CN114736341A - Cross-linked polycarboxylate superplasticizer and preparation method thereof - Google Patents
Cross-linked polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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- 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
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Abstract
The invention belongs to the technical field of preparation of concrete admixtures, and particularly relates to a cross-linking type polycarboxylate superplasticizer and a preparation method thereof. The method comprises (I) preparing hydroxyalkyl-terminated polyoxyethylene ethylene polyoxypropylene ether; preparing trimethylolpropane polyoxyethylene polyoxypropylene ether triacrylate; and (III) carrying out free radical polymerization reaction on hydroxyalkyl-terminated vinyl polyoxypropylene polyoxyethylene ether and trimethylolpropane polyoxyethylene polyoxypropylene ether triacrylate to prepare the cross-linked polycarboxylic acid water reducer. The polymerization process has controllable reaction rate, mild and stable heat release, avoids the phenomena of local implosion and the like caused by high temperature in the polymerization reaction process, can stably control the reaction speed, obtains the polycarboxylic acid water reducing agent with high water reducing rate, high protection and collapse, good wrapping property and excellent workability under the normal temperature condition, is used in concrete, cannot generate adverse effect on the performance of the concrete, and is suitable for most production lines.
Description
Technical Field
The invention belongs to the technical field of concrete admixture preparation, and particularly relates to a cross-linking type polycarboxylate superplasticizer and a preparation method thereof.
Background
The water reducing agent (also called Superplasticizer) is one of the most used concrete admixtures, and has the main functions of hindering or destroying the flocculation structure of cement particles through surface activity, complexation, electrostatic repulsion force or three-dimensional repulsion force and the like, thereby greatly improving the workability and the fluidity of the concrete, and achieving the effects of saving the cement using amount, reducing the mixing water consumption of the concrete and improving the strength of the concrete. The polycarboxylate superplasticizer serving as a third-generation water reducer product quickly occupies most markets due to the advantages of low mixing amount, high water reducing rate, high degree of freedom of molecular structure design, environmental friendliness and the like, and is widely applied to projects such as high-speed rails, roads, bridges, tunnels, high-rise buildings and the like.
The polycarboxylic acid water reducing agent is a high molecular polymer with a comb-shaped structure, and is prepared by carrying out free radical copolymerization on an unsaturated polyether macromonomer and an unsaturated small monomer. The use of polyether macromonomers proceeds through the following stages: MPEGMA (methoxy polyoxyethylene ether methacrylate), APEG (allyl polyoxyethylene ether), SPEG (methyl allyl alcohol polyoxyethylene ether) and TPEG (isopentenol polyoxyethylene ether). At present, SPEG and TPEG account for over 90% of the market share of the Chinese polycarboxylic acid market.
In recent years, a novel hydroxyalkyl vinyl-terminated polyoxyethylene ether is widely concerned by various research organizations, such as EPEG (hydroxyethyl vinyl polyoxyethylene ether, VOPEG (hydroxybutyl vinyl polyoxyethylene ether), because the carbon atoms of the terminal double bonds in the polymer molecular chain are connected with oxygen atoms, so that the double bond copolymerization activity is very high, the activity matching degree with small monomers is better when the polycarboxylate superplasticizer is synthesized.
However, the novel monomer has high activity and short polymerization time, heat release is severe in the polymerization reaction process, the concentration of a reaction system is increased along with the increase of the reaction temperature, the dispersion uniformity of the active comonomer is deteriorated, and side reactions such as self-polymerization and local sudden polymerization are easily generated locally, so that the performance of the synthesized polycarboxylic acid water reducing agent is seriously reduced. In addition, the Plank group reports that the monomer has poor stability, the terminal vinyl ether has very high activity due to the fact that carbon-carbon double bonds are connected with electron-donating groups in the polymerization process, the monomer is easy to decompose after the reaction temperature is higher than 35 ℃, formaldehyde is released from decomposition products, and great influence is caused on human health and environment.
The synthesis process for preparing the water reducing agent disclosed at present needs complex and harsh process conditions, for example, ultralow temperature is needed in the whole reaction process, the requirement of a reaction system on the pH value is severe, the temperature needs to be controlled to be 15-30 ℃ in the whole polymerization process to synthesize the water reducing agent with excellent performance, the requirement on equipment is high, and the energy consumption and process control in the synthesis process are complex. And most of the existing water reducing agent manufacturers can not meet the conditions for producing the water reducing agent mother liquor, so that the popularization and the application of the water reducing agent mother liquor are greatly limited.
Under the conditions of natural sandstone resource exhaustion and government's prohibition on mining, inferior high-mud-content concrete materials such as machine-made sand become a careless choice. However, the current TPEG and SPEG cannot be effectively adapted, so that the problems of quick slump loss, high viscosity and the like of concrete are caused. Aiming at the current market situation, a novel polycarboxylic acid water reducing agent and a preparation method thereof need to be developed.
The cross-linked or star-shaped polymer has excellent fluidity and collapse resistance, has great potential to replace the traditional comb-shaped polycarboxylic acid water reducing agent, and becomes one of the research contents of more and more scholars. However, the cross-linked or star-shaped polymer generally has more functionality, high activity, fast molecular weight increase in the synthesis process, larger system viscosity, high heat release, difficult control of the polymerization speed, poor product stability and influence on the application of the polymer in concrete. Therefore, the development and research of a novel crosslinking type or star type polycarboxylic acid polymer have great significance to the field of concrete.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the problems that in the prior art, the hydroxyalkyl-terminated vinyl polyoxyethylene ether polycarboxylate superplasticizer with excellent performance needs to be prepared at low temperature, has high requirements on equipment and high energy consumption, and cannot have high water reducing rate and slump loss and the like; and in the prior art, the problems of difficult control of polymerization speed, poor product stability and the like in the process of preparing the cross-linked polycarboxylic acid water reducing agent are solved, so that the cross-linked polycarboxylic acid water reducing agent and the preparation method thereof are provided.
Therefore, the invention provides the following technical scheme.
The invention provides a preparation method of a crosslinking type polycarboxylate superplasticizer, which comprises the following steps,
preparing hydroxyalkyl-terminated ethylene polyoxypropylene polyoxyethylene ether; the hydroxyalkyl-terminated ethylene polyoxypropylene polyoxyethylene ether has the following structural formula,
wherein R is1Is hydrogen or methyl, R2Is C1-C4Alkylene of (A), R3Is hydrogen, methyl or ethyl, m is 0-6, n is 10-150;
preparing trimethylolpropane polyoxyethylene polyoxypropylene ether triacrylate, wherein the specific steps comprise that trimethylolpropane is sequentially subjected to alkoxylation and esterification reaction to obtain the trimethylolpropane polyoxyethylene polyoxypropylene ether triacrylate;
the trimethylolpropane polyoxyethylene polyoxypropylene ether triacrylate has the following structural formula,
wherein, b1、b2、b3All are 0-4, b is more than or equal to 01+b2+b3≤6；a1、a2、a3Is 6-20, 6 is less than or equal to a1+a2+a3≤30。
(III) preparation of Cross-linking type polycarboxylate superplasticizer
And (3) carrying out free radical polymerization reaction on hydroxyalkyl-terminated ethylene polyoxypropylene polyoxyethylene ether and trimethylolpropane polyoxyethylene polyoxypropylene ether triacrylate to prepare the cross-linked polycarboxylic acid water reducer.
In the step (two), the specific steps for preparing the trimethylolpropane polyoxyethylene polyoxypropylene ether triacrylate comprise,
(1) carrying out alkoxylation reaction on trimethylolpropane, ethylene oxide and propylene oxide in sequence to obtain trimethylolpropane polyoxyethylene polyoxypropylene ether;
(2) obtaining trimethylolpropane polyoxyethylene polyoxypropylene ether triacrylate after esterification reaction of trimethylolpropane polyoxyethylene polyoxypropylene ether and acrylic acid monomers;
wherein the trimethylolpropane polyoxyethylene polyoxypropylene ether has the following structural formula,
wherein, b1、b2、b3All are 0-4, b is more than or equal to 01+b2+b3≤6；a1、a2、a3Is 6-20, a is more than or equal to 61+a2+a3≤30。
In the step (2), a polymerization inhibitor and a catalyst are added before the esterification reaction;
the polymerization inhibitor is at least one of p-hydroxyanisole, hydroquinone, phenothiazine, cuprous chloride and copper formate;
the catalyst is at least one of sulfamic acid, methanesulfonic acid, p-toluenesulfonic acid, clay-loaded sulfuric acid, diatomite-loaded sulfuric acid, clay-loaded phosphotungstic acid, diatomite-loaded phosphotungstic acid, phosphomolybdic acid, heteropoly acid and sulfonic acid resin; the catalyst may also be a solid super acid.
The temperature of the esterification reaction is 70-100 ℃, and the time is 8-10 h.
In the step (2), after the esterification reaction, stopping the reaction when the acid value is qualified, and removing the solvent to obtain trimethylolpropane polyoxyethylene polyoxypropylene ether triacrylate; wherein, the qualified acid value means that the acid value is less than 56mgkOH/g, or the reduction amount is less than 2mgkOH/g per hour.
In the step (II), the molar ratio of the trimethylolpropane to the propylene oxide to the ethylene oxide is 1 (0-6) to 6-30; in the case of preparing trimethylolpropane polyoxyethylene polyoxypropylene ether triacrylate, when trimethylolpropane is reacted with ethylene oxide and propylene oxide in this order, the amount of propylene oxide used may be 0.
The molar ratio of the trimethylolpropane polyoxyethylene polyoxypropylene ether to the acrylic acid monomer is 1: 3-3.6;
the dosage of the polymerization inhibitor is 0.1 to 0.2 percent of the total mass of the monomers;
the dosage of the catalyst is 1-2% of the total mass of the monomers; wherein the total mass of the monomers refers to the total mass of trimethylolpropane polyoxyethylene polyoxypropylene ether and acrylic monomers.
In the step (three), the first step of the method,
mixing hydroxyalkyl-terminated ethylene polyoxypropylene polyoxyethylene ether and trimethylolpropane polyoxyethylene polyoxypropylene triacrylate, adding an initiator, unsaturated carboxylic acid and a chain transfer agent, and carrying out aqueous solution free radical polymerization reaction to obtain a cross-linked polycarboxylic acid water reducer;
wherein the starting temperature of the free radical polymerization reaction is 20-30 ℃; the reaction time is 1-3 h;
the mass ratio of the hydroxyalkyl-terminated ethylene polyoxypropylene polyoxyethylene ether, the unsaturated carboxylic acid, the trimethylolpropane polyoxyethylene polyoxypropylene ether triacrylate, the initiator and the chain transfer agent is 1: (0.06-0.18): (0.0004-0.01): (0.002-0.009): (0.0015-0.006).
The initiator is a Fenton initiation system;
preferably, the fenton initiation system is a cuprous salt-hydrogen peroxide-reducing agent system;
the reducing agent is at least one of VC, sodium formaldehyde sulfoxylate, E51, sodium bisulfite and sodium hypophosphite;
the mass ratio of the hydrogen peroxide solution, the cuprous salt and the reducing agent in the Fenton initiation system is 1: (0.01-0.2): (0.1-1).
The unsaturated carboxylic acid is at least one of acrylic acid, methacrylic acid, itaconic acid and maleic acid;
the chain transfer agent is at least one of thioglycolic acid, mercaptopropionic acid, mercaptoethanol and sodium hypophosphite.
In the step (one), the specific steps for preparing the hydroxyalkyl-terminated polyoxyethylene polyoxypropylene ether comprise,
mixing unsaturated alcohol serving as an initiator with an alkali catalyst, sequentially adding propylene oxide and ethylene oxide in an oxygen-free environment, controlling the reaction temperature to be 100-130 ℃, and performing polymerization reaction to obtain hydroxyalkyl-terminated vinyl polyoxypropylene polyoxyethylene ether; wherein the molar ratio of propylene oxide to ethylene oxide is (0-6): (10-150); the amount of the unsaturated alcohol is determined according to the designed molecular weight of the hydroxyalkyl-terminated polyoxyethylene ethylene oxide and the mole number of the ethylene oxide and the propylene oxide, and the amount of the alkali catalyst is 0.1 to 0.5 percent of the mass of the hydroxyalkyl-terminated polyoxyethylene ethylene oxide.
The unsaturated alcohol is at least one of 4-hydroxybutyl vinyl ether, ethylene glycol monovinyl ether or diethylene glycol monovinyl ether.
In the step (III), before the cross-linked polycarboxylic acid water reducing agent is obtained, the step of adjusting the pH value to 6-7 is further included;
the pH regulator is organic amine;
the organic amine is trihydroxypropyl hydroxyethyl ethylenediamine and/or tetrahydroxypropyl ethylenediamine.
The invention provides a cross-linking type polycarboxylate superplasticizer prepared by the preparation method.
The technical scheme of the invention has the following advantages:
1. the invention provides a preparation method of a cross-linking type polycarboxylate superplasticizer, which comprises the steps of (I) preparing hydroxyalkyl-terminated ethylene polyoxypropylene polyoxyethylene ether; preparing trimethylolpropane polyoxyethylene polyoxypropylene ether triacrylate; and (III) carrying out free radical polymerization reaction on hydroxyalkyl-terminated vinyl polyoxypropylene polyoxyethylene ether and trimethylolpropane polyoxyethylene polyoxypropylene ether triacrylate to prepare the cross-linked polycarboxylic acid water reducer. The reaction rate of the polymerization process is controllable, the heat release is mild and stable, the phenomena of local implosion and the like caused by high temperature in the polymerization process are avoided, the reaction speed can be stably controlled, the polycarboxylate water reducing agent which has high water reducing rate, high slump retention, good wrapping property and excellent workability is produced under the normal temperature condition, and the polycarboxylate water reducing agent can not generate adverse effect on the performance of concrete when being used in the concrete; the preparation method of the water reducer is suitable for most production lines, has no strict requirements on equipment, is easy to realize industrial production, and also overcomes the related defects that in the prior art, when the water reducer is prepared by taking the vinyl-terminated polyoxyethylene ether as a monomer, the temperature is firstly reduced to 15 ℃, and then is increased to 25-30 ℃, and due to fast reaction and difficult heat release control, the requirements on the cooling and heat exchange efficiency of production equipment are high, the production stability is difficult to guarantee, and the requirements on pH, equipment and the like are strict.
The trimethylolpropane polyoxyethylene polyoxypropylene ether triacrylate is taken as a cross-linking agent and is subjected to polymerization reaction with hydroxyalkyl-end vinyl polyoxypropylene polyoxyethylene ether, on one hand, the trimethylolpropane polyoxyethylene polyoxypropylene ether triacrylate cross-linking agent is trifunctional, has larger steric hindrance and can ensure spatial extension, has proper spatial chemical structure and polymerization reaction activation energy with the hydroxyalkyl-end vinyl polyoxypropylene polyoxyethylene ether, can be matched with the hydroxyalkyl-end vinyl polyoxypropylene polyoxyethylene ether to participate in the polymerization reaction as an effective reaction medium, reduces the temperature of the polymerization reaction, improves the reaction polymerization rate, effectively controls the reaction efficiency, ensures that the viscosity of a system is not rapidly increased in the synthesis process, and the obtained cross-linked polycarboxylic acid water reducing agent has a polyether cross-linking structure with mutually matched length and length, forms good extension conformation, and can exert better steric hindrance effect after being adsorbed on cement particles, continuously providing dispersing capacity, obviously improving the collapse protection effect of the water reducing agent, and synthesizing the polycarboxylic acid water reducing agent with high water reducing performance and high collapse protection performance.
On the other hand, more carboxylic ester groups can be introduced into the main chain of the polycarboxylate water reducer, the carboxylic ester groups can be slowly hydrolyzed in the alkaline environment of cement to release carboxyl groups, and the carboxyl groups can be adsorbed on the cement, so that the water reducer is ensured to be more firmly adsorbed on cement particles and not easily adsorbed by soil, and a good collapse protection effect is obtained through slow release.
The invention provides a preparation method of a water reducing agent, wherein when trimethylolpropane polyoxyethylene polyoxypropylene ether triacrylate is prepared, a method of alkoxylation and esterification is adopted, so that the conversion rate of a product can be improved, the problem of self-polymerization is not easy to occur in the esterification synthesis process, no waste water or waste residue is generated in the whole synthesis process, the post-treatment processes such as alkali washing, water washing and the like are not needed, and the trimethylolpropane polyoxyethylene polyoxypropylene ether triacrylate can be directly used after the esterification reaction; overcomes the problem that the prior art needs to adopt a specific catalyst when preparing the trimethylolpropane polyoxyethylene polyoxypropylene ether triacrylate.
The hydroxyalkyl-terminated ethylene polyoxypropylene polyoxyethylene ether can introduce a hydrophobic group of terminal methyl into a polyether long chain of the water reducer, so that the HLB value of the polycarboxylate water reducer is effectively reduced, and the capability of polyether long chain associated water is reduced after the HLB value is reduced, so that more free water is released, and the viscosity of concrete is effectively reduced.
The preparation process of the water reducing agent provided by the invention has no waste water and waste residue, the reaction product can be directly used for the next polymerization reaction, the energy is saved, the consumption is saved, the environment is protected, and the steps of water washing and alkali washing after the esterification reaction in the prior art are omitted.
The molecular weight of the cross-linking type polycarboxylate superplasticizer obtained by the invention is 10000-50000; when the solid content of the crosslinking type polycarboxylate superplasticizer is 35-45%, the viscosity is 500-1000 mPas.
2. According to the preparation method of the cross-linking type polycarboxylate water reducer, provided by the invention, the paraffin main chain with carboxylic acid groups and the hydrophilic polyether side chain molecular structure can be formed by hydroxyalkyl-terminated ethylene polyoxypropylene polyoxyethylene ether, hydroxymethyl propane polyoxyethylene polyoxypropylene ether triacrylate and unsaturated carboxylic acid under the action of an initiator and a chain transfer agent, so that the water reducer can be further ensured to be firmly adsorbed on cement particles and not easily adsorbed by soil, and a better collapse protection effect is obtained.
The mass ratio of hydroxyalkyl-terminated ethylene polyoxypropylene polyoxyethylene ether, hydroxymethyl propane polyoxyethylene polyoxypropylene ether triacrylate, an initiator and a chain transfer agent is limited, so that the high conversion rate of the polymerization reaction is ensured; on the other hand, the molecular weight and molecular weight distribution of the polymer can be controlled, the spatial configuration of a cross-linked structure is adjusted, mutual winding between chains is avoided, and good stretching conformation is guaranteed to be formed, so that the steric hindrance effect of the tree-shaped polycarboxylate superplasticizer and the electrostatic repulsion force of carboxylic acid groups on the polycarboxylate superplasticizer chains are in synergistic effect to block and destroy the flocculation structure of cement particles, thereby saving the cement consumption, guaranteeing the activity and the strength of concrete, and improving the application performance of the superplasticizer.
3. According to the preparation method of the cross-linking type polycarboxylate water reducer, the Fenton initiator system adopted by the invention has proper activation energy, can be matched with the melting temperature of the polyether composition to initiate polymerization reaction at normal temperature, has proper reaction rate, can avoid side reaction caused by violent heat release at the too high reaction rate, and ensures the performance of the polycarboxylate water reducer. The cuprous Fenton initiation system is preferably selected, the stability of the product is basically not influenced by the change of the environmental temperature, the stability of the water reducing agent product can be improved by taking the cuprous Fenton initiation system as the initiator, and the product performance difference obtained in different batches is small.
The cuprous chloride Fenton initiation system is preferably selected, the stability of the product is basically not influenced by the change of the environmental temperature, the stability of the water reducing agent product in different batches can be improved by taking the cuprous chloride Fenton initiation system as the initiator, and the product performance difference obtained in different batches is small.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
The specific embodiment provides a preparation method of a crosslinking type polycarboxylate superplasticizer, which comprises the following steps,
(I) preparation of hydroxyalkyl-terminated polyoxyethylene ethylene polyoxypropylene ether
Placing unsaturated alcohol as an initiator into a high-pressure reaction kettle, adding an alkali catalyst for mixing, introducing nitrogen for replacement, adding propylene oxide in an oxygen-free environment, controlling the reaction temperature to be 100-130 ℃, adding ethylene oxide after the reaction is completed, cooling the reaction kettle after the ethylene oxide is completely reacted, adding acid for neutralization reaction, and adjusting the pH value to be 6-7 to obtain the hydroxyalkyl-terminated vinyl polyoxypropylene polyoxyethylene ether.
(II) preparation of trimethylolpropane polyoxyethylene polyoxypropylene Ether triacrylate
(1) Adding trihydroxy propane and an alkali catalyst into a reaction kettle, replacing air in the reaction kettle with nitrogen, controlling the temperature in the kettle to be 100-130 ℃, adding ethylene oxide for curing reaction, then adding propylene oxide for curing reaction, and then adjusting the pH value to be 5-6 to obtain trihydroxymethyl polyoxyethylene polyoxypropylene ether;
(2) adding the trimethylolpropane polyoxyethylene polyoxypropylene ether into an esterification reaction bottle, stirring uniformly, heating, adding a polymerization inhibitor, a solvent, a catalyst and an acrylic acid monomer, heating to 70-100 ℃, carrying out esterification reaction, stopping the reaction after the acid value is qualified, wherein the qualified acid value means that the acid value is less than 56mgkOH/g or the reduction amount is less than 2mgkOH/g per hour, and removing the solvent cyclohexane to obtain the cross-linking agent trimethylolpropane polyoxyethylene polyoxypropylene ether triacrylate.
(III) preparation of Cross-linking type polycarboxylate superplasticizer
Mixing hydroxyalkyl-terminated ethylene polyoxypropylene polyoxyethylene ether and trimethylolpropane polyoxyethylene polyoxypropylene ether triacrylate, adjusting the pH to 5-6, sequentially adding cuprous salt and hydrogen peroxide in a Fenton initiation system, then simultaneously dropwise adding the solution A and the solution B, performing free radical polymerization, adjusting the pH and the solid content after dropwise adding is finished, and obtaining a cross-linked polycarboxylic acid water reducer, wherein the initial temperature of the polymerization is 20-30 ℃; the solution A comprises unsaturated carboxylic acid, chain transfer agent and water, and can also comprise part of reducing agent in a Fenton initiation system; solution B includes some or all of the reducing agents in the fenton initiation system.
Example 1
The embodiment provides a cross-linking type polycarboxylate superplasticizer and a preparation method thereof, the preparation method comprises the following steps,
preparation of hydroxyalkyl-terminated ethylene polyoxypropylene polyoxyethylene ether
Adding 100g of ethylene glycol monovinyl ether and 0.25g of sodium hydroxide into a high-pressure reaction kettle, replacing with nitrogen for three times, starting stirring, heating the reaction kettle to 110 ℃, introducing 160g of propylene oxide into the reaction kettle in an oxygen-free environment, carrying out curing reaction for 1 hour, adding 2000g of ethylene oxide into the reaction kettle after the reaction is completed, carrying out curing reaction for 1 hour, cooling the reaction kettle to 90 ℃ after the ethylene oxide is completely reacted, adding acetic acid, carrying out neutralization reaction, and adjusting the pH value to 6-7 to obtain hydroxyalkyl-terminated ethylene-polyoxypropylene polyoxyethylene ether with the average molecular weight of 2000; wherein, the ethylene oxide and the propylene oxide are added into the reaction kettle under the condition of no oxygen.
(II) preparation of trimethylolpropane polyoxyethylene polyoxypropylene Ether triacrylate
(1) Adding 125g of trimethylolpropane and 0.125g of KOH base catalyst into a reaction kettle, replacing air in the reaction kettle with nitrogen, controlling the temperature in the kettle to be 100 ℃, adding 460g of ethylene oxide, controlling the temperature in the reaction kettle to be 130 ℃ and the pressure to be 0.35MPa, then adding 153g of propylene oxide, carrying out curing reaction for 1 hour, then adding acetic acid, adjusting the pH value to be 5-6, and degassing in the reaction kettle to obtain trimethylolpropane polyoxyethylene polyoxypropylene ether (TMPEP) with the average molecular weight of 750;
(2) adding 120g of TMPEP into an esterification reaction bottle, stirring uniformly, slowly heating to 65 +/-5 ℃, sequentially adding 0.18g of p-hydroxyanisole, 85g of cyclohexane, 1.9g of methanesulfonic acid and 36g of acrylic acid into the esterification reaction bottle, heating to 78 +/-3 ℃, then starting reflux, starting sampling after 8 hours, reacting for 8 hours to 10 hours, sampling every 1 hour, sampling every 0.5 hour after 10 hours of reaction, detecting the acid value of a sample, if the acid value is less than 56mgkOH/g or the reduction is less than 2mgkOH/g every hour, cooling a reaction kettle to 70 ℃, stopping the reaction, and removing the solvent cyclohexane to obtain a cross-linking agent trimethylolpropane polyoxyethylene polyoxypropylene ether triacrylate (TMPEPTA), wherein the average molecular weight is 960.
(III) preparation of Cross-linking type polycarboxylate superplasticizer
(1) Preparing 28g of acrylic acid, 0.75g of mercaptopropionic acid and 56g of water to obtain a mixed solution A; preparing 1.2g of E51 and 60g of water to obtain a mixed solution B for later use;
(2) adding 350g of hydroxyalkyl vinyl polyoxypropylene polyoxyethylene ether obtained in the step (I), 0.5g of TMPEPTA and 350g of water into a flask, slowly adding a 40% sodium hydroxide aqueous solution to neutralize until the pH value is 5-5.5, sequentially adding 0.15g of cuprous chloride and 1.2g of 30% hydrogen peroxide, stirring for dissolving, then simultaneously dropwise adding the solution A and the solution B under the condition of room temperature (25 +/-2 ℃) while stirring, wherein the dropwise adding time of the solution A is 60min, the dropwise adding time of the solution B is 70min, after dropwise adding, adding tetrahydroxyethyl ethylenediamine to adjust the pH value to 6, and adding water for diluting to obtain the crosslinked polycarboxylate water reducer with the solid content of 40%.
Example 2
The embodiment provides a cross-linking type polycarboxylate superplasticizer and a preparation method thereof, the preparation method comprises the following steps,
preparation of hydroxyalkyl-terminated ethylene polyoxypropylene polyoxyethylene ether
Adding 100g of ethylene glycol monovinyl ether and 0.25g of sodium hydroxide into a high-pressure reaction kettle, replacing with nitrogen for three times, starting stirring, heating the temperature in the reaction kettle to 110 ℃, introducing 160g of propylene oxide into the reaction kettle, carrying out curing reaction for 1h, adding 2000g of ethylene oxide into the reaction kettle after the reaction is completed, carrying out curing reaction for 1h, cooling the temperature in the reaction kettle to 90 ℃ after the ethylene oxide is completely reacted, adding acetic acid, carrying out neutralization reaction, and adjusting the pH value of a product to 6-7 to obtain hydroxyethyl-terminated vinyl polyoxypropylene polyoxyethylene ether with the average molecular weight of 2000; wherein, the ethylene oxide and the propylene oxide are added into the reaction kettle under the condition of no oxygen.
(II) preparation of trimethylolpropane polyoxyethylene polyoxypropylene ether triacrylate
(1) Adding 125g of trimethylolpropane and 0.125g of KOH alkali catalyst into a reaction kettle, replacing air in the reaction kettle with nitrogen, controlling the temperature in the reaction kettle to be 100 ℃, adding 950g of ethylene oxide, controlling the temperature in the reaction kettle to be 130 ℃ and the pressure to be 0.35MPa, then adding 153g of propylene oxide, curing for 1 hour, then adding acetic acid, adjusting the pH value to be 5-6, and degassing in the reaction kettle to obtain the trimethylolpropane polyoxyethylene polyoxypropylene ether (TMPEP) with the molecular weight of 1200;
(2) adding 120g of TMPEP into an esterification reaction bottle, stirring uniformly, slowly heating to 65 +/-5 ℃, sequentially adding 0.18g of p-hydroxyanisole, 85g of cyclohexane, 1.8g of methanesulfonic acid and 23g of acrylic acid into the esterification reaction bottle, heating to 78 +/-3 ℃, then starting reflux, starting sampling after 8 hours, reacting for 8 hours to 10 hours, sampling every 1 hour, sampling every 0.5 hour after 10 hours of reaction, detecting the acid value of a sample, if the acid value is less than 56mgkOH/g or the reduction is less than 2mgkOH/g every hour, cooling a reaction kettle to 70 ℃, stopping the reaction, and removing the solvent cyclohexane to obtain the cross-linking agent trimethylolpropane polyoxyethylene polyoxypropylene ether triacrylate (TMPEPTA), wherein the average molecular weight is 1416.
(III) preparation of Cross-linking type polycarboxylate superplasticizer
(1) Preparing a mixed solution A by taking 38g of acrylic acid, 0.8g of mercaptopropionic acid and 56g of water; preparing 0.9g of E51 and 60g of water into a mixed solution B for later use;
(2) adding 350g of hydroxyalkyl-terminated ethylene-polyoxypropylene polyoxyethylene ether obtained in the step (I), 0.5g of TMPEPTA and 350g of water into a flask, slowly adding 40% sodium hydroxide aqueous solution to neutralize until the pH value is 5-5.5, sequentially adding 0.15g of cuprous chloride and 1.2g of 30% hydrogen peroxide, stirring to dissolve, then simultaneously dropwise adding the solution A and the solution B under room temperature (25 +/-2 ℃) while stirring, wherein the dropwise adding time of the solution A is 60min, the dropwise adding time of the solution B is 70min, after dropwise adding, adding tetraethylene diamine to adjust the pH value to 6, and adding water to dilute to obtain the crosslinked polycarboxylate water reducer with the solid content of 40%.
Example 3
The embodiment provides a cross-linking type polycarboxylate superplasticizer and a preparation method thereof, the preparation method comprises the following steps,
preparation of hydroxyalkyl-terminated ethylene polyoxypropylene polyoxyethylene ether
Adding 88g of ethylene glycol monovinyl ether and 0.18g of sodium hydroxide into a high-pressure reaction kettle, replacing with nitrogen for three times, starting stirring, heating the temperature in the reaction kettle to 110 ℃, introducing 120g of propylene oxide into the reaction kettle, carrying out curing reaction for 1h, adding 2600g of ethylene oxide into the reaction kettle after the reaction is completed, carrying out curing reaction for 1h, cooling the temperature in the reaction kettle to 90 ℃ after the ethylene oxide is completely reacted, adding acetic acid, carrying out neutralization reaction, and adjusting the pH value of a product to 6-7 to obtain hydroxyethyl-terminated vinyl polyoxypropylene polyoxyethylene ether with the average molecular weight of 3000; wherein, the ethylene oxide and the propylene oxide are added into the reaction kettle under the condition of no oxygen.
(II) preparation of trimethylolpropane polyoxyethylene polyoxypropylene Ether triacrylate
The same as in example 2.
(III) preparation of Cross-linking type polycarboxylate superplasticizer
(1) Preparing 50g of acrylic acid, 1.45g of mercaptopropionic acid and 56g of water to obtain a mixed solution A; preparing 0.9g of E51 and 60g of water into a mixed solution B for later use;
(2) adding 450g of hydroxyalkyl vinyl polyoxypropylene polyoxyethylene ether obtained in the step (I), 0.5g of TMPEPTA and 350g of water into a flask, slowly adding a 40% sodium hydroxide aqueous solution to neutralize until the pH value is 5-5.5, sequentially adding 0.15g of cuprous chloride and 1.2g of 30% hydrogen peroxide, stirring for dissolving, then simultaneously dropwise adding the solution A and the solution B under the condition of room temperature (25 +/-2 ℃) while stirring, wherein the dropwise adding time of the solution A is 60min, the dropwise adding time of the solution B is 70min, after dropwise adding, adding tetrahydroxyethyl ethylenediamine to adjust the pH value to 6, and adding water for diluting to obtain the crosslinked polycarboxylate water reducer with the solid content of 40%.
Example 4
The embodiment provides a cross-linking type polycarboxylate superplasticizer and a preparation method thereof, the preparation method comprises the following steps,
preparation of hydroxyalkyl-terminated ethylene polyoxypropylene polyoxyethylene ether
Adding 150g of 4-hydroxybutyl vinyl ether and 0.5g of sodium hydroxide into a high-pressure reaction kettle, replacing with nitrogen for three times, starting stirring, heating the reaction kettle to 110 ℃, introducing 210g of propylene oxide into the reaction kettle in an anaerobic environment, reacting for 1h until the reaction is complete, adding 3500g of ethylene oxide in the anaerobic environment, reacting for 1h until the reaction is complete, cooling the reaction kettle to 90 ℃, adding acetic acid, and carrying out a neutralization reaction to obtain 4-hydroxybutyl vinyl polyoxyethylene polyoxypropylene ether with the pH of 6-7, wherein the average molecular weight is 3000.
(II) preparation of trimethylolpropane polyoxyethylene polyoxypropylene Ether triacrylate
The same as in example 2.
(III) preparation of Cross-linking type polycarboxylate superplasticizer
(1) Mixing 45g of acrylic acid, 0.45gVC, 1.6g of mercaptopropionic acid and 50g of water to obtain a solution A; taking 1.9g E51 and 90g of water, and mixing to obtain a solution B;
(2) 550g of 4-hydroxybutyl vinyl polyoxyethylene polyoxypropylene ether obtained in the step (I), 0.9g of TMPEPTA and 550g of water are added into a flask, then 6g of 40% sodium hydroxide aqueous solution is slowly added to neutralize until the pH value is 5-5.5, 0.3g of cuprous sulfate and 2.2g of 30% hydrogen peroxide are sequentially added to the flask to be stirred and dissolved, then the solution A and the solution B are simultaneously dropwise added under stirring at room temperature (25 +/-2 ℃), the dropwise adding time of the solution A is 60min, the dropwise adding time of the solution B is 65min, and after the dropwise adding is finished, tetrahydroxyethyl ethylenediamine is added to adjust the pH value to 6, so that the cross-linked polycarboxylic acid water reducer is obtained.
Example 5
This example provides a cross-linked polycarboxylic acid water reducing agent and a preparation method thereof, which is different from example 3 in that cuprous chloride is replaced by ferrous sulfate in the same molar amount, and the rest is the same.
Comparative example 1
This comparative example provides a polycarboxylic acid water reducing agent, which is different from example 1 in that step (ii) is eliminated, trimethylolpropane polyoxyethylene polyoxypropylene ether triacrylate is not added in step (iii), and the other steps are the same as example 1; the method comprises the following steps:
preparation of hydroxyalkyl-terminated polyoxyethylene ethylene polyoxypropylene Ether
Adding 100g of ethylene glycol monovinyl ether and 0.25g of sodium hydroxide into a high-pressure reaction kettle, replacing with nitrogen for three times, starting stirring, heating the reaction kettle to 110 ℃, introducing 160g of propylene oxide into the reaction kettle in an oxygen-free environment, carrying out curing reaction for 1h, adding 2000g of ethylene oxide into the reaction kettle after the reaction is completed, carrying out curing reaction for 1h, cooling the reaction kettle to 90 ℃ after the ethylene oxide is completely reacted, adding acetic acid, carrying out neutralization reaction, and adjusting the pH to 6-7 to obtain hydroxyalkyl-end vinyl polyoxypropylene polyoxyethylene ether with the average molecular weight of 2000; wherein, the ethylene oxide and the propylene oxide are added into the reaction kettle under the condition of no oxygen.
Preparation of ordinary polycarboxylic acid water reducing agent
(1) Preparing 28g of acrylic acid, 0.75g of mercaptopropionic acid and 56g of water to obtain a mixed solution A; preparing 1.2g of E51 and 60g of water to obtain a mixed solution B for later use;
(2) adding 350g of hydroxyalkyl-terminated ethylene-polyoxypropylene polyoxyethylene ether obtained in the step (I) and 350g of water into a flask, slowly adding 40% of sodium hydroxide aqueous solution to neutralize until the pH value is 5-5.5, sequentially adding 0.15g of cuprous chloride and 1.2g of 30% hydrogen peroxide, stirring and dissolving, then simultaneously dropwise adding the solution A and the solution B under stirring at room temperature (25 +/-2 ℃), wherein the dropwise adding time of the solution A is 60min, the dropwise adding time of the solution B is 70min, after the dropwise adding is finished, adding tetrahydroxyethyl ethylenediamine to adjust the pH value to 6, and adding water to dilute to obtain the polycarboxylic acid water reducer with the solid content of 40%.
Comparative example 2
This comparative example provides a polycarboxylic acid water reducing agent which differs from example 1 in that trimethylolpropane trimethacrylate-CAS: 3290-92-4 is used in place of TMPEPTA in example 1, otherwise the same as example 1.
Test examples
The test example provides performance tests and test results of the polycarboxylic acid water reducing agent prepared in each example and comparative example, and the performance test method comprises the following steps:
the clear slurry test refers to the GB/T8077-2000 Standard of the homogeneity test method of concrete admixtures, and the concrete test refers to the GB/T50080-2002 Standard of the Performance test method of common concrete mixtures.
The commercial water reducing agents used as comparison are a water-reducing and slump-retaining polycarboxylic acid water reducing agent PC-1 (the trade name is BASF RHEOPLUS 410) with the solid content of 40% and a water-reducing and slump-retaining polycarboxylic acid water reducing agent PC-2 (the trade name is SILKROAD SRE 110); the cement is grade P.O 42.5.5 of conch cement; the addition amount of the water reducing agent in the cement paste is 0.2 percent of the weight of the cement, and the water cement ratio is 0.29; the amount of water reducing agent added to the concrete was 0.4% by weight based on the weight of cement in the concrete. The water-reducing rate, slump and slump loss with time of each water-reducing agent were measured and the results are shown in Table 1.
TABLE 1 test results of examples, comparative examples and commercial water reducers
Note: the "-" in the table indicates that the fluidity was small and out of the measurement range.
The experiment results in the table 1 show that the polycarboxylate water reducer prepared by the invention has a high collapse prevention effect, and compared with the water reducer in the prior art, the collapse prevention effect is excellent. Compared with comparative examples 1-2, the water reducing agent prepared by the specific method of the invention has good collapse protection effect.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. A preparation method of a crosslinking type polycarboxylate superplasticizer is characterized by comprising the following steps,
preparation of hydroxyalkyl-terminated ethylene polyoxypropylene polyoxyethylene ether
The hydroxyalkyl-terminated ethylene polyoxypropylene polyoxyethylene ether has the following structural formula,
wherein R is1Is hydrogen or methyl, R2Is C1-C4Alkylene of (A), R3Is hydrogen, methyl or ethyl, m is 0-6, n is 10-150;
(II) preparation of trimethylolpropane polyoxyethylene polyoxypropylene Ether triacrylate
Carrying out alkoxylation and esterification reactions on trimethylolpropane in sequence to obtain trimethylolpropane polyoxyethylene polyoxypropylene ether triacrylate;
the trimethylolpropane polyoxyethylene polyoxypropylene ether triacrylate has the following structural formula,
wherein, b1、b2、b3All are 0-4, b is more than or equal to 01+b2+b3≤6；a1、a2、a3Is 6-20, a is more than or equal to 61+a2+a3≤30；
(III) preparation of Cross-linking type polycarboxylate superplasticizer
And (3) carrying out free radical polymerization reaction on hydroxyalkyl-terminated ethylene polyoxypropylene polyoxyethylene ether and trimethylolpropane polyoxyethylene polyoxypropylene ether triacrylate to prepare the cross-linked polycarboxylic acid water reducer.
2. The method according to claim 1, wherein the step (II) comprises a specific step of preparing trimethylolpropane polyoxyethylene polyoxypropylene ether triacrylate,
(1) carrying out alkoxylation reaction on trimethylolpropane, ethylene oxide and propylene oxide in sequence to obtain trimethylolpropane polyoxyethylene polyoxypropylene ether;
(2) carrying out esterification reaction on trimethylolpropane polyoxyethylene polyoxypropylene ether and an acrylic acid monomer to obtain trimethylolpropane polyoxyethylene polyoxypropylene ether triacrylate;
wherein the trimethylolpropane polyoxyethylene polyoxypropylene ether has the following structural formula,
wherein, b1、b2、b3All are 0-4, b is more than or equal to 01+b2+b3≤6；a1、a2、a3Is 6-20, a is more than or equal to 61+a2+a3≤30。
3. The method according to claim 2, wherein in the step (2), a step of adding a polymerization inhibitor and a catalyst is further included before the esterification reaction;
preferably, the polymerization inhibitor is at least one of p-hydroxyanisole, hydroquinone, phenothiazine, cuprous chloride and copper formate;
preferably, the catalyst is at least one of sulfamic acid, methanesulfonic acid, p-toluenesulfonic acid, clay-supported sulfuric acid, kieselguhr-supported sulfuric acid, clay-supported phosphotungstic acid, kieselguhr-supported phosphotungstic acid, phosphomolybdic acid, heteropoly acid and sulfonic acid resin;
preferably, the esterification reaction is carried out at 70-100 ℃ for 8-10 h.
4. The method according to claim 3, wherein in the step (two), the molar ratio of trimethylolpropane, propylene oxide and ethylene oxide is 1 (0-6) to (6-30);
preferably, the molar ratio of the trimethylolpropane polyoxyethylene polyoxypropylene ether to the acrylic monomer is 1 (3-3.6);
preferably, the amount of the polymerization inhibitor is 0.1-0.2% of the total mass of the monomers;
preferably, the amount of the catalyst is 1-2% of the total mass of the monomers.
5. The production method according to any one of claims 1 to 4, wherein, in the step (III),
mixing hydroxyalkyl-terminated ethylene polyoxypropylene polyoxyethylene ether and trimethylolpropane polyoxyethylene polyoxypropylene triacrylate, adding an initiator, unsaturated carboxylic acid and a chain transfer agent, and carrying out aqueous solution free radical polymerization reaction to obtain a cross-linked polycarboxylic acid water reducer;
preferably, the starting temperature of the radical polymerization reaction is 20 to 30 ℃; the reaction time is 1-3 h;
preferably, the mass ratio of the hydroxyalkyl-terminated ethylene polyoxypropylene polyoxyethylene ether, the unsaturated carboxylic acid, the trimethylolpropane polyoxyethylene polyoxypropylene ether triacrylate, the initiator and the chain transfer agent is 1: (0.06-0.18): (0.0004-0.01): (0.002-0.009): (0.0015-0.006).
6. The method according to claim 5, wherein the initiator is a Fenton initiation system;
preferably, the fenton initiation system is a cuprous salt-hydrogen peroxide-reducing agent system;
preferably, the reducing agent is at least one of VC, sodium formaldehyde sulfoxylate, E51, sodium bisulfite, and sodium hypophosphite.
7. The production method according to claim 5 or 6, characterized in that the unsaturated carboxylic acid is at least one of acrylic acid, methacrylic acid, itaconic acid, and maleic acid;
preferably, the chain transfer agent is at least one of thioglycolic acid, mercaptopropionic acid, mercaptoethanol and sodium hypophosphite.
8. The production method according to any one of claims 1 to 7, wherein the specific step of producing the hydroxyalkyl-terminated polyoxyethylene vinylpolyoxypropylene ether in the step (one) comprises,
mixing unsaturated alcohol serving as an initiator with an alkali catalyst, sequentially adding propylene oxide and ethylene oxide in an oxygen-free environment, controlling the reaction temperature to be 100-130 ℃, and performing polymerization reaction to obtain hydroxyalkyl-terminated vinyl polyoxypropylene polyoxyethylene ether;
preferably, the molar ratio of propylene oxide to ethylene oxide is (0-6): (10-150).
9. The preparation method according to any one of claims 1 to 8, characterized in that the step (III) further comprises a step of adjusting the pH to 6 to 7 before obtaining the cross-linked polycarboxylic acid water reducing agent;
preferably, the pH adjuster is an organic amine;
preferably, the organic amine is trimethylolpropane hydroxyethyl ethylenediamine and/or tetrahydroxypropyl ethylenediamine.
10. A cross-linking type polycarboxylic acid water reducing agent prepared by the preparation method of any one of claims 1 to 9.
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| CN117534827B (en) * | 2023-12-08 | 2024-06-07 | 四川嘉兆丰新材料科技有限公司 | Sulfonic group end-capped vinyl polyether monomer for water reducer and synthesis method thereof |
| CN118978647A (en) * | 2024-09-12 | 2024-11-19 | 江苏斯尔邦石化有限公司 | A kind of polycarboxylic acid collapse-preserving mother solution and preparation method thereof |
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