CN101838122B - Compound additive of unshaped refractory material system, preparation method and application - Google Patents

Compound additive of unshaped refractory material system, preparation method and application Download PDF

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CN101838122B
CN101838122B CN 200910047858 CN200910047858A CN101838122B CN 101838122 B CN101838122 B CN 101838122B CN 200910047858 CN200910047858 CN 200910047858 CN 200910047858 A CN200910047858 A CN 200910047858A CN 101838122 B CN101838122 B CN 101838122B
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fluidizer
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acid
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CN101838122A (en
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高群
王礼玮
赵玲娣
杨玲
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Shanghai Kerui Metallurgical Furnace Burden Co ltd
SHANGHAI PENGPU SPECIAL REFRACTORY FACTORY
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Shanghai Kerui Metallurgical Furnace Burden Co ltd
SHANGHAI PENGPU SPECIAL REFRACTORY FACTORY
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Abstract

The invention relates to a multifunctional compound additive of an unshaped refractory material, a preparation method and application, suitable for an unshaped refractory material system without silica fume. The preparation method comprises the following steps of: (1) copolymerizing free radicals of monomers respectively containing unsaturated double-bonds of carboxyl, sulfonic groups and estolide groups and a macromolecular active monomer containing double-bond polyethylene glycol or ether in an aqueous solution at 60-90 DEG C, wherein the dosage of a molecular weight regulator mercaptoethanol is 2-10 percent of monomers by weight, the dosage of an initiator is 2-10 percent of monomers by weight, the reaction lasts 4-8h, the mol ratio of the main functional groups: sulfonic groups/ carboxyl/ estolide groups in the monomers is 1: (1-5): (1-3), and the mold ratio of the polyethylene glycol or ether to the sulfonic groups is 1: (5-10); and (2) respectively mixing the synthetic product with a retarder or a coagulant according to a weight ratio of 1: (1-0.1) and then spraying and drying. The compound additive prepared by the method has higher water-reducing rate and favorable fluidity and fluidity-keeping performance, and the condensing time can be adjusted according to the construction requirements and environmental temperature variance.

Description

The compound additive of unshaped refractory material system, preparation method and application
Technical field
The present invention relates to a kind of multi-functional compound additive of unshape refractory, preparation method and application of not siliceous ash, belong to the refractory additive technical field.
Background technology
In recent years, because high-quality, high-performance raw material comprise the employing of wedding agent, the application of ultrafine powder and dispersion technology, the introducing of efficient additive, the FR optimization of size-grade distribution, introduce some non-oxidized substance and make oxide compound-non-oxidized substance matrix material, adopt novel advanced constructional method and the reinforcement of fundamental research etc., unshape refractory is very active in the development of aspects such as material, kind, performance, construction, application.
Unshape refractory requirement wedding agent has dispersiveness, the oilness to the refractory particle material, from keeping on the meaning of filling tissue, needs hardening strength simultaneously.And unshape refractory is owing to adopt low pressure, and that perhaps utilizes deadweight or vibration flows filling molding, so the quality of wedding agent determines the compactness of formed body and even the performance of refractory materials.The operation technique of wedding agent has become one of most important factor that determines the unshape refractory performance.
The articulated system of unshape refractory mainly comprises cement wedding agent and fluidizer (polymer wedding agent).It is the mould material of wedding agent that high-alumina cement has appearred in nineteen sixty, occurred low cement and ultra-low cement deposit material after the eighties, the main component of used cement is replaced with superplasticizer by the dispersed fine powder of polymolecularity or superelevation such as silicon ash, activated alumina etc.
Unshape refractory then is a kind of novel articulated system that integrates dispersiveness, flowability, water reducing ability that grew up in recent years with polymeric admixture, and its main effect comprises 2 points: (1) plastification.Be used for improving the flowability of unshape refractory, thereby but but improve its workability pumping.(2) water-reduction: improve physicals, the physical strength of refractory materials by the consumption that reduces water, increase the service life.
Unshape refractory uses polymeric admixture to start from the nineties in 20th century, and it is base growth with third generation concrete polycarboxylate water-reducer.The development of cement water reducing agent is divided into following three phases: be the first-generation ordinary water-reducing agent stage of representative with wooden calcium; Be the s-generation high efficiency water reducing agent stage of representative and be the third generation high-performance water reducing agent stage of representative with the polycarboxylic acid series with naphthalene.Poly carboxylic acid series concrete high efficiency water reducing agent is novel, the environmental type high-performance water reducing agent of generally acknowledging both at home and abroad, and the great advantage of this class water reducer is the water-reducing rate height, concrete slump through the time loss little, concrete intensity height, good to the adaptability of cement.At present both at home and abroad polycarboxylate water-reducer has been carried out a large amount of for many years fundamental research and applied research, domestic also industrialization, external polycarboxylate water-reducer has accounted for the 40-50% of water reducer gross weight, and domestic application also increases gradually.
Because concrete and unshape refractory are essentially different at composition, so polycarboxylate water-reducer can not directly apply to unshape refractory.Manufacturer's major part of domestic unshape refractory is still used phosphoric acid salt articulated systems such as traditional tripoly phosphate sodium STPP or Sodium hexametaphosphate 99, though, described phosphoric acid salt articulated system exists the defective of aspects such as the low and degree of mobilization loss of hot strength is bigger, but low price.A small amount of producer uses the polymeric admixture system of offshore company, though it is little, expensive to add consumption, has significantly increased product cost, has therefore limited application and the popularization at home of this series products.
The common phosphoric acid salt admixture, polyacrylic ester also has been applied to unshaped refractory material system (N.Bunt, et al., LAFARGE, UNITECR in unshape refractory; Vol, 3, p.1347,1997, New Orleans), its main component is the copolymerization product of acrylic or methacrylic acid and various esters of acrylic acids, but its flowability is compared no clear superiority with phosphoric acid salt, the slump is bigger, can't satisfy the more and more higher requirement to refractory materials serviceability and hot strength at present.US5739212 has proposed a kind of main chain and side chain all is the refractory materials fluidizer that polyoxyethylene and polyoxypropylene graft copolymerization obtain, can be applicable to gravity flow pouring material, have higher flowability and less slump-loss for the refractory material system of siliceous ash not.Yet because the synthesis material reactive behavior is low, preparation technology needed for two steps finished, the temperature of reaction height, and complex process, it has higher gas retaining simultaneously, causes the refractory materials high-temperature behavior to reduce.
The research at home of unshape refractory compound additive still is a multi-functional compound additive that blank, particularly time of coagulation the are controlled also application of relevant patent at home and abroad.Along with developing rapidly of domestic unshape refractory, increasing to the demand of wedding agent.The development of this product has great importance for the development that promotes domestic unshape refractory and the raising of state of the art.
Summary of the invention
In order to overcome the shortcoming of at present used unshape refractory fluidizer, the object of the present invention is to provide a kind of for not multi-functional compound additive, preparation method and the application of the unshape refractory of siliceous ash.It is characterized in that described compound additive be by poly carboxylic acid fluidizer and retardant and/or setting accelerator by mass ratio 1: the 1-0.1 mixed forms;
Described poly carboxylic acid fluidizer molecule has following structure:
Figure G2009100478582D00031
R wherein 1=H or CH 3R 2=CH 2Or
Figure G2009100478582D00032
R 3=H or CH 3
R 4=H or CH 3R 5=-O-or-COO-; R 6H or CH 3
The preparation process of described compound additive comprises following two steps:
(1) at first prepares a kind of poly carboxylic acid fluidizer;
(2) with above-mentioned synthetic product respectively with retardant and/or setting accelerator according to weight ratio 1: 1~0.1 mixed, spraying drying then.
Concrete steps are as follows: will have carboxyl respectively, the monomer that contains unsaturated double-bond of sulfonic group and anhydride group and the double bond containing macrogol ester of macromole reactive monomer or polyglycol ether (MPEG) are soluble in water, under nitrogen atmosphere, under molecular weight regulator and action of evocating, carry out free-radical polymerized, the temperature of reaction of solution is 60-90 ℃, total reaction times is 4~8h, wherein, molecular weight regulator is mercaptoethanol, initiator is persulphate or persulphate-sodium bisulfite, the add-on of mercaptoethanol is 2~10% of total monomer weight, the add-on of initiator is 2~10% of total monomer weight, has sulfonic monomer, monomer with carboxyl, mol ratio with monomer of anhydride group is 1: 1~5: 1~3, macrogol ester or polyglycol ether and to have sulfonic mol ratio be 1: 5~10.The weight ratio of monomer and water is 1: 1~3.
Among the present invention, the described monomer that contains unsaturated double-bond with carboxyl be in vinylformic acid, methacrylic acid or the methylene-succinic acid any.
Among the present invention, described have sulfonic monomer be in 2-acrylamide-2-methyl propane sulfonic acid, methylpropene sodium sulfonate or the sodium allylsulfonate any.
The poly carboxylic acid fluidizer with polarity anion active group such as SO 3 -, COO -Deng the cement particle surface that is adsorbed on strong polarity by interactions such as ionic linkage, covalent linkage, hydrogen bond and Van der Waals forces tightly, thereby make cement granules charged, same sex electric charge repels each other, stoped approaching mutually of adjacent cement granules, increased the contact area of cement and water, made the abundant aquation of cement, and in the process of cement granules diffusion, discharge the free-water that aggregate comprises, improved workability, reduced and mixed the water yield.R-COO -With Ca 2+Ionization forms complex compound, reduces the Ca in the solution 2+Ionic concn delays Ca (OH) 2Form crystallization, reduce the formation of C-H-S gel, delayed hydrated cementitious, so carboxyl has significant delayed coagulation, this retarding effect is favourable to flowability and the retentivity thereof of cement slurry.Studies show that, sulfonic acid group is conducive to the increase of degree of mobilization, and carboxylic acid has tangible delayed coagulation, based on above understanding, therefore these two groups are as main functional group in synthetic product of the present invention, the mol ratio of sulfonic acid group and carboxyl group has significant effects to flowability and the retentivity of product, so select both mol ratio (sulfonic group/carboxyl)=1: 1~5.Suitable mol ratio is sulfonic group/carboxyl=1: 2~3.
Among the present invention, described monomer with anhydride group is maleic anhydride or itaconic anhydride.Cement is a kind of material with hydration activity, newly mixes the cement slurry slump and reduces in time, and be the normal phenomenon in the cement setting process of setting.The initial flow of cement slurry depends on the initial adsorption amount of fluidizer on the cement particle surface unit surface, and the initial release amount is more big, and then the initial flow of cement slurry is more good; The flowability of cement slurry keeps effect then to depend on after for some time the concentration of fluidizer in the cement slurry solution, and concentration is more big, and then the effect that keeps of the flowability of cement slurry is more good.The anhydride group that maleic anhydride and itaconic anhydride have, in the alkaline water-based slurry of fire-resistant micro mist and high-alumina cement, hydrolysis slowly can take place, produce more carboxyl, therefore constantly replenish the polar group that is consumed in the hydration process, thereby improve the degree of mobilization retention of polymkeric substance.
Among the present invention, described pair of key macromole reactive monomer comprises any of polyethylene glycol monomethyl ethermethacrylic acid esters, allyl polyglycol ether, and the molecular weight control of macromole reactive monomer is 500~3000.Introduced side chain in molecular structure, main effect provides space steric effect, when be adsorbed with the macromolecular cement granules of polycarboxylate water-reducer near the time, the side chain of polyethers is more long in the poly carboxylic acid, and the macromole adsorption layer is just more thick, sterically hindered more big, system more tends towards stability, and dispersiveness is also more good.Have short circuit branch side chain comb-shaped copolymer since space steric effect a little less than, its dispersing property is lower, but disperses retentivity fine.And have the multipolymer of longer graft side chain, because space steric effect is very strong favourable to early stage flowing property.The MPEG of macromolecule can play water-reduction, and the MPEG of small molecular weight can play the effect of control slump-loss.The molecular weight of the suitable macromole reactive monomer of selecting for use is 1000~2000.
Among the present invention, the molecular weight of the fluidizer that is synthesized is between 3000-10000, and pH value of water solution is 4-6.Solution can obtain yellow or brown solid powder by spraying drying.Molecular weight of polymer and distribution thereof have very significant effects to the dispersing property of dispersion agent.Because synthetic product contains hydrophilic groups such as a large amount of carboxyls, sulfonic group.If relative molecular mass is excessive, the polymer dispersed performance is bad.Relative molecular mass is too little, and then to keep slump ability not high for polymkeric substance.Among the present invention, adopt mercaptoethanol as molecular weight regulator one chain-transfer agent, control the molecular weight of polymkeric substance by its add-on.The mercaptoethanol consumption is monomer weight 2~10%, suitable consumption 3~6%.The control molecular weight is conducive to adopt the fluidizer of spray drying method for preparation solid in lower scope, because for unshaped refractory material system, the liquid fluidizer that contains big water gaging is unfavorable for the application of construction process.
Among the present invention, the main raw material that adopts all is the water-soluble monomer that contains two keys.Therefore reaction is carried out in the aqueous solution, adopts water miscible radical initiator, and common is exactly persulphate (as ammonium persulphate), also can adopt the redox initiator of low temperature polymerization: as persulphate-sodium bisulfite etc.Initiator amount increases, and molecular weight diminishes, and system viscosity descends.The add-on of initiator has certain influence to the degree of mobilization of product.Consumption is less than 2%, and reaction is incomplete, and consumption is greater than 10%, because the influence of residual sulfur hydrochlorate reduces degree of mobilization.Comparatively suitable consumption is 2-4%.The temperature of reaction of described solution is divided into 2 stages: at 60-70 ℃, the insulation reaction stage is brought up to 80-90 ℃ in the control of monomer dropping stage, and total reaction time is 4-8h.
In the present invention, used retardant can delay that refractory castable condenses and setting time, and the mechanism of action of retardant also is different with the nature difference of used wedding agent and retardant.Following two kinds of main mechanisms of action are generally arranged: (1) forms the generation that complex compound has suppressed hydrate, and namely the positive ion that dissociates of retardant and wedding agent forms complex compound, and suppressed generation or the reaction product crystallization of hydrate and separated out, or the inhibition grain growing; (2) form thin film adsorbs and wrapped up cement granules, namely retardant adsorbs the dry cement particle surface and forms film, has stoped the cement particle to contact with water, has suppressed hydration reaction speed.Retardant mainly is used in the mould material of the aluminous cement combination that contains fast hard mineral, and used retardant has citric acid, tartrate, gluconic acid, ethylene glycol, glycerine, starch, phosphoric acid salt, ligninsulfonate etc.
In the present invention, setting accelerator is to shorten that refractory castable condenses and the material of setting time.The mechanism of action of setting accelerator is more complicated, and is different with the nature difference of used wedding agent and setting accelerator.Different wedding agents will use setting accelerator of different nature.As being basic cpd: NaOH, KOH, Ca (OH) with the used setting accelerator majority of the mould material of aluminous cement combination 2, Na 2CO 3, K 2CO 3, Na 2SiO 3, K 2SiO3, trolamine; The setting accelerator that uses with the mould material of phosphoric acid and aluminium dihydrogen phosphate combination has: active aluminium hydroxide, talcum, magnesium oxide, aluminous cement, aluminium chlorohydroxide etc.; And the setting accelerator that uses with the mould material of water glass (water glass) combination has Sodium Silicofluoride, aluminum phosphate, sodium phosphate, Pure Silicon Metal, lime, Dicalcium Phosphate (Feed Grade), polymerize aluminum chloride, oxalic dialdehyde etc.Setting accelerator is except outside the Pass having with wedding agent, and also the dispersion agent of selecting for use with refractory material system is relevant, as select Sodium hexametaphosphate 99 for use, when tripoly phosphate sodium STPP is dispersion agent, the calcium salt setting accelerator is to make mobile forfeiture by quick consumption phosphate anion.Water glass and yellow soda ash be by with refractory material system in calcium ion form gelling system, thereby make the current system multiviscosisty, they are less to the influence of dispersion agent, for the system that does not contain cement, almost do not have blood coagulation enhancing effect.Sodium aluminate is to form gelling system by itself running into water, increases the viscosity plays blood coagulation enhancing effect of system.The refractory materials that the present invention is suitable for is to be wedding agent with the aluminous cement, and poly carboxylic acid is dispersion agent, therefore should select and the poly carboxylic acid consistency, condenses and setting time by promoting hydrated cementitious to shorten.Therefore can selective polymerization aluminum chloride, magnesium chloride, aluminium dihydrogen phosphate or yellow soda ash.
The high performance indefinite refractory material system compound additive that the present invention synthesized, be applicable to the not unshaped refractory material system of siliceous ash, wherein the poly carboxylic acid fluidizer has the molecular structure of comb type, carboxyl, sulfonic group and anhydride group provide short-term and long-term electrostatic repulsion, long polyoxyethylene glycol side chain provides the steric exclusion effect, make system have higher water-reducing rate and degree of mobilization, degree of mobilization retention excellence, the selection by retardant and/or setting accelerator is to satisfy the requirement of regulating time of coagulation according to construction requirement and variation of ambient temperature.(seeing embodiment for details)
Embodiment
Provided more detailed description of the present invention with embodiment below, helped to understand the present invention.Yet, this should be interpreted as limitation of the scope of the invention.
Embodiment 1
Take by weighing 2-acrylamide-2-methyl propane sulfonic acid 41.4g (0.2mol), vinylformic acid 14.4g (0.2mol), maleic anhydride 19.6g (0.2mol), macromole reactive monomer polyethylene glycol monomethyl ethermethacrylic acid esters 32.5g (0.025mol) all is dissolved in the 250ml water, adds ammonium persulphate 2.7g (2.5%) simultaneously, mercaptoethanol 5.4g (5%), getting 1/5 after stirring joins in three mouthfuls of reaction flasks, keep 70 ℃ of the interior temperature of bottle, drive agitator, feed N 2, reacted about 30 minutes; To remain 4/5 mixing solutions dripped in two hours.Be warming up to 90 ℃, add 0.5% initiator, react 4h again, cooling.Sample solution is drained the moisture of sample by rotatory evaporator, obtains the yellowish brown powder.The clean slurry degree of mobilization measurement result of the fire-resistant micro mist system of siliceous ash is not 215mm.
Shown in the main table composed as follows of unshape refractory of the not siliceous ash of the clean slurry of test degree of mobilization.
Figure G2009100478582D00071
Embodiment 2
Take by weighing methylpropene sodium sulfonate 0.2mol, methacrylic acid 0.5mol, itaconic anhydride 0.3mol, macromole reactive monomer allyl polyglycol ether 0.04mol all is dissolved in the 250ml water, adding ammonium persulphate weight then is 5.0% of total monomer weight, mercaptoethanol 2% is got 1/5 and is joined in three mouthfuls of reaction flasks after stirring, keep 60 ℃ of the interior temperature of bottle, drive agitator, feed N 2, reacted about 30 minutes; To remain 4/5 mixing solutions dripped in two hours.Be warming up to 80 ℃, add 0.5% initiator, react 6h again, cooling.Sample solution is drained the moisture of sample by rotatory evaporator, obtains the yellowish brown powder.Measuring not, the clean slurry degree of mobilization of the fire-resistant micro mist system of siliceous ash is 170mm.
Embodiment 3
Take by weighing sodium allylsulfonate 0.2mol, vinylformic acid 1.0mol, methylene-succinic acid 0.3mol, maleic anhydride 0.6mol, macromole reactive monomer polyethylene glycol monomethyl ethermethacrylic acid esters 0.02mol, all be dissolved in the 250ml water, adding ammonium persulphate weight then is 9% of total monomer weight, mercaptoethanol 10%, getting 1/5 after stirring joins in three mouthfuls of reaction flasks, keep 80 ℃ of the interior temperature of bottle, drive agitator, feed N 2, reacted about 30 minutes; To remain 4/5 mixing solutions dripped in two hours.Be warming up to 90 ℃, add 0.5% initiator, react 2h again, cooling.Sample solution is drained the moisture of sample by rotatory evaporator, obtains the yellowish brown powder.Measuring not, the clean slurry degree of mobilization of the fire-resistant micro mist system of siliceous ash is 190mm.
Embodiment 4
Take by weighing 2-acrylamide-2-methyl propane sulfonic acid 0.2mol, vinylformic acid 0.4mol, macromole reactive monomer polyethylene glycol monomethyl ethermethacrylic acid esters 0.025mol, all be dissolved in the 200ml water, adding ammonium persulphate weight is total monomer weight 2.5%, mercaptoethanol 5%, getting 1/5 after stirring joins in three mouthfuls of reaction flasks, keep 70 ℃ of the interior temperature of bottle, drive agitator, feed N 2, reacted about 30 minutes; To remain 4/5 mixing solutions dripped in two hours.Be warming up to 90 ℃, add 0.5% initiator, react 4h again, cooling.Sample solution is drained the moisture of sample by rotatory evaporator, obtains the yellowish brown powder.Measuring not, the clean slurry degree of mobilization of the fire-resistant micro mist system of siliceous ash is 205mm.
Embodiment 5-8
The preparation process of fluidizer is identical with embodiment 1, only changes the add-on of polyethylene glycol monomethyl ethermethacrylic acid esters (MPEG), and its add-on is respectively 0.0125mol, 0.01875mol, 0.0375mol and 0.05mol.The degree of mobilization of measuring institute's synthetic product is as shown in the table.
Embodiment 5 Embodiment 6 Embodiment 1 Embodiment 7 Embodiment 8
MPEG/mol 0.0125 0.01875 0.025 0.0375 0.05
Clean slurry degree of mobilization/mm 185 195 215 190 145
Embodiment 9-11
Take by weighing the poly carboxylic acid fluidizer 10g (solid content 30%) that embodiment 1 synthesizes respectively, add tripoly phosphate sodium STPP 0.3g, 1.5g, 3g, mix the final vacuum drying, obtain the faint yellow solid powder.Form batching according to unshape refractory among the embodiment 1, measure clean slurry degree of mobilization and the time of coagulation of fire-resistant micro mist system.
Embodiment 9 Embodiment 10 Embodiment 11
Clean slurry degree of mobilization/mm 175 185 190
Initial set/h 3 5 8
Embodiment 12-14
Take by weighing the poly carboxylic acid fluidizer 10g (solid content 30%) that embodiment 1 synthesizes respectively, add yellow soda ash 0.3g, 1.5g, 3g, mix the final vacuum drying, obtain the faint yellow solid powder.Form batching according to unshape refractory among the embodiment 1, measure clean slurry degree of mobilization and the time of coagulation of fire-resistant micro mist system.
Embodiment 12 Embodiment 13 Embodiment 14
Clean slurry degree of mobilization/mm 175 185 190
Initial set/h 2.5 2 0.5

Claims (9)

1. the compound additive of a unshaped refractory material system, it is characterized in that described compound additive by poly carboxylic acid fluidizer and retardant and/or setting accelerator by mass ratio 1: the 1-0.1 mixed forms; The general structure of described poly carboxylic acid fluidizer molecule is
Figure FSB00001085693000011
R wherein 1=H or CH 3R 2=CH 2Or
Figure FSB00001085693000012
R 3=H or CH 3
R 4=H or CH 3R 5=polyoxyethylene glycol ehter bond-O-or be polyoxyethylene glycol ester bond-COO-; R 6H or CH 3,
1. the molecular weight of described poly carboxylic acid fluidizer has comb shaped molecular structure between 3000-10000;
2. described retardant is citric acid, tartrate, gluconic acid, ethylene glycol, glycerine, starch, phosphoric acid salt or ligninsulfonate;
3. different wedding agents will use setting accelerator of different nature, are NaOH, KOH, Ca (OH) in the basic cpd with the used setting accelerator of the mould material of aluminous cement combination wherein 2, Na 2CO 3, K 2CO 3, Na 2SiO 3, K 2SiO 3Or trolamine; The setting accelerator that uses with the mould material of phosphoric acid and aluminium dihydrogen phosphate combination is active aluminium hydroxide, talcum, magnesium oxide, aluminous cement or aluminium chlorohydroxide; The setting accelerator that uses with the mould material of water glass combination is Sodium Silicofluoride, aluminum phosphate, sodium phosphate, Pure Silicon Metal, lime, Dicalcium Phosphate (Feed Grade), polymerize aluminum chloride or oxalic dialdehyde.
2. by the described compound additive of claim 1, the molecular weight that it is characterized in that described poly carboxylic acid fluidizer is by as the add-on control of the mercaptoethanol of molecular weight regulator.
3. the method for preparing compound additive as claimed in claim 1 or 2 is characterized in that preparation process comprises following two steps:
(1) at first prepares the poly carboxylic acid fluidizer;
(2) fluidizer that step (1) is prepared and retardant and/or setting accelerator are according to weight ratio 1: 1~0.1 mixed, spraying drying then;
The preparation process of described poly carboxylic acid fluidizer is 1. at first that the monomer that contains unsaturated double-bond and the macromole reactive monomer that have carboxyl, sulfonic group and anhydride group respectively is soluble in water, and described macromole reactive monomer is double bond containing macrogol ester or polyglycol ether; 2. under nitrogen atmosphere, under molecular weight regulator and action of evocating, to carry out free-radical polymerizedly, the temperature of reaction of solution is 60-90 ℃; Wherein, molecular weight regulator is mercaptoethanol, initiator is persulphate or persulphate-sodium bisulfite, the add-on of mercaptoethanol is 2~10% of monomer total mass, the add-on of initiator is 2~10% of monomer total mass, have sulfonic monomer, have the monomer of carboxyl, the mol ratio with monomer of anhydride group is 1: 1~5: 1~3, macrogol ester or polyglycol ether and the mol ratio with sulfonic group material are 1: 5~10; The weight ratio of monomer and water is 1: 1~3.
4. press the preparation method of the compound additive of the described unshaped refractory material system of claim 3, it is characterized in that:
(1) the described monomer that contains unsaturated double-bond with hydroxyl is vinylformic acid, methacrylic acid or methylene-succinic acid;
It is (2) described that to have sulfonic monomer be 2-acrylamide-2-methyl propane sulfonic acid, methylpropene sodium sulfonate or sodium allylsulfonate;
(3) described monomer with anhydride group is maleic anhydride or itaconic anhydride;
5. by the described method of claim 3, it is characterized in that:
A) molecular weight of the described macromole reactive monomer of step (1) is 500-3000;
B) the free-radical polymerized reaction times is 4-8h in the step (2);
C) the described initiator add-on 2-4% that is the monomer total mass;
D) mol ratio of sulfonic group and hydroxyl is 1: 2-3;
E) add-on of mercaptoethanol is the 3-6% of monomer total mass.
6. by the described method of claim 5, it is characterized in that the molecular weight of the described macromole reactive monomer of step (1) is 1000-2000.
7. by the described method of claim 3, it is characterized in that the temperature of reaction of solution is divided into two stages: at 60-70 ℃, the insulation reaction stage is brought up to 80-90 ℃ in the control of monomer dropping stage.
8. by the application of claim 1 or 2 described compound additives, it is characterized in that being applicable to the not unshaped refractory material system of siliceous ash.
9. by the described application of claim 8, it is characterized in that selecting by retardant and/or setting accelerator, regulate time of coagulation.
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