CN114380955B - Siliceous modified polycarboxylic acid reinforcing agent for refractory material and preparation method thereof - Google Patents
Siliceous modified polycarboxylic acid reinforcing agent for refractory material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a siliceous modified polycarboxylic acid reinforcing agent for refractory materials and a preparation method thereof, which are characterized in that: the polycarboxylic acid is modified by using colloidal silica, lithium silicate or a mixture thereof to obtain a polymer reinforcing agent containing silicon or silicon oxide groups, and an excessive amount of silicon or silicon oxide remains in the system. The siliceous modified polycarboxylic acid reinforcing agent has good dispersibility, improves the fluidity of the additive in the unshaped refractory material, can improve the mechanical strength of the unshaped refractory material, and inhibits the strength reduction of the unshaped refractory material at high temperature.
Description
Technical Field
The invention relates to a refractory material additive, in particular to a reinforcing agent for refractory materials and a preparation method thereof, and especially relates to a siliceous modified polycarboxylic acid reinforcing agent and a preparation method thereof.
Background
The unshaped refractory material using high alumina cement as the cementing material has wide application in industrial construction. Compared with the sintered refractory, the unshaped refractory has the advantages of energy conservation, good integrity, flexibility in adjustment of composition, high production efficiency, good comprehensive use effect and the like, and therefore, the unshaped refractory has very rapid development. During construction and use, the unshaped refractory materials, particularly refractory castable and pumpable materials, are required to have good flowability and as little water usage as possible, thereby improving the strength of the refractory materials. The high alumina cement-based refractory material has a tendency of crystal form conversion at high temperature along with the service time, and the strength of the material subjected to crystal form conversion is obviously reduced.
In the field of refractory materials, high alumina cement is mainly used as a binding agent in unshaped refractory castable to prepare quick-hardening and high-strength mortar or concrete, shrinkage-free or micro-expansion dry-mixed mortar or concrete and sulfate corrosion-resistant mortar or concrete. The main driving force for the development of the unshaped refractory material is the superfine powder technology and the water reducing agent, and the water reducing agent with good dispersion performance is required to be relied on to uniformly disperse the superfine powder, so that the water reducing agent plays a vital role in the development of the unshaped refractory material.
The polycarboxylic acid has the surface activity in the high alumina cement, and can improve the compactness of the refractory material, thereby improving the mechanical strength of the refractory material. The Chinese patent No. 103922764A discloses a bonding agent for unshaped refractory materials, which comprises the following raw materials in parts by mass: 30-70% of aluminum oxide, 20-60% of magnesium oxide and 5-20% of excitant, wherein the excitant is a mixture of metasilicic acid, polycarboxylic acid and simple substance silicon, the mass fraction of the metasilicic acid in the excitant mixture is 40-80%, the mass fraction of the polycarboxylic acid in the excitant mixture is 0-40%, and the mass fraction of the simple substance silicon in the excitant mixture is 0-50%. The binding agent is used in aluminate cement-based refractory materials, and enables aluminum oxide and magnesium oxide to be controllably and rapidly coagulated in aqueous solution to generate binding strength.
However, the dispersibility and fluidity of the binder in the unshaped refractory material are still to be improved, and at the same time, the mixing of the simple substance silicon has a certain inhibition effect on the high-alumina cement to be converted into the high Wen Xiajing type, but the mixing of the simple substance mode has the same problems of dispersibility and the like.
Disclosure of Invention
The invention aims to provide a siliceous modified polycarboxylic acid reinforcing agent for refractory materials, which is used for improving the dispersibility and mechanical strength of an amorphous alumina cement-based refractory material and simultaneously inhibiting the strength reduction of alumina cement at high temperature.
Another object of the present invention is to provide a process for the preparation of siliceous modified polycarboxylic acid reinforcing agents for refractory materials.
In order to achieve the aim of the invention, the invention adopts the following technical scheme: a siliceous modified polycarboxylic acid reinforcing agent for refractory materials comprises a main component of siliceous modified polycarboxylic acid polymer, and has the following structural general formula:
wherein: m is M 1 One or more selected from hydrogen ions, monovalent metal ions and divalent metal ions;
M 2 one or more selected from hydrogen ions, monovalent metal ions and divalent metal ions;
R 1 is H or-CH 3
R 2 is-CH 3 or-C 2 H 5
R 3 Is H or-CH 3
R 4 is-H 2 or-COOM 1
R 5 is-C 2 H 5 or-C 3 H 7
R 6 Is H or-CH 3
R 7 Is CONHC (CH) 3 ) 2 CH 2
R8 is H or-CH 3
R9 is C 2 H 5 O or C 3 H 7 O
a is a positive integer, b, c, d, e, n 1 、n 2 Are allAn integer of zero or more and not zero at the same time, and the molecular weight is 5000-20000.
In the above technical scheme, the siliceous modified polycarboxylic acid polymer contains silicon or silicon oxide groups in the molecule, and excessive silicon or silicon oxide remains in the reinforcing agent system. The polymer molecule has a comb structure.
In order to achieve another object of the present invention, there is provided a method for producing a siliceous modified polycarboxylic acid reinforcing agent for refractory materials, comprising the steps of:
(1) Dissolving a monomer B, C, D containing unsaturated double bonds and a macromolecular active monomer A containing carboxyl or anhydride groups, sulfonic groups and ester groups in deionized water respectively, stirring and dissolving, adding an oxidant, dropwise adding an aqueous solution of a molecular weight regulator and a reducing agent, simultaneously dropwise adding an aqueous solution of a silane monomer E containing alkenyl groups, carrying out free radical copolymerization at 10-90 ℃, keeping the temperature for half an hour after the dropwise adding is finished, adjusting the pH value to 7.5-9.5 after the constant temperature is finished, dropwise adding a monomer F while stirring for 30 minutes-3 hours, continuing to keep the constant temperature, and keeping the system temperature below 40 ℃ after the reaction is finished to prepare a siliceous modified polycarboxylic acid reinforcing agent mother solution;
wherein, the monomer A is selected from isopentenyl alcohol polyoxyethylene ether (TPEG 2400), isobutenyl alcohol polyoxyethylene ether (HPEG 2400) and six-carbon polyether (GPEG 3000);
the monomer F is colloidal silicon dioxide, lithium silicate or a mixture thereof;
(2) And (3) spray drying the siliceous modified polycarboxylic acid reinforcing agent mother liquor prepared in the step (1) to obtain the siliceous modified polycarboxylic acid reinforcing agent for refractory materials.
In the above technical scheme, sodium hydroxide, calcium hydroxide, potassium hydroxide, ammonia or organic amine and aqueous solutions thereof can be selected for adjusting the pH value.
In the technical scheme, the mol ratio of the monomer A, B, C, D, E is 1:1-5.5:0.1-0.5:1-3:0.01-0.03, and the monomer F is 10-20% of the mass of the monomer A.
In a preferred embodiment, the monomer B is selected from acrylic acid, methacrylic acid, itaconic acid, citric acid, and maleic anhydride.
In a preferred embodiment, the monomer C is selected from sodium allylsulfonate, sodium methallylsulfonate, 2-acrylamido-2-methylpropanesulfonic acid.
In a preferred technical scheme, the monomer D is selected from hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and glyceryl itaconate.
In a preferred embodiment, the monomer E is selected from vinyltrimethoxysilane, vinyltriethoxysilane, propenyl trimethoxysilane, propenyl triethoxysilane, silica sol or mixtures thereof.
According to the preferable technical scheme, the monomer F is a mixture of colloidal silicon dioxide and lithium silicate, and the mass ratio of the colloidal silicon dioxide to the lithium silicate=8-9:2-1.
In the technical scheme, the molecular weight regulator is selected from thioglycollic acid, mercaptopropionic acid, mercaptoethanol, sodium bisulphite and sodium methallyl sulfonate, and the molecular weight regulator is 0.1-0.5% of the mass of the monomer A; the oxidant is ammonium persulfate, potassium persulfate, sodium persulfate or a mixture thereof, and the oxidant is 0.3-0.8% of the mass of the monomer A; the reducing agent is vitamin C, sodium bisulphite, sodium thiosulfate, sodium bisulphite formaldehyde or a mixture thereof, and the reducing agent accounts for 0.05-0.2% of the mass of the monomer A.
The reinforcing agent of the present invention can be used in refractory materials together with known dispersing agents, retarders, air entraining agents, early strength agents, defoamers.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
1. compared with the prior art, the side chain of the siliceous modified polycarboxylic acid reinforcing agent introduces silane groups to play a role of steric hindrance, and the molecular weight of the additive is controlled by utilizing the molecular weight regulator to obtain a polymer with proper molecular weight and uniform molecular weight distribution, so that the siliceous modified polycarboxylic acid reinforcing agent is more suitable for unshaped refractory materials and has better dispersibility.
2. The siliceous modified polycarboxylic acid reinforcing agent synthesized by the invention improves the fluidity of the additive in unshaped refractory materials.
3. The invention utilizes silicon or silicon oxygen polymer to carry out physical and chemical modification on high molecular polymer, improves the high temperature performance of unshaped refractory material and improves the high temperature strength.
Detailed Description
The invention is further described below with reference to examples:
example 1:
230g (0.1 mol) of isopentenyl polyoxyethylene ether, 24.5g (0.5 mol) of maleic anhydride, 1.58g (0.01 mol) of sodium methacrylate, 23.2g (0.2 mol) of hydroxyethyl acrylate and 230g of deionized water are weighed into a four-necked flask to be stirred and dissolved, 1.38g of oxidant sodium persulfate and 0.296g (0.002 mol) of vinyl trimethoxysilane are dropwise added into a reactor, simultaneously 0.92g of thioglycollic acid and 20g of deionized water are dropwise added into the reactor, the temperature is controlled between 75 ℃ and 80 ℃, dropwise addition is completed within 3 hours, the constant temperature is kept for half an hour, sodium hydroxide is used for adjusting the pH value to 8.5, 61.3g of 30% colloidal silica and 4.6g of lithium silicate mixture (silica: lithium silicate: mass ratio of 8:2) solution are dropwise added while stirring, the mixture is continuously kept constant temperature for half an hour, the sample solution is cooled to below 40 ℃ after the half an hour, and deep yellow powder is obtained through high temperature spray drying.
The main composition of the silica fume free unshaped refractory tested for net slurry fluidity is shown in the following table.
| Material | Dosage/g |
| Micro powder (corundum, alumina) | 115 |
| High alumina cement | 17 |
| Water and its preparation method | 25 |
| Siliceous modified polycarboxylic acid reinforcing agent | 0.36 |
Example 2:
230g (0.1 mol) of isobutene polyoxyethylene ether, 34.4g (0.4 mol) of methacrylic acid, 2.88g (0.02 mol) of sodium acrylate, 19.5g (0.15 mol) of hydroxypropyl acrylate and 230g of deionized water are weighed into a four-necked flask to be stirred and dissolved, 1.15g of oxidant ammonium persulfate and 0.285g (0.002 mol) of vinyl triethoxysilane are dropwise added into a reactor together with 50g of deionized water solution, 0.46g of mercaptopropionic acid, 0.184g of vitamin C and 20g of deionized water solution are dropwise added into the reactor, the temperature is controlled between 50 ℃ and 55 ℃, the dropwise addition is completed within 2.5 hours, the constant temperature is kept for half an hour, the pH is adjusted to 8 by using calcium hydroxide, the mass ratio of 61.3g of 30% colloidal silica to 4.6g of lithium silicate mixture (silica: lithium silicate is 8:2) is dropwise added while stirring, the constant temperature is kept for half an hour, and the constant temperature is cooled to below 40 ℃. The sample solution was spray dried at high temperature to give pale yellow powder.
Example 3:
300g (0.1 mol) of novel water reducer polyether monomer (GPEG), 25.2g (0.35 mol) of acrylic acid, 3.1g (0.015 mol) of 2-acrylamide-2-methylpropanesulfonic acid, 13g (0.10 mol) of hydroxyethyl methacrylate and 230g of deionized water are weighed into a four-neck flask to be stirred and dissolved, 4.8g of oxidant 50% hydrogen peroxide and 0.486g (0.003 mol) of propenyl trimethoxysilane are added dropwise into a reactor together with 50g of deionized water solution, 0.9g of mercaptopropionic acid, 0.3g of sodium bisulfate formaldehyde and 20g of deionized water solution are added dropwise into the reactor simultaneously, the temperature is controlled to be between 35 and 40 ℃, the dripping is completed within 1.5 hours, the PH is regulated to 8.5 by using organic amine while stirring, 80g of colloidal silica with the concentration of 30% and 6g of lithium silicate mixture (the mass ratio of silicon dioxide: lithium silicate is 8:2) are dropwise added while keeping constant temperature for half an hour, and the sample is continuously dried through high spray drying to obtain pale yellow powder.
Example 4:
150g (0.05 mol) of novel water reducer polyether monomer (GPEG), 115g (0.05 mol) of isobutene polyoxyethylene ether, 21.6g (0.30 mol) of acrylic acid, 4.74g (0.03 mol) of sodium 2-methyl propylene sulfonate, 19g (0.10 mol) of itaconic acid glyceride and 230g of deionized water are weighed into a four-port flask to be stirred and dissolved, 0.93g of ammonium persulfate and 1.86g of hydrogen peroxide with concentration and 0.204g (0.003 mol) of propenyl triethoxysilane and 50g of deionized water are dropwise added into the reactor, 0.66g of mercaptoethanol, 0.3g of sodium bisulfate, 0.3g of sodium thiosulfate and 20g of deionized water are dropwise added into the reactor at the same time, natural temperature rise is achieved within 2 hours, constant temperature is kept for half an hour, 61.3g of solution of mixture of 30% colloidal silica and 4.6g of lithium silicate (silicon dioxide: lithium mass ratio of 8:2) is dropwise added while stirring, and the mixture of the silicon dioxide and the solution is dropwise added at the same time is kept at the same temperature, and the mixture is kept at the same time, and a pale yellow powder is obtained after the semi-hour of drying of the sample is continuously sprayed and the semi-finished.
Comparative example 1:
230g (0.1 mol) of isopentenyl polyoxyethylene ether, 24.5g (0.5 mol) of maleic anhydride, 1.58g (0.01 mol) of sodium methacrylate, 23.2g (0.2 mol) of hydroxyethyl acrylate and 230g of deionized water are weighed into a four-necked flask to be stirred and dissolved, 1.38g of oxidant sodium persulfate and 0.296g (0.002 mol) of vinyl trimethoxysilane are dropwise added into a reactor, and simultaneously 0.92g of thioglycollic acid and 20g of deionized water are dropwise added into the reactor, the temperature is controlled between 75 ℃ and 80 ℃, the dropwise addition is completed within 3 hours, the constant temperature is kept for half an hour, the PH is adjusted to 8.5 by sodium hydroxide, the temperature is reduced and cooled to below 40 ℃, and the sample solution is subjected to high-temperature spray drying to obtain deep yellow powder.
Comparative example 2:
230g (0.1 mol) of isobutene polyoxyethylene ether, 34.4g (0.4 mol) of methacrylic acid, 2.88g (0.02 mol) of sodium acrylate, 19.5g (0.15 mol) of hydroxypropyl acrylate and 230g of deionized water are weighed into a four-necked flask to be stirred and dissolved, 1.15g of oxidant ammonium persulfate and 0.285g (0.002 mol) of vinyl triethoxysilane are added dropwise into a reactor, and simultaneously 0.46g of mercaptopropionic acid, 0.184g of vitamin C and 20g of deionized water are added dropwise into the reactor, the temperature is controlled between 50 ℃ and 55 ℃, the dropwise addition is completed within 2.5 hours, the constant temperature is kept for half an hour, the PH is regulated to 8 by using calcium hydroxide, and the temperature is reduced and cooled to below 40 ℃. The sample solution was spray dried at high temperature to give pale yellow powder.
Comparative example 3:
300g (0.1 mol) of novel water reducer polyether monomer (GPEG), 25.2g (0.35 mol) of acrylic acid, 3.1g (0.015 mol) of 2-acrylamide-2-methylpropanesulfonic acid, 13g (0.10 mol) of hydroxyethyl methacrylate and 230g of deionized water are weighed into a four-necked flask to be stirred and dissolved, 4.8g of oxidant solution with 50 percent concentration hydrogen peroxide and 0.486g (0.003 mol) of propenyl trimethoxysilane are dropwise added into a reactor, 0.9g of mercaptopropionic acid, 0.3g of sodium bisulfate formaldehyde and 20g of deionized water solution are dropwise added into the reactor, the temperature is controlled to be between 35 and 40 ℃, dropwise addition is completed within 1.5 hours, the mixture is kept at a constant temperature for half an hour, the PH is adjusted to 8.5 by using organic amine, and the sample solution is subjected to high-temperature spray drying to obtain pale yellow powder.
Comparative example 4:
150g (0.05 mol) of novel water reducer polyether monomer (GPEG), 115g (0.05 mol) of isobutylene polyoxyethylene ether, 21.6g (0.30 mol) of acrylic acid, 4.74g (0.03 mol) of sodium 2-methyl propylene sulfonate, 19g (0.10 mol) of itaconic acid glyceride and 230g of deionized water are weighed into a four-port flask to be stirred and dissolved, 0.93g of ammonium persulfate, 1.86g of hydrogen peroxide with concentration and 0.204g (0.003 mol) of propenyl triethoxysilane and 50g of deionized water are added dropwise into a reactor, 0.66g of mercaptoethanol, 0.3g of sodium bisulfate formaldehyde, 0.3g of sodium thiosulfate and 20g of deionized water are added dropwise into the reactor simultaneously, natural temperature rising is achieved, the dropwise adding is completed within 2 hours, the constant temperature is kept for half an hour, the PH is adjusted to 7.5, and the sample solution is subjected to high-temperature spray drying to obtain pale yellow potassium hydroxide powder.
Comparative example 5:
150g (0.05 mol) of novel water reducer polyether monomer (GPEG), 115g (0.05 mol) of isobutene polyoxyethylene ether, 21.6g (0.30 mol) of acrylic acid, 4.74g (0.03 mol) of sodium 2-methyl propylene sulfonate, 19g (0.10 mol) of itaconic acid glyceride and 230g of deionized water are weighed into a four-port flask to be stirred and dissolved, 0.93g of ammonium persulfate, 1.86g of hydrogen peroxide with concentration and 0.204g (0.003 mol) of propenyl triethoxysilane and 50g of deionized water are dropwise added into the reactor, 0.66g of mercaptoethanol, 0.3g of sodium bisulfate, 0.3g of sodium thiosulfate and 20g of deionized water are dropwise added into the reactor, natural temperature rising is achieved within 2 hours, constant temperature half an hour is achieved, 88.3g of colloidal silica solution with concentration being dropwise added while stirring, half an hour is completed dropwise adding is continued, and constant temperature half an hour is continued, and the sample solution is subjected to high temperature spray drying, so as to obtain pale yellow powder.
Comparative example 6:
150g (0.05 mol) of novel water reducer polyether monomer (GPEG), 115g (0.05 mol) of isobutene polyoxyethylene ether, 21.6g (0.30 mol) of acrylic acid, 4.74g (0.03 mol) of sodium 2-methyl propylene sulfonate, 19g (0.10 mol) of itaconic acid glyceride and 230g of deionized water are weighed into a four-port flask to be stirred and dissolved, 0.93g of ammonium persulfate, 1.86g of hydrogen peroxide with concentration and 0.204g (0.003 mol) of propenyl triethoxysilane and 50g of deionized water are dropwise added into the reactor, 0.66g of mercaptoethanol, 0.3g of sodium bisulfate, 0.3g of sodium thiosulfate and 20g of deionized water are dropwise added into the reactor, natural heating is finished within 2 hours, the constant temperature is kept for half an hour, the PH is adjusted to 7.5, 26.5g of lithium silicate solution is dropwise added while stirring, the dropwise adding is finished for half an hour, the constant temperature is continued for half an hour, and the sample solution is subjected to spray drying at high temperature, so as to obtain pale yellow potassium hydroxide powder.
Comparative example 7:
150g (0.05 mol) of novel water reducer polyether monomer (GPEG), 115g (0.05 mol) of isobutylene polyoxyethylene ether, 21.6g (0.30 mol) of acrylic acid, 4.74g (0.03 mol) of 2 sodium methyl propylene sulfonate, 19g (0.10 mol) of itaconic acid glyceride and 230g of deionized water are weighed into a four-necked flask to be stirred and dissolved, 0.93g of ammonium persulfate, 1.86g of hydrogen peroxide with concentration of 50% and 0.204g (0.003 mol) of propenyl triethoxysilane and 50g of deionized water are dropwise added into the reactor, 0.66g of mercaptoethanol, 0.3g of sodium bisulfate formaldehyde, 0.3g of sodium thiosulfate and 20g of deionized water are dropwise added into the reactor, natural temperature rising is achieved within 2 hours, and the obtained product is dropwise added with potassium silicate under an ultrasonic dispersion state to enable the pH of the system to be 10. The sample solution was spray dried at high temperature to give pale yellow powder.
The slurry fluidity of the refractory powder system and the compressive strength after firing at 1400℃for 5 hours were measured according to the unshaped refractory composition formulation in example 1. The results are shown in the following table:
as can be seen from the table, the addition of the silica and lithium silicate mixtures in examples 1-4 provides little change in the net slurry flow relative to comparative examples 1-4, but the addition of the silica and lithium silicate mixtures significantly improves the refractory high temperature strength, and comparative examples 5-7 provide a single colloidal silica or lithium silicate, potassium silicate in the formulation of comparative example 4, and provide an improvement in the high temperature strength relative to comparative example 4, but still less than the high temperature strength of example 4.
Claims (9)
1. A method for preparing a siliceous modified polycarboxylic acid reinforcing agent for refractory materials, which is characterized by comprising the following steps:
(1) Dissolving a monomer B, C, D containing unsaturated double bonds and a macromolecular active monomer A containing carboxyl or anhydride groups, sulfonic groups and ester groups in deionized water respectively, stirring and dissolving, adding an oxidant, dropwise adding an aqueous solution of a molecular weight regulator and a reducing agent, simultaneously dropwise adding an aqueous solution of a silane monomer E containing alkenyl groups, carrying out free radical copolymerization at 10-90 ℃, keeping the temperature for half an hour after the dropwise adding is finished, adjusting the pH value to 7.5-9.5 after the constant temperature is finished, dropwise adding a monomer F while stirring for 30 minutes-3 hours, continuing to keep the constant temperature, and keeping the system temperature below 40 ℃ after the reaction is finished to prepare a siliceous modified polycarboxylic acid reinforcing agent mother solution;
wherein the monomer A is selected from isopentenyl alcohol polyoxyethylene ether, isobutenyl alcohol polyoxyethylene ether and six-carbon polyether;
monomer F is a mixture of colloidal silicon dioxide and lithium silicate;
(2) And (3) spray drying the siliceous modified polycarboxylic acid reinforcing agent mother liquor prepared in the step (1) to obtain the siliceous modified polycarboxylic acid reinforcing agent for refractory materials.
2. The method for producing a siliceous modified polycarboxylic acid reinforcing agent for refractory according to claim 1, wherein: the mol ratio of the monomer A, B, C, D, E is 1:1-5.5:0.1-0.5:1-3:0.01-0.03, and the monomer F accounts for 10-20% of the mass of the monomer A.
3. The method for producing a siliceous modified polycarboxylic acid reinforcing agent for refractory according to claim 1, wherein: the monomer B is selected from acrylic acid, methacrylic acid, itaconic acid and maleic anhydride.
4. The method for producing a siliceous modified polycarboxylic acid reinforcing agent for refractory according to claim 1, wherein: the monomer C is selected from sodium allylsulfonate, sodium methallyl sulfonate and 2-acrylamide-2-methylpropanesulfonic acid.
5. The method for producing a siliceous modified polycarboxylic acid reinforcing agent for refractory according to claim 1, wherein: the monomer D is selected from hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate and glyceryl itaconate.
6. The method for producing a siliceous modified polycarboxylic acid reinforcing agent for refractory according to claim 1, wherein: the monomer E is selected from vinyltrimethoxysilane, vinyltriethoxysilane, propenyl trimethoxysilane, propenyl triethoxysilane or a mixture thereof.
7. The method for producing a siliceous modified polycarboxylic acid reinforcing agent for refractory according to claim 1, wherein: the monomer F is a mixture of colloidal silicon dioxide and lithium silicate, and the mass ratio of the colloidal silicon dioxide to the lithium silicate=8-9:2-1.
8. The method for producing a siliceous modified polycarboxylic acid reinforcing agent for refractory according to claim 1, wherein: the molecular weight regulator is selected from thioglycollic acid, mercaptopropionic acid, mercaptoethanol, sodium bisulphite and sodium methallyl sulfonate, and the molecular weight regulator is 0.1-0.5% of the mass of the monomer A; the oxidant is ammonium persulfate, potassium persulfate, sodium persulfate or a mixture thereof, and the oxidant is 0.3-0.8% of the mass of the monomer A; the reducing agent is vitamin C, sodium bisulphite, sodium thiosulfate, sodium bisulphite formaldehyde or a mixture thereof, and the reducing agent accounts for 0.05-0.2% of the mass of the monomer A.
9. A siliceous modified polycarboxylic acid reinforcing agent for refractory produced by the production method according to any one of claims 1 to 8.
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