CN101885798A - Preparation method of plasticizing agent with thixotropy for unshaped refractory - Google Patents
Preparation method of plasticizing agent with thixotropy for unshaped refractory Download PDFInfo
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- CN101885798A CN101885798A CN2009100511449A CN200910051144A CN101885798A CN 101885798 A CN101885798 A CN 101885798A CN 2009100511449 A CN2009100511449 A CN 2009100511449A CN 200910051144 A CN200910051144 A CN 200910051144A CN 101885798 A CN101885798 A CN 101885798A
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- fluidizer
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- unshape refractory
- siliceous
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Abstract
The invention relates to a preparation method of plasticizing agent with thixotropy special for siliceous dust containing unshaped refractory. The method includes the concrete steps that: unsaturated double bond containing monomers respectively provided with carboxyl group, sulphonic acid group and anhydride group are subject to free radical copolymerization in aqueous solution at 60-90 DEG C, molecular weight regulators 2-10% of mercaptoethanol and 2-10% of initiator are added, and the mol ratio of sulphonic acid group, carboxyl group and anhydride group in synthesized product molecule is 1: 1-5: 1-3; and pH value of solution is regulated to 9-10, and then spray drying is carried out. The synthesized plasticizing agent overcomes the inadaptability of comb-type polycarboxylic acid in siliceous dust containing micro powder system, can be mutually matched with the action of siliceous dust, can obviously improve the fluidity and thixotropy of siliceous dust containing unshaped refractory and is applicable to ramming refractories.
Description
Technical field
The present invention relates to a kind of preparation method with fluidizer that thixotropic siliceous grey unshape refractory uses.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, 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, the polyacrylate(s) dispersion agent also has been applied to unshaped refractory material system (N.Bunt, et al., LAFARGE, UNITECR in unshape refractory; Vol, 3, p.1347,1997, NewOrleans), 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.Experiment showed, in addition when present concrete comb type polycarboxylate water-reducer commonly used is applied to the unshaped refractory material system of siliceous ash, can cause degree of mobilization forfeiture (Liu Xingyu, Jiang Jianhua, the Fu Lefeng etc. of slurry.Water reducer and raw material for refractory Study on Compatibility, material of construction journal, 2007,10 (4): 424-429).
Know by retrieval and know, the special-purpose fluidizer of the unshape refractory research at home with thixotropic siliceous ash also is a blank.For fire-resistance rammed mass, thixotropy and good flowability are complementary, and particularly for siliceous grey system, most admixture all can not organically combine both, along with developing rapidly of unshape refractory, increasing to the demand of wedding agent.Be the development of promotion unshape refractory and the raising of state of the art, a kind of preparation method of the special-purpose fluidizer of unshape refractory of siliceous ash is provided, become the task of top priority, thereby be guided out design of the present invention.
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 the preparation method of the fluidizer that a kind of unshape refractory with thixotropic siliceous ash uses.
A kind of preparation method that the present invention proposes with special-purpose fluidizer of unshape refractory of thixotropic siliceous ash, the molecule of described special-purpose fluidizer has following structure:
R wherein
1=H or CH
3R
2=CH
2Or
R3=H or CH
3
The concrete steps of preparation are as follows: will have carboxyl respectively, the monomer that contains unsaturated double-bond of sulfonic group and anhydride group is 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 4～8h, wherein molecular weight regulator is a mercaptoethanol, initiator is persulphate or persulphate-sodium bisulfite, the mercaptoethanol add-on is 2～10% of a total monomer weight, the initiator add-on 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.The weight ratio of monomer and water is 1: 1～3; The pH value of regulator solution was 9-10, spraying drying then after reaction was finished.
Among the present invention, the described monomer that contains unsaturated double-bond with carboxyl is any of vinylformic acid, methacrylic acid or methylene-succinic acid.
Among the present invention, described any that to have the sulfonic monomer that contains unsaturated double-bond be 2-acrylamide-2-methyl propane sulfonic acid, methylpropene sodium sulfonate or sodium allylsulfonate.
Fluidizer with polarity anion active group such as SO
3-, 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 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 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 delayed coagulation, based on above understanding, therefore in the product that forms in preparation process of the present invention, these two groups are as main functional group, and the mol ratio of sulfonic acid group and carboxyl has significant effects to the flowability of product, therefore among the present invention, select both mol ratio (sulfonic group/carboxyl)=1: 1～5.Suitable sulfonic group/carboxyl mol ratio is 1: 2～3.
Among the present invention, the described monomer that contains unsaturated double-bond 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 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, the fluidizer molecular weight that is provided is between 1000-8000, and pH value of water solution is 9-10.Solution can obtain the pale yellow 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%, optimum consumption 3～6%.After polyreaction is finished, with among the NaOH and the pH value be 9-10, this is very important to the thixotropy and the flowability that improve siliceous grey system.This with under alkaline condition, OH
-With the H in the Si-OH key
+Neutralization makes the SiO in the silicon ash
2Aggregating into the Si-O-Si bond, to close the degree of netted chain relevant greatly.The silicon ash is introduced in the mould material, it forms numerous netted chains after aquation, and store a considerable amount of free water therein, can discharge free water under external force and flow, when external force vibration disappears, netted chain can be store entry again and material is lost flowability, and solidifies under the network chain effect, and this phenomenon is undoubtedly important to ramming mass.
Among the present invention, the main raw material that is adopted all is the water-soluble monomer that contains two keys.Therefore the reaction that relates in the preparation process 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.
The special-purpose fluidizer of the unshaped refractory material system of the siliceous ash of institute's synthetic of the present invention, its molecular structure contains carboxyl, sulfonic group and anhydride group provides short-term and secular electrostatic repulsion, cooperatively interact with the effect of silicon ash in fire-resistant micro mist system, thereby make the unshaped refractory material system of siliceous ash have good mobility, higher thixotropy and excellent mechanical behavior under high temperature are specially adapted to fire-resistance rammed mass.
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) all is dissolved in the 200ml water, add ammonium persulphate 1.9g (2.5%) simultaneously, mercaptoethanol 3.80g (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 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, the cooling, with among the NaOH with the pH value be 9-10 spraying drying then, obtain pale yellow powder.The clean slurry degree of mobilization of measuring the fire-resistant micro mist system of siliceous ash is 150mm (vibrations).
Shown in the main table composed as follows of unshape refractory of the 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 all is dissolved in the 200ml 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, the cooling with among the NaOH with the pH value be 9-10 spraying drying then, obtain pale yellow powder.The clean slurry degree of mobilization of measuring the fire-resistant micro mist system of siliceous ash is 140mm (vibrations).
Embodiment 3
Take by weighing sodium allylsulfonate 0.2mol, vinylformic acid 1.0mol, methylene-succinic acid 0.3mol, maleic anhydride 0.6mol all is dissolved in the 200ml water, and 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 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 2h again, the cooling with among the NaOH with the pH value be 9-10 spraying drying then, obtain pale yellow powder.The clean slurry degree of mobilization of measuring the fire-resistant micro mist system of siliceous ash is 130mm (vibrations).
Embodiment 4
Take by weighing 2-acrylamide-2-methyl propane sulfonic acid 0.2mol, vinylformic acid 0.4mol is dissolved in the 200ml water, adding ammonium persulphate weight is total monomer weight 2.5%, and mercaptoethanol 5% is got 1/5 and joined in three mouthfuls of reaction flasks after stirring, 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, the cooling with among the NaOH with the pH value be 9-10 spraying drying then, obtain pale yellow powder.The clean slurry degree of mobilization of measuring the fire-resistant micro mist system of siliceous ash is 165mm (vibrations).
Embodiment 5-8
The preparation process of fluidizer is identical with EXAMPLE l, only changes the vinylformic acid add-on and is respectively 0.4mol, 0.6mol, 0.8mol and 1.0mol.The degree of mobilization of measuring institute's synthetic product is as shown in the table.
Claims (10)
1. the unshape refractory of a siliceous ash is with the preparation method of fluidizer, it is characterized in that concrete steps are as follows: carboxyl will be had respectively, the monomer that contains unsaturated double-bond of sulfonic group and anhydride group is soluble in water, under nitrogen atmosphere, under molecular weight regulator and action of evocating, carry out free radicals copolymerization reaction, the temperature of reaction is 60-90 ℃, wherein molecular weight regulator is a mercaptoethanol, initiator is persulphate or persulphate-sodium bisulfite, the mercaptoethanol add-on is 2～10% of a monomer total mass, the initiator add-on is 2～10% of a monomer total mass, and described have a sulfonic monomer, monomer with carboxyl, the mol ratio that contains undersaturated double bond monomer with anhydride group is 1: 1～5: 1～3.The mass ratio of monomer and water is 1: 1～3; The pH value of regulator solution was 9-10, spraying drying then after reaction was finished.
2. the unshape refractory of siliceous ash according to claim 1 is characterized in that with the preparation method of fluidizer the described monomer that contains unsaturated double-bond with carboxyl is any in vinylformic acid, methacrylic acid and the methylene-succinic acid.
3. the unshape refractory of siliceous ash according to claim 1 is with the preparation method of fluidizer, it is characterized in that described to have the sulfonic monomer that contains unsaturated double-bond be in 2-acrylamide-2-methyl propane sulfonic acid, methylpropene sodium sulfonate and the sodium allylsulfonate any.
4. the unshape refractory of siliceous ash according to claim 1 is characterized in that with the preparation method of fluidizer the described monomer that contains unsaturated double-bond with anhydride group is maleic anhydride or itaconic anhydride.
5. the unshape refractory of siliceous ash according to claim 1 is characterized in that with the preparation method of fluidizer:
(1) add-on of initiator is the 2-4% of monomer total mass;
(2) having sulfonic monomer is 1 with the monomer mole ratio with carboxyl: 2-3.
6. the unshape refractory of siliceous ash according to claim 1 is characterized in that with the preparation method of fluidizer described polyreaction is to regulate pH value with NaOH solution.
7. the unshape refractory of siliceous ash according to claim 1 is characterized in that with the preparation method of fluidizer described free radicals copolymerization reaction temperature is 60-90 ℃, and total reaction times is 4-8h.
8. the unshape refractory of siliceous ash according to claim 1 is with the preparation method of fluidizer, it is characterized in that described free radicals copolymerization reaction holding stage adds the initiator into monomer total mass 0.5% again.
9. according to the unshape refractory of each described siliceous ash among the claim 1-8 preparation method, it is characterized in that the general structure of the fluidizer for preparing is with fluidizer:
R wherein
1=H or CH
3R
2=CH
2Or
R3=H or CH
3
10. the unshape refractory of siliceous ash according to claim 9 is with the preparation method of fluidizer, and the fluidizer molecular weight that it is characterized in that preparing obtains the pale yellow powder solid by spraying drying between 1000-8000.
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| US9738565B2 (en) | 2012-08-13 | 2017-08-22 | Verdesian Life Sciences, Llc | Method of reducing atmospheric ammonia in livestock and poultry containment facilities |
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| US10059636B2 (en) | 2013-08-27 | 2018-08-28 | Verdesian Life Sciences, Llc | Pesticide product including polyanionic polymers |
| US10519070B2 (en) | 2014-05-21 | 2019-12-31 | Verdesian Life Sciences U.S., Llc | Polymer soil treatment compositions including humic acids |
| US10737988B2 (en) | 2013-09-05 | 2020-08-11 | Verdasian Life Sciences U.S., LLC | Polymer-boric acid compositions |
| US10822487B2 (en) | 2014-05-22 | 2020-11-03 | Verdesian Life Sciences Llc | Polymeric compositions |
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| US9738565B2 (en) | 2012-08-13 | 2017-08-22 | Verdesian Life Sciences, Llc | Method of reducing atmospheric ammonia in livestock and poultry containment facilities |
| US9961922B2 (en) | 2012-10-15 | 2018-05-08 | Verdesian Life Sciences, Llc | Animal feed and/or water amendments for lowering ammonia concentrations in animal excrement |
| US11254620B2 (en) | 2013-08-05 | 2022-02-22 | Verdesian Life Sciences U.S., Llc | Micronutrient-enhanced polymeric seed coatings |
| US10059636B2 (en) | 2013-08-27 | 2018-08-28 | Verdesian Life Sciences, Llc | Pesticide product including polyanionic polymers |
| US10065896B2 (en) | 2013-08-27 | 2018-09-04 | Verdesian Life Sciences, Llc | Seed product having polyanionic polymers |
| US10173941B2 (en) | 2013-08-27 | 2019-01-08 | Verdesian Life Sciences, Llc | Fertilizers with polyanionic polymers and method of applying polyanionic polymer to plants |
| US10377680B2 (en) | 2013-08-27 | 2019-08-13 | Verdesian Life Sciences, Llc | Polyanionic polymers |
| US10737988B2 (en) | 2013-09-05 | 2020-08-11 | Verdasian Life Sciences U.S., LLC | Polymer-boric acid compositions |
| US10519070B2 (en) | 2014-05-21 | 2019-12-31 | Verdesian Life Sciences U.S., Llc | Polymer soil treatment compositions including humic acids |
| US10822487B2 (en) | 2014-05-22 | 2020-11-03 | Verdesian Life Sciences Llc | Polymeric compositions |
| EP3056476A1 (en) * | 2015-02-16 | 2016-08-17 | Sabanci Üniversitesi | An additive for suspensions |
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Application publication date: 20101117 |