CN109503017A - A kind of hydrated cementitious enhancer compositions and preparation method thereof - Google Patents
A kind of hydrated cementitious enhancer compositions and preparation method thereof Download PDFInfo
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- CN109503017A CN109503017A CN201811631091.3A CN201811631091A CN109503017A CN 109503017 A CN109503017 A CN 109503017A CN 201811631091 A CN201811631091 A CN 201811631091A CN 109503017 A CN109503017 A CN 109503017A
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- 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/24—Alkaline-earth metal silicates
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- General Life Sciences & Earth Sciences (AREA)
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- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a kind of hydrated cementitious enhancer compositions and preparation method thereof, the hydrated cementitious enhancer compositions be reacted in the composite diffusion agent solution containing cation dispersing agent and anionic dispersing agents by water-soluble calcium solution with water-soluble silicate solution it is obtained.The hydrated cementitious enhancer compositions are widely used in including cement products that section of jurisdiction, tubular pole, PC component, extraordinary mortar etc. have early strength particular/special requirement, strength development speeds can be greatly improved, accelerates mold turnover, improves production capacity, maintenance energy consumption, save the cost can be reduced simultaneously.
Description
Technical field
The invention belongs to building material technical field, be related to a kind of hybrid hydrated calcium silicate suspension and its
Preparation method, specifically a kind of hydrated cementitious promotor.
Background technique
Gain in strength speed is improved in prefabricated components production process, can be accelerated mold turnover, be improved production efficiency.Component
Factory generallys use the method for autoclave at high temperature maintenance and addition early strength agent to improve mold turnaround speed.Autoclave at high temperature conserves energy consumption
Height is unfavorable for energy-saving and emission-reduction.Screening suitable early strength agent becomes raising prefabricated components production efficiency, reduces the optimization technique of energy consumption
Approach.
Early strength agent based on inorganic, organic is applied generally for many years, but there are many drawbacks, Chang Yinqi concrete
The reduction of workability and durability as triethanolamine class early strength agent dosage is not easy to control, and crosses to mix and easily causes extra retarded set or fast solidifying；
Early strength agent containing chlorine easily causes reinforcement corrosion；Sulfates early strength agent improves macropore content in Behavior of Hardened Cement Paste, leads to the anti-of concrete
Infiltration property and corrosion resistance reduce.
Summary of the invention
The object of the present invention is to provide a kind of hydrated cementitious promotors and preparation method thereof.As a kind of novel nucleus class
Early strength agent, preparation method is simple to operation, early to have excellent performance by force.
Realizing the specific technical solution of the object of the invention is:
A kind of hydrated cementitious enhancer compositions, feature is: water-soluble calcium solution and water-soluble silicate solution are being contained
It reacts in the composite diffusion agent solution for having cation dispersing agent and anionic dispersing agents, generates the water of hybrid
SiClx acid calcium sol particle, i.e. the hydrated cementitious enhancer compositions containing cation and anion composite dispersing agent.
The chemical structural formula of the cation dispersing agent is such as shown in (1):
Wherein, the value of a is 0-100；The value of b is 200-3000；The value of c is 2-10；R1For methyl or hydrogen atom；
R2For methyl, hydrogen atom, chlorine atom or bromine atom；R3For methyl, hydrogen atom, chlorine atom, bromine atom or hydroxyl；R4For methyl or
Hydrogen atom.
The anionic dispersing agents contain the structural unit (2) below from unsaturated polyether monomer and below are originated from
The polycarboxylic acid polymer of the structural unit (3) of unsaturated carboxylic acid monomer, in which:
Structural unit (2) is
Wherein: R5Indicate hydrogen or methyl；R6Indicate hydrogen, methyl or ethyl；R7Indicate the alkane of hydrogen or 1-6 carbon atom
Base；X is linking group, is-O- ,-CH2O-、-CH2CH2O-、Or-O-CH2CH2CH2CH2O-；n
It indicates the average addition molal quantity of oxyalkylene group, is the arbitrary integer in 1-300.
Structural unit (3) is
Wherein: R8Indicate hydrogen, methyl or COOM group, R9Indicate hydrogen, methyl or CH2COOM group, M indicate hydrogen, monovalence gold
Category, (1/2) divalent metal, ammonium or organic amino group.
The anionic dispersing agents, it is characterised in that contain the structural unit below from unsaturated polyether monomer
(4) and the polycarboxylic acid polymer of the structural unit (5) below from unsaturated carboxylic acid monomer, wherein structural unit (4) is
Wherein: R10Indicate hydrogen or methyl；R11O indicates the oxyalkylene group and its mixture of 2-8 carbon atom；N indicates oxygen
Change the average addition molal quantity of alkenyl, is the arbitrary integer in 1-180；R12Indicate the alkyl of hydrogen or 1-6 carbon atom.
Structural unit (5) is
Wherein: R13Indicate hydrogen, methyl or group, R14Indicate that hydrogen, methyl or group, M indicate hydrogen, monovalent metal, (1/2)
Divalent metal, ammonium or organic amino group.
The molar ratio of the water-soluble Ca salt and water-soluble silicate is 1-3:2-1.
The cation dispersing agent and anionic dispersing agents mass ratio are 1:1-5.
The water-soluble Ca salt is calcium chloride, calcium nitrate, calcium formate, calcium acetate, calcium citrate, calcium hydroxide and calcium oxide
Or mixtures thereof one of.
The water-soluble silicate be one of sodium metasilicate, potassium silicate, sodium metasilicate, potassium metasilicate, waterglass or its
Mixture.
It is described to include: containing the cationic preparation method with the hydrated cementitious enhancer compositions of anion composite dispersing agent
(1) water-soluble Ca salt, water-soluble silicate difference obtained solution are weighed；Cation is weighed according to mass ratio 1:1-5
Dispersing agent and anionic dispersing agents configure composite diffusion agent solution.
(2) control temperature is under the conditions of 10-90 DEG C, by water-soluble calcium solution and water-soluble silicate solution according to 1-3:2-
1 molar ratio is added dropwise into composite diffusion agent solution, is kept stirring simultaneously, and time for adding is set as 1-8 hours；Completion of dropwise addition after
Continuous stirring 1-3 hours, is then slowly dropped to room temperature, and the hydrated cementitious containing cation and anion composite dispersing agent is made and promotes
Agent composition.
The solid content of the described hydrated cementitious enhancer compositions containing cation and anion composite dispersing agent is
5%-50%.
The aquation silicon that the hydrated cementitious enhancer compositions containing cation and anion composite dispersing agent contain
The partial size of sour calcium sol particle is 50-250 nanometers.
Hydrated cementitious enhancer compositions provided by the invention containing cation and anion composite dispersing agent, can be substantially
The crystallization nucleation potential barrier of hydrated calcium silicate (C-S-H) gel is reduced, promotes hydrated reaction of cement rate, significantly improves cement products
Extreme early intensity within 12 hours.Be conducive to control using cation dispersing agent and anionic dispersing agents configuration composite dispersing agent
The scale of hydrated calcium silicate sol particle and the stability of suspension in suspension system processed.Can be widely applied to include section of jurisdiction,
The cement-based articles that tubular pole, PC component, extraordinary mortar etc. require early strength, can greatly improve strength development speeds, add
Fast mold turnover, improves production capacity, while can reduce maintenance energy consumption, save the cost.
Specific embodiment
Present invention will be further explained below with reference to specific examples, it should be understood that embodiment be merely to illustrate the present invention without
For limiting the scope of the invention.Those skilled in the art fall within the application institute to the modification of various equivalent forms of the invention
Attached claim limited range.
Embodiment 1
The calcium chloride and 50.15g water configuration calcium chloride water for weighing 38.25g, weigh 43.74g potassium silicate and 44.26g
Water configures potassium silicate solution, weighs 13.28g anionic dispersing agents, 11.53g cation dispersing agent and the configuration of 158.2g water respectively
Composite dispersing agent aqueous solution.Composite diffusion agent solution is imported into three-necked flask, temperature is set as 15 DEG C, dispersant solution is stirred equal
It is even.Under conditions of being kept stirring, while calcium chloride water and potassium silicate aqueous solution is added dropwise, when adjusting rate of addition to be added dropwise
Between control in 1h or so.It is added dropwise and continues to stir 1h, then slow cooling to room temperature, hydration promoting agents HA-1 is made.
Embodiment 2
The calcium nitrate and 55.29g water configuration calcium nitrate aqueous solution for weighing 54.85g, weigh 53.74g waterglass and 44.26g
Water configures water glass solution, weighs 10.28g anionic dispersing agents, 13.53g cation dispersing agent and the configuration of 141.5g water respectively
Composite dispersing agent aqueous solution.Composite diffusion agent solution is imported into three-necked flask, temperature is set as 15 DEG C, dispersant solution is stirred equal
It is even.Under conditions of being kept stirring, while calcium chloride water and potassium silicate aqueous solution is added dropwise, when adjusting rate of addition to be added dropwise
Between control in 2h or so.It is added dropwise and continues to stir 4h, then slow cooling to room temperature, hydration promoting agents HA-2 is made.
Embodiment 3
Weigh 44.85g calcium formate and 53.57g water configuration calcium formate water solution, weigh 48.36g potassium metasilicate and
43.78g water configure potassium metasilicate solution, weigh respectively 17.65g anionic dispersing agents, 14.19g cation dispersing agent and
133.5g water configures composite dispersing agent aqueous solution.Composite diffusion agent solution is imported into three-necked flask, temperature is set as 15 DEG C, will disperse
Agent solution stirs evenly.Under conditions of being kept stirring, while calcium chloride water and potassium silicate aqueous solution is added dropwise, adjusts and speed is added dropwise
Degree is so that time for adding is controlled in 7h or so.It is added dropwise and continues to stir 3h, then slow cooling to room temperature, aquation is made and promotes
Agent HA-3.
Embodiment 4
Weigh 39.64g calcium nitrate and 54.20g water configuration calcium nitrate aqueous solution, weigh 54.37g sodium metasilicate and
52.68g water configure solution of sodium metasilicate through, weigh respectively 18.22g anionic dispersing agents, 19.36g cation dispersing agent and
145.62g water configures composite dispersing agent aqueous solution.Composite diffusion agent solution is imported into three-necked flask, temperature is set as 15 DEG C, will divide
Dispersant solution stirs evenly.Under conditions of being kept stirring, while calcium chloride water and potassium silicate aqueous solution is added dropwise, adjusts and be added dropwise
Speed makes time for adding control in 2h or so.It is added dropwise and continues stirring 4, then slow cooling to room temperature, aquation is made and promotees
Into agent HA-4.
Application examples
The early epistasis energy of hydration promoting agents obtained, experiment raw material difference are evaluated using the mortar mix ratio that table 1 lists
For benchmark cement PO42.5, normal sand, polycarboxylate water-reducer (VIVID-500 (D), commercially available).
1 mortar mix ratio of table
| Cement | Normal sand | Hydration promoting agents | VIVID-500(D) | Water | Curing condition |
| 600g | 1350g | 1.0-5.0% | 2.5g | 210g | Mark is supported |
2 mortar strength test result of table
As can be seen from Table 2, hydration promoting agents mortar-like bulk strength is added in Examples 1 to 4 to be obviously improved, especially
It is 7h compression strength up to 815% (embodiment 4), and is only had using traditional anhydrous sodium sulfite 7h compressive strength rate
261%.Meanwhile in terms of 28d compression strength, addition hydration promoting agents do not have retraction phenomenon, this is also to be different from traditional early strength agent
A big advantage.
Claims (3)
1. a kind of hydrated cementitious enhancer compositions, which is characterized in that water-soluble calcium solution and water-soluble silicate solution exist
It reacts in composite diffusion agent solution containing cation dispersing agent and anionic dispersing agents, generates hybrid
Hydrated calcium silicate sol particle, the hydrated cementitious promotor as containing cation and anion composite dispersing agent combine
Object；
The chemical structural formula of the cation dispersing agent such as (1) is shown,
Wherein, the value of a is 0-100；The value of b is 200-3000；The value of c is 2-10；R1For methyl or hydrogen atom；R2For
Methyl, hydrogen atom, chlorine atom or bromine atom；R3For methyl, hydrogen atom, chlorine atom, bromine atom or hydroxyl；R4It is former for methyl or hydrogen
Son；
The anionic dispersing agents contain the structural unit (2) below from unsaturated polyether monomer and it is below be originated from insatiable hunger
With the polycarboxylic acid polymer of the structural unit (3) of carboxylic acid monomer, in which:
Structural unit (2) is
Wherein: R5Indicate hydrogen or methyl；R6Indicate hydrogen, methyl or ethyl；R7Indicate the alkyl of hydrogen or 1-6 carbon atom；X
It is-O- ,-CH for linking group2O-、-CH2CH2O-、Or-O-CH2CH2CH2CH2O-；N is indicated
The average addition molal quantity of oxyalkylene group is the arbitrary integer in 1-300；
Structural unit (3) is
Wherein: R8Indicate hydrogen, methyl or COOM group, R9Indicate hydrogen, methyl or CH2COOM group, M indicate hydrogen, monovalent metal,
(1/2) divalent metal, ammonium or organic amino group；
The anionic dispersing agents are containing the structural unit (4) below from unsaturated polyether monomer and below to be originated from
The polycarboxylic acid polymer of the structural unit (5) of unsaturated carboxylic acid monomer, in which:
Structural unit (4) is
Wherein: R10Indicate hydrogen or methyl；R11O indicates the oxyalkylene group and its mixture of 2-8 carbon atom；N indicates oxyalkylene
The average addition molal quantity of base is the arbitrary integer in 1-180；R12Indicate the alkyl of hydrogen or 1-6 carbon atom；
Structural unit (5) is
Wherein: R13Indicate hydrogen, methyl or group, R14Indicate that hydrogen, methyl or group, M indicate hydrogen, monovalent metal, (1/2) divalent gold
Category, ammonium or organic amino group；
The molar ratio of the water-soluble Ca salt and water-soluble silicate is 1-3:2-1；
The cation dispersing agent and anionic dispersing agents mass ratio are 1:1-5；
The water-soluble Ca salt is in calcium chloride, calcium nitrate, calcium formate, calcium acetate, calcium citrate, calcium hydroxide and calcium oxide
Or mixtures thereof one kind；
The water-soluble silicate is one of sodium metasilicate, potassium silicate, sodium metasilicate, potassium metasilicate, waterglass or its mixing
Object；
The preparation method of the hydrated cementitious enhancer compositions, specifically includes:
(1) water-soluble Ca salt, water-soluble silicate difference obtained solution are weighed；Cation dispersion is weighed according to mass ratio 1:1-5
Agent and anionic dispersing agents configure composite diffusion agent solution；
(2) control temperature is under the conditions of 10-90 DEG C, by water-soluble calcium solution and water-soluble silicate solution according to 1-3:2-1's
Molar ratio is added dropwise into composite diffusion agent solution, is kept stirring simultaneously, and time for adding is set as 1-8 hours；Completion of dropwise addition continues
Stirring 1-3 hours, is then slowly dropped to room temperature, and hydrated cementitious enhancer compositions are made.
2. hydrated cementitious enhancer compositions according to claim 1, which is characterized in that the hydrated cementitious promotor group
The solid content for closing object is 5%-50%.
3. hydrated cementitious enhancer compositions according to claim 1, which is characterized in that the hydrated calcium silicate colloidal sol contained
The partial size of particle is 50-250 nanometers.
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| CN109940744A (en) * | 2019-04-24 | 2019-06-28 | 刘翠芬 | A kind of Concrete Surface Durability elevator and preparation method thereof and application method |
| CN110981273A (en) * | 2019-12-31 | 2020-04-10 | 上海三瑞高分子材料股份有限公司 | Cement hydration hardening accelerator composition and preparation method thereof |
| CN110981269A (en) * | 2019-12-31 | 2020-04-10 | 上海三瑞高分子材料股份有限公司 | Cement early strength agent composition and preparation method thereof |
| CN113511850A (en) * | 2021-08-19 | 2021-10-19 | 中国石油大学(华东) | Low-heat early-strength cement paste system composition with low-temperature synergistic hydration and application |
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| CN109940744A (en) * | 2019-04-24 | 2019-06-28 | 刘翠芬 | A kind of Concrete Surface Durability elevator and preparation method thereof and application method |
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| CN113511850A (en) * | 2021-08-19 | 2021-10-19 | 中国石油大学(华东) | Low-heat early-strength cement paste system composition with low-temperature synergistic hydration and application |
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Application publication date: 20190322 |