using a peristaltic pump, controlling the dropwise adding time for 3 hours for the A material and 3.5 hours for the B material, and keeping the temperature and aging for 1 hour after dropwise adding; after the aging is finished, the temperature can be reduced to room temperature, 46 parts of liquid caustic soda and 218.3 parts of deionized water are added to adjust the pH value to 6-7 (wherein the concentration of the liquid caustic soda is 30%), and a finished product polycarboxylate superplasticizer h-1 with the weight-average molecular weight of 39800 is obtained.
The water reducing agent synthesized in the above examples 1 to 3 and comparative examples is weighed according to the reference mixing ratio of sand, gravel, cement, water and the like according to JGJ55, introduced into a concrete mixer for fully mixing, after the concrete is taken out of a pot, a slump cone is inverted, a sealing cover is added to the bottom of the slump cone, the slump cone is quickly filled with the concrete and is leveled by a shovel, a bottom cover is quickly slid open, at the moment, the timing is started by a stopwatch, the time for measuring the concrete flowing empty is recorded as the backflow time of the concrete, and other data acquisition methods or detailed descriptions refer to part B/8076-wall 2008.
The results of the experiments are shown in the following table:
TABLE 1 concrete Properties test results
Sample name The blending amount is% Content of gas% Slump mm Extension degree mm Reverse flow time s
P-1 0.19 2.0 253 580 14.42
p-2 0.19 2.1 245 585 15.76
P-3 0.19 1.8 240 570 14.93
p-4 0.19 1.7 235 570 15.18
p-5 0.18 2.3 230 565 16.32
P-6 0.18 1.6 235 575 15.09
h-1 0.18 2.5 230 575 18.89
The experimental result shows that compared with a commercially available ultrahigh-performance polycarboxylate superplasticizer (h-1), the synthetic viscosity-reducing polycarboxylate superplasticizer disclosed by the invention has the advantages that under the condition of similar concrete expansion degree, the required mixing amount is similar, the air content is equivalent, the slump is better than or equal to that of a commercially available product, the concrete backflow time is obviously better than that of the commercially available product (h-1), and the very obvious reduction is realized, so that the synthetic viscosity-reducing polycarboxylate superplasticizer disclosed by the invention has a good viscosity-reducing effect on concrete. In particular, while the example h-1 uses methyl allyl butyl polyoxyethylene polyoxypropylene ether as one of the raw materials, the unsaturated polyether monomer with longer carbon chain used in the embodiment of the present invention can increase the viscosity reducing effect of the water reducing agent by increasing the carbon chain, which is unexpected to those skilled in the art.
It should be noted that the above-mentioned embodiments are only some of the preferred embodiments for implementing the present invention, and are not intended to limit the present invention. Various other substitutions, alterations and modifications within the scope of the present invention are also intended to be encompassed within the scope of the present invention.

Claims (10)

1. A viscosity-reducing polycarboxylate superplasticizer comprises a unit derived from an unsaturated polyether monomer with a structure shown in formula I and a unit derived from a micromolecule monomer containing an unsaturated bond,
the unsaturated polyether monomer has a structure shown in a formula (I):
R 1 O(R 2 ) m (R 3 ) n R 4 (Ⅰ)
wherein R is 1 Represents a terminal alkenyl group having 9 to 24 carbon atoms, R 2 Represents an acyloxy group having 1 to 6 carbon atoms, m represents 0 or 1, R 3 Represents an alkoxy group having 2 to 12 carbon atoms, n represents the number of alkylene oxide additions, n is an integer of 1 to 400, R 4 Represents a hydrogen atom or an alkyl group having 6 to 9 carbon atoms.
2. The viscosity-reducing polycarboxylate water reducer according to claim 1, wherein the unsaturated bond-containing small-molecule monomer is one or more selected from acrylic acid, methacrylic acid, maleic anhydride, sodium allyl sulfonate and sodium methallyl sulfonate.
3. The viscosity-reducing polycarboxylic acid water-reducing agent according to claim 1, wherein the weight-average molecular weight thereof is 20000-70000.
4. The viscosity-reducing polycarboxylate water reducer according to claim 1, wherein the weight ratio of the units derived from the unsaturated polyether monomer having the structure of formula I to the units derived from the unsaturated bond-containing small-molecule monomer is 6-20: 1.
5. The method for preparing the viscosity-reducing polycarboxylic acid water reducing agent of any one of claims 1 to 4, comprising:
and (2) carrying out polymerization reaction on the unsaturated polyether monomer with the structure shown in the formula I and the micromolecule monomer containing an unsaturated bond in the presence of an initiator and an optional chain transfer agent to obtain the viscosity-reducing polycarboxylate superplasticizer.
6. The preparation method according to claim 5, wherein the polymerization reaction system comprises the following raw materials in parts by weight:
Figure FDA0002961401430000011
7. the preparation method according to claim 5, wherein the initiator is one or more of hydrogen peroxide, sodium formaldehyde sulfoxylate, vitamin C, ferrous sulfate, ammonium persulfate, sodium sulfite, and sodium bisulfite.
8. The preparation method according to claim 5, wherein the chain transfer agent is one or more of mercaptopropionic acid, thioglycolic acid, sodium hypophosphite and sodium aluminum phosphate.
9. The production method according to claim 5, wherein performing the polymerization reaction includes:
a. adding deionized water and an unsaturated polyether monomer with a structure shown in formula I into a reactor;
b. adding an initiator to the reactor;
c. simultaneously adding deionized water and a mixture of small molecule monomers containing unsaturated bonds and an optional chain transfer agent and deionized water into a reactor;
d. reacting the contents of the reactor;
e. adding alkali to adjust the pH value to obtain the viscosity-reducing polycarboxylic acid water reducer.
10. The method of claim 9, wherein the temperature of step d is 40-70 ℃ for 2-4 hours.
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