CN109293850B - Preparation method of small-molecule water reducing agent with slump retaining, slow setting and anti-mud effects - Google Patents
Preparation method of small-molecule water reducing agent with slump retaining, slow setting and anti-mud effects Download PDFInfo
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- 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
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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
- 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
- C04B24/2605—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
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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
- 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
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Abstract
The invention belongs to the technical field of building materials, and particularly relates to a preparation method of a micromolecule water reducing agent with slump retaining, slow setting and mud resisting effects. Meanwhile, the topological structure of the water reducing agent can be further adjusted by the quantity of polyethylene glycol side chains on amine nitrogen. The obtained water reducing agent has a block micromolecule structure different from the traditional comb-shaped polycarboxylic acid and a relatively high acid group proportion, and has the beneficial effects of long-time retardation, slump retention and clay resistance.
Description
Technical Field
The invention belongs to the technical field of building materials, and particularly relates to a preparation method of a small-molecular water reducing agent with slump retaining, slow setting and mud resisting effects.
Background
The polycarboxylic acid high-performance water reducing agent (hereinafter abbreviated as polycarboxylic acid) is the concrete water reducing agent type which has the best water reducing performance and is most widely applied to large-scale engineering at present. In the molecular structure, the polycarboxylic acid is a comb-shaped topological structure with an acidic anionic monomer such as acrylic acid, methacrylic acid and the like as a main chain and polyethylene glycol as a side chain, and although the structure endows the polycarboxylic acid with excellent water reducing performance, the polycarboxylic acid is easy to perform intercalation reaction with certain lamellar compounds to cause failure, wherein the most typical structure is clay. Because the breadth of our country is wide, the concrete aggregate sources are different in various places, the quality is different, many raw materials or clay mixed with the raw materials in the production process are quite equivalent, and the performance of the polycarboxylic acid when the aggregate contains the clay is greatly limited due to the characteristic that the polyethylene glycol side chain of the polycarboxylic acid is easy to be intercalated with the clay. Meanwhile, in some special occasions, such as high-temperature scenes of oil well construction and the like, the slow setting and slump retaining performances of the polycarboxylate superplasticizer are not satisfactory.
How to overcome various problems in the application of the polycarboxylic acid water reducing agent is an important subject in the development of the water reducing agent. The optimization of the structure of the polycarboxylic acid is the key point of the modification and design of the molecular structure. Patent CN104262548A reports a preparation method of an anti-mud water reducer, which is characterized in that a special quaternary ammonium salt group is introduced into a polycarboxylic acid chain, but a monomer corresponding to the group needs to be prepared through a complex substitution reaction, and the steps are complicated. CN107987231A reports a method for preparing an anti-mud polycarboxylate superplasticizer with a comb-shaped side chain based on secondary polymerization, which relates to atom transfer radical polymerization and has harsh conditions. Patent CN104861127B improves the mud resistance by introducing cyclodextrin groups into the polycarboxylic chain, but the cost and availability of cyclodextrin is not satisfactory. Besides modifying the molecules of the polycarboxylic acid, some patents try to break through the traditional comb-octyl structure of the polycarboxylic acid and then break the weakness that the polycarboxylic acid is easy to be intercalated with clay to lose effectiveness. CN105542147B reports a preparation method and application of a mud-resistant water reducing agent with a hyperbranched structure, the mud resistance of the mud-resistant water reducing agent is obviously superior to that of the traditional polycarboxylic acid, but the post-treatment of the method after condition control is harsh and tedious. For the problem of high temperature retardation and slump retention of polycarboxylic acid, the industry attempts to develop a low molecular water reducer which has polyethylene glycol and acidic anionic groups similar to polycarboxylic acid, but both are in head-to-tail block distribution. CN108239279A reports a preparation method of a small-molecular water reducer with retarding, slump retaining and mud resisting effects, but the method involves a more complex polyethylene glycol end modification reaction.
Based on the technical background, the invention provides a method for preparing a micromolecule polycarboxylic acid type water reducing agent with a block structure by grafting acrylic acid chains on amine-initiated polyether based on free radical reaction generated by redox of the amine-initiated polyether and persulfate, the method has simple steps and mild conditions, and the obtained water reducing agent has a topological structure of the block micromolecule different from the traditional comb-shaped polycarboxylic acid and relatively higher acid group ratio; has the beneficial characteristics of long-term slump retaining and retarding and clay resistance.
Disclosure of Invention
The invention discloses a preparation method of a micromolecule water reducing agent with slump retaining, slow setting and mud resisting effects, which has the following specific technical scheme:
a preparation method of a micromolecule water reducing agent with slump retaining, slow setting and mud resisting effects is based on the process of generating free radicals by redox of persulfate and tertiary amine, amine initiated polyethylene glycol E is used as a polyethylene glycol chain segment with steric hindrance effect in water reducing agent molecules and a reducing agent in polymerization reaction, and forms a redox initiation system with persulfate to initiate graft polymerization of acid monomers on adjacent carbon of amino, and the preparation method specifically comprises the following steps:
adding amine-initiated polyethylene glycol E accounting for 25-40% of the total feeding mass into a reactor, adding water to prepare a solution with the mass concentration of 40-60%, adding a certain amount of alkali B, and stirring until all materials are uniformly mixed and dissolved to the maximum extent;
and (2) dropping 5-10% of persulfate solution I into the mixture at a constant speed, beginning to drop a mixed water solution M with the total mass concentration of 40% -60% of acid monomer and residual amine starting polyethylene glycol E (60-75% of the total feeding mass) at a constant speed after 5-15min, wherein the dropping of M lasts for 1.5-3h, the dropping of I lasts for 1.75-3.5h and is 15-30min longer than the dropping time of M, after the dropping is finished, neutralizing the mixed water solution with dilute nitric acid to the pH value of 7-8, and discharging.
The invention further improves the amine-initiated polyethylene glycol E, which is prepared by using ammonia or methyl or hydroxyethyl substituted monoamine initiator except trimethylamine and a known polyethylene glycol anion ring-opening polymerization method, wherein the amine group of the E is connected with 1-3 polyethylene glycol chains and 2-0 methyl, and the structure of the amine-initiated polyethylene glycol E is shown as the following formula 1-3:
according to the further improvement of the invention, the weight average molecular weight of the amine-initiated polyethylene glycol E is 1800-6500, and the total feeding mass of E is 75-125 parts by mass.
In a further improvement of the present invention, in the step (1) above, the base B is sodium and potassium hydroxide, carbonate or bicarbonate. The function is as follows: keeping the amine in the amine-initiated polyethylene glycol from being neutralized by the added acid monomer during polymerization results in reduced reducibility and initiation activity. The total base equivalent (molar amount x number of base elements) of the base B should be equal to the total molar amount of the acidic monomers added. The mass is calculated from the conversion relation.
In a further improvement of the present invention, during the polymerization reaction in the step (2), amine-initiated polyethylene glycol E as a reducing agent reacts with persulfate under alkaline conditions to generate redox radicals, which initiate the graft polymerization of monomers on the α -carbon to which the polyethylene glycol chain is connected with the nitrogen atom, as follows:
in the above reaction formula, PEG is polyethylene glycol chain
Me is methyl, Base is alkali, and for multi-chain amine-initiated polyethylene glycol, after the reaction is grafted with a first (methyl) acrylic acid chain, the reaction is further grafted on alpha-carbon connected with nitrogen atoms of the polyethylene glycol chain through initiation reactions and chain transfer on other chains, so that the micromolecule water reducing agent with different topological structures is finally obtained:
in the above formula, Chain Transfer effect between the free radical and the polyethylene glycol E subjected to primary grafting in the reaction system is shown by the Chain Transfer effect.
Meanwhile, carbon around the amine-initiated polyethylene glycol can undergo a chain transfer reaction, a certain chain transfer effect (for example, the following formula) is achieved, and the control of the polymerization degree of the acid monomer and the improvement of the utilization efficiency of free radicals can be achieved by putting a corresponding part of the amine-initiated polyethylene glycol into a reaction system in advance.
In the step (2), the acidic monomer is acrylic acid or methacrylic acid, the molar ratio of the acidic monomer to the amine-initiated polyethylene glycol is 8-20, and the mass of the acidic monomer is calculated according to the conversion relation.
In the step, the molar ratio of the persulfate to the amine-initiated polyethylene glycol E in the solution I is 1: 1.2-2.0, and the mass of the solution I is calculated according to the relationship and the concentration range in the step. Below this value, the probability of persulfate self-initiation reaction in the system increases, and above this value, it becomes difficult for radical reaction to spread over all the amine-initiated polyethylene glycol molecules, resulting in raw material residue and reduced conversion.
In the above step (2), the mass of the solution M is calculated based on the mass of the acrylic acid used and the polyethylene glycol E which is not previously added, and the aforementioned mass concentration range.
The weight average molecular weight of the water reducing agent prepared by the method provided by the invention is 2200-8000.
The invention has the beneficial effects that:
(1) under mild conditions, the small-molecular water reducing agent can be obtained by free radical polymerization which is relatively simple and convenient to operate, and the steps of complicated operation, harsh conditions, multiple side reactions, substitution reaction, addition reaction and the like which are often involved in the preparation of similar water reducing agents are avoided. Simple operation and convenient batch production.
(2) The obtained water reducing agent has the beneficial effects of long-term slow setting and slump retaining and soil adhesion resistance.
Detailed Description
In order to enhance the understanding of the method, the method will be described in further detail with reference to the following examples, which are only used for explaining the method and do not limit the scope of the method.
The following examples are provided to illustrate the specific operation of the preparation process and the efficacy of the product obtained. The products obtained in each example were characterized by Gel Permeation Chromatography (GPC) using a miniDAWN Tristar aqueous gel permeation chromatograph manufactured by Wyatt technology corporation. The test parameters are: the column was TSK-GELSW (TOSOH Corp.), the mobile phase was 0.1mol/L NaNO3, the flow rate was 1mL/min, the sample was a 1% mobile phase solution, the sample volume was 20. mu.L, and the detector was a differential refractometer.
Example 1
Polyethylene glycol E-1 (measured weight average molecular weight 4107) having a theoretical average molecular weight of 4000 was prepared using dimethylethanolamine as an initiator.
At 25 ℃, 40 parts by mass of E-1 is added into a reactor, water is added to prepare a 50% mass concentration solution, 15 parts by mass of sodium hydroxide is added, 61.7 parts by mass of a solution I-1 containing 3.7 parts by mass of sodium persulfate is dripped into the solution at a constant speed, and after 8min, a 50% mass concentration mixed aqueous solution M-1 containing 27 parts by mass of acrylic acid and 60 parts by mass of E-1 is dripped into the solution at a constant speed. M-1 was added continuously for 2.5h, and I-1 was added continuously for 3 h. And after the dropwise addition is finished, neutralizing and discharging. The product has a weight average molecular weight of 5039.
Example 2
Using dimethylethanolamine as an initiator, polyethylene glycol E-2 (measured weight-average molecular weight 2061) having a theoretical average molecular weight of 2000 was prepared
At 15 ℃, adding 24 parts by mass of E-2 into a reactor, adding water to prepare a 40% solution by mass, adding 12.8 parts by mass of sodium hydroxide, dropwise adding 96 parts by mass of a solution I-1 containing 4.8 parts by mass of sodium persulfate at a constant speed, and after 5min, beginning to dropwise add a 40% solution M-2 containing 23 parts by mass of acrylic acid and 56 parts by mass of E-2 at a constant speed. M-2 was added dropwise for 1.5h, and I-2 was added dropwise for 1h45 min. And after the dropwise addition is finished, neutralizing and discharging. The product had a weight average molecular weight of 2573.
Example 3
Preparing polyethylene glycol E-3 with weight average molecular weight of 6000 (measured weight average molecular weight 5963) with triethanolamine as initiator
At 35 ℃, adding 30 parts by mass of E-3 into a reactor, adding water to prepare a solution with the mass concentration of 60%, adding 21.2 parts by mass of sodium carbonate, dropwise adding 40 parts by mass of a solution I-3 containing 4.0 parts by mass of sodium persulfate into the solution at a constant speed, and after 15min, beginning to dropwise add a mixed aqueous solution M-3 with the mass concentration of 60% containing 28.8 parts by mass of acrylic acid and 90 parts by mass of E-3 at a constant speed. M-3 was added dropwise for 3h, and I-3 was added dropwise for 3.5 h. And after the dropwise addition is finished, neutralizing and discharging. The product has a weight average molecular weight of 7233.
Example 4
Using dimethylethanolamine as an initiator to prepare polyethylene glycol E-4 with a weight average molecular weight of 3000 (measured weight average molecular weight 3055)
At normal temperature, adding 35 parts by mass of E-4 into a reactor, adding water to prepare a solution with the mass concentration of 50%, adding 22.4 parts by mass of potassium hydroxide, dropwise adding 62.5 parts by mass of a solution I-4 containing 5.0 parts by mass of sodium persulfate into the solution at a constant speed, and after 6min, beginning to dropwise add a mixed aqueous solution M-4 with the mass concentration of 45% containing 34.4 parts by mass of methacrylic acid and 65 parts by mass of E-4. M-4 is continuously added for 2h, and I-4 is continuously added for 2h and 20 min. And after the dropwise addition is finished, neutralizing and discharging. The product had a weight average molecular weight of 4113.
Example 5
Preparing polyethylene glycol E-5 with weight average molecular weight of 4000 (measured weight average molecular weight 4076) by using dimethylethanolamine as initiator
At normal temperature, 40 parts by mass of E-5 is added into a reactor, water is added to prepare a 50% mass concentration solution, 10 parts by mass of sodium hydroxide is added, 61.7 parts by mass of a solution I-7 containing 3.7 parts by mass of sodium persulfate is dripped into the solution at a constant speed, and after 10min, a 50% mass concentration mixed aqueous solution M-5 containing 18 parts by mass of acrylic acid and 60 parts by mass of E-5 is dripped into the solution at a constant speed. M-5 was added continuously for 2.5h, and I-5 was added continuously for 3 h. And after the dropwise addition is finished, neutralizing and discharging. The product had a weight average molecular weight of 4680.
Example 6
Preparing polyethylene glycol E-6 with weight average molecular weight of 4000 (measured weight average molecular weight 4003) by using methyldiethanolamine as initiator
At normal temperature, adding 30 parts by mass of E-5 into a reactor, adding water to prepare a 50% solution by mass, adding 31.5 parts by mass of sodium bicarbonate, dropwise adding 42 parts by mass of a solution I-8 containing 4.2 parts by mass of sodium persulfate at a constant speed, and after 10min, beginning to dropwise add a 50% solution M-6 containing 32.3 parts by mass of methacrylic acid and 70 parts by mass of E-6 at a constant speed. M-6 is continuously added for 2h, and I-6 is continuously added for 2h and 15 min. And after the dropwise addition is finished, neutralizing and discharging. The product has a weight average molecular weight of 4867.
In order to illustrate the efficacy advantages of the water reducer prepared by the method of the present invention in slump retention, set retardation and mud resistance, typical ester-type and ether-type polycarboxylic acid water reducers were prepared in the following comparative examples as performance comparisons, respectively.
Comparative example 1
This comparative example is a typical ester type polycarboxylate water reducer prepared via a well-known free radical copolymerization process
100 parts by mass of methoxy polyethylene glycol 2000 methacrylate (weight average molecular weight 2055), 21.5 parts by mass of methacrylic acid, 0.7 part by mass of mercaptopropionic acid and 122.2 parts by mass of water are mixed to prepare a 50% monomer solution M-r1, 40 parts by mass of water are added into a reaction kettle, the temperature is raised to 80 ℃, and M-r1 and 20 parts by mass of 10% ammonium persulfate solution I-r1 are added at a constant speed. Wherein M-r6 is added dropwise for 3h, and I-r1 is added dropwise for 3.5 h. And after the dropwise addition is finished, adjusting the pH to 5-6 by using liquid alkali, and discharging. The weight average molecular weight of the product was 21525, and the conversion was 91.3%.
Comparative example 2
This comparative example is a typical ether type polycarboxylic acid water reducing agent prepared via a known process
100 parts by mass of methallyl polyethylene glycol-2000 (weight average molecular weight 2020) and 1 part by mass of ammonium persulfate are taken, water is added to prepare a 50% solution, the temperature is raised to 55 ℃, 60 parts by mass of a solution M-r2 containing 18 parts by mass of acrylic acid and 0.8 part by mass of mercaptopropionic acid and 20 parts by mass of a solution I-r2 containing 1.2 parts by mass of sodium bisulfite are respectively and uniformly dripped into the solution, wherein the dripping of the M-r2 lasts for 2.5 hours, and the dripping of the I-r2 lasts for 3 hours. And after the dropwise addition is finished, adjusting the pH to 5-6 by using liquid alkali, and discharging. The weight average molecular weight of the product was 19763 and the conversion was 87.9%.
Evaluation of the Properties of examples
In order to further verify the effectiveness of the small-molecular water reducing agent prepared by the method disclosed by the invention and further verify the effectiveness and the benefits of the method disclosed by the invention, the performance of the water reducing agent obtained in each example is evaluated by the following performance tests:
concrete setting time and flow test over time
The purpose of this test was to characterize the retarding and slump retaining efficacy of the examples. The raw materials and procedures for the tests are based on the GB 8076 + 2008 standard. The cement is P.I.42.5 cement, and the water-cement ratio is 0.48; the sand adopts medium sand, and coarse aggregate is secondary crushed stone with the proportion of 4: 6. The mixing ratio is as follows:
TABLE 1 concrete mix proportions used in the tests of the examples
During testing, the water reducing and slump retaining performances of the water reducing agent are represented by actually measured fluidity difference, and the results are shown in table 2:
TABLE 2 Effect of examples and comparative examples on setting time and flowability of concrete with time
As can be seen from the above table, the water reducing agents described in the examples, although having a smaller initial slump (spread) of concrete, lost much more slowly over time than the two comparative examples, compared to the typical ester (comparative example 1) and ether (comparative example 2) water reducing agents, confirm the outstanding slump retaining efficacy of the water reducing agents prepared by the process of the present invention. Meanwhile, the initial setting time of concrete mixed by the water reducer prepared by the method is more than 2 hours later than that of the typical ester type and ether type polycarboxylic acid water reducer prepared by the comparative example. The experimental results prove the advantages of the water reducer prepared by the method in slump retaining and slow setting.
Clay-containing mortar flow test
The purpose of this test is to characterize the clay resistance of the examples and comparative examples, the test materials and procedures being based on GB/T17671-1999. During testing, the glue-sand ratio is 1:3, kaolin is taken as a typical clay sample, the water-glue ratio is 0.5, and the kaolin replaces 0.5 percent of the amount of sand. The mixing amount of the water reducing agent is shown below
From the above results, it can be seen that the water reducing agents prepared in the examples of the present invention still maintain good water reducing effect in the presence of kaolin, while the comb-shaped polycarboxylic acid type water reducing agent in the comparative example shows a significant decrease in effect, and the mortar initial fluidity is not affected by kaolin as in the examples, and the loss with time is more serious. The results prove that the water reducer prepared by the method disclosed by the invention has good adaptability to a clay-containing cement mortar system.
The foregoing shows and describes the basic principles, principal features and advantages of the present method. It will be understood by those skilled in the art that the present method is not limited to the embodiments described above, which are merely illustrative of the principles of the method, but that various changes and modifications may be made to the method without departing from the spirit and scope of the method, which changes and modifications are within the scope of the method as claimed. The scope of the method claimed is defined by the appended claims and equivalents thereof.
Claims (4)
1. A preparation method of a micromolecule water reducing agent with slump retaining, slow setting and mud resisting effects is characterized in that the principle is based on the process of generating free radicals through redox of persulfate and tertiary amine, amine-initiated polyethylene glycol E is used as a polyethylene glycol chain segment with steric hindrance effect in water reducing agent molecules and a reducing agent in polymerization reaction, and forms a redox initiation system with persulfate to initiate graft polymerization of acid monomers on adjacent carbon of amino, and the preparation method specifically comprises the following steps:
adding amine-initiated polyethylene glycol E accounting for 25-40% of the total feeding mass into a reactor, adding water to prepare a solution with the mass concentration of 40-60%, adding a certain amount of alkali B, and stirring until all materials are uniformly mixed and dissolved to the maximum extent;
and (2) dropping 5-10% of persulfate solution I into the mixture at a constant speed, beginning to drop a mixed water solution M with the total mass concentration of 40% -60% of acid monomer and residual amine starting polyethylene glycol E (60-75% of the total feeding mass) at a constant speed after 5-15min, wherein the dropping of M lasts for 1.5-3h, the dropping of I lasts for 1.75-3.5h and is 15-30min longer than the dropping time of M, after the dropping is finished, neutralizing the mixed water solution with dilute nitric acid to the pH value of 7-8, and discharging.
2. The preparation method of the small-molecular water reducer with slump retaining, slow setting and mud resisting effects according to claim 1, wherein the weight average molecular weight of the amine-initiated polyethylene glycol E is 1800-6500, and the total feeding mass of E is 75-125 parts by unit mass.
3. The method for preparing the small molecule water reducing agent with slump retaining, slow setting and mud resisting effects as claimed in claim 1, wherein in the step (1), the alkali B is hydroxide, carbonate and bicarbonate of sodium and potassium, and the total alkali equivalent of the alkali B is equal to the total molar amount of the added acidic monomers.
4. The preparation method of the small-molecule water reducing agent with slump retaining, slow setting and anti-mud effects as claimed in claim 1, wherein in the polymerization reaction process in the step (2), amine-initiated polyethylene glycol E as a reducing agent and persulfate undergo redox free radical reaction under alkaline conditions to generate free radicals to initiate monomer graft polymerization on alpha-carbon with polyethylene glycol chains connected with nitrogen atoms, as follows:
in the above reaction formula, PEG is polyethylene glycol chain
Me is methyl, Base is alkali, and for multi-chain amine-initiated polyethylene glycol, after the first (methyl) acrylic acid chain is grafted in the reaction, the multi-chain amine-initiated polyethylene glycol is further grafted on alpha-carbon connected with nitrogen atoms of the polyethylene glycol chain through initiation reactions and chain transfer on other chains, and finally the micromolecule water reducing agent with different topological structures is obtained.
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