CN102532560A - Method for preparing cement dispersing agent based on polyvinyl alcohol Michael addition reaction - Google Patents
Method for preparing cement dispersing agent based on polyvinyl alcohol Michael addition reaction Download PDFInfo
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Abstract
The invention relates to a method for preparing a cement dispersing agent based on polyvinyl alcohol Michael addition reaction, which comprises the following steps of: firstly leading polyvinyl alcohol and an alpha, beta-unsaturated carbonyl compound to be subjected to the Michael addition reaction under the action of a catalyst and then leading a product obtained by full hydrolysis and a methoxy polyoxyethylene ether compound to be subjected to condensation reaction under the action of a catalyst. The method has the beneficial effects that in the process, the water-soluble polymer polyvinyl alcohol is taken as a main chain, and a micromolecule strong polarity group and a macromolecule polyoxyethylene ether structure introduced by the Michael addition reaction and the condensation reaction are taken as branch chains to comprehensively exert the characteristics of all functional groups; the method has the advantages of simple and easy operation step, mild and controllable reaction condition, and clean and environmentally-friendly whole process; and meanwhile, the cement can be endowed with good flowing property, so that the flowability retention ability and the cement adaptability are remarkably improved. Therefore, the cement dispersing agent is an excellent cement dispersing agent with a novel structure.
Description
Technical field
The present invention relates to the technical field of a kind of cement concrete with dispersion agent; Specially refer to a kind of Z 150PH and α, the Michael addition adducts of beta-unsaturated carbonyl compound again with the concrete preparation method of methoxy polyoxyethylene ether compound condensation synthetic water cement dispersant.
Background technology
The most frequently used dispersion agent of concrete field surely belongs to the water reducer in the admixture now; The mid-80 Japan at first develops the third generation product of cement water reducing agent from 20th century---behind the polycarboxylate high performance water-reducing agent; The mid-90 is formally realized suitability for industrialized production, and has become a kind of novel commercialization concrete admixture that is widely used in the building operation.At present in China; Polycarboxylate high performance water-reducing agent relies on its low-dosage, high diminishing, the high advantage such as collapse of protecting; Become one of focus and emphasis of research, and just advanced and apply, will become one of 21 century important admixture of using of concrete works with the speed of making rapid progress.
Polycarboxylate high performance water-reducing agent is a kind of admixture that cement paste, mortar, concrete mix is had good dispersion effect.The structure of present universally recognized poly carboxylic acid series water reducer is a kind of comb shaped structure; Be side chain as its hydrophobic nature main chain, polar hydrophilic functional group (typical case is represented as the long side chain of polyoxy alkyl alkene class) promptly with aliphatic hydrocarbon; The polycarboxylate high performance water-reducing agent that uses in the current concrete industry is structure for this reason mostly, can realize good diminishing dispersing property.
The diminishing dispersion mechanism corresponding with the comb shaped structure of polycarboxylate high performance water-reducing agent is that some polar groups on its main chain are adsorbed on cement particle surface; Its hydrophilic long side chain forms adsorption layer, keeps the particulate dispersion stabilization, can in liquid phase, stretch simultaneously; Thereby form huge three-dimensional adsorption structure at cement particle surface; Produce space steric effect, reduce the flucculation structure between the cement granules, make cement granules realize good distribution and stable existence.Therefore, along with the development of water reducer diversification, design novel molecular structure and the diminishing dispersion agent with premium properties have become the development trend and the inevitable requirement of concrete industry.
In organic chemistry filed; The α that the nucleophilic carbanion of active methylene compound formation is arranged parent's electricity; The nucleophilic addition of the carbon-carbon double bond conjugated system of beta-unsaturated carbonyl compound; Being called Micheal (Michael) addition reaction, is the alkylating a kind of important method of active methylenation thing.
Patent CN101186670 (open day: on May 28th, 2008) reported a kind of method, belonged to the organic synthesis field with microwave promotion synthesizing polycarboxylic acid series cement water reducer.This patent is optimized the selection and the monomer ratio of monomer molecule structure based on to the performance requriements of cement water reducing agent and the analysis of monomer molecule structure activity relationship.Select for use methylacrylic acid, methyl acrylate, polyethylene glycol monomethyl ethermethacrylic acid esters, methylpropene sodium sulfonate as polymerization single polymerization monomer; With the Ammonium Persulfate 98.5 is initiator; Introduce the microwave irradiation technology of 200-1500W on this basis, utilize the synthetic fast polycarboxylate water-reducer product of microwave.This product under low-dosage and low water-cement ratio, possesses higher initial flow degree value and degree of mobilization keeps performance, and does not produce segregation phenomenon.The method that this patent provides can shorten the reaction times greatly, cuts down the consumption of energy, and reduces and pollutes, and improves the clean slurry flowing property of product, is a kind of novel method safe, efficient, energy-conservation, green and simple to operate.
Patent CN101538134 (open day: on September 23rd, 2009) reported a kind of polyether class polycarboxylic acid high-efficiency water reducing agent and preparation method thereof, belonged to concrete material in the material of construction, structure and engineering field.This water reducer is warmed up to 50-90 ℃ with the aqueous solution of the chain-transfer agent of the allyl polyethenoxy ether of 15%-55% mass percent and 0%-6% mass percent; Drip the initiator solution of 0.01%-0.9% mass percent on one side; Drip on one side one or more mixed solution of unsaturated acid and the verivate thereof of 3%-15% mass percent, keep temperature-resistant, in 2-6 hour, drip off; Be incubated 1-6 hour; Naturally cool to room temperature, be neutralized to the pH value to 6.8-7.2, obtain polyether class polycarboxylic acid high-efficiency water reducing agent with sig water.This water reducer and preparation method thereof technology is simple, cost is low and excellent performance; Can effectively reduce concrete wc; Improve concrete hole structure and compaction rate, improve concrete intensity and weather resistance, to improving construction quality and work-ing life; Reduce engineering cost, aspects such as minimizing environmental pollution are significant.
Patent CN101954296 (open day: on January 26th, 2011) reported chiral catalyst of a kind of asymmetric Michael addition reaction and preparation method thereof, related to asymmetric Michael addition reaction field.Derive obtains this kind catalyzer by natural (L)-Proline (L-proline(Pro)), and it is applied in the asymmetric Michael addition reaction of catalysis.Through the catalyzer that this patented technology scheme prepares, used natural cheap amino acid and more cheap acylthioureas, can the catalysis nitroolefin and ketone carry out asymmetric Micheal addition reaction, and catalytic efficiency (is high, corresponding selection property is good.
Patent CN101973917 (open day: on February 16th, 2011) reported a kind of α; The method of the asymmetric Michael addition of the catalysis of alpha, beta-unsaturated ketone and sulfuryl compound and the application in synthetic celery ketone thereof; Being to be raw material with alpha, beta-unsaturated ketone and sulfuryl compound, is catalystsystem to contain chiral catalyst or its salt that one or more primary amine, tertiary amine, urea or thiocarbamide are functional group respectively; With the organic solvent is reaction carriers; In reaction kettle, react, temperature of reaction is 0～50 ℃, and the reaction times is 48～168 hours; Obtain adduct.Its positively effect is: realized the reaction of alpha, beta-unsaturated ketone and sulfuryl compound first, and transformation efficiency is high, selectivity is good, reaction substrate is in extensive range, reaction reagent is cheap and easy to get, yield is up to 97%; Can successful synthesis of chiral apione.
Patent US5350801 (open day: on September 27th, 1994) reported a kind of method that realizes modified polyvinyl alcohol through the mode of solid state reaction by Michael addition principle; Be that Michael addition monomer solution with capacity is sprayed on the exsiccant pva powder; Make its abundant swelling but do not form The dissolved; Be sprayed on the appropriate catalyst swelling thing and intensification again, realize the Michael addition reaction between the two.Owing to be solid state reaction, this patent has selected GMO (glyceryl monooleate) to make dispersion medium, is convenient to reduce viscosity and stirs.This patent provides uses simple relatively solid phase reaction method to prepare the functionalization product of a series of modified poly ethylene alcoholic extract hydroxyl groups, and solid product is low-cost, need not deep processing, and has a recoverable value.
In the above-mentioned patent; Great majority about the research patents of polycarboxylic acid series cement water reducer all be synthetic through a series of polyreactions be the structure product of molecular chain main chain with poly carboxylic acid (ester); Innovative point concentrates on the improvement aspect to synthetic technological condition mostly, so that reaction product cooperates the optimization that is issued to performance at existing raw material.Yet, from the angle of structure-performance relation and diminishing dispersion mechanism, synthetic and design theory of molecular structure preparation has the cement dispersants of novel texture, still rarely has the report of high-lighting with the work that realizes excellent over-all properties aspect through organic chemistry.
In the above-mentioned patent; Z 150PH (PVA) is a kind of important chemical material; Can be used for making polyvinyl acetal, anti-gasoline pipeline, vinylon synthon, fabric-treating agent, chiral catalyst, emulsifying agent, organic intermediate, paper coating, tackiness agent or the like, of many uses, have excellent in chemical character; Be a kind of typical water soluble polymers, but do not have PVA to be used for the bibliographical information of synthetic water cement dispersant aspect as yet.In addition; The Michael addition reaction is a kind of important nucleophilic addition, and PVA is that a kind of important electron is given body simultaneously, can react with the unsaturated conjugated system (electron acceptor(EA)) of parent's electricity; It is an effective way that realizes the PVA modification; Yet great majority all are the building-up processes for preparing chiral catalyst or organic intermediate through the Michael addition reaction about the research patent of Michael addition reaction, promptly are used in the patent of PVA modification, and also emphasis concentrates on synthesis technique and the preparation method; Relevant its gos deep into modification and designs novel texture to be used for the work in cement dispersants field, do not appear in the newspapers both at home and abroad.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing cement dispersants based on the Z 150PH Michael addition; Through Z 150PH and α; The Michael addition adducts of beta-unsaturated carbonyl compound; Synthesize the backbone structure that possesses design functional group through hydrolysis,, thereby be implemented in the structure of the long side chain of grafting wetting ability on the main chain again with the condensation of methoxy polyoxyethylene ether compound.The cement dispersants that is made by this patent method is to be main body with the polyvinyl alcohol structures; Abandoned the method that traditional dependence acrylic compounds prepares cement dispersants; Give full play to the design freedom of molecular structure; Realize diminishing dispersion effect with a kind of brand-new chemical structure to cement granules, this for the research thinking of widening the cement dispersants field, enrich its synthetic preparation means and have great significance.Adopt present method synthetic cement dispersants to have that building-up process safety and environmental protection, operation steps are convenient to be prone to control, production cost and energy consumption is low, the mobile maintenance and advantage, the ability that in the cement slurry system, has excellent discrete particles and diminishing guarantor to collapse simultaneously such as cement adaptability is strong.
The invention provides and a kind ofly prepare the method for cement dispersants, adopt the Michael addition adducts of Z 150PH to prepare the cement dispersants material, may further comprise the steps based on the Z 150PH Michael addition:
(1) Z 150PH is joined in the middle of the aqueous solution of catalyzer that massfraction is 1-30%; 15-35 ℃ was stirred 0.5-6 hour, was warming up to 35-60 ℃ then, and the adding massfraction is that the A component and the B component blended aqueous solution of 20-80% carries out Michael reaction; React after 0.5-10 hour; Be warming up to 60-95 ℃, adding massfraction is the alkaline solution of 20-80%, after hydrolysis 0.5-6 hour; 15-50 ℃ is used carbonatoms to wash as the Fatty Alcohol(C12-C14 and C12-C18) of 1-3, and obtains Michael addition adducts 90-120 ℃ of drying.
(2) the methoxy polyoxyethylene ether compound is joined in the reactor drum; Be warming up to 45-65 ℃, add the product that obtains in the step (1), hydrochloric acid soln, the catalyzer that massfraction is 5%-36% successively, stir to add when being warming up to 80-100 ℃ and be with aqua; Continue to be warming up to 105-160 ℃ and carry out condensation reaction; Reaction the time will react the gained water sepn and gone out, and react after 0.5-10 hour and slough the band aqua through vacuumizing, and lower the temperature to use massfraction to be neutralized to the pH value as the alkaline solution of 10-50% when being cooled to 25-40 ℃ to be 6-8; Obtain condensation product, add the cement dispersants that the entry dilution obtains required massfraction at last.
Catalyzer in the above-mentioned steps (1) is a basic catalyst, comprises sodium hydroxide, Pottasium Hydroxide, Lithium Hydroxide MonoHydrate, triethylamine, hexahydropyridine, sodium ethylate or sodium amide; A component in the above-mentioned steps (1) is the amides α of facile hydrolysis; Beta-unsaturated carbonyl compound or ester class α; Beta-unsaturated carbonyl compound comprises acrylic amide, USAF RH-1, methyl acrylate, TEB 3K, Hydroxyethyl acrylate, 2-hydroxy ethyl methacrylate, 2-hydroxyethyl meth acrylate or 2-sulfopropyl propenoate; B component in the above-mentioned steps (1) is the amides α of not facile hydrolysis, and the verivate of beta-unsaturated carbonyl compound comprises N-(propanesulfonic acid) acrylic amide, N-(methyl propane sulfonic acid) acrylic amide or N-(oxyacetic acid) acrylic amide; The solute of the alkaline solution in the above-mentioned steps (1) is sodium hydroxide, Pottasium Hydroxide, Lithium Hydroxide MonoHydrate, ammoniacal liquor, quadrol, diethylamine, triethylamine or trolamine; Carbonatoms in the above-mentioned steps (1) is that the Fatty Alcohol(C12-C14 and C12-C18) of 1-3 is methyl alcohol, ethanol, n-propyl alcohol or Virahol.
Methoxy polyoxyethylene ether compound in the above-mentioned steps (2) is methoxy polyoxyethylene ether or holds amino methoxy polyoxyethylene ether; Catalyzer in the above-mentioned steps (2) is that tosic acid, massfraction are the vitriol oil, ETHYLE ACETATE, phosphoric acid or the thionamic acid of 80-98%; Band aqua in the above-mentioned steps (2) is hexanaphthene, toluene or YLENE; The solute of the alkaline solution in the above-mentioned steps (2) is sodium hydroxide, Pottasium Hydroxide, Lithium Hydroxide MonoHydrate, ammoniacal liquor, quadrol, diethylamine, triethylamine or trolamine.
The catalyzer solute in the above-mentioned steps (1) and the mol ratio of polyvinyl alcohol units are 0.05: 1-1: 1; The A in the step (1) and the mol ratio of B blending ingredients and polyvinyl alcohol units are 0.3: 1-1.2: 1; The 30%-100% of A ingredients constitute A in the step (1) and B blending ingredients amount of substance; The mol ratio of the A component in the solute of the alkaline solution in the step (1) and the step (1) is 0.5: 1-1: 1; Carbonatoms in the step (1) is that the Fatty Alcohol(C12-C14 and C12-C18) quality of 1-3 is the 50%-100% of all reactant total masses in the step (1); The polymerization degree of the Z 150PH in the step (1) is 50-300.
The mol ratio of A component is 0.1 in methoxy polyoxyethylene ether compound in the above-mentioned steps (2) and the step (1): 1-0.5: 1; The mol ratio of the middle alkaline solution solute sum of catalyzer and step (1) is 0.5 in the solute of the hydrochloric acid soln in the step (2) and the step (1): 1-1: 1; Catalyst quality in the step (2) is the 1.5-10% of methoxy polyoxyethylene ether compound quality; Band aqua quality in the step (2) is the 8-30% of step (1) and step (2) reactant total mass.
The structure expression of this cement dispersants of synthetic is:
R in the said structure formula
1Be ethyl, sec.-propyl, hydroxyethyl ethyl, 2-hydroxyethyl sec.-propyl or sulfopropyl ethyl; R
2Be methoxy polyoxyethylene ether oxygen base or methoxy polyoxyethylene ether amino; R
3Be N-(propanesulfonic acid) propionamido-, N-(methyl propane sulfonic acid) propionamido-or N-(oxyacetic acid) propionamido-.
X in the said structure formula, y, p, q are positive integer; The quantity of each repeating unit that expression distributes in polymerization with random fashion; (y+p+q)/(x+y+p+q) scope is 0.3: 1-1: 1, and scope (y+p)/(y+p+q) is 0.3: 1-1: 1, the scope of p/ (y+p) is 0.1: 1-0.5: 1.
The number-average molecular weight of the methoxy polyoxyethylene ether compound in the inventive method is 500-3000.
The inventive method compared with prior art has following beneficial effect:
(1) agent structure of current polycarboxylic acid cement dispersants is made main chain with (gathering) acrylic compounds mostly; The preparation method is also more is confined to the method for functionalization after direct copolymerization of polymerisable monomer or the polymerization; And depending on unduly of (gathering) acrylic compounds understood the development in pluralism that hinders the concrete admixture industry; Novelty of the present invention ground adopts Z 150PH as main raw material; And, be aided with the Michael nucleophilic addition with this molecular chain main chain as cement dispersants, prepare that a kind of molecular chain agent structure does not rely on (gathering) acrylic compounds but each item performance index cement dispersants of excellent novel texture still; Help increasing the market competitiveness of new structured type cement dispersants, promote the mass development and the application of diversified product.
(2) be distributed with a large amount of functional groups on the main chain of the cement dispersants of the present invention preparation: micromolecular group such as sulfonic group, carboxyl, hydroxyl play the effect of absorption cement particulate, and it is sterically hindered to reduce flucculation structure and to improve and disperse and the effect of hold facility that macromole polyethers side chain plays and forms solvent membrane, provides.This cement dispersants has and common polycarboxylic acids dehydragent various structure, disperses cement particulate ability and the advantage that improves cement slurry flowability and retentivity but still possess, and the cement of different varieties is shown very strong flexibility.The inventive method has not only expanded the intension and the application of design theory of molecular structure, has also further enriched " electrostatic repulsion " and " sterically hindered " mechanism of comb property molecular structure.
(3) the present invention adopts the Michael nucleophilic addition as synthesizing mean; With electron donor(ED) Z 150PH and electron acceptor(EA) α; The Michael addition reaction takes place in beta-unsaturated carbonyl compound; Adduct that obtains and the condensation of methoxy polyoxyethylene ether compound obtain cement dispersants, and involved Michael addition reaction step is simple, mild condition, raw material are easy to get, and need not other complicated reaction process or harsh reaction conditions; Used main raw material Z 150PH is a kind of common water-soluble polymer; With used methoxy polyoxyethylene ether compound the wider molecular weight scope of application is arranged all, used catalyzer also is common common basic catalyst, has excellent popularization and using value.
(4) the present invention relies on the condensation reaction of Michael addition adducts and methoxy polyoxyethylene ether compound to prepare cement dispersants; This condensation reaction is carried out under non-water surrounding; The condensation product that obtains is that the cement of 100% concentration disperses water reducer, can be mixed with the product of any concentration according to the water that market demand adds corresponding amount, and this Product Status is stable; It is not stratified to leave standstill the back under the high density; Deposit non-crystallizablely under the low temperature, and performance is unaffected after the low-temperature storage, is a kind of cement dispersants with unique advantage and distinguishing feature.
(5) safe preparation process environmental protection, cleanliness without any pollution, reaction process need not nitrogen protection, and used band aqua also can be recycled after separatory separates, and has reduced wastage of material.The condensing reflux of band aqua can also keep system temperature steady, and can reduce the viscosity of HMW reaction system, makes to mix more fully, improves the speed of reaction of system and the percentage of grafting of product.These advantages all help the enforcement of suitability for industrialized production, therefore have good economic benefits and social effect.
Embodiment
Below in conjunction with embodiment to the present invention about Z 150PH elder generation Michael addition again the concrete grammar of functional group's condensation prepared cement dispersants do further detailed description, but enforcement of the present invention is not limited thereto.
Embodiment 1
It is in the middle of 30% the sodium hydroxide solution that 8.8g Z 150PH (polymerization degree=164) is joined the 8g massfraction, and 25 ℃ were stirred 2 hours, and were warming up to 40 ℃ then; Add the 28.4g massfraction and be 20% acrylamide soln and carry out Michael reaction, react after 2 hours, be warming up to 70 ℃; Adding 8.96g massfraction is 50% potassium hydroxide solution; After the hydrolysis 2 hours, use the 14.48g washed with isopropyl alcohol for 40 ℃, and obtain Michael addition adducts 100 ℃ of dryings.
48g methoxy polyoxyethylene ether (molecular weight=1200) is joined in the reactor drum; Be warming up to 50 ℃, dry Michael addition adducts, the 20.44g massfraction that obtains of adding is 20% hydrochloric acid soln, 2.4g tosic acid successively, stirs to add the 18.74g hexanaphthene when being warming up to 80 ℃; Continue to be warming up to 105 ℃ and carry out condensation reaction; Reaction the time will react the gained water sepn and gone out, and react and slough hexanaphthene through vacuumizing after 6 hours, and the use 14.4g massfraction when being cooled to 25 ℃ of lowering the temperature is that to be neutralized to the pH value be 6.5 for 10% sodium hydroxide solution; Obtain condensation product, add the cement dispersants that the dilution of 90.25g water obtains 40% massfraction at last.
Embodiment 2
The massfraction that embodiment 1 is obtained be 40% cement dispersants 6 ℃ deposit 30 days after, measure its implementation result.
Embodiment 3
It is in the middle of 10% the potassium hydroxide solution that 13.2g Z 150PH (polymerization degree=286) is joined the 8.4g massfraction; 15 ℃ were stirred 6 hours, were warming up to 60 ℃ then, added the 15.98g massfraction successively and were 80% acrylic amide and 46.58g massfraction and be 80% N-(methyl propane sulfonic acid) acrylic amide and carry out Michael reaction; React after 4 hours; Be warming up to 95 ℃, adding 32.85g massfraction is 20% diethylamine solution, and hydrolysis is after 0.5 hour; Use the 31.62g methanol wash for 50 ℃, and obtain Michael addition adducts 120 ℃ of dryings.
Hold amino methoxy polyoxyethylene ether (molecular weight=2000) to join in the reactor drum 36g; Be warming up to 65 ℃; Dry Michael addition adducts, the 10.65g massfraction that obtains of adding is 36% hydrochloric acid soln, 3.6g thionamic acid successively; Add 17.86g toluene when stirring is warming up to 100 ℃, continue to be warming up to 160 ℃ and carry out condensation reaction, will react the gained water sepn in the time of reaction and go out; React and slough toluene through vacuumizing after 0.5 hour; Cooling use when being cooled to 40 ℃ the 34.47g massfraction be 50% potassium hydroxide solution to be neutralized to pH value be 7.2, obtain condensation product, add 225.24g water at last and dilute the cement dispersants that obtains 30% massfraction.
Embodiment 4
The massfraction that embodiment 3 is obtained be 30% cement dispersants 5 ℃ deposit 20 days after, measure its implementation result.
Embodiment 5
It is in the middle of 1% the lithium hydroxide solution that 4.4g Z 150PH (polymerization degree=65) is joined the 24g massfraction, and 35 ℃ were stirred 0.5 hour, and were warming up to 60 ℃ then; Add the 5.1g massfraction and be 50% USAF RH-1 and carry out Michael reaction, react after 0.5 hour, be warming up to 65 ℃; Adding 4.47g massfraction is 80% triethanolamine solution; After the hydrolysis 6 hours, 15 ℃ with 5.56g n-propyl alcohol washing, and obtains Michael addition adducts 90 ℃ of dryings.
Hold amino methoxy polyoxyethylene ether (molecular weight=2400) to join in the reactor drum 21.6g; Be warming up to 45 ℃; Dry Michael addition adducts, the 45.26g massfraction that obtains of adding is 5% hydrochloric acid soln, the 0.33g vitriol oil (massfraction is 98%) successively; Add 8.57g YLENE when stirring is warming up to 90 ℃, continue to be warming up to 125 ℃ and carry out condensation reaction, will react the gained water sepn in the time of reaction and go out; React and slough YLENE through vacuumizing after 10 hours; Cooling use when being cooled to 30 ℃ the 6.36g massfraction be 30% triethylamine solution to be neutralized to pH value be 6.2, obtain condensation product, add 126.13g water at last and dilute the cement dispersants that obtains 20% massfraction.
Embodiment 6
The massfraction that embodiment 5 is obtained be 20% cement dispersants 7 ℃ deposit 40 days after, measure its implementation result.
Embodiment 7
It is in the middle of 30% the alcohol sodium solution that 11g Z 150PH (polymerization degree=209) is joined the 45.33g massfraction; 20 ℃ were stirred 3 hours, were warming up to 35 ℃ then, added the 12.9g massfraction and were 40% USAF RH-1 and 67.55g massfraction and be 40% N-(propanesulfonic acid) acrylic amide and carry out Michael reaction; React after 10 hours; Be warming up to 60 ℃, adding 4g massfraction is 60% sodium hydroxide solution, and hydrolysis is after 4 hours; Use the 30.23g washing with alcohol for 20 ℃, and obtain Michael addition adducts 105 ℃ of dryings.
15g methoxy polyoxyethylene ether (molecular weight=500) is joined in the reactor drum; Be warming up to 55 ℃, dry Michael addition adducts, the 18.98g massfraction that obtains of adding is 30% hydrochloric acid soln, 1.2g phosphoric acid successively, stirs to add the 4.65g hexanaphthene when being warming up to 80 ℃; Continue to be warming up to 110 ℃ and carry out condensation reaction; Reaction the time will react the gained water sepn and gone out, and react and slough hexanaphthene through vacuumizing after 5 hours, and the use 13.39g massfraction when being cooled to 35 ℃ of lowering the temperature is that to be neutralized to the pH value be 8 for 40% ammonia soln; Obtain condensation product, add the cement dispersants that the dilution of 52.4g water obtains 50% massfraction at last.
Embodiment 8
The massfraction that embodiment 7 is obtained be 50% cement dispersants 6 ℃ deposit 30 days after, measure its implementation result.
Embodiment 9
It is in the middle of 15% the sodium hydroxide solution that 6.6g Z 150PH (polymerization degree=127) is joined the 20g massfraction, and 30 ℃ were stirred 1 hour, and were warming up to 50 ℃ then; Add the 15g massfraction and be 60% TEB 3K and carry out Michael reaction, react after 6 hours, be warming up to 85 ℃; Adding 7.2g massfraction is 30% lithium hydroxide solution; After the hydrolysis 1.5 hours, use the 15.6g washed with isopropyl alcohol for 35 ℃, and obtain Michael addition adducts 110 ℃ of dryings.
54g methoxy polyoxyethylene ether (molecular weight=3000) is joined in the reactor drum; Be warming up to 50 ℃, dry Michael addition adducts, the 24.09g massfraction that obtains of adding is 25% hydrochloric acid soln, 2.7g tosic acid successively, stirs to add the 8.35g hexanaphthene when being warming up to 80 ℃; Continue to be warming up to 115 ℃ and carry out condensation reaction; Reaction the time will react the gained water sepn and gone out, and react and slough hexanaphthene through vacuumizing after 4 hours, and the use 19.44g massfraction when being cooled to 30 ℃ of lowering the temperature is that to be neutralized to the pH value be 6 for 20% ethylenediamine solution; Obtain condensation product, add the cement dispersants that the dilution of 83.09g water obtains 45% massfraction at last.
Embodiment 10
The massfraction that embodiment 9 is obtained be 45% cement dispersants 5 ℃ deposit 20 days after, measure its implementation result.
Embodiment 11
It is in the middle of 25% the triethylamine solution that 17.6g Z 150PH (polymerization degree=242) is joined the 16.16g massfraction; 25 ℃ were stirred 2.5 hours, were warming up to 55 ℃ then, added the 19.66g massfraction and were 70% methyl acrylate and 47.31g massfraction and be 70% N-(methyl propane sulfonic acid) acrylic amide and carry out Michael reaction; React after 3.5 hours; Be warming up to 75 ℃, adding 8.96g massfraction is 60% potassium hydroxide solution, and hydrolysis is after 3.5 hours; Use the 32.24g methanol wash for 25 ℃, and obtain Michael addition adducts 95 ℃ of dryings.
Hold amino methoxy polyoxyethylene ether (molecular weight=1000) to join in the reactor drum 56g; Be warming up to 55 ℃; Dry Michael addition adducts, the 19.86g massfraction that obtains of adding is 15% hydrochloric acid soln, the 2.8g vitriol oil (massfraction is 80%) successively; Add 18.07g toluene when stirring is warming up to 95 ℃, continue to be warming up to 135 ℃ and carry out condensation reaction, will react the gained water sepn in the time of reaction and go out; React and slough toluene through vacuumizing after 4.5 hours; Cooling use when being cooled to 30 ℃ the 15.8g massfraction be 35% lithium hydroxide solution to be neutralized to pH value be 7.1, obtain condensation product, add 205.58g water at last and dilute the cement dispersants that obtains 35% massfraction.
Embodiment 12
The massfraction that embodiment 11 is obtained be 35% cement dispersants 7 ℃ deposit 40 days after, measure its implementation result.
Implementation result:
1. flowing degree of net paste of cement
Be to investigate the various dissemination effects of synthetic of the present invention with cement dispersants of new texture to different cement, test determination the clean slurry degree of mobilization of each embodiment to different cement types.Test is undertaken by GB/T8077-2000 " Methods for testing uniformity of concrete admixture ", W/C=0.29, and volume is the solid volume of folding.Test-results is seen table 1.
Table 1 cement paste flowing property result
Can find out that from table more than 1 kinds of cement dispersants with new texture of the inventive method synthetic all can show excellent dispersive ability and cement adaptability.
2. concrete slump and divergence
Test determination the divergence that in concrete system, shows of each embodiment and the slump and keep performance.Test-results is seen table 2.
Table 2 concrete flowability can the result
Can find out that from table more than 2 kinds of cement dispersants with new texture of the inventive method synthetic all can show the excellent divergence and the hold facility of the slump in concrete system.
Claims (6)
1. the preparation method based on Z 150PH Michael reaction synthetic water cement dispersant is characterized in that, may further comprise the steps:
(1) Z 150PH is joined in the middle of the aqueous solution of catalyzer that massfraction is 1-30%; 15-35 ℃ was stirred 0.5-6 hour, was warming up to 35-60 ℃ then, and the adding massfraction is that the A component and the B component blended aqueous solution of 20-80% carries out Michael reaction; React after 0.5-10 hour; Be warming up to 60-95 ℃, adding massfraction is the alkaline solution of 20-80%, after hydrolysis 0.5-6 hour; 15-50 ℃ is used carbonatoms to wash as the Fatty Alcohol(C12-C14 and C12-C18) of 1-3, and obtains Michael addition adducts 90-120 ℃ of drying; Described catalyzer is a basic catalyst, and described A component is amides α, beta-unsaturated carbonyl compound or ester class α, beta-unsaturated carbonyl compound; Described B component is amides α, the verivate of beta-unsaturated carbonyl compound;
(2) the methoxy polyoxyethylene ether compound is joined in the reactor drum; Be warming up to 45-65 ℃, add the product that obtains in the step (1), hydrochloric acid soln, the catalyzer that massfraction is 5%-36% successively, stir to add when being warming up to 80-100 ℃ and be with aqua; Continue to be warming up to 105-160 ℃ and carry out condensation reaction; Reaction the time will react the gained water sepn and gone out, and react after 0.5-10 hour and slough the band aqua through vacuumizing, and lower the temperature to use massfraction to be neutralized to the pH value as the alkaline solution of 10-50% when being cooled to 25-40 ℃ to be 6-8; Obtain condensation product, add the cement dispersants that the entry dilution obtains required massfraction at last.
2. the preparation method of cement dispersants according to claim 1 is characterized in that, the described catalyzer of step (1) is sodium hydroxide, Pottasium Hydroxide, Lithium Hydroxide MonoHydrate, triethylamine, hexahydropyridine, sodium ethylate or sodium amide; The described A component of step (1) is acrylic amide, USAF RH-1, methyl acrylate, TEB 3K, Hydroxyethyl acrylate, 2-hydroxy ethyl methacrylate, 2-hydroxyethyl meth acrylate or 2-sulfopropyl propenoate; The described B component of step (1) is N-(propanesulfonic acid) acrylic amide, N-(methyl propane sulfonic acid) acrylic amide or N-(oxyacetic acid) acrylic amide; The solute of the described alkaline solution of step (1) is sodium hydroxide, Pottasium Hydroxide, Lithium Hydroxide MonoHydrate, ammoniacal liquor, quadrol, diethylamine, triethylamine or trolamine; The described carbonatoms of step (1) is that the Fatty Alcohol(C12-C14 and C12-C18) of 1-3 is methyl alcohol, ethanol, n-propyl alcohol or Virahol.
3. the preparation method of cement dispersants according to claim 1 is characterized in that, the described methoxy polyoxyethylene ether compound of step (2) is methoxy polyoxyethylene ether or holds amino methoxy polyoxyethylene ether; The described catalyzer of step (2) is that tosic acid, massfraction are the vitriol oil, ETHYLE ACETATE, phosphoric acid or the thionamic acid of 80-98%; The described band aqua of step (2) is hexanaphthene, toluene or YLENE; The solute of the described alkaline solution of step (2) is sodium hydroxide, Pottasium Hydroxide, Lithium Hydroxide MonoHydrate, ammoniacal liquor, quadrol, diethylamine, triethylamine or trolamine.
4. the preparation method of cement dispersants according to claim 1 is characterized in that, the mol ratio of described catalyzer solute of step (1) and polyvinyl alcohol units is 0.05: 1-1: 1; The mol ratio of the A described in the step (1) and B blending ingredients and polyvinyl alcohol units is 0.3: 1-1.2: 1; The 30%-100% of A ingredients constitute A described in the step (1) and B blending ingredients amount of substance; The mol ratio of the A component described in the solute of the alkaline solution described in the step (1) and the step (1) is 0.5: 1-1: 1; Carbonatoms described in the step (1) is that the Fatty Alcohol(C12-C14 and C12-C18) quality of 1-3 is the 50%-100% of all reactant total masses in the step (1); The polymerization degree of the Z 150PH described in the step (1) is 50-300.
5. the preparation method of cement dispersants according to claim 1 is characterized in that, the mol ratio of A component is 0.1 in described methoxy polyoxyethylene ether compound of step (2) and the step (1): 1-0.5: 1; The mol ratio of the middle alkaline solution solute sum of catalyzer and step (1) is 0.5 in the solute of the hydrochloric acid soln described in the step (2) and the step (1): 1-1: 1; Catalyst quality described in the step (2) is the 1.5-10% of methoxy polyoxyethylene ether compound quality; Band aqua quality described in the step (2) is the 8-30% of step (1) and step (2) reactant total mass.
Application rights require the preparation of 1 said method based on Z 150PH Michael reaction synthetic cement dispersants, it is characterized in that its structure expression is:
R wherein
1Be ethyl, sec.-propyl, hydroxyethyl ethyl, 2-hydroxyethyl sec.-propyl or sulfopropyl ethyl; R
2Be methoxy polyoxyethylene ether oxygen base or methoxy polyoxyethylene ether amino; R
3Be N-(propanesulfonic acid) propionamido-, N-(methyl propane sulfonic acid) propionamido-or N-(oxyacetic acid) propionamido-;
Wherein x, y, p, q are positive integer; The quantity of each repeating unit that expression distributes in polymerization with random fashion; (y+p+q)/(x+y+p+q) scope is 0.3: 1-1: 1, and scope (y+p)/(y+p+q) is 0.3: 1-1: 1, the scope of p/ (y+p) is 0.1: 1-0.5: 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106519082A (en) * | 2016-11-04 | 2017-03-22 | 广东天安新材料股份有限公司 | Cross-linking agent as well as preparation method and application thereof |
| CN112978942A (en) * | 2019-12-17 | 2021-06-18 | 天津农学院 | Preparation method of controllable brush-shaped structure environment-friendly scale inhibitor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5783628A (en) * | 1996-03-07 | 1998-07-21 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Modified polyvinyl alcohol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5783628A (en) * | 1996-03-07 | 1998-07-21 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Modified polyvinyl alcohol |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106519082A (en) * | 2016-11-04 | 2017-03-22 | 广东天安新材料股份有限公司 | Cross-linking agent as well as preparation method and application thereof |
| CN106519082B (en) * | 2016-11-04 | 2018-12-28 | 广东天安新材料股份有限公司 | A kind of crosslinking agent and its preparation method and application |
| CN112978942A (en) * | 2019-12-17 | 2021-06-18 | 天津农学院 | Preparation method of controllable brush-shaped structure environment-friendly scale inhibitor |
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