CN113912752A - Composite polymerization inhibitor and application thereof, high-stability polyether for polycarboxylate superplasticizer and preparation method thereof - Google Patents
Composite polymerization inhibitor and application thereof, high-stability polyether for polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
- Publication number
- CN113912752A CN113912752A CN202111168474.3A CN202111168474A CN113912752A CN 113912752 A CN113912752 A CN 113912752A CN 202111168474 A CN202111168474 A CN 202111168474A CN 113912752 A CN113912752 A CN 113912752A
- Authority
- CN
- China
- Prior art keywords
- polymerization inhibitor
- composite
- polyether
- composite polymerization
- parts
- 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
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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
- C08F2/42—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using short-stopping agents
-
- 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
- C08G65/26—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 from cyclic ethers and other compounds
- C08G65/2603—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 from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—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 from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—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 from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention relates to the technical field of concrete admixtures, in particular to a composite polymerization inhibitor and application thereof, and high-stability polyether for a polycarboxylic acid water reducing agent and a preparation method thereof. The composite polymerization inhibitor comprises, by weight, 10-50 parts of a phenol polymerization inhibitor, 10-50 parts of a hindered amine polymerization inhibitor, 1-10 parts of an auxiliary polymerization inhibitor, 0.1-5 parts of a metal salt and 0.5-5 parts of an emulsifier; the auxiliary polymerization inhibitor is a thioester antioxidant. The composite polymerization inhibitor can effectively inhibit the generation of polymers through the synergistic polymerization inhibition of all components, and has better polymerization inhibition efficiency; the polyether macromonomer is applied to the polyether macromonomer for the polycarboxylic acid water reducing agent, can effectively inhibit the generation of polymers in the polyether macromonomer, and can prepare polyether which is not easy to decompose and has high stability.
Description
Technical Field
The invention relates to the technical field of concrete admixtures, in particular to a composite polymerization inhibitor and application thereof, and high-stability polyether for a polycarboxylic acid water reducing agent and a preparation method thereof.
Background
The polycarboxylate superplasticizer is widely applied to various concrete construction projects and is mainly prepared by free radical copolymerization of a polyether macromonomer, an unsaturated small monomer, an initiator and a chain transfer agent in an aqueous solution. The common polyether macromonomer contains unsaturated double bonds on the terminal group, common varieties comprise methyl allyl polyoxyethylene ether, isopentenyl polyoxyethylene ether, 4-hydroxybutyl polyoxyethylene ether, ethylene glycol monovinyl polyoxyethylene ether, diethylene glycol monovinyl polyoxyethylene ether, allyl polyoxyethylene ether, polyethylene glycol monomethyl ether methacrylate and the like, and the polyether macromonomer is generally prepared by ethoxylation ring-opening addition of ethylene oxide and unsaturated enol in the presence of a catalyst, and the molecular weight of the polyether monomer can be controlled by the addition number of epoxy compounds. At present, the following three types of common ethoxylation reactor technologies exist in China: production technologies such as an external circulation spray type reactor (PRESS), a Venturi jet type loop reactor (BUSS), a combined external circulation spray and Venturi jet type reactor, a stirred tank type reactor and the like.
However, the polyether macromonomer is generally used in the form of tablets, powders, molten or aqueous solutions. In the preservation process of the polyether macromonomer, due to the action of factors such as external environment light, heat effect and the like, unsaturated double bonds on the polyether macromonomer are easily subjected to thermal decomposition to generate free radicals; or free radicals generated by impurities such as an initiator and the like introduced into the raw materials can initiate the polyether macromonomer to generate free radical reaction, so that the performance of the polyether is reduced. In the case of tablet and powder polyether products, the polyether is caused to generate a gel-like substance in the slicing and spraying processes, and the gel-like substance forms lumps to a certain extent; meanwhile, heat is released in the process of free radical polymerization, and if the heat is not discharged in time, the degradation speed of the performance of the polyether macromonomer is accelerated due to the accumulation of the heat, especially in a high-temperature environment in summer. Meanwhile, the polyether is continuously contacted with air in the storage and transportation processes, so that the peroxide value of the product is increased, and the decomposition reaction of the polyether macromonomer is also initiated. In the prior art, a small amount of polymerization inhibitor or stabilizer is generally added to solve the problem of stability of polyether in the process of storage and transfer, so that the destructive reaction can be avoided. However, the polymerization inhibition is often not well solved by a single polymerization inhibitor. Therefore, in order to solve the above problems, those skilled in the art have made an effort to develop a composite polymerization inhibitor which can inhibit the formation of polymer efficiently by its synergistic polymerization inhibition effect, and has a better polymerization inhibition effect and efficiency.
The application number is CN201510981503.6, the publication date is 2016, 06 and 22, and discloses a method for synthesizing polycarboxylate superplasticizer monomeric polyether, which comprises the following steps: adding an alkali metal hydride or borohydride to a starting agent to prepare a sodium salt of the starting agent; introducing a predetermined amount of ethylene oxide into the sodium salt of the initiator to form a prepolymer; continuously introducing ethylene oxide into the prepolymer, and keeping the preset feeding speed and the preset reflux speed to generate unsaturated polyether; adding carboxylic acid or carboxylic anhydride with a preset proportion, keeping a preset temperature, and continuously stirring for a preset time; adding a stabilizing agent with preset types and proportions. The polyether polyol prepared by the method has the characteristics of good storage stability, difficult degradation, long shelf life and higher performance of the synthesized polycarboxylic acid water reducer. The terminal of the monomer polyether polyol prepared in the invention is not hydroxyl but esterified by carboxyl, so that the stability of the product is greatly improved, but the kind and the adding amount of the stabilizer are not described in the patent.
Disclosure of Invention
The problems of easy degradation and poor stability in the process of storing or transferring the polyether macromonomer mentioned in the background technology are solved. The invention provides a composite polymerization inhibitor which comprises, by weight, 10-50 parts of a phenolic polymerization inhibitor, 10-50 parts of a hindered amine polymerization inhibitor, 1-10 parts of an auxiliary polymerization inhibitor, 0.1-5 parts of a metal salt and 0.5-5 parts of an emulsifier;
the auxiliary polymerization inhibitor is a thioester antioxidant.
In one embodiment, the phenolic polymerization inhibitor is one or more of 4-methoxyphenol, p-tert-butylcatechol, 2, 4-dimethyl-6-tert-butylphenol, 2, 5-di-tert-butylhydroquinone, 2, 6-di-tert-butyl-4-methylphenol, 2, 6-di-tert-butyl-4-ethylphenol, 2, 6-di-tert-butyl-4-dimethylaminomethylphenol, and 2- (5-chloro-2-benzotriazolyl) -6-tert-butyl-4-methylphenol.
In one embodiment, the hindered amine polymerization inhibitor is 4-hydroxy-2, 2,6, 6-tetramethylpiperidine-1-oxyl, 4-benzoyloxy-2, 2,6, 6-tetramethylpiperidine-1-oxyl radical, polysuccinic acid (4-hydroxyethyl-2, 2,6, 6-tetramethyl-1-piperidineethanol), N, one or more of N' -bis (2,2,6, 6-tetramethylpiperidyl) hexanediamine, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate and 4-oxo-2, 2,6, 6-tetramethyl-1-piperidinyloxy free radical.
In one embodiment, the metal salt is one or more of copper bis (N, N-dibutyldithiocarbamate), cuprous chloride, copper sulfate and basic copper carbonate;
the auxiliary polymerization inhibitor is one or more of dilauryl thiodipropionate, ditetradecyl 3,3' -thiodipropionate and distearyl thiodipropionate.
In one embodiment, the emulsifier has the chemical formula RO- (CH)2CH2O)n-H；R＝iso-C13H27(ii) a Wherein n is 3, 6, 10, 20, 40, 60.
The invention also provides the application of the composite polymerization inhibitor, which is to mix the composite polymerization inhibitor emulsion with the polyether macromonomer to prepare high-stability polyether for the polycarboxylic acid water reducer; the composite polymerization inhibitor emulsion is formed by adding a composite polymerization inhibitor into a solvent for emulsification, and the composite polymerization inhibitor is the composite polymerization inhibitor.
The invention also provides high-stability polyether for the polycarboxylate superplasticizer, which is prepared by mixing the composite polymerization inhibitor emulsion and the polyether macromonomer; the composite polymerization inhibitor emulsion is formed by adding the composite polymerization inhibitor into a solvent for emulsification, and the mass ratio of the composite polymerization inhibitor to a polyether macromonomer is (10-40) ppm: 1; the composite polymerization inhibitor is the composite polymerization inhibitor.
In one embodiment, the polyether macromonomer is prepared by ethoxylation of an epoxy compound and an unsaturated enol in the presence of an alkoxylation catalyst; the mass ratio of the unsaturated enol to the epoxy compound to the alkoxylation catalyst is 100 (1-5) to (0.0005-0.0020).
In one embodiment, the unsaturated enol is one or more of 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, and vinyl glycol ether in combination; the epoxy compound is one or a combination of more of ethylene oxide, propylene oxide and butylene oxide; the alkoxylation catalyst is one or more of sodium methoxide, potassium methoxide, double metal cyanide, metallic sodium and sodium hydride.
The invention also provides a preparation method of the high-stability polyether for the polycarboxylate superplasticizer, which comprises the following steps:
s100, preparing a composite polymerization inhibitor: weighing a phenolic polymerization inhibitor, a hindered amine polymerization inhibitor, an auxiliary polymerization inhibitor, a metal salt and an emulsifier according to a certain weight, and mixing to obtain a composite polymerization inhibitor in a uniform state;
s200, adding the composite polymerization inhibitor prepared in the S100 into a solvent, and stirring and mixing to obtain a composite polymerization inhibitor emulsion;
and S300, mixing the polyether macromonomer with the composite polymerization inhibitor emulsion obtained in the S200 to obtain the high-stability polyether.
Compared with the prior art, the invention has the following effects:
the composite polymerization inhibitor provided by the invention can effectively inhibit the generation of polymers through the synergistic polymerization inhibition of all components, has better polymerization inhibition efficiency, and obviously reduces the dosage compared with a single polymerization inhibitor;
the polyether macromonomer is applied to the polyether macromonomer for the polycarboxylic acid water reducing agent, can effectively inhibit the generation of polymers in the polyether macromonomer, can prepare polyether which is not easy to decompose and has high stability, and can solve the problem of polyether performance reduction caused by easy degradation and poor stability in the process of storing or transferring the polyether macromonomer.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the following description will clearly and completely describe the embodiments of the present invention, and obviously, the described embodiments are a part of the embodiments of the present invention, but not all 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.
The invention also provides a preparation method of the composite polymerization inhibitor and the high-stability polyether for the polycarboxylate superplasticizer, which comprises the following steps:
(1) weighing 10-50 parts by weight of a phenolic polymerization inhibitor, 10-50 parts by weight of a hindered amine polymerization inhibitor, 1-10 parts by weight of an auxiliary polymerization inhibitor, 0.1-5 parts by weight of a metal salt and 0.5-5 parts by weight of an emulsifier;
(2) the raw material components are put into a preparation tank, the temperature is raised to 40-60 ℃, the raw material components are stirred by a high-speed dispersion shearing machine for 30-60 min to form the uniform composite polymerization inhibitor, wherein the stirring speed is 500-8000 rpm/min.
(3) And (3) adding 100 parts by weight of solvent into the composite polymerization inhibitor obtained in the step (2), and continuously stirring for 30-60 min to obtain the composite polymerization inhibitor emulsion in an emulsion state.
(4) And adding the composite polymerization inhibitor emulsion into a polyether macromonomer, mixing and stirring for a certain time, and neutralizing with glacial acetic acid until the pH value is 6-7 to obtain the high-stability polyether for the polycarboxylate superplasticizer. Wherein the temperature of the materials discharged from the kettle is controlled to be 60-90 ℃, and when the temperature is too low, the composite polymerization inhibitor is easy to form a paste.
Preferably, in one embodiment, in step (3), the solvent is water; preferably, deionized water is used as the solvent.
Preferably, in one embodiment, the mass ratio of the composite polymerization inhibitor to the polyether macromonomer is (10-40) ppm: 1; in the mass ratio of the composite polymerization inhibitor to the polyether macromonomer, the mass of the composite polymerization inhibitor means: the quality of the composite polymerization inhibitor is compounded by a phenol polymerization inhibitor, a hindered amine polymerization inhibitor, an auxiliary polymerization inhibitor, metal salt and an emulsifier, but not the quality of the emulsion of the composite polymerization inhibitor.
Preferably, in one embodiment, the polyether macromonomer is prepared by ethoxylating an epoxy compound with an unsaturated enol in the presence of an alkoxylation catalyst; the preparation method specifically adopts the following preparation scheme: carrying out air tightness inspection and dewatering and drying on each part of the high-pressure reaction kettle with magnetic stirring; adding an initiator unsaturated enol and an alkoxylation catalyst into a high-pressure reaction kettle, replacing for 3 times by nitrogen, vacuumizing the reaction kettle, stirring, heating, continuously introducing epoxy compound gas, and stopping heating when the temperature reaches 60 ℃; wherein, in the process of introducing the epoxy compound gas, the reaction pressure is controlled to be 0.1 MPa-0.5 MPa, the reaction temperature is controlled to be 90-130 ℃, and the mass ratio of the unsaturated enol to the epoxy compound to the alkoxylation catalyst is 100 (1-5) to (0.0005-0.0020);
it should be noted that the ring-opening polymerization process of the epoxy compound, i.e., the above-mentioned ethoxylation reaction, is a strongly exothermic reaction, and the reaction temperature can be controlled by controlling the feed rate of ethylene oxide during the reaction.
Preferably, in one embodiment, the unsaturated enol is one or more of 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, and vinyl glycol ether in combination; the epoxy compound is one or a combination of more of ethylene oxide, propylene oxide and butylene oxide, and the ethylene oxide is preferably selected; the alkoxylation catalyst is one or more of sodium methoxide, potassium methoxide, double metal cyanide, metallic sodium and sodium hydride, preferably sodium methoxide.
The invention also provides the following examples and comparative examples:
the formulations (unit: parts by weight) of the composite polymerization inhibitor in the examples and comparative examples provided by the present invention are shown in table 1 below:
TABLE 1
The specific examples and comparative examples were prepared as follows:
example 1
(1) Adding a phenolic polymerization inhibitor, a hindered amine polymerization inhibitor, an auxiliary polymerization inhibitor, metal salt and an emulsifier into a polymerization inhibitor preparation tank, heating to 40 ℃, stirring by using a high-speed dispersion shearing machine at the stirring speed of 6000rpm/min for 30min to form the uniform composite polymerization inhibitor. Then 100 parts of deionized water is added into the composite polymerization inhibitor, and the mixture is continuously stirred for 60min to obtain composite polymerization inhibitor emulsion in an emulsion state;
the composite polymerization inhibitor is compounded according to the following mass ratio: 10 parts of 2- (5-chloro-2-phenyltriazolyl) -6-tert-butyl-4-methylphenol, 50 parts of 4-hydroxy-2, 2,6, 6-tetramethylpiperidine-1-oxyl, 10 parts of dilauryl thiodipropionate, 0.1 part of copper bis (N, N-dibutyldithiocarbamate) and 5 parts of emulsifier 1360.
(2) Carrying out air tightness inspection and dewatering and drying on each part of the high-pressure reaction kettle with magnetic stirring; adding 4-hydroxybutyl vinyl ether and sodium methoxide into a high-pressure reaction kettle, replacing the mixture with nitrogen for 3 times, vacuumizing the reaction kettle, stirring, heating, continuously introducing ethylene oxide, and stopping heating when the temperature reaches 60 ℃; in the process of introducing ethylene oxide, controlling the reaction pressure to be 0.3MPa and the reaction temperature to be 90 ℃, wherein the mass ratio of the unsaturated enol 4-hydroxybutyl vinyl ether to the ethylene oxide to the sodium methoxide is 100: 2.5: 0.001.
(3) after the ethylene oxide is added, curing and degassing are carried out to prepare a polyether macromonomer, then the reaction system is cooled to 80 ℃, the prepared composite polymerization inhibitor emulsion is added, stirring is carried out for 30min, and the mixture is neutralized by glacial acetic acid until the pH value is 6.5, and then the high-stability polyether for the polycarboxylic acid water reducing agent is obtained. Wherein, the mass of the added composite polymerization inhibitor is 10ppm of the total mass of the polyether macromonomer, and the mass needs to be described as follows: the quality of the composite polymerization inhibitor refers to the quality of the composite polymerization inhibitor compounded by a phenol polymerization inhibitor, a hindered amine polymerization inhibitor, an auxiliary polymerization inhibitor, a metal salt and an emulsifier, but not the quality of the composite polymerization inhibitor emulsion.
Example 2
(1) Adding a phenolic polymerization inhibitor, a hindered amine polymerization inhibitor, an auxiliary polymerization inhibitor, metal salt and an emulsifier into a polymerization inhibitor preparation tank, heating to 40 ℃, stirring by using a high-speed dispersion shearing machine at the stirring speed of 8000rpm/min for 60min to form the uniform composite polymerization inhibitor. Then 100 parts of deionized water is added into the composite polymerization inhibitor, and the mixture is continuously stirred for 60min to obtain composite polymerization inhibitor emulsion in an emulsion state;
the composite polymerization inhibitor is compounded according to the following mass ratio: 20 parts of 2, 4-dimethyl-6-tert-butylphenol, 40 parts of 4-benzoyloxy-2, 2,6, 6-tetramethylpiperidine-1-oxyl radical, 5 parts of ditetradecyl 3,3' -thiodipropionate, 1 part of basic copper carbonate and 0.5 part of emulsifier 1340.
(2) And (4) carrying out air tightness inspection and dewatering and drying on each part of the high-pressure reaction kettle with magnetic stirring. Adding diethylene glycol monovinyl ether and sodium methoxide into a high-pressure reaction kettle, replacing the mixture with nitrogen for 3 times, vacuumizing the reaction kettle, starting stirring and heating, continuously introducing ethylene oxide, and stopping heating when the temperature reaches 60 ℃; in the process of introducing ethylene oxide, controlling the reaction pressure to be 0.1MPa and the reaction temperature to be 100 ℃, wherein the mass ratio of the unsaturated enol (diethylene glycol monovinyl ether), the ethylene oxide and the sodium methoxide is 100: 2.5: 0.001.
(3) after the ethylene oxide is added, curing and degassing are carried out to prepare a polyether macromonomer, then the reaction system is cooled to 80 ℃, the prepared composite polymerization inhibitor emulsion is added, stirring is carried out for 30min, glacial acetic acid is used for neutralizing to pH6.5, and discharging is carried out, thus obtaining the high-stability polyether for the polycarboxylic acid water reducing agent. Wherein, the mass of the added composite polymerization inhibitor is 20ppm of the total mass of the polyether macromonomer, and the mass needs to be described as follows: the quality of the composite polymerization inhibitor refers to the quality of the composite polymerization inhibitor compounded by a phenol polymerization inhibitor, a hindered amine polymerization inhibitor, an auxiliary polymerization inhibitor, a metal salt and an emulsifier, but not the quality of the composite polymerization inhibitor emulsion.
Example 3
(1) Adding a phenolic polymerization inhibitor, a hindered amine polymerization inhibitor, an auxiliary polymerization inhibitor, metal salt and an emulsifier into a polymerization inhibitor preparation tank, heating to 60 ℃, stirring by using a high-speed dispersion shearing machine at a stirring speed of 500rpm/min for 30min to form the uniform composite polymerization inhibitor. Then 100 parts of deionized water is added into the composite polymerization inhibitor, and the mixture is continuously stirred for 60min to obtain composite polymerization inhibitor emulsion in an emulsion state;
the composite polymerization inhibitor is compounded according to the following mass ratio: 50 parts of 2, 6-di-tert-butyl-4-methylphenol, 10 parts of poly (4-hydroxyethyl-2, 2,6, 6-tetramethyl-1-piperidineethanol) succinate, 1 part of dilauryl thiodipropionate, 5 parts of copper sulfate and 1 part of emulsifier 1310.
(2) And (4) carrying out air tightness inspection and dewatering and drying on each part of the high-pressure reaction kettle with magnetic stirring. Adding vinyl glycol ether and sodium methoxide into a high-pressure reaction kettle, replacing the mixture with nitrogen for 3 times, vacuumizing the reaction kettle, starting stirring and heating, continuously introducing ethylene oxide, and stopping heating when the temperature reaches 60 ℃; in the process of introducing ethylene oxide, controlling the reaction pressure to be 0.5MPa and the reaction temperature to be 130 ℃, wherein the mass ratio of the unsaturated enol (vinyl glycol ether), the ethylene oxide and the sodium methoxide is 100: 2.5: 0.001.
(3) after the ethylene oxide is added, curing and degassing are carried out to prepare a polyether macromonomer, then the reaction system is cooled to 80 ℃, the prepared composite polymerization inhibitor emulsion is added, stirring is carried out for 30min, and the mixture is neutralized by glacial acetic acid until the pH value is 6.5, and then the high-stability polyether for the polycarboxylic acid water reducing agent is obtained. Wherein, the mass of the added composite polymerization inhibitor is 30ppm of the total mass of the polyether macromonomer, and the mass needs to be described as follows: the quality of the composite polymerization inhibitor refers to the quality of the composite polymerization inhibitor compounded by a phenol polymerization inhibitor, a hindered amine polymerization inhibitor, an auxiliary polymerization inhibitor, a metal salt and an emulsifier, but not the quality of the composite polymerization inhibitor emulsion.
Example 4
(1) Adding a phenolic polymerization inhibitor, a hindered amine polymerization inhibitor, an auxiliary polymerization inhibitor, metal salt and an emulsifier into a polymerization inhibitor preparation tank, heating to 50 ℃, stirring by using a high-speed dispersion shearing machine at the stirring speed of 3000rpm/min for 60min to form the uniform composite polymerization inhibitor. Then 100 parts of deionized water is added into the composite polymerization inhibitor, and the mixture is continuously stirred for 30min to obtain composite polymerization inhibitor emulsion in an emulsion state;
the composite polymerization inhibitor is compounded according to the following mass ratio: 30 parts of 2, 6-di-tert-butyl-4-ethylphenol, 30 parts of N, N' -bis (2,2,6, 6-tetramethylpiperidyl) hexamethylenediamine, 6 parts of dioctadecyl thiodipropionate, 1.5 parts of cuprous chloride and 3 parts of an emulsifier 1303.
(2) And (4) carrying out air tightness inspection and dewatering and drying on each part of the high-pressure reaction kettle with magnetic stirring. Adding 4-hydroxybutyl vinyl ether and sodium methoxide into a high-pressure reaction kettle, replacing the mixture with nitrogen for 3 times, vacuumizing the reaction kettle, stirring, heating, continuously introducing ethylene oxide, and stopping heating when the temperature reaches 60 ℃; in the process of introducing ethylene oxide, controlling the reaction pressure to be 0.4MPa and the reaction temperature to be 120 ℃, wherein the mass ratio of the unsaturated enol (4-hydroxybutyl vinyl ether), the ethylene oxide and the sodium methoxide is 100: 2.5: 0.001.
(3) after the ethylene oxide is added, curing and degassing are carried out to prepare a polyether macromonomer, then the reaction system is cooled to 80 ℃, the prepared composite polymerization inhibitor emulsion is added, stirring is carried out for 30min, and the mixture is neutralized by glacial acetic acid until the pH value is 6.5, and then the high-stability polyether for the polycarboxylic acid water reducing agent is obtained. Wherein, the mass of the added composite polymerization inhibitor is 40ppm of the total mass of the polyether macromonomer, and the mass needs to be explained as follows: the quality of the composite polymerization inhibitor refers to the quality of the composite polymerization inhibitor compounded by a phenol polymerization inhibitor, a hindered amine polymerization inhibitor, an auxiliary polymerization inhibitor, a metal salt and an emulsifier, but not the quality of the composite polymerization inhibitor emulsion.
Comparative example 1
Based on example 4, comparative example 1 differs from example 4 in that: no composite polymerization inhibitor is added into the polyether macromonomer;
(1) and (4) carrying out air tightness inspection and dewatering and drying on each part of the high-pressure reaction kettle with magnetic stirring. Adding 4-hydroxybutyl vinyl ether and sodium methoxide into a high-pressure reaction kettle, replacing the mixture with nitrogen for 3 times, vacuumizing the reaction kettle, stirring, heating, continuously introducing ethylene oxide, and stopping heating when the temperature reaches 60 ℃; in the process of introducing ethylene oxide, controlling the reaction pressure to be 0.4MPa and the reaction temperature to be 120 ℃, wherein the mass ratio of the unsaturated enol (4-hydroxybutyl vinyl ether), the ethylene oxide and the sodium methoxide is 100: 2.5: 0.001.
(2) after the ethylene oxide is added, curing and degassing are carried out to prepare the polyether macromonomer, then the reaction system is cooled to 80 ℃, glacial acetic acid is used for neutralizing until the pH value is 6.5, and the polyether product is obtained after discharging.
Comparative example 2
Based on example 4, comparative example 2 differs from example 4 only in that: 4-Methoxyphenol (MEHQ) is adopted to replace the composite polymerization inhibitor in the embodiment;
(1) adding 100 parts by weight of deionized water into 70.5 parts by weight of 2, 6-di-tert-butyl-4-ethylphenol, and continuously stirring for 30min to obtain a polymerization inhibitor emulsion in an emulsion state;
(2) and (4) carrying out air tightness inspection and dewatering and drying on each part of the high-pressure reaction kettle with magnetic stirring. Adding 4-hydroxybutyl vinyl ether and sodium methoxide into a high-pressure reaction kettle, replacing the mixture with nitrogen for 3 times, vacuumizing the reaction kettle, stirring, heating, continuously introducing ethylene oxide, and stopping heating when the temperature reaches 60 ℃; in the process of introducing ethylene oxide, controlling the reaction pressure to be 0.4MPa and the reaction temperature to be 120 ℃, wherein the mass ratio of the unsaturated enol (4-hydroxybutyl vinyl ether), the ethylene oxide and the sodium methoxide is 100: 2.5: 0.001.
(3) after the ethylene oxide is added, curing and degassing are carried out to prepare a polyether macromonomer, then the reaction system is cooled to 80 ℃, the prepared 2, 6-di-tert-butyl-4-ethylphenol emulsion is added, the stirring is carried out for 30min, the neutralization is carried out by glacial acetic acid until the pH value is 6.5, and the discharging is carried out to obtain the polyether product. Wherein, the mass of the added 2, 6-di-tert-butyl-4-ethylphenol polymerization inhibitor is 40ppm of the total mass of the polyether macromonomer, and the mass needs to be explained as follows: the mass of inhibitor refers to the mass of 2, 6-di-tert-butyl-4-ethylphenol, not to the mass of inhibitor emulsion.
Comparative example 3
Based on example 4, comparative example 3 differs from example 4 in that: n, N' -bis (2,2,6, 6-tetramethylpiperidyl) hexamethylenediamine is adopted to replace the composite polymerization inhibitor in the embodiment;
(1) adding 100 parts by weight of deionized water into 70.5 parts by weight of N, N' -bis (2,2,6, 6-tetramethylpiperidyl) hexanediamine, and continuously stirring for 30min to obtain a polymerization inhibitor emulsion in an emulsion state;
(2) and (4) carrying out air tightness inspection and dewatering and drying on each part of the high-pressure reaction kettle with magnetic stirring. Adding 4-hydroxybutyl vinyl ether and sodium methoxide into a high-pressure reaction kettle, replacing the mixture with nitrogen for 3 times, vacuumizing the reaction kettle, stirring, heating, continuously introducing ethylene oxide, and stopping heating when the temperature reaches 60 ℃; in the process of introducing ethylene oxide, controlling the reaction pressure to be 0.4MPa and the reaction temperature to be 120 ℃, wherein the mass ratio of the unsaturated enol (4-hydroxybutyl vinyl ether), the ethylene oxide and the sodium methoxide is 100: 2.5: 0.001.
(3) after the ethylene oxide is added, curing and degassing are carried out to prepare a polyether macromonomer, then the reaction system is cooled to 80 ℃, the prepared N, N' -bis (2,2,6, 6-tetramethyl piperidyl) hexamethylene diamine polymerization inhibitor emulsion is added, stirring is carried out for 30min, and the mixture is neutralized by glacial acetic acid until the pH value is 6.5, and then the polyether product is obtained. Wherein, the mass of the added N, N' -bis (2,2,6, 6-tetramethylpiperidyl) hexanediamine is 40ppm of the total mass of the polyether macromonomer, and the following should be mentioned: the polymerization inhibitor mass refers to the mass of N, N' -bis (2,2,6, 6-tetramethylpiperidyl) hexamethylenediamine, not to the polymerization inhibitor emulsion mass.
It should be noted that:
in addition to the practical choices presented in the above specific examples, the phenolic polymerization inhibitor may be selected from one or more combinations of 4-methoxyphenol, p-tert-butylcatechol, 2, 4-dimethyl-6-tert-butylphenol, 2, 5-di-tert-butylhydroquinone, 2, 6-di-tert-butyl-4-methylphenol, 2, 6-di-tert-butyl-4-ethylphenol, 2, 6-di-tert-butyl-4-dimethylaminomethylphenol, 2- (5-chloro-2-benzotriazolyl) -6-tert-butyl-4-methylphenol, including but not limited to the practical choices presented in the above examples;
in addition to the practical options shown in the above specific examples, the hindered amine-based polymerization inhibitor may be selected from 4-hydroxy-2, 2,6, 6-tetramethylpiperidine-1-oxyl radical, 4-benzoyloxy-2, 2,6, 6-tetramethylpiperidine-1-oxyl radical, poly (4-hydroxyethyl-2, 2,6, 6-tetramethyl-1-piperidineethanol) succinate, N' -bis (2,2,6, 6-tetramethylpiperidyl) hexanediamine, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate, 4-oxo-2, one or more combinations of 2,6, 6-tetramethyl-1-piperidinyloxy, including but not limited to the actual choices embodied in the above examples;
in addition to the practical choices embodied in the above specific examples, the metal salt may be selected from one or more of copper bis (N, N-dibutyldithiocarbamate), cuprous chloride, copper sulfate, and basic copper carbonate, including but not limited to the practical choices embodied in the above examples;
in addition to the practical choices embodied in the above specific examples, the auxiliary polymerization inhibitor is a thioester antioxidant, and one or more combinations of dilauryl thiodipropionate, ditetradecyl 3,3' -thiodipropionate and distearyl thiodipropionate can be selected, including but not limited to the practical choices embodied in the above examples;
besides the practical choices of the specific embodiments, the emulsifier can also be selected from other emulsifiersThe chemical structural formula of the emulsifier is RO- (CH)2CH2O)n-H；R＝iso-C13H27N is 3, 6, 10, 20, 40, 60; including but not limited to the actual choices embodied by the above-described embodiments; wherein, the "iso-" is the abbreviation of isomeric, and means the isomeric and "iso" groups, which is the expression mode of the existing chemical structural formula, and the specific meanings represented in the chemical structural formula are not repeated. Specifically, commercially available emulsifiers such as isotridecanol polyoxyethylene ether, emulsifier 1303, emulsifier 1306, emulsifier 1310, emulsifier 1320, emulsifier 1340, and emulsifier 1360 can be used as the emulsifier.
In addition to the practical choices embodied in the above specific embodiments, the composite polymerization inhibitor comprises 10-50 parts of a phenolic polymerization inhibitor, 10-50 parts of a hindered amine polymerization inhibitor, 1-10 parts of an auxiliary polymerization inhibitor, 0.1-5 parts of a metal salt and 0.5-5 parts of an emulsifier; the composite polymerization inhibitor combinations within the above mass ratio range can include, but are not limited to, the practical choices as embodied in the above examples.
In addition to the practical choices embodied in the above embodiments, the polyether macromonomer can also be used in other existing polyether macromonomers for polycarboxylic acid water reducing agent, including but not limited to the practical choices embodied in the above embodiments.
In addition to the practical choices embodied in the above specific embodiments, the mass ratio of the composite polymerization inhibitor to the polyether macromonomer is (10-40) ppm:1, including but not limited to the practical choices embodied by the above-described embodiments.
The products obtained in the above examples and comparative examples were subjected to the relevant index test, and the test results are shown in the following table 2:
TABLE 2
Wherein, the test standard of the double bond content performance index is as follows: JC/T2033-; the iodine value is determined according to the standard GBT13892-2012 'determination of iodine value of surfactant'; in table 2, the 1d, 90d and 180d represent double bond retention rates of the polyether product after 1 day, 90 days and 180 days, respectively.
From the results of table 2, it can be seen that:
compared with the example 4, the difference of the comparative example 1 is that no composite polymerization inhibitor is used, and the result shows that the double bond retention rate of the polyether product prepared in the comparative example 1 is obviously reduced along with the passage of time, and the double bond retention rate is only 25.1% at 180 d;
compared with the example 4, the difference is that the phenolic polymerization inhibitor 2, 6-di-tert-butyl-4-ethylphenol is used for replacing the composite polymerization inhibitor, and the result shows that the double bond retention rate of the polyether product prepared in the example 2 is reduced along with the passage of time, the double bond retention rate is only 83.4% at 180d, and the double bond retention rate is kept at 94.7% at 180d in the example 4;
comparative example 3 is different from example 4 in that N, N' -bis (2,2,6, 6-tetramethylpiperidyl) hexamethylenediamine, which is a hindered amine polymerization inhibitor, is used instead of the composite polymerization inhibitor, and the result shows that the double bond retention rate of the polyether product prepared in comparative example 3 is reduced with the passage of time, and the double bond retention rate is only 75.1% at 180d, while the double bond retention rate is maintained at 94.7% at 180d in example 4;
in the embodiments 1-4 of the invention, the high-stability polyether for the polycarboxylate superplasticizer is prepared by mixing the composite polymerization inhibitor and the polyether macromonomer, and the double bond content of the polyether is still kept at a higher level after a long time, which shows that the composite polymerization inhibitor provided by the invention can effectively inhibit the generation of polymers through the synergistic polymerization inhibition of all components, has better polymerization inhibition efficiency, and has obviously reduced dosage compared with a single polymerization inhibitor; the composite polymerization inhibitor is applied to the polyether macromonomer for the polycarboxylate superplasticizer, can effectively inhibit the generation of polymers in the polyether macromonomer, prepares polyether with difficult decomposition and high stability, and can solve the problem of polyether performance reduction caused by easy degradation and poor stability in the process of storing or transferring the polyether macromonomer.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The composite polymerization inhibitor is characterized by comprising 10-50 parts by weight of a phenolic polymerization inhibitor, 10-50 parts by weight of a hindered amine polymerization inhibitor, 1-10 parts by weight of an auxiliary polymerization inhibitor, 0.1-5 parts by weight of a metal salt and 0.5-5 parts by weight of an emulsifier;
the auxiliary polymerization inhibitor is a thioester antioxidant.
2. The composite polymerization inhibitor according to claim 1, characterized in that: the phenolic polymerization inhibitor is one or a combination of more of 4-methoxyphenol, p-tert-butylcatechol, 2, 4-dimethyl-6-tert-butylphenol, 2, 5-di-tert-butylhydroquinone, 2, 6-di-tert-butyl-4-methylphenol, 2, 6-di-tert-butyl-4-ethylphenol, 2, 6-di-tert-butyl-4-dimethylaminomethylphenol and 2- (5-chloro-2-phenyltriazolyl) -6-tert-butyl-4-methylphenol.
3. The composite polymerization inhibitor according to claim 1, characterized in that: the hindered amine polymerization inhibitor is 4-hydroxy-2, 2,6, 6-tetramethylpiperidine-1-oxyl, 4-benzoyloxy-2, 2,6, 6-tetramethylpiperidine-1-oxyl free radical, polysuccinic acid (4-hydroxyethyl-2, 2,6, 6-tetramethyl-1-piperidineethanol) ester and N, one or more of N' -bis (2,2,6, 6-tetramethylpiperidyl) hexanediamine, bis (2,2,6, 6-tetramethyl-4-piperidyl) sebacate and 4-oxo-2, 2,6, 6-tetramethyl-1-piperidinyloxy free radical.
4. The composite polymerization inhibitor according to claim 1, characterized in that: the metal salt is one or a combination of more of copper bis (N, N-dibutyl dithiocarbamate), cuprous chloride, copper sulfate and basic copper carbonate;
the auxiliary polymerization inhibitor is one or more of dilauryl thiodipropionate, ditetradecyl 3,3' -thiodipropionate and distearyl thiodipropionate.
5. The composite polymerization inhibitor according to claim 1, characterized in that: the chemical structural formula of the emulsifier is RO- (CH)2CH2O)n-H；R＝iso-C13H27(ii) a Wherein n is 3, 6, 10, 20, 40, 60.
6. Use of the composite polymerization inhibitor according to any one of claims 1 to 5, characterized in that: mixing the composite polymerization inhibitor emulsion with a polyether macromonomer to prepare high-stability polyether for the polycarboxylic acid water reducing agent;
the composite polymerization inhibitor emulsion is formed by adding a composite polymerization inhibitor into a solvent for emulsification, and the composite polymerization inhibitor is the composite polymerization inhibitor in any one of claims 1 to 5.
7. The high-stability polyether for the polycarboxylate superplasticizer is characterized by being prepared by mixing a composite polymerization inhibitor emulsion and a polyether macromonomer;
the composite polymerization inhibitor emulsion is formed by adding the composite polymerization inhibitor into a solvent for emulsification, and the mass ratio of the composite polymerization inhibitor to a polyether macromonomer is (10-40) ppm: 1; the composite polymerization inhibitor is the composite polymerization inhibitor described in any one of claims 1 to 5.
8. The high-stability polyether for a polycarboxylic acid water-reducing agent according to claim 7, characterized in that: the polyether macromonomer is prepared by ethoxylation reaction of an epoxy compound and unsaturated enol in the presence of an alkoxylation catalyst;
the mass ratio of the unsaturated enol to the epoxy compound to the alkoxylation catalyst is 100 (1-5) to (0.0005-0.0020).
9. The high-stability polyether for a polycarboxylic acid water-reducing agent according to claim 8, characterized in that: the unsaturated enol is one or a combination of more of 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether and vinyl glycol ether;
the epoxy compound is one or a combination of more of ethylene oxide, propylene oxide and butylene oxide;
the alkoxylation catalyst is one or more of sodium methoxide, potassium methoxide, double metal cyanide, metallic sodium and sodium hydride.
10. The method for preparing the high-stability polyether for the polycarboxylic acid water reducer according to any one of claims 7 to 9, comprising the steps of:
s100, preparing a composite polymerization inhibitor: weighing a phenolic polymerization inhibitor, a hindered amine polymerization inhibitor, an auxiliary polymerization inhibitor, a metal salt and an emulsifier according to a certain weight, and mixing to obtain a composite polymerization inhibitor in a uniform state;
s200, adding the composite polymerization inhibitor prepared in the S100 into a solvent, and stirring and mixing to obtain a composite polymerization inhibitor emulsion;
and S300, mixing the polyether macromonomer with the composite polymerization inhibitor emulsion obtained in the S200 to obtain the high-stability polyether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111168474.3A CN113912752B (en) | 2021-09-29 | 2021-09-29 | Composite polymerization inhibitor and application thereof, high-stability polyether for polycarboxylate superplasticizer and preparation method of high-stability polyether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111168474.3A CN113912752B (en) | 2021-09-29 | 2021-09-29 | Composite polymerization inhibitor and application thereof, high-stability polyether for polycarboxylate superplasticizer and preparation method of high-stability polyether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113912752A true CN113912752A (en) | 2022-01-11 |
| CN113912752B CN113912752B (en) | 2023-08-29 |
Family
ID=79238030
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111168474.3A Active CN113912752B (en) | 2021-09-29 | 2021-09-29 | Composite polymerization inhibitor and application thereof, high-stability polyether for polycarboxylate superplasticizer and preparation method of high-stability polyether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113912752B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114685854A (en) * | 2022-04-25 | 2022-07-01 | 萧县新秀新材料有限公司 | Stabilizer for trans-isoprene rubber and application |
| CN115975257A (en) * | 2023-02-15 | 2023-04-18 | 连云港石化有限公司 | HPEG polyether macromonomer composite liquid stabilizer and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000198782A (en) * | 1998-10-30 | 2000-07-18 | Dai Ichi Kogyo Seiyaku Co Ltd | New decomposition type reactive emulsifying agent and polymer modification using the same |
| US20030073771A1 (en) * | 2001-09-27 | 2003-04-17 | Sanders Brent M. | Process for improving the shelf life of a hindered phenol antioxidant |
| JP2006076950A (en) * | 2004-09-10 | 2006-03-23 | Asahi Denka Kogyo Kk | Piperidyl group-containing compound, its polymer and copolymer, and method for production of the compound |
| CN1821207A (en) * | 2006-01-23 | 2006-08-23 | 上海华谊丙烯酸有限公司 | Composite polymerzation inhibitor for producing methyl propenoic acid and its ester |
| US20190023641A1 (en) * | 2015-09-07 | 2019-01-24 | Rhodia Operations | Use of polymerization inhibitor compositions |
| CN112708041A (en) * | 2019-11-25 | 2021-04-27 | 科之杰新材料集团有限公司 | Esterification product for preparing water reducing agent and preparation method thereof, and reduction type ether polycarboxylic acid water reducing agent and preparation method thereof |
-
2021
- 2021-09-29 CN CN202111168474.3A patent/CN113912752B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000198782A (en) * | 1998-10-30 | 2000-07-18 | Dai Ichi Kogyo Seiyaku Co Ltd | New decomposition type reactive emulsifying agent and polymer modification using the same |
| US20030073771A1 (en) * | 2001-09-27 | 2003-04-17 | Sanders Brent M. | Process for improving the shelf life of a hindered phenol antioxidant |
| JP2006076950A (en) * | 2004-09-10 | 2006-03-23 | Asahi Denka Kogyo Kk | Piperidyl group-containing compound, its polymer and copolymer, and method for production of the compound |
| CN1821207A (en) * | 2006-01-23 | 2006-08-23 | 上海华谊丙烯酸有限公司 | Composite polymerzation inhibitor for producing methyl propenoic acid and its ester |
| US20190023641A1 (en) * | 2015-09-07 | 2019-01-24 | Rhodia Operations | Use of polymerization inhibitor compositions |
| CN112708041A (en) * | 2019-11-25 | 2021-04-27 | 科之杰新材料集团有限公司 | Esterification product for preparing water reducing agent and preparation method thereof, and reduction type ether polycarboxylic acid water reducing agent and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114685854A (en) * | 2022-04-25 | 2022-07-01 | 萧县新秀新材料有限公司 | Stabilizer for trans-isoprene rubber and application |
| CN115975257A (en) * | 2023-02-15 | 2023-04-18 | 连云港石化有限公司 | HPEG polyether macromonomer composite liquid stabilizer and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113912752B (en) | 2023-08-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113912752B (en) | Composite polymerization inhibitor and application thereof, high-stability polyether for polycarboxylate superplasticizer and preparation method of high-stability polyether | |
| TW515811B (en) | Preparation of functionalised polyethers | |
| EP1209178B1 (en) | Process for the production of (meth)acrylic polymers | |
| CN109320710A (en) | A kind of polymeric monomer and the method for preparing polycarboxylate water-reducer with it | |
| CN105330830B (en) | A kind of end alkenyl unsaturated polyether and application thereof | |
| JP2002510276A (en) | Method for producing water reducing agent for cement | |
| US20090240023A1 (en) | Anion polymers | |
| CN107200839B (en) | Methallyl alcohol random polyether and preparation method thereof | |
| CN114085334A (en) | Slump-retaining type polycarboxylate superplasticizer with vinyl ether ester mixed structure and preparation method thereof | |
| CN104530410B (en) | A kind of high molecular weight unsaturated polyether polymeric monomer and its preparation method and application | |
| JPH04213343A (en) | Stabilized polymer latex composition | |
| CN108218278A (en) | A kind of preparation method of esters high dispersive high-slump-retentionpolycarboxylate polycarboxylate water reducer | |
| CN106883403A (en) | The preparation method of maleic acid mono alkyl ester polyether | |
| CN112011050B (en) | Ultrahigh-performance water reducing agent and preparation method thereof | |
| CN113698545B (en) | Hydrolysis type water reducing agent and preparation method thereof | |
| CN112375186A (en) | Synthetic method of polycarboxylate superplasticizer | |
| EP2864367B1 (en) | Process for emulsion polymerization | |
| CN112011043A (en) | High-stability polyether and production method and application thereof | |
| JP5151620B2 (en) | Method for producing copolymer | |
| EP1383805A2 (en) | Method for producing chemical reactive substance and polycarboxylic acid produced thereby | |
| CN112708047B (en) | Mud-blocking super-early-strength polycarboxylate superplasticizer and preparation method thereof | |
| CN115536829B (en) | Synthesis method of fatty acid monoethanolamide polyoxyethylene ether | |
| CN110643001B (en) | Preparation method of powdery polycarboxylate superplasticizer | |
| CN112409512B (en) | Composite terminator emulsion for vinyl chloride polymerization and preparation method thereof | |
| KR20180036875A (en) | Cement admixture composition and method for preparing the same |
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 |