CN101333092B - Cement concrete superplasticizer and method for preparing same - Google Patents
Cement concrete superplasticizer and method for preparing same Download PDFInfo
- Publication number
- CN101333092B CN101333092B CN 200710076173 CN200710076173A CN101333092B CN 101333092 B CN101333092 B CN 101333092B CN 200710076173 CN200710076173 CN 200710076173 CN 200710076173 A CN200710076173 A CN 200710076173A CN 101333092 B CN101333092 B CN 101333092B
- Authority
- CN
- China
- Prior art keywords
- potassium
- sodium
- initiator
- derivative
- cement concrete
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2652—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/32—Superplasticisers
Abstract
The invention discloses a concrete superplasticizer and a preparation method. Based on weight proportion, 1-50% of nitrogen-containing functional monomer a, 5-50% of unsaturated carboxylic acid and the derivative b of the unsaturated carboxylic acid, 15-94% of polyoxyethylene vinyl propionate ester ene single-ether and the derivative c of the polyoxyethylene vinyl propionate ester ene single-ether, as well as 0-50% of allyl sulfonate d are mixed to prepare a mixed monomer solution; the initiator which takes up 0.5-15% of the total weight of the mixed monomer, and the chain transfer agent which takes up 0-15% of the total weight of the mixed monomer are added into the mixed monomer solution so as to prepare the concrete super plasticizer through ternary or quaternary copolymerization. Without going through analysis purification, the invention can directly obtain the product and has simple synthetic process, less equipment investment, simple operation and easily controlled reaction conditions; the obtained product has better compatibility with cement and good adaptability with other additives, and is free from segregation and bleeding phenomena; the product also has good concrete slump retentivity and high water reduction rate.
Description
Technical field
The present invention relates to a kind of cement concrete superplasticizer.
The invention still further relates to the preparation method of cement concrete superplasticizer.
Background technology
Cement concrete is modal material of construction, and concrete mixture will keep flow state before casting, to strengthen workability and serviceability.And current concrete faces concrete weak point process period, and the problem that workability is poor is mixed and stirred simultaneously for a long time, and concrete is usually emanated, bleeding, even can't cast.In order to overcome the above problems, the polymkeric substance such as the more use sulfonated lignin of early stage concrete admixture, naphthalenesulfonate formaldehyde condensation compound NSF, condensate of melamine sulfonate and formaldehyde MSF, aliphatics thionamic acid ASPF, under the prerequisite that does not change workability of concrete, can reduce significantly the concrete mixing water consumption, and improve significantly concrete intensity, concrete serviceability is greatly improved.What but these concrete admixtures mainly played is water-reduction, they exist, and volume is higher, workability is poor, bad adaptability, concrete through the time problems such as loss is large.Volume is too high, can cause that water-retentivity is bad, the segregation consequences such as bleeding is serious, so that concrete is clamminess, and the poor stability of product, the modification difficulty, producing simultaneously and using all has pollution to environment.In its manufacturing processed, use formaldehyde, can cause environmental pollution, the large and generation slow setting of Slump Time losing of Large; It may be carcinogenic substance that the naphthalene that uses is considered to, thereby the water reducer that has limited to raise variety further develops.
In recent years, both at home and abroad in order overcoming the above problems, to study energetically the water soluble polycarboxylic acid polymkeric substance, and to make concrete reach a new height at aspects such as workability, homogeneity, stability, weather resistance, diversity.Satisfied the service requirements of concrete under high stratification, large load, large volume, large span, deep-sea, underground, corrosive environment, under the rigor condition.Towards lightweight, the future development such as high-strength, durable, economic, energy-conservation, green.Greatly expanded concrete use range, also greatly improved concrete work-ing life simultaneously.
The polycarboxylic acid series multipolymer is as the most promising concrete admixture kind on the present world market, be used widely in a lot of countries, such as in states such as Japan, the U.S., Italy, the polymkeric substance of maleic anhydride class, acrylic acid or the like has replaced traditional naphthalene series additive substantially.
But the patent for the polycarboxylic acid polymer that improves concrete performance of announcing at present, what disclose technical scheme is to adopt the carboxylic-acid comonomer to be polymerized mostly, and does not disclose the polymkeric substance of nitrogenous functional monomer:
US4814014: adopt the grafting method preparation, connect thing and a homopolymer but the problem that exists is that existence is non-in a large number in the multipolymer, thereby conversion rate of products is low, cost is high, weak effect.
US5362324: low fluidity loss and low bleed.Reducing bleed can be by introducing sulfonate radical, increases water-soluble or realizes with cross-linked polymer.Use cross-linked polymer in strong base solution, can be hydrolyzed, generate the simple linear polymer chain, reduce fluidity loss.Water reducer is comprised of the terpolymer of vinylformic acid, macromonomer and difunctionality macromonomer.
US5614017: the water reducer that is used for cement composition is to be reacted by the polyethers that hydroxy acid polymkeric substance and the epoxide that contains two to four carbon form to generate.When reacting, esterification also occurs in the polyether moiety division, and other reactant also divides.And in concrete reaction process, sulfonic acid is used as catalyzer and comes the oxyethane of catalysis polyacrylic acid and simple function and the multipolymer of propylene oxide to be higher than 140 ℃ of reactions in temperature.
US5985989: the cement composition water reducer is that the polyethers (as: multipolymer of polypropylene glycol or oxyethane and propylene oxide) that the polymerized in-situ by ethylene-unsaturated acid monomer (as: vinylformic acid or maleic anhydride) forms generates carboxylic acid polyalcohol.Carboxylic acid polyalcohol and polyether reactant, the synthetics of generation and the character of water reducer can be according to the acid mono of the difference amount of adding, polyethers, reaction conditions, reagent dosage and difference.
External preparation technology's more complicated, and higher to the conversion unit requirement, stricter to reflection condition control ratio.
The publication number that Chinese patent is announced is the patent of invention of CN1316398: the preparation method who has introduced a kind of polycarboxylic acid series water reducing agents for efficient aerocrote.The concrete technology method is carried out in two steps: the first step, methyl Soxylat A 25-7, Resorcinol, tosic acid are put into reaction vessel, under 85 ± 3 ℃ temperature, after stirring is dissolved Resorcinol and tosic acid fully, drip methyl methacrylate in container, speed is dripped in control, drips off in 15 ± 5 minutes, then maintain the temperature in 85 ± 3 ℃ of scopes, reacted 8 ± 0.5 hours.Reaction generates methacrylic acid methyl polyoxyethylene ether-ester, contains polymerizable double bond in its molecular structure; Second step, at first to the middle 20-30% that adds the butanone total amount of the first step product (being methacrylic acid methyl polyoxyethylene ether-ester), temperature is controlled at 83 ± 3 ℃, stir, then with dripping in remaining butanone dissolving methacrylic acid and the backward methacrylic acid methyl of dibenzoyl peroxide (BPO) polyoxyethylene ether-ester, with polymerization reaction take place.Speed is dripped in control, makes it to drip off in 1.5 ± 0.5 hours, and the control temperature of reaction is in 83 ± 3 ℃ of scopes, reacts 3 ± 0.3 hours.After question response was substantially complete, underpressure distillation under 80 ± 5 ℃ of conditions desolventized with steaming, obtains polycarboxylic acid series water reducing agents for efficient aerocrote of the present invention.
The publication number that Chinese patent is announced is the patent of invention of CN1636922: introduced a kind of polycarboxylic acid series water reducing agent and preparation method, this water reducer is to react synthetic carboxylate PEA by polyoxyethylene glycol and vinylformic acid under catalyst, that utilizes that synthetic PEA and methylpropene sodium sulfonate and acrylic acid copolymer synthesize contains carboxyl, the water reducer of sulfonic group and polyoxyethylene chain side chain.
The publication number that Chinese patent is announced is the patent of invention of CN1261599: three (four) membered copolymers of maleic anhydride and toxilic acid PEO half ester and comonomer (vinylbenzene, vinyl ether, ethyl acetate).Toxilic acid provides the grappling function.Two kinds of different PEO molecular weight toxilic acid PEO half esters provide respectively stably dispersing and their defoaming function.The polymerization degree that plays the PEO of divergent function is 140-180.The n=20. molecular weight of copolymer that plays their defoaming function is not less than 10000.It can and polycarboxylic acid series (n=25) share.The former provides good divergent function.The latter is not hydrolyzed under highly basic yet, and Ying Erneng keeps degree of mobilization
The publication number that Chinese patent is announced is the patent of invention of CN1550474: collapsing keeps index 80%.Two membered copolymers of PEG acrylate (N=100-200) and (methyl) acrylate or add again the terpolymer (N=2-300) of sulfonate monomer.Purpose improves the production efficiency of concrete secondary product.This patent is mentioned among the JP 62-119147 as preventing that fluidity loss from using a large amount of 2-sulfo group ethylacrylic acid sodium (N=10).Increase the EO chain length and can reduce solidification delay.Sulfonic acid monomer can reduce the degree of solidification delay.Sulfonic acid monomer: 2-acrylamide-2-methyl propane sulfonic, (methyl) ethyl propenoate sulfonate.The chain-transfer agent 2 mercaptopropionic acid.Temperature of reaction 60-85oC. Acrylic Acid Monomer degree of neutralization is less than 10%.
The publication number that Chinese patent is announced is the patent of invention of CN1165795: the slump is good, and N=4 and 23 PEO blend or copolymerization reduce fluidity loss.Think that the mechanism of fluidity loss is that the PEO wetting ability of N=4 is relatively poor, has delayed the hydration rate of C3A in the cement.Hydration reduces mixing water, and dispersion agent is buried in hydrate simultaneously.
The publication number that Chinese patent is announced is the patent of invention of CN1436158: backbone molecule amount 5000-20000, the side chain polymerization degree 50-500, carboxyl/sulfonic group 3-5.The synergy of silica gel and dispersion agent makes non-bleeding good.
The publication number that Chinese patent is announced is the patent of invention of CN1135207: product is made of imido acrylate copolymer.Keep than high fluidity in a long time, and do not have undue slow setting.The acrylamide direct polymerization is difficult to control, makes product molecular weight distribution wider.Z (BO) zN, Z=primary amine or hydroxyl, this compound provides slump preserving property.Aminate is 10-20% acrylic acid units.Imidization forms by acrylate copolymer and alkoxylated amines reaction.Reaction will form under dehydration conditions and catalyst action.
The publication number that Chinese patent is announced is the patent of invention of CN1673163: 8-40% (methyl) vinylformic acid, 55-85% large monomer, and the 2-20% cationic monomer, the 0-15% acrylate is used epoxy cross-linking after the polymerization.Air content is less than 3.2%.Think that if (methyl) acrylic acid content is too high cause multipolymer absorption too fast, then mobile loss is also very fast.Large monomer is excessive then same problem.Cationic monomer can improve saturated adulterate capacity.The too high generation precipitation of consumption, dispersiveness and dispersion retentivity are all bad.
Reaching the polymerization process of mentioning the preparation polymkeric substance on the document at home and abroad generally adopts two-step approach or connects a method, two-step approach prepares the production technique more complicated, reaction conditions is relatively harsher, wayward, the particularly preparation of the first step product, the product that obtains contains too many impurity, and is very large on the impact of second step polyreaction.Production time is long, and restriction is many, and efficient is low, and influence factor is complicated, the relatively more difficult control of the purity of intermediate, and above preparation method has plenty of in organic solvent and carries out, and is unfavorable for cleaner production and protection of the environment.Also make process complications, cost increases, and all brings inconvenience for production and use.By the polycarboxylate water-reducer of two-step approach preparation, its water-reducing rate fluctuation ratio is larger, and is poor with the compatibleness of other admixture to the bad adaptability of cement, simultaneously to the poor stability of temperature.
Therefore, can make blended stock that higher flowability is arranged, the actual mixing water content of energy decrease, effectively improve concrete intensity and weather resistance, cement concrete superplasticizer with characteristics such as low-dosage, polymolecularity, high dispersive retentivity, high slump retainings has very large development prospect, also becomes the existing aborning essential technical problem that solves.
Summary of the invention
The technical problem to be solved in the present invention is in order to overcome technological deficiency recited above, a kind of low-dosage polymolecularity that has is provided, high slump retaining, adaptability to cement is good, good with the compatibleness of other admixture, to the good stability of envrionment temperature, increase substantially the characteristics of concrete strength and weather resistance and have the cement concrete superplasticizer of nitrogenous functional monomer, and the preparation method of this kind cement concrete superplasticizer is provided.
In order to solve technical problem recited above, the present invention takes following technical scheme:
The invention provides a kind of cement concrete superplasticizer, have nitrogenous functional monomer a, unsaturated carboxylic acid and derivative b thereof and polyoxyethylene groups acid allyl ester alkene monomethyl ether and derivative c thereof as terpolymer; Or as quarternary copolymerized nitrogenous functional monomer a, unsaturated carboxylic acid and derivative b thereof, polyoxyethylene groups acid allyl ester alkene monomethyl ether and derivative c and allylsulfonate d;
Its general structure is:
Or
R in the upper general formula
1-R
12Expression hydrogen atom or have the alkyl of 1-10 carbon atoms, R can be the same or different; M represents hydrogen atom, sodium, potassium or NH
4 +That n represents is CH
2CH
2The average addition mole number of O, its value is 4-150.
Wherein, described nitrogenous functional monomer a is vinyl pyrrolidone, N,N-DMAA, N, N-methylene radical acrylamide, N hydroxymethyl acrylamide, acrylamide, Methacrylamide, diacetone-acryloamide(DAA) one or a combination set of.
Described unsaturated carboxylic acid and derivative b thereof are vinylformic acid, methacrylic acid, maleic anhydride, methyl acrylate, methyl methacrylate, butyl methacrylate, hydroxyethyl methylacrylate, butyl acrylate, ethyl acrylate, ethyl propenoate, Hydroxyethyl acrylate, Rocryl 410, lauryl methacrylate(LMA), polymethylmethacrylate, β-crotonic acid, toxilic acid, methylene-succinic acid, itaconic anhydride, citraconic anhydride, citraconic acid, fumaric acid, Propylene glycol monoacrylate, methyl propenoic acid glycidyl fat, sodium methacrylate one or a combination set of.
Described polyoxyethylene groups acid allyl ester alkene monomethyl ether and derivative c thereof are methoxy polyethylene glycol acrylate, methoxy polyethylene glycol methacrylate-styrene polymer, methoxyl group polypropylene glycol acrylate, methoxyl group polytetramethylene glycol mono acrylic ester, methoxyl group polytetramethylene glycol methacrylic ester, methoxy poly (ethylene glycol) polypropylene glycol mono acrylic ester, methoxy poly (ethylene glycol) polypropylene glycol methacrylic ester, methoxy poly (ethylene glycol) polytetramethylene glycol mono acrylic ester, methoxy poly (ethylene glycol) polytetramethylene glycol methacrylic ester, the methoxy polyoxyethylene acrylate, the methoxy polyoxyethylene methacrylic ester, the polyoxyethylene acrylate, polyoxyethylene diacrylate, the polyoxyethylene dimethacrylate, the polyoxypropylene diacrylate, the polyoxypropylene dimethacrylate, the polyoxypropylene acrylate, polyethylene glycol acrylate, polyethylene glycol methacrylate-styrene polymer, the polytetramethylene glycol mono acrylic ester, the polytetramethylene glycol methacrylic ester, polyoxyethylene nonylphenol ether, nonyl phenol poly-oxypropylene ether one or a combination set of.
As a kind of preferred version, CH among polyoxyethylene groups acid allyl ester alkene monomethyl ether and the derivative c thereof
2CH
2The average addition mole number n value of O is 9-120; More excellent scheme is that average addition mole number n value is 23-115.
Described allylsulfonate d is sodium allylsulfonate, methylpropene sodium sulfonate, 2-acrylamide 2-methacrylic sulfonic acid, vinylbenzenesulfonic acid sodium one or a combination set of.
The present invention also provides a kind of preparation method of cement concrete superplasticizer as described above, weight proportion is respectively 1-50% nitrogenous functional monomer a, 5-50% unsaturated carboxylic acid and derivative b thereof, 15-94% polyoxyethylene groups acid allyl ester alkene monomethyl ether and the allylsulfonate d of derivative c and 0-50% thereof mix, after making mixed monomer solution, 0.5-15% the initiator that accounts for mix monomer weight that adds and account for 0-15% chain-transfer agent of mix monomer weight, by ternary or quarternary copolymerized reaction, make cement concrete superplasticizer.
As a kind of preferred version, the preparation method of cement concrete superplasticizer may further comprise the steps,
(i) bed material solution processed: one of mixed solution that adds entry, water and allylsulfonate d in the reactor is made bed material, under the stirring of rotating speed 60-100rpm, with nitrogen purging 20-60 minute, and in nitrogen atmosphere heating in water bath to 50-95 ℃;
(ii) monomer solution is closed in compounding: in the component of setting and ratio preparation mixed monomer solution, and use nitrogen purging 0-60min;
(iii) join initiator: in the ratio preparation initiator of setting, and with the initiator nitrogen purging 0-60min for preparing;
(iv) copolyreaction: the initiator that the mixed monomer solution that step I i is made and step I ii make is added drop-wise in the reactor that bed material solution is housed, and the copolyreaction temperature is controlled at 50-95 ℃;
(v) finished product: after copolyreaction is finished, with concentration be the alkaline solution of 20-50% to regulate pH value be 6-9, make cement concrete superplasticizer.
As a kind of optimal way, in the ratio preparation chain-transfer agent of setting, and before copolyreaction occurs, in mixed monomer solution, add chain-transfer agent.
As a kind of preferred version, in step I i, the pH value that adds an amount of alkaline solution adjusting mixed monomer solution is 1.5-7, and preferred version is 3-6 for the pH value of regulating mixed monomer solution, and more excellent scheme is 4-5 for the pH value of regulating mixed monomer solution.
As a kind of preferred version, among the step I v, the initiator time for adding is 1-10h, and more excellent scheme is that time for adding is 2.5-8h, and preferred embodiment is that time for adding is 3.5-6h.The time for adding of control mixed monomer solution is 1-15h.
As a kind of preferred version, among the step I v, the temperature of copolyreaction is controlled at 60-85 ℃, and preferred embodiment is that the temperature of copolyreaction is 70-85 ℃.
As a kind of preferred version, described initiator divides two portions to add: first part adopts the mode that drips continuously to add the initiator that accounts for total amount 40-95% in copolyreaction; Remaining initiator adds in the reaction later stage that mixed monomer solution dropwises as second section.
As a kind of preferred version, after initiator all dropwises, temperature is controlled at 85-95 ℃, behind insulation 0.5-2h, with below the drop in temperature to 40 ℃, regulate pH value 6-9 with alkaline solution again, make cement concrete superplasticizer.
The molecular weight of the Concrete superplastizer that obtains after the copolyreaction is 1000-100000, and more excellent is 6000-80000, and more excellent is 10000-50000.
Wherein, described chain-transfer agent is 2 mercapto ethanol, mercaptoethanol, 3-thiohydracrylic acid, Thiovanic acid, n-butyl mercaptan, tert-butyl mercaptan, octyl mercaptan, positive Dodecyl Mercaptan, Virahol one or a combination set of.
Described initiator is ammonium persulphate, hydrogen peroxide, Sodium Persulfate/potassium, S-WAT/potassium, Sulfothiorine/potassium, sodium bisulfite/potassium one or a combination set of.
Described alkaline solution is the aqueous solution of sodium hydroxide/potassium, sodium hydroxide/potassium, sodium carbonate/potassium, sodium bicarbonate/potassium, trisodium phosphate/potassium, tripoly phosphate sodium STPP/potassium, sodium polyphosphate/potassium, sodium phosphate/potassium, sodium hydrogen phosphate/potassium, trolamine, tri-isopropanolamine, diethanolamine one or a combination set of.
Cement concrete superplasticizer of the present invention need not to purify by analysis, directly obtain product, synthesis technique is simple, and facility investment is few, simple to operate, easy control of reaction conditions, the product of gained and the adaptability of cement are relatively good, and is good with the compatibleness of other admixture, adaptability to cement is good, without the segregation excreting water phenomenon, the concrete slump retentivity is good, and water-reducing rate is high.Polymerization of the present invention is not used formaldehyde or other harmful raw material in producing, and does not use environmentally hazardous organic solvent, employing be aqueous solution polymerization, produce and the life-time service process in to human body without harm, environment is not caused any pollution.
Embodiment
The present invention is further illustrated below by embodiment:
Embodiment 1
In the reactor that thermometer, agitator, opening for feed, reflux condensing tube, nitrogen ingress pipe are housed, add 132g water, pass into nitrogen purging 30min, heating in water bath to 60 ℃, the methylpropene sodium sulfonate that adds again 5.5g is made bed material solution.The rotating speed that stirs is 60-100rpm.Take by weighing 8.4g vinylformic acid, 30.9g methoxy polyethylene glycol acrylate (n=9) and 2.1g vinyl pyrrolidone, add again 15g water and be made into mixed monomer solution.Take by weighing 3.6g ammonium persulphate and 3.6g sodium bisulfite, add 68g water and be made into initiator.With mixed monomer solution and the initiator nitrogen purging 30min that configures, be added drop-wise in the reaction flask with charge pump respectively, time for adding is controlled at 3h, drips off the initiator 27.2g that rear continuation drips same concentrations, and time for adding is controlled at 1h, after dripping off temperature is raised to 95 ℃, behind the insulation 2h, cooling to below 40 ℃, is 30% aqueous sodium hydroxide solution adjusting PH=8 with concentration, both obtained product of the present invention, product is transparent thick liquid.
Embodiment 2
In the reactor four-hole bottle of thermometer, agitator, dropping funnel, reflux condensing tube, nitrogen ingress pipe is housed, use first the air in the nitrogen replacement bottle, add the 6.5g sodium allylsulfonate in the bottle, 86g water is made bed material solution, heating in water bath to 70 ℃.The rotating speed that stirs is 60-100rpm.Take by weighing 9.98g methacrylic acid, 28.84g methoxy polyoxyethylene methacrylic ester (n=23) and 3.3g vinyl pyrrolidone, add again 15g water and be made into mixed monomer solution.Take by weighing 9.98g methacrylic acid and 28.84g methoxy polyoxyethylene methacrylic ester (n=23), add 45g water and be made into mixed monomer solution.Take by weighing the 3.6g ammonium persulphate, add 68g water and be made into initiator.Behind the mixed monomer solution and initiator usefulness nitrogen purging 30min that configure, be added drop-wise in the reaction flask with charge pump respectively, time for adding is controlled at 4h, drip off the initiator 27.2g that rear continuation drips same concentrations, time for adding is 1h, after dripping off temperature is raised to 95 ℃, behind the insulation 2h, cooling to below 40 ℃, is that 30 the trolamine aqueous solution is regulated PH=7 with concentration, and obtaining product of the present invention is transparent thick liquid
Embodiment 3
In the reactor four-hole bottle of thermometer, agitator, dropping funnel, reflux condensing tube, nitrogen ingress pipe is housed, use first the air in the nitrogen replacement bottle, add 17g water in the bottle and do bed material solution, heating in water bath to 80 ℃.The rotating speed that stirs is 60-100rpm.Take by weighing 35.67g methoxy polyethylene glycol methacrylate-styrene polymer (n=35), 4.97g methacrylic acid, 1.02g vinyl pyrrolidone and 2.4g thiohydracrylic acid, add again 163g water and be made into the mixed monomer solution that contains chain-transfer agent, be adjusted to again the PH=5.0 of mixed monomer solution with sodium bicarbonate.Take by weighing the 3.6g ammonium persulphate, add 68g water and be made into initiator.With the mixed monomer solution that configures and initiator with after purging 30min in the nitrogen, be added drop-wise in the reaction flask with charge pump respectively, time for adding is controlled at 5h, drips off the initiator 27.2g that rear continuation drips same concentrations, and time for adding is 2h, after dripping off temperature is raised to 95 ℃, behind the insulation 2h, cools to below 40 ℃, be that 30% aqueous sodium hydroxide solution is regulated PH=6-8 with concentration, obtaining product of the present invention is transparent thick liquid.
Embodiment 4
In the reactor four-hole bottle of thermometer, agitator, dropping funnel, reflux condensing tube, nitrogen ingress pipe is housed, use first the air in the nitrogen replacement bottle, heating in water bath to 85 ℃.The 2-acrylamide 2-methacrylic sulfonic acid and the 29g water that add inwards 0.13g are made bed material solution again.The rotating speed that stirs is 60-100rpm.The 2-acrylamide 2-methacrylic sulfonic acid and the 1.21g vinyl pyrrolidone that take by weighing 5.6g methacrylic acid, 34.5g polyethylene glycol methacrylate-styrene polymer (n=115), 1.3g mix, adding 111g water and mix thoroughly and be made into mixed monomer solution, is to pour dropping funnel into behind 30% the sodium bicarbonate aqueous solution adjusting PH=3.5 with concentration; Take by weighing the 4.12g Potassium Persulphate, adding 54g water is made into initiator and pours another dropping funnel into.With mixed monomer solution and the initiator nitrogen purging 30min that configures, be added drop-wise in the reaction flask with charge pump respectively, time for adding is controlled at 3h, drip off the initiator 20.2g that rear continuation drips same concentrations, time for adding is 1h, after dripping off temperature is raised to 95 ℃, behind the insulation 2h, cooling to below 40 ℃, is that 30% aqueous sodium hydroxide solution is regulated PH=7 with concentration, and obtaining product of the present invention is transparent thick liquid.
Embodiment 5
In the reactor that thermometer, agitator, dropping funnel, reflux condensing tube, nitrogen ingress pipe are housed, use first the air in the nitrogen replacement bottle, heating in water bath to 65 ℃ takes by weighing the 0.532g methylpropene sodium sulfonate and 21g water is made bed material solution.The rotating speed that stirs is 60-100rpm.Take by weighing 12.1g methacrylic acid, 0.532g methylpropene sodium sulfonate, 12.57g methoxy polyoxyethylene methacrylic ester and 1.85g diacetone-acryloamide(DAA), adding 97g water is made into mixed monomer solution and pours dropping funnel into.Take by weighing ammonium persulphate 2.06g and 0.94g sodium bisulfite, adding 27g water is made into initiator and pours another dropping funnel into.The mode that mixed monomer solution and initiator are taked to drip joins in the reaction flask, and time for adding is controlled at 8h, does not add or add a small amount of chain-transfer agent after reaction is carried out to a certain degree.Drip off follow-up continuation of insurance temperature 3-5h, regulate pH value between 6-8 with 20% aqueous sodium hydroxide solution after reaction finishes.Obtaining product of the present invention is transparent thick liquid.
Embodiment 6
In the reactor that thermometer, agitator, dropping funnel, reflux condensing tube, nitrogen ingress pipe are housed, use first the air in the nitrogen replacement bottle, heating in water bath to 75 ℃ takes by weighing the 3.84g sodium allylsulfonate and 15g water is made bed material solution.The rotating speed that stirs is 60-100rpm.Take by weighing 2.88g methacrylic acid, 3.90g methyl methacrylate, 18g methoxy polyoxyethylene methacrylic ester, 12g polyethylene glycol acrylate and 2.05g Methacrylamide, adding 147g water is made into mixed monomer solution and pours dropping funnel into.Take by weighing ammonium persulphate 2.06g and 0.94g sodium bisulfite, adding 27 gram water are made into initiator and pour another dropping funnel into.The mode that mixed monomer solution and initiator are taked to drip joins in the reactor, and time for adding is controlled at 6h.Drip off follow-up continuation of insurance temperature 1h, reaction finishes, and the aqueous sodium hydroxide solution with 20% is regulated pH value between 6-8.Obtaining product of the present invention is transparent thick liquid.
Although the present invention has done to describe in detail and quoted embodiment as proof, for those of ordinary skill in the art, various schemes, modification and the change that obviously can make according to above-mentioned explanation all should be included within the scope of claim.
Claims (14)
1. a cement concrete superplasticizer is characterized in that: have nitrogenous functional monomer a, unsaturated carboxylic acid and derivative b thereof and polyoxyethylene groups acid allyl ester alkene monomethyl ether and derivative c thereof as terpolymer; Or as quarternary copolymerized nitrogenous functional monomer a, unsaturated carboxylic acid and derivative b thereof, polyoxyethylene groups acid allyl ester alkene monomethyl ether and derivative c and allylsulfonate d;
Its general structure is:
R in the upper general formula
1-R
12Expression hydrogen atom or have the alkyl of 1-10 carbon atom, R can be the same or different; M represents hydrogen atom, sodium, potassium or NH
4 +That n represents is CH
2CH
2The average addition mole number of O, its value is 4-150.
2. cement concrete superplasticizer according to claim 1, it is characterized in that: described nitrogenous functional monomer a is vinyl pyrrolidone.
3. cement concrete superplasticizer according to claim 1, it is characterized in that: described unsaturated carboxylic acid and derivative b thereof are vinylformic acid, methacrylic acid, sodium methacrylate one or a combination set of.
4. cement concrete superplasticizer according to claim 1, it is characterized in that: described polyoxyethylene groups acid allyl ester alkene monomethyl ether and derivative c thereof are methoxy polyethylene glycol acrylate, methoxy polyethylene glycol methacrylate-styrene polymer one or a combination set of.
5. cement concrete superplasticizer according to claim 1 is characterized in that: CH among polyoxyethylene groups acid allyl ester alkene monomethyl ether and the derivative c thereof
2CH
2The average addition mole number n value of O is 9-120.
6. cement concrete superplasticizer according to claim 5 is characterized in that: average addition mole number n value is 23-115.
7. cement concrete superplasticizer according to claim 1, it is characterized in that: described allylsulfonate d is sodium allylsulfonate, methylpropene sodium sulfonate one or a combination set of.
8. preparation method such as the arbitrary described cement concrete superplasticizer of claim 1-7, it is characterized in that: the nitrogenous functional monomer a that weight proportion is respectively 1-50%, the unsaturated carboxylic acid of 5-50% and derivative b thereof, the polyoxyethylene groups acid allyl ester alkene monomethyl ether of 15-94% and the allylsulfonate d of derivative c and 0-50% thereof mix, after making mixed monomer solution, the initiator of the 0.5-15% that accounts for mix monomer weight that adds and the chain-transfer agent that accounts for the 0-15% of mix monomer weight, by ternary or quarternary copolymerized reaction, make cement concrete superplasticizer.
9. preparation method according to claim 8 is characterized in that: may further comprise the steps,
(i) bed material solution processed: one of mixed solution of reactor Zhong Jiashui, water and allylsulfonate d is made bed material, under the stirring of rotating speed 60-100rpm, with nitrogen purging 20-60 minute, and in nitrogen atmosphere heating in water bath to 50-95 ℃;
(ii) monomer solution is closed in compounding: in the component of setting and ratio preparation mixed monomer solution, and use nitrogen purging 0-60min;
(iii) join initiator: in the ratio preparation initiator of setting, and with the initiator for preparing nitrogen purging 0-60min;
(iv) copolyreaction: the initiator that the mixed monomer solution that step I i is made and step I ii make is added drop-wise in the reactor that bed material solution is housed, and the copolyreaction temperature is controlled at 50-95 ℃;
(v) finished product: after copolyreaction is finished, with concentration be the alkaline solution of 20-50% to regulate the pH value be 6-9, make cement concrete superplasticizer.
10. preparation method according to claim 9 is characterized in that: in the ratio preparation chain-transfer agent of setting, and before copolyreaction occurs, add chain-transfer agent in mixed monomer solution.
11. preparation method according to claim 9 is characterized in that: described chain-transfer agent is 2 mercapto ethanol, mercaptoethanol, 3-thiohydracrylic acid, Thiovanic acid, n-butyl mercaptan, tert-butyl mercaptan, octyl mercaptan, positive Dodecyl Mercaptan, Virahol one or a combination set of.
12. preparation method according to claim 9 is characterized in that: described initiator is ammonium persulphate, hydrogen peroxide, Sodium Persulfate/potassium, S-WAT/potassium, Sulfothiorine/potassium, sodium bisulfite/potassium one or a combination set of.
13. preparation method according to claim 9 is characterized in that: described alkaline solution is the aqueous solution of sodium hydroxide/potassium, sodium carbonate/potassium, sodium bicarbonate/potassium, trisodium phosphate/potassium, tripoly phosphate sodium STPP/potassium, sodium polyphosphate/potassium, sodium phosphate/potassium, sodium hydrogen phosphate/potassium, trolamine, tri-isopropanolamine, diethanolamine one or a combination set of.
14. preparation method according to claim 9 is characterized in that: described initiator divides two portions to add: first part adopts the mode that drips continuously to add the initiator that accounts for total amount 40-95% in copolyreaction; Remaining initiator adds in the reaction later stage that mixed monomer solution dropwises as second section.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710076173 CN101333092B (en) | 2007-06-25 | 2007-06-25 | Cement concrete superplasticizer and method for preparing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710076173 CN101333092B (en) | 2007-06-25 | 2007-06-25 | Cement concrete superplasticizer and method for preparing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101333092A CN101333092A (en) | 2008-12-31 |
| CN101333092B true CN101333092B (en) | 2013-04-10 |
Family
ID=40196014
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200710076173 Expired - Fee Related CN101333092B (en) | 2007-06-25 | 2007-06-25 | Cement concrete superplasticizer and method for preparing same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101333092B (en) |
Families Citing this family (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475659B (en) * | 2009-01-08 | 2011-01-19 | 同济大学 | Preparation of special plasticizer for unshaped refractory containing silica fume |
| CN101538344B (en) * | 2009-04-27 | 2011-05-04 | 中国地质科学院矿产综合利用研究所 | Preparation method of slime dispersant suitable for primary slime and secondary slime |
| FR2974090B1 (en) * | 2011-04-15 | 2013-05-31 | Chryso | COPOLYMERS WITH GEM-BISPHOSPHONE GROUPS |
| CN103183796B (en) * | 2011-12-28 | 2015-04-22 | 辽宁奥克化学股份有限公司 | Allyl sulfonic glycerin polyoxyethylene polyoxypropylene ether polycarboxylic acid water reducer and its synthesis method |
| CN102617065B (en) * | 2012-03-06 | 2013-11-13 | 上海市建筑科学研究院(集团)有限公司 | Multi-branch polycarboxylic acid water reducing agent with slump-retaining performance and preparation method thereof |
| CN103145928A (en) * | 2012-08-29 | 2013-06-12 | 成都理工大学 | Low-cost polyester polycarboxylic acid water reducer |
| CN102849978B (en) * | 2012-09-10 | 2014-12-31 | 重庆健杰科技有限公司 | Sustained-release polycarboxylic high-performance water reducing agent and preparation method thereof |
| CN102910855B (en) * | 2012-10-18 | 2014-10-29 | 江苏苏博特新材料股份有限公司 | Super plasticizer for precast concrete component |
| CN103772628B (en) * | 2012-10-24 | 2016-04-27 | 中国石油化工股份有限公司 | A kind of acrylamide based copolymer and its preparation method and application |
| CN103214209A (en) * | 2013-01-07 | 2013-07-24 | 辽宁工业大学 | Portland cement fluidizing agent preparation method |
| CN103183491B (en) * | 2013-03-20 | 2015-10-28 | 嘉兴市广兴建材科技有限公司 | The preparation method of crosslinking polymer cement waterproofing paint |
| CN104628292A (en) * | 2013-11-12 | 2015-05-20 | 上海东大化学有限公司 | Ultra-high concentration polycarboxylic water reducer, preparation method and use method thereof |
| CN103951308B (en) * | 2014-04-17 | 2015-08-19 | 山东卓星化工有限公司 | Sulfonic group modified Soxylat A 25-7 superplasticizer and preparation method thereof |
| CN104446105B (en) * | 2014-11-04 | 2016-08-24 | 上海三瑞高分子材料有限公司 | A kind of polycarboxylic acid super-plasticizer |
| CN104817658A (en) * | 2015-05-21 | 2015-08-05 | 苏州市湘园特种精细化工有限公司 | Acrylic acid water reducing agent and preparation method thereof |
| CN104829791A (en) * | 2015-05-21 | 2015-08-12 | 苏州市湘园特种精细化工有限公司 | Water reducer with low slump loss and preparation method of water reducer |
| CN105504184B (en) * | 2016-01-15 | 2018-01-02 | 江苏苏博特新材料股份有限公司 | The preparation method and application of anti-chamotte mould polycarboxylate water-reducer |
| CN106122893A (en) * | 2016-06-23 | 2016-11-16 | 青岛海川建设集团有限公司 | Large-scale interior space duct type daylight illuminating system construction technology |
| CN105948565B (en) * | 2016-06-24 | 2018-05-22 | 桂林华越环保科技有限公司 | A kind of plasticizing intensifier for dry powder and mortar |
| CN106519141B (en) * | 2016-11-15 | 2018-11-13 | 湖北工业大学 | A kind of width molecular weight distribution high-adaptability type polycarboxylic acid slump retaining agent masterbatch |
| CN106608950A (en) * | 2016-12-22 | 2017-05-03 | 江苏奥克化学有限公司 | Lactam polycarboxylic water reducing agent and preparation method thereof |
| CN108529918B (en) * | 2018-05-04 | 2020-10-30 | 武汉理工大学 | Modified aluminum-silicon particles and modifier thereof |
| CN110804471A (en) * | 2019-11-19 | 2020-02-18 | 安徽鑫固环保股份有限公司 | Sodium styrene sulfonate modified comb-type coal water slurry dispersing agent and preparation method thereof |
| CN111234889A (en) * | 2019-12-23 | 2020-06-05 | 安徽鑫固环保股份有限公司 | Comb type coal water slurry additive and preparation method thereof |
| CN112110670B (en) * | 2020-09-23 | 2022-03-29 | 四川鼎德商品混凝土有限公司 | Preparation method of segregation-resisting agent for concrete and product thereof |
| CN114478940A (en) * | 2022-01-25 | 2022-05-13 | 重庆彼目加科技有限公司 | Special dispersant for light cement base and preparation method thereof |
| CN114523742B (en) * | 2022-02-08 | 2024-04-16 | 广德辉龙环保科技有限公司 | Normal-temperature blended three-proofing filter bag and preparation method thereof |
-
2007
- 2007-06-25 CN CN 200710076173 patent/CN101333092B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101333092A (en) | 2008-12-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101333092B (en) | Cement concrete superplasticizer and method for preparing same | |
| CN101333091B (en) | Method for preparing high-efficiency water-reducing agent of poly-carboxylic acid | |
| CN105367721B (en) | The preparation method and application of viscosity reduction type polycarboxylic acid super-plasticizer | |
| CN102976655B (en) | Slump retaining polycarboxylic acid superplasticizer | |
| CN103724557B (en) | A kind of preparation method of ultra early-strength polycarboxylic admixture | |
| CN102504238B (en) | Unsaturated polyether monomer, comb-like branched copolymer cement dispersant prepared by the same, and preparation method thereof | |
| CN110938176B (en) | Super-long slump loss resistant cement-based polycarboxylate superplasticizer mother liquor and application thereof | |
| CN101066851B (en) | Concrete slump maintaining agent of polycarboxylate | |
| CN101357833B (en) | Slump retaining polyocarboxy acid superplasticiser | |
| CN101244907A (en) | Polycarboxylic acids series concrete high efficiency water reducing agent and synthesizing process | |
| CN101701050B (en) | Preparation method of comb formation cement dispersant and comb formation cement dispersant | |
| WO2014085996A1 (en) | Slump retaining polycarboxylic acid superplasticizer | |
| CN102120805A (en) | Method for preparing slump-retaining type polycarboxylic acid series high-performance water reducing agent in one step | |
| CN114195421A (en) | Preparation method of polycarboxylic acid admixture for machine-made sand concrete | |
| CN109970922A (en) | A kind of shrinkage type Early-strength polycarboxylate superplasticizer mother liquor and preparation process | |
| CN113736036B (en) | Multi-arm polycarboxylate superplasticizer and preparation method thereof | |
| CN109776021A (en) | A kind of low entraining type clear-water concrete additive and preparation method thereof | |
| CN104628972A (en) | Preparation method of anti-crack shrinkage reducing polycarboxylate based superplasticizer | |
| CN103373831A (en) | Early-strength polycarboxylate superplasticizer and high-early-strength cement | |
| CN111349199B (en) | Steady-state polycarboxylic acid superplasticizer with core-shell structure and preparation method thereof | |
| CN102503221B (en) | Cyclohexanol grafted polycarboxylic acid water reducing agent and preparation method thereof | |
| CN105949409A (en) | Polycarboxylate-series concrete water reducing agent containing chitosan, and preparation method thereof | |
| CN111961148B (en) | Reaction air-entraining type polycarboxylate superplasticizer and preparation method thereof | |
| CN103011674B (en) | Polyether amine modified polycarboxylate-type concrete slump retaining agent and preparation method thereof | |
| CN109912752A (en) | A kind of water-reducing agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: SHENZHEN OCEANPOWER NEW MATERIALS TECHNOLOGY CO., Free format text: FORMER OWNER: HAICHUAN INDUSTRY CO., LTD., SHENZHEN Effective date: 20140409 Free format text: FORMER OWNER: OCEANPOWER CORP. SHANGHAI KNP CHEMICAL CO., LTD. HEYUAN OCEANPOWER TECHNOLOGY CO., LTD. Effective date: 20140409 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20140409 Address after: 518040. Building 7 and 8, building CD, Che Kung Temple Industrial Zone, Cheonan, Shenzhen, Guangdong, Futian District, Patentee after: Shenzhen Oceanpower New Material Technology Co., Ltd. Address before: 518040 Guangdong city of Shenzhen province Futian District Che Kung Temple Cheonan digital city building F3.8, block D, floor seven C Patentee before: Haichuan Industry Co., Ltd., Shenzhen Patentee before: Oceanpower Corp. Patentee before: Shanghai KNP Chemical Co., Ltd. Patentee before: Heyuan Oceanpower Technology Co., Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130410 Termination date: 20160625 |