A kind of high dispersive polycarboxylic acid super-plasticizer solidifying at a low speed and its preparation method and application
Technical field
The invention belongs to super plasticizer field, and in particular to a kind of solidifying at a low speed high dispersive polycarboxylic acid super-plasticizer and its preparation
Methods and applications.
Background technology
Polycarboxylate high performance water-reducing agent is largely used in ceramics, cement and plastering field, and it is to positively charged
Particle not only has suction-operated, also space steric effect.For cement granules, cement can be increased anti-with mixing water
Contact surface is answered, and increases aquation film thickness at the hydration reaction initial stage, hinder the release of cement granules intermediate ion, make hydration reaction speed
Degree is reduced, and shows deferred action.
However, in the production process of precast concrete, concrete job mix cast in situs, it is not necessary to by one
The process of individual long-distance transportation, it is but unfavorable that such deferred action is improved for precast concrete production efficiency.
Total amount, improve production efficiency is used to realize maximum economy in order to accelerate form cycling rate or reduce template
Benefit, it is necessary to coordinate the method that steam curing process is protected using addition early strength agent to promote generally while using polycarboxylate water-reducer
Enter hydrated cementitious and condensation.
Most of early strength agent has the effect for improving early strong intensity, and the slow setting that can not but suppress poly carboxylic acid series water reducer is made
With.The inorganic general volume of early strength agent is larger just to play the solidifying effect of rush, and the compatibility with poly carboxylic acid series water reducer is bad, easily divides
Fleece coagulates, and can not play the due peptizaiton of polycarboxylate water-reducer, and wherein villaumite more can Corrosion Reinforcement;Organic Alcohol amine is mixed
Amount and promote solidifying effect and be difficult to control, bad adaptability and expensive.
Additionally, there is part to study to report by macromolecular structure improvement to reach promotion hydrated cementitious, such as on main chain
Some function monomers without suction-operated are simply introduced, but such consequence will certainly weaken the dispersive property of water reducer.
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%, natrium nitrosum 10~20%, triethanolamine 1~3%, its
Yu Weishui.The water reducer is obtained by compounding on the basis of common polycarboxylate water-reducer, and advantage can be raising concrete
The early strength of product, but suppress the deferred action of polycarboxylate water-reducer not from molecular structure, adaptability is bad, easily divides
Fleece coagulates, and the volume of additive is higher.
Chinese patent CN200810201010.6 proposes a kind of poly carboxylic acid series water reducer, and its preparation technology is using poly- second
Glycol monomethyl ether methacrylate or monomethyl polyethylene glycol acrylate ester (degree of polymerization is between 20~60), (methyl) propylene
Acid, (methyl) ALS, alkoxy polyethylene glycol (polypropylene glycol) acrylate copolymerization in aqueous.The water reducer
Acted on certain promotion cement setting, but two kinds of esters monomers are both needed to be obtained by high temperature esterification reaction, and course of reaction is multiple
It is miscellaneous, it is time-consuming more long, and polymerization inhibitor remaining in course of reaction has certain influence on secondary polymerization reaction.
World patent WO2011/076655A1 reports a kind of polycarboxylic acid super-plasticizer, and its preparation method is using poly- third
Olefin(e) acid (molecular weight is 4000) and poly glycol monomethyl ether (molecular weight is 5000), neutralize after being esterified at 165 DEG C and obtain.The party
Method also can effectively shorten the setting time of concrete, however it is necessary that first synthesizing polyacrylic acid, preparation difficulty is larger, relatively costly,
Secondly viscosity is larger, and the conversion rate of esterification with polyethers is relatively low, thus the volume of additive is of a relatively high, and cost performance is low.
In recent years, the continuous speedup of domestic investment, infrastructure construction dynamics and scale are also continued to increase, precast concrete
Consumption also constantly rises.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, to promoting building material industry energy-saving and emission-reduction to be of great significance.
The content of the invention
In order to solve the above-mentioned technical problem, primary and foremost purpose of the invention is to provide a kind of high dispersive polycarboxylic acids solidifying at a low speed to surpass
The preparation method of plasticiser.
Another object of the present invention is to provide a kind of high dispersive polycarboxylic acids solidifying at a low speed prepared by the above method
Super plasticizer.
It is still another object of the present invention to provide above-mentioned high dispersive polycarboxylic acid super-plasticizer 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 process:
Polyether macromonomer A, initiator and water are added in reactor, stirred under nitrogen atmosphere is well mixed, together
When be heated to 10~100 DEG C, the aqueous solution of small molecule monomer B, reducing agent and chain-transferring agent is then added dropwise respectively, after being added dropwise to complete
1~6h of insulation reaction, neutralizes, and obtains the high dispersive polycarboxylic acid super-plasticizer solidifying at a low speed;
Wherein, polyether macromonomer A has the structural formula shown in formula (1):
In formula:R1It is-H or the alkyl of carbon number 1~5, R2It is carbonyl or the alkyl of carbon number 1~10, R3For-H or
The alkyl of carbon number 1~5, n and m are respectively the average addition molal quantity of oxirane and expoxy propane chain link, wherein n=10
~200, m=0~40;
Small molecule monomer B refer to acrylic acid (AA), 2- acrylamide-2-methyl propane sulfonics (AMPS), methacrylic acid (MA),
At least one in acrylamide (AM), maleic anhydride (MAH), itaconic acid (IA);
Described chain-transferring agent refers to glycol dimercaptoacetate, double TGA trihydroxymethylpropanyl esters, double sulfydryls
At least one in pentaerythritol tetraacetate, double mercaptopropionic acid mesoinositols, the consumption of the chain-transferring agent for macromonomer A and
The 0.1%~3% of small molecule monomer B gross masses.
Preferably, the mass ratio of the polyether macromonomer A and small molecule monomer B is (85~97):(3~15).
Preferably, described initiator includes ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, hydrogen peroxide and benzoyl peroxide first
At least one in acyl, the consumption of initiator is the 0.1%~2% of macromonomer A and small molecule monomer B gross masses.
Preferably, described reducing agent include rongalite, bisulfites, sulphite, thiosulfate,
At least one in pyrosulfite, ascorbic acid and ferrous salt, the consumption of reducing agent is macromonomer A and small molecule monomer
The 0.01%~1% of B gross masses.
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, described neutralization refers to be neutralized using dilute alkaline soln, and described 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 is obtained
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, its application
When the solid volume of folding 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 the electrostatic interaction and combed side chain for being based on negative electrical charge functional group, is made
It has excellent dispersive property to cement and potter's clay particle.Usual adsorbance is bigger, and deferred action is stronger.The present invention is ensureing
Under the premise of polycarboxylate water-reducer excellent initial stage dispersion effect, by reducing the adsorbance to cement or potter's clay particle, so that
Reach the purpose for suppressing deferred action.
The new polycarboxylic acid super-plasticizer that the present invention is provided is adjusted from macromolecular structure.Subtract with common polycarboxylic acids
Aqua difference is, by using double sulfydryl esters transfer agents, the ester group of two to be introduced on main chain center, its
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 the electrostatic adsorption to cement granules weakens, but by increasing branch chain length
Degree, strengthens space steric effect, and the peptizaiton for this ensures that thering plasticiser does not reduce stronger on the contrary, and cement not only
The polymer barrier layer on grain surface is thicker, and the aquation space between polymer is bigger, is conducive to the carrying out 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, and main chain can occur fracture drop in hydration process
Solution, makes the Electrostatic Absorption group in single macromolecular tail off, and later stage 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 more advantageous for the hair of early strength
Exhibition, thus had broad application prospects in precast concrete field.
With unsaturated carboxylic acid/sulfonate, HMW unsaturated polyether enters water-filling phase radical polymerization to the present invention for monomer,
Ester group is introduced on polymeric carbon chain by special chain-transferring agent, the degradable poly carboxylic of a kind of short main chain, side chain long is prepared
Sour super plasticizer.The poly carboxylic acid series super plasticizer of latest generation provides the method that can much change polymer architecture, makes spy
The polymer not designed is possibly realized for changing adsorbed state, and macromolecular is realized to water by adjusting its master/side chain configuration
The controllable adsorption of mud component, had both maintained the high dispersive effect of common polycarboxylic acid super-plasticizer, and it can be farthest suppressed again
Deferred action, makes poly carboxylic acid series super plasticizer be more particularly for the production and early solidifying desired coagulation soil application of precast concrete
Work.
Relative to prior art, the invention has the advantages that and beneficial effect:
(1) present invention prepared by polycarboxylic acid super-plasticizer 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 main chain can occur fracture degraded in hydration process, make list
Electrostatic Absorption group in individual macromolecular tails off, and later stage suction-operated thus weakens significantly;
(2) polycarboxylic acid super-plasticizer preparation method of the invention is simple, and water-reducing rate is high, dispersive property is excellent, using when make
Hydrated cementitious speed is fast, setting time is short, and early strength is high, is had broad application prospects in precast concrete field;
(3) polycarboxylic acid super-plasticizer of the invention is such as appropriately used in precast concrete, may replace flow it is cumbersome two
Secondary maintaining process, it is to avoid the potential high-risk of secondary maintenance, and a large amount of consumption steam coal resources.
Brief description of the drawings
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 the hydration heat RATES test of the gained PCE-4 of the embodiment of the present invention 4 and comparative example gained control sample 1
Curve map.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Raw material code name is as shown in table 1 in following examples and comparative example:
Table 1
A-1 |
Isopentene group APEO (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 sulfonics |
E-2 |
TGA |
Embodiment 1
77.8g is sequentially added in equipped with agitator, thermometer, nitrogen ingress pipe, the 250mL four-hole boiling flasks of Dropping feeder
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
Add 7.5g B-1 and 0.01g D-1, the aqueous solution of 0.44g E-1, time for adding to be respectively 2h and 2.5h, protected after completion of dropping
Temperature reaction 1.5h, after reaction terminates, to 40 DEG C, the product mass concentration for obtaining is 30% sodium hydroxide solution to slow cooling
Adjust pH value to 5 or so.Normal temperature is cooled to, the super modeling of high dispersive polycarboxylic acids solidifying at a low speed for obtaining that mass concentration is 40% is diluted with water
Agent, labeled as PCE-1.
Embodiment 2
79.1g is sequentially added in equipped with agitator, thermometer, nitrogen ingress pipe, the 250mL four-hole boiling flasks of Dropping feeder
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
Add 7.5g B-1,1.2g B-2 and 0.01g D-1, the aqueous solution of 0.52g E-1, time for adding to be respectively 2.5h and 3h, drip
Insulation reaction 1.5h after finishing is added, after reaction terminates, to 40 DEG C, the product mass concentration for obtaining is 30% hydrogen to slow cooling
Sodium hydroxide solution adjusts pH value to 5 or so.Normal temperature is cooled to, the high dispersive solidifying at a low speed for obtaining that mass concentration is 40% is diluted with water
Polycarboxylic acid super-plasticizer, labeled as PCE-2.
Embodiment 3
76.8g is sequentially added in equipped with agitator, thermometer, nitrogen ingress pipe, the 250mL four-hole boiling flasks of Dropping feeder
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
6.5g B-1 and 0.12g D-1, the aqueous solution of 0.36g E-1 are added dropwise to, time for adding is respectively 3h and 3.5h, after completion of dropping
Insulation reaction 1h, after reaction terminates, to 40 DEG C, the product mass concentration for obtaining is 30% sodium hydroxide solution to slow cooling
Adjust pH value to 5 or so.Normal temperature is cooled to, the super modeling of high dispersive polycarboxylic acids solidifying at a low speed for obtaining that mass concentration is 40% is diluted with water
Agent, labeled as PCE-3.
Embodiment 4
76.1g is sequentially added in equipped with agitator, thermometer, nitrogen ingress pipe, the 250mL four-hole boiling flasks of Dropping feeder
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
5.5g B-1 and 0.20g D-2, the aqueous solution of 0.60g E-1 are added dropwise to, time for adding is respectively 3.5h and 4h, after completion of dropping
Insulation reaction 1h, after reaction terminates, the product mass concentration for obtaining is that 30% sodium hydroxide solution adjusts pH value to 5 left
It is right.Normal temperature is cooled to, the high dispersive polycarboxylic acid super-plasticizer solidifying at a low speed for obtaining that mass concentration is 40% is diluted with water, is labeled as
PCE-4。
Embodiment 5
81.1g is sequentially added in equipped with agitator, thermometer, nitrogen ingress pipe, the 250mL four-hole boiling flasks of Dropping feeder
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
The aqueous solution of 5.4g B-1,6.4g B-3 and 0.24g D-2,0.48g E-1 is added dropwise to, time for adding is respectively 3h and 3.5h,
Insulation reaction 1h after completion of dropping, after reaction terminates, the product mass concentration for obtaining is 30% sodium hydroxide solution regulation
PH value is to 5 or so.Normal temperature is cooled to, is diluted with water that to obtain the high dispersive polycarboxylic acids solidifying at a low speed that mass concentration is 40% super plasticized
Agent, labeled as PCE-5.Comparative example
76.8g water, 72.8g A- are sequentially added in equipped with agitator, thermometer, the 250mL four-hole boiling flasks of Dropping feeder
3,65 DEG C are warming up to, 0.30g C-2 are stirring evenly and then adding into, 10min is stirred for, 6.5g B-1 and 0.12g D- are added dropwise to respectively
1st, the aqueous solution of 0.32g E-2, time for adding is respectively 3h and 3.5h, insulation reaction 1.5h after completion of dropping, after reaction terminates,
To 40 DEG C, the product mass concentration for obtaining is that 30% sodium hydroxide solution adjusts pH value to 5 or so to slow cooling.It is cooled to
Normal temperature, is diluted with water the polycarboxylic acid super-plasticizer for obtaining that mass concentration is 40%, labeled as control sample 1.
Implementation result:
Using reference cement, control sample 1 is medium-sized polycarboxylic acid super-plasticizer, according to GB/T8077-2000《Concrete
Additive homogeneity test method》The paste flowing degree of cement is tested, the ratio of mud is 0.35, volume (the solid volume of folding of water reducer
0.1%) on the basis of the quality of cement, test result is as shown in table 2 below.
The paste flowing degree test result of table 2
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 and water-reducing rate of solidifying high dispersive polycarboxylic acid super-plasticizer are higher at a low speed, have more preferable initial dispersion to cement
Performance, and initial set and final setting time also have different degrees of shortening than plain edition polycarboxylate water-reducer.
Choose PCE-4 carries out hydration heat RATES's test with control sample 1.The TAM Air of TA companies of U.S. production
The micro- calorimeter of 08Isothermal Calorimeter isothermals, the ratio of mud is 0.4, the solid volume 0.2% of polycarboxylate water-reducer folding.Institute
There is material and 1min is first stirred with 500r/min, then 1min is stirred with 1500r/min, control temperature for 20 ± 0.1 DEG C, its aquation is put
Hot rate curve is as shown in Figure 3.Be 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 is appeared earlier, and this shows that solidifying high dispersive polycarboxylic acid super-plasticizer can effectively suppress its slow setting work to present invention gained at a low speed
With the early stage hydration process of promotion cement slurry.
Above-described embodiment is the present invention preferably implementation method, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from Spirit Essence of the invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.