CN106008865B - A kind of preparation method of distress in concrete inhibitor - Google Patents
A kind of preparation method of distress in concrete inhibitor Download PDFInfo
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- CN106008865B CN106008865B CN201610339930.9A CN201610339930A CN106008865B CN 106008865 B CN106008865 B CN 106008865B CN 201610339930 A CN201610339930 A CN 201610339930A CN 106008865 B CN106008865 B CN 106008865B
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- beta
- concrete
- cyclodextrin
- double bond
- distress
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
-
- 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
- C04B24/38—Polysaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
- C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
-
- 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
- C04B2103/0068—Ingredients with a function or property not provided for elsewhere in C04B2103/00
- C04B2103/0089—Agents for reducing heat of hydration
Abstract
The present invention discloses the preparation method that a kind of distress in concrete inhibits.The method is first beta cyclodextrin powder of the synthesis containing multiple double bond, the beta cyclodextrin powder containing multiple double bond under the effect of initiator azo dicyano valeric acid is crosslinked again, is filtered, vacuum drying, sieving is ground to get to distress in concrete inhibitor of the present invention.Distress in concrete inhibitor of the present invention can significantly regulate and control hydrated cementitious rate, reduce concentration heat release of the cement in hydration process, so as to reduce the shrinkage cracking in temperature changing process, the purpose of the crack inhibition especially under the conditions of construction at high temperature.
Description
Technical field：
The present invention relates to concrete admixture fields, and in particular to one kind inhibits distress in concrete by heat of hydration regulation and control
Distress in concrete inhibitor preparation method.
Background technology：
Concrete is generated there are many kinds of the reason of crack, wherein since shrinkage cracking caused by internal-external temperature difference is one very heavy
It is even more especially common particularly in mass concrete the reason of wanting.Since the thermal conductivity factor of concrete is not high, hydrated cementitious
When can release a large amount of heat, these heats can not shed in a short time, and concrete internal temperature is caused to increase, controlled
Under the conditions of, it may result in concrete deformation cracking.
In recent years, a large amount of scholars have been engaged in a large amount of research to reduce influence of the hydration heat of concrete to concrete structure.
Patent CN102464478A discloses a kind of utilize the strontium base latent heat compound [Sr (OH) of 0.5~10wt%2·8H2O], barium
Base latent heat compound [Ba (OH)2·8H2O], magnesium-based latent heat compound [Mg (NO3)2·6H2O] and iron-based latent heat compound [Fe
(NO3)2·6H2O] in a kind of compound and 100wt% ternarys binding agent mix ultralow hot adhesion to prepare by premixing method
The heat of hydration controlled material of agent composition.
CN103739722A patents of invention disclose a kind of heat of hydration controlled material containing dextrin, and ingredient is by outer
Crosslinking agent is added to carry out surface-crosslinked dextrin；The Chinese invention patent of Publication No. CN102674738A discloses one kind by 25-
The Multifunctional anti-crack additive of 40% calcium oxide expansive clinker, 1-3% dextrin and flyash, dextrin are commercially available dextrin.
Presently disclosed patent is also mainly starch base type mostly, such as starch pyrolysis, acidolysis or enzymolysis, Yi Jili
It is obtained with the directly crosslinking of commercially available dextrin, but the material of starch base type is at construction temperature higher (~35 DEG C), in coagulation
Native alkaline condition, which can decompose, releases part small molecule glucide, causes slow setting serious, is unfavorable for improving construction speed.In height
Under warm environment, the molding temperature of concrete is high, and aquation is fast, and aquation peak value is high, and excessively high aquation peak value can cause the coagulation of bigger
Native internal-external temperature difference so as to generate the temperature stress of bigger, leads to the increase of distress in concrete risk.
Invention content
Inhibit the deficiency present in material for the heat of hydration reported at present：Heat of hydration ability of regulation and control is limited, and high temperature is applied
There is the characteristics of slow setting, crack risk increase in labour union, and the present invention provides one kind and inhibits distress in concrete by heat of hydration regulation and control
Additive preparation method, effectively can significantly regulate and control hydrated cementitious rate, reduce temperature difference between inside and outside concrete (especially
Under the conditions of construction at high temperature), setting time of concrete is not influenced.
Distress in concrete inhibitor of the present invention, main component are pasted by the crosslinked β of hot polymerization reaction height-ring
Essence.Highly cross-linked beta-cyclodextrin is because crosslinking, can be greatly reduced the generation of small molecular sugar in use, so as to not
The setting time of concrete can therefore be influenced.
The preparation method of distress in concrete inhibitor of the present invention, includes the following steps：
(1) beta-cyclodextrin powder of the synthesis containing multiple double bond：First beta-cyclodextrin is distributed in anhydrous dimethyl sulphoxide,
In the case where being stirred continuously, the anhydrous dimethyl sulphoxide solution containing acryloyl chloride mass fraction 10wt% is gradually added dropwise to, is added dropwise
The mole of the acryloyl chloride entered is 8-21 times of beta-cyclodextrin；
10h is reacted at 60 DEG C, then with unreacted acryloyl chloride in oil pump extraction system and the HCl of generation, is obtained
Dispersion liquid,
Gained dispersion liquid is added dropwise in acetone again, and is cooled down with mixture of ice and water, is used after centrifuging out precipitation
Ice acetone washing precipitation three times, is dried in vacuo for 24 hours, the as described beta-cyclodextrin powder containing multiple double bond；
The dosage of the acetone is 3-5 times of the dispersion liquid volume；
(2) the beta-cyclodextrin powder containing multiple double bond and initiator azo dicyano valeric acid are distributed in water,
The molar ratio of the beta-cyclodextrin powder containing multiple double bond and initiator azo dicyano valeric acid is (10-30):1；Acutely
20h is reacted at 80 DEG C under stirring, after reaction, is filtered, vacuum drying grinds sieving, as of the present invention mixed
Solidifying soil cracking seam inhibitor.
In step (2) described reaction process, the reactivity of acryloyl chloride and hydroxyl is very high, it is believed that conversion ratio is big
In 95% or close to 100%, the extent of reaction of beta-cyclodextrin is speculated by controlling the usage amount of acryloyl chloride.
Preferably, the mole for the acryloyl chloride being added dropwise to is 12-16 times of beta-cyclodextrin
The present invention terminates by adjusting the addition of acryloyl chloride, the beta-cyclodextrin powder containing multiple double bond and reaction
Double bond residual ratio afterwards carries out reasonable disposition, just reaches effect of the present invention.
The beneficial effects of the invention are as follows：
(1) present invention is carried out beta-cyclodextrin by hot polymerization reaction highly cross-linked, can not only greatly improve heat of hydration rate
Rejection ability, reduce the risk of concrete cracking, and avoid a large amount of uses of swelling agent, flyash and cooling water pipe,
With advantage easy to operate, environmentally protective.
(2) distress in concrete inhibitor of the present invention mixes in concrete and does not interfere with concrete in the construction temperature
Under the conditions of setting time.
Specific embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not restricted to following embodiment.
Following embodiment is described in more detail prepares heat of hydration regulation and control lotion and its performance according to the method for the present invention,
And these embodiments provide by way of illustration, but these embodiments do not limit the scope of the invention.
In the embodiment of the present invention, cement uses 52.5 cement of small wild field；Water-cement ratio is 0.4, and fine aggregate is river sand, apparent close
Spend 2.63g/cm3, fineness modulus 2.60；Coarse aggregate is 5~20mm continuous grading rubbles, and water-reducing agent selects Jiangsu Su Botexin
Material limited companyNaphthalene series high-efficiency water-reducing agent.
The detection method of double bond residual volume：Accurate 1,3, the 5- trioxane solids for weighing certain mass (as internal standard, are not joined
With cross-linking reaction), quality is about 1/10th of the beta-cyclodextrin quality containing multiple double bond before reacting, adds in the crosslinking
It in preceding solution, stirs evenly, fully after dissolving, a drop reaction solution is taken to be added drop-wise to 0.6mL heavy water (D2O it is done in)1H NMR nuclear-magnetisms
Test；After reaction, then a drop reaction solution is taken, same method carries out1H NMR nuclear-magnetisms are tested.Due to internal standard 1 before and after reaction,
3,5- trioxane moles remain unchanged, and double bond content is reducing, and are inhaled by comparing the double bond proton before reacting and after reaction
The integral area at peak is received, calculates double bond residual volume.
Hydrated cementitious heat testing method is with reference to GB/T 2022-1980.
Concrete crushing strength is with reference to GB/T50081-2002《Standard for test methods of mechanical properties of ordinary concrete》It performs.
Concrete coagulating time is with reference to GB/T50080-2002《Standard for test methods of properties of ordinary concrete mixture standard》It holds
Row.
In terms of crack resistance evaluation：It is tested using concrete temperature stress testing machine, coagulation is evaluated with Cracking Temperature
Native crack resistance, the lower cracking resistance of Cracking Temperature are better.RILEM voluntary standards TC119-TCE3 " is commented using Cracking test frame
Valency early-age concrete crack resistance " is just using " Cracking Temperature " as crack resistance evaluation index, and the practical table of engineering of concrete
It is now fine with the consistency of conclusion (of pressure testing).
Embodiment 1
300g beta-cyclodextrins are distributed in 500g anhydrous dimethyl sulphoxides, is stirred continuously down and is added dropwise to 1914g mass point
Number is the anhydrous dimethyl sulphoxide solution of the acryloyl chloride of 10wt%, and 10h is reacted at 60 DEG C, then in oil pump extraction system
Unreacted acryloyl chloride and the HCl of generation, then solution is added dropwise in excessive acetone, and cold with mixture of ice and water
But, it centrifuges out and washs precipitation three times with ice acetone after precipitation, vacuum drying for 24 hours, obtains the β containing multiple double bond-ring and pastes
Fine powder end.
By the molar ratio of the beta-cyclodextrin powder containing multiple double bond of above-mentioned synthesis and initiator azo dicyano valeric acid
It is 15：1 ratio is added in water of the quality for 3 times of the beta-cyclodextrin powder quality containing multiple double bond, is vigorously stirred down
20h is reacted at 80 DEG C, after reaction, is filtered, vacuum drying grinds sieving (100 mesh), as of the present invention mixed
Solidifying soil cracking seam inhibitor.
Embodiment 2
The anhydrous dimethyl sulphoxide solution for the acryloyl chloride for being 10wt% in addition to being added dropwise to 2392g mass fractions, other with
Embodiment 1 is consistent.
Embodiment 3
The anhydrous dimethyl sulphoxide solution for the acryloyl chloride for being 10wt% in addition to being added dropwise to 2870g mass fractions, other with
Embodiment 1 is consistent.
Embodiment 4
The anhydrous dimethyl sulphoxide solution for the acryloyl chloride for being 10wt% in addition to being added dropwise to 3588g mass fractions, other with
Embodiment 1 is consistent.
Embodiment 5
The anhydrous dimethyl sulphoxide solution for the acryloyl chloride for being 10wt% in addition to being added dropwise to 4306g mass fractions, other with
Embodiment 1 is consistent.
Embodiment 6
The anhydrous dimethyl sulphoxide solution for the acryloyl chloride for being 10wt% in addition to being added dropwise to 5023g mass fractions, other with
Embodiment 1 is consistent.
The heat of hydration data result of 1 embodiment 1-6 of table and benchmark
Under conditions of different acryloyl chloride dripping quantities, the distress in concrete of preparation inhibits the present invention as can be seen from Table 1
Agent is respectively provided with good heat of hydration ability of regulation and control, and concrete cracking temperature reduction can be significantly increased, this is largely
The cracking risk of concrete is reduced, the crack resistance of concrete is significantly improved, at the same time, 28 days intensity of concrete
It is held essentially constant, illustrates that the distress in concrete inhibitor only plays regulating and controlling effect to Hydration, do not interfere with cement
The total thermal discharge of aquation.
Comparative example 1
With reference to heat of hydration controlled material made from process described in embodiment 1 in patent CN103739722A.
Comparative example 2
With reference to heat of hydration controlled material made from process described in embodiment 5 in patent CN103739722A.
Comparative example 3
With reference to heat of hydration controlled material made from process described in embodiment 1 in patent CN104592403A.
The setting time comparison of construction concrete under 2 room temperature of table (20 DEG C) and high temperature (35 DEG C)
The data of embodiment 1-6 and benchmark, which can be seen that, from table 2 adds concrete of the present invention into concrete
Crack inhibitor does not interfere with the setting time of concrete at such a temperature.Numerous studies report that concrete is in construction at high temperature
In the case of, since hydration rate is accelerated, setting time can be greatly shortened, and retardation phenomenon occurs in comparative example 1-3, this is
Because under high temperature meta-alkali shear environment, crosslinking dextrin has a small amount of glucide for decomposing and being dissolved as small molecule, slow setting
The extension value of setting time caused by effect is higher than the decreasing value of setting time caused by high temperature, causes deferred action more obvious
Embody, and beta-cyclodextrin has unique cavity structure, and inner cavity is hydrophobic and peripheral hydrophilic, has stable molecule knot
Structure is not easily decomposed under high temperature meta-alkali shear environment as small molecular sugar so that it does not interfere with the temperature under construction at high temperature environment
Setting time under degree.
Claims (2)
1. a kind of preparation method of distress in concrete inhibitor, which is characterized in that include the following steps：
(1) beta-cyclodextrin powder of the synthesis containing multiple double bond：First beta-cyclodextrin is distributed in anhydrous dimethyl sulphoxide, not
Under disconnected stirring, the anhydrous dimethyl sulphoxide solution containing acryloyl chloride mass fraction 10wt% is gradually added dropwise to, is added dropwise to
The mole of acryloyl chloride is 8-21 times of beta-cyclodextrin；
10h is reacted at 60 DEG C, then with unreacted acryloyl chloride in oil pump extraction system and the HCl of generation, is disperseed
Liquid,
Gained dispersion liquid is added dropwise in acetone again, and is cooled down with mixture of ice and water, ice third is used after centrifuging out precipitation
Ketone washing precipitation three times, is dried in vacuo for 24 hours, the as described beta-cyclodextrin powder containing multiple double bond；
The dosage of the acetone is 3-5 times of the dispersion liquid volume；
(2) the beta-cyclodextrin powder containing multiple double bond and initiator azo dicyano valeric acid are distributed in water, it is described
The molar ratio of beta-cyclodextrin powder containing multiple double bond and initiator azo dicyano valeric acid is (10-30):1；It is vigorously stirred
Under at 80 DEG C react 20h, after reaction, filter, vacuum drying grinds sieving, and the as described distress in concrete presses down
Preparation.
2. the method as described in claim 1, which is characterized in that the mole of the acryloyl chloride is the 12-16 of beta-cyclodextrin
Times.
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| CN109333828B (en) * | 2018-11-10 | 2023-09-08 | 山东交通学院 | Method for reinforcing recycled concrete |
| CN111608408B (en) * | 2019-02-23 | 2022-03-22 | 西北民族大学 | Repairing system for concrete cracks |
| CN111205395B (en) * | 2020-01-16 | 2020-11-24 | 中国地质大学（北京） | Star-shaped copolymer, preparation method and application thereof, constant-current modified water-based drilling fluid, and preparation method and application thereof |
| CN113213807B (en) * | 2021-05-29 | 2022-08-30 | 石家庄市长安育才建材有限公司 | Composite anti-cracking agent for ultra-long large-volume concrete and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104610503A (en) * | 2015-02-05 | 2015-05-13 | 江苏苏博特新材料股份有限公司 | Crosslinked hydration heat regulating agent as well as preparation method and application of crosslinked hydration heat regulating agent |
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| EP0602149A1 (en) * | 1991-09-06 | 1994-06-22 | Commonwealth Scientific And Industrial Research Organisation | Composition and method for reducing cholesterol concentration |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104610503A (en) * | 2015-02-05 | 2015-05-13 | 江苏苏博特新材料股份有限公司 | Crosslinked hydration heat regulating agent as well as preparation method and application of crosslinked hydration heat regulating agent |
Non-Patent Citations (1)
| Title |
|---|
| Cyclodextrin-Containing Polymers. 1. Preparation of Polymers;Akira Harada et al;《Macromolecules》;19761231;第9卷(第5期);第701-704页 * |
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