CN110078910B - Branched polyether monomer for polycarboxylic acid water reducing agent and synthesis method thereof - Google Patents
Branched polyether monomer for polycarboxylic acid water reducing agent and synthesis method thereof Download PDFInfo
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- 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
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- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2605—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
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- 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
- C08G65/2615—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 the other compounds containing carboxylic acid, ester or anhydride groups
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
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Abstract
The invention belongs to the field of synthesis of polycarboxylate water reducing agent monomers, and particularly relates to a branched polyether monomer for a polycarboxylate water reducing agent and a synthesis method thereof, wherein the method comprises the following steps: the method comprises the following steps: the reaction vessel is anhydrous, inert gas purging is carried out after vacuum pumping, and maleic anhydride and a catalyst are added into a high-pressure reaction kettle; step two: heating the high-pressure reaction kettle in the step I to 105-150 ℃, introducing alkylene oxide under the inert atmosphere condition, and carrying out ring-opening polymerization reaction on maleic acid ester and alkylene oxide under the action of a catalyst; step three: and (5) cooling to 65-70 ℃ after the addition reaction in the second step is finished, and adding a neutralizing agent to adjust the pH value to obtain the polyether monomer. The maleic acid polyol ester branched polyether monomer has a special molecular structure, the price of the raw materials of maleic anhydride and polyol substances is low, the performance of the synthesized polycarboxylic acid water reducing agent is good, the water reducing rate of the obtained water reducing agent is high, the slump retention is good, the reinforcing effect is good, the production is simple and easy, the environment is protected, the cost is saved, and the application is wide.
Description
Technical Field
The invention belongs to the field of synthesis of polycarboxylate water reducing agent monomers, and particularly relates to a branched polyether monomer for a polycarboxylate water reducing agent and a synthesis method thereof.
Background
The known high-efficiency water reducing agents such as naphthalene sulfonate systems, melamine formaldehyde resin systems and the like have high alkali content, so that the naphthalene sulfonate water reducing agent product is not beneficial to preventing the alkali aggregate activity of cement concrete from harming reaction and is processed by adopting industrial naphthalene, sulfuric acid and formaldehyde to carry out chemical reaction, and pollution is caused by harmful gas volatilized by sulfonation and formaldehyde condensation reaction in the process. From the 90 s in the 20 th century, Japan invented a carboxylic acid polymer water reducing agent which was initiated by different unit organic compounds and copolymerized, the molecular structure of this kind of product is sparse, has higher water reducing rate than naphthalene sulfonate and good maintaining performance for concrete mixture, and it quickly replaced the traditional naphthalene sulfonate and melamine formaldehyde resin water reducing agent.
The polycarboxylate superplasticizer has the advantages of high water reducing rate, good slump retention, good reinforcing effect, simple production, environmental protection and the like, and is widely applied to engineering such as traffic, hydroelectric dams, bridges, tunnels, civil buildings and the like. The polycarboxylate superplasticizer has the advantages of being capable of carrying out molecular design, being capable of obtaining products with different performances, different costs and various purposes by changing various polymerizable chemical components and synthesis conditions, and having great technical updating potential.
In recent years, China carries out a great deal of technical research and popularization on polycarboxylic acid water reducing agents. Many patents have been reported about long side chains of polyoxyalkylene monoalkenyl ether macromonomers, mainly containing more than about 85% by weight of the main component, and small amounts of small monomers such as acrylic acid, maleic anhydride, hydroxyethyl acrylate, hydroxypropyl acrylate, etc., to initiate copolymerization in aqueous solution. Through the development of several generations of polycarboxylic acid technologies, the macromonomer varieties have evolved from MPEGAA (polyethylene glycol monomethyl ether methacrylate), APEG (allyl polyoxyethylene ether) to HPEG (methyl allyl polyoxyethylene ether) and TPEG (isopentenol polyoxyethylene ether) which are most applied at present, and the performance of the synthesized polycarboxylic acid water reducing agent is gradually improved. The method has the problems that the technology of the polyether monomer which is depended on by the latest generation of polycarboxylate superplasticizer technology is not improved for many years, the performance still can not well meet the requirement of the change of concrete raw materials, and the production of the initiator (such as methyl allyl alcohol, isopentenol and the like which account for absolute portions) used by the polyether monomer is under the environmental protection pressure, the supply is tight, and the cost is continuously increased. Therefore, the research and development of polycarboxylic acid macromonomer are urgently needed.
Disclosure of Invention
In order to solve the problems, the invention provides a method for synthesizing a branched polyether monomer of a polycarboxylic acid water reducer, which comprises the following steps:
the method comprises the following steps: the reaction vessel is anhydrous, inert gas purging is carried out after vacuum pumping, maleic anhydride and a catalyst are added into a high-pressure reaction kettle, wherein the molar ratio of the catalyst to maleate is 0.014-0.125: 1;
step two: heating the high-pressure reaction kettle in the first step to 105-150 ℃, introducing alkylene oxide under the condition of inert atmosphere, and carrying out ring-opening polymerization reaction on maleic acid ester and alkylene oxide under the action of a catalyst, wherein the molar ratio of the alkylene oxide to the maleic acid ester is 13-195: 1;
step three: and (5) cooling to 65-70 ℃ after the addition reaction in the second step is finished, adding a neutralizing agent to adjust the pH value to 5-6.5, and thus obtaining the branched polyether monomer for the polycarboxylic acid water reducing agent.
Further, in the first step, the maleic acid ester is one of dipropyl alcohol maleate, ditriethanolamine maleate, monoethylene glycol maleate or dibutylene glycol maleate.
Further, in the first step, the catalyst is one of potassium hydroxide, sodium hydride, sodium methoxide, sodium ethoxide, boron trifluoride and boron trifluoride ethyl ether.
Further, in the second step, the alkylene oxide is ethylene oxide, and the molar ratio of the ethylene oxide to the maleate is 30-70: 1.
Further, the ethylene oxide in the second step is subjected to addition reaction at the temperature of 105-130 ℃.
Further, the maleic acid ester is one of maleic acid monoethylene glycol ester or maleic acid dibutyl glycol ester.
Further, in the second step, the alkylene oxide is ethylene oxide and propylene oxide, the molar ratio of the ethylene oxide to the maleate is 10-180:1, and the molar ratio of the propylene oxide to the maleate is 3-15: 1.
Further, in the second step, ethylene oxide is introduced into a reaction kettle at the temperature of 105-: 1, the mol ratio of the propylene oxide to the maleic ester is 2-8: 1.
Further, the maleic acid ester is one of dipropylene glycol maleate, ditriethanolamine maleate or monoethylene glycol maleate.
Further, the weight average molecular weight of the branched polyether monomer of the polycarboxylic acid water reducing agent is 1480-9186, and the structural formula of the branched polyether monomer is one of the following six structures, and the structure is as follows:
wherein R1-R4 are
The total number of a and b is 33-145, R' is-CXH2XR' is-CXH2X-1，X＝3-6。
The advantages and effects obtained by implementing the invention are as follows:
the invention is characterized in that the maleic acid polyol ester branched polyether monomer has a special molecular structure, the raw materials of maleic anhydride and polyol substances are easy to obtain, the price is low, and the synthesized polycarboxylic acid water reducing agent has good performance. The water reducing agent can be added into cement paste, and can be added into a cement, fly ash, mineral powder, sand and stone composition together with water for stirring. The amount added is suitably controlled as required, and the amount of the admixture of the present invention in the cement concrete is preferably 0.1 to 0.20% by weight based on the cement material (solid weight).
Compared with the common carboxylic acid water reducing agent, the water reducing agent has the characteristics of high water reducing rate and low mixing amount, the mixing amount of common effective substances is 0.10-0.20% of the weight of cement (calculated by solid content), the water reducing effect is good, the fluidity of the cement concrete can be obviously increased after the cement concrete is mixed, the change of the fluidity or consistency of the concrete over time can be effectively inhibited, the bleeding and segregation phenomena of the concrete can be improved, the problem that the consistency of the cement concrete is influenced by temperature factors and is rapidly lost is solved, the water reducing rate can reach 25-40% through testing, the slump of the cement concrete is not basically lost within 60-120 min, the construction of the cement concrete under various seasonal conditions is met, and the cement concrete water reducing agent can be applied to common concrete, long-distance transportation concrete, high-fluidity concrete, high-strength concrete and the like.
The polycarboxylate superplasticizer synthesized by the method can enable cement concrete to have high-efficiency dispersing performance and excellent slump resistance, maleic anhydride and polyol substances used for synthesizing polyether monomers are common chemical raw materials with more applications, so that more manufacturers are available, the price is low, the cost of the monomers can be greatly reduced, and the cost performance of the polycarboxylate superplasticizer is improved. The obtained water reducer has the advantages of high water reducing rate, good slump retaining property, good reinforcing effect, simple production, environmental protection, cost saving and wide application.
Detailed Description
The maleic anhydride molecule is in five-membered ring shape, the maleic anhydride reacts with the hydroxyl group of the polyhydric alcohol under the attack of alcohol to generate maleic acid polyhydric alcohol monoester or maleic acid polyhydric alcohol diester, because the molecular structures of the maleic anhydride and the polyhydric alcohol are both provided with a plurality of branches, carboxyl, hydroxyl and ester groups on the molecule form a plurality of branch structures after the esterification of the maleic anhydride and the polyhydric alcohol, the esterification product of the maleic anhydride and the polyhydric alcohol further react with ethylene oxide (propylene oxide) through ring-opening polymerization, and the epoxy addition reaction is carried out on the hydroxyl and the carboxyl and the ethylene oxide or the block propylene oxide, so that polyether (namely polyoxyethylene (EO) or polyoxyethylene (EO) and Polyoxypropylene (PO) block polymer) monomers with a plurality of long and short branches and branched structures are further formed. The molecular structure of the polycarboxylic acid water reducing agent with the branched structure side chain, which is prepared by the monomer through initiating the water solution free radical copolymerization, is beneficial to the adsorption on the surface of cement particles and the improvement of the extension of the side chain in cement paste, thereby achieving the purposes of improving the water reducing rate and slump retaining property of the polycarboxylic acid, and simultaneously reducing the concrete viscosity, improving the concrete workability and improving the concrete strength.
The researchers of the invention find that the monomer with the branched structure and the synthesized polycarboxylate superplasticizer have larger steric hindrance effect, and are beneficial to improving the water reducing and slump retaining performances of the polycarboxylate superplasticizer. The maleic acid polyol ester branched polyether monomer has a plurality of unique long and short chain branched molecular structures, and the cement concrete can have high-efficiency dispersing performance and excellent slump retaining performance through the polycarboxylic acid water reducing agent synthesized by the maleic acid polyol ester branched polyether monomer.
The synthesis of the maleic acid polyol ester branched polyether monomer is that carboxyl and hydroxyl on the molecular structure of the maleic acid polyol ester are subjected to epoxidation addition reaction with ethylene oxide and propylene oxide to form branched polyoxyethylene (EO) or polyoxyethylene (EO) and Polyoxypropylene (PO) block polyether. The addition mole numbers of polyoxyethylene (EO) and Polyoxypropylene (PO) are 23-150 and 0-23 respectively, the sum of the numbers of EO and PO repeating units is an integer between 23-150, and the weight average molecular weight is 1480-6246. The structural formula is one of the following six structures:
wherein R1-R4 are
The total number of a and b is 33-145, R' is-CXH2XR' is-CXH2X-1，X＝3-6。
The maleic acid polyol ester, including maleic acid monopolyol ester or maleic acid dipentaol ester, is formed by the reaction of maleic anhydride and hydroxyl of polyol substances. Wherein the synthesis reaction of the maleic acid monopolyol ester can be carried out under the conditions of no solvent, no catalyst and the temperature of 40-120 ℃; the reaction for synthesizing the maleic acid polyol ester is carried out in the presence of a catalyst (concentrated sulfuric acid, methyl benzenesulfonic acid, sodium acetate and the like) at a temperature of between 80 and 125 ℃.
The polyhydric alcohol substance refers to alcohols containing two or more hydroxyl groups in the molecule, and includes ethylene glycol, propylene glycol, butanediol, pentanediol, triethylene glycol, glycerol, diethanolamine, triethanolamine, pentaerythritol, etc.
The epoxidation addition reaction of the maleic acid polyol ester is preferably carried out under an inert gas blanket, particularly preferably under a nitrogen blanket, and the temperature is selected to be in the range from 105 ℃ to 150 ℃.
The epoxidation addition reaction is carried out under the condition of a catalyst, and the catalyst comprises potassium hydroxide, sodium hydride, sodium methoxide, sodium ethoxide, boron trifluoride and boron trifluoride diethyl etherate. The mole ratio of the catalyst to the maleic acid polyol ester polyether monomer is 0.014-0.125: 1 (i.e. 0.0057-0.014% by weight of the prepared polyether monomer).
The polycarboxylic acid water reducing agent is synthesized by water-soluble initiated free radical polymerization of a maleic acid polyol ester polyether monomer, a polyoxyalkene monoalkenyl ether monomer, monocarboxylic acid with unsaturated double bonds and derivatives thereof, and polymerizable unsaturated dicarboxylic acid anhydride and ester derivatives thereof.
The polyoxyalkene monoalkenyl ether monomer is methyl allyl polyoxyethylene ether monomer, methyl allyl polyoxyethylene ether and polyoxypropylene ether block polyether, or isopentenyl polyoxyethylene ether, isopentenyl polyoxyethylene ether and polyoxypropylene block polyether.
Monocarboxylic acids having an unsaturated double bond and derivatives thereof, represented by the general formula: R3-CH ═ CH-COR 4, R3 represents hydrogen, methyl, R4 represents OM, M represents hydrogen, monovalent metal, divalent metal, ammonium or amine. The polyoxyalkylene monoalkenyl ether monomers represent monomers corresponding to the above general formula or combinations thereof. Such as (meth) acrylic acid, (meth) acrylamide, hydroxyethyl (meth) acrylate, and the like.
Polymerizable unsaturated dicarboxylic acid anhydride and ester derivatives, such as maleic anhydride, fumaric acid, ethylene glycol maleic anhydride, monoethyl maleic anhydride, ethyl maleic anhydride, monomethyl fumarate, etc.
The mole ratio of the maleic acid polyol ester polyether monomer, the polyoxyalkene monoalkenyl ether monomer, the monocarboxylic acid with unsaturated double bond and the derivative thereof, and the polymerizable unsaturated dicarboxylic acid anhydride and ester derivative can be 1: 0-1: 3-7: 0 to 3.
The chain transfer agent is one or a combination of mercaptopropionic acid, thioglycolic acid, mercaptoethanol and sodium hypophosphite.
The synthesis method of the polycarboxylic acid water reducing agent is characterized in that according to the molar ratio of monomers, aqueous solution copolymerization is initiated by heating or initiated by an oxidation-reduction system aqueous solution. The initiator required for initiating the aqueous solution copolymerization by heating comprises ammonium persulfate, potassium persulfate and the like. The oxidizing agent for initiating the aqueous solution polymerization by the redox system is selected from hydrogen peroxide, persulfate or the combination thereof, and the reducing agent is selected from L ascorbic acid, D isoascorbic acid, L sodium ascorbate, D sodium erythorbate, sodium bisulfite, sodium formaldehyde sulfoxylate or the combination thereof.
The heating-initiated aqueous solution copolymerization is to add part of water, a maleic acid polyol ester polyether monomer, a polyoxyalkene monoalkenyl ether monomer, monocarboxylic acid with unsaturated double bonds and derivatives thereof into a reaction kettle, heat the mixture to 50-75 ℃ and stir the mixture, dropwise add an aqueous solution of polymerizable unsaturated dicarboxylic acid anhydride and ester derivatives and an aqueous solution of an initiator, dropwise add a chain transfer agent or put the mixture at the bottom of the kettle for 2-4 hours to perform polymerization reaction, keep the temperature for 1-4 hours after the polymerization reaction is finished, add the rest water until the solid content is 40% to obtain the colorless transparent liquid water reducing agent, wherein the solid content refers to the weight percentage of liquid active ingredients in the water reducing agent solution.
The redox system aqueous solution initiated copolymerization is that part of water, a maleic acid polyol ester polyether monomer, a polyoxyalkene monoalkenyl ether monomer, monocarboxylic acid with unsaturated double bonds and derivatives thereof are added into a reaction kettle, the mixture is stirred at normal temperature until the monomers are basically dissolved, all or part of an oxidizing agent is added, aqueous solution of polymerizable unsaturated dicarboxylic acid anhydride and ester derivatives, aqueous solution of a reducing agent and the rest of the oxidizing agent are dropwise added, a chain transfer agent is dropwise added or placed at the bottom of the kettle for 2-4 hours, so that polymerization reaction occurs, the temperature is kept for 1-4 hours after the polymerization is finished, the rest of water is added until the solid content is 40%, and the solid content refers to the weight percentage of liquid effective components in the water reducing agent solution in the invention to the water reducing agent solution.
And (3) neutralizing the solution after the reaction of the polycarboxylic acid water reducing agent by using alkali as required to adjust the pH value of the reaction product, wherein the alkali for neutralization is sodium hydroxide or potassium hydroxide or the aqueous solution of sodium hydroxide or potassium hydroxide.
The technical solution of the present invention is further illustrated below by way of example.
Example 1
Adding 1 mole (282g) of dipropyltriol maleate into a high-pressure reaction kettle, adding 0.125 mole (3g) of catalyst sodium hydride, heating to 105 ℃ after nitrogen replacement, gradually introducing 50 moles (2200g) of ethylene oxide for addition reaction, heating to 150 ℃, gradually introducing 5 moles (290g) of propylene oxide, after the reaction is finished, introducing 50 moles (2200g) of ethylene oxide at 120 ℃ for reaction, introducing 5 moles (290g) of propylene oxide, introducing 50 moles (2200g) of ethylene oxide, obtaining dipropyltriol maleate polyoxyethylene ether after the reaction is finished, cooling to 70 ℃, discharging, and obtaining the product with the weight-average molecular weight of 7462.
Example 2
Adding 1 mole of ditriethanolamine maleate (396g) into a high-pressure reaction kettle, adding 0.09 mole of sodium ethoxide (6g) as a catalyst, heating to 120 ℃ after nitrogen replacement, gradually introducing 45 moles of ethylene oxide (1980g) for addition reaction, heating to 140 ℃, gradually introducing 2 moles of propylene oxide (290g), after the reaction is finished, adding 35 moles of ethylene oxide (1540g) and 5 moles of propylene oxide (290g), introducing 45 moles of ethylene oxide (1980g) at 120 ℃ for reaction, heating to 150 ℃ after the reaction is finished, adding 8 moles of propylene oxide (290g) for addition reaction, introducing 55 moles of ethylene oxide (2420g) for addition reaction, after the reaction is finished, obtaining ditriethanolamine maleate polyoxyethylene ether, cooling to 70 ℃, discharging, and obtaining a weight-average molecular weight of 9186.
Example 3
Adding 1 mole of maleic acid monoethylene glycol ester (160g) into a high-pressure reaction kettle, adding 0.1 mole of catalyst sodium hydride (2.5g), heating to 120 ℃ after nitrogen replacement, gradually introducing 10 moles of ethylene oxide (440g) for addition reaction, introducing 3 moles of propylene oxide (174g) into a midblock, finally introducing 30 moles of ethylene oxide (1320g), cooling to 65 ℃ after the reaction is finished, and discharging, wherein the weight average molecular weight is 2094.
Example 4
Adding 1 mole of maleic acid monoethylene glycol ester (160g) into a high-pressure reaction kettle, adding 0.054 mole of catalyst potassium hydroxide (3g), heating to 120 ℃ after nitrogen replacement, gradually introducing 10 moles of ethylene oxide (440g) for addition reaction, introducing 3 moles of propylene oxide (174g) into a middle block, finally introducing 30 moles of ethylene oxide (1320g), after the reaction is finished, obtaining maleic acid monoethylene glycol ester polyoxyethylene ether, cooling to 65 ℃, discharging, and obtaining the maleic acid monoethylene glycol ester polyoxyethylene ether with the weight-average molecular weight of 2094.
Example 5
Adding 1 mole of maleic acid monoethylene glycol ester (160g) into a high-pressure reaction kettle, gradually adding 0.05 mole of catalyst sodium hydride (1.2g), heating to 110 ℃ after nitrogen replacement, introducing 30 moles of ethylene oxide (1320g), obtaining maleic acid ethylene glycol ester monopolyoxyethylene ether after the reaction is finished, cooling to 65 ℃, discharging, and obtaining the material with the weight-average molecular weight 1480.
Example 6
Adding 1mol of maleic acid dibutyl glycol ester (278g) into a high-pressure reaction kettle, adding 0.014 mol of boron trifluoride diethyl etherate (1.98g) serving as a catalyst, heating to 120 ℃ after nitrogen replacement, gradually introducing 50 mol of ethylene oxide (2200g) for addition reaction to obtain maleic acid dibutyl glycol ester polyoxyethylene ether after the reaction is finished, cooling to 65 ℃, discharging, and obtaining the maleic acid dibutyl glycol ester polyoxyethylene ether with the weight average molecular weight of 2478.
Example 7
Adding 1mol of maleic acid dibutyl glycol ester (278g) into a high-pressure reaction kettle, adding 0.036 mol of catalyst sodium ethoxide (2.45g), heating to 130 ℃ after nitrogen replacement, gradually introducing 40 mol of ethylene oxide (1760g) for addition reaction, introducing 10 mol of propylene oxide (580g) into the middle block, finally introducing 20 mol of ethylene oxide (880g), after the reaction is finished, obtaining maleic acid dibutyl glycol ester polyoxyethylene ether, cooling to 65 ℃, discharging, and obtaining the maleic acid dibutyl glycol ester polyoxyethylene ether with the weight average molecular weight of 3498.
Example 8
Adding 1 mole of maleic acid monoethylene glycol ester (160g) into a high-pressure reaction kettle, adding 0.027 mole of boron trifluoride diethyl etherate (3.9g) serving as a catalyst, heating to 130 ℃ after nitrogen replacement, gradually introducing 70 moles of ethylene oxide (3080g) for addition reaction, obtaining maleic acid monoethylene glycol ester polyoxyethylene ether after the reaction is finished, cooling to 65 ℃, discharging, and obtaining the maleic acid monoethylene glycol ester polyoxyethylene ether with the weight average molecular weight of 3240.
Comparative example
Taking the prior art as a comparative example, the water reducing agent is synthesized by taking a methyl allyl polyoxyethylene ether monomer as a raw material (straight chain) and comparing the raw material with the polycarboxylic acid water reducing agent synthesized by maleic acid polyol ester polyoxyethylene ether (example PC-4). 1 thermometer and 1 dropping funnel are arranged on a reactor, a stirrer is arranged in the middle, a certain amount of water is added, 1mol of methyl allyl polyoxyethylene ether monomer is added into the reactor, the mixture is stirred and dissolved, the mixture is heated to 65 ℃, 5mol of acrylic acid aqueous solution is dropwise added at the same time, 0.13mol of ammonium persulfate solution is dropwise added, the dropwise addition time is 2.5h, the temperature is kept for 1h after the dropwise addition is finished, NaOH is added into the reactor for neutralization, the PH value is 6, water is added until the solid content is 40%, and the colorless transparent liquid water reducing agent is obtained.
The polyether monomers prepared in examples 1 to 8 were used in place of the raw material of the methallyl polyoxyethylene ether monomer in the comparative example to prepare a water reducing agent, and the water reducing agent prepared from the raw materials in examples 1 to 8 and the water reducing agent prepared from the methallyl polyoxyethylene ether monomer in the comparative example were used as raw materials were compared in terms of water reducing effect.
Taking example 1 as an example, the dipropylene glycol maleate polyoxyethylene ether in example 1 is prepared into a water reducing agent PC-1 by the same method as the comparison example, and the examples 2-8 are sequentially analogized to PC-2, PC-3, PC-4, PC-5, PC-6, PC-7 and PC-8.
The comparison of the performances of the above examples and the comparative examples can be seen (table below), and the polycarboxylic acid water reducer of the present invention can obtain excellent water-reducing dispersibility and slump retention performance under the condition of lower mixing amount than the conventional carboxylic acid products, which indicates that the novel maleic acid polyol ester polyether monomer has better molecular structure and reactivity than the currently used polyether monomer, and the prepared polycarboxylic acid water reducer has more obvious steric hindrance and better product effect.
Performance test comparison table
As can be seen from the comparison between the concrete slump and the concrete expansion in the above table, the water reducing agents PC-1 to PC-8 prepared by the invention have a folding and fixing amount of 0.13% and a consumption amount of less than 0.15% in the comparative example under the same environment, which shows that the performance is not reduced and improved while the cost is reduced.
The polyether monomer with the branched structure of the maleic acid polyol ester enriches the selection range of the polyether monomer of the polycarboxylic acid water reducing agent, and the technology for synthesizing the polycarboxylic acid water reducing agent by adopting the polyether monomer with the branched structure and changing the performance of the polycarboxylic acid water reducing agent is not disclosed and reported, so that the polyether monomer with the branched structure has an innovative promotion effect on the technical progress of the polycarboxylic acid water reducing agent. Maleic anhydride and polyalcohol substances used for synthesizing the polyether monomer are common chemical raw materials, so that more manufacturers and low price are provided, the cost of the monomer can be greatly reduced, and the cost performance of the synthesized polycarboxylic acid water reducing agent is improved.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the invention and are not to be construed as limiting the embodiments of the present invention, and it will be apparent to those skilled in the art that other variations and modifications can be made on the basis of the above description.
Claims (9)
1. A method for synthesizing a branched polyether monomer for a polycarboxylic acid water reducing agent is characterized by comprising the following steps: the method comprises the following steps:
the method comprises the following steps: the reaction vessel is anhydrous, inert gas purging is carried out after vacuum pumping, and the maleate and the catalyst are added into a high-pressure reaction kettle, wherein the molar ratio of the catalyst to the maleate is 0.014-0.125: 1;
step two: heating the high-pressure reaction kettle in the first step to 105-150 ℃, introducing alkylene oxide under the condition of inert atmosphere, and carrying out ring-opening polymerization reaction on maleic acid ester and alkylene oxide under the action of a catalyst, wherein the molar ratio of the alkylene oxide to the maleic acid ester is 13-195: 1;
step three: after the addition reaction in the second step is finished, cooling to 65-70 ℃, adding a neutralizing agent to adjust the pH value to 5-6.5 to obtain the branched polyether monomer for the polycarboxylic acid water reducing agent,
the weight average molecular weight of the branched polyether monomer for the polycarboxylic acid water reducing agent is 1480-9186, and the structural formula of the branched polyether monomer is one of the following six structures:
wherein R is1-R4Is composed of
The total number of a and b is 33-145, R' is-CXH2XR' is-CXH2X-1，X=3-6。
2. The method for synthesizing the branched polyether monomer for the polycarboxylic acid water reducer according to claim 1, wherein the method comprises the following steps: in the first step, the maleic acid ester is one of dipropyl alcohol maleate, ditriethanolamine maleate, monoethylene glycol maleate or dibutylene glycol maleate.
3. The method for synthesizing the branched polyether monomer for the polycarboxylic acid water reducer according to claim 1, wherein the method comprises the following steps: in the first step, the catalyst is one of potassium hydroxide, sodium hydride, sodium methoxide, sodium ethoxide, boron trifluoride and boron trifluoride ethyl ether.
4. The method for synthesizing the branched polyether monomer for the polycarboxylic acid water reducer according to claim 1, wherein the method comprises the following steps: in the second step, the alkylene oxide is ethylene oxide, and the molar ratio of the ethylene oxide to the maleate is 30-70: 1.
5. The method for synthesizing the branched polyether monomer for the polycarboxylic acid water reducer according to claim 4, wherein the method comprises the following steps: the ethylene oxide in the second step is subjected to addition reaction at the temperature of 105-130 ℃.
6. The method for synthesizing the branched polyether monomer for the polycarboxylic acid water reducer according to claim 4, wherein the method comprises the following steps: the maleic acid ester is one of maleic acid monoethylene glycol ester or maleic acid dibutyl glycol ester.
7. The method for synthesizing the branched polyether monomer for the polycarboxylic acid water reducer according to claim 1, wherein the method comprises the following steps: in the second step, the alkylene oxide is ethylene oxide and propylene oxide, the molar ratio of the ethylene oxide to the maleate is 40-180:1, and the molar ratio of the propylene oxide to the maleate is 3-15: 1.
8. The method for synthesizing the branched polyether monomer for the polycarboxylic acid water reducer according to claim 7, wherein the method comprises the following steps: in the second step, ethylene oxide is introduced into a reaction kettle at the temperature of 105-: 1, the mol ratio of the propylene oxide to the maleic ester is 2-8: 1.
9. The method for synthesizing the branched polyether monomer for the polycarboxylic acid water reducer according to claim 7 or 8, characterized in that: the maleic acid ester is one of dipropyl alcohol maleate, ditriethanolamine maleate or monoethylene glycol maleate.
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| CN102336845A (en) * | 2010-07-27 | 2012-02-01 | 上海台界化工有限公司 | Method for synthesizing polycarboxylic acid water reducer |
| CN106883403A (en) * | 2017-04-10 | 2017-06-23 | 甘肃九桓新材料有限公司白银分公司 | The preparation method of maleic acid mono alkyl ester polyether |
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| CN101700964A (en) * | 2009-11-26 | 2010-05-05 | 辽宁科隆精细化工股份有限公司 | Water reducing agent, preparation method thereof and maleic acid mono alkyl ester polyether |
| CN102336845A (en) * | 2010-07-27 | 2012-02-01 | 上海台界化工有限公司 | Method for synthesizing polycarboxylic acid water reducer |
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