CN114805785A - Preparation method and application of vinyl alcohol amine and polyether thereof - Google Patents
Preparation method and application of vinyl alcohol amine and polyether thereof Download PDFInfo
- Publication number
- CN114805785A CN114805785A CN202210484963.8A CN202210484963A CN114805785A CN 114805785 A CN114805785 A CN 114805785A CN 202210484963 A CN202210484963 A CN 202210484963A CN 114805785 A CN114805785 A CN 114805785A
- Authority
- CN
- China
- Prior art keywords
- alcohol amine
- vinyl alcohol
- polyether
- reaction
- temperature
- 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
Images
Classifications
-
- 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
- C08G65/2618—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 nitrogen
- C08G65/2621—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 nitrogen containing amine groups
- C08G65/2624—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 nitrogen containing amine groups containing aliphatic amine groups
-
- 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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Landscapes
- Chemical & Material Sciences (AREA)
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method and application of vinyl alcohol amine and polyether thereof, wherein the preparation method specifically comprises the following steps: step one, preparing a crude product; step two, purification; the invention relates to the technical field of concrete admixture synthesis, and particularly relates to polyether preparation. The vinyl alcohol amine structure increases double-bond electron cloud density, enhances the polymerization activity of double bonds due to the conjugation of the double bonds and nitrogen atoms, and can better play an early-strength function due to the strong coordination of the nitrogen atoms.
Description
Technical Field
The invention relates to the technical field of concrete admixture synthesis, in particular to a preparation method and application of vinyl alcohol amine and polyether thereof.
Background
In recent years, with the rapid development of the market of the polyether macromonomer for the domestic water reducing agent, differentiated and functionalized novel macromonomer varieties are continuously provided, wherein the most representative are novel monomers with a monovinyl ether structure, such as VPEG and EPEG which are polymerized by 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether and ethylene glycol monovinyl ether serving as initiators and ethylene oxide. The macromonomers have better polymerization activity than the conventional monomers such as methyl vinyl alcohol polyoxyethylene ether (such as HPEG and TPEG) due to the conjugated effect of double bonds and oxygen. Therefore, the polycarboxylic acid high-performance water reducing agent synthesized by the novel polyether monomer has higher retentivity and water reducing rate, and can meet the use requirement of high strength required by commercial concrete.
The early-strength polycarboxylate superplasticizer is an additive which can improve the early strength of concrete and has no obvious influence on the later strength. The early-strength polycarboxylate superplasticizer has all the characteristics of polycarboxylate superplasticizers, overcomes the potential danger of white salting-out or alkali aggregate reaction on the surface of concrete caused by compounding the conventional polycarboxylate superplasticizer with an inorganic early strength agent and the problem that a chloride early strength agent has obvious corrosion on reinforcing steel bars, and has better application prospect. The early strength type polycarboxylate superplasticizer generally realizes the early strength function by introducing an early strength monomer into the molecules of the water reducer. An amide group and a sulfonic acid group are introduced into a molecule of the early strength type water reducing agent disclosed in Chinese patent CN 106367985B; chinese patent CN109134784B discloses a coagulation-accelerating early-strength polycarboxylic acid superplasticizer, which introduces unsaturated alcohol amine ester and amide group into the molecule; chinese patent CN111454405A discloses a slump retaining agent with early strength function, which is synthesized by using high molecular weight isopentenol polyether, amide monomers and ester monomers.
Although the early-strength polycarboxylate superplasticizer is developed more quickly, the following problems generally exist in the prior art scheme, such as low electron cloud density of introduced amide groups, limited improvement of early strength, and influence on the water-reducing and slump-retaining effects of the superplasticizer due to the fact that the adsorption effect of the amide groups on the cement surface is weaker than that of carboxyl groups; after the alcohol amine ester group is hydrolyzed in the alkaline environment of the cement, more alcohol amine ester groups are dissociated in the water phase, so that the alcohol amine ester groups are not beneficial to the contact with the surface of the cement and can influence the early strength of the cement; the activity of the polyether monomer with larger molecular weight is reduced, higher requirements on polymerization conditions are provided, and the cost is indirectly increased.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a preparation method and application of vinyl alcohol amine and polyether thereof, which solves the problems that the introduced amide group has low electron cloud density and limited improvement on early strength, and the introduction of the amide group can influence the water reducing and slump retaining effects of a water reducing agent because the adsorption effect of the amide group on the cement surface is weaker than that of a carboxyl group; after the alcohol amine ester group is hydrolyzed in the alkaline environment of the cement, more alcohol amine ester groups are dissociated in the water phase, so that the alcohol amine ester groups are not beneficial to the contact with the surface of the cement and can influence the early strength of the cement; the activity of the polyether monomer with larger molecular weight is reduced, higher requirements are put forward on polymerization conditions, and the cost is also increased indirectly.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a method for preparing vinyl alcohol amine and polyether thereof comprises the following steps:
polyether of the formula II
Wherein M is- (CH) 2 ) 2 -、-CH 2 CH(CH 3 ) -or- (CH) 2 ) 4 -a group; x and y are integers which are more than zero, x + y is more than or equal to 10 and less than or equal to 100, and x and y are not zero at the same time;
the preparation method specifically comprises the following steps:
step one, crude product preparation: adding quantitative alcohol amine into a stainless steel high-pressure reactor with a stirring device, sealing the device, then replacing and heating by nitrogen, introducing acetylene gas and nitrogen into the reactor when the temperature reaches 100-180 ℃, controlling the reaction pressure to be 0.05-0.6 MPa, closing an air inlet valve to start reaction after the reaction pressure is reached, continuing introducing the acetylene gas and the nitrogen after the pressure is reduced until the reaction pressure is not obviously changed, cooling to below 80 ℃, replacing the nitrogen to normal pressure, and discharging to obtain a crude product of the vinyl alcohol amine.
Step two, purification: carrying out reduced pressure rectification on the vinyl alcohol amine crude product obtained in the step one to obtain a vinyl alcohol amine finished product;
step three, polyether preparation: and (2) adding a specified amount of the finished vinyl alcohol amine product prepared in the second step into an ethoxylation reaction kettle with a stirring function, adding a catalyst, sealing equipment, then replacing with nitrogen, starting stirring, heating, introducing a small amount of alkylene oxide when the temperature reaches 100-plus-material temperature of 120 ℃, introducing a specified amount of alkylene oxide when the temperature rises and the pressure drops to initiate the reaction, controlling the reaction temperature at 110-plus-material temperature and the pressure in the kettle at 0.2-0.4MPa, controlling the temperature in the reaction kettle at 110-130 ℃ after all the alkylene oxide is added, keeping the temperature for 0.2-2 hours, cooling to room temperature, and discharging to obtain the vinyl alcohol amine polyether.
The invention is further configured to: the alcohol amine in the first step is one of diethanolamine, diisopropanolamine and dibutanolamine.
The invention is further configured to: and when acetylene gas and nitrogen gas are introduced in the first step, the volume of acetylene accounts for 70-80%.
The invention is further configured to: the catalyst in the third step is one or more of sodium hydroxide, potassium hydroxide or potassium methoxide, and the dosage of the catalyst is 0.1-0.2% of the amount of the finished product of the vinyl alcohol amine.
The invention is further configured to: the alkylene oxide in the third step is one of ethylene oxide and propylene oxide.
The invention also provides application of the vinyl alcohol amine prepared by any one of the methods and polyether thereof in synthesis of the early-strength polycarboxylate superplasticizer.
The invention is further configured to: the application of the vinyl alcohol amine and the polyether thereof in the synthesis of the early-strength polycarboxylate superplasticizer specifically comprises the following steps:
s1, dropwise adding reaction: adding a specified amount of deionized water, vinyl alcohol amine polyether, small monomers, hydrogen peroxide and ferrous sulfate into a reactor, controlling the reaction temperature to be 10-20 ℃, then dropwise adding a mixture aqueous solution of acrylic acid and mercaptoethanol and an aqueous solution of epoxy resin E51 with a set ratio, wherein the dropwise adding time is 1 hour, and the reaction time is 1.5 hours;
s2, pH adjustment: and after the reaction is finished, adjusting the pH value to be neutral by using a NaOH aqueous solution with the mass concentration of 30%, and discharging to obtain the early-strength polycarboxylate superplasticizer product.
The invention is further configured to: the small monomer in the S1 is one or two of vinyl alcohol amine, diethylene glycol monovinyl ether and 4-hydroxybutyl vinyl ether, wherein the small monomer C is acrylic acid.
(III) advantageous effects
The invention provides a preparation method and application of vinyl alcohol amine and polyether thereof. The method has the following beneficial effects:
(1) the vinyl alcohol amine and the preparation method and the application of the polyether thereof have the advantages that through the preparation of the vinyl alcohol amine and the polyether thereof, the molecule of the vinyl alcohol amine has a vinyl alcohol amine structure, so that the double-bond electron cloud density is increased, the vinyl alcohol amine has excellent polymerization activity, and on the other hand, the early strength type water reducing agent mother liquor synthesized by the vinyl alcohol amine has a good early strength function and good slump retaining and water reducing performances.
(2) The vinyl alcohol amine and the polyether thereof enhance the polymerization activity of double bonds due to the conjugation of the double bonds and nitrogen atoms, thereby being beneficial to the synthesis of the early strength water reducing agent, and the early strength function can be better played through the strong coordination of the nitrogen atoms in the synthesized early strength water reducing agent.
(3) According to the vinyl alcohol amine and the preparation method and application of the polyether thereof, the double-tail structure provided by the vinyl alcohol amine can effectively improve the side chain density of the early-strength water reducing agent, so that the synthesized water reducing agent has a better early-strength function and a better slump-retaining and water-reducing function.
Drawings
FIG. 1 is a table of results of the vinylamine indicator test of the present invention;
FIG. 2 is a table of the results of the polyether indicator test of the present invention;
FIG. 3 is a table of performance test results of synthetic early strength water reducing agents, commercially available normal water reducing agents and commercially available amide early strength water reducing agents in application examples of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in 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.
Referring to fig. 1-3, the embodiment of the present invention provides the following technical solutions:
the first embodiment,
A preparation method of vinyl alcohol amine and polyether thereof comprises the following steps:
step one, crude product preparation: 630.8g of diethanolamine is added into a stainless steel high-pressure reactor with a stirring device, equipment is sealed, then nitrogen is replaced and heated, when the temperature reaches 150 ℃, acetylene gas and nitrogen are introduced into the reactor, wherein the volume of acetylene accounts for 70%, the reaction pressure is controlled at 0.3Mpa, an air inlet valve is closed to start reaction after the reaction pressure is reached, the acetylene gas and the nitrogen are continuously introduced after the pressure is reduced to 0.15Mpa, the operation is repeated, when the reaction pressure is not obviously changed for 30min, the total volume of the acetylene gas is reduced to 60 ℃, the nitrogen is replaced to the normal pressure, and the crude product of the vinyl diethanolamine is obtained after discharging.
Step two, purification: carrying out reduced pressure rectification on the crude product of the vinyl diethanolamine obtained in the step one to obtain a finished product of the vinyl diethanolamine;
step three, polyether preparation: adding 26.2g of the finished product of the vinyl diethanolamine prepared in the second step into an ethoxylation reaction kettle with a stirring function, adding 1.0g of potassium hydroxide, sealing the device, replacing with nitrogen for 3 times, starting stirring, heating, introducing 2g of ethylene oxide when the temperature reaches 100 ℃, introducing 790g of ethylene oxide when the temperature rises and the pressure drops, controlling the reaction temperature at 130 ℃ of 110 and the pressure in the kettle at 0.2-0.4MPa, controlling the temperature in the reaction kettle at 110-130 ℃ after the feeding is finished, keeping the temperature for 0.2-2 hours, cooling to room temperature, and discharging to obtain polyether I, wherein x =45 and y = 0;
and a comparison shows that 26.2g of the finished product of the vinyl diethanolamine prepared in the second step is added into an ethoxylation reaction kettle with a stirring function, 1.0g of potassium methoxide is added, equipment is sealed, nitrogen is replaced for 3 times, stirring is started, the temperature is raised, 2g of mixed alkylene oxide (440 g of ethylene oxide and 162g of propylene oxide) is introduced when the temperature reaches 100 ℃, the reaction is initiated when the temperature is raised and the pressure is reduced, 600g of the mixed alkylene oxide is introduced, the reaction temperature is controlled to be 110-130 ℃ and the pressure in the kettle is controlled to be 0.2-0.4MPa, after the addition is finished, the temperature in the reaction kettle is controlled to be 110-130 ℃, the temperature is kept for 0.2-2 hours, the mixture is cooled to room temperature, and the polyether II is prepared, wherein x =25 and y = 7.
Example II,
A preparation method of vinyl alcohol amine and polyether thereof comprises the following steps:
step one, crude product preparation: 666g of diisopropanolamine is added into a stainless steel high-pressure reactor with a stirring device, equipment is sealed, then nitrogen gas is used for replacement and temperature rise, when the temperature reaches 130 ℃, acetylene gas and nitrogen gas are introduced into the reactor, wherein the volume of acetylene accounts for 75%, the reaction pressure is controlled to be 0.4Mpa, an air inlet valve is closed to start reaction after the reaction pressure is reached, the acetylene gas and the nitrogen gas are continuously introduced after the pressure is reduced to 0.2Mpa, the operation is repeated, when the reaction pressure is not obviously changed for 30min, the reaction is finished, the total volume of the introduced acetylene gas is 62L, the temperature is reduced to 60 ℃, the nitrogen gas is used for replacement to the normal pressure, and a crude product of the ethylene diisopropanolamine is obtained after discharging.
Step two, purification: carrying out reduced pressure rectification on the vinyl diisopropanolamine crude product obtained in the step one to obtain a vinyl diisopropanolamine finished product;
step three, polyether preparation: adding 31.8g of the finished product of the vinyl diisopropanolamine prepared in the second step into an ethoxylation reaction kettle with a stirring function, adding 1.0g of potassium hydroxide, sealing the device, replacing 3 times with nitrogen, starting stirring, heating, introducing 2g of ethylene oxide when the temperature reaches 100 ℃, introducing 868g of ethylene oxide slowly when the temperature is increased and the pressure is reduced to initiate a reaction, then introducing 48g of propylene oxide slowly, controlling the reaction temperature at 130 ℃ of 110 and the pressure in the kettle at 0.2-0.4MPa, controlling the temperature in the reaction kettle at 110-130 ℃ after all the propylene oxide is added, keeping the temperature for 0.2-2 hours, cooling to room temperature, and discharging to obtain polyether III, wherein x =48 and y = 2;
and a comparison shows that 31.8g of the finished product of the vinyl diisopropanolamine prepared in the second step is added into an ethoxylation reaction kettle with a stirring function, 1.0g of sodium hydroxide is added, equipment is sealed, nitrogen is replaced for 3 times, stirring is started, the temperature is raised, 2g of propylene oxide is introduced when the temperature reaches 100 ℃, reaction is initiated when the temperature is raised and the pressure is reduced, then 48g of propylene oxide is slowly introduced, 868g of ethylene oxide is slowly introduced, the reaction temperature is controlled to be 130 ℃ and the pressure in the kettle is controlled to be 0.2-0.4MPa, after the reaction is finished, the temperature in the reaction kettle is controlled to be 110-130 ℃, the reaction is kept for 0.2-2 hours, and the mixture is cooled to room temperature to be discharged to prepare polyether IV, wherein x =48 and y = 2.
Example III,
A preparation method of vinyl alcohol amine and polyether thereof comprises the following steps:
step one, crude product preparation: adding 644g of dibutanolamine into a stainless steel high-pressure reactor with a stirring device, sealing the device, then replacing with nitrogen, heating, introducing acetylene gas and nitrogen into the reactor when the temperature reaches 170 ℃, wherein the volume of acetylene accounts for 80%, the reaction pressure is controlled at 0.5Mpa, closing an air inlet valve to start reaction after the reaction pressure is reached, continuing introducing acetylene gas and nitrogen when the pressure is reduced to 0.2Mpa, repeating the operation, when the reaction pressure is not obviously changed for 30min, finishing the reaction, reducing the total volume of the acetylene gas to 44L, cooling to 60 ℃, replacing with nitrogen to normal pressure, and discharging to obtain a crude product of vinyl dibutanolamine.
Step two, purification: carrying out reduced pressure rectification on the vinyl dibutanolamine crude product obtained in the step one to obtain a vinyl dibutanolamine finished product;
step three, polyether preparation: adding 70.8g of the finished product of the vinyl dibutanolamine prepared in the second step into an ethoxylation reaction kettle with a stirring function, adding 0.8g of potassium methoxide, sealing the device, replacing for 3 times by nitrogen, starting stirring, heating, introducing 2g of ethylene oxide when the temperature reaches 100 ℃, introducing 526g of ethylene oxide when the temperature is increased and the pressure is reduced, controlling the reaction temperature at 130 ℃ of 110 plus materials and the pressure in the kettle at 0.2-0.4MPa, controlling the temperature in the reaction kettle at 110-130 ℃ after all the ethylene oxide is added, keeping the temperature for 0.2-2 hours, cooling to room temperature, and discharging to obtain polyether V, wherein x =15 and y = 0;
application example one,
The application of the vinyl alcohol amine and the polyether thereof in the synthesis of the early-strength polycarboxylate superplasticizer specifically comprises the following steps:
s1, dropwise adding reaction: adding 360g of polyether I and 5g of synthesized vinyl diethanolamine polyether into a reactor, adding 400g of deionized water, 2.5g of hydrogen peroxide and 10mg of ferrous sulfate, controlling the reaction temperature to be 10-20 ℃, then dropwise adding an aqueous solution of a mixture of acrylic acid and mercaptoethanol (26 g of acrylic acid, 0.5g of mercaptoethanol and 30g of deionized water) and an aqueous solution of epoxy resin E51 (0.8 g of epoxy resin E51 and 50g of deionized water) in a set ratio for 1 hour, and reacting for 1.5 hours;
s2, pH adjustment: and after the reaction is finished, adjusting the pH value to be neutral by using a NaOH aqueous solution with the mass concentration of 30%, supplementing water until the solid content of the finished product is 40%, and discharging to obtain the early-strength polycarboxylate superplasticizer product ZQ-I.
Application examples two,
The application of the vinyl alcohol amine and the polyether thereof in the synthesis of the early-strength polycarboxylate superplasticizer specifically comprises the following steps:
s1, dropwise adding reaction: adding 360g of synthesized polyether II and 5g of diethylene glycol monovinyl ether into a reactor, adding 400g of deionized water, 2.5g of hydrogen peroxide and 10mg of ferrous sulfate, controlling the reaction temperature to be 10-20 ℃, then dropwise adding a mixture (34 g of acrylic acid, 0.5g of mercaptoethanol and 30g of deionized water) of acrylic acid and mercaptoethanol and an aqueous solution of epoxy resin E51 (0.8 g of epoxy resin E51 and 50g of deionized water) in a set ratio in a double manner, wherein the dropwise adding time is 1 hour, and the reaction time is 1.5 hours;
s2, pH adjustment: and after the reaction is finished, adjusting the pH value to be neutral by using a NaOH aqueous solution with the mass concentration of 30%, supplementing water until the solid content of the finished product is 40%, and discharging to obtain the early-strength polycarboxylate superplasticizer product ZQ-II.
Application examples three,
The application of the vinyl alcohol amine and the polyether thereof in the synthesis of the early-strength polycarboxylate superplasticizer specifically comprises the following steps:
s1, dropwise adding reaction: 380g of synthesized polyether III and 5g of 4-hydroxybutyl vinyl ether are added into a reactor, 400g of deionized water, 2.5g of hydrogen peroxide and 10mg of ferrous sulfate are added, the reaction temperature is controlled to be 10-20 ℃, then an aqueous solution of a mixture of acrylic acid and mercaptoethanol (24 g of acrylic acid, 0.5g of mercaptoethanol and 30g of deionized water) and an aqueous solution of epoxy resin E51 (0.8 g of epoxy resin E51 and 50g of deionized water) in a set ratio are added dropwise, the dropwise adding time is 1 hour, and the reaction time is 1.5 hours;
s2, pH adjustment: and after the reaction is finished, adjusting the pH value to be neutral by using a NaOH aqueous solution with the mass concentration of 30%, supplementing water until the solid content of the finished product is 40%, and discharging to obtain the early-strength polycarboxylate superplasticizer product ZQ-III.
Application examples four,
The application of the vinyl alcohol amine and the polyether thereof in the synthesis of the early-strength polycarboxylate superplasticizer specifically comprises the following steps:
s1, dropwise adding reaction: 380g of synthesized polyether II and 5g of synthesized vinyl diisopropanolamine are added into a reactor, 400g of deionized water, 2.5g of hydrogen peroxide and 10mg of ferrous sulfate are added, the reaction temperature is controlled to be 10-20 ℃, then the aqueous solution of a mixture of acrylic acid and mercaptoethanol (24 g of acrylic acid, 0.5g of mercaptoethanol and 30g of deionized water) and the aqueous solution of epoxy resin E51 (0.8 g of epoxy resin E51 and 50g of deionized water) with a set ratio are added dropwise for 1 hour, and the reaction time is 1.5 hours;
s2, pH adjustment: and after the reaction is finished, adjusting the pH value to be neutral by using a NaOH aqueous solution with the mass concentration of 30%, supplementing water until the solid content of the finished product is 40%, and discharging to obtain the early-strength polycarboxylate superplasticizer product ZQ-IV.
Application examples five,
The application of the vinyl alcohol amine and the polyether thereof in the synthesis of the early-strength polycarboxylate superplasticizer specifically comprises the following steps:
s1, dropwise adding reaction: adding 300g of synthesized polyether II, 2g of diethylene glycol monovinyl ether and 3g of synthesized vinyl dibutanolamine into a reactor, adding 400g of deionized water, 2.5g of hydrogen peroxide and 10mg of ferrous sulfate, controlling the reaction temperature to be 10-20 ℃, then dropwise adding an aqueous solution of a mixture of acrylic acid and mercaptoethanol (43 g of acrylic acid, 0.5g of mercaptoethanol and 30g of deionized water) and an aqueous solution of epoxy resin E51 (0.8 g of epoxy resin E51 and 50g of deionized water) in a set ratio, wherein the dropwise adding time is 1h, and the reaction time is 1.5 h;
s2, pH adjustment: and after the reaction is finished, adjusting the pH value to be neutral by using a NaOH aqueous solution with the mass concentration of 30%, supplementing water until the solid content of the finished product is 40%, and discharging to obtain the early-strength polycarboxylate superplasticizer product ZQ-V.
In conclusion, the purity test of the vinyl alcohol amine adopts a gas chromatography, the moisture test refers to a test method specified in GB/T11257-2008, the color test refers to a test method specified in GB/T3143-1982, the index measurement of the polyether refers to a test method specified in the industry standard HG/T4490-2013, the performance test of the water reducing agent refers to a test method specified in JG/T223-2007, and the test results are shown in the attached drawings 1, 2 and 3, wherein the attached drawing 1 is a vinyl alcohol amine index test result, the attached drawing 2 is a polyether index test result, and the attached drawing 3 is a test result of synthesizing an early strength water reducing agent, a commercially available common water reducing agent and a commercially available amide early strength water reducing agent in an application example of the invention.
As a detailed description, as shown in figure 2, the polyether of the invention has narrower molecular weight distribution and higher double bond retention rate, the product index meets the requirement, and guarantees are provided for synthesizing the early strength water reducing agent, as shown in figure 3, the early strength water reducing agent synthesized by the invention has self water reducing slump retaining property which is obviously superior to that of the market early strength water reducing agent, the slump retaining property which is slightly superior to that of the market common water reducing agent, and the compression strength ratios of 1 day, 3 days and 28 days which are all superior to that of the market early strength water reducing agent, especially the early stage is more obvious, so that the water reducing agent mother liquor synthesized by the vinyl alcohol amine and the polyether thereof has better early strength function.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. A preparation method of vinyl alcohol amine and polyether thereof is characterized in that: comprises a formula I and a vinyl alcohol amine:
polyether of the formula II
Wherein M is- (CH) 2 ) 2 -、-CH 2 CH(CH 3 ) -or- (CH) 2 ) 4 -a group; x and y are integers which are more than zero, x + y is more than or equal to 10 and less than or equal to 100, and x and y are not zero at the same time;
the preparation method specifically comprises the following steps:
step one, crude product preparation: adding quantitative alcohol amine into a stainless steel high-pressure reactor with a stirring device, sealing the device, then replacing and heating by nitrogen, introducing acetylene gas and nitrogen into the reactor when the temperature reaches 100-180 ℃, controlling the reaction pressure to be 0.05-0.6 MPa, closing an air inlet valve to start reaction after the reaction pressure is reached, continuing introducing the acetylene gas and the nitrogen after the pressure is reduced until the reaction pressure is not obviously changed, cooling to below 80 ℃, replacing the nitrogen to normal pressure, and discharging to obtain a crude product of the vinyl alcohol amine;
step two, purification: carrying out reduced pressure rectification on the vinyl alcohol amine crude product obtained in the step one to obtain a vinyl alcohol amine finished product;
step three, polyether preparation: and (2) adding a specified amount of the finished vinyl alcohol amine product prepared in the second step into an ethoxylation reaction kettle with a stirring function, adding a catalyst, sealing equipment, then replacing with nitrogen, starting stirring, heating, introducing a small amount of alkylene oxide when the temperature reaches 100-plus-material temperature of 120 ℃, introducing a specified amount of alkylene oxide when the temperature rises and the pressure drops to initiate the reaction, controlling the reaction temperature at 110-plus-material temperature and the pressure in the kettle at 0.2-0.4MPa, controlling the temperature in the reaction kettle at 110-130 ℃ after all the alkylene oxide is added, keeping the temperature for 0.2-2 hours, cooling to room temperature, and discharging to obtain the vinyl alcohol amine polyether.
2. The method for preparing vinyl alcohol amine and polyether thereof according to claim 1, characterized in that: the alcohol amine in the first step is one of diethanolamine, diisopropanolamine and dibutanolamine.
3. The method for preparing vinyl alcohol amine and polyether thereof according to claim 1, characterized in that: and when acetylene gas and nitrogen gas are introduced in the first step, the volume of acetylene accounts for 70-80%.
4. The method for preparing vinyl alcohol amine and polyether thereof according to claim 1, characterized in that: the catalyst in the third step is one or more of sodium hydroxide, potassium hydroxide or potassium methoxide, and the dosage of the catalyst is 0.1-0.2% of the amount of the finished product of the vinyl alcohol amine.
5. The method for preparing vinyl alcohol amine and polyether thereof according to claim 1, characterized in that: the alkylene oxide in the third step is one of ethylene oxide and propylene oxide.
6. The use of the vinyl alcohol amine and the polyether thereof prepared by the method of any one of claims 1 to 5 in the synthesis of an early-strength polycarboxylate superplasticizer.
7. The use of vinyl alcohol amine and polyether thereof in the synthesis of an early strength polycarboxylate water reducer according to claim 6, characterized in that: the method specifically comprises the following steps:
s1, dropwise adding reaction: adding a specified amount of deionized water, vinyl alcohol amine polyether, small monomers, hydrogen peroxide and ferrous sulfate into a reactor, controlling the reaction temperature to be 10-20 ℃, then dropwise adding a mixture aqueous solution of acrylic acid and mercaptoethanol and an aqueous solution of epoxy resin E51 with a set ratio, wherein the dropwise adding time is 1 hour, and the reaction time is 1.5 hours;
s2, pH adjustment: and after the reaction is finished, adjusting the pH value to be neutral by using a NaOH aqueous solution with the mass concentration of 30%, and discharging to obtain the early-strength polycarboxylate superplasticizer product.
8. The method for preparing vinyl alcohol amine and polyether thereof according to claim 7, characterized in that: the small monomer in the S1 is one or two of vinyl alcohol amine, diethylene glycol monovinyl ether and 4-hydroxybutyl vinyl ether, wherein the small monomer C is acrylic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210484963.8A CN114805785B (en) | 2022-05-06 | 2022-05-06 | Preparation method and application of vinyl alcohol amine and polyether thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210484963.8A CN114805785B (en) | 2022-05-06 | 2022-05-06 | Preparation method and application of vinyl alcohol amine and polyether thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114805785A true CN114805785A (en) | 2022-07-29 |
| CN114805785B CN114805785B (en) | 2023-09-26 |
Family
ID=82510698
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210484963.8A Active CN114805785B (en) | 2022-05-06 | 2022-05-06 | Preparation method and application of vinyl alcohol amine and polyether thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114805785B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105801831A (en) * | 2014-12-30 | 2016-07-27 | 辽宁奥克化学股份有限公司 | Unsaturated quaternary ammonium salt polyether, preparation method and application thereof |
| CN106928440A (en) * | 2015-12-29 | 2017-07-07 | 辽宁奥克化学股份有限公司 | A kind of polyetheramides, water reducer and preparation method as obtained in the polyetheramides |
| CN112708045A (en) * | 2019-12-23 | 2021-04-27 | 科之杰新材料集团有限公司 | Low-sensitivity super-early-strength polycarboxylate superplasticizer and preparation method thereof |
-
2022
- 2022-05-06 CN CN202210484963.8A patent/CN114805785B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105801831A (en) * | 2014-12-30 | 2016-07-27 | 辽宁奥克化学股份有限公司 | Unsaturated quaternary ammonium salt polyether, preparation method and application thereof |
| CN106928440A (en) * | 2015-12-29 | 2017-07-07 | 辽宁奥克化学股份有限公司 | A kind of polyetheramides, water reducer and preparation method as obtained in the polyetheramides |
| CN112708045A (en) * | 2019-12-23 | 2021-04-27 | 科之杰新材料集团有限公司 | Low-sensitivity super-early-strength polycarboxylate superplasticizer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114805785B (en) | 2023-09-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2657264B1 (en) | Preparation method of hyperbranched polycarboxylic acid type copolymer cement dispersant | |
| CN105418857A (en) | Preparation method and application of polycarboxylate water reducer containing phosphate group | |
| CN110845672B (en) | Polycarboxylic acid type concrete glue reducing agent and preparation method thereof | |
| WO2021103473A1 (en) | Shrinkage-reducing polycarboxylic acid water reducing agent and preparation method thereof | |
| CN102504238A (en) | Unsaturated polyether monomer, comb-like branched copolymer cement dispersant prepared by the same, and preparation method thereof | |
| CN108948288B (en) | Preparation method of crosslinking type polycarboxylate superplasticizer by adopting carboxyl functional monomer | |
| CN109970922A (en) | A kind of shrinkage type Early-strength polycarboxylate superplasticizer mother liquor and preparation process | |
| CN105037658B (en) | A kind of polycarboxylate water-reducer preparation method, product and the application with high water-reducing property of carboxyl integrated distribution | |
| CN113121751B (en) | High-adaptability concrete superplasticizer, preparation method and application thereof | |
| CN109320710A (en) | A kind of polymeric monomer and the method for preparing polycarboxylate water-reducer with it | |
| CN108276533A (en) | A kind of high ecad polycarboxylate water-reducer and preparation method thereof | |
| CN112898501A (en) | Low-slump water reducer and preparation method thereof | |
| CN111349199B (en) | Steady-state polycarboxylic acid superplasticizer with core-shell structure and preparation method thereof | |
| CN106496441B (en) | A kind of lower valency appraises at the current rate cation-modified polycarboxylate water-reducer masterbatch and its low temperature preparation method | |
| CN104945576A (en) | Preparation method, products and application of high efficiency slushing agent | |
| CN114805785B (en) | Preparation method and application of vinyl alcohol amine and polyether thereof | |
| CN109161011A (en) | A kind of production method of butylene glycol polyoxyethylene ether | |
| CN106188418B (en) | A kind of preparation method of amphoteric polycarboxylate water-reducer | |
| CN112940199B (en) | Water-retaining internal curing anti-cracking concrete water reducer and preparation method thereof | |
| CN112011050B (en) | Ultrahigh-performance water reducing agent and preparation method thereof | |
| CN109776786A (en) | A kind of synthesis Early-strength polycarboxylate superplasticizer blocks the preparation method of amidogen ether with monomer | |
| CN113121755B (en) | Viscosity-reducing concrete superplasticizer, preparation method and application thereof | |
| CN114702683A (en) | Hyperbranched polycarboxylic acid water reducer and preparation method thereof | |
| CN114805829A (en) | Template agent and preparation method and application thereof | |
| CN114561003B (en) | Synthetic method of isopentenol block polyether |
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 |