CN111363084A - Nitrogen-containing polycarboxy acrylate copolymer water reducing agent, and preparation method and application thereof - Google Patents
Nitrogen-containing polycarboxy acrylate copolymer water reducing agent, and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of fine chemical engineering of ceramic industrial chains, and discloses a nitrogenous polycarboxy acrylate copolymer water reducing agent, a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing 10-45 parts by mass of a monomer shown in the formula (1) or a monomer solution (calculated by non-volatile parts) with 90-55 parts by mass of (meth) acrylate, 0-10 parts by mass of (meth) acrylic acid, a reducing agent and water, stirring after dissolving, dropwise adding a chain initiator solution at 40-50 ℃, and stopping dropwise adding after completing 1/2-2/3 dropwise adding; and (3) reacting for 0.5-1 hour at 50-70 ℃, then dropwise adding the rest chain initiator solution, reacting for 4-2 hours at 50-70 ℃, adding a chain transfer agent solution, and cooling to obtain the nitrogenous polycarboxy acrylate copolymer water reducing agent. The polymer water reducing agent is used for waste water containing a certain proportion of ceramicsThe ceramic slurry has the advantages of good fluidity, good de-gluing effect, small thixotropy and the like.
Description
Technical Field
The invention relates to the field of fine chemical industry of ceramic industrial chains, in particular to a nitrogenous polycarboxy acrylate copolymer water reducing agent for ceramic wastewater.
Background
With the rapid development of social economy and ceramic industry, the waste materials in the ceramic industry are increasing day by day. According to statistics, the annual output of the national ceramic waste is estimated to be more than 1800 ten thousand tons, and the national ceramic waste mainly comprises waste water, waste residues and waste gas in the three wastes of the ceramic. The recycling of ceramic waste water is one of the most common methods for treating ceramic waste and effectively reducing the discharge of the ceramic waste. The recycled water contains a large amount of soluble high-valence metal ions which can interact with the internal structure of the slurry to cause great problems and uncertainty, and the diversity and complexity of the source and components of the slurry cause the serious degradation of the fluidity of the slurry, which leads to the difficult dispergation of the slurry, the large operation difficulty of the thixotropy of the slurry and the unstable use.
Disclosure of Invention
The invention aims to provide a nitrogenous polycarboxy acrylate copolymer water reducing agent for ceramic wastewater, which is used for solving the outstanding problems of difficult debonding, large contact, unstable use and the like of ceramic slurry of the existing ceramic water reducing agent under the condition of reuse water containing ceramic wastewater.
The invention also aims to provide a preparation method of the water reducing agent.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a nitrogenous polycarboxy acrylate copolymer water reducer comprises the following preparation methods:
mixing 10-45 parts by mass of a monomer shown in the formula (1) or a monomer solution (calculated by non-volatile parts) with 90-55 parts by mass of (meth) acrylate, 0-10 parts by mass of (meth) acrylic acid, a reducing agent and water, stirring after dissolving, dropwise adding a chain initiator solution at 40-50 ℃, and stopping dropwise adding after completing 1/2-2/3 dropwise adding; reacting at 50-70 ℃ for 0.5-1 hour, then dropwise adding the rest chain initiator solution, reacting at 50-70 ℃ for 4-2 hours after dropwise adding, adding a chain transfer agent solution, and cooling to obtain the nitrogenous polycarboxy acrylate copolymer water reducing agent;
the 2- (meth) acryloyloxy- (1-methyl) ethyl ester-ethylenediaminetetraacetic acid monoester salt represented by the formula (1) is 2-acryloyloxy-ethyl ester-ethylenediaminetetraacetic acid salt, 2-methacryloyloxy-ethyl ester-ethylenediaminetetraacetic acid salt, 2-acryloyloxy-1-methylethyl ester-ethylenediaminetetraacetic acid salt, 2-methacryloyloxy-1-methylethyl ester-ethylenediaminetetraacetic acid salt, and the salt is tripotassium salt, trisodium salt, hydrodipotassium salt, hydrodisodium salt, or hydropotassium sodium salt.
The (meth) acrylate is sodium salt or potassium salt of acrylic acid or methacrylic acid, and the (meth) acrylic acid is acrylic acid or methacrylic acid.
Preferably, the preparation of the monomer solution: dissolving ethylenediaminetetraacetic dianhydride (EDTAD) in a water-soluble organic solvent at the temperature of 60-70 ℃ to prepare an EDTAD solution with the concentration of 15-30 wt%, preserving heat, adding 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate, reacting for 4-2 hours, adding a carbonate or bicarbonate aqueous solution, neutralizing for 0.5-1 hour, and cooling to obtain the EDTAD solution, wherein the volatile matters (water, organic solvent and volatile gas CO generated by the neutralization reaction) are removed2Other substances) content of 15 to 30 wt%; the ethylene diamine tetraacetic dianhydride and (methyl) acrylic acid-2-hydroxyethyl ester or (methyl) acrylic acid-2-hydroxypropyl esterIs 1: 1.
The (methyl) acrylic acid-2-hydroxyethyl ester is acrylic acid-2-hydroxyethyl ester and methacrylic acid-2-hydroxyethyl ester, and the (methyl) acrylic acid-2-hydroxypropyl ester is acrylic acid-2-hydroxypropyl ester and methacrylic acid-2-hydroxypropyl ester.
Preferably, the water-soluble organic solvent is one or two of dimethylformamide and dimethylacetamide.
Preferably, the chain initiator is hydrogen peroxide and the reducing agent is ascorbic acid or N-hydroxydiethylamine; the chain terminator is one or two of potassium hypophosphite and sodium hypophosphite.
Preferably, the total amount of the (meth) acrylate and the (meth) acrylic acid is 60-85 wt% of the total amount of the water reducing agent monomers, wherein the total amount of the (meth) acrylic acid is not higher than 10 wt%.
Preferably, the amount of the chain initiator is 0.5-2 wt% of the total amount of the monomers, the amount of the reducing agent is 0.4-1.5 wt% of the total amount of the monomers, and the amount of the terminating agent is 0.1-0.3 wt% of the total amount of the monomers.
Preferably, the solvent in the chain initiator solution and the chain terminator solution is water, the concentration of the chain initiator solution is 2-10 wt%, and the concentration of the chain terminator solution is 5-10 wt%; the total content of all monomers accounts for 20-40 wt% of the total weight of the water reducing agent.
Preferably, the stirring speed is 100-350 rpm, and the dropping speed is 7-20 drops/min.
The nitrogenous polycarboxy acrylate copolymer water reducing agent prepared by the method is applied to recycling of ceramic wastewater.
The invention is characterized in that (methyl) acrylic acid-2-hydroxyethyl ester or (methyl) acrylic acid-2-hydroxypropyl ester and nitrogen-containing (tertiary amine N) anhydride compound ethylene diamine tetraacetic dianhydride are heated in a non-aqueous medium DMF or DMA to accelerate esterification reaction to form monoester, the rest anhydride groups are further hydrolyzed by weak alkaline carbonate or bicarbonate solution to neutralize most part of the anhydride groups to form water-soluble nitrogen-containing polycarboxyl acrylate monomer, the solution after the reaction forms a solution mainly containing the nitrogen-containing polycarboxyl acrylate monomer, and the reaction process is as follows:
the water-soluble nitrogenous polycarboxyl acrylate monomer composition or the nitrogenous polycarboxyl acrylate monomer is copolymerized with (methyl) acrylate and (methyl) acrylic acid in a free radical redox initiation system under heating to form a copolymer with a side chain containing a large number of carboxyl groups and a large number of nitrogen atoms through free radicals, COO-in the side chain of the copolymer is adsorbed to the surface of mud particles to form electrostatic repulsion and steric hindrance effects, the fluidity of the mud under normal water is greatly improved and contributed, and the reaction process is as follows:
the test result of the slurry fluidity test of the water reducing agent under different ceramic wastewater contents shows that the traditional inorganic water reducing agent water glass contains a small amount of ceramic wastewater (contains a large amount of high-valence metal ions such as Ca) in ceramic slurry2+、Mg2+、Al3+、Fe2+、Fe3+Etc.) still lose fluidity at a higher water content of 38-40 wt%, and the gum can not be effectively peptized. The polymer formed by polymerizing the nitrogenous polycarboxy acrylate monomer and the compound of the polymer and nitrogenous micromolecular ethylene diamine tetraacetic acid tripotassium salt or sodium salt have large slurry viscosity, poor fluidity and large contact when containing a small amount of ceramic wastewater, and can not be effectively applied to actual degumming. The nitrogen-containing polycarboxy acrylate copolymer water reducing agent prepared by the embodiment of the invention can keep good fluidity for water quality of 10 wt% ceramic wastewater when the water content is lower than 35 wt% within the range of 0.2-0.4 wt%, has small thixotropy, and can effectively decompose glue; when the amount is 0.4-0.6 wt%, the ceramic slurry can be effectively dispergated when the ceramic wastewater content is below 20 wt% at a low slurry water content, and the slurry fluidity is increased with the increase of the amount of the water reducing agent or the increase of the slurry water content. Thus, the nitrogen-containing polycarboxy acrylate prepared by the present invention is copolymerizedThe water reducing agent can utilize ceramic waste water in a certain range, and has remarkable economic benefits of energy conservation, emission reduction and the like.
According to the nitrogen-containing polycarboxy acrylate copolymer water reducing agent prepared by the invention, a large number of COOM' in a polymer molecule side chain pairs with high-valence metal ions in ceramic wastewater to form a reversible and unstable charge attraction compound (as shown in the following reaction formula (a)), and on one hand, carboxyl negative ions and the metal ions form a charge adsorption effect on the nitrogen-containing polycarboxy side chain, and on the other hand, lone pair electrons on N atoms form coordinate bonds with empty tracks of the high-valence metal ions, so that a stable 5-6-membered ring polycyclic compound (as shown in the following reaction formula (b)) is integrally formed, and the formed compound can be dissolved and dispersed in medium water by adding strong hydrophilicity of the N atoms, so that the interference of the high-valence metal ions on slurry is greatly eliminated, and the dispersibility and the fluidity of slurry particles in an aqueous medium are continuously maintained.
(a):
Compared with the prior art, the invention has the following beneficial effects:
the polymer water reducing agent is used for ceramic slurry containing a certain proportion of ceramic wastewater, has the advantages of good fluidity, good de-gumming effect, small thixotropy and the like, has remarkable economic benefits of energy conservation, emission reduction and the like, and has wide application prospect in ceramic wastewater utilization and sustainable development of ceramic industry.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The ceramic water reducing agent was prepared as in examples 1 to 7 below.
Example 1
(1) Dissolving 1 mol part of ethylene diamine tetraacetic acid di-N, N-dimethylformamide DMF in 768 g of N, N-dimethylformamide DMF at the temperature of 60-70 DEG C256 g of anhydride (EDTAD), preparing a 25 wt% solution, keeping the temperature, adding 116 g of 1 mol part of 2-hydroxyethyl acrylate, reacting for 2 hours, adding 750 g of an aqueous solution containing 1.5 mol parts of sodium carbonate, neutralizing for 0.5 hour, and cooling to obtain a monomer solution MS1 mainly consisting of the nitrogen-containing polycarboxy acrylate shown in the formula (1), wherein the non-volatile matter (volatile CO generated by removing water, organic solvent and neutralization and water) is not volatilized2Gas) content 25 wt%;
(2) then 100 g of MS1 is taken to be mixed with 75 g of sodium acrylate, 0.5 g of reducing agent ascorbic acid and 88.2 g of deionized water, 10 g of 5 wt% hydrogen peroxide solution is dripped at the stirring speed of 150rpm and the speed of 10 drops/min at 40 ℃ after dissolution, 10 g of 5 wt% hydrogen peroxide solution is dripped at the same speed after 1 hour reaction at 50-60 ℃, then the reaction is carried out for 2 hours at 60-70 ℃ after the dripping is finished, 2 g of 5 wt% sodium hypophosphite solution is added after cooling, and 285.7 g of nitrogen-containing polycarboxy acrylate type copolymer ceramic water reducer JSJJ 1 is obtained, wherein the concentration is 35 wt% (excluding initiator, reducing agent and chain transfer agent).
The preparation process is as follows:
example 2
160 g of MS1 solution obtained in the step (1) in the example 1 is mixed with 60 g of sodium acrylate, 0.5 g of reducing agent ascorbic acid and 90.8 g of deionized water, 10 g of 5 wt% hydrogen peroxide solution is dripped into the mixture after the mixture is dissolved under the stirring speed of 150rpm and the temperature of 50 ℃ at the speed of 10 drops/min, 10 g of 5 wt% hydrogen peroxide solution is dripped into the mixture after the mixture reacts at the temperature of 50-60 ℃ for 1 hour at the same speed, the mixture reacts at the temperature of 60-70 ℃ for 2 hours after the dripping is finished, and 2 g of 5 wt% sodium hypophosphite solution is added into the mixture after the mixture is cooled, so that 333.3 g of nitrogen-containing polycarboxy acrylate copolymer ceramic water reducer JSJ2 with the concentration of 30 wt% (excluding initiator, reducing agent and chain transfer agent).
Example 3
(1) Dissolving 256 g of 1 mol part of ethylenediamine tetraacetic dianhydride (EDTAD) in 1024 g of N, N-Dimethylacetamide (DMA) at 60-70 ℃ to prepare a 20 wt% solution, preserving heat, adding 130 g of 1 mol part of 2-hydroxypropyl acrylate, reacting for 4 hours, adding 1246 g of an aqueous solution containing 1.5 mol parts of potassium carbonate, neutralizing for 1 hour, and cooling to obtain a monomer composition solution MS2 mainly composed of nitrogen-containing polycarboxy acrylate shown in the formula (1), wherein the content of non-volatile parts is 20 wt%;
(2) and then 80 g of MS2 is taken to be mixed with 80 g of sodium acrylate, 4 g of methacrylic acid, 0.4 g of reducing agent ascorbic acid and 203.6 g of deionized water, after dissolution, 15 g of 3 wt% hydrogen peroxide solution is dripped at the stirring speed of 300rpm and the speed of 15 drops/min at 45 ℃, after reaction for 1 hour at 55-65 ℃, 15 g of 3 wt% hydrogen peroxide solution is dripped at the same speed, after dripping, the reaction is carried out for 2 hours at 60-70 ℃, after cooling, 2 g of 10 wt% potassium hypophosphite solution is added to obtain 400 g of nitrogen-containing polycarboxy acrylate type copolymer ceramic water reducer JSJJ 3, wherein the concentration is 25 wt% (excluding initiator, reducing agent and chain transfer agent).
The preparation process is as follows:
example 4
160 g of MS1 solution obtained in the step (1) in the example 1 is mixed with 60 g of sodium acrylate, 1.0 g of reducing agent N-hydroxyethylenediamine and 80.3 g of deionized water, after dissolution, 20 g of 5 wt% hydrogen peroxide solution is dripped at a stirring speed of 150rpm and a speed of 10 drops/min at 50 ℃, 10 g of 5 wt% hydrogen peroxide solution is dripped at the same speed after reaction for 1 hour at 60-70 ℃, reaction is carried out for 4 hours at 60-70 ℃ after dripping is finished, and after cooling, 2 g of 5 wt% sodium hypophosphite solution is added to obtain 333.3 g of nitrogen-containing polycarboxy acrylate type copolymer ceramic water reducer JSJSJ 4, wherein the concentration is 30 wt% (excluding initiator, reducing agent and chain transfer agent).
Example 5
200 g of MS2 obtained in the step (1) in the embodiment 3 is mixed with 55 g of sodium acrylate, 5 g of methacrylic acid, 0.4 g of reducing agent ascorbic acid and 107.6 g of deionized water, after dissolution, 15 g of 3 wt% hydrogen peroxide solution is dripped at the stirring speed of 300rpm and the speed of 15 drops/min at 50 ℃, after reaction for 1 hour at 55-65 ℃, 15 g of 3 wt% hydrogen peroxide solution is dripped at the same speed, after dripping, the reaction is carried out for 2 hours at 60-70 ℃, and after cooling, 2 g of 10 wt% potassium hypophosphite solution is added to obtain 400 g of JSJ5, wherein the concentration is 25 wt% (excluding initiator, reducing agent and chain transfer agent).
Example 6
Taking 150 g of MS2 obtained in the step (1) in the example 3, mixing the MS2 with 65 g of sodium acrylate, 5 g of methacrylic acid, 0.8 g of reducing agent N-hydroxydiethylamine and 157.2 g of deionized water, stirring at the stirring speed of 300rpm after dissolution, dripping 10 g of 10 wt% hydrogen peroxide solution at the speed of 8 drops/min at 50 ℃, reacting at the temperature of 60-70 ℃ for 1 hour, dripping 10 g of 5 wt% hydrogen peroxide solution at the same speed, reacting at the temperature of 60-70 ℃ for 2 hours, cooling, and adding 2 g of 10 wt% potassium hypophosphite solution to obtain 400 g of the nitrogen-containing polycarboxy acrylate type copolymer ceramic water reducer JSJJ 6, wherein the concentration is 25 wt% (excluding initiator, reducing agent and chain transfer agent).
Example 7
Mixing 16 g of 2-acryloyloxy-1-methylethyl-ethylene diamine tetraacetic acid tripotassium with 80 g of sodium acrylate, 4 g of methacrylic acid, 0.4 g of reducing agent ascorbic acid and 267.6 g of deionized water, stirring at a stirring speed of 200rpm after dissolving, dropwise adding 15 g of 3 wt% hydrogen peroxide solution at a speed of 15 drops/min at 50 ℃, reacting at 55-65 ℃ for 1 hour, dropwise adding 15 g of 3 wt% hydrogen peroxide solution at the same speed, reacting at 60-70 ℃ for 2 hours after completing dropwise adding, cooling, and adding 2 g of 10 wt% potassium hypophosphite solution to obtain 400 g of nitrogen-containing polycarboxy acrylate type copolymer ceramic water reducer JSJJ 7, wherein the concentration is 25 wt% (excluding initiator, reducing agent and chain transfer agent).
Table 1: water reducing agent monomer and initiation system composition
Comparative example polymer (no nitrogen-containing polycarboxy acrylate type monomer):
mixing 16 g of acrylic acid-2-hydroxypropyl ester with 80 g of sodium acrylate, 4 g of methacrylic acid, 0.4 g of reducing agent ascorbic acid and 267.6 g of deionized water, stirring at a stirring speed of 200rpm after dissolution, dropwise adding 15 g of 3 wt% hydrogen peroxide solution at a speed of 15 drops/min at 40-50 ℃, dropwise adding 15 g of 3 wt% hydrogen peroxide solution at the same speed after reacting for 1 hour at 55-65 ℃, reacting for 2 hours at 60-70 ℃ after dropwise adding, and adding 2 g of 10 wt% potassium hypophosphite solution after cooling to obtain a comparative polymer solution P1, wherein the concentration is 25 wt% (excluding an initiator, a reducing agent and a chain transfer agent);
mixing 4 g of acrylic acid-2-hydroxypropyl ester, 12 g of ethylene diamine tetraacetic acid tripotassium, 80 g of sodium acrylate, 4 g of methacrylic acid, 0.4 g of reducing agent ascorbic acid and 267.6 g of deionized water, stirring at a stirring speed of 200rpm after dissolving, dropwise adding 15 g of 3 wt% hydrogen peroxide solution at a speed of 15 drops/min at 40-50 ℃, reacting for 1 hour at 55-65 ℃, dropwise adding 15 g of 3 wt% hydrogen peroxide solution at the same speed, reacting for 2 hours at 60-70 ℃, cooling, and adding 2 g of 10 wt% potassium hypophosphite solution to obtain a comparative polymer solution P2, wherein the concentration is 25 wt% (excluding initiator, reducing agent and chain transfer agent).
Example 8: water reducing agent performance test
(1) Comparative experiment 1: water glass (potash water glass, modulus 2.1, solid content 50 wt%) was added to a mixture of ceramic clay and water of different water qualities (including 100 wt% deionized water and 10 wt% ceramic wastewater (golden pottery ceramic wastewater) +90 wt% deionized water) at a ratio of 0.4 wt% and 0.8 wt% of water reducing agent solid/dry clay (ball clay powder for ceramic glaze BC01 (jiangmen seiko ceramics materials ltd)) at 25 ℃ respectively so that the total water content of the slurry was 40 wt%, after grinding for 10 minutes, the fluidity at 25 ℃ was measured by using a 4-cup coater, and the experimental results are listed in table 2.
(2) Comparative experiment 2: the polymers P1 and P2 prepared in the above comparative examples were added to a mixture of ceramic clay and water of different water qualities (including 100 wt% deionized water and 10 wt% ceramic waste water +90 wt% deionized water) at room temperature of 25 ℃ in such proportions that the polymer solids/dry clay (ball clay powder for ceramic glaze BC01) were 0.2 wt% and 0.4 wt%, respectively, so that the total water content of the slurry was 35 wt%, after grinding for 10 minutes, the fluidity thereof at room temperature of 25 ℃ was measured by 4-cup painting, and the experimental results are shown in Table 2
(3) The water reducing agents prepared in the above examples 1 to 7 were taken one by one at room temperature of 25 ℃ and added to a mixture of ceramic clay and water of different water qualities (including 100 wt% deionized water, 10 wt% ceramic wastewater and 90 wt% deionized water, wherein the ceramic wastewater contains four metal ions of high-valent calcium, magnesium, ferrous and aluminum, and the concentrations are 2260, 1930, 520 and 950ppm respectively) according to the proportion that the solid/dry clay of the water reducing agent (ball clay powder for ceramic glaze BC01) is 0.2 wt% and 0.4 wt% respectively, so that the total water content of the slurry is 35 wt%, after grinding for 10 minutes, the slurry was tested for fluidity at room temperature of 25 ℃ by coating 4 cups, and the experimental results are listed in Table 2.
Table 2: test result 1 of ceramic slurry flowability of water reducing agent under different ceramic wastewater contents
As can be seen from the above Table 2, the inorganic water reducing agent, namely, the potassium water glass, still loses fluidity under the condition of higher water content of 38-40 wt% when the ceramic slurry contains 10 wt% of ceramic wastewater, and a part or even all of the inorganic water reducing agent, namely, the potassium water glass, cannot flow out of a coating cup for 4 cups, and cannot effectively decompose the glue. In the comparative example, the polymer P1 (only 100 wt% of nitrogen-free polymer and no nitrogen-containing small molecule ethylene diamine tetraacetic acid tripotassium or trisodium salt) and the polymer composite P2 (84 wt% of nitrogen-free polymer and 4 wt% of nitrogen-containing small molecule ethylene diamine tetraacetic acid tripotassium or trisodium salt) which are not polymerized by nitrogen-containing polycarboxylic acrylate type monomer and 12 wt% of nitrogen-containing small molecule ethylene diamine tetraacetic acid tripotassium or trisodium salt) have certain fluidity in deionized water, but the time required for flowing out and coating 4 cups in 10 wt% ceramic waste water at the water reducing agent content of 0.4 wt% or less is long, the viscosity is high, the fluidity is poor, particularly the viscosity is increased after standing for 5 minutes in the actual operation process, the contact size is large (the ratio of the time for flowing out and coating 4 cups after standing for 5 minutes to the initial flowing out and coating 4 cups without standing), the polymer composition cannot be effectively applied to actual dispergation, and the P2 containing 12 wt% of nitrogen-containing small molecule ethylene P1 did not differ significantly. The water reducing agent prepared by the preparation embodiment of the invention can keep good fluidity for the water quality of ceramic wastewater containing 10 wt% when the water content is lower than 35 wt% within the range of 0.2-0.4 wt%, has small thixotropy, and can effectively decompose glue.
As can also be seen from Table 2, the nitrogen-containing polycarboxy acrylate copolymer water reducing agent prepared by the embodiment of the invention, under the conditions that the water quality of the ceramic wastewater containing 10 wt% and the water content of the slurry are 35 wt%, the fluidity is increased and the thixotropy is reduced along with the increase of the content of the nitrogenous polycarboxy acrylate monomer, as in example 3 (16 wt% of the nitrogen-containing polycarboxy acrylate monomer composition) → example 7 (16 wt% of the nitrogen-containing polycarboxy acrylate monomer composition) → example 1 (25 wt% of the nitrogen-containing polycarboxy acrylate monomer composition) → example 6 (30 wt% of the nitrogen-containing polycarboxy acrylate monomer composition) → example 2 (40 wt% of the nitrogen-containing polycarboxy acrylate monomer composition) the initial viscosities of the slurries at a use level of 0.2 wt% of the water reducing agent were 63.51s → 61.29s → 57.92s → 55.73s → 48.12s, respectively, and the thixotropy was 1.458 → 1.445 → 1.407 → 1.384 → 1.321; the initial viscosity of the slurry is 46.75s → 44.18s → 41.74s → 39.88s → 34.48s and the thixotropic property is 1.336 → 1.309 → 1.281 → 1.265 → 1.215 at the dosage of 0.4 wt% of the water reducing agent. It is also seen that as the amount of water reducing agent is increased (0.2 wt% → 0.4 wt%), the time for the slurry to flow out of the coating cup 4 is shortened, thixotropy is reduced, and fluidity is increased.
Table 3: ceramic slurry fluidity test result 2 of water reducing agent under different ceramic wastewater contents
The flow properties of the slurry when the amount of water reducing agent was increased and the ceramic wastewater content was increased were further tested as follows.
(4) Comparative experiment 3: the polymer solutions P1 and P2 prepared in the comparative example were added to the mixed solution of ceramic clay and ceramic waste water (including 20 wt% ceramic waste water +80 wt% deionized water and 40 wt% ceramic waste water +60 wt% deionized water) in the proportions of 0.4 wt% and 0.6 wt% of polymer solid/dry clay (ball clay powder for ceramic glaze BC01) at room temperature and 25 ℃ respectively, so that the total water content of the slurry was 38 wt% and 38 wt%, respectively, and after grinding for 10 minutes, the fluidity at room temperature and 25 ℃ was measured by using a 4-cup coater, and the experimental results are shown in Table 3;
(5) the water reducing agents prepared in the above examples 1 to 7 were added to the mixed solution of ceramic clay and ceramic wastewater of different contents (including 20 wt% ceramic wastewater, 80 wt% deionized water, and 40 wt% ceramic wastewater, and 60 wt% deionized water) in a ratio of 0.4 wt%, and 0.6 wt% of the water reducing agent solid/dry clay (ball clay powder for ceramic glaze BC01) at room temperature of 25 ℃ one by one, so that the total water content of the slurry was 36 wt%, 38 wt%, and 36 wt%, respectively, and after grinding for 10 minutes, the fluidity at room temperature of 25 ℃ was measured by a 4-cup coater, and the experimental results are listed in table 3.
As shown in the test results of the water reducing agent on the mud fluidity when the using amount of the water reducing agent and the content of the ceramic wastewater are increased in the table 3, the water reducing agent prepared in the embodiment of the invention has poor dispergation effect and large contact when the content of the ceramic wastewater reaches 40 wt%, and has excellent fluidity and small contact when the water content of the mud is lower than 36 wt% when the content of the ceramic wastewater is lower than 20 wt%, while the polymers P1 and P2 in the comparative example can not effectively dispergate when the using amount is higher than 0.6 wt% and the water content is higher than 38 wt%.
In addition, table 3 also shows that, when the ceramic wastewater content is 20 wt%, the time required for the slurry to flow out of the coating cup 4 is shortened with the increase of the amount of the water reducing agent (from 0.4 wt% → 0.6 wt%), the viscosity becomes lower, the fluidity increases, and the slurry still has good fluidity when the water content of the slurry is reduced. It can be further seen that the nitrogen-containing polycarboxy acrylate copolymer water reducing agent prepared by the embodiment of the invention, when the water content of the slurry with the water reducing agent of 0.6 wt% is 36 wt%, the fluidity is increased and the thixotropy is reduced along with the increase of the content of the nitrogenous polycarboxy acrylate monomer under the condition of the ceramic wastewater with the water content of 20 wt%, as in example 3 (16 wt% of the nitrogen-containing polycarboxy acrylate monomer composition) → example 7 (16 wt% of the nitrogen-containing polycarboxy acrylate monomer composition) → example 1 (25 wt% of the nitrogen-containing polycarboxy acrylate monomer composition) → example 6 (30 wt% of the nitrogen-containing polycarboxy acrylate monomer composition) → example 2 (40 wt% of the nitrogen-containing polycarboxy acrylate monomer composition), the initial viscosity of the slurry was 41.64s → 40.72s → 37.34s → 35.12s → 29.13s, and the thixotropy was 1.689 → 1.603 → 1.485 → 1.416 → 1.3, respectively.
From the test results shown in tables 2 and 3, the nitrogen-containing polycarboxy acrylate copolymer water reducing agent prepared by the invention can effectively unglue ceramic slurry when the content of the ceramic wastewater is below 20 wt% at a low slurry water content when the dosage is 0.4-0.6 wt%, and the slurry fluidity is increased along with the increase of the dosage of the water reducing agent or the increase of the slurry water content. Therefore, the nitrogen-containing polycarboxy acrylate copolymer water reducing agent prepared by the invention can utilize ceramic wastewater to a certain extent, and has remarkable social and economic benefits of energy conservation, emission reduction and the like.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a nitrogenous polycarboxy acrylate copolymer water reducing agent is characterized by comprising the following preparation methods:
mixing 10-45 parts by mass of a monomer shown in the formula (1) or a monomer solution (calculated by non-volatile parts) with 90-55 parts by mass of (meth) acrylate, 0-10 parts by mass of (meth) acrylic acid, a reducing agent and water, stirring after dissolving, dropwise adding a chain initiator solution at 40-50 ℃, and stopping dropwise adding after completing 1/2-2/3 dropwise adding; reacting at 50-70 ℃ for 0.5-1 hour, then dropwise adding the rest chain initiator solution, reacting at 50-70 ℃ for 4-2 hours after dropwise adding, adding a chain transfer agent solution, and cooling to obtain the nitrogenous polycarboxy acrylate copolymer water reducing agent;
2. the method according to claim 1, wherein the preparation of the monomer solution:
dissolving ethylenediamine tetraacetic dianhydride in a water-soluble organic solvent at the temperature of 60-70 ℃ to prepare an EDTAD solution with the weight percent of 15-30%, preserving heat, adding 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate, reacting for 4-2 hours, adding a carbonate or bicarbonate aqueous solution, neutralizing for 0.5-1 hour, and cooling to obtain the EDTAD solution, wherein the non-volatile content is 15-30 wt%; the molar ratio of the ethylenediamine tetraacetic dianhydride to the 2-hydroxyethyl (meth) acrylate or the 2-hydroxypropyl (meth) acrylate is 1: 1.
3. The method according to claim 2, wherein the water-soluble organic solvent is one or both of dimethylformamide and dimethylacetamide.
4. The production method according to claim 1, 2 or 3, wherein the chain initiator is hydrogen peroxide, and the reducing agent is ascorbic acid or N-hydroxydiethylamine; the chain terminator is one or two of potassium hypophosphite and sodium hypophosphite.
5. The preparation method according to claim 4, wherein the total amount of the (meth) acrylate and the (meth) acrylic acid is 60-85 wt% of the total amount of the water reducing agent monomers.
6. The method according to claim 5, wherein the amount of the chain initiator is 0.5 to 2 wt% of the total amount of the monomers, the amount of the reducing agent is 0.4 to 1.5 wt% of the total amount of the monomers, and the amount of the terminating agent is 0.1 to 0.3 wt% of the total amount of the monomers.
7. The method according to claim 6, wherein the solvent in the chain initiator solution and the chain terminator solution is water, the concentration of the chain initiator solution is 2-10 wt%, and the concentration of the chain terminator solution is 5-10 wt%; the total content of all monomers accounts for 20-40 wt% of the total weight of the water reducing agent.
8. The preparation according to claim 1 or 2 or 3, characterized in that: the stirring speed is 100-350 rpm, and the dropping speed is 7-20 drops/min.
9. The nitrogen-containing polycarboxy acrylate copolymer water reducing agent prepared by the method of any one of claims 1 to 8.
10. The use of the water reducer of claim 9 in the recycling of ceramic wastewater.
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