CN106749981B - It is a kind of to coagulate high dispersive polycarboxylic acid super-plasticizer and its preparation method and application at a low speed - Google Patents

It is a kind of to coagulate high dispersive polycarboxylic acid super-plasticizer and its preparation method and application at a low speed Download PDF

Info

Publication number
CN106749981B
CN106749981B CN201611241646.4A CN201611241646A CN106749981B CN 106749981 B CN106749981 B CN 106749981B CN 201611241646 A CN201611241646 A CN 201611241646A CN 106749981 B CN106749981 B CN 106749981B
Authority
CN
China
Prior art keywords
plasticizer
low speed
solidifying
polycarboxylic acid
high dispersive
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.)
Active
Application number
CN201611241646.4A
Other languages
Chinese (zh)
Other versions
CN106749981A (en
Inventor
黄健恒
庞浩
廖兵
年福伟
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guoke Guanghua (Nanxiong) New Materials Research Institute Co.,Ltd.
Guangzhou Chemical Co Ltd of CAS
Original Assignee
Guangzhou Chemical Co Ltd of CAS
Nanxiong Material Production Base of Guangzhou Chemical Co Ltd of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Guangzhou Chemical Co Ltd of CAS, Nanxiong Material Production Base of Guangzhou Chemical Co Ltd of CAS filed Critical Guangzhou Chemical Co Ltd of CAS
Priority to CN201611241646.4A priority Critical patent/CN106749981B/en
Publication of CN106749981A publication Critical patent/CN106749981A/en
Application granted granted Critical
Publication of CN106749981B publication Critical patent/CN106749981B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/16Sulfur-containing compounds
    • C04B24/161Macromolecular compounds comprising sulfonate or sulfate groups
    • C04B24/163Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/165Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24Macromolecular compounds
    • C04B24/26Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2605Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24Macromolecular compounds
    • C04B24/26Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2652Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles
    • C04B24/2658Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles containing polyether side chains
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632Organic additives
    • C04B35/634Polymers
    • C04B35/63404Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632Organic additives
    • C04B35/634Polymers
    • C04B35/63404Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63444Nitrogen-containing polymers, e.g. polyacrylamides, polyacrylonitriles, polyvinylpyrrolidone [PVP], polyethylenimine [PEI]
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/30Water reducers, plasticisers, air-entrainers, flow improvers
    • C04B2103/32Superplasticisers

Abstract

The invention belongs to super plasticizer field, a kind of high dispersive polycarboxylic acid super-plasticizer solidifying at a low speed and its preparation method and application is disclosed.The preparation method is that: polyether macromonomer, initiator and water are added in reactor; stirred under nitrogen atmosphere is uniformly mixed; it is heated to 10~100 DEG C simultaneously; then the aqueous solution of small molecule monomer, reducing agent and chain-transferring agent is added dropwise respectively; it is added dropwise to complete rear 1~6h of insulation reaction; it neutralizes, obtains the high dispersive polycarboxylic acid super-plasticizer solidifying at a low speed;The chain-transferring agent refers at least one of glycol dimercaptoacetate, double thioacetic acid trihydroxymethylpropanyl esters, double thioglycolic acid pentaerythritol esters, double mercaptopropionic acid mesoinositols.By the present invention in that with special chain-transferring agent, two ester groups are introduced on main chain center, products therefrom dispersion performance is excellent, and when application has the advantages that hydration rate is fast, setting time is short, early strength is high.

Description

It is a kind of to coagulate high dispersive polycarboxylic acid super-plasticizer and its preparation method and application at a low speed
Technical field
The invention belongs to super plasticizer fields, and in particular to a kind of to coagulate high dispersive polycarboxylic acid super-plasticizer and its preparation at a low speed Methods and applications.
Background technique
Polycarboxylate high performance water-reducing agent largely uses in ceramics, cement and plastering field, to positively charged Particle not only has suction-operated, and there are also space steric effects.For cement granules, the anti-of cement and mixing water can be increased Contact surface is answered, and increases aquation film thickness at hydration reaction initial stage, hinders the release of cement granules intermediate ion, keeps hydration reaction fast Degree reduces, and shows deferred action.
However, in the production process of precast concrete, concrete job mix cast in situs needs not move through one The process of a long-distance transportation, such deferred action are unfavorable for the raising of precast concrete production efficiency.
In order to accelerate form cycling rate or reduce template using total amount, production efficiency is improved, realizes maximum economy Benefit needs to promote using the method for addition early strength agent cooperation steam curing process shield usually while using polycarboxylate water-reducer Into hydrated cementitious and condensation.
Most of early strength agent has the effect of improving early strong intensity, and the slow setting of poly carboxylic acid series water reducer cannot but be inhibited to make With.The larger rush that can just play of the inorganic general volume of early strength agent coagulates effect, bad with the compatibility of poly carboxylic acid series water reducer, is easy to divide Fleece is solidifying, and cannot play the due peptizaiton of polycarboxylate water-reducer, and wherein villaumite but will Corrosion Reinforcement;Organic Alcohol amine is mixed Amount and to promote solidifying effect not easy to control, bad adaptability and expensive.
In addition, having part research to report through macromolecular structure improvement reaches promotion hydrated cementitious, such as on main chain Some function monomers without suction-operated are simply introduced, but such consequence will certainly weaken the dispersion performance of water-reducing agent.
Chinese patent CN103304181A discloses a kind of high performance water reducing agent of polyocarboxy acid, composition and by weight percentage It is as follows: poly carboxylic acid series water reducer 10~20%, calcium chloride 10~17%, sodium nitrite 10~20%, triethanolamine 1~3%, Yu Weishui.The water-reducing agent is to be obtained on the basis of common polycarboxylate water-reducer by compounding, and advantage is that concrete can be improved The early strength of product, but not from molecular structure inhibit polycarboxylate water-reducer deferred action, adaptability is bad, be easy point Fleece is solidifying, and the volume of additive is higher.
Chinese patent CN200810201010.6 proposes a kind of poly carboxylic acid series water reducer, and preparation process is to use poly- second Glycol monomethyl ether methacrylate or monomethyl polyethylene glycol acrylate ester (degree of polymerization is between 20~60), (methyl) propylene Acid, (methyl) Sodium Allyl Sulfonate, alkoxy polyethylene glycol (polypropylene glycol) acrylate are copolymerized in aqueous solution.The water-reducing agent With certain promotion cement setting effect, but two kinds of esters monomers are both needed to react to obtain by high temperature esterification, and reaction process is multiple It is miscellaneous, it takes a long time, and polymerization inhibitor remaining in reaction process has certain influence to secondary polymerization reaction.
World patent WO2011/076655A1 reports a kind of polycarboxylic acid super-plasticizer, and preparation method is to use poly- third Olefin(e) acid (molecular weight 4000) and poly glycol monomethyl ether (molecular weight 5000), after being esterified at 165 DEG C in and obtain.The party Method can also effectively shorten the setting time of concrete, but need first to synthesize polyacrylic acid, and preparation difficulty is larger, higher cost, Secondly viscosity is larger, lower with the conversion rate of esterification of polyethers, thus the volume of additive is relatively high, and cost performance is low.
In recent years, the continuous speedup of domestic investment, infrastructure construction dynamics and scale also continue to increase, precast concrete Dosage is also constantly soaring.A kind of polycarboxylic acid super-plasticizer with low and slow solidifying high dispersive effect is developed to improve precast concrete row The production efficiency of industry is of great significance to promotion building material industry energy-saving and emission-reduction.
Summary of the invention
In order to solve the above-mentioned technical problem, the primary purpose of the present invention is that provide a kind of high dispersive polycarboxylic acids solidifying at a low speed super The preparation method of plasticiser.
Another object of the present invention is to provide a kind of low and slow solidifying high dispersive polycarboxylic acids being prepared by the above method Super plasticizer.
A further object of the present invention is to provide above-mentioned high dispersive polycarboxylic acid super-plasticizers solidifying at a low speed in ceramics, cement, stone Application in cream production of articles.
The object of the invention is achieved through the following technical solutions:
A kind of preparation method of high dispersive polycarboxylic acid super-plasticizer solidifying at a low speed, including following preparation step:
Polyether macromonomer A, initiator and water are added in reactor, stirred under nitrogen atmosphere is uniformly mixed, together When be heated to 10~100 DEG C, then respectively be added dropwise small molecule monomer B, reducing agent and chain-transferring agent aqueous solution, after being added dropwise to complete 1~6h of insulation reaction is neutralized, and obtains the high dispersive polycarboxylic acid super-plasticizer solidifying at a low speed;
Wherein, polyether macromonomer A has structural formula shown in formula (1):
In formula: R1For-H or the alkyl of carbon atom number 1~5, R2For carbonyl or the alkyl of carbon atom number 1~10, R3For-H or The alkyl of carbon atom number 1~5, n and m are respectively the average addition molal quantity of ethylene oxide and propylene oxide chain link, wherein n=10 ~200, m=0~40;
Small molecule monomer B refer to acrylic acid (AA), 2- acrylamide-2-methyl propane sulfonic (AMPS), methacrylic acid (MA), At least one of acrylamide (AM), maleic anhydride (MAH), itaconic acid (IA);
The chain-transferring agent refers to glycol dimercaptoacetate, double thioacetic acid trihydroxymethylpropanyl esters, double sulfydryls At least one of pentaerythritol tetraacetate, double mercaptopropionic acid mesoinositols, the dosage of the chain-transferring agent be macromonomer A and The 0.1%~3% of small molecule monomer B gross mass.
Preferably, the mass ratio of the polyether macromonomer A and small molecule monomer B is (85~97): (3~15).
Preferably, the initiator includes ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, hydrogen peroxide and benzoyl peroxide first At least one of acyl, the dosage of initiator are the 0.1%~2% of macromonomer A and small molecule monomer B gross mass.
Preferably, the reducing agent include rongalite, bisulfites, sulphite, thiosulfate, At least one of pyrosulfite, ascorbic acid and ferrous salt, the dosage of reducing agent are macromonomer A and small molecule monomer The 0.01%~1% of B gross mass.
Preferably, the time of the aqueous solution that small molecule monomer B, reducing agent and chain-transferring agent is added dropwise is 2~4h.
Preferably, the neutralization refers to is neutralized using dilute alkaline soln, and the dilute alkaline soln refers to that mass concentration is 10%~40% NaOH, KOH, hexamethylene diamine or triethanolamine solution.
A kind of high dispersive polycarboxylic acid super-plasticizer solidifying at a low speed, is prepared by the above method.The super modeling that the present invention obtains Agent is colourless or light yellow transparent liquid.
Application of the above-mentioned high dispersive polycarboxylic acid super-plasticizer solidifying at a low speed in ceramics, cement, plastering production, application When folding consolidate volume be 0.05%~0.3%.
The schematic arrangement that gained of the invention coagulates high dispersive polycarboxylic acid super-plasticizer at a low speed is as shown in Figure 1.
Polycarboxylate water-reducer is the space steric effect of electrostatic interaction and combed branch based on negative electrical charge functional group, is made It has excellent dispersion performance to cement and clay particle.Usual adsorbance is bigger, and deferred action is stronger.The present invention is guaranteeing Under the premise of polycarboxylate water-reducer excellent initial stage dispersion effect, by reducing the adsorbance to cement or clay particle, thus Achieve the purpose that inhibit deferred action.
Novel polycarboxylic acid super-plasticizer provided by the invention is adjusted from macromolecular structure.Subtract with common polycarboxylic acids Aqua the difference is that, by using double sulfydryl esters transfer agents, two ester groups are introduced on main chain center, Middle main chain configuration is straight chain type structure, and by the adjustment to reaction system, the main chain of polymer is shorter, and side chain is longer.Although Backbone length shortens, and negative electrical charge functional group tails off, and weakens to the electrostatic adsorption of cement granules, but by increasing branch chain length Degree enhances space steric effect, ensures that the peptizaiton of plasticiser is not only stronger instead without reducing in this way, and cement The polymer barrier layer on grain surface is thicker, and the aquation gap between polymer is bigger, is conducive to the progress of aquation, and present invention gained is low Slow setting high dispersive polycarboxylic acid super-plasticizer is as shown in Figure 2 to the adsorbed state schematic diagram of cement granules.
Secondly, the ester group on main chain can be hydrolyzed gradually in alkaline environment, fracture drop can occur for main chain in hydration process Solution, makes the Electrostatic Absorption group in single macromolecular tail off, and later period suction-operated weakens significantly, and the slow setting of polycarboxylate water-reducer is made With being further restricted.Hydrated cementitious speed is accelerated, and not only shortens setting time, is even more conducive to the hair of early strength Exhibition, thus have broad application prospects in precast concrete field.
For the present invention with unsaturated carboxylic acid/sulfonate, high molecular weight unsaturated polyether is that monomer carries out water phase free radical polymerization, Ester group is introduced on polymeric carbon chain by special chain-transferring agent, prepares the degradable poly carboxylic of a kind of short main chain, long side chain Sour super plasticizer.The poly carboxylic acid series super plasticizer of latest generation provides the method that much can change polymer architecture, makes spy The polymer not designed is possibly realized for changing adsorbed state, realizes macromolecular to water by adjusting its master/side chain configuration The controllable adsorption of mud component, had not only maintained the high dispersive effect of common polycarboxylic acid super-plasticizer, but also can inhibit it to the greatest extent Deferred action, the concrete for making poly carboxylic acid series super plasticizer be more particularly for production and the early solidifying requirement of precast concrete are applied Work.
Compared with the existing technology, the invention has the following advantages and beneficial effects:
(1) polycarboxylic acid super-plasticizer prepared by the present invention is by using special chain-transferring agent, in main chain center Two ester groups of upper introducing, ester group can be hydrolyzed gradually in alkaline environment, and fracture degradation can occur for main chain in hydration process, make list Electrostatic Absorption group in a macromolecular tails off, and later period suction-operated thus weakens significantly;
(2) polycarboxylic acid super-plasticizer preparation method of the invention is simple, and water-reducing rate is high, dispersion performance is excellent, and when application makes Hydrated cementitious speed is fast, setting time is short, and early strength is high, has broad application prospects in precast concrete field;
(3) polycarboxylic acid super-plasticizer of the invention such as appropriately uses in precast concrete, may replace process it is cumbersome two Secondary maintaining process avoids the potential high-risk of secondary maintenance, and a large amount of consumption steam coal resources.
Detailed description of the invention
Fig. 1 is the schematic arrangement that present invention gained coagulates high dispersive polycarboxylic acid super-plasticizer at a low speed;
Fig. 2 is present invention gained adsorbed state schematic diagram of the solidifying high dispersive polycarboxylic acid super-plasticizer to cement granules at a low speed;
Fig. 3 is that the hydration heat rate comparison of comparative sample 1 obtained by 4 gained PCE-4 of the embodiment of the present invention and comparative example is tested Curve graph.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Raw material code name is as shown in table 1 in following embodiment and comparative example:
Table 1
A-1 Isopentene group polyoxyethylene ether (Mn=6000) C-1 Ammonium persulfate
A-2 Methyl allyl polyoxyethylene ether (Mn=4000) C-2 Hydrogen peroxide (35%)
A-3 Methyl allyl polyoxyethylene ether (Mn=2400) D-1 Ascorbic acid
B-1 Acrylic acid D-2 Rongalite
B-2 Acrylamide E-1 Glycol dimercaptoacetate
B-3 2- acrylamide-2-methyl propane sulfonic E-2 Thioacetic acid
Embodiment 1
77.8g is sequentially added in the 250mL four-hole boiling flask that blender, thermometer, nitrogen ingress pipe, Dropping feeder are housed Water, 71.8g A-1 are warming up to 85 DEG C under nitrogen protection, are stirring evenly and then adding into 1.6g C-1, are stirred for 10min, drip respectively The aqueous solution of 7.5g B-1 and 0.01g D-1,0.44g E-1 is added, time for adding is respectively 2h and 2.5h, is protected after being added dropwise Temperature reaction 1.5h, after reaction, slow cooling is to 40 DEG C, sodium hydroxide solution that obtained product mass concentration is 30% PH value is adjusted to 5 or so.It is cooled to room temperature, is diluted with water to obtain the low and slow solidifying super modeling of high dispersive polycarboxylic acids that mass concentration is 40% Agent is labeled as PCE-1.
Embodiment 2
79.1g is sequentially added in the 250mL four-hole boiling flask that blender, thermometer, nitrogen ingress pipe, Dropping feeder are housed Water, 70.7g A-2 are warming up to 65 DEG C under nitrogen protection, are stirring evenly and then adding into 0.3g C-1, are stirred for 10min, drip respectively The aqueous solution of 7.5g B-1,1.2g B-2 and 0.01g D-1,0.52g E-1 is added, time for adding is respectively 2.5h and 3h, drop Insulation reaction 1.5h after adding, after reaction, slow cooling is to 40 DEG C, hydrogen that obtained product mass concentration is 30% Sodium hydroxide solution adjusts pH value to 5 or so.It is cooled to room temperature, is diluted with water to obtain the low and slow solidifying high dispersive that mass concentration is 40% Polycarboxylic acid super-plasticizer is labeled as PCE-2.
Embodiment 3
76.8g is sequentially added in the 250mL four-hole boiling flask that blender, thermometer, nitrogen ingress pipe, Dropping feeder are housed Water, 72.8g A-3 are warming up to 45 DEG C under nitrogen protection, are stirring evenly and then adding into 0.68g C-2, are stirred for 10min, respectively It is added dropwise to the aqueous solution of 6.5g B-1 and 0.12g D-1,0.36g E-1, time for adding is respectively 3h and 3.5h, after being added dropwise Insulation reaction 1h, after reaction, slow cooling is to 40 DEG C, sodium hydroxide solution that obtained product mass concentration is 30% PH value is adjusted to 5 or so.It is cooled to room temperature, is diluted with water to obtain the low and slow solidifying super modeling of high dispersive polycarboxylic acids that mass concentration is 40% Agent is labeled as PCE-3.
Embodiment 4
76.1g is sequentially added in the 250mL four-hole boiling flask that blender, thermometer, nitrogen ingress pipe, Dropping feeder are housed Water, 73.8g A-1 are warming up to 25 DEG C under nitrogen protection, are stirring evenly and then adding into 0.48g C-2, are stirred for 10min, respectively It is added dropwise to the aqueous solution of 5.5g B-1 and 0.20g D-2,0.60g E-1, time for adding is respectively 3.5h and 4h, after being added dropwise Insulation reaction 1h, after reaction, the sodium hydroxide solution that obtained product mass concentration is 30% adjust pH value to 5 left sides It is right.It is cooled to room temperature, is diluted with water to obtain the low and slow solidifying high dispersive polycarboxylic acid super-plasticizer that mass concentration is 40%, be labeled as PCE-4。
Embodiment 5
81.1g is sequentially added in the 250mL four-hole boiling flask that blender, thermometer, nitrogen ingress pipe, Dropping feeder are housed Water, 67.5g A-2 are warming up to 25 DEG C under nitrogen protection, are stirring evenly and then adding into 0.52g C-2, are stirred for 10min, respectively It is added dropwise to the aqueous solution of 5.4g B-1,6.4g B-3 and 0.24g D-2,0.48g E-1, time for adding is respectively 3h and 3.5h, Rear insulation reaction 1h is added dropwise, after reaction, the sodium hydroxide solution that obtained product mass concentration is 30% is adjusted PH value is to 5 or so.It is cooled to room temperature, being diluted with water to obtain mass concentration is that coagulate high dispersive polycarboxylic acids super plasticized for 40% low and slow Agent is labeled as PCE-5.Comparative example
76.8g water, 72.8g A- are sequentially added in the 250mL four-hole boiling flask that blender, thermometer, Dropping feeder are housed 3,65 DEG C are warming up to, 0.30g C-2 is stirring evenly and then adding into, is stirred for 10min, is added dropwise to 6.5g B-1 and 0.12g D- respectively 1, the aqueous solution of 0.32g E-2, time for adding are respectively 3h and 3.5h, and rear insulation reaction 1.5h is added dropwise, after reaction, For slow cooling to 40 DEG C, the sodium hydroxide solution that obtained product mass concentration is 30% adjusts pH value to 5 or so.It is cooled to Room temperature is diluted with water to obtain the polycarboxylic acid super-plasticizer that mass concentration is 40%, is labeled as comparative sample 1.
Implementation result:
Using reference cement, comparative sample 1 is medium-sized polycarboxylic acid super-plasticizer, according to GB/T8077-2000 " concrete Additive homogeneity test method " test cement paste flowing degree, the volume of the ratio of mud 0.35, water-reducing agent (rolls over solid volume 0.1%) on the basis of the quality of cement, test result is as follows shown in table 2.
2 paste flowing degree test result of table
By the above results as can be seen that relative to plain edition polycarboxylate water-reducer (comparative example 1), prepared by the present invention The paste flowing degree of solidifying high dispersive polycarboxylic acid super-plasticizer and water-reducing rate are higher at a low speed, have better initial dispersion to cement Performance, and initial set and final setting time also have different degrees of shortening than plain edition polycarboxylate water-reducer.
It chooses PCE-4 and comparative sample 1 carries out the test of hydration heat rate comparison.The TAM Air of TA company of U.S. production The micro- calorimeter of 08Isothermal Calorimeter isothermal, the ratio of mud 0.4, polycarboxylate water-reducer roll over solid volume 0.2%.Institute There is material first to stir 1min with 500r/min, then 1min is stirred with 1500r/min, controlled at 20 ± 0.1 DEG C, aquation is put Hot rate curve is as shown in Figure 3.It can be seen that compared with plain edition polycarboxylic acids (comparative example 1) from hydration heat curve, mix this hair When bright gained coagulates high dispersive polycarboxylic acid super-plasticizer at a low speed, the induction period in cement slurry hydration process is shorter, the main heat release of aquation Peak appears earlier, this shows that solidifying high dispersive polycarboxylic acid super-plasticizer can effectively inhibit its slow setting to make at a low speed obtained by the present invention With promoting the early stage hydration process of cement slurry.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention, It should be equivalent substitute mode, be included within the scope of the present invention.

Claims (8)

1. a kind of preparation method of high dispersive polycarboxylic acid super-plasticizer solidifying at a low speed, it is characterised in that including following preparation step:
Polyether macromonomer A, initiator and water are added in reactor, stirred under nitrogen atmosphere is uniformly mixed, and is added simultaneously Then the aqueous solution of small molecule monomer B, reducing agent and chain-transferring agent is added dropwise respectively, keeps the temperature after being added dropwise to complete to 10~100 DEG C for heat 1~6h is reacted, is neutralized, the high dispersive polycarboxylic acid super-plasticizer solidifying at a low speed is obtained;
Wherein, polyether macromonomer A has structural formula shown in formula (1):
In formula: R1For-H or the alkyl of carbon atom number 1~5, R2For the alkyl of carbon atom number 1~10, R3For-H or carbon atom number 1 ~5 alkyl, n and m are respectively the average addition molal quantity of ethylene oxide and propylene oxide chain link, wherein n=10~200, m= 0~40;
Small molecule monomer B refer to acrylic acid, 2- acrylamide-2-methyl propane sulfonic, methacrylic acid, acrylamide, maleic anhydride, At least one of itaconic acid;
The chain-transferring agent refers to glycol dimercaptoacetate, double thioacetic acid trihydroxymethylpropanyl esters, double thioacetic acid At least one of pentaerythritol ester, double mercaptopropionic acid mesoinositols, the dosage of the chain-transferring agent are macromonomer A and small point The 0.1%~3% of sub- monomer B gross mass.
2. a kind of preparation method of high dispersive polycarboxylic acid super-plasticizer solidifying at a low speed according to claim 1, it is characterised in that: The mass ratio of the polyether macromonomer A and small molecule monomer B is (85~97): (3~15).
3. a kind of preparation method of high dispersive polycarboxylic acid super-plasticizer solidifying at a low speed according to claim 1, it is characterised in that: The initiator includes at least one of ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, hydrogen peroxide and benzoyl peroxide, The dosage of initiator is the 0.1%~2% of macromonomer A and small molecule monomer B gross mass.
4. a kind of preparation method of high dispersive polycarboxylic acid super-plasticizer solidifying at a low speed according to claim 1, it is characterised in that: The reducing agent includes rongalite, bisulfites, sulphite, thiosulfate, pyrosulfite, anti-bad At least one of hematic acid and ferrous salt, the dosage of reducing agent are the 0.01% of macromonomer A and small molecule monomer B gross mass ~1%.
5. a kind of preparation method of high dispersive polycarboxylic acid super-plasticizer solidifying at a low speed according to claim 1, it is characterised in that: The time of the aqueous solution that small molecule monomer B, reducing agent and chain-transferring agent is added dropwise is 2~4h.
6. a kind of preparation method of high dispersive polycarboxylic acid super-plasticizer solidifying at a low speed according to claim 1, it is characterised in that: The neutralization refers to be neutralized using dilute alkaline soln, the dilute alkaline soln refer to mass concentration be 10%~40% NaOH, KOH, hexamethylene diamine or triethanolamine solution.
7. a kind of high dispersive polycarboxylic acid super-plasticizer solidifying at a low speed, it is characterised in that: described in any item by claim 1~6 Method is prepared.
8. high dispersive polycarboxylic acid super-plasticizer solidifying at a low speed answering in ceramics, cement, plastering production as claimed in claim 7 With, it is characterised in that: it is 0.05%~0.3% that folding when application, which consolidates volume,.
CN201611241646.4A 2016-12-29 2016-12-29 It is a kind of to coagulate high dispersive polycarboxylic acid super-plasticizer and its preparation method and application at a low speed Active CN106749981B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611241646.4A CN106749981B (en) 2016-12-29 2016-12-29 It is a kind of to coagulate high dispersive polycarboxylic acid super-plasticizer and its preparation method and application at a low speed

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611241646.4A CN106749981B (en) 2016-12-29 2016-12-29 It is a kind of to coagulate high dispersive polycarboxylic acid super-plasticizer and its preparation method and application at a low speed

Publications (2)

Publication Number Publication Date
CN106749981A CN106749981A (en) 2017-05-31
CN106749981B true CN106749981B (en) 2019-02-01

Family

ID=58923535

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611241646.4A Active CN106749981B (en) 2016-12-29 2016-12-29 It is a kind of to coagulate high dispersive polycarboxylic acid super-plasticizer and its preparation method and application at a low speed

Country Status (1)

Country Link
CN (1) CN106749981B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110922538B (en) * 2019-11-08 2022-08-16 中科广化(重庆)新材料研究院有限公司 Early-strength polycarboxylate superplasticizer and preparation method and application thereof
CN112812238B (en) * 2020-12-30 2023-06-06 山西佳维新材料股份有限公司 Polycarboxylate superplasticizer and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1379789A (en) * 1999-08-12 2002-11-13 阿托菲纳公司 Detergent biodegradable polyacrylates
CN102887979A (en) * 2012-10-22 2013-01-23 北京工业大学 Preparation method of star polycarboxylic acid high-performance water reducing agent
CN105669912A (en) * 2016-03-03 2016-06-15 江苏中铁奥莱特新材料有限公司 Method for preparing star polycarboxylate water reducing agent
CN106146859A (en) * 2016-07-11 2016-11-23 济南大学 A kind of four arm high-efficiency water-reducing agent of poly-carboxylic acid and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1379789A (en) * 1999-08-12 2002-11-13 阿托菲纳公司 Detergent biodegradable polyacrylates
CN102887979A (en) * 2012-10-22 2013-01-23 北京工业大学 Preparation method of star polycarboxylic acid high-performance water reducing agent
CN105669912A (en) * 2016-03-03 2016-06-15 江苏中铁奥莱特新材料有限公司 Method for preparing star polycarboxylate water reducing agent
CN106146859A (en) * 2016-07-11 2016-11-23 济南大学 A kind of four arm high-efficiency water-reducing agent of poly-carboxylic acid and preparation method thereof

Also Published As

Publication number Publication date
CN106749981A (en) 2017-05-31

Similar Documents

Publication Publication Date Title
CN106674439B (en) It is a kind of to coagulate hyperbranched polycarboxylic acid super-plasticizer and its preparation method and application at a low speed
CN109354654B (en) Early-strength polycarboxylate superplasticizer and preparation method thereof
CN104558434B (en) Siliceous polycarboxylate water-reducer, preparation method and the usage
CN110790872B (en) Viscosity-reducing polycarboxylate superplasticizer with micro-crosslinking structure and preparation method thereof
CN104371073A (en) Normal-temperature preparation method of slow-release polycarboxylic acid water reducing agent
CN107652405B (en) Polycarboxylate superplasticizer with amide/imide structure and preparation method thereof
CN104628967B (en) A kind of Early-strength polycarboxylate superplasticizer and preparation method thereof
CN108948288B (en) Preparation method of crosslinking type polycarboxylate superplasticizer by adopting carboxyl functional monomer
CN103396031B (en) A kind of carboxylic acid water reducer and preparation method thereof
CN105254819A (en) Room-temperature preparation method of early strength type polycarboxylate superplasticizer
CN104649608A (en) Additive for improving early strength of cement based material as well as preparation method and application of additive
CN105218757B (en) Early-strength polycarboxylate superplasticizer with slump retaining function and preparation method thereof
CN105601843A (en) Early-strength ethers polycarboxylic acid water reducing agent and preparation method thereof
CN106519137A (en) Cross-star-shaped slow-release slump-retaining type polycarboxylic-acid water-reducing agent and preparation method thereof
CN108912279B (en) High-adaptability multi-branched-chain amide imine polycarboxylic water reducer and preparation method thereof
CN105778009B (en) A kind of Early-strength polycarboxylate superplasticizer and preparation method thereof and a kind of cement admixture
CN111349199B (en) Steady-state polycarboxylic acid superplasticizer with core-shell structure and preparation method thereof
CN101885798A (en) Preparation method of plasticizing agent with thixotropy for unshaped refractory
CN104497230A (en) Ester-ether copolymerization type polycarboxylate superplasticizer as well as preparation method and application thereof
CN106749981B (en) It is a kind of to coagulate high dispersive polycarboxylic acid super-plasticizer and its preparation method and application at a low speed
CN110643003B (en) Preparation method of retarding type ester polycarboxylate superplasticizer
CN104945576A (en) Preparation method, products and application of high efficiency slushing agent
CN102503221A (en) Cyclohexanol grafted polycarboxylic acid water reducing agent and preparation method thereof
CN106366258A (en) Preparation method of modified polycarboxylic acid slump-retaining agent masterbatch
CN103588413A (en) Polyether crosslinked concrete water reducer, and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20200611

Address after: 512400 No.3 comprehensive building, Ping'an 1st Road, industrial transfer park, Dalingshan (Nanxiong), Dongguan, Nanxiong City, Shaoguan City, Guangdong Province

Co-patentee after: CAS GUANGZHOU CHEMISTRY Co.,Ltd.

Patentee after: Guoke Guanghua (Nanxiong) New Materials Research Institute Co.,Ltd.

Address before: 512400 Guangdong city of Shaoguan province Nanxiong City Abas Industrial Park (Guangdong Nanxiong fine chemical base)

Co-patentee before: CAS GUANGZHOU CHEMISTRY Co.,Ltd.

Patentee before: NANXIONG MATERIAL PRODUCTION BASE OF CHINESE ACADEMY OF SCIENCES GUANGZHOU CHEMICAL Co.,Ltd.