CN101885888A - Preparation method of slow-release type unshaped refractory additive - Google Patents

Abstract

The invention relates to a preparation method of a slow-release type unshaped refractory additive. The method comprises the following steps of: (1) carrying out a free radical copolymerization reaction on monomers which respectively have carboxyl groups, sulfonic acid groups and anhydride groups and contain unsaturated double bonds and macromolecule activated monomers containing double-bonded polyethylene glycol ester or ether in an aqueous solution at 60-90 DEG C, wherein based on the weight of the monomers, mercaptoethanol as a molecular weight regulator is present in an amount of 2-10%, and an initiator is present in an amount of 2-10%; and the reaction time is 4-8 hours, the molar ratio of the sulfonic acid groups to the carboxyl groups to the anhydride groups which are main functional groups is 1:(1-5):(1-3), and the molar ratio of the polyethylene glycol ester or ether to the sulfonic acid groups is 1:(5-10); and (2) mixing a synthesized product with a water-soluble macromolecule slow-release material by a weight ratio of 1:(1-0.1) and then spraying as well as drying. The prepared slow-release type unshaped refractory additive has higher water-reducing rate and good fluidity and fluidity maintaining property.

Description

The preparation method of slow-release type unshaped refractory additive

Technical field

The present invention relates to a kind of preparation method of slow-release type unshaped refractory additive.The invention belongs 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, some non-oxidized substance that induces one is made oxide compound-non-oxidized substance compound material, adopts the novel advanced constructional method and the reinforcement of fundamental research etc., and 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, perhaps adopt utilize deadweight and vibration flow filling molding, so the compactness of the quality of wedding agent decision formed body and even the performance of refractory materials.The use technology of wedding agent has become one of most important factor of decision 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.

The unshape refractory polymeric admixture is a kind of novel articulated system that integrates dispersiveness, flowability, water reducing ability that grew up in recent years, and its main effect comprises 2 points: (1) plastification.Be used to improve 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.

The unshape refractory polymeric admixture is to be that base growth is got up with the third generation concrete polycarboxylate water-reducer that occurs the nineties.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 naphthalene with the polycarboxylic acid series.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 polycarboxylate water-reducer has been carried out a large amount of for many years fundamental research and applied research both at home and abroad, 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 on forming, 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 exist the defective of aspects such as the low and degree of mobilization loss of hot strength is bigger, low price.A small amount of producer uses the polymeric admixture system of offshore company, though it is little to add consumption, costs an arm and a leg, and 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.USP5739212 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.

Through discovering, the major cause of fluidizer degree of mobilization maintenance in use poor performance is because cement aquation constantly consumes fluidizer, the concentration of fluidizer in the aqueous solution constantly reduces, degree of mobilization be with the aqueous solution in the concentration of fluidizer proportional, be a kind of important method that addresses this problem so preparation has the fluidizer of slow releasing function.Slow-release type unshaped refractory adds agent research and rarely has report, and is along with developing rapidly of domestic unshape refractory, increasing to the demand of wedding agent.Be the development that promotes domestic unshape refractory and the raising of state of the art, the present invention intends providing a kind of preparation method of slow-release type unshaped refractory additive.

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 preparation method of slow-release type unshaped refractory additive.It is characterized in that preparation process comprises following two steps:

(1) at first prepares the poly carboxylic acid fluidizer that a kind of unshape refractory is used;

(2) poly carboxylic acid fluidizer that above-mentioned steps 1 is prepared and water-soluble polymer slow-release material are according to weight ratio 1: 1～0.1 mixed, spraying drying then.

In the present invention, the poly carboxylic acid fluidizer molecule used of described unshape refractory has following structure:

R wherein₁=H or CH₃R₂=CH₂

Or R₃=H or CH₃

R₄=H or CH₃R₅=-O-or-COO-; R₆=H or CH₃

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, temperature of reaction is 60-90 ℃, reaction times is 4～8h, wherein, molecular weight regulator is a mercaptoethanol, initiator is persulphate or persulphate-sodium bisulfite, the add-on of mercaptoethanol is 2～10% of a total monomer weight, the add-on of initiator is 2～10% of a total monomer weight, has sulfonic monomer, monomer with carboxyl, monomeric mol ratio with 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.

Therefore in the present invention, used water-soluble high-molecular material is as sustained release matrix, requires will have water-soluble under certain condition, can dissolve slowly or swelling, and the fluidizer molecule that is included in the inside is slowly released.Will chemical reaction taking place with the fluidizer molecule, make the degradation of fluidizer, preferably has collaborative reinforced effects with the poly carboxylic acid fluidizer simultaneously.Therefore in the present invention, we select polyvinyl alcohol, polyvinylpyrrolidone, gelatine any.

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.

Fluidizer with polarity anion active group such as SO₃^-, COO^-Be adsorbed on strong polar cement particle surface tightly Deng by interactions such as ionic linkage, covalent linkage, hydrogen bond and Van der Waals forces, thereby make cement granules charged, same sex electric charge repels each other, stoped the 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 Ca²⁺Ionization forms complex compound, reduces the Ca in the solution²⁺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 slow release effect is favourable to the flowability and the retentivity thereof of cement slurry.Studies show that, sulfonic acid group helps the increase of degree of mobilization, and carboxylic acid has tangible slow releasing function, based on above understanding, these two groups are as main functional group in the product of synthetic poly carboxylic acid fluidizer of the present invention, the mol ratio of sulfonic acid group and carboxyl has significant effects to the 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 monomeric maleic anhydride or itaconic anhydride with anhydride group.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 big more, and then the initial flow of cement slurry is good more; 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 big more, and then the effect that keeps of the flowability of cement slurry is good more.The anhydride group that maleic anhydride and itaconic anhydride had, 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 the degree of mobilization that improves polymkeric substance keeps performance.

Among the present invention, described 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 long more in the poly carboxylic acid, and the macromole adsorption layer is just thick more, sterically hindered big more, system tends towards stability more, and dispersiveness is also good more.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, between 3000-10000, pH value of water solution is 4-6 by the molecular weight of step 1 synthetic poly carboxylic acid fluidizer.Solution can obtain yellow or brown ceramic powder solid by spraying drying.Molecular weight of polymer and distribution thereof have crucial influence 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, come the molecular weight of controlling polymers by its add-on as chain-transfer agent.The mercaptoethanol consumption is a monomer weight 2～10%, suitable consumption 3～6%.The control molecular weight helps adopting spray drying method for preparation solid fluidizer 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 is adopted all is the water-soluble monomer that contains two keys.Therefore this reaction is to carry 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 solution is controlled at 60-70 ℃ in the monomer dropping stage, and the insulation reaction stage is brought up to 80-90 ℃, and the reaction times is 4-6h.

Institute of the present invention synthetic slow-release type unshaped refractory system admixture, be applicable to the not unshaped refractory material system of siliceous ash, wherein said 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, by compound water-soluble polymer slow-release material, the degree of mobilization that improves fluidizer significantly keeps performance.

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, add ammonium persulphate 2.7g (2.5%) simultaneously, mercaptoethanol 5.4g (5%) gets 1/5 and joins in three mouthfuls of reaction flasks after stirring, keep 70 ℃ of the interior temperature of bottle, drive agitator, feed N₂, 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.

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 N₂, 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 N₂, 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 N₂, 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 polyethylene glycol monomethyl ethermethacrylic acid esters (MPEG) add-on and 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 embodiment 1 synthetic poly carboxylic acid fluidizer 10g (solid content 30%) respectively, add polyvinyl alcohol 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 the 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	??190	??185	??170

Embodiment 12-14

Take by weighing embodiment 1 synthetic poly carboxylic acid fluidizer 10g (solid content 30%) respectively, add gelatine 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 the 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	??160	??145

Claims (10)

1. the preparation method of a slow-release type unshaped refractory additive is characterized in that preparation process comprises following two steps:

(1) at first prepares the poly carboxylic acid fluidizer that a kind of unshape refractory is used;

(2) poly carboxylic acid fluidizer that step (1) is prepared and water-soluble polymer slow-release material are according to weight ratio 1: 1～0.1 mixed, spraying drying then.

2. the preparation method of slow-release type unshaped refractory according to claim 1 is characterized in that the molecule of this special use fluidizer has following structure:

R wherein₁=H or CH₃R₂=CH₂Or

R₃=H or CH₃

R₄=H or CH₃R₅=-O-is-COO-; R₆=H or CH₃

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 are soluble in water, under nitrogen atmosphere, under molecular weight regulator and action of evocating, carry out free-radical polymerized, temperature of reaction is 60-90 ℃, wherein, molecular weight regulator is a mercaptoethanol, initiator is persulphate or persulphate-sodium bisulfite, the add-on of mercaptoethanol is 2～10% of a monomer total mass, the add-on of initiator is 2～10% of a monomer total mass, has sulfonic monomer, monomer with carboxyl, monomeric mol ratio with anhydride group is 1: 1～5: 1～3, and 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.

3. the preparation method of slow-release type unshaped refractory according to claim 2 is characterized in that:

(1) the described monomer that contains unsaturated double-bond with carboxyl is that vinylformic acid, methacrylic acid close any in the methylene-succinic acid;

It is (2) described that to have sulfonic monomer be that 2-acrylamide-2-methyl propane sulfonic acid, methylpropene sodium sulfonate close any in the sodium allylsulfonate;

(3) described monomer maleic anhydride or itaconic anhydride with anhydride group.

4. the preparation method of slow-release type unshaped refractory according to claim 2 is characterized in that:

(1) add-on of mercaptoethanol is the 3-6% of monomer total mass;

(2) add-on of initiator is the 2-4% of monomer total mass;

(3) having sulfonic monomer is 1 with the monomeric mol ratio with poly-carboxyl: 2-3;

(4) molecular weight of macromole reactive monomer is 500-3000.

5. the preparation method of slow-release type unshaped refractory according to claim 4, the molecular weight that it is characterized in that described macromole reactive monomer is 1000～2000.

6. according to the preparation method of claim 2,4 or 5 described slow-release type unshaped refractories, it is characterized in that described macromole reactive monomer comprises polyethylene glycol monomethyl ethermethacrylic acid esters or allyl polyglycol ether.

7. the preparation method of the special-purpose fluidizer of the unshape refractory of not siliceous ash according to claim 1 and 2, the molecular weight that it is characterized in that prepared poly carboxylic acid fluidizer is 3000-10000, pH value of water solution is 4-6; Solution obtains yellow or brown ceramic powder solid by spraying drying.

8. the preparation method of a kind of slow-release type unshaped refractory additive according to claim 1 is characterized in that used water-soluble high-molecular material slow-release material and poly carboxylic acid fluidizer have consistency and synergistic effect.

9. the preparation method of a kind of slow-release type unshaped refractory additive according to claim 8 is characterized in that described slow-release material is polyvinyl alcohol, polyvinylpyrrolidone or gelatine.

10. the preparation method of a kind of slow-release type unshaped refractory additive according to claim 9 is characterized in that described slow-release material is polyvinyl alcohol or gelatine.