CN114685089B - Slow-release defoaming nano-porous composite material and preparation method and application thereof - Google Patents
Slow-release defoaming nano-porous composite material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 122
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 100
- 239000004567 concrete Substances 0.000 claims abstract description 52
- 239000002245 particle Substances 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 239000007783 nanoporous material Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 62
- 229920000570 polyether Polymers 0.000 claims description 62
- 239000013530 defoamer Substances 0.000 claims description 58
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 45
- 239000000377 silicon dioxide Substances 0.000 claims description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 22
- 239000010703 silicon Substances 0.000 claims description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 13
- 230000009471 action Effects 0.000 claims description 12
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 239000000693 micelle Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 229920001296 polysiloxane Polymers 0.000 claims description 8
- 239000004568 cement Substances 0.000 claims description 7
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 5
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 5
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 239000012670 alkaline solution Substances 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 27
- 238000002156 mixing Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 238000003980 solgel method Methods 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 239000004566 building material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 24
- 230000000694 effects Effects 0.000 description 17
- 235000012239 silicon dioxide Nutrition 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000009826 distribution Methods 0.000 description 12
- 238000002296 dynamic light scattering Methods 0.000 description 12
- 229910021426 porous silicon Inorganic materials 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- 239000004408 titanium dioxide Substances 0.000 description 9
- 238000013268 sustained release Methods 0.000 description 8
- 239000012730 sustained-release form Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000005543 nano-size silicon particle Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003254 anti-foaming effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009440 infrastructure construction Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000008030 superplasticizer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
-
- 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
- C04B2103/50—Defoamers, air detrainers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
The invention belongs to the technical field of building material additives, and particularly discloses a slow-release defoaming nano porous composite material and a preparation method thereof. The slow-release defoaming nano-porous composite material comprises a nano-porous material and a defoaming agent coated by the nano-porous material; wherein the nanoporous composite has channels for escape of the anti-foaming agent. According to the invention, the nano-porous composite material formed by the defoaming agent and the nano-porous material is prepared by a sol-gel method, and the defoaming agent molecules are ensured to escape at a certain speed by regulating the particle size and the pore size of the nano-porous composite material, so that the purpose of slow release defoaming is realized. The invention also provides the application of the nano porous composite material in concrete, when the nano porous composite material is applied to the concrete, the nano porous composite material can slowly release the defoaming agent in the concrete stirring process, so that the concrete still keeps better defoaming capability in the middle and later mixing period, the gas content in the concrete is obviously reduced, and the strength of hardened concrete is improved.
Description
Technical Field
The invention belongs to the technical field of building material additives, and particularly relates to a slow-release defoaming nano porous composite material, a preparation method thereof and application thereof in the field of concrete.
Background
With the rapid development of infrastructure construction in China, concrete is used as one of the most important engineering materials in the construction of modern civil engineering facilities, and the market has higher and higher requirements on the comprehensive properties of workability, durability, constructability and the like. However, in the actual application of concrete at present, due to the addition of the admixture, the content of air bubbles in the concrete is increased, and a large number of large-aperture air holes can seriously influence the hardening strength and durability of the concrete; therefore, during the stirring process of concrete, an antifoaming agent is generally required to be added to eliminate redundant air bubbles so as to regulate the air pore structure of the concrete. The antifoaming agent is a surfactant having a hydrophilic-lipophilic balance (HLB) within a certain range in terms of structure, that is, an amphiphilic molecule having a hydrophobic group at one end and a hydrophilic group at the other end. At present, the types of defoaming agents are roughly classified into mineral oil type, silicone type and polyether type, and the defoaming agents are widely applied to the fields of paper making, coating, textile and the like. A plurality of concrete defoaming agents are developed in the field of concrete, and the application effect is obvious.
In practical application, sometimes a proper amount of air bubbles are needed to improve the workability of concrete in the initial stage of concrete, and the excessive air bubbles need to be eliminated only after the concrete is hardened in the later stage, so that the strength and the durability of the concrete are improved. However, the conventional defoaming agent on the market can only adjust the initial gas content of the concrete, and does not have the slow release performance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a slow-release defoaming nano-porous composite material, which can achieve the purpose of slow-release defoaming by controlling the aperture of the nano-porous composite material, thereby effectively reducing the gas content in concrete in application.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
the slow-release defoaming nano-porous composite material comprises a nano-porous material and a defoaming agent coated by the nano-porous material; wherein the nano-porous composite material is provided with a channel for the escape of the defoaming agent, and the pore size of the channel is 2 nm-20 nm.
Further, the nano-porous material is nano-titanium dioxide or nano-silicon dioxide.
Further, the defoaming agent is selected from any one of polyether defoaming agents, silicone defoaming agents and polyether modified silicone defoaming agents.
Further, the polyether defoamer has a general structural formula shown as the following formula A:
the organic silicon defoaming agent has a structural general formula shown as the following formula B:
the polyether modified organic silicon defoaming agent has a structural general formula shown as the following formula C:
wherein X is an alkyl group having 14 to 42 carbon atoms, and R is a methyl group; the value range of the average addition mole number m of the propylene oxide is 0-40, and the value range of the average addition mole number n of the ethylene oxide is 2-80; a ranges from 10 to 500, and b = a-1.
Further, the particle size of the slow-release defoaming nano-porous composite material is 50 nm-500 nm.
Another object of the present invention is to provide a method for preparing the slow release defoaming nano-porous composite material, which comprises the following steps:
s1, stirring and dispersing a defoaming agent and alkali liquor uniformly to obtain a defoaming agent solution;
s2, dropwise adding an inorganic precursor into the defoaming agent solution, fully stirring, taking a defoaming agent micelle in the defoaming agent solution as a growth point, hydrolyzing the inorganic precursor under the action of the alkali liquor, and carrying out sol-gel reaction to generate a nano porous material;
s3, continuously stirring the reaction system in the step S2 for 2-5 hours, then carrying out solid-liquid separation, washing and drying the obtained filter cake, and obtaining the slow-release defoaming nano-porous composite material;
wherein the mass ratio of the defoaming agent to the alkali liquor to the inorganic precursor is 10-30.
Further, the alkali liquor is selected from any one of ammonia water, triethanolamine, tetraethylammonium hydroxide and tetramethylammonium hydroxide.
Further, the inorganic precursor is selected from tetraethyl orthosilicate, methyl orthosilicate, butyl orthosilicate, tetraethyl titanate, or tetrabutyl titanate.
The invention also aims to provide an application of the slow-release defoaming nano-porous composite material, which is prepared by mixing the slow-release defoaming nano-porous composite material with cement and concrete raw materials and stirring to obtain concrete; wherein the dosage of the slow-release defoaming nano-porous composite material is 0.001-0.01% of the mass of the cementing material in the concrete.
The invention designs a nano-porous composite material formed by a nano-porous material and a defoaming agent coated by the nano-porous material, which is prepared by a sol-gel method, and ensures that molecules of the defoaming agent escape at a certain speed by regulating the particle size and the pore size of the nano-porous composite material, thereby realizing the purpose of slow-release defoaming. When the nano porous composite material is applied to concrete, the nano porous composite material can slowly release a defoaming agent in concrete stirring to play a role in regulating the air content of the concrete at the later stage; meanwhile, the nano-porous material in the nano-porous composite material can be directly used as an aggregate component in concrete after the defoaming agent is completely released, no additional adverse component is added to cause negative effects on a cement matrix in the concrete, and the residual nano-porous material can also play a role in realizing micropore filling for cement hardening in the concrete, so that the strength of the concrete is improved.
Drawings
The above and other aspects, features and advantages of embodiments of the present invention will become more apparent from the following description taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a schematic diagram of the preparation and sustained release principle of the sustained release defoaming nano-porous composite material according to the invention; wherein 1 represents an antifoaming agent, 2 represents a nanoporous material, and 21 represents a channel;
FIG. 2 is a particle size distribution plot of the product of example 1 according to the present invention;
FIG. 3 is a particle size distribution diagram of the product of example 2 according to the present invention;
FIG. 4 is a particle size distribution plot of the product of example 3 according to the present invention;
FIG. 5 is a particle size distribution plot of the product of example 4 according to the present invention;
FIG. 6 is a particle size distribution plot of the product of example 5 according to the present invention;
FIG. 7 is a particle size distribution diagram of the product of example 6 according to the present invention.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided to explain the principles of the invention and its practical application to thereby enable others skilled in the art to understand the invention for various embodiments and with various modifications as are suited to the particular use contemplated. In the drawings, the shapes and sizes of elements may be exaggerated for clarity, and the same reference numerals will be used throughout to designate the same or similar elements.
It should be noted that the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
Based on the current situation that the general defoaming agent in the prior art can not realize the purpose of slow release, the inventor of the invention researches and develops a slow release defoaming type nano porous composite material, and the slow release effect of the defoaming agent molecules is realized by controlling the aperture and the particle size of the nano porous composite material, so that the gas content of a concrete system is adjusted.
Specifically, the slow-release defoaming nano-porous composite material comprises a nano-porous material and a defoaming agent coated by the nano-porous material; wherein the nano-porous composite material is provided with a channel with the aperture size of 2 nm-20 nm for the escape of the defoaming agent.
In the slow-release defoaming nano-porous composite material, the nano-porous material is nano titanium dioxide or nano silicon dioxide, and the defoaming agent can be any one of polyether defoaming agent, organosilicon defoaming agent and polyether modified organosilicon defoaming agent, preferably polyether defoaming agent.
Further, the polyether defoamer can be represented by the following general structural formula A:
the silicone-based defoaming agent can be generally represented by the following general structural formula B:
the polyether modified organic silicon defoamer can be generally represented by the following structural general formula C:
in the above formulas A to C, X is an alkyl group having 14 to 42 carbon atoms, and R is a methyl group; the average addition mole number m of the propylene oxide ranges from 0 to 40, and the average addition mole number n of the ethylene oxide ranges from 2 to 80; the value range of a is 10-500, and b = a-1.
The particle size of the slow-release defoaming nano-porous composite material is generally 50 nm-500 nm; the particle size will affect the release efficiency to some extent, i.e. a larger particle size will generally have a larger pore size, whereby the escape rate of the anti-foaming agent inside will be relatively larger.
The slow-release defoaming nano-porous composite material can be prepared by adopting the following preparation method:
firstly, stirring and dispersing the defoaming agent and alkali liquor uniformly to obtain a defoaming agent solution.
Specifically, the alkali solution is selected from one of ammonia water triethanolamine, tetraethylammonium hydroxide and tetramethylammonium hydroxide.
And then, dropwise adding an inorganic precursor into the defoaming agent solution, fully stirring, taking the defoaming agent micelle in the defoaming agent solution as a growth point, hydrolyzing the inorganic precursor under the action of alkali liquor, and carrying out sol-gel reaction to generate the nano porous material.
Specifically, the inorganic precursor is selected from tetraethyl orthosilicate, methyl orthosilicate, butyl orthosilicate, tetraethyl titanate, or tetrabutyl titanate.
In the two steps, the mass ratio of the defoaming agent, the alkali liquor and the inorganic precursor is controlled to be 10-30. The control of the dosage of the alkali liquor is important for the slow release performance of the nano-porous composite material, the control determines the pore size of the nano-porous composite material obtained by hydrolyzing the precursor, obviously, if the pore size is too small, the defoaming agent in the nano-porous composite material cannot be smoothly released, and if the pore size is too large, the releasing is too fast, so that the slow release effect cannot be achieved, and the control is the same as that of the conventional defoaming agent in the prior art.
And finally, continuously stirring the reaction system obtained in the second step for 2-5 h, then carrying out solid-liquid separation, washing and drying the obtained filter cake, and obtaining the slow-release defoaming nano-porous composite material.
Fig. 1 shows a sol-gel process for preparing the slow-release defoaming nano-porous composite material and a principle of the slow-release process, that is, an inorganic precursor is hydrolyzed under the action of alkali liquor, and nano silicon dioxide or titanium dioxide is generated through a sol-gel reaction, wherein the nano silicon dioxide or titanium dioxide has a three-dimensional network structure, has a large specific surface area, has a large amount of hydroxyl groups on the surface, is highly hydrophilic, and a plurality of particles are linked to form a chain, continuously grow in a combined manner under the action of hydrogen bonds between the chain structures and molecular micelles of the defoaming agent, and independently grow into a porous sphere with a three-dimensional network structure in a combined manner, so that the slow-release defoaming nano-porous composite material is prepared.
The above-mentioned slow release defoaming type nanoporous composite material and the preparation method thereof according to the present invention will be embodied by the following specific examples, but those skilled in the art will appreciate that the following examples are only specific examples of the slow release defoaming type nanoporous composite material and the preparation method thereof according to the present invention, and are not intended to limit the entirety thereof.
Example 1
Firstly, 4mol of polyether defoamer is placed in a three-neck flask, and 0.06mol of ammonia water is added and stirred to obtain a polyether defoamer solution.
And then, 0.2mol of tetraethyl orthosilicate is dropwise added into the obtained polyether defoamer solution, the mixture is fully stirred at the temperature of 23 ℃, the polyether defoamer solution in the polyether defoamer sol is taken as a growth point in the reaction system, the tetraethyl orthosilicate is hydrolyzed under the action of ammonia water, and the sol-gel reaction is carried out, so that the porous nano silicon dioxide is generated.
And finally, continuously stirring the reaction system obtained after the tetraethyl orthosilicate is dropwise added in the second step for 3 hours, then carrying out solid-liquid separation, washing the obtained filter cake with ethanol for several times to remove the polyether defoamer attached to the surface of the porous nano-silica, and drying to obtain the nano-porous composite material formed by the polyether defoamer and the porous nano-silica.
That is, the present example provides a nanoporous composite material using a polyether defoamer as a defoamer and using nanosilica as a coating.
The pore size of this nanoporous composite was measured by nitrogen adsorption specific surface area analyzer (BET) and the average pore size was 10nm, i.e., the pore size of the channels in the nanoporous composite was 10nm.
The particle size of the nanoporous composite material was examined by Dynamic Light Scattering (DLS), and fig. 2 shows the particle size distribution of the nanoporous composite material, and it can be seen that the particle size of the obtained slow release antifoaming type nanoporous composite material was about 150 nm.
Example 2
Firstly, 4mol of polyether modified organic silicon defoamer is placed in a three-neck flask, and 0.06mol of ammonia water is added and stirred to obtain polyether modified organic silicon defoamer solution.
Then, 0.2mol of methyl orthosilicate is dripped into the obtained polyether modified organic silicon defoamer solution and is fully stirred at the temperature of 21 ℃, in the reaction system, the polyether modified organic silicon defoamer micelle in the polyether modified organic silicon defoamer solution is taken as a growth point, the methyl orthosilicate is hydrolyzed under the action of ammonia water and is subjected to sol-gel reaction, and the nano porous silicon dioxide is generated.
And finally, continuously stirring the reaction system obtained after the methyl orthosilicate is dropwise added in the second step for 2.5 hours, carrying out solid-liquid separation, washing the obtained filter cake with ethanol for several times to remove the polyether modified organic silicon defoamer attached to the surface of the nano porous silicon dioxide, and drying to obtain the nano porous composite material formed by the polyether modified organic silicon defoamer and the nano porous silicon dioxide.
That is, the present example provides a nanoporous composite material using a polyether modified silicone defoamer as a defoamer and using nanoporous silica as a coating.
The pore size of this nanoporous composite was measured by nitrogen adsorption specific surface area analyzer (BET) and the average pore size was 12nm, i.e. the pore size of the channels in the nanoporous composite was 12nm.
The particle size of the nanoporous composite material was examined by Dynamic Light Scattering (DLS) and the particle size distribution of the nanoporous composite material is shown in fig. 3. It can be seen that the particle size of the obtained slow-release defoaming nano-porous composite material is about 200 nm.
Example 3
Firstly, 4mol of organic silicon defoaming agent is put into a three-neck flask, and 0.06mol of ammonia water is added and stirred to obtain an organic silicon defoaming agent solution.
Then, 0.4mol of n-butyl silicate is dripped into the obtained organic silicon defoamer solution, the mixture is fully stirred at the temperature of 22 ℃, organic silicon defoamer micelles in the organic silicon defoamer solution are taken as growth points in the reaction system, the n-butyl silicate is hydrolyzed under the action of ammonia water, and sol-gel reaction is carried out, so that the nano porous silicon dioxide is generated.
And finally, continuously stirring the reaction system obtained after the dropwise addition of the n-butyl silicate in the second step for 3.5 hours, carrying out solid-liquid separation, washing the obtained filter cake with ethanol for several times to remove the organic silicon defoamer attached to the surface of the nano porous silicon dioxide, and drying to obtain the nano porous composite material formed by the organic silicon defoamer and the nano porous silicon dioxide.
That is, the present example provides a nanoporous composite material using a silicone defoamer as a defoamer and nanoporous silica as a coating.
The pore size of this nanoporous composite was tested by nitrogen adsorption specific surface area analyzer (BET) and the average pore size was 14nm, i.e. the pore size of the channels in the nanoporous composite was 14nm.
The particle size of the nanoporous composite material was examined by Dynamic Light Scattering (DLS), and fig. 4 shows a distribution of the particle size of the nanoporous composite material. It can be seen that the particle size of the obtained slow-release defoaming nano-porous composite material is about 250 nm.
Example 4
Firstly, 3mol of polyether defoamer is placed in a three-neck flask, 0.005mol of triethanolamine is added, and stirring is carried out to obtain polyether defoamer solution.
Then 0.1mol of tetraethyl titanate is dripped into the obtained polyether defoamer solution and fully stirred at 25 ℃, the polyether defoamer micelle in the polyether defoamer solution is taken as a growth point in the reaction system, the tetraethyl titanate is hydrolyzed under the action of triethanolamine and is subjected to sol-gel reaction, and the nano porous titanium dioxide is generated.
And finally, continuously stirring the reaction system obtained after the dropwise addition of the tetraethyl titanate in the second step for 3.5 hours, carrying out solid-liquid separation, washing the obtained filter cake with ethanol for several times to remove the polyether defoamer attached to the surface of the nano-porous titanium dioxide, and drying to obtain the nano-porous composite material formed by the polyether defoamer and the nano-porous titanium dioxide.
That is, the present example provides a nanoporous composite material using a polyether defoamer as a defoamer and using nanoporous titanium dioxide as a coating.
The pore size of this nanoporous composite was tested by nitrogen adsorption specific surface area analyzer (BET) with an average pore size of 2nm, i.e. the pore size of the channels in the nanoporous composite was 2nm.
The particle size of the nanoporous composite material was examined by Dynamic Light Scattering (DLS), and fig. 5 shows a distribution of the particle size of the nanoporous composite material. It can be seen that the particle size of the obtained slow-release defoaming nano-porous composite material is about 50 nm.
Example 5
Firstly, 6.6mol of polyether defoamer is put into a three-neck flask, and 0.6mol of tetraethylammonium hydroxide is added and stirred to obtain a polyether defoamer solution.
Then, 1mol of tetrabutyl titanate is dripped into the obtained polyether defoamer solution and fully stirred at the temperature of 24 ℃, in the reaction system, the polyether defoamer micelle in the polyether defoamer solution is taken as a growth point, tetrabutyl titanate is hydrolyzed under the action of tetraethylammonium hydroxide and undergoes sol-gel reaction to generate the nano-porous titanium dioxide.
And finally, continuously stirring the reaction system obtained after the dropwise addition of the tetrabutyl titanate in the second step for 4 hours, carrying out solid-liquid separation, washing the obtained filter cake with ethanol for several times to remove the polyether defoamer attached to the surface of the nano-porous titanium dioxide, and drying to obtain the nano-porous composite material formed by the polyether defoamer and the nano-porous titanium dioxide.
That is, the present example provides a nanoporous composite material using a polyether defoamer as a defoamer and using nanoporous silica as a coating.
The pore size of this nanoporous composite was measured by nitrogen adsorption specific surface area analyzer (BET) and the average pore size was 17nm, i.e. the pore size of the channels in the nanoporous composite was 17nm.
The particle size of the nanoporous composite material was examined by Dynamic Light Scattering (DLS) and fig. 6 shows a distribution of the particle size of the above nanoporous composite material. It can be seen that the particle size of the obtained slow-release defoaming nano-porous composite material is about 350 nm.
Example 6
Firstly, 15mol of polyether defoamer is placed in a three-neck flask, 0.8mol of tetramethylammonium hydroxide is added and stirred to obtain polyether defoamer solution.
Then, 1mol of tetraethyl orthosilicate is dripped into the obtained polyether defoamer solution and fully stirred at the temperature of 20 ℃, and the tetraethyl orthosilicate is hydrolyzed under the action of tetramethylammonium hydroxide and subjected to sol-gel reaction by taking the polyether defoamer micelle in the polyether defoamer solution as a growth point in the reaction system to generate the nano porous silicon dioxide.
And finally, continuously stirring the reaction system obtained after the tetraethyl orthosilicate is dropwise added in the second step for 2 hours, carrying out solid-liquid separation, washing the obtained filter cake with ethanol for several times to remove the polyether defoamer attached to the surface of the nano porous silica, and drying to obtain the nano porous composite material formed by the polyether defoamer and the nano porous silica.
That is, the present example provides a nanoporous composite material using a polyether defoamer as a defoamer and using nanoporous silica as a coating.
The pore size of this nanoporous composite was measured by nitrogen adsorption specific surface area analyzer (BET) and the average pore size was 20nm, i.e., the pore size of the channels in the nanoporous composite was 20nm.
The particle size of the nanoporous composite material was examined by Dynamic Light Scattering (DLS), and fig. 7 shows a distribution of the particle size of the nanoporous composite material. It can be seen that the particle size of the obtained slow-release defoaming nano-porous composite material is about 500nm.
In the slow-release defoaming nano-porous composite material prepared by the sol-gel method provided by the invention, the porous property of the composite material is very important for realizing the slow-release effect, and in order to reflect the influence of the structure on the performance of the composite material, a polyether defoaming agent, a polyether modified organic silicon defoaming agent and an organic silicon defoaming agent are provided respectively, which are respectively compared with the above examples 1-3 and are sequentially used as comparative examples 1-3. Meanwhile, the order of addition of the raw materials in the above preparation method also plays an important role in whether the slow-release defoaming nano-porous composite material can be synthesized, and for this reason, the following comparative experiment was performed in comparison with the preparation method in example 1.
Comparative example 4
Firstly, 0.06mol of ammonia water is put into a three-neck flask, 0.2mol of tetraethyl orthosilicate is dripped into the ammonia water, the mixture is fully stirred at the temperature of 23 ℃, and the tetraethyl orthosilicate is hydrolyzed under the action of the ammonia water to generate the nano porous silicon dioxide.
And then stirring the nano porous silicon dioxide and 4mol of polyether defoaming agent in a beaker for 12h, allowing the polyether defoaming agent to enter the nano porous silicon dioxide and reach balance, washing with ethanol to remove the polyether defoaming agent attached to the surface of the nano porous silicon dioxide, and drying to obtain the comparative composite defoaming agent.
In order to verify the sustained release effect of the sustained release defoaming nano-porous composite material provided in each of the above embodiments of the present invention, an organic carbon desorption test was performed to investigate the sustained release effect. The instrument used was a Muti Toc 3000Analyzer Total organic carbon Analyzer from Jiangsu Su Bote New materials, inc.
Comparative defoamers provided in comparative examples 1 to 4 above were also tested accordingly.
The specific test operations were as follows: 0.3g of each defoaming agent sample in examples 1-6 and comparative examples 1-4 is weighed and dissolved in 150g of water to be stirred, 10g of supernatant is taken at 0h, 0.25h, 0.5h, 1h, 1.5h, 2h and 3h respectively, 1g of 1mol/L HCl is added, and the content of organic matters in the slowly released defoaming agent is tested.
Table 1 shows the TOC values at different times for each composite in the examples described above and for each defoamer in the comparative examples.
TABLE 1 TOC values at different times for each of the composites in examples 1-6 and each of the defoamers in comparative examples 1-4
In table 1 above, each data unit is desorption amount (g)/1 g of slow-release defoaming nano-porous composite material or defoaming agent; the denominator part in examples 1 to 6 shows a slow-release defoaming type nano-porous composite material, the denominator part in comparative examples 1 to 3 shows a defoaming agent, and the denominator part in comparative example 4 shows a comparative composite defoaming agent.
As can be seen from table 1, the amount of the desorbed antifoaming agent gradually increases with the time of the sustained-release defoaming nano-porous composite materials provided in examples 1 to 6 of the present invention, indicating that the sustained-release effect is significant. The simple antifoaming agents provided in comparative examples 1 to 3 had very high TOC values at the initial stage and did not change with time, indicating that there was no slow release effect by directly using the antifoaming agent. The comparative composite antifoaming agent obtained in comparative example 4 has a lower TOC value all the time and does not have the effect of gradually desorbing the antifoaming agent, that is, it does not have a slow release effect, and it can be seen from the analysis that the antifoaming agent cannot enter the inside of the nanoporous silica through a channel due to the way that the nanoporous silica is prepared in advance to subsequently adsorb the antifoaming agent, and the antifoaming agent is only adsorbed on the surface of the nanoporous silica and is removed through the final washing process, that is, the product obtained in comparative example 4 is substantially nanoporous silica with a small amount of the antifoaming agent adsorbed on the surface, and is not a composite antifoaming agent in a strict sense.
Meanwhile, compared with the slow release effect of the slow release defoaming nano-porous composite material in each embodiment at the same time, the slow release speed of the product obtained when the using amount of the ammonia water is larger during the preparation is found to be faster, because more ammonia water can obtain the pore diameter of the nano-porous composite material with larger size.
The slow-release defoaming nano-porous composite material provided by the invention can be well applied to the preparation of concrete and provides a good slow-release effect. Generally, the concrete can be obtained by preparing and stirring the slow-release defoaming nano-porous composite material, cement and concrete raw materials.
The dosage of the general slow-release defoaming nano-porous composite material is controlled to be 0.001-0.01% of the mass of the cementing material in the concrete.
The application experiment of the slow release defoaming nano-porous composite material obtained in the above embodiments in concrete is performed as follows.
Application examples
The slow-release defoaming nano-porous composite materials in the above examples 1 to 6 were prepared into concrete by using the concrete mixing ratios shown in table 2 below.
TABLE 2 concrete mix proportions
The cement is P.II 52.5 cement of small open field in south of the Yangtze river, the fly ash is II-grade fly ash, the sand is medium sand with fineness modulus Mx =2.7, and the coarse aggregate is 5 mm-20 mm continuous graded broken stone. The used polycarboxylate superplasticizer is provided by Jiangsu Su Bote New material Co. The test is carried out according to the conditions and the method specified in GB 8076-2008, and the mixing amount of all the slow-release defoaming nano-porous composite materials, the single defoaming agent or the comparative composite defoaming agent is the same, and the folding and fixing mixing amount is kept to be 0.8 ten thousandth of the mass of the rubber material.
The air contents of the concrete obtained by the slow-release defoaming nano-porous composite material in each example, the defoaming agent in comparative examples 1 to 3 and the comparative composite defoaming agent in comparative example 4 at different times were tested, and the test results are shown in table 3.
TABLE 3 test results of concrete gas content of each composite material and comparative material at different times
As can be seen from table 3, the concrete prepared by using the slow-release defoaming nano-porous composite material in the above embodiment of the invention has a gradually increased air content in the concrete with the passage of time, i.e., it has a significant effect on the slow decrease of the air content in the concrete; the slow-release defoaming nano-porous composite material starts to defoam in the later period, so that the gas content of the concrete in the later period is obviously reduced, and the strength of hardened concrete can be improved. The concrete prepared by the pure defoaming agent in the comparative examples 1 to 3 has obvious defoaming effect at the beginning, and the defoaming capability is polyether defoaming agent > polyether modified organosilicon defoaming agent > organosilicon defoaming agent, but no slow release effect exists as the time is prolonged. Meanwhile, the concrete prepared by the comparative composite antifoaming agent obtained in comparative example 4 is shown to be incapable of releasing the antifoaming agent according to the data in table 1, and thus does not show a sustained release effect.
All the materials are commercial products, wherein all reagents (analytically pure) used for preparing the slow-release defoaming nano-porous composite material are purchased from Shanghai Aladdin Biotechnology, inc., polyether defoaming agent, organic silicon defoaming agent and polyether modified defoaming agent in the preparation examples, and polycarboxylic acid water reducing agent in the application examples is from Jiangsu Su Bote New Material, inc.
While the invention has been shown and described with reference to certain embodiments, those skilled in the art will understand that: various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.
Claims (7)
1. The preparation method of the slow-release defoaming nano-porous composite material is characterized in that the slow-release defoaming nano-porous composite material comprises a nano-porous material and a defoaming agent coated by the nano-porous material; wherein the particle size of the slow-release defoaming nano-porous composite material is 50 nm-500 nm; the nano-porous composite material is provided with a channel for the escape of the defoaming agent, and the aperture size of the channel is 2-20 nm;
the preparation method comprises the following steps:
s1, stirring and dispersing a defoaming agent and alkali liquor uniformly to obtain a defoaming agent solution;
s2, dropwise adding an inorganic precursor into the defoaming agent solution, fully stirring, taking a defoaming agent micelle in the defoaming agent solution as a growth point, hydrolyzing the inorganic precursor under the action of the alkali liquor, and carrying out sol-gel reaction to generate a nano porous material;
s3, continuously stirring the reaction system in the step S2 for 2-5 hours, then carrying out solid-liquid separation, washing and drying the obtained filter cake, and obtaining the slow-release defoaming nano-porous composite material;
wherein the mass ratio of the defoaming agent to the alkali liquor to the inorganic precursor is 10-30.
2. The method according to claim 1, wherein the nanoporous material is nano-titania or nano-silica.
3. The method according to claim 1, wherein the defoaming agent is selected from any one of polyether defoaming agents, silicone defoaming agents, and polyether-modified silicone defoaming agents.
4. The preparation method according to claim 3, wherein the polyether defoamer has a general structural formula shown in the following formula A:
the organic silicon defoaming agent has a structural general formula shown as the following formula B:
the polyether modified organic silicon defoamer has a general structural formula shown as the following formula C:
wherein X is an alkyl group having 14 to 42 carbon atoms, and R is a methyl group; the average addition mole number m of the propylene oxide ranges from 0 to 40, and the average addition mole number n of the ethylene oxide ranges from 2 to 80; a ranges from 10 to 500, and b = a-1.
5. The method according to any one of claims 1 to 4, wherein the alkaline solution is selected from any one of ammonia, triethanolamine, tetraethylammonium hydroxide, and tetramethylammonium hydroxide.
6. The method according to any one of claims 1 to 4, wherein the precursor is selected from tetraethyl orthosilicate, methyl orthosilicate, butyl orthosilicate, tetraethyl titanate, and tetrabutyl titanate.
7. The use of the slow-release defoaming nano-porous composite material obtained by the preparation method according to any one of claims 1 to 6, characterized in that the concrete is obtained by preparing and stirring the slow-release defoaming nano-porous composite material, cement and concrete raw materials; wherein the dosage of the slow-release defoaming nano-porous composite material is 0.001-0.01% of the mass of the cementing material in the concrete.
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