CN111348858A - Early-strength polycarboxylate superplasticizer and preparation method thereof - Google Patents

Early-strength polycarboxylate superplasticizer and preparation method thereof Download PDF

Info

Publication number
CN111348858A
CN111348858A CN201811634113.1A CN201811634113A CN111348858A CN 111348858 A CN111348858 A CN 111348858A CN 201811634113 A CN201811634113 A CN 201811634113A CN 111348858 A CN111348858 A CN 111348858A
Authority
CN
China
Prior art keywords
glycol ether
vinyl
monomer
terminated
methyl
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.)
Granted
Application number
CN201811634113.1A
Other languages
Chinese (zh)
Other versions
CN111348858B (en
Inventor
周栋梁
杨勇
冉千平
李申桐
严涵
刘金芝
黄振
张志勇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Bote New Materials Co Ltd
Bote New Materials Taizhou Co Ltd
Original Assignee
Jiangsu Bote New Materials Co Ltd
Bote New Materials Taizhou Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Jiangsu Bote New Materials Co Ltd, Bote New Materials Taizhou Co Ltd filed Critical Jiangsu Bote New Materials Co Ltd
Priority to CN201811634113.1A priority Critical patent/CN111348858B/en
Publication of CN111348858A publication Critical patent/CN111348858A/en
Application granted granted Critical
Publication of CN111348858B publication Critical patent/CN111348858B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C04B24/24—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
    • 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
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • 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
    • C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/302—Water reducers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (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 discloses an early-strength polycarboxylate superplasticizer and a preparation method thereof. The early-strength polycarboxylate superplasticizer is prepared by copolymerizing unsaturated reactive polyether and unsaturated comonomer with active hydrogen under the condition of no water or solvent, and then performing ring-opening grafting on epoxy groups and the active hydrogen contained in a silane monomer. The invention introduces the silicon element which is the same as the cement component, and uses silane groups to completely replace anionic groups to be used as the adsorption groups of the polymer, thereby changing the electrical property of the polycarboxylate superplasticizer molecules, reducing the sensitivity of the polycarboxylate superplasticizer to the electrical property of the material surface, obviously improving the early strength of the concrete, and ensuring that the later strength of the concrete is not shrunk.

Description

Early-strength polycarboxylate superplasticizer and preparation method thereof
Technical Field
The invention belongs to the technical field of concrete admixtures, and particularly relates to a polycarboxylic acid water reducing agent with a function of improving the early strength of concrete and a preparation method thereof.
Background
The large-scale infrastructure and urbanization process of the country is a great trend of development, the construction industry still is one of the most beneficial industries, and the building industrialization rate is rapidly improved along with the development of the construction industry. The construction of a series of heavy projects including large bridges, nuclear power, hydropower, super high-rise buildings and the like puts higher requirements on concrete. The engineering construction difficulty is gradually increased, the construction environment is more and more complex, especially the strength requirement of high-performance concrete is more and more high, and the use amount of industrial waste residue components is more and more large. Therefore, the stable and fast construction performance of the high-performance concrete under different regions and temperature conditions is very important.
The Chinese territory has wide breadth, and the geological conditions and mineral composition have obvious difference, which causes great difference in the quality of cement components, admixtures and sandstone materials. The temperature difference between China and the temperature difference between the south and the north in four seasons is obvious, and the factors bring challenges to concrete construction in different regions. High performance concrete admixtures have become an indispensable component for the preparation of high performance concrete. The quality fluctuation of the high-performance concrete can be caused by the different performances of the high-performance concrete admixture under different construction temperature conditions. Therefore, the high-performance concrete admixture is required to provide higher requirements on the aspects of improving the product dispersing capacity, the compatibility and adaptability to concrete materials, the early reinforcing capacity and the like.
The concrete admixture has various types, the performance of the concrete can be improved by selecting a proper water reducing agent variety, and the engineering requirement can be met by adding micromolecular components with various functions into a concrete system. In order to solve the problems of adaptability and early strength application, constructors generally adopt a mode of increasing the admixture dosage or the micromolecule early strength agent, the method undoubtedly increases the cost, and the micromolecule early strength agent also brings the problem of later strength shrinkage. In order to solve the problems, researchers at home and abroad carry out a great deal of improvement work, and the research in the field is focused on polycarboxylic acid series water reducing agents by virtue of excellent comprehensive properties and modifiable molecular structures. A great number of Chinese patents already disclose related polycarboxylic acid dispersants and preparation methods thereof, and also provide more methods for improving material adaptability and early strength capability, but certain problems still exist.
Patents CN107163201A and CN107245131A propose a method of modifying polyether macromonomer with silane coupling agent, and then copolymerizing with polyether macromonomer and unsaturated carboxylic acid, and the water reducing agent prepared by the method shows more excellent slump retaining property than common polycarboxylic acid water reducing agent. The method modifies the polyether macromonomer to ensure that partial side chain molecules in the molecules have adsorption groups, and the method changes the conformation of the polycarboxylic acid molecules.
Patents such as CN104311753B, CN105754045B, CN105837763A, CN104945572A, CN103073687B and CN107629163A all adopt a double-bond-containing silane coupling agent or prepare an unsaturated silane coupling agent containing double bonds to be copolymerized with a polyether macromonomer and an unsaturated carboxylic acid monomer, and a small amount of silane groups are introduced into molecules so as to improve the adaptability, the dispersibility and the plasticity retention of the polycarboxylic acid water reducing agent molecules. The method can introduce a small amount of silane groups into molecules, has insufficient influence on the action process of the polycarboxylic acid water reducing agent, has poor water solubility of unsaturated silane monomers, generates heterogeneous reaction during aqueous solution polymerization, and has certain problem of monomer conversion rate.
Disclosure of Invention
In order to improve the selective behavior of the conventional polycarboxylate water reducer in adsorption on the surface of cement through anionic groups, the silicon element which is the same as the cement component is introduced, and the silane groups are used for completely replacing the anionic groups to serve as the adsorption groups of the polymer, so that the electrical property of the polycarboxylate water reducer molecules is changed, the sensitivity of the polycarboxylate water reducer to the electrical property of the material surface is reduced, the early strength of concrete can be obviously improved, and the later strength of the concrete is ensured not to be shrunk.
The invention provides an early-strength polycarboxylate superplasticizer which is prepared by copolymerizing unsaturated reactive polyether and unsaturated comonomer with active hydrogen under the condition of no water or solvent and then performing ring-opening grafting on epoxy groups and active hydrogen contained in a silane monomer. Compared with the conventional polycarboxylic acid molecular structure, the early strength polycarboxylic acid water reducing agent has no carboxylic acid groups in the molecules, and silane groups are adopted to completely replace the carboxylic acid groups in the conventional polycarboxylic acid water reducing agent.
The early-strength polycarboxylate superplasticizer is prepared by copolymerizing polymerizable unsaturated monomer A, B, C, D to form a prepolymer with a comb-shaped structure, and then adding monomer E into the prepolymer for grafting reaction;
the molar ratio of the monomer A, B, C, D is 1 (0-4): 0-4, and the molar number of the monomer B, C, D is not 0 at the same time;
the total molar ratio of the monomer E to the monomer (B + C + D) is the same;
the monomer A is represented by the general formula (1):
Figure BDA0001929627190000031
in the general formula (1), R1Represents H or CH3；R2Representative O, CH2O、CH2CH2O、CH2CH2CH2O or CH2CH2CH2CH2O；R3Represents an alkyl group having 1 to 4 carbon atoms; p is the average addition mole number of the ethylene oxide and is an integer of 50-180;
the monomer B is represented by the general formula (2):
Figure BDA0001929627190000032
in the general formula (2), R4Represents H or CH3(ii) a m represents the number of repeating units of an ethylene oxide group in the structural formula, n represents the number of repeating units of a propylene oxide group, and m and n take the values of 0 and 1, and are not 0 nor 1 at the same time;
the monomer C is represented by the general formula (3):
Figure BDA0001929627190000033
in the general formula (3), R5Represents H or CH3(ii) a k represents the number of repeating units of methylene, and the value of k is an integer of 0-4; x represents the number of repeating units of an ethylene oxide group in the structural formula, y represents the number of repeating units of a propylene oxide group, and x and y are integers of 0-2 and are not 0 at the same time;
the monomer D is represented by the general formula (4):
Figure BDA0001929627190000034
in the general formula (4), R6And R7Each independently represents H or CH3；
The monomer E is an epoxy silane compound.
The structural formula of the prepolymer of the invention conforms to the following general formula (5):
Figure BDA0001929627190000041
in the general formula (5), a, B, C and D respectively represent the number of repeating units of a monomer A, a monomer B, a monomer C and a monomer D, the values of B, C and D satisfy the condition that the ratio of (B + C + D)/a is any value of 3-10, and the values of B, C and D are not zero at the same time.
The weight average molecular weight of the prepolymer is 50000-120000. If the molecular weight is too small and too large, it brings about adverse effects on the dispersion property, slump-retaining property and material suitability of the concrete.
R in the general formula (1)1When H, monomer A is selected from methoxy terminated vinyl polyalkylene glycol ethers, ethoxy terminated vinyl polyalkylene glycol ethers, propoxy terminated vinyl polyalkylene glycol ethers, butoxy terminated vinyl polyalkylene glycol ethers, methoxy terminated hydroxyethyl vinyl polyalkylene glycol ethers, ethoxy terminated hydroxyethyl vinyl polyalkylene glycol ethers, propoxy terminated hydroxyethyl vinyl polyalkylene glycol ethers, butoxy terminated hydroxyethyl vinyl polyalkylene glycol ethers, methoxy terminated hydroxypropyl vinyl polyalkylene glycol ethers, ethoxy terminated hydroxypropyl vinyl polyalkylene glycol ethers, propoxy terminated hydroxypropyl vinyl polyalkylene glycol ethers, butoxy terminated hydroxypropyl vinyl polyalkylene glycol ethers, methoxy terminated hydroxybutyl vinyl polyalkylene glycol ethers, methoxy terminated hydroxypropyl vinyl polyalkylene glycol ethers, methoxy terminated vinyl polyalkylene glycol ethers, and mixtures thereof, Any one or more than one of ethoxy terminated hydroxybutyl vinyl polyalkylene glycol ether, propoxy terminated hydroxybutyl vinyl polyalkylene glycol ether and butoxy terminated hydroxybutyl vinyl polyalkylene glycol ether are mixed in any proportion.
R in the general formula (1)1Is CH3When monomer A is selected from methoxy terminated 3-methyl-hydroxyethyl vinyl polyalkylene glycol ether, ethoxy terminated 3-methyl-hydroxyethyl vinyl polyalkylene glycol ether, propoxy terminated 3-methyl-hydroxyethyl vinyl polyalkylene glycol ether, butoxy terminated 3-methyl-hydroxyethyl vinyl polyalkylene glycol ether, methoxy terminated 3-methyl-hydroxypropyl vinyl polyalkylene glycol etherAny one or more than one of ethylene glycol ether, 3-methyl-hydroxypropyl vinyl polyalkylene glycol ether terminated by ethoxy group, 3-methyl-hydroxypropyl vinyl polyalkylene glycol ether terminated by propoxy group, 3-methyl-hydroxypropyl vinyl polyalkylene glycol ether terminated by butoxy group, 3-methyl-hydroxybutyl vinyl polyalkylene glycol ether terminated by methoxy group, 3-methyl-hydroxybutyl vinyl polyalkylene glycol ether terminated by ethoxy group, 3-methyl-hydroxybutyl vinyl polyalkylene glycol ether terminated by propoxy group, 3-methyl-hydroxybutyl vinyl polyalkylene glycol ether terminated by butoxy group, and any mixture ratio of them.
The general formula (1) of the invention adopts R3The polyether is an alkyl-terminated reactive polyether with 1-4 carbon atoms, and aims to prevent the common hydroxyl-terminated reactive polyether commonly applied in the water reducer industry in the first copolymerization process from possibly carrying out ester exchange reaction with a polycarboxylic acid monomer in an anhydrous state or carrying out reaction which is incompatible with the design of the invention with a grafting monomer in the subsequent grafting reaction. The monomer A may be selected from one or more of the above monomers and used in any proportion.
In the invention, the monomer B is selected from one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate, and is mixed and used in any proportion.
The monomer C in the invention is selected from vinyl monoethyl glycol ether, vinyl monopropylene glycol ether, vinyl monoethylene glycol monopropylene glycol ether, vinyl diethylene glycol ether, vinyl dipropylene glycol ether, hydroxyethyl vinyl monoethyl glycol ether, hydroxyethyl vinyl monopropylene glycol ether, hydroxyethyl vinyl monoethyl glycol ether, hydroxyethyl vinyl dipropylene glycol ether, hydroxypropyl vinyl monoethyl glycol ether, hydroxypropyl vinyl monopropylene glycol ether, hydroxypropyl vinyl monoethyl glycol monopropylene glycol ether, hydroxypropyl vinyl diethylene glycol ether, hydroxypropyl vinyl dipropylene glycol ether, hydroxybutyl vinyl monoethyl glycol ether, hydroxybutyl vinyl monopropylene glycol ether, hydroxybutyl vinyl diethylene glycol ether, hydroxybutyl vinyl dipropylene glycol ether, 3-methyl-hydroxyethyl vinyl monoethyl glycol ether, hydroxyethyl vinyl monopropylene glycol ether, hydroxyethyl, 3-methyl-hydroxyethyl vinyl monopropylene glycol ether, 3-methyl-hydroxyethyl vinyl diethylene glycol ether, 3-methyl-hydroxyethyl vinyl dipropylene glycol ether, 3-methyl-hydroxypropyl vinyl monopropylene glycol ether, 3-methyl-hydroxypropyl vinyl diethylene glycol ether, 3-methyl-hydroxypropyl vinyl dipropylene glycol ether, 3-methyl-hydroxybutyl vinyl monopropylene glycol ether, 3-methyl-hydroxybutyl vinyl monoethylene glycol monopropylene glycol ether, propylene glycol, One or more of 3-methyl-hydroxybutyl vinyl diethylene glycol ether and 3-methyl-hydroxybutyl vinyl dipropylene glycol ether are mixed in an arbitrary ratio.
The monomer D in the present invention is one or more selected from allylamine, 3-buten-1-amine and 3-methyl-2-buten-1-amine, and is used in a mixture at an arbitrary ratio.
The monomer E is selected from gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, 2- (3, 4 epoxycyclohexyl) -ethyltrimethoxysilane and gamma-glycidoxypropylmethyldiethoxysilane. In actual use, one or more of the components can be selected and mixed in any proportion.
The preparation method of the early-strength polycarboxylate superplasticizer specifically comprises the following steps:
(1) preparation of a prepolymer: placing the monomer A in a reactor with stirring, heating to the reaction temperature of 60-80 ℃, and continuously stirring until the monomer A is completely dissolved; adding the initiator in batches, and ensuring that the first batch of initiator is added before the monomer B, C, D enters the system; then, simultaneously dripping the monomer B, the monomer C, the monomer D and a chain transfer agent to carry out copolymerization reaction, continuously stirring and keeping the temperature in the reaction process, and continuing the reaction for 1 hour after the material addition is finished to obtain a polymer, namely the prepolymer;
feeding the monomer A in the step (1) at one time, feeding the monomer B, the monomer C and the monomer D in a uniform-speed dropwise adding mode, and controlling the dropwise adding time to be 2-5 hours;
water and organic solvent are not used in the whole reaction process;
(2) preparing a water reducing agent: dropwise adding a monomer E into the prepolymer prepared in the step (1), controlling the grafting reaction temperature, raising the reaction temperature after the dropwise adding of the monomer E is finished, and continuously carrying out heat preservation reaction for 5 hours; n is introduced in the whole reaction process2Deoxidizing, discharging and cooling after the reaction is finished to obtain the early-strength polycarboxylate superplasticizer;
in the step (2), the monomer E is added into a reaction system in a continuous dropwise adding mode, and the dropwise adding time is controlled to be 4-6 hours; the temperature of the dripping stage is controlled to be 120 ℃, and the temperature of the heat preservation stage is controlled to be 150 ℃.
According to the most suitable initiation rate of the free radical polymerization, the initiator in the step (1) can be selected from azo compounds and peroxide initiators, and is specifically selected from one or more of azodiisobutyronitrile, azodiisoheptonitrile, benzoyl peroxide, potassium persulfate, ammonium persulfate and sodium persulfate. The initiator molar amount accounts for 0.5-5% of the sum of the A, B, C, D moles of the monomers, and is added into the reaction system in 3-6 batches in equal parts, wherein the initiator in the first batch is added into the reaction container before the monomers B, C and D are added, the initiator in the last batch is added into the reaction container after all the monomers are added, and the initiators in other batches are equally added into the reaction system in batches according to the adding time of the monomers B, C, D.
The chain transfer agent in the step (1) can be a mercapto chain transfer agent, and is specifically selected from one or more of mercaptoethanol, mercaptopropanol, mercaptoacetic acid and mercaptopropionic acid. The molar amount of the chain transfer agent accounts for 0.5-5% of the sum of the A, B, C, D molar numbers of the monomers, the chain transfer agent is added into the reaction system in a continuous dropwise adding mode, the dropwise adding time is controlled to be 2-5 hours, and the consistency of the feeding time of the chain transfer agent and the feeding time of the monomer B, C, D is ensured.
In the practice of the present invention, no water or any organic solvent is required, and the polymerization concentration is 100%. The temperature of the first step copolymerization reaction is strictly controlled within the range of 60-80 ℃. Too low a temperature reduces the monomer conversion rate and efficiency of the polymerization system, while too high a temperature causes too fast reaction of the polymerization system and too large heat release to facilitate process control.
In the second step of the grafting reaction of the preparation method, the hydroxyl group or the amino group in the molecule of the monomer B, C, D and the epoxy group of the monomer E are subjected to ring-opening polymerization, and the mole numbers of the monomer E and the monomer (B + C + D) are controlled to be the same. The reaction process adopts the introduction of N2Oxygen in the system is removed to promote the completion of the grafting reaction.
The grafting temperature is controlled at 120 ℃ in the dropping stage of the monomer E and at 150 ℃ in the heat preservation stage. And (3) discharging, cooling and crushing after heat preservation is finished, or properly cooling to 60 ℃, and adding water to dilute until the mass concentration is 50% to obtain the early-strength polycarboxylate superplasticizer.
The early-strength polycarboxylate superplasticizer can be used as a concrete dispersant, and the conventional mixing amount of the early-strength polycarboxylate superplasticizer is 0.03-0.5% of the total mass of a cement concrete adhesive material. If the amount added is less than 0.03%, the dispersing property and the early strength effect are unsatisfactory. If, on the other hand, the addition is above 0.5%, the overdosing proves to be merely an economic waste, since no corresponding increase in effect is brought about.
The early strength polycarboxylate water reducer of the invention can also be mixed with at least one water reducer selected from the group consisting of sulfamic acid water reducers, lignin common water reducers and existing polycarboxylate water reducers known in the prior art. In addition, besides the above-mentioned known water reducing agent for concrete, air entraining agent, expanding agent, retarder, early strength agent, tackifier, shrinkage reducing agent, defoaming agent, etc. may be added thereto according to the actual need.
Compared with the conventional polycarboxylate superplasticizer technology, the early strength polycarboxylate superplasticizer provided by the invention has the following obvious difference advantages in the aspects of dispersing capacity, improving the early strength and adaptability of concrete:
(1) the method creatively introduces the same silicon element as the cement component used in the polycarboxylate superplasticizer into the polycarboxylate superplasticizer molecules, and adopts silane groups to completely replace carboxylic acid groups in the polycarboxylate superplasticizer molecules, so that the adsorption driving force of the early-strength polycarboxylate superplasticizer molecules is substantially changed. The cement component contains a large amount of silicon elements, the water reducing agent with silane groups as adsorption groups has stronger adsorption driving force, and the adsorption effect is an irreversible process, so that the polycarboxylic acid water reducing agent molecules can exert dispersing capacity more favorably.
(2) The early-strength polycarboxylate superplasticizer prepared by the method can obviously improve the early strength of concrete, and the later strength is not shrunk. The early-strength polycarboxylate water reducer disclosed by the invention introduces a silane component capable of promoting cement hydration into molecules, so that the silane component acts on a cement active component from the beginning of adding the water reducer in an application process, the hydration speed of the cement active component is promoted, the initial hydration degree is improved, and the early strength of concrete is improved.
(3) The silane group replaces carboxylic acid group to be used as an adsorption group of the early-strength polycarboxylate water reducer, so that the electrical property of the water reducer molecules is changed, and no anion exists in the polymer molecules. The change can obviously reduce the sensitivity of the polycarboxylate superplasticizer molecules to the surface charge properties of cement and admixture components, obviously enhance the dispersing capacity in a large-mixing-amount industrial waste residue concrete system, and improve the adaptability of the superplasticizer to concrete materials.
Detailed Description
The following examples describe in more detail the preparation of the polymer product according to the process of the invention and are given by way of illustration and are intended to enable one skilled in the art to understand the contents of the invention and to carry out the invention, without limiting the scope of the invention in any way. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
The monomers used in the following examples are shown in Table 1, and the synthesized early strength polycarboxylate superplasticizer is abbreviated as ESPC.
In the examples of the present invention, the weight average molecular weight of the polymer was measured by Agilent 1260 chromatography. (gel column: Shodex SB806+803 two chromatographic columns in series; eluent: 0.1M NaNO3A solution; velocity of mobile phase: 1.0 ml/min; and (3) injection: 20 μ l of 0.5% aqueous solution; a detector: a differential refractive detector; standard substance: poly(s) are polymerizedEthylene glycol GPC standards (Sigma-Aldrich, molecular weight 1010000, 478000, 263000, 118000, 44700, 18600, 6690, 1960, 628, 232).
In the application embodiment of the invention, the adopted cement is 52.5 R.P.II cement in a small open field unless otherwise specified, the sand is medium sand with fineness modulus Mx of 2.6, and the stones are continuous graded broken stones with the grain size of 5-20 mm.
The compound numbers described in table 1 were used in the synthesis examples of the present invention:
table 1 example compound designations
Figure BDA0001929627190000081
Figure BDA0001929627190000091
Example 1
In a container equipped with a thermometer, a stirrer and N22400g A-1(1mol) was charged into a glass reactor of an inlet tube, and the reaction vessel was purged with nitrogen gas with stirring and heated to 60 ℃ to dissolve the compound. After the polyether is completely dissolved, 3.3g of azobisisobutyronitrile is accurately weighed, and is equally divided into 3 parts, 1.1g of azobisisobutyronitrile is added before the reaction is started, and the mixture is uniformly stirred. 348g B-1(3mol) and 1.56g of mercaptoethanol were mixed and added dropwise to the reactor by means of a peristaltic pump over a period of 2 hours. In the reaction process, 1.1g of azobisisobutyronitrile is added every 60 minutes, and after the materials are dripped, the reaction is carried out for 1 hour under the condition of heat preservation, so as to obtain prepolymer 1 with the molecular weight of 114,000.
Heating the materials in the reaction bottle to 120 ℃ and continuously introducing N2Deoxygenation was performed and 708g E-1(3mol) was added dropwise over a period of 4 hours. After the reaction is finished, the temperature is raised to 150 ℃, the reaction is carried out for 5 hours, and the material is discharged and cooled to obtain yellow block-shaped substance, namely ESPC-1.
Example 2
In a container equipped with a thermometer, a stirrer and N24000g A-2(1mol) was charged into a glass reactor of an inlet tube, and the reaction vessel was purged with nitrogen gas with stirring and heated to 70 ℃ to dissolve the compound. Accurately weighing the azobisisoheptonitrile 18 after the polyether is completely dissolved6g, which was divided into 4 portions and 4.65g was added before the start of the reaction and stirred well. 260g B-2(2mol), 88g C-1(1mol), 57g D-1(1mol) and 13.8g of mercaptopropanol were mixed and added dropwise to the reactor by a peristaltic pump for 3 hours. In the reaction process, 4.65g of azobisisobutyronitrile is added every 60 minutes, and after the materials are dripped, the reaction is carried out for 1 hour under the condition of heat preservation, so as to obtain prepolymer 2 with the molecular weight of 102,000.
Heating the materials in the reaction bottle to 120 ℃ and continuously introducing N2Deoxygenation was performed, 1108g E-2(4mol) was added dropwise over a period of 5 hours. After the reaction is finished, the temperature is raised to 150 ℃, the reaction is kept for 5 hours, and the reaction product is cooled and diluted to 50 percent by adding water to obtain light yellow transparent liquid, namely ESPC-2.
Example 3
In a container equipped with a thermometer, a stirrer and N26500g A-3(1mol) was charged into a glass reactor of an inlet tube, and the reaction vessel was purged with nitrogen gas with stirring and heated to 80 ℃ to dissolve the compound. After the polyether is completely dissolved, 42.5g of benzoyl peroxide is accurately weighed and equally divided into 5 parts, 8.5g of benzoyl peroxide is added before the reaction is started, and the mixture is uniformly stirred. 130g B-3(1mol), 232g C-2(2mol), 142g D-2(3mol) and 12.9g of thioglycolic acid were mixed and added dropwise to the reactor by a peristaltic pump over 4 hours. In the reaction process, 8.5g of benzoyl peroxide is added every 60 minutes, and after the materials are dripped, the heat preservation reaction is carried out for 1 hour, so as to obtain prepolymer 3 with the molecular weight of 85,000.
Heating the materials in the reaction bottle to 120 ℃ and continuously introducing N2After oxygen removal, 1476g E-3(6mol) was added dropwise over a period of 6 hours. After the reaction is finished, the temperature is raised to 150 ℃, the reaction is carried out for 5 hours, and the material is discharged and cooled to obtain yellow block-shaped substance, namely ESPC-3.
Example 4
In a container equipped with a thermometer, a stirrer and N28000g A-4(1mol) was charged into a glass reactor of an inlet tube, and the reaction vessel was purged with nitrogen gas with stirring and heated to 60 ℃ to dissolve the compound. 148.8g of potassium persulfate is accurately weighed after the polyether is completely dissolved, the potassium persulfate is equally divided into 6 parts, 24.8g of potassium persulfate is added before the reaction is started, and the mixture is uniformly stirred. 576g B-4(4mol), 522gC-3(3mol), 255g D-3(3mol) and 58.3g mercaptopropionic acid were mixed and dropped into the mixture by a peristaltic pump to carry out a reactionThe dropping time was 5 hours. And (3) adding 24.8g of potassium persulfate every 60 minutes in the reaction process, and after the dropwise addition of the materials is finished, carrying out heat preservation reaction for 1 hour to obtain prepolymer 4 with molecular weight of 51,800.
Heating the materials in the reaction bottle to 120 ℃ and continuously introducing N2After deoxygenation, 2930g E-4(10mol) was added dropwise over a period of 5 hours. After the reaction is finished, the temperature is raised to 150 ℃, the reaction is kept for 5 hours, and the reaction product is cooled and diluted to 50 percent by adding water to obtain light yellow transparent liquid, namely ESPC-4.
Example 5
In a container equipped with a thermometer, a stirrer and N23500g A-5(1mol) was charged into a glass reactor of an inlet tube, and the reaction vessel was purged with nitrogen gas with stirring and heated to 70 ℃ to dissolve the compound. After the polyether is completely dissolved, 11.4g of ammonium persulfate is accurately weighed, and is equally divided into 5 parts, 2.28g of ammonium persulfate is added before the reaction is started, and the mixture is uniformly stirred. 752g C-4(4mol) was mixed with 12.9g of mercaptoethanol and added dropwise to the reactor by means of a peristaltic pump over 4 hours. 2.28g of ammonium persulfate is added every 60 minutes in the reaction process, and after the dropwise addition of the materials is finished, the reaction is carried out for 1 hour under the condition of heat preservation, so that prepolymer 5 with the molecular weight of 67,000 is obtained.
Heating the materials in the reaction bottle to 120 ℃ and continuously introducing N2Deoxygenation was carried out and 944g E-1(4mol) was added dropwise over a period of 4 hours. After the reaction is finished, the temperature is raised to 150 ℃, the reaction is carried out for 5 hours, and the material is discharged and cooled to obtain yellow block-shaped substance, namely ESPC-5.
Example 6
In a container equipped with a thermometer, a stirrer and N25000g A-6(1mol) was charged into a glass reactor of the introduction tube, and the reaction vessel was purged with nitrogen gas with stirring and heated to 80 ℃ to dissolve the compound. After the polyether is completely dissolved, 35.6g of sodium persulfate is accurately weighed and equally divided into 4 parts, 8.9g of sodium persulfate is added before the reaction is started, and the mixture is uniformly stirred. 130g B-2(1mol), 188g C-5(1mol), 142g D-2(2mol) and 11.52g of mercaptopropanol were mixed and added dropwise to the reactor by a peristaltic pump for 3 hours. And 8.9g of sodium persulfate is added every 60 minutes in the reaction process, and after the dropwise addition of the materials is finished, the heat preservation reaction is carried out for 1 hour to obtain prepolymer 6 with the molecular weight of 80,000.
Heating the materials in the reaction bottle to 1At 20 ℃ with continuous introduction of N2Deoxygenation was performed, 1108g E-2(4mol) was added dropwise over a period of 5 hours. After the reaction is finished, the temperature is raised to 150 ℃, the reaction is kept for 5 hours, and the reaction product is cooled and diluted to 50 percent by adding water to obtain light yellow transparent liquid, namely ESPC-6.
Example 7
In a container equipped with a thermometer, a stirrer and N27000g A-7(1mol) was charged into the glass reactor of the introduction tube, and the reaction vessel was purged with nitrogen gas with stirring and heated to 60 ℃ to dissolve. After the polyether was completely dissolved, 59.1g of azobisisobutyronitrile was accurately weighed, and the mixture was divided into 3 parts by equal weight, 19.7g of azobisisobutyronitrile was added before the start of the reaction, and the mixture was stirred uniformly. 576g C-6(4mol), 228g D-1(4mol) and 29g of thioglycolic acid were mixed and added dropwise to the reactor using a peristaltic pump over 2 hours. In the reaction process, 19.7g of azobisisobutyronitrile is added every 60 minutes, and after the materials are dripped, the reaction is carried out for 1 hour under the condition of heat preservation, so as to obtain prepolymer 7 with molecular weight of 71,900.
Heating the materials in the reaction bottle to 120 ℃ and continuously introducing N2Deoxygenation was carried out by dropwise addition of 1968g E-3(8mol) over a period of 6 hours. After the reaction is finished, the temperature is raised to 150 ℃, the reaction is carried out for 5 hours, and the material is discharged and cooled to obtain yellow block-shaped substance, namely ESPC-7.
Example 8
In a container equipped with a thermometer, a stirrer and N24000g A-2(1mol) was charged into a glass reactor of an inlet tube, and the reaction vessel was purged with nitrogen gas with stirring and heated to 70 ℃ to dissolve the compound. After the polyether is completely dissolved, 27g of potassium persulfate is accurately weighed and equally divided into 4 parts, 6.75g of potassium persulfate is added before the reaction is started, and the mixture is uniformly stirred. 348g C-7(2mol), 142g D-2(2mol) and 7.95g of mercaptopropionic acid were mixed and added dropwise to the reactor by means of a peristaltic pump over 3 hours. 6.75g of potassium persulfate is added every 60 minutes in the reaction process, and after the materials are dripped, the reaction is carried out for 1 hour under the condition of heat preservation, thus obtaining prepolymer 8 with molecular weight of 93,600.
Heating the materials in the reaction bottle to 120 ℃ and continuously introducing N2Deoxygenation was carried out by dropwise addition of 1172g E-4(4mol) over a period of 5 hours. After the reaction is finished, the temperature is raised to 150 ℃, the reaction is kept for 5 hours, and the reaction product is cooled and diluted to 50 percent by adding water to obtain light yellow transparent liquid, namely ESPC-8.
Example 9
In a container equipped with a thermometer, a stirrer and N26500g A-4(1mol) was charged into a glass reactor of an inlet tube, and the reaction vessel was purged with nitrogen gas with stirring and heated to 80 ℃ to dissolve the compound. After the polyether is completely dissolved, 17g of benzoyl peroxide is accurately weighed, the benzoyl peroxide is equally divided into 5 parts, 3.4g of benzoyl peroxide is added before the reaction is started, and the mixture is uniformly stirred. 232g B-1(2mol), 340g D-3(4mol) and 24.6g mercaptoethanol were mixed and added dropwise to the reactor by means of a peristaltic pump over 4 hours. 3.4g of benzoyl peroxide is added every 60 minutes in the reaction process, and after the materials are dripped, the heat preservation reaction is carried out for 1 hour, so as to obtain prepolymer 9 with molecular weight of 62,500.
Heating the materials in the reaction bottle to 120 ℃ and continuously introducing N2Deoxygenation was performed and 1416g E-1(6mol) was added dropwise over a period of 4 hours. After the reaction is finished, the temperature is raised to 150 ℃, the reaction is carried out for 5 hours, and the material is discharged and cooled to obtain yellow block-shaped substance, namely ESPC-9.
Example 10
In a container equipped with a thermometer, a stirrer and N25000g A-6(1mol) was charged into a glass reactor of the introduction tube, and the reaction vessel was purged with nitrogen gas with stirring and heated to 60 ℃ to dissolve the compound. After the polyether is completely dissolved, 39.6g of ammonium persulfate is accurately weighed, the ammonium persulfate is equally divided into 6 parts, 6.6g of ammonium persulfate is added before the reaction is started, and the mixture is uniformly stirred. 260g B-3(2mol), 146g C-8(1mol), 213g D-2(3mol) and 22.26g of mercaptopropionic acid were mixed and dropped into the reactor by a peristaltic pump for 5 hours. 6.6g of ammonium persulfate is added every 60 minutes in the reaction process, and after the materials are dripped, the reaction is carried out for 1 hour under the condition of heat preservation, thus obtaining prepolymer 10 with molecular weight of 83,500.
Heating the materials in the reaction bottle to 120 ℃ and continuously introducing N2After oxygen removal, 1476g E-3(6mol) was added dropwise over a period of 5 hours. After the reaction is finished, the temperature is raised to 150 ℃, the reaction is kept for 5 hours, and the reaction product is cooled and diluted to 50 percent by adding water to obtain light yellow transparent liquid, namely ESPC-10.
Comparative example 1
In a container equipped with a thermometer, a stirrer and N22400g A-1(1mol) was charged into a glass reactor of an inlet tube, and the reaction vessel was purged with nitrogen while stirring, andheating to 60 ℃ to dissolve. After the polyether was completely dissolved, 8.1g of azobisisobutyronitrile was accurately weighed, and the mixture was divided into 3 parts, 2.7g of azobisisobutyronitrile was added before the start of the reaction, and the mixture was stirred uniformly. 344g of methacrylic acid (4mol) and 11.72g of mercaptoethanol were mixed and added dropwise to the reactor by means of a peristaltic pump over a period of 2 hours. In the reaction process, 2.7g of azobisisobutyronitrile is added every 60 minutes, after the materials are dripped, the reaction is carried out for 1 hour under the condition of heat preservation, and the materials are discharged and cooled to obtain yellow blocky substances with the molecular weight of 76,000, namely the conventional polycarboxylic acid water reducing agent PC-1.
Comparative example 2
In a container equipped with a thermometer, a stirrer and N26500g A-3(1mol) was charged into a glass reactor of an inlet tube, and the reaction vessel was purged with nitrogen gas with stirring and heated to 70 ℃ to dissolve the compound. After the polyether is completely dissolved, 32.4g of potassium persulfate is accurately weighed and equally divided into 4 parts, 8.1g of potassium persulfate is added before the reaction is started, and the mixture is uniformly stirred. 360g of acrylic acid (5mol) and 5.5g of mercaptopropanol were mixed and added dropwise to the reactor by means of a peristaltic pump over a period of 3 hours. Adding 8.1g of potassium persulfate every 60 minutes in the reaction process, preserving heat for 1 hour after the dropwise addition of the materials is finished, discharging and cooling to obtain a yellow blocky substance with the molecular weight of 108,000, namely the conventional polycarboxylic acid water reducing agent PC-2.
Comparative example 3
In a container equipped with a thermometer, a stirrer and N23500g A-5(1mol) and 294g of maleic anhydride (3mol) were charged into a glass reactor of an inlet tube, and the reaction vessel was purged with nitrogen gas with stirring and heated to 60 ℃ to dissolve. After the polyether is completely dissolved, 29g of benzoyl peroxide is accurately weighed and equally divided into 5 parts, 5.8g of benzoyl peroxide is added before the reaction is started, and the mixture is uniformly stirred. 11.5g of thioglycolic acid is uniformly dripped into the reactor by a peristaltic pump for 4 hours. And 5.8g of benzoyl peroxide is added every 60 minutes in the reaction process, after the materials are dripped, the heat preservation reaction is carried out for 1 hour, the materials are discharged and cooled, and a yellow blocky substance with the molecular weight of 82,500, namely the conventional polycarboxylic acid water reducing agent PC-3 is obtained.
Comparative example 4
In a container equipped with a thermometer, a stirrer and N27000g A-7(1mol) was added to a glass reactor through a tube and stirredThe reaction vessel was purged with nitrogen and warmed to 80 ℃ for dissolution. After the polyether is completely dissolved, 91.2g of ammonium persulfate is accurately weighed, the ammonium persulfate is equally divided into 6 parts, 15.2g of ammonium persulfate is added before the reaction is started, and the mixture is uniformly stirred. 504g of acrylic acid (7mol) and 33.92g of mercaptopropionic acid were mixed and added dropwise to the reactor by means of a peristaltic pump over a period of 5 hours. And (3) adding 15.2g of ammonium persulfate every 60 minutes in the reaction process, preserving heat for 1 hour after the dropwise addition of the materials is finished, discharging and cooling to obtain a yellow blocky substance with the molecular weight of 53,100, namely the conventional polycarboxylic acid water reducer PC-4.
Application example 1:
testing the fluidity of the cement paste: according to the GB/T8077-2012 standard, 300g of 52.5R.P. II cement is adopted in a small open field, the water adding amount is 87g, and the net cement slurry fluidity is measured on flat glass after the stirring is finished. The results of the cement paste fluidity test are shown in Table 2.
TABLE 2 neat paste fluidity test
Figure BDA0001929627190000141
As can be seen from the test results in Table 2, the cement prepared by using the early-strength polycarboxylate superplasticizer prepared by the method of the invention has good dispersing ability, and the dispersing ability exceeds the level of a comparison sample. The continuous dispersing capacity of the series of early-strength polycarboxylate superplasticizers gradually decreases along with time, so that the method is favorable for quickly collecting the early-strength concrete, shortens the setting time, shortens the construction time and improves the construction efficiency.
Application example 2:
testing air content, compressive strength and slump: the air content is determined according to the relevant specified test method of GB8076-2008 concrete admixture; the concrete compressive strength is tested according to relevant regulations of GB/T50081-2016 standard of test method for mechanical properties of common concrete; slump tests and slump loss tests over time are carried out according to relevant regulations of GB50080-2016 standard on common concrete mixture performance test methods. In the test, the water-cement ratio of the concrete is fixed, and the mixing amount of the water reducing agent is adjusted to ensure that the initial slump of the fresh concrete is 21 +/-1 cm, and the test result is shown in Table 3.
TABLE 3 concrete Properties
Figure BDA0001929627190000151
The tests show that the early-strength polycarboxylate superplasticizer prepared by the method shows very strong water reducing capacity at relatively low mixing amount, and the dispersing capacity of the early-strength polycarboxylate superplasticizer exceeds that of a comparative sample series. The dispersing ability showed a tendency to decrease slightly over 1 hour, which is an advantageous advantage in early strength demand concrete. Compared with the conventional polycarboxylate superplasticizer, the concrete doped with the series early-strength polycarboxylate superplasticizer has relatively low gas content, the initial setting time of the concrete is advanced by more than 1 hour, and the final setting time is advanced by more than 1.5 hours. Compared with a comparative sample, the 16-hour compressive strength can be improved by 100 percent, the 1-day compressive strength can be improved by more than 50 percent, and the strength of the concrete in the subsequent age shows that the later strength of the concrete does not shrink and shows a good strength development trend. The early strength performance especially meets the requirements of products and projects in the product industry, rapid pavement repair and the like.
Application example 3:
by adopting the method for testing gas content, compressive strength and slump in the application example 2, the adaptability difference between the early-strength polycarboxylate superplasticizer disclosed by the invention and a conventional polycarboxylate superplasticizer under the condition of large mixing amount of fly ash (35% of substituted cement) is verified, and the experimental results are shown in table 4.
TABLE 4 Adaptation comparative concrete Properties
Figure BDA0001929627190000161
A test of a large-volume fly ash system shows that the early-strength polycarboxylate superplasticizer prepared by the method shows stable dispersing performance and has very stable tendency of dispersion retention capacity compared with the conventional polycarboxylate dispersant in the system. The conventional polycarboxylate superplasticizer shows obvious adaptability difference, basically equivalent dispersing performance can be achieved only by adjusting the mixing amount, the 1d compressive strength of the concrete still shows obvious advantages, and the 28d compressive strength shows slightly obvious advantages.
By adopting the method for testing gas content, compressive strength and slump in the application example 2, the adaptability difference between the early-strength polycarboxylate water reducer disclosed by the invention and a conventional polycarboxylate water reducer under the conditions of large mixing amount of mineral powder (replacing 30% of cement) and silica fume (replacing 10% of cement) is verified, and the experimental results are shown in table 5.
TABLE 5 Adaptation comparative concrete Properties
Figure BDA0001929627190000171
Tests of a large-mixing-amount mineral powder and silica fume system show that the early-strength polycarboxylate superplasticizer prepared by the method shows stable dispersing performance and has very stable tendency of dispersion retention capacity compared with the conventional polycarboxylate dispersant in the system. The adaptability problem of the conventional polycarboxylate superplasticizer to mineral powder and silica fume systems is more obvious, the basically equivalent dispersing performance can be achieved only by adjusting the mixing amount by about 15%, and the difference of the dispersion retaining capacity is obvious. The concrete doped with the series early-strength polycarboxylate superplasticizers still has obvious advantages in 1d compressive strength and slightly has advantages in 28d compressive strength.
The invention can be realized by all the listed raw materials and the upper and lower limit values of the raw materials, and the examples are not listed.

Claims (10)

1. The early-strength polycarboxylate superplasticizer is characterized by being prepared by copolymerizing unsaturated reactive polyether and unsaturated comonomer with active hydrogen under the condition of no water or solvent and then performing ring-opening grafting on epoxy groups and the active hydrogen contained in a silane monomer.
2. The early-strength polycarboxylate superplasticizer according to claim 1, wherein the early-strength polycarboxylate superplasticizer is prepared by copolymerizing a polymerizable unsaturated monomer A, B, C, D to form a prepolymer with a comb-shaped structure, and then adding a monomer E into the prepolymer to perform a grafting reaction;
the molar ratio of the monomer A, B, C, D is 1 (0-4): 0-4, and the molar number of the monomer B, C, D is not 0 at the same time;
the total molar ratio of the monomer E to the monomer (B + C + D) is the same;
the monomer A is represented by the general formula (1):
Figure FDA0001929627180000011
in the general formula (1), R1Represents H or CH3；R2Representative O, CH2O、CH2CH2O、CH2CH2CH2O or CH2CH2CH2CH2O；R3Represents an alkyl group having 1 to 4 carbon atoms; p is the average addition mole number of the ethylene oxide and is an integer of 50-180;
the monomer B is represented by the general formula (2):
Figure FDA0001929627180000012
in the general formula (2), R4Represents H or CH3(ii) a m represents the number of repeating units of an ethylene oxide group in the structural formula, n represents the number of repeating units of a propylene oxide group, and m and n take the values of 0 and 1, and are not 0 nor 1 at the same time;
the monomer C is represented by the general formula (3):
Figure FDA0001929627180000013
in the general formula (3), R5Represents H or CH3(ii) a k represents the number of repeating units of methylene, and the value of k is an integer of 0-4; x represents the number of repeating units of an ethylene oxide group in the structural formula, y represents the number of repeating units of a propylene oxide group, and x and y are integers of 0-2 and are not 0 at the same time;
the monomer D is represented by the general formula (4):
Figure FDA0001929627180000021
in the general formula (4), R6And R7Each independently represents H or CH3；
The monomer E is an epoxy silane compound;
the structural formula of the prepolymer conforms to the following general formula (5):
Figure FDA0001929627180000022
in the general formula (5), a, B, C and D respectively represent the number of repeating units of a monomer A, a monomer B, a monomer C and a monomer D, the values of B, C and D meet the condition that the ratio of (B + C + D)/a is any value of 3-10, and the values of B, C and D are not zero at the same time;
the weight average molecular weight of the prepolymer is 50000-120000.
3. The early strength polycarboxylate superplasticizer according to claim 2, wherein R in the general formula (1)1When H, monomer A is selected from methoxy terminated vinyl polyalkylene glycol ethers, ethoxy terminated vinyl polyalkylene glycol ethers, propoxy terminated vinyl polyalkylene glycol ethers, butoxy terminated vinyl polyalkylene glycol ethers, methoxy terminated hydroxyethyl vinyl polyalkylene glycol ethers, ethoxy terminated hydroxyethyl vinyl polyalkylene glycol ethers, propoxy terminated hydroxyethyl vinyl polyalkylene glycol ethers, butoxy terminated hydroxyethyl vinyl polyalkylene glycol ethers, methoxy terminated hydroxypropyl vinyl polyalkylene glycol ethers, ethoxy terminated hydroxypropyl vinyl polyalkylene glycol ethers, propoxy terminated hydroxypropyl vinyl polyalkylene glycol ethers, butoxy terminated hydroxypropyl vinyl polyalkylene glycol ethers, methoxy terminated hydroxybutyl vinyl polyalkylene glycol ethers, methoxy terminated hydroxypropyl vinyl polyalkylene glycol ethers, methoxy terminated vinyl polyalkylene glycol ethers, and mixtures thereof, Ethoxy-terminated hydroxybutyl vinyl polyalkylene glycol ethers, propoxy-terminated hydroxybutyl vinyl polyalkylene glycolsAny one or more than one of glycol ether and butoxy terminated hydroxybutyl vinyl polyalkylene glycol ether are mixed in any proportion.
4. The early strength polycarboxylate superplasticizer according to claim 2, wherein R in the general formula (1)1Is CH3When monomer A is selected from the group consisting of methoxy-terminated 3-methyl-hydroxyethyl vinyl polyalkylene glycol ether, ethoxy-terminated 3-methyl-hydroxyethyl vinyl polyalkylene glycol ether, propoxy-terminated 3-methyl-hydroxyethyl vinyl polyalkylene glycol ether, butoxy-terminated 3-methyl-hydroxyethyl vinyl polyalkylene glycol ether, methoxy-terminated 3-methyl-hydroxypropyl vinyl polyalkylene glycol ether, ethoxy-terminated 3-methyl-hydroxypropyl vinyl polyalkylene glycol ether, propoxy-terminated 3-methyl-hydroxypropyl vinyl polyalkylene glycol ether, butoxy-terminated 3-methyl-hydroxypropyl vinyl polyalkylene glycol ether, methoxy-terminated 3-methyl-hydroxybutyl vinyl polyalkylene glycol ether, methoxy-terminated 3-methyl-hydroxyethyl vinyl polyalkylene glycol ether, propoxy-terminated 3-methyl-hydroxypropyl vinyl polyalkylene glycol ether, butoxy-terminated 3-methyl-hydroxypropyl vinyl polyalkylene, Any one or more than one of 3-methyl-hydroxybutyl vinyl polyalkylene glycol ether terminated by ethoxy group, 3-methyl-hydroxybutyl vinyl polyalkylene glycol ether terminated by propoxy group and 3-methyl-hydroxybutyl vinyl polyalkylene glycol ether terminated by butoxy group is mixed in any proportion.
5. The early strength polycarboxylate superplasticizer according to claim 2, wherein said monomer B is selected from one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate, and is used in any proportion.
6. The water-reducing agent according to claim 2, wherein the monomer C is selected from the group consisting of vinyl monoethylene glycol ether, vinyl monopropylene glycol ether, vinyl monoethylene glycol monopropylene glycol ether, vinyl diethylene glycol ether, vinyl dipropylene glycol ether, hydroxyethyl vinyl monoethylene glycol ether, hydroxyethyl vinyl monopropylene glycol ether, hydroxyethyl vinyl monoethylene glycol monopropylene glycol ether, hydroxyethyl vinyl diethylene glycol ether, hydroxyethyl vinyl dipropylene glycol ether, hydroxypropyl vinyl monoethylene glycol ether, hydroxypropyl vinyl monopropylene glycol ether, hydroxypropyl vinyl monoethylene glycol ether, hydroxypropyl vinyl dipropylene glycol ether, hydroxybutyl vinyl monoethylene glycol ether, hydroxybutyl vinyl monopropylene glycol ether, hydroxybutyl vinyl monoethylene glycol ether, hydroxybutyl vinyl diethylene glycol ether, and mixtures thereof, Hydroxybutyl vinyl dipropylene glycol ether, 3-methyl-hydroxyethyl vinyl monoethyl glycol ether, 3-methyl-hydroxyethyl vinyl monopropylene glycol ether, 3-methyl-hydroxyethyl vinyl diethylene glycol ether, 3-methyl-hydroxyethyl vinyl dipropylene glycol ether, 3-methyl-hydroxypropyl vinyl monoethyl glycol ether, 3-methyl-hydroxypropyl vinyl monopropylene glycol ether, 3-methyl-hydroxypropyl vinyl monoethyl glycol monopropylene glycol ether, 3-methyl-hydroxypropyl vinyl diethylene glycol ether, 3-methyl-hydroxypropyl vinyl dipropylene glycol ether, 3-methyl-hydroxybutyl vinyl monoethyl glycol ether, 3-methyl-hydroxybutyl vinyl monopropylene glycol ether, mixtures thereof, and the like, One or more of 3-methyl-hydroxybutyl vinyl monoethylene glycol monopropylene glycol ether, 3-methyl-hydroxybutyl vinyl diethylene glycol ether and 3-methyl-hydroxybutyl vinyl dipropylene glycol ether are mixed in any proportion.
7. The water reducing agent according to claim 2, wherein the monomer D is one or more selected from allyl amine, 3-butene-1-amine, and 3-methyl-2-butene-1-amine mixed in any ratio.
8. The early strength polycarboxylate water reducer according to claim 2, wherein the monomer E is one or more selected from gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, 2- (3, 4 epoxycyclohexyl) -ethyltrimethoxysilane, and gamma-glycidoxypropylmethyldiethoxysilane.
9. The preparation method of the early-strength polycarboxylate superplasticizer according to any one of claims 1 to 8, characterized by comprising the following steps:
(1) preparation of a prepolymer: placing the monomer A in a reactor with stirring, heating to the reaction temperature of 60-80 ℃, and continuously stirring until the monomer A is completely dissolved; adding the initiator in batches, and ensuring that the first batch of initiator is added before the monomer B, C, D enters the system; then, simultaneously dripping the monomer B, the monomer C, the monomer D and a chain transfer agent to carry out copolymerization reaction, continuously stirring and keeping the temperature in the reaction process, and continuing the reaction for 1 hour after the material addition is finished to obtain a polymer, namely the prepolymer;
feeding the monomer A in the step (1) at one time, feeding the monomer B, the monomer C and the monomer D in a uniform-speed dropwise adding mode, and controlling the dropwise adding time to be 2-5 hours;
(2) preparing a water reducing agent: dropwise adding a monomer E into the prepolymer prepared in the step (1), controlling the grafting reaction temperature, raising the reaction temperature after the dropwise adding of the monomer E is finished, and continuously carrying out heat preservation reaction for 5 hours; n is introduced in the whole reaction process2Deoxidizing, discharging and cooling after the reaction is finished to obtain the early-strength polycarboxylate superplasticizer;
in the step (2), the monomer E is added into a reaction system in a continuous dropwise adding mode, and the dropwise adding time is controlled to be 4-6 hours; the temperature is controlled to be 120 ℃ in the dripping stage and 150 ℃ in the heat preservation stage;
in the step (1), the initiator can be selected from azo compounds and peroxide initiators, and is specifically selected from one or more of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, potassium persulfate, ammonium persulfate and sodium persulfate; the initiator is added into the reaction system in 3-6 batches in equal parts, wherein the molar amount of the initiator accounts for 0.5-5% of the sum of the A, B, C, D moles of the monomers, the initiator in the first batch is added into the reaction container before the monomers B, C and D are added, the initiator in the last batch is added into the reaction container after all the monomers are added, and the initiators in other batches are equally added into the reaction system in batches according to the adding time of the monomer B, C, D;
the chain transfer agent in the step (1) can be a mercapto chain transfer agent, and is specifically selected from one or more of mercaptoethanol, mercaptopropanol, mercaptoacetic acid and mercaptopropionic acid; the molar amount of the chain transfer agent accounts for 0.5-5% of the sum of the A, B, C, D molar numbers of the monomers, the chain transfer agent is added into the reaction system in a continuous dropwise adding mode, the dropwise adding time is controlled to be 2-5 hours, and the consistency of the feeding time of the chain transfer agent and the feeding time of the monomer B, C, D is ensured.
10. The application method of the early-strength polycarboxylate superplasticizer according to any one of claims 1 to 8, wherein the conventional mixing amount of the early-strength polycarboxylate superplasticizer is 0.03-0.5% of the total mass of the cement concrete cement.
CN201811634113.1A 2018-12-29 2018-12-29 Early-strength polycarboxylate superplasticizer and preparation method thereof Active CN111348858B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811634113.1A CN111348858B (en) 2018-12-29 2018-12-29 Early-strength polycarboxylate superplasticizer and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811634113.1A CN111348858B (en) 2018-12-29 2018-12-29 Early-strength polycarboxylate superplasticizer and preparation method thereof

Publications (2)

Publication Number Publication Date
CN111348858A true CN111348858A (en) 2020-06-30
CN111348858B CN111348858B (en) 2022-03-18

Family

ID=71190391

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811634113.1A Active CN111348858B (en) 2018-12-29 2018-12-29 Early-strength polycarboxylate superplasticizer and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111348858B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112341564A (en) * 2020-11-25 2021-02-09 上海台界化工有限公司 Polycarboxylic acid building additive and synthesis method thereof
CN114685707A (en) * 2020-12-30 2022-07-01 南京博特新材料有限公司 Preparation method of high-regularity polycarboxylic acid superplasticizer

Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1203046A1 (en) * 1999-07-09 2002-05-08 Mbt Holding Ag Oligomeric dispersant
CN103011680A (en) * 2012-12-13 2013-04-03 中国矿业大学(北京) Sulfate-resistant organosilicone modified polycarboxylic superplasticizer and preparation method thereof
CN103073687A (en) * 2013-01-18 2013-05-01 科之杰新材料集团有限公司 Method for preparing high-dispersity polycarboxylic super plasticizer
US20140256857A1 (en) * 2013-03-06 2014-09-11 Construction Research & Technology Gmbh Polycarboxylate ethers with branched side chains
CN104193985A (en) * 2014-09-09 2014-12-10 江苏苏博特新材料股份有限公司 Preparation method of esterified macromer for polycarboxylate water-reducer
CN104311753A (en) * 2014-10-11 2015-01-28 上海东大化学有限公司 Silane modified polycarboxylate-type water reducing agent as well as preparation method and use method thereof
US20150065615A1 (en) * 2012-03-30 2015-03-05 Technische Universitat Munchen Copolymer for dispersant for cement, dispersant for cement, and cement composition
CN104649608A (en) * 2014-10-11 2015-05-27 江苏苏博特新材料股份有限公司 Additive for improving early strength of cement based material as well as preparation method and application of additive
CN104945572A (en) * 2015-05-25 2015-09-30 江苏奥莱特新材料有限公司 Low-air-entraining enhanced solid polycarboxylic acid water reducing agent and preparation method thereof
CN105504185A (en) * 2016-01-28 2016-04-20 青海金佳源建材有限公司 Polycarboxylate water reducing agent and preparation technology thereof
CN105754045A (en) * 2016-03-02 2016-07-13 海南太和科技有限公司 Silane coupling agent modified polycarboxylate superplasticizer and preparation method thereof
CN105837763A (en) * 2016-06-04 2016-08-10 石家庄市长安育才建材有限公司 Silane polycarboxylate water-reducing agent and preparation method thereof
CN107337757A (en) * 2016-12-22 2017-11-10 江苏苏博特新材料股份有限公司 A kind of preparation method of collapse protection type shrinkage type polycarboxylate water-reducer
CN107777910A (en) * 2017-09-28 2018-03-09 湖北工业大学 A kind of prefabricated components normal temperature Early-strength polycarboxylate superplasticizer and preparation method
CN108192044A (en) * 2017-12-28 2018-06-22 科之杰新材料集团有限公司 A kind of preparation method of responsive type polycarboxylate water-reducer low to concrete clay content
CN108219128A (en) * 2017-12-20 2018-06-29 江苏苏博特新材料股份有限公司 The preparation method of cement dispersants with sulfate adaptability and viscosity reducing effect
CN108976355A (en) * 2018-06-15 2018-12-11 北京工业大学 A kind of polycarboxylate water-reducer and preparation method with high absorption property and low surface tension
CN111825373A (en) * 2020-08-11 2020-10-27 贵州石博士科技有限公司 Preparation method for synthesizing high-performance polycarboxylate superplasticizer from novel VPEG polyether

Patent Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1203046A1 (en) * 1999-07-09 2002-05-08 Mbt Holding Ag Oligomeric dispersant
US20150065615A1 (en) * 2012-03-30 2015-03-05 Technische Universitat Munchen Copolymer for dispersant for cement, dispersant for cement, and cement composition
CN103011680A (en) * 2012-12-13 2013-04-03 中国矿业大学(北京) Sulfate-resistant organosilicone modified polycarboxylic superplasticizer and preparation method thereof
CN103073687A (en) * 2013-01-18 2013-05-01 科之杰新材料集团有限公司 Method for preparing high-dispersity polycarboxylic super plasticizer
US20140256857A1 (en) * 2013-03-06 2014-09-11 Construction Research & Technology Gmbh Polycarboxylate ethers with branched side chains
CN104193985A (en) * 2014-09-09 2014-12-10 江苏苏博特新材料股份有限公司 Preparation method of esterified macromer for polycarboxylate water-reducer
CN104311753A (en) * 2014-10-11 2015-01-28 上海东大化学有限公司 Silane modified polycarboxylate-type water reducing agent as well as preparation method and use method thereof
CN104649608A (en) * 2014-10-11 2015-05-27 江苏苏博特新材料股份有限公司 Additive for improving early strength of cement based material as well as preparation method and application of additive
CN104945572A (en) * 2015-05-25 2015-09-30 江苏奥莱特新材料有限公司 Low-air-entraining enhanced solid polycarboxylic acid water reducing agent and preparation method thereof
CN105504185A (en) * 2016-01-28 2016-04-20 青海金佳源建材有限公司 Polycarboxylate water reducing agent and preparation technology thereof
CN105754045A (en) * 2016-03-02 2016-07-13 海南太和科技有限公司 Silane coupling agent modified polycarboxylate superplasticizer and preparation method thereof
CN105837763A (en) * 2016-06-04 2016-08-10 石家庄市长安育才建材有限公司 Silane polycarboxylate water-reducing agent and preparation method thereof
CN107337757A (en) * 2016-12-22 2017-11-10 江苏苏博特新材料股份有限公司 A kind of preparation method of collapse protection type shrinkage type polycarboxylate water-reducer
CN107777910A (en) * 2017-09-28 2018-03-09 湖北工业大学 A kind of prefabricated components normal temperature Early-strength polycarboxylate superplasticizer and preparation method
CN108219128A (en) * 2017-12-20 2018-06-29 江苏苏博特新材料股份有限公司 The preparation method of cement dispersants with sulfate adaptability and viscosity reducing effect
CN108192044A (en) * 2017-12-28 2018-06-22 科之杰新材料集团有限公司 A kind of preparation method of responsive type polycarboxylate water-reducer low to concrete clay content
CN108976355A (en) * 2018-06-15 2018-12-11 北京工业大学 A kind of polycarboxylate water-reducer and preparation method with high absorption property and low surface tension
CN111825373A (en) * 2020-08-11 2020-10-27 贵州石博士科技有限公司 Preparation method for synthesizing high-performance polycarboxylate superplasticizer from novel VPEG polyether

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
OROZCO, CA ET.AL: ""Characterization of the Bonds Developed between Calcium Silicate Hydrate and Polycarboxylate-Based Superplasticizers with Silyl Functionalities"", 《LANGMUIR》 *
何燕等: ""硅烷改性聚羧酸减水剂对水泥浆体流动性及水化进程的影响"", 《硅酸盐学报》 *
阳凯丽等: "有机硅类材料对水泥基材料抗硫酸盐侵蚀性能的影响", 《混凝土与水泥制品》 *
陈文红等: ""硅烷偶联剂改性聚羧酸保坍剂的制备与应用"", 《新型建筑材料》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112341564A (en) * 2020-11-25 2021-02-09 上海台界化工有限公司 Polycarboxylic acid building additive and synthesis method thereof
CN114685707A (en) * 2020-12-30 2022-07-01 南京博特新材料有限公司 Preparation method of high-regularity polycarboxylic acid superplasticizer

Also Published As

Publication number Publication date
CN111348858B (en) 2022-03-18

Similar Documents

Publication Publication Date Title
JP6074517B2 (en) Method for producing slump retention type polycarboxylate-based high performance fluidizing agent
US11548967B2 (en) Preparation method for polycarboxylate water reducer having regular sequence structure
CN101357833B (en) Slump retaining polyocarboxy acid superplasticiser
EP1655272A1 (en) Superplasticizers for extending the workability of mortars
CN109734833B (en) Short-side-chain anti-mud polycarboxylate superplasticizer and preparation method thereof
CN100526248C (en) Reduction-reducing crack-resisting concrete superplasticizer of graft copolymer and method for preparing the same
CN111348858B (en) Early-strength polycarboxylate superplasticizer and preparation method thereof
CN111349199B (en) Steady-state polycarboxylic acid superplasticizer with core-shell structure and preparation method thereof
CN111533862A (en) High-water-retention type lipid polycarboxylate superplasticizer and preparation method thereof
CN109320714B (en) Special small-molecule superplasticizer for medium-low slump concrete and preparation method thereof
CN108948283B (en) Phthalic anhydride modified polycarboxylate superplasticizer and preparation method thereof
US8907016B2 (en) Dispersing agent containing copolymer mixture
CN101602834B (en) Preparation method of polycarboxylic acid concrete dispersers
CN111349198B (en) Enhanced polycarboxylate superplasticizer and preparation method thereof
CN109762114B (en) Early-strength viscosity-reduction type polycarboxylate superplasticizer containing double viscosity-reduction functional groups and preparation method thereof
CN109956697B (en) Multi-adsorption-group intermediate, preparation method and application of polymer thereof
CN111087552A (en) Synthetic method of polycarboxylic acid water reducer with high water reducing rate and mud resistance
CN111377644A (en) Polycarboxylate superplasticizer containing phosphate groups, and preparation method and application thereof
CN111363159A (en) Sulfonated styrene-maleic anhydride grafted polyether type reduction type polycarboxylate superplasticizer
CN116265500A (en) Viscosity-reducing polycarboxylate superplasticizer and preparation method thereof
CN113896845A (en) Low-sensitivity slow-release polycarboxylic slump retaining agent and preparation method thereof
CN117024669B (en) Mud-resistant polycarboxylate superplasticizer and preparation method thereof
CN113980203B (en) Polycarboxylate superplasticizer with controllable structure based on EPEG polyether macromonomer and preparation method thereof
CN114685707A (en) Preparation method of high-regularity polycarboxylic acid superplasticizer
CN113801330B (en) Preparation method of block-type organic silicon polycondensate mud-resistant high-efficiency 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