CN107056123A - A kind of concrete activeness and quietness composite and preparation method thereof - Google Patents
A kind of concrete activeness and quietness composite and preparation method thereof Download PDFInfo
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- CN107056123A CN107056123A CN201710399892.0A CN201710399892A CN107056123A CN 107056123 A CN107056123 A CN 107056123A CN 201710399892 A CN201710399892 A CN 201710399892A CN 107056123 A CN107056123 A CN 107056123A
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- halloysite nanotubes
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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
Abstract
The invention belongs to Material Field, and in particular to a kind of concrete activeness and quietness composite and preparation method thereof.On the basis of the composite is the activated processing of original halloysite nanotubes, reacted with thionyl chloride, the surface carboxyl groups of halloysite nanotubes are converted into after acid chloride functional groups, with difunctional organic compound reaction, reacted again with Cyanuric Chloride, the halloysite nanotubes that surface has active chloride triazine ring are obtained, are finally prepared with methylcellulose by nucleophilic substitution.It can be fully dispersed in concrete, effectively play the effect of material coordination plasticizing, make concrete that integrally there is good toughness, fatigue resistance and isotropism, it is a kind of high performance concrete activeness and quietness composite, it, which easily can prepare material with other concrete and mixes, is uniformly dispersed, toughness reinforcing concrete product is can obtain after being supported again through mark, the application requirement in terms of river-spanning bridge over strait and tunnel arch wall can be met.
Description
Technical field
The invention belongs to Material Field, and in particular to a kind of concrete activeness and quietness composite and preparation method thereof.
Background technology
Normal concrete bending strength is relatively low, fragility is high.The structural stress of the building such as tunnel arch wall and river-spanning bridge over strait
Environment is extremely complex, and normal concrete easily produces crack and is even broken in use, has a strong impact on the safety of building and uses
Life-span, it is therefore necessary to using intensity and toughness high concrete as far as possible.
The composite of the concrete activeness and quietness of the present invention, by the halloysite nanotubes and first of activeness and quietness excellent performance
Base cellulose is combined, by multi-step surface covalent reaction, forms a kind of unique compound system, the composite wood prepared
Material can be fully dispersed in concrete, effectively plays the effect of material coordination plasticizing, concrete is integrally had well tough
Property, fatigue resistance and isotropism, are a kind of high performance concrete activeness and quietness composites.With halloysite nanotubes and methyl
The mass content ratio about 1 of cellulose:Exemplified by 0.5 composite products, using the kg/m of cement 3803, the composite
3.5 kg/m3, the kg/m of fine aggregate 6303, the kg/m of flyash 403, the kg/m of slag powders 393, the kg/m of rubble 10003, water reducer
3.8 kg/m3With the kg/m of water 1503, the bending strength of the concrete sample of preparation is 24 MPa, and tensile strength is 13 MPa, is resisted
Compressive Strength is 82 MPa.
Goal of the invention
The present invention be a kind of concrete activeness and quietness composite and preparation method thereof is provided.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of concrete activeness and quietness composite, on the basis of it is the activated processing of original halloysite nanotubes, with Asia
Chlorosulfuric acid is reacted, and the surface carboxyl groups of halloysite nanotubes are converted into after acid chloride functional groups, anti-with difunctional organic compound
Should, then reacted with Cyanuric Chloride, obtain the halloysite nanotubes that surface has active chloride triazine ring, finally and methylcellulose
Prepared by nucleophilic substitution.In the composite, the mass ratio of halloysite nanotubes and methylcellulose is 1:
0.1-0.5。
The preparation method of the concrete activeness and quietness composite, it comprises the following steps：
1st, the halloysite nanotubes and thionyl chloride of activated processing are stirred into 6-15 in organic solvent P at 40-55 DEG C
After h, in ultrasound 10-16 h at 70-80 DEG C in 40 kHz, 200 KW supersonic wave cleaning machine, then with 4000-5000
Rpm rotating speed centrifuges 30-40 min, after separating solid and being cleaned through organic solvent Q, then is dried in vacuo 30-50 at 25-35 DEG C
h；
2nd, halloysite nanotubes, difunctional organic compound and the triethylamine handled above-mentioned steps 1 is mixed in organic solvent P
Close, stirred at 50-60 DEG C after 5-15 h, under nitrogen protection, in 20 kHz, 150 KW supersonic wave cleaning machine in 70-
At 85 DEG C after ultrasonic reaction 6-10 h, triethylamine and solvent P are removed under reduced pressure, then after blended solvent R is cleaned, at 10-20 DEG C
It is dried in vacuo 24-48 h；
3rd, the halloysite nanotubes and Cyanuric Chloride handled above-mentioned steps 2 are mixed in tetrahydrofuran, are stirred at 0-10 DEG C
12-24 h, in after ultrasound 3-8 h at 0-10 DEG C in 40 kHz, 200 KW supersonic wave cleaning machine, then at 0-10 DEG C it is anti-
Answer after 24-72 h, cleaned through tetrahydrofuran, 24-56 h are dried in vacuo at 10-15 DEG C；
4th, after the halloysite nanotubes for handling above-mentioned steps 3 dissolve in N, N '-dimethyl formamide, it is added to and is dissolved with first
In the N of base cellulose, N '-dimethyl formamide solution, 5-10 h are stirred at 10-20 DEG C, 40 kHz, 300 KW it is super
In ultrasound 1-5 h at 10-20 DEG C in sound wave cleaning machine, it is warming up under nitrogen protection after 40-60 DEG C of isothermal reaction 36-56 h,
80-95 DEG C of isothermal reaction 24-48h is warming up to again, solvent is removed under reduced pressure, and after being eluted with water, 24-48 h are dried in vacuo at 40 DEG C
After obtain composite products.
The halloysite nanotubes of activated processing are 6-30 kg in above-mentioned steps 1, and thionyl chloride is 10-60 kg；It is organic
Solvent P is 50-230 L.
Organic solvent P in above-mentioned steps 1 is one in toluene, 1-METHYLPYRROLIDONE or N, N '-dimethyl acetamide
Plant or several.
Organic solvent Q in above-mentioned steps 1 is anhydrous propanone or carbon tetrachloride.
Halloysite nanotubes in above-mentioned steps 2 are 5-30 kg；Difunctional organic compound is 1-8 kg；Triethylamine
For 1-6 L；Organic solvent P is 50-220 L.
Difunctional organic compound in above-mentioned steps 2 is one in 1,3- propane diamine, ethylenediamine and l, 6- hexamethylene diamine
Kind.
Mixed solvent R in above-mentioned steps 2 is made up of ethanol, acetone and water, and the volume ratio of wherein ethanol, acetone and water is
2:2:6。
Halloysite nanotubes in above-mentioned steps 3 are 5-20 kg；Cyanuric Chloride is 0.5-5 kg；Tetrahydrofuran is 60-
230 L。
Halloysite nanotubes in above-mentioned steps 4 are 5-20 kg；Dissolve the N of halloysite nanotubes, N '-dimethyl formyl
Amine is 50-200 L；Methylcellulose is 1-5 kg；The N of methylcellulose is dissolved, N '-dimethyl formamide is 10-50 L.
The viscosity average molecular weigh of methylcellulose in above-mentioned steps 4 is 3000-20000, and substitution value is 0.5-2.0.
Increase the activation process step of halloysite nanotubes before above-mentioned steps 1：
（1）Halloysite nanotubes are taken, is handled through mechanical crushing and uses 350 mesh sieves stand-by after selecting；
（2）Each stainless steel ball for loading 60 a diameter of 5 mm and 50 a diameter of 10 in two L nylon tanks of identical 15
Mm stainless steel ball, is then respectively adding the kg of the halloysite nanotubes after being handled through previous step 6, then 600 are added dropwise respectively
Ml absolute ethyl alcohols, and sealed with nylon lid.Two ball grinders are symmetrically put into planetary ball mill, are 350 in rotating speed
Under conditions of rpm and every 30 minutes automatic conversion direction of rotation after ball milling 40-56 h, average length is obtained for 200-230 nm
Chopped halloysite nanotubes.
（3）It is that 8, concentration is 15 wt% to take the halloysite nanotubes after the chopped processing of previous step to be added to pH
Ultrasonic 24 h in Tween 20 aqueous solution, filtering is stand-by after 30 h in being dried in vacuo at 68-70 DEG C after being eluted with water.
Described halloysite nanotubes are commercially available prod, its main specifications：Character：White powder；Composition：SiO2：
58.1wt%、Al2O3：41.02wt%、TiO2：0.17wt%、Fe2O3：0.38wt%、P2O5：0.16wt%；Remaining is loss on ignition.Pipe
Internal diameter：15-22 nm；Pipe external diameter：40-70 nm；Length：<1.5 μm；Specific surface area：53.4 m2/g；Density：2.5-2.6g/
cm3。
Described polysorbas20 is commercially available, its main specifications：Character：Pale yellow viscous liquid；Active matter：98-99%；Acid number
(KOHmg/g)：≤1.0；Hydroxyl value (KOHmg/g)：80-108；HLB value：16.7；Saponification number (KOHmg/g)：40-50；Moisture content
(%)：≤1.0.
Compared with the prior art, technical scheme has the advantages that：
Composite environment provided by the present invention available for concrete activeness and quietness is friendly, has in conventional organic solvent
Good dissolubility, has good dispersiveness in water.The preparation condition of the composite is readily satisfied, and raw material sources are rich
Richness, cost is relatively low.
The composite of the concrete activeness and quietness of the present invention, by the halloysite nanotubes and first of activeness and quietness excellent performance
Base cellulose is combined, by multi-step surface covalent reaction, forms a kind of unique compound system, can be in concrete
It is fully dispersed, effectively play the effect of material coordination plasticizing, make concrete integrally have good toughness, fatigue resistance and it is each to
The same sex, is a kind of high performance concrete activeness and quietness composite.
The concrete activeness and quietness of the present invention easily can prepare material with other concrete with composite and mix
It is uniformly dispersed, then can obtain toughness reinforcing concrete product after being supported through mark, in terms of can meets river-spanning bridge over strait and tunnel arch wall
Application requirement.
Embodiment
The present invention is prepared for a kind of available for concrete enhancing using halloysite nanotubes and methylcellulose as raw material first
The composite of toughness reinforcing.Technical scheme is described further below in conjunction with specific embodiment：
Embodiment 1
Activation process is carried out to halloysite nanotubes first：
（1）Galapectite is taken, is handled through mechanical crushing and uses 350 mesh sieves stand-by after selecting；
（2）Each stainless steel ball for loading 60 a diameter of 5 mm and 50 a diameter of 10 in two L nylon tanks of identical 15
Mm stainless steel ball, is then respectively adding the kg of the halloysite nanotubes after being handled through previous step 6, then 600 are added dropwise respectively
Ml absolute ethyl alcohols, and sealed with nylon lid.Two ball grinders are symmetrically put into planetary ball mill, are 350 in rotating speed
Under conditions of rpm and every 30 minutes automatic conversion direction of rotation after the h of ball milling 50, average length being chopped angstrom for 210 nm is obtained
Lip river stone nanotube.
（3）It is that 8, concentration is 15 wt% to take the halloysite nanotubes after the chopped processing of previous step to be added to pH
Ultrasonic 24 h in Tween 20 aqueous solution, filtering is stand-by after 30 h in being dried in vacuo at 70 DEG C after being eluted with water.
Described halloysite nanotubes are commercially available prod, its main specifications：Character：White powder；Composition：SiO2：
58.1wt%、Al2O3：41.02 wt%、TiO2：0.17 wt%、Fe2O3：0.38 wt%、P2O5：0.16 wt%, remaining loses to burn
Amount；Bore：15-22 nm；Pipe external diameter：40-70 nm；Length：<1.5 μm；Specific surface area：53.4 m2/g；Density：2.5-
2.6g/cm3。
Described polysorbas20 is commercially available, its main specifications：Character：Pale yellow viscous liquid；Active matter：98-99%；Acid number
(KOHmg/g)：≤1.0；Hydroxyl value (KOHmg/g)：80-108；HLB value：16.7；Saponification number (KOHmg/g)：40-50；Moisture content
(%)：≤1.0.
Further prepared using halloysite nanotubes and methylcellulose as raw material available for the compound of concrete activeness and quietness
Material：
1st, by the kg of halloysite nanotubes 20 and the kg of thionyl chloride 45 of activated processing in 180 L 1-METHYLPYRROLIDONEs,
Stirred at 50 DEG C after 12 h, in ultrasonic 14 h at 75 DEG C in 40 kHz, 200 KW supersonic wave cleaning machine, then with
4500 rpm rotating speed centrifuges 35 min, after separating solid and being cleaned through anhydrous propanone, then is dried in vacuo at 25 DEG C 50 h；
2nd, the kg of halloysite nanotubes 20, the kg of ethylenediamine 5 and triethylamine 1-6 L handled above-mentioned steps 1, in 160 L N,
Mix, stirred at 60 DEG C after 12 h, under nitrogen protection, in 20 kHz, 150 KW ultrasound in N '-dimethyl acetamide
In after the h of ultrasonic reaction 8 at 80 DEG C, removing triethylamine and N under reduced pressure in ripple cleaning machine, N '-dimethyl acetamide, then it is blended molten
After agent R is cleaned, 40 h are dried in vacuo at 18 DEG C；
3rd, the kg of halloysite nanotubes 15 and the kg of Cyanuric Chloride 3.5 handled above-mentioned steps 2 is mixed in 180 L tetrahydrofurans
Close, 20 h are stirred at 2 DEG C, in after ultrasonic 6 h at 2 DEG C in 40 kHz, 200 KW supersonic wave cleaning machine, then at 0 DEG C
React after 60 h, cleaned through tetrahydrofuran, 48 h are dried in vacuo at 13 DEG C；
4th, after the kg of halloysite nanotubes 14 for handling above-mentioned steps 3 dissolves in 150 L N, N '-dimethyl formamide, plus
Enter to the 40 L N for being dissolved with 4 kg methylcellulose, in N '-dimethyl formamide solution, 8 h are stirred at 15 DEG C, 40
In ultrasonic 4 h at 15 DEG C in kHz, 300 KW supersonic wave cleaning machine, 55 DEG C of h of isothermal reaction 48 are warming up under nitrogen protection
Afterwards, then 90 DEG C of h of isothermal reaction 40 are warming up to, remove solvent under reduced pressure, after being eluted with water, 4024-48 h are dried in vacuo at 40 DEG C
After obtain composite products.In the composite products, the mass ratio of halloysite nanotubes and methylcellulose is 1:0.3,
It can be applied to the activeness and quietness field of concrete.
Mixed solvent R in above-mentioned steps 2 is made up of ethanol, acetone and water, and the volume ratio of wherein ethanol, acetone and water is
2:2:6。
Embodiment 2
Activation process is carried out to halloysite nanotubes first：
（1）Galapectite is taken, is handled through mechanical crushing and uses 350 mesh sieves stand-by after selecting；
（2）Each stainless steel ball for loading 60 a diameter of 5 mm and 50 a diameter of 10 in two L nylon tanks of identical 15
Mm stainless steel ball, is then respectively adding the kg of the halloysite nanotubes after being handled through previous step 6, then 600 are added dropwise respectively
Ml absolute ethyl alcohols, and sealed with nylon lid.Two ball grinders are symmetrically put into planetary ball mill, are 350 in rotating speed
Under conditions of rpm and every 30 minutes automatic conversion direction of rotation after the h of ball milling 40, average length being chopped angstrom for 230 nm is obtained
Lip river stone nanotube.
（3）It is that 8, concentration is 15 wt% to take the halloysite nanotubes after the chopped processing of previous step to be added to pH
Ultrasonic 24 h in Tween 20 aqueous solution, filtering is stand-by after 30 h in being dried in vacuo at 68 DEG C after being eluted with water.
Described halloysite nanotubes, Tween 20 specification be the same as Example 1.
1st, by the kg of halloysite nanotubes 30 and the kg of thionyl chloride 60 of activated processing in 230 L N- crassitudes
In ketone, stirred at 55 DEG C after 15 h, in ultrasonic 16 h at 80 DEG C in 40 kHz, 200 KW supersonic wave cleaning machine, so
30 min are centrifuged with 5000 rpm rotating speed afterwards, after separating solid and being cleaned through anhydrous carbon tetrachloride, then at 35 DEG C vacuum is done
Dry 50 h；
2nd, the kg of halloysite nanotubes 30, the kg of 1,3- propane diamine 8 and triethylamine 1-6 L handled above-mentioned steps 1, in 220 L
Mix, stirred at 60 DEG C after 15 h, under nitrogen protection, in 20 kHz, 150 KW ultrasonic wave in 1-METHYLPYRROLIDONE
In after the h of ultrasonic reaction 10 at 85 DEG C, removing triethylamine and 1-METHYLPYRROLIDONE, then blended solvent R under reduced pressure in cleaning machine
After cleaning, 48 h are dried in vacuo at 20 DEG C；
3rd, the kg of halloysite nanotubes 20 and the kg of Cyanuric Chloride 5 handled above-mentioned steps 2 is mixed in 230 L tetrahydrofurans,
24 h are stirred at 0 DEG C, in after ultrasonic 8 h at 0 DEG C in 40 kHz, 200 KW supersonic wave cleaning machine, then at 2 DEG C it is anti-
Answer after 72 h, cleaned through tetrahydrofuran, 36 h are dried in vacuo at 15 DEG C；
4th, after the kg of halloysite nanotubes 20 for handling above-mentioned steps 3 dissolves in 200 L N, N '-dimethyl formamide, plus
Enter to the 50 L N for being dissolved with 5 kg methylcellulose, in N '-dimethyl formamide solution, 10 h stirred at 20 DEG C,
In ultrasonic 5 h at 20 DEG C in 40 kHz, 300 KW supersonic wave cleaning machine, 60 DEG C of isothermal reactions 56 are warming up under nitrogen protection
After h, then 95 DEG C of isothermal reaction 48h are warming up to, remove solvent under reduced pressure, after being eluted with water, be dried in vacuo after 48 h and obtain at 40 DEG C
To composite products, the toughness reinforcing field of concrete can be applied to.In the composite products, halloysite nanotubes are fine with methyl
The mass content ratio of dimension element is 1:0.5, it can be applied to the activeness and quietness field of concrete.
Mixed solvent R be the same as Examples 1 in above-mentioned steps 2.
Embodiment 3
Activation process is carried out to halloysite nanotubes first：
（1）Galapectite is taken, is handled through mechanical crushing and uses 350 mesh sieves stand-by after selecting；
（2）Each stainless steel ball for loading 60 a diameter of 5 mm and 50 a diameter of 10 in two L nylon tanks of identical 15
Mm stainless steel ball, is then respectively adding the kg of the halloysite nanotubes after being handled through previous step 6, then 600 are added dropwise respectively
Ml absolute ethyl alcohols, and sealed with nylon lid.Two ball grinders are symmetrically put into planetary ball mill, are 350 in rotating speed
Under conditions of rpm and every 30 minutes automatic conversion direction of rotation after ball milling 56h, average length being chopped angstrom for 200 nm is obtained
Lip river stone nanotube.
（3）It is that 8, concentration is 15 wt% to take the halloysite nanotubes after the chopped processing of previous step to be added to pH
Ultrasonic 24 h in Tween 20 aqueous solution, filtering is stand-by after 30 h in being dried in vacuo at 70 DEG C after being eluted with water.
Described halloysite nanotubes, Tween 20 specification be the same as Example 1.
1st, by the kg of halloysite nanotubes 6 and the kg of thionyl chloride 10 of activated processing in 50 L toluene, N- methylpyrroles
In alkanone or N, N '-dimethyl acetyl, stirred at 40 DEG C after 6 h, in 40 kHz, 200 KW supersonic wave cleaning machine in
Ultrasonic 10 h at 70 DEG C, then centrifuges 40 min with 4000 rpm rotating speed, after separating solid and being cleaned through anhydrous propanone, then
30 h are dried in vacuo at 30 DEG C；
2nd, the kg of halloysite nanotubes 5, the kg of ethylenediamine 1 and triethylamine 1-6 L handled above-mentioned steps 1, in 50 L toluene
Mixing, stirred at 50 DEG C after 5 h, under nitrogen protection, in 20 kHz, 150 KW supersonic wave cleaning machine at 70 DEG C
After the h of ultrasonic reaction 6, triethylamine and toluene are removed under reduced pressure, then after blended solvent R is cleaned, 30 h are dried in vacuo at 10 DEG C；
3rd, the kg of halloysite nanotubes 5 and the kg of Cyanuric Chloride 0.5 handled above-mentioned steps 2 is mixed in 60 L tetrahydrofurans,
12 h are stirred at 10 DEG C, in after ultrasonic 3 h at 10 DEG C in 40 kHz, 200 KW supersonic wave cleaning machine, then at 5 DEG C
React after 24 h, cleaned through tetrahydrofuran, 56 h are dried in vacuo at 10 DEG C；
4th, after the kg of halloysite nanotubes 5 for handling above-mentioned steps 3 dissolves in 50 L N, N '-dimethyl formamide, add
To the 10 L N for being dissolved with 1 kg methylcellulose, in N '-dimethyl formamide solution, 5 h are stirred at 10 DEG C, 40
In ultrasonic 1 h at 10 DEG C in kHz, 300 KW supersonic wave cleaning machine, 40 DEG C of h of isothermal reaction 36 are warming up under nitrogen protection
Afterwards, then 80 DEG C of h of isothermal reaction 24 are warming up to, remove solvent under reduced pressure, after being eluted with water, be dried in vacuo at 40 DEG C after 24 h
To composite products, the toughness reinforcing field of concrete can be applied to.In the composite products, halloysite nanotubes are fine with methyl
The mass content ratio of dimension element is 1:0.16, it can be applied to the activeness and quietness field of concrete.
Mixed solvent R be the same as Examples 1 in above-mentioned steps 2.
Embodiment 4
Activation process is carried out to halloysite nanotubes first：
（1）Galapectite is taken, is handled through mechanical crushing and uses 350 mesh sieves stand-by after selecting；
（2）Each stainless steel ball for loading 60 a diameter of 5 mm and 50 a diameter of 10 in two L nylon tanks of identical 15
Mm stainless steel ball, is then respectively adding the kg of the halloysite nanotubes after being handled through previous step 6, then 600 are added dropwise respectively
Ml absolute ethyl alcohols, and sealed with nylon lid.Two ball grinders are symmetrically put into planetary ball mill, are 350 in rotating speed
Under conditions of rpm and every 30 minutes automatic conversion direction of rotation after the h of ball milling 45, average length being chopped angstrom for 220 nm is obtained
Lip river stone nanotube.
（3）It is that 8, concentration is 15 wt% to take the halloysite nanotubes after the chopped processing of previous step to be added to pH
Ultrasonic 24 h in Tween 20 aqueous solution, filtering is stand-by after 30 h in being dried in vacuo at 69 DEG C after being eluted with water.
Described halloysite nanotubes, Tween 20 specification be the same as Example 1.
1st, by the kg of halloysite nanotubes 15 and the kg of thionyl chloride 30 of activated processing in 120 L N, N '-dimethyl second
In acid amides, stirred at 45 DEG C after 8 h, in ultrasonic 12 h at 72 DEG C in 40 kHz, 200 KW supersonic wave cleaning machine, so
32 min are centrifuged with 4200 rpm rotating speed afterwards, after separating solid and being cleaned through anhydrous carbon tetrachloride, then at 30 DEG C vacuum is done
Dry 40 h；
2nd, halloysite nanotubes 14 kg, the l handled above-mentioned steps 1, the kg of 6- hexamethylene diamines 4 and triethylamine 1-6 L, in 120 L
Mix, stirred at 55 DEG C after 9 h, under nitrogen protection, in 20 kHz, 150 KW ultrasonic wave in 1-METHYLPYRROLIDONE
In after the h of ultrasonic reaction 7 at 75 DEG C, removing triethylamine and 1-METHYLPYRROLIDONE under reduced pressure in cleaning machine, then blended solvent R is washed
After net, 24 h are dried in vacuo at 15 DEG C；
3rd, the kg of halloysite nanotubes 12 and the kg of Cyanuric Chloride 2 handled above-mentioned steps 2 is mixed in 130 L tetrahydrofurans,
15 h are stirred at 5 DEG C, in after ultrasonic 5 h at 5 DEG C in 40 kHz, 200 KW supersonic wave cleaning machine, then at 10 DEG C
React after 40 h, cleaned through tetrahydrofuran, 24 h are dried in vacuo at 12 DEG C；
4th, after the kg of halloysite nanotubes 12 for handling above-mentioned steps 3 dissolves in 110 L N, N '-dimethyl formamide, plus
Enter to the 20 L N for being dissolved with 2 kg methylcellulose, in N '-dimethyl formamide solution, 7 h are stirred at 12 DEG C, 40
In ultrasonic 2.5 h at 12 DEG C in kHz, 300 KW supersonic wave cleaning machine, 50 DEG C of isothermal reactions 40 are warming up under nitrogen protection
After h, then 85 DEG C of h of isothermal reaction 32 are warming up to, remove solvent under reduced pressure, after being eluted with water, be dried in vacuo at 40 DEG C after 36 h
Composite products are obtained, the toughness reinforcing field of concrete is can be applied to.In the composite products, halloysite nanotubes and methyl
The mass content ratio of cellulose is 1:0.1, it can be applied to the activeness and quietness field of concrete.
Mixed solvent R be the same as Examples 1 in above-mentioned steps 2.
The present invention is not limited to above example, as long as the scheme referred in this specification can be implemented.
Claims (9)
1. a kind of preparation method of concrete activeness and quietness composite, it is characterised in that：Passed through by original halloysite nanotubes
On the basis of activation process, reacted with thionyl chloride, the surface carboxyl groups of halloysite nanotubes are converted into after acid chloride functional groups, with
Difunctional organic compound reaction, then reacted with Cyanuric Chloride, the galapectite for obtaining surface in the presence of active chloride triazine ring is received
Mitron, is finally prepared with methylcellulose by nucleophilic substitution.
2. the preparation method of concrete activeness and quietness composite according to claim 1, it is characterised in that：This is combined
In material, the mass ratio of halloysite nanotubes and methylcellulose is 1:0.1-0.5.
3. the preparation method of concrete activeness and quietness composite according to claim 1, it is characterised in that：
Concretely comprise the following steps：
（1）By the halloysite nanotubes and thionyl chloride of activated processing in organic solvent P, 6-15 is stirred at 40-55 DEG C
After h, in ultrasound 10-16 h at 70-80 DEG C in 40 kHz, 200 KW supersonic wave cleaning machine, then with 4000-5000
Rpm rotating speed centrifuges 30-40 min, after separating solid and being cleaned through organic solvent Q, then is dried in vacuo 30-50 at 25-35 DEG C
h；
（2）By above-mentioned steps（1）Halloysite nanotubes, difunctional organic compound and the triethylamine of processing are in organic solvent P
Middle mixing, is stirred after 5-15 h at 50-60 DEG C, under nitrogen protection, in 20 kHz, 150 KW supersonic wave cleaning machine
In after ultrasonic reaction 6-10 h at 70-85 DEG C, removing triethylamine and solvent P under reduced pressure, then after blended solvent R is cleaned, in 10-
24-48 h are dried in vacuo at 20 DEG C；
（3）By above-mentioned steps（2）The halloysite nanotubes and Cyanuric Chloride of processing are mixed in tetrahydrofuran, are stirred at 0-10 DEG C
12-24 h are mixed, in after ultrasound 3-8 h at 0-10 DEG C in 40 kHz, 200 KW supersonic wave cleaning machine, then at 0-10 DEG C
React after 24-72 h, cleaned through tetrahydrofuran, 24-56 h are dried in vacuo at 10-15 DEG C；
（4）By above-mentioned steps（3）After the halloysite nanotubes of processing dissolve in N, N '-dimethyl formamide, dissolving is added to
Have in the N of methylcellulose, N '-dimethyl formamide solution, 5-10 h are stirred at 10-20 DEG C, in 40 kHz, 300 KW
Supersonic wave cleaning machine in ultrasound 1-5 h at 10-20 DEG C, 40-60 DEG C of isothermal reaction 36-56 h is warming up under nitrogen protection
Afterwards, then 80-95 DEG C of isothermal reaction 24-48h is warming up to, removes solvent under reduced pressure, after being eluted with water, 24- is dried in vacuo at 40 DEG C
Composite products are obtained after 48 h.
4. the preparation method of concrete activeness and quietness composite according to claim 3, it is characterised in that：
The step（1）In activated processing halloysite nanotubes be 6-30 kg, thionyl chloride be 10-60 kg；It is organic molten
Agent P is 50-230 L；Organic solvent P is the one or more in toluene, 1-METHYLPYRROLIDONE, N, N '-dimethyl acetamide；
Organic solvent Q is anhydrous propanone or carbon tetrachloride.
5. the preparation method of concrete activeness and quietness composite according to claim 3, it is characterised in that：The step
Halloysite nanotubes in rapid 2 are 5-30 kg；Difunctional organic compound is 1-8 kg；Triethylamine is 1-6 L；It is organic molten
Agent P is 50-220 L；Difunctional organic compound is 1,3- propane diamine, ethylenediamine or l, 6- hexamethylene diamine；Mixed solvent R is by second
Alcohol, acetone and water composition, the wherein volume ratio of ethanol, acetone and water are 2:2:6.
6. the preparation method of concrete activeness and quietness composite according to claim 3, it is characterised in that：
Halloysite nanotubes in the step 3 are 5-20 kg；Cyanuric Chloride is 0.5-5 kg；Tetrahydrofuran is 60-230 L.
7. the preparation method of concrete activeness and quietness composite according to claim 3, it is characterised in that：
Halloysite nanotubes in the step 4 are 5-20 kg；The N of halloysite nanotubes is dissolved, N '-dimethyl formamide is
50-200 L；Methylcellulose is 1-5 kg；The N of methylcellulose is dissolved, N '-dimethyl formamide is 10-50 L；Methyl is fine
The viscosity average molecular weigh of dimension element is 3000-20000, and substitution value is 0.5-2.0.
8. the preparation method of concrete activeness and quietness composite according to claim 3, it is characterised in that：
The halloysite nanotubes of activated processing, its specific activation step is：
（1）Halloysite nanotubes are taken, is handled through mechanical crushing and uses 350 mesh sieves stand-by after selecting；
（2）Each stainless steel ball for loading 60 a diameter of 5 mm and 50 a diameter of 10 in two L nylon tanks of identical 15
Mm stainless steel ball, is then respectively adding the kg of the halloysite nanotubes after being handled through previous step 6, then 600 are added dropwise respectively
Ml absolute ethyl alcohols, and sealed with nylon lid；Two ball grinders are symmetrically put into planetary ball mill, are 350 in rotating speed
Under conditions of rpm, and every 30 minutes automatic conversion direction of rotation after ball milling 40-56 h, average length is obtained for 200-230 nm
Chopped halloysite nanotubes；
（3）It is the Tween 20 that 8, concentration is 15 wt% to take the halloysite nanotubes after the chopped processing of previous step to be added to pH
The aqueous solution in ultrasonic 24 h, filtering, it is stand-by after 30 h in being dried in vacuo at 68-70 DEG C after being eluted with water.
9. concrete activeness and quietness composite made from a kind of preparation method as described in claim 1-8.
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| CN111233362A (en) * | 2020-03-25 | 2020-06-05 | 福建江夏学院 | Preparation method and application of concrete toughening material |
| CN113429142A (en) * | 2021-05-14 | 2021-09-24 | 深圳大学 | Enzyme modified halloysite nanotube and preparation method and application thereof |
| CN113429146A (en) * | 2021-05-14 | 2021-09-24 | 深圳大学 | Lithium carbonate-halloysite nanotube and preparation method and application thereof |
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