CN112724340A - Viscosity-reducing composite polycarboxylate superplasticizer and preparation method thereof - Google Patents
Viscosity-reducing composite polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
- Publication number
- CN112724340A CN112724340A CN202011578985.8A CN202011578985A CN112724340A CN 112724340 A CN112724340 A CN 112724340A CN 202011578985 A CN202011578985 A CN 202011578985A CN 112724340 A CN112724340 A CN 112724340A
- Authority
- CN
- China
- Prior art keywords
- parts
- solution
- acid
- viscosity
- reducing agent
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Polyethers (AREA)
Abstract
The invention discloses a viscosity reduction type composite polycarboxylic acid water reducer and a preparation method thereof, belonging to the technical field of water reducers, and the viscosity reduction type composite polycarboxylic acid water reducer comprises the following raw materials in parts by weight: 80-150 parts of prenyl alcohol polyoxyethylene ether, 30-40 parts of acrylic acid, 20-30 parts of 6-caprolactone, 1-5 parts of hydroxy propionic acid, 2-5 parts of an initiator, 1-5 parts of a reducing agent, 8-10 parts of methacryloxypropyltrimethoxysilane, 5-8 parts of gluconolactone, 6-8 parts of maleic anhydride, 0.1-0.5 part of p-toluenesulfonic acid, 0.02-0.05 part of toluene and 70-80 parts of deionized water; according to the invention, 6-caprolactone is added, under the catalytic action of dialkyl tin dimaleate and dithiol alkyl tin, 6-caprolactone and prenyl polyoxyethylene ether are subjected to ring-opening reaction, and a hydrophobic group is grafted on the prenyl polyoxyethylene ether, so that the viscosity reduction effect is realized; according to the invention, by adding methacryloxypropyltrimethoxysilane, a carboxylic acid functional group and a siloxane functional group are grafted on the main chain of the prepared polycarboxylate superplasticizer, so that the dispersing ability is improved, and the viscosity reduction effect is good.
Description
Technical Field
The invention relates to the technical field of water reducing agents, in particular to a viscosity reduction type composite polycarboxylic acid water reducing agent and a preparation method thereof.
Background
The polycarboxylate water reducing agent is a high-performance water reducing agent, and is a cement dispersing agent in the application of cement concrete. The method is widely applied to projects such as highways, bridges, dams, tunnels, high-rise buildings and the like. The polycarboxylic acid high-efficiency water reducing agent products can be divided into two main types according to the difference of the main chain structure: the polyether with different side chain lengths is grafted by taking acrylic acid or methacrylic acid as a main chain. The other type is polyether with different side chain lengths grafted by maleic anhydride as a main chain. Based on the water reducer, a series of high-performance water reducer products with different characteristics are derived. Before the advent of polycarboxylic acid water reducing agents, there were lignosulfonate water reducing agents, naphthalene sulfonate formaldehyde condensates, melamine formaldehyde condensates, acetone sulfonate formaldehyde condensates, sulfamate formaldehyde condensates, and the like. The polycarboxylic acid water reducing agent is successfully developed in Japan in the beginning of the 80 s in the 20 th century. The new generation of polycarboxylic acid high-efficiency water reducing agent overcomes the defects of the traditional water reducing agent, and has the outstanding advantages of low mixing amount, good slump keeping performance, low concrete shrinkage, strong adjustability on molecular structure, large high-performance potential, no use of formaldehyde in the production process and the like.
For the synthesis of the polycarboxylic acid water reducing agent, the design of the molecular structure is crucial, wherein the design comprises a main chain group, a side chain density, a side chain length and the like in a molecule. The synthesis method mainly comprises an in-situ polymerization grafting method, a polymerization-first functionalization method and a monomer direct copolymerization method. In-situ polymerization grafting method: polyether is used as a medium for unsaturated monomer polymerization reaction, so that main chain polymerization and side chain introduction are carried out simultaneously, the process is simple, the molecular mass of the synthesized water reducing agent can be controlled to a certain extent, but the esterification reaction involved in the method is a reversible reaction, the grafting rate is low when the esterification reaction is carried out in an aqueous solution, and the polyether is gradually eliminated; polymerization-first and functionalization method: the method mainly comprises the steps of firstly synthesizing the main chain of the water reducing agent, and then introducing the side chain into the main chain for functionalization by other methods, wherein the method has higher operation difficulty, inflexible molecular structure of the water reducing agent and poor compatibility among monomers, so that the use of the method is greatly limited; direct monomer copolymerization: the method is characterized in that an active macromonomer is prepared firstly, and then a small monomer and a large monomer are subjected to copolymerization reaction in an aqueous solution under the initiation of an initiator, and the synthesis method is the most common method for synthesizing the polycarboxylic acid water reducing agent at the present stage along with the increasing maturity and variety of the synthesis process of the large monomer.
At present, a polycarboxylate superplasticizer is usually prepared by a monomer direct copolymerization method, but the viscosity reduction effect of the polycarboxylate superplasticizer in the prior art is relatively common, and the concrete added with the polycarboxylate superplasticizer has high viscosity and is not beneficial to construction.
Therefore, a viscosity-reducing composite polycarboxylate superplasticizer is provided to solve the problems.
Disclosure of Invention
The invention aims to provide a viscosity-reducing composite polycarboxylic acid water reducer and a preparation method thereof, and aims to solve the problems in the background art.
In order to achieve the purpose, the invention provides the following scheme to realize the following steps: the viscosity reduction type composite polycarboxylate superplasticizer comprises the following raw materials in parts by weight: 80-150 parts of prenyl alcohol polyoxyethylene ether, 30-40 parts of acrylic acid, 20-30 parts of 6-caprolactone, 1-5 parts of hydroxypropionic acid, 2-5 parts of an initiator, 1-5 parts of a reducing agent, 8-10 parts of methacryloxypropyltrimethoxysilane, 5-8 parts of gluconolactone, 6-8 parts of maleic anhydride, 0.1-0.5 part of p-toluenesulfonic acid, 0.02-0.05 part of toluene and 70-80 parts of deionized water.
Preferably, 90-130 parts of prenyl alcohol polyoxyethylene ether, 34-38 parts of acrylic acid, 24-26 parts of 6-caprolactone, 2-4 parts of hydroxypropionic acid, 3-4 parts of an initiator, 2-4 parts of a reducing agent, 8.5-9.5 parts of methacryloxypropyltrimethoxysilane, 6-7 parts of gluconolactone, 6.5-7.5 parts of maleic anhydride, 0.2-0.4 part of p-toluenesulfonic acid, 0.02-0.04 part of toluene and 72-76 parts of deionized water.
Preferably, 120 parts of prenyl alcohol polyoxyethylene ether, 35 parts of acrylic acid, 25 parts of 6-caprolactone, 34 parts of hydroxypropionic acid, 4 parts of an initiator, 3 parts of a reducing agent, 9 parts of methacryloxypropyl trimethoxysilane, 6.5 parts of gluconolactone, 7 parts of maleic anhydride, 0.3 part of p-toluenesulfonic acid, 0.03 part of toluene and 75 parts of deionized water.
Preferably, the initiator is ammonium persulfate and hydrogen peroxide, and the mass ratio of the ammonium persulfate to the hydrogen peroxide is 2: 1.
Preferably, the reducing agent is sodium sulfite and ascorbic acid, and the mass ratio of the sodium sulfite to the ascorbic acid is 1: 2.
The invention also provides a preparation method of the viscosity-reducing composite polycarboxylic acid water reducer, which comprises the following steps:
(1) putting prenyl alcohol polyoxyethylene ether and 6-caprolactone into a reactor, adding a catalyst into the reactor, uniformly stirring, reacting at the temperature of 100 ℃ and 110 ℃ for 6-7h, and naturally cooling to obtain modified polyether;
(2) putting gluconolactone, maleic anhydride, p-toluenesulfonic acid and toluene into a reactor for reflux reaction for 7-7.5h, and removing the toluene to obtain composite ester;
(3) uniformly stirring the modified polyether and 60% of deionized water, adding a reducing agent, and completely dissolving to obtain a base solution;
(4) mixing acrylic acid, composite ester, methacryloxypropyltrimethoxysilane and 20% of deionized water, and uniformly stirring to obtain a solution A; mixing hydroxypropionic acid with 20% of deionized water, and uniformly stirring to obtain a solution B;
(5) adding an initiator into the base liquid, stirring uniformly, slowly dropwise adding the solution A and the solution B, adjusting the pH to 6.5-7, and obtaining the viscosity-reducing type composite polycarboxylic acid water reducer after the reaction is finished.
Preferably, in the step (1), the catalyst is formed by mixing dialkyl tin dimaleate and dithiol alkyl tin according to the mass ratio of 1: 1.
Preferably, in the step (2), the reaction temperature is 70-80 ℃, and the reactor is vacuumized at the beginning of the reaction.
Preferably, in the step (5), the dropping time of the solution A is 1.5-2h, and the dropping time of the solution B is 1-1.5 h.
Preferably, in the step (5), the reaction temperature is 50-60 ℃, and the solution A and the solution B are continuously kept for 2-3 hours after the dropwise addition is finished.
The invention has the beneficial effects that:
according to the invention, 6-caprolactone, dialkyl tin dimaleate and dithiol alkyl tin are added, under the catalytic action of dialkyl tin dimaleate and dithiol alkyl tin, 6-caprolactone and isopentenol polyoxyethylene ether are subjected to a ring-opening reaction, a hydrophobic group is grafted on the isopentenol polyoxyethylene ether to obtain modified polyether with a hydrophobic group at the tail end, and then the polycarboxylic acid water reducing agent is prepared, wherein the tail end of a side chain of the polycarboxylic acid water reducing agent contains the hydrophobic group, more hydrophobic functional groups are introduced, so that the surface tension of the water reducing agent is reduced, the water reducing agent has certain hydrophobic association capability, more free water is released, the thickness of a water film layer between concrete particles is increased, the slippage between the particles is relatively easy, the acting force between the particles is reduced, and the viscosity reduction effect is realized;
according to the invention, by adding methacryloxypropyl trimethoxysilane, a carboxylic acid functional group and a siloxane functional group are grafted on the main chain of the prepared polycarboxylate water reducer, siloxane is subjected to hydrolysis reaction and is chemically bonded with silicon hydroxyl on the surface of cement particles, so that the adsorption driving force of the polycarboxylate water reducer on the surface of cement is greatly improved, the dispersing capacity is improved, and the viscosity reduction effect is good;
according to the invention, the gluconic acid lactone and maleic anhydride are added to prepare the composite ester containing more lactone groups, and the lactone groups are hydrolyzed to generate carboxyl groups, so that the water reducing agent is preferentially adsorbed on cement particles, and the dispersibility of the water reducing agent is improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The viscosity reduction type composite polycarboxylate superplasticizer comprises the following raw materials in parts by weight: 80 parts of prenyl alcohol polyoxyethylene ether, 35 parts of acrylic acid, 20 parts of 6-caprolactone, 1 part of hydroxypropionic acid, 4 parts of an initiator, 1 part of a reducing agent, 9 parts of methacryloxypropyl trimethoxy silane, 5 parts of gluconolactone, 7 parts of maleic anhydride, 0.1 part of p-toluenesulfonic acid, 0.02 part of toluene and 75 parts of deionized water.
The initiator is ammonium persulfate and hydrogen peroxide, and the mass ratio of the ammonium persulfate to the hydrogen peroxide is 2: 1; the reducing agent is sodium sulfite and ascorbic acid, and the mass ratio of the sodium sulfite to the ascorbic acid is 1: 2.
The preparation method of the viscosity-reducing composite polycarboxylate superplasticizer specifically comprises the following steps:
(1) putting prenyl alcohol polyoxyethylene ether and 6-caprolactone into a reactor, adding a catalyst into the reactor, uniformly stirring, reacting for 6 hours at 100 ℃, and naturally cooling to obtain modified polyether;
(2) putting gluconolactone, maleic anhydride, p-toluenesulfonic acid and toluene into a reactor for reflux reaction for 7 hours, removing the toluene to obtain composite ester, wherein the reaction temperature is 70 ℃, and vacuumizing the reactor when the reaction starts;
(3) uniformly stirring the modified polyether and 60% of deionized water, adding a reducing agent, and completely dissolving to obtain a base solution;
(4) mixing acrylic acid, composite ester, methacryloxypropyltrimethoxysilane and 20% of deionized water, and uniformly stirring to obtain a solution A; mixing hydroxypropionic acid with 20% of deionized water, and uniformly stirring to obtain a solution B;
(5) adding an initiator into the base liquid, stirring uniformly, slowly dropwise adding the solution A and the solution B, adjusting the pH to 7, keeping the reaction temperature at 50 ℃, keeping the dropwise adding time of the solution A at 1.5h, keeping the dropwise adding time of the solution B at 1h, and continuously preserving the heat for 2.5h after the dropwise adding of the solution A and the solution B is finished to obtain the viscosity-reduction type composite polycarboxylic acid water reducer.
The catalyst is formed by mixing dialkyl tin dimaleate and dithiol alkyl tin according to the mass ratio of 1: 1.
Example 2
The viscosity reduction type composite polycarboxylate superplasticizer comprises the following raw materials in parts by weight: 90 parts of prenyl alcohol polyoxyethylene ether, 40 parts of acrylic acid, 24 parts of 6-caprolactone, 2 parts of hydroxypropionic acid, 3 parts of an initiator, 2 parts of a reducing agent, 10 parts of methacryloxypropyl trimethoxy silane, 6 parts of gluconolactone, 6 parts of maleic anhydride, 0.2 part of p-toluenesulfonic acid, 0.02 part of toluene and 72 parts of deionized water.
The initiator is ammonium persulfate and hydrogen peroxide, and the mass ratio of the ammonium persulfate to the hydrogen peroxide is 2: 1; the reducing agent is sodium sulfite and ascorbic acid, and the mass ratio of the sodium sulfite to the ascorbic acid is 1: 2.
The preparation method of the viscosity-reducing composite polycarboxylate superplasticizer specifically comprises the following steps:
(1) putting prenyl alcohol polyoxyethylene ether and 6-caprolactone into a reactor, adding a catalyst into the reactor, uniformly stirring, reacting for 6 hours at 110 ℃, and naturally cooling to obtain modified polyether;
(2) putting gluconolactone, maleic anhydride, p-toluenesulfonic acid and toluene into a reactor for reflux reaction for 7 hours, removing the toluene to obtain composite ester, wherein the reaction temperature is 70 ℃, and vacuumizing the reactor when the reaction starts;
(3) uniformly stirring the modified polyether and 60% of deionized water, adding a reducing agent, and completely dissolving to obtain a base solution;
(4) mixing acrylic acid, composite ester, methacryloxypropyltrimethoxysilane and 20% of deionized water, and uniformly stirring to obtain a solution A; mixing hydroxypropionic acid with 20% of deionized water, and uniformly stirring to obtain a solution B;
(5) adding an initiator into the base liquid, stirring uniformly, slowly dropwise adding the solution A and the solution B, adjusting the pH to 6.5, keeping the reaction temperature at 50 ℃, keeping the dropwise adding time of the solution A at 1.5h, keeping the dropwise adding time of the solution B at 1h, and continuously preserving the heat for 2.5h after the dropwise adding of the solution A and the solution B is finished to obtain the viscosity-reducing type composite polycarboxylic acid water reducer.
The catalyst is formed by mixing dialkyl tin dimaleate and dithiol alkyl tin according to the mass ratio of 1: 1.
Example 3
The viscosity reduction type composite polycarboxylate superplasticizer comprises the following raw materials in parts by weight: 120 parts of prenyl alcohol polyoxyethylene ether, 30 parts of acrylic acid, 25 parts of 6-caprolactone, 5 parts of hydroxypropionic acid, 3 parts of an initiator, 2 parts of a reducing agent, 10 parts of methacryloxypropyl trimethoxy silane, 6 parts of gluconolactone, 6 parts of maleic anhydride, 0.2 part of p-toluenesulfonic acid, 0.02 part of toluene and 80 parts of deionized water.
The initiator is ammonium persulfate and hydrogen peroxide, and the mass ratio of the ammonium persulfate to the hydrogen peroxide is 2: 1; the reducing agent is sodium sulfite and ascorbic acid, and the mass ratio of the sodium sulfite to the ascorbic acid is 1: 2.
The preparation method of the viscosity-reducing composite polycarboxylate superplasticizer specifically comprises the following steps:
(1) putting prenyl alcohol polyoxyethylene ether and 6-caprolactone into a reactor, adding a catalyst into the reactor, uniformly stirring, reacting for 7 hours at 100 ℃, and naturally cooling to obtain modified polyether;
(2) putting gluconolactone, maleic anhydride, p-toluenesulfonic acid and toluene into a reactor for reflux reaction for 7 hours, removing the toluene to obtain composite ester, wherein the reaction temperature is 70 ℃, and vacuumizing the reactor when the reaction starts;
(3) uniformly stirring the modified polyether and 60% of deionized water, adding a reducing agent, and completely dissolving to obtain a base solution;
(4) mixing acrylic acid, composite ester, methacryloxypropyltrimethoxysilane and 20% of deionized water, and uniformly stirring to obtain a solution A; mixing hydroxypropionic acid with 20% of deionized water, and uniformly stirring to obtain a solution B;
(5) adding an initiator into the base liquid, stirring uniformly, slowly dropwise adding the solution A and the solution B, adjusting the pH to 7, keeping the reaction temperature at 60 ℃, keeping the dropwise adding time of the solution A at 2h, keeping the dropwise adding time of the solution B at 1.5h, and continuously preserving the heat for 3h after the dropwise adding of the solution A and the solution B is finished to obtain the viscosity-reducing type composite polycarboxylic acid water reducer.
The catalyst is formed by mixing dialkyl tin dimaleate and dithiol alkyl tin according to the mass ratio of 1: 1.
Example 4
The viscosity reduction type composite polycarboxylate superplasticizer comprises the following raw materials in parts by weight: 140 parts of prenyl alcohol polyoxyethylene ether, 32 parts of acrylic acid, 30 parts of 6-caprolactone, 4 parts of hydroxy propionic acid, 5 parts of an initiator, 4 parts of a reducing agent, 8 parts of methacryloxypropyl trimethoxy silane, 7 parts of gluconolactone, 7.5 parts of maleic anhydride, 0.5 part of p-toluenesulfonic acid, 0.05 part of toluene and 70 parts of deionized water.
The initiator is ammonium persulfate and hydrogen peroxide, and the mass ratio of the ammonium persulfate to the hydrogen peroxide is 2: 1; the reducing agent is sodium sulfite and ascorbic acid, and the mass ratio of the sodium sulfite to the ascorbic acid is 1: 2.
The preparation method of the viscosity-reducing composite polycarboxylate superplasticizer specifically comprises the following steps:
(1) putting prenyl alcohol polyoxyethylene ether and 6-caprolactone into a reactor, adding a catalyst into the reactor, uniformly stirring, reacting for 7 hours at 105 ℃, and naturally cooling to obtain modified polyether;
(2) putting gluconolactone, maleic anhydride, p-toluenesulfonic acid and toluene into a reactor for reflux reaction for 7 hours, removing the toluene to obtain composite ester, wherein the reaction temperature is 70 ℃, and vacuumizing the reactor when the reaction starts;
(3) uniformly stirring the modified polyether and 60% of deionized water, adding a reducing agent, and completely dissolving to obtain a base solution;
(4) mixing acrylic acid, composite ester, methacryloxypropyltrimethoxysilane and 20% of deionized water, and uniformly stirring to obtain a solution A; mixing hydroxypropionic acid with 20% of deionized water, and uniformly stirring to obtain a solution B;
(5) adding an initiator into the base liquid, stirring uniformly, slowly dropwise adding the solution A and the solution B, adjusting the pH to 7, keeping the reaction temperature at 55 ℃, keeping the dropwise adding time of the solution A at 2h, keeping the dropwise adding time of the solution B at 1.5h, and continuously preserving the heat for 3h after the dropwise adding of the solution A and the solution B is finished to obtain the viscosity-reducing type composite polycarboxylic acid water reducer.
The catalyst is formed by mixing dialkyl tin dimaleate and dithiol alkyl tin according to the mass ratio of 1: 1.
Example 5
The viscosity reduction type composite polycarboxylate superplasticizer comprises the following raw materials in parts by weight: 150 parts of prenyl alcohol polyoxyethylene ether, 35 parts of acrylic acid, 28 parts of 6-caprolactone, 5 parts of hydroxypropionic acid, 3 parts of an initiator, 5 parts of a reducing agent, 10 parts of methacryloxypropyl trimethoxy silane, 8 parts of gluconolactone, 85 parts of maleic anhydride, 0.2 part of p-toluenesulfonic acid, 0.04 part of toluene and 80 parts of deionized water.
The initiator is ammonium persulfate and hydrogen peroxide, and the mass ratio of the ammonium persulfate to the hydrogen peroxide is 2: 1; the reducing agent is sodium sulfite and ascorbic acid, and the mass ratio of the sodium sulfite to the ascorbic acid is 1: 2.
The preparation method of the viscosity-reducing composite polycarboxylate superplasticizer specifically comprises the following steps:
(1) putting prenyl alcohol polyoxyethylene ether and 6-caprolactone into a reactor, adding a catalyst into the reactor, uniformly stirring, reacting for 7 hours at 105 ℃, and naturally cooling to obtain modified polyether;
(2) putting gluconolactone, maleic anhydride, p-toluenesulfonic acid and toluene into a reactor for reflux reaction for 7.5h, removing the toluene to obtain composite ester, wherein the reaction temperature is 80 ℃, and vacuumizing the reactor when the reaction starts;
(3) uniformly stirring the modified polyether and 60% of deionized water, adding a reducing agent, and completely dissolving to obtain a base solution;
(4) mixing acrylic acid, composite ester, methacryloxypropyltrimethoxysilane and 20% of deionized water, and uniformly stirring to obtain a solution A; mixing hydroxypropionic acid with 20% of deionized water, and uniformly stirring to obtain a solution B;
(5) adding an initiator into the base liquid, stirring uniformly, slowly dropwise adding the solution A and the solution B, adjusting the pH to 7, keeping the reaction temperature at 55 ℃, keeping the dropwise adding time of the solution A at 2h, keeping the dropwise adding time of the solution B at 1.5h, and continuously preserving the heat for 2h after the dropwise adding of the solution A and the solution B is finished to obtain the viscosity-reducing type composite polycarboxylic acid water reducer.
The catalyst is formed by mixing dialkyl tin dimaleate and dithiol alkyl tin according to the mass ratio of 1: 1.
Comparative example 1
The viscosity reduction type composite polycarboxylate superplasticizer comprises the following raw materials in parts by weight: 150 parts of prenyl alcohol polyoxyethylene ether, 35 parts of acrylic acid, 5 parts of hydroxypropionic acid, 3 parts of an initiator, 5 parts of a reducing agent, 10 parts of methacryloxypropyl trimethoxy silane, 8 parts of gluconolactone, 85 parts of maleic anhydride, 0.2 part of p-toluenesulfonic acid, 0.04 part of toluene and 80 parts of deionized water.
The initiator is ammonium persulfate and hydrogen peroxide, and the mass ratio of the ammonium persulfate to the hydrogen peroxide is 2: 1; the reducing agent is sodium sulfite and ascorbic acid, and the mass ratio of the sodium sulfite to the ascorbic acid is 1: 2.
The preparation method of the viscosity-reducing composite polycarboxylate superplasticizer specifically comprises the following steps:
(1) putting gluconolactone, maleic anhydride, p-toluenesulfonic acid and toluene into a reactor for reflux reaction for 7.5h, removing the toluene to obtain composite ester, wherein the reaction temperature is 80 ℃, and vacuumizing the reactor when the reaction starts;
(2) stirring the isoamylol polyoxyethylene ether and 60% of deionized water uniformly, adding a reducing agent, and completely dissolving to obtain a base solution;
(3) mixing acrylic acid, composite ester, methacryloxypropyltrimethoxysilane and 20% of deionized water, and uniformly stirring to obtain a solution A; mixing hydroxypropionic acid with 20% of deionized water, and uniformly stirring to obtain a solution B;
(4) adding an initiator into the base liquid, stirring uniformly, slowly dropwise adding the solution A and the solution B, adjusting the pH to 7, keeping the reaction temperature at 55 ℃, keeping the dropwise adding time of the solution A at 2h, keeping the dropwise adding time of the solution B at 1.5h, and continuously preserving the heat for 2h after the dropwise adding of the solution A and the solution B is finished to obtain the viscosity-reducing type composite polycarboxylic acid water reducer.
Comparative example 2
The viscosity reduction type composite polycarboxylate superplasticizer comprises the following raw materials in parts by weight: 150 parts of prenyl alcohol polyoxyethylene ether, 35 parts of acrylic acid, 28 parts of 6-caprolactone, 5 parts of hydroxy propionic acid, 3 parts of an initiator, 5 parts of a reducing agent, 8 parts of gluconolactone, 85 parts of maleic anhydride, 0.2 part of p-toluenesulfonic acid, 0.04 part of toluene and 80 parts of deionized water.
The initiator is ammonium persulfate and hydrogen peroxide, and the mass ratio of the ammonium persulfate to the hydrogen peroxide is 2: 1; the reducing agent is sodium sulfite and ascorbic acid, and the mass ratio of the sodium sulfite to the ascorbic acid is 1: 2.
The preparation method of the viscosity-reducing composite polycarboxylate superplasticizer specifically comprises the following steps:
(1) putting prenyl alcohol polyoxyethylene ether and 6-caprolactone into a reactor, adding a catalyst into the reactor, uniformly stirring, reacting for 7 hours at 105 ℃, and naturally cooling to obtain modified polyether;
(2) putting gluconolactone, maleic anhydride, p-toluenesulfonic acid and toluene into a reactor for reflux reaction for 7.5h, removing the toluene to obtain composite ester, wherein the reaction temperature is 80 ℃, and vacuumizing the reactor when the reaction starts;
(3) uniformly stirring the modified polyether and 60% of deionized water, adding a reducing agent, and completely dissolving to obtain a base solution;
(4) mixing acrylic acid, composite ester and 20% deionized water, and uniformly stirring to obtain a solution A; mixing hydroxypropionic acid with 20% of deionized water, and uniformly stirring to obtain a solution B;
(5) adding an initiator into the base liquid, stirring uniformly, slowly dropwise adding the solution A and the solution B, adjusting the pH to 7, keeping the reaction temperature at 55 ℃, keeping the dropwise adding time of the solution A at 2h, keeping the dropwise adding time of the solution B at 1.5h, and continuously preserving the heat for 2h after the dropwise adding of the solution A and the solution B is finished to obtain the viscosity-reducing type composite polycarboxylic acid water reducer.
The catalyst is formed by mixing dialkyl tin dimaleate and dithiol alkyl tin according to the mass ratio of 1: 1.
Result detection
1. The test method comprises the following steps: the products in examples 1-5 and comparative examples 1-2 were selected, and a C60 concrete application performance comparison test was performed on a control group using a commercially available common water reducing agent PC-1. Specific detection results are shown in table 1.
TABLE 1 Performance test
As can be seen from Table 1, the emptying time in examples 1 to 5 is less than the emptying time in comparative examples 1 to 2 and the control group, which indicates that the viscosity reduction effect of the viscosity reduction type composite polycarboxylic acid water reducer is better, and the fluidity of the concrete added with the product of the invention is better; the flowing time of the comparative example 1 and the comparative example 2 is less than that of the control group, which shows that the viscosity reduction effect of the polycarboxylic acid water reducer is improved by the modified polyether and the methacryloxypropyltrimethoxysilane added in the invention.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments have not been described in detail in order to not unnecessarily obscure the present invention in detail. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (10)
1. The viscosity reduction type composite polycarboxylate superplasticizer is characterized by comprising the following raw materials in parts by weight: 80-150 parts of prenyl alcohol polyoxyethylene ether, 30-40 parts of acrylic acid, 20-30 parts of 6-caprolactone, 1-5 parts of hydroxypropionic acid, 2-5 parts of an initiator, 1-5 parts of a reducing agent, 8-10 parts of methacryloxypropyltrimethoxysilane, 5-8 parts of gluconolactone, 6-8 parts of maleic anhydride, 0.1-0.5 part of p-toluenesulfonic acid, 0.02-0.05 part of toluene and 70-80 parts of deionized water.
2. The viscosity reduction type composite polycarboxylate water reducer according to claim 1, characterized by comprising 90-130 parts of prenyl polyoxyethylene ether, 34-38 parts of acrylic acid, 24-26 parts of 6-caprolactone, 2-4 parts of hydroxypropionic acid, 3-4 parts of initiator, 2-4 parts of reducing agent, 8.5-9.5 parts of methacryloxypropyl trimethoxysilane, 6-7 parts of gluconolactone, 6.5-7.5 parts of maleic anhydride, 0.2-0.4 part of p-toluenesulfonic acid, 0.02-0.04 part of toluene and 72-76 parts of deionized water.
3. The viscosity reduction type composite polycarboxylate water reducer according to claim 2, characterized by comprising 120 parts of prenyl polyoxyethylene ether, 35 parts of acrylic acid, 25 parts of 6-caprolactone, 34 parts of hydroxypropionic acid, 4 parts of initiator, 3 parts of reducing agent, 9 parts of methacryloxypropyl trimethoxysilane, 6.5 parts of gluconolactone, 7 parts of maleic anhydride, 0.3 part of p-toluenesulfonic acid, 0.03 part of toluene and 75 parts of deionized water.
4. The viscosity-reduction type composite polycarboxylic acid water reducer according to claim 1, characterized in that the initiator is ammonium persulfate and hydrogen peroxide, and the mass ratio of the ammonium persulfate to the hydrogen peroxide is 2: 1.
5. The viscosity reduction type composite polycarboxylic acid water reducing agent according to claim 1, characterized in that the reducing agent is sodium sulfite and ascorbic acid, and the mass ratio of sodium sulfite to ascorbic acid is 1: 2.
6. The viscosity-reducing composite polycarboxylate superplasticizer according to any one of claims 1 to 5, characterized in that the preparation method of the viscosity-reducing composite polycarboxylate superplasticizer comprises the following steps:
(1) putting prenyl alcohol polyoxyethylene ether and 6-caprolactone into a reactor, adding a catalyst into the reactor, uniformly stirring, reacting at the temperature of 100 ℃ and 110 ℃ for 6-7h, and naturally cooling to obtain modified polyether;
(2) putting gluconolactone, maleic anhydride, p-toluenesulfonic acid and toluene into a reactor for reflux reaction for 7-7.5h, and removing the toluene to obtain composite ester;
(3) uniformly stirring the modified polyether and 60% of deionized water, adding a reducing agent, and completely dissolving to obtain a base solution;
(4) mixing acrylic acid, composite ester, methacryloxypropyltrimethoxysilane and 20% of deionized water, and uniformly stirring to obtain a solution A; mixing hydroxypropionic acid with 20% of deionized water, and uniformly stirring to obtain a solution B;
(5) adding an initiator into the base liquid, stirring uniformly, slowly dropwise adding the solution A and the solution B, adjusting the pH to 6.5-7, and obtaining the viscosity-reducing type composite polycarboxylic acid water reducer after the reaction is finished.
7. The viscosity-reducing composite polycarboxylate superplasticizer according to claim 6, wherein in step (1), the catalyst is a mixture of dialkyl tin dimaleate and alkyl tin mercaptide in a mass ratio of 1: 1.
8. The viscosity-reducing composite polycarboxylate superplasticizer according to claim 6, wherein in step (2), the reaction temperature is 70-80 ℃, and the reactor is vacuumized at the beginning of the reaction.
9. The viscosity-reducing composite polycarboxylate superplasticizer according to claim 6, wherein in step (5), the dropping time of the solution A is 1.5-2h, and the dropping time of the solution B is 1-1.5 h.
10. The viscosity reduction type composite polycarboxylate superplasticizer according to claim 9, wherein in step (5), the reaction temperature is 50-60 ℃, and the temperature is kept for 2-3h after the solution A and the solution B are added dropwise.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011578985.8A CN112724340A (en) | 2020-12-28 | 2020-12-28 | Viscosity-reducing composite polycarboxylate superplasticizer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011578985.8A CN112724340A (en) | 2020-12-28 | 2020-12-28 | Viscosity-reducing composite polycarboxylate superplasticizer and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112724340A true CN112724340A (en) | 2021-04-30 |
Family
ID=75607277
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011578985.8A Pending CN112724340A (en) | 2020-12-28 | 2020-12-28 | Viscosity-reducing composite polycarboxylate superplasticizer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112724340A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114672295A (en) * | 2022-01-27 | 2022-06-28 | 中海油(天津)油田化工有限公司 | Crude oil wax-proof pour point depressant and preparation method thereof |
| CN115872661A (en) * | 2022-12-28 | 2023-03-31 | 科之杰新材料集团有限公司 | Viscosity-reducing polycarboxylate superplasticizer and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104479082A (en) * | 2014-11-21 | 2015-04-01 | 萧县鑫固混凝土外加剂有限公司 | Slow-release type polycarboxylic acid water reducer 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 |
| CN108430625A (en) * | 2015-08-14 | 2018-08-21 | 英佩雷尔创新有限公司 | Segmented copolymer |
| CN109053974A (en) * | 2018-07-23 | 2018-12-21 | 中铁四局集团有限公司 | A kind of preparation method of viscosity reduction type polycarboxylate water-reducer |
| CN110003405A (en) * | 2019-04-24 | 2019-07-12 | 四川同舟化工科技有限公司 | Comprehensive high-performance polycarboxylic acids diminishing |
-
2020
- 2020-12-28 CN CN202011578985.8A patent/CN112724340A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104479082A (en) * | 2014-11-21 | 2015-04-01 | 萧县鑫固混凝土外加剂有限公司 | Slow-release type polycarboxylic acid water reducer and preparation method thereof |
| CN108430625A (en) * | 2015-08-14 | 2018-08-21 | 英佩雷尔创新有限公司 | Segmented copolymer |
| 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 |
| CN109053974A (en) * | 2018-07-23 | 2018-12-21 | 中铁四局集团有限公司 | A kind of preparation method of viscosity reduction type polycarboxylate water-reducer |
| CN110003405A (en) * | 2019-04-24 | 2019-07-12 | 四川同舟化工科技有限公司 | Comprehensive high-performance polycarboxylic acids diminishing |
Non-Patent Citations (2)
| Title |
|---|
| 汪海林: "《中国化学外加剂及矿物外加剂研究与应用新进展》", 30 April 2019 * |
| 黄振等: "己内酯改性聚醚合成聚羧酸及其性能研究", 《广州化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114672295A (en) * | 2022-01-27 | 2022-06-28 | 中海油(天津)油田化工有限公司 | Crude oil wax-proof pour point depressant and preparation method thereof |
| CN114672295B (en) * | 2022-01-27 | 2023-06-02 | 中海油(天津)油田化工有限公司 | Crude oil wax-proof pour point depressant and preparation method thereof |
| CN115872661A (en) * | 2022-12-28 | 2023-03-31 | 科之杰新材料集团有限公司 | Viscosity-reducing polycarboxylate superplasticizer and preparation method thereof |
| CN115872661B (en) * | 2022-12-28 | 2024-02-20 | 科之杰新材料集团有限公司 | Viscosity-reducing polycarboxylate superplasticizer and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109627397B (en) | Polycarboxylate superplasticizer for improving rheological property of cement paste and preparation method thereof | |
| CN108948288B (en) | Preparation method of crosslinking type polycarboxylate superplasticizer by adopting carboxyl functional monomer | |
| WO2014085996A1 (en) | Slump retaining polycarboxylic acid superplasticizer | |
| WO2021103473A1 (en) | Shrinkage-reducing polycarboxylic acid water reducing agent and preparation method thereof | |
| CN109627396B (en) | Preparation method of ether ester copolymerization type polycarboxylate superplasticizer with improved rheological property | |
| CN112979887B (en) | Modified polycarboxylic acid, preparation method thereof and application of modified polycarboxylic acid as water reducing agent | |
| WO2020001169A1 (en) | Preparation method for retarding ether type polycarboxylic acid water reducing agent | |
| CN112724340A (en) | Viscosity-reducing composite polycarboxylate superplasticizer and preparation method thereof | |
| CN112851850B (en) | Preparation method of silicon-acrylic emulsion for preparing polymer cement-based waterproof coating | |
| CN111154048A (en) | Long-branch-chain-end hydroxyl-grafted sugar molecule mud-resistant polycarboxylate superplasticizer and application thereof | |
| CN111019057B (en) | Viscosity-reducing polycarboxylate superplasticizer and preparation method thereof | |
| CN114014999A (en) | Method for preparing polycarboxylate superplasticizer from six-carbon polyether and polycarboxylate superplasticizer | |
| CN112876667A (en) | Ferrocene modified polyoxyethylene ether monomer, ferrocene modified mud-resistant polycarboxylic acid water reducer and preparation method | |
| CN109180876B (en) | Preparation method of viscosity-reducing polycarboxylate superplasticizer | |
| CN114163577A (en) | Viscosity-reducing water reducer and preparation method and application thereof | |
| CN112094385B (en) | Polycarboxylate superplasticizer and preparation method thereof | |
| CN109880030B (en) | One-step method for preparing polycarboxylic acid high-efficiency water reducing agent with three-arm branched structure | |
| CN112608424B (en) | Ester ether copolymerization low-bleeding type polycarboxylate superplasticizer and preparation method thereof | |
| CN109320668B (en) | Viscosity-reducing polycarboxylate superplasticizer and preparation method thereof | |
| CN111333787A (en) | Gradient release type long-acting slump loss resistant polycarboxylic acid water reducing agent and preparation and application thereof | |
| CN108084358B (en) | Preparation method of collapse-proof polycarboxylate superplasticizer | |
| CN115215972B (en) | Preparation method of quick-dispersion polycarboxylate superplasticizer | |
| CN109880018B (en) | One-step method for preparing polycarboxylic acid high-efficiency water reducing agent with four-arm branched structure | |
| CN114702683A (en) | Hyperbranched polycarboxylic acid water reducer and preparation method thereof | |
| CN110642991B (en) | Preparation method of ether viscosity-reducing polycarboxylic acid superplasticizer |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210430 |