CN107200491A - Concrete toughness reinforcing modified galapectite and preparation method thereof - Google Patents
Concrete toughness reinforcing modified galapectite and preparation method thereof Download PDFInfo
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- CN107200491A CN107200491A CN201710399026.1A CN201710399026A CN107200491A CN 107200491 A CN107200491 A CN 107200491A CN 201710399026 A CN201710399026 A CN 201710399026A CN 107200491 A CN107200491 A CN 107200491A
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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
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
- C04B14/10—Clay
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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
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
- C04B20/023—Chemical treatment
-
- 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
-
- 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
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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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
Abstract
The invention belongs to field of material technology, and in particular to a kind of concrete toughness reinforcing modified galapectite and preparation method thereof.The preparation method of the modified galapectite is：Reacted first with thionyl chloride using the galapectite of activated processing, then with difunctional organic compound reaction, make galapectite area load labile functional groups, reacted again with Cyanuric Chloride, the galapectite that surface has chloride triazine ring is obtained, is finally prepared with hydroxyethyl cellulose by nucleophilic substitution.The modification galapectite that the present invention is prepared can be fully dispersed in concrete, effectively play the effect of material coordination plasticizing, assigning concrete integrally has good toughness, isotropism, fatigue resistance, it is a kind of high performance concrete toughening material, it can apply to the concrete material fields such as the bridge floor of Longspan Bridge and overpass, and all types of tunnel arch walls.
Description
Technical field
The invention belongs to field of material technology, and in particular to a kind of concrete toughness reinforcing modified galapectite and preparation method thereof.
Background technology
For building structure and the positions such as Longspan Bridge, the bridge floor of overpass and all types of tunnel arch walls, its NOL ring
Border is extremely complex.The fragility of normal concrete is high, and bending strength is relatively low, therefore easily produces crack very in complex stress environment
To being broken, the safety and service life of such building are had a strong impact on.
The concrete toughness reinforcing of the present invention is fine using the excellent modification galapectite of toughness reinforcing efficiency and ethoxy with modified galapectite
Dimension element, by multi-step surface modification reaction, two kinds of toughening materials is effectively combined, so as to form a kind of unique composite toughening
System.The modification galapectite prepared can be fully dispersed in concrete, effectively plays the effect of material coordination plasticizing, assigns mixed
The good toughness of solidifying soil, isotropism, fatigue resistance, are a kind of high performance concrete toughening materials.The concrete of the present invention increases
It is tough to be easily well mixed with modified galapectite with other concrete components, then can obtain toughness reinforcing coagulation after marking and supporting
Native product, can be applied to the concrete material fields such as the bridge floor of Longspan Bridge and overpass, and all types of tunnel arch walls.
The content of the invention
It is an object of the invention to provide a kind of available for modification galapectite of concrete toughness reinforcing and preparation method thereof.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of modification galapectite available for concrete toughness reinforcing, it be using activated processing galapectite first with thionyl chloride
Reaction, then with difunctional organic compound reaction, makes galapectite area load labile functional groups, then anti-with Cyanuric Chloride
Should, the galapectite that surface has chloride triazine ring is obtained, is finally prepared with hydroxyethyl cellulose by nucleophilic substitution.
In the modification galapectite, the mass ratio of hydroxyethyl cellulose and galapectite is 0.1-0.3:1.
The preparation method of the modified galapectite, it comprises the following steps：
1. by the galapectite and thionyl chloride of activated processing in organic solvent J, stirred at 30-50 DEG C after 5-12 h,
In ultrasound 8-12 h at 60-80 DEG C in 20 kHz, 100 KW supersonic wave cleaning machine, then with 3500-5000 rpm turn
Speed centrifugation 20-30 min, after separating solid and being cleaned through organic solvent K, then the vacuum drying 24-48 h at 30-40 DEG C；
2. the galapectite that above-mentioned steps 1 are handled, difunctional organic compound and 3- picolines are mixed in organic solvent J
Close, stirred at 40-50 DEG C after 3-12 h, under nitrogen protection, in 20 kHz, 100 KW supersonic wave cleaning machine in 80-
At 90 DEG C after ultrasonic reaction 5-8 h, 3- picolines and solvent J are evaporated off, then after blended solvent L is cleaned, at 10-20 DEG C
It is dried in vacuo 24-36 h；
3. galapectite and Cyanuric Chloride that above-mentioned steps 2 are handled are mixed in tetrahydrofuran, 12-24 is stirred at 0-10 DEG C
H, in after ultrasound 2-6 h at 0-10 DEG C in 20 kHz, 100 KW supersonic wave cleaning machine, then at 0-10 DEG C reacts 30-
After 72 h, cleaned through tetrahydrofuran, 24-48 h are dried in vacuo at 10-15 DEG C；
4. after the galapectite that above-mentioned steps 3 are handled dissolves in 1-METHYLPYRROLIDONE, it is added to and is dissolved with hydroxy ethyl fiber
In the pyridine solution of element, 3-10 h are stirred at 10-20 DEG C, in 10-20 DEG C in 40 kHz, 200 KW supersonic wave cleaning machine
Lower ultrasonic 1-3 h, are warming up to after 40-60 DEG C of isothermal reaction 24-48 h under nitrogen protection, then to be warming up to 83-95 DEG C of constant temperature anti-
24-48 h are answered, solvent is evaporated off, after being eluted with water, obtain being modified galapectite product after being dried in vacuo 24-48 h at 50 DEG C.
The galapectite of activated processing is 1-20 kg in above-mentioned steps 1, and thionyl chloride is 5-50 kg；Organic solvent J is
30-200 L。
During organic solvent J in above-mentioned steps 1 is dimethylbenzene, 1-METHYLPYRROLIDONE or N, N '-dimethyl formamide
It is a kind of.
Organic solvent K in above-mentioned steps 1 is one kind in tetrahydrofuran or acetone.
Galapectite in above-mentioned steps 2 is 3-20 kg；Difunctional organic compound is 1-5 kg；3- picolines are
1-5 L；Organic solvent J is 50-200 L.
Difunctional organic compound in above-mentioned steps 2 is one kind in ethylene glycol and 1,3- propane diols.
Mixed solvent L in above-mentioned steps 2 is made up of ethanol, acetone and water, and the volume ratio of wherein ethanol, acetone and water is
3:1:6。
Galapectite in above-mentioned steps 3 is 2-18 kg；Cyanuric Chloride is 0.5-5 kg；Tetrahydrofuran is 50-200 L.
Galapectite in above-mentioned steps 4 is 2-15 kg；1-METHYLPYRROLIDONE is 50-260 L；Hydroxyethyl cellulose is
1-5 kg；Pyridine is 20-80 L.
The viscosity average molecular weigh of hydroxyethyl cellulose in above-mentioned steps 4 is 5000-30000, and substitution value is 0.5-2.5.
The activation process step of galapectite before above-mentioned steps 1：
（1）Galapectite is taken, is handled through mechanical crushing and uses 400 mesh sieves stand-by after selecting；
（2）Each stainless steel ball for loading 55 a diameter of 5 mm and 50 a diameter of 10 in two L nylon tanks of identical 12
Mm stainless steel ball, is then respectively adding the kg of the galapectite after being handled through previous step 5, then that 500 ml are added dropwise respectively is anhydrous
Ethanol, and sealed with nylon lid.Two ball grinders are symmetrically put into planetary ball mill, are 300 rpm and every in rotating speed
Under conditions of 60 minutes automatic conversion direction of rotation after ball milling 45-50 h, obtain average length for 180-200 nm be chopped angstrom
Lip river stone.
（3）It is the Tween 40 that 8, concentration is 12 wt% to take the galapectite after the chopped processing of previous step to be added to pH
Ultrasonic 20 h in the aqueous solution, filtering is stand-by after 24 h in being dried in vacuo at 65-67 DEG C after being eluted with water.
Described galapectite is commercially available, its main specifications：Character：White powder；Density：2.4-2.5g/cm3；Constitute into
Point：SiO2：58.28wt%、Al2O3：40.98wt%、Fe2O3：0.38wt%、TiO2：0.18wt%、P2O5：0.18wt%；Remainder is burning
Vector.
Pipe external diameter：40-60 nm；Bore：15-20 nm；Length：<1.1 μm；Specific surface area：52.6 m2/g。
Described Tween 40 (CAS No. 9005-66-7) is commercially available, its main specifications：Character：Amber oily liquid
Body；Acid number (KOHmg/g)：≤2.0；Hydroxyl value (KOHmg/g)：85-100；HLB value：15.5；Saponification number (KOHmg/g)：40-55；
Moisture content (%)：≤2.5.
Compared with the prior art, technical scheme has the advantages that：
（1）Concrete toughness reinforcing provided by the present invention is environment-friendly with modified galapectite, has good dispersiveness in water.
（2）The preparation technology of the modified galapectite of the present invention is simple, and raw material sources are abundant, and cost is relatively low.
（3）The concrete toughness reinforcing of the present invention is with modified galapectite, using the excellent modification galapectite of toughness reinforcing efficiency and hydroxyl second
Base cellulose, by multi-step surface modification reaction, two kinds of toughening materials are effectively combined, so as to form a kind of unique be combined
Toughened system.The modification galapectite prepared can be fully dispersed in concrete, effectively plays the effect of material coordination plasticizing,
Assigning concrete integrally has good toughness, isotropism, fatigue resistance, is a kind of high performance concrete toughening material.
（4）The modified galapectite of the concrete toughness reinforcing of the present invention can easily mix scattered with other concrete components
Uniformly, toughness reinforcing concrete product is can obtain after then being supported through mark, the bridge floor of Longspan Bridge and overpass is can apply to, and respectively
The concrete material such as type tunnel arch wall field.
Embodiment
The present invention is prepared for a kind of changing available for concrete toughness reinforcing using galapectite and hydroxyethyl cellulose as raw material first
Property galapectite.Technical scheme is described further below in conjunction with specific embodiment：
Embodiment 1
Activation process is carried out to galapectite first：
（1）Galapectite is taken, is handled through mechanical crushing and uses 400 mesh sieves stand-by after selecting；
（2）Each stainless steel ball for loading 55 a diameter of 5 mm and 50 a diameter of 10 in two L nylon tanks of identical 12
Mm stainless steel ball, is then respectively adding the kg of the galapectite after being handled through previous step 5, then that 500 ml are added dropwise respectively is anhydrous
Ethanol, and sealed with nylon lid.Two ball grinders are symmetrically put into planetary ball mill, are 300 rpm and every in rotating speed
Under conditions of 60 minutes automatic conversion direction of rotation after the h of ball milling 45, the chopped galapectite that average length is 200 nm is obtained.
（3）It is the Tween 40 that 8, concentration is 12 wt% to take the galapectite after the chopped processing of previous step to be added to pH
Ultrasonic 20 h in the aqueous solution, filtering is stand-by after 24 h in being dried in vacuo at 65-67 DEG C after being eluted with water.
Described galapectite is commercially available, its main specifications：Character：White powder；Density：2.4-2.5g/cm3；Constitute into
Point：SiO2：58.23、Al2O3：40.96、Fe2O3：0.34、TiO2：0.15、P2O5：0.14；Pipe external diameter：40-60 nm；Bore：
15-20 nm；Length：<1.1 μm；Specific surface area：52.6 m2/g。
Described Tween 40 (CAS No. 9005-66-7) is commercially available, its main specifications：Character：Amber oily liquid
Body；Acid number (KOHmg/g)：≤2.0；Hydroxyl value (KOHmg/g)：85-100；HLB value：15.5；Saponification number (KOHmg/g)：40-55；
Moisture content (%)：≤2.5.
Further prepare modified galapectite：
（1）By the galapectite 15kg and the kg of thionyl chloride 35 of activated processing in 150 L dimethylbenzene, 10 are stirred at 40 DEG C
After h, in ultrasonic 10 h at 70 DEG C in 20 kHz, 100 KW supersonic wave cleaning machine, then centrifuged with 4000 rpm rotating speed
25 min, after separating solid and being cleaned through acetone, then are dried in vacuo at 35 DEG C 40 h；
（2）The kg of galapectite 12, the L of 3.5 kg and 3- picolines of ethylene glycol 3.5 that above-mentioned steps 1 are handled are in 120 L N- first
Mix, stirred at 45 DEG C after 8 h in base pyrrolidones, under nitrogen protection, in 20 kHz, 100 KW ultrasonic wave cleaning
In after the h of ultrasonic reaction 6 at 85 DEG C, being evaporated off 3- picolines and 1-METHYLPYRROLIDONE in machine, then blended solvent L is cleaned
Afterwards, 30 h are dried in vacuo at 15 DEG C；
（3）The kg of galapectite 10 and the kg of Cyanuric Chloride 3 that above-mentioned steps 2 are handled are mixed in 130 L tetrahydrofurans, at 0 DEG C
20 h of lower stirring, in after ultrasonic 4 h at 0 DEG C in 20 kHz, 100 KW supersonic wave cleaning machine, then at 0 DEG C react 60
After h, cleaned through tetrahydrofuran, 40 h are dried in vacuo at 12 DEG C；
（4）After the kg of galapectite 9 that above-mentioned steps 3 are handled dissolves in 200 L 1-METHYLPYRROLIDONEs, it is added to and is dissolved with
In 60 L pyridine solutions of 3 kg hydroxyethyl celluloses, 6 h are stirred at 15 DEG C, are cleaned in 40 kHz, 200 KW ultrasonic wave
In ultrasonic 2 h at 15 DEG C in machine, it is warming up under nitrogen protection after 55 DEG C of h of isothermal reaction 40, then be warming up to 90 DEG C of isothermal reactions
36 h, are evaporated off solvent, after being eluted with water, and are dried in vacuo at 50 DEG C after 32 h and obtain 10.2 kg modification galapectite products.This changes
Property galapectite in, the mass ratio of hydroxyethyl cellulose and galapectite is 0.1-0.3:1, it can be applied to the toughness reinforcing field of concrete.
Above-mentioned steps（2）In mixed solvent L be made up of ethanol, acetone and water, the wherein volume ratio of ethanol, acetone and water
For 3:1:6.
Embodiment 2
Activation process is carried out to galapectite first：
（1）Galapectite is taken, is handled through mechanical crushing and uses 400 mesh sieves stand-by after selecting；
（2）Each stainless steel ball for loading 55 a diameter of 5 mm and 50 a diameter of 10 in two L nylon tanks of identical 12
Mm stainless steel ball, is then respectively adding the kg of the galapectite after being handled through previous step 5, then that 500 ml are added dropwise respectively is anhydrous
Ethanol, and sealed with nylon lid.Two ball grinders are symmetrically put into planetary ball mill, are 300 rpm and every in rotating speed
Under conditions of 60 minutes automatic conversion direction of rotation after the h of ball milling 48, the chopped galapectite that average length is 190 nm is obtained；
（3）It is the water-soluble of the Tween 40 that 8, concentration is 12 wt% to take the galapectite after the chopped processing of previous step to be added to pH
Ultrasonic 20 h in liquid, filtering is stand-by after 24 h in being dried in vacuo at 65-67 DEG C after being eluted with water.
Described galapectite, Tween 40 specification be the same as Example 1.
Further prepare modified galapectite：
（1）By the kg of galapectite 20 and the kg of thionyl chloride 50 of activated processing in 200 L 1-METHYLPYRROLIDONE, 50
Stirred at DEG C after 12 h, in ultrasonic 12 h at 80 DEG C in 20 kHz, 100 KW supersonic wave cleaning machine, then with 5000
Rpm rotating speed centrifuges 30 min, after separating solid and being cleaned through tetrahydrofuran, then is dried in vacuo at 40 DEG C 48 h；
（2）The L of 20 kg, 1,3- propane diols of galapectite, 5 kg and 3- picolines 5 that above-mentioned steps 1 are handled in 200 L N,
Mix, stirred at 50 DEG C after 12 h, under nitrogen protection, in 20 kHz, 100 KW ultrasound in N '-dimethyl formamide
In after the h of ultrasonic reaction 8 at 90 DEG C, being evaporated off 3- picolines and N in ripple cleaning machine, N '-dimethyl formamide, then it is blended molten
After agent L is cleaned, 36 h are dried in vacuo at 20 DEG C；
（3）The kg of galapectite 18 and the kg of Cyanuric Chloride 5 that above-mentioned steps 2 are handled are mixed in 200 L tetrahydrofurans, at 5 DEG C
24 h of lower stirring, in after ultrasonic 6 h at 0 DEG C in 20 kHz, 100 KW supersonic wave cleaning machine, then at 0 DEG C react 72
After h, cleaned through tetrahydrofuran, 48 h are dried in vacuo at 10 DEG C；
（4）After the kg of galapectite 15 that above-mentioned steps 3 are handled dissolves in 260 L 1-METHYLPYRROLIDONEs, dissolving is added to
Have in 80 L pyridine solutions of 5 kg hydroxyethyl celluloses, 10 h are stirred at 20 DEG C, it is clear in 40 kHz, 200 KW ultrasonic wave
In ultrasonic 3 h at 10 DEG C in washing machine, it is warming up under nitrogen protection after 60 DEG C of h of isothermal reaction 48, then to be warming up to 95 DEG C of constant temperature anti-
48 h are answered, solvent is evaporated off, after being eluted with water, is dried in vacuo at 50 DEG C after 48 h and obtains 17.6 modification galapectite products.This changes
Property galapectite in, the mass ratio of hydroxyethyl cellulose and galapectite is 0.1-0.3:1, it can be applied to the toughness reinforcing field of concrete.
Above-mentioned steps（2）In mixed solvent L be the same as Examples 1.
Using the mass ratio of hydroxyethyl cellulose and galapectite as 0.3:Exemplified by 1 modification galapectite, using the kg/ of cement 420
m3, the modified kg/m of galapectite 5.23, the kg/m of rubble 11003, the kg/m of fine aggregate 6503, the kg/m of slag powders 353, flyash 38
kg/m3, the kg/m of water reducer 3.93With the kg/m of water 1803, the bending strength of the concrete sample of preparation is 25 MPa, tensile strength
For 14 MPa, compression strength is 85 MPa.
Embodiment 3
Activation process is carried out to galapectite first：
（1）Galapectite is taken, is handled through mechanical crushing and uses 400 mesh sieves stand-by after selecting；
（2）Each stainless steel ball for loading 55 a diameter of 5 mm and 50 a diameter of 10 in two L nylon tanks of identical 12
Mm stainless steel ball, is then respectively adding the kg of the galapectite after being handled through previous step 5, then that 500 ml are added dropwise respectively is anhydrous
Ethanol, and sealed with nylon lid.Two ball grinders are symmetrically put into planetary ball mill, are 300 rpm and every in rotating speed
Under conditions of 60 minutes automatic conversion direction of rotation after the h of ball milling 50, the chopped galapectite that average length is 180 nm is obtained.
（3）It is the Tween 40 that 8, concentration is 12 wt% to take the galapectite after the chopped processing of previous step to be added to pH
Ultrasonic 20 h in the aqueous solution, filtering is stand-by after 24 h in being dried in vacuo at 65-67 DEG C after being eluted with water.
Described galapectite, Tween 40 specification be the same as Example 1.
Further prepare modified galapectite：
（1）By the kg of galapectite 10 and the kg of thionyl chloride 25 of activated processing 100 L N, in N '-dimethyl formamide,
Stirred at 30 DEG C after 8 h, in ultrasonic 9 h at 75 DEG C in 20 kHz, 100 KW supersonic wave cleaning machine, then with 4500
Rpm rotating speed centrifuges 25 min, after separating solid and being cleaned through acetone, then is dried in vacuo at 35 DEG C 36 h；
（2）The kg of galapectite 8, the L of 2.5 kg and 3- picolines of ethylene glycol 2.5 that above-mentioned steps 1 are handled are in 150 L N- first
Mix, stirred at 45 DEG C after 10 h in base pyrrolidones, under nitrogen protection, in 20 kHz, 100 KW ultrasonic wave cleaning
In after the h of ultrasonic reaction 7 at 85 DEG C, being evaporated off 3- picolines and 1-METHYLPYRROLIDONE in machine, then blended solvent L is cleaned
Afterwards, 28 h are dried in vacuo at 18 DEG C；
（3）The kg of galapectite 6 and the kg of Cyanuric Chloride 2 that above-mentioned steps 2 are handled are mixed in 100 L tetrahydrofurans, at 3 DEG C
15 h are stirred, in after ultrasound 3h at 5 DEG C in 20 kHz, 100 KW supersonic wave cleaning machine, then 48 h are reacted at 5 DEG C
Afterwards, cleaned through tetrahydrofuran, 30 h are dried in vacuo at 12 DEG C；
（4）After the kg of galapectite 6 that above-mentioned steps 3 are handled dissolves in 150 L 1-METHYLPYRROLIDONEs, it is added to and is dissolved with
In 40 L pyridine solutions of 2 kg hydroxyethyl celluloses, 5 h are stirred at 12 DEG C, are cleaned in 40 kHz, 200 KW ultrasonic wave
In ultrasonic 2 h at 12 DEG C in machine, it is warming up under nitrogen protection after 50 DEG C of h of isothermal reaction 32, then be warming up to 85 DEG C of isothermal reactions
30 h, are evaporated off solvent, after being eluted with water, and are dried in vacuo at 50 DEG C after 40 h and obtain 7.2 kg modification galapectite products.This changes
Property galapectite in, the mass content ratio of hydroxyethyl cellulose and galapectite is 0.1-0.3:1, it can be applied to the toughness reinforcing neck of concrete
Domain.
Above-mentioned steps（2）In mixed solvent L be the same as Examples 1.
Embodiment 4
Activation process is carried out to galapectite first：
（1）Galapectite is taken, is handled through mechanical crushing and uses 400 mesh sieves stand-by after selecting；
（2）Each stainless steel ball for loading 55 a diameter of 5 mm and 50 a diameter of 10 in two L nylon tanks of identical 12
Mm stainless steel ball, is then respectively adding the kg of the galapectite after being handled through previous step 5, then that 500 ml are added dropwise respectively is anhydrous
Ethanol, and sealed with nylon lid.Two ball grinders are symmetrically put into planetary ball mill, are 300 rpm and every in rotating speed
Under conditions of 60 minutes automatic conversion direction of rotation after the h of ball milling 46, the chopped galapectite that average length is 190 nm is obtained.
（3）It is the Tween 40 that 8, concentration is 12 wt% to take the galapectite after the chopped processing of previous step to be added to pH
Ultrasonic 20 h in the aqueous solution, filtering is stand-by after 24 h in being dried in vacuo at 65-67 DEG C after being eluted with water.
Described galapectite, Tween 40 specification be the same as Example 1.
Further prepare modified galapectite：
（1）By the kg of galapectite 1 and the kg of thionyl chloride 5 of activated processing in 30 L 1-METHYLPYRROLIDONE, at 35 DEG C
After 5 h of lower stirring, in ultrasonic 8 h at 80 DEG C in 20 kHz, 100 KW supersonic wave cleaning machine, then with 3500 rpm's
Rotating speed centrifuges 20 min, after separating solid and being cleaned through tetrahydrofuran, then is dried in vacuo at 30 DEG C 24 h；
（2）The L of 3 kg, 1,3- propane diols of galapectite, 1 kg and 3- picolines 1 that above-mentioned steps 1 are handled is in 50 L dimethylbenzene
Middle mixing, is stirred at 40 DEG C after 3 h, under nitrogen protection, in 20 kHz, 100 KW supersonic wave cleaning machine in 80 DEG C
After the lower h of ultrasonic reaction 5,3- picolines and dimethylbenzene are evaporated off, then after blended solvent L is cleaned, 24 are dried in vacuo at 10 DEG C
h；
（3）The kg of galapectite 2 and the kg of Cyanuric Chloride 0.5 that above-mentioned steps 2 are handled are mixed in 50 L tetrahydrofurans, at 10 DEG C
12 h of lower stirring, in after ultrasonic 2 h at 10 DEG C in 20 kHz, 100 KW supersonic wave cleaning machine, then react at 10 DEG C
After 30 h, cleaned through tetrahydrofuran, 24 h are dried in vacuo at 15 DEG C；
（4）After the kg of galapectite 2 that above-mentioned steps 3 are handled dissolves in 50 L 1-METHYLPYRROLIDONEs, it is added to and is dissolved with 1
In 20 L pyridine solutions of kg hydroxyethyl celluloses, 3 h are stirred at 10 DEG C, in 40 kHz, 200 KW supersonic wave cleaning machine
In in ultrasonic 1 h at 20 DEG C, be warming up under nitrogen protection after 40 DEG C of h of isothermal reaction 24, then be warming up to 83 DEG C of isothermal reactions 24
H, is evaporated off solvent, after being eluted with water, and is dried in vacuo at 50 DEG C after 24 h and obtains 2.9 kg modification galapectite products.The modification angstrom
In the stone of Lip river, the mass content ratio of hydroxyethyl cellulose and galapectite is 0.1-0.3:1, it can be applied to the toughness reinforcing field of concrete.
Above-mentioned steps（2）In mixed solvent L be the same as Examples 1.
The present invention is not limited to embodiment of above, as long as the scheme referred in this specification can be implemented.
Claims (10)
1. a kind of concrete toughness reinforcing preparation method of modified galapectite, it is characterised in that：Using the galapectite of activated processing
Reacted first with thionyl chloride, then with difunctional organic compound reaction, make galapectite area load labile functional groups, then
Reacted with Cyanuric Chloride, obtain the galapectite that surface has chloride triazine ring, finally pass through nucleophilic displacement of fluorine with hydroxyethyl cellulose
Reaction is prepared.
2. the concrete toughness reinforcing according to claim 1 preparation method of modified galapectite, it is characterised in that：The modification
In galapectite, the mass ratio of hydroxyethyl cellulose and galapectite is 0.1-0.3:1.
3. the concrete toughness reinforcing according to claim 1 preparation method of modified galapectite, it is characterised in that：Specific steps
It is as follows：
（1）By the galapectite and thionyl chloride of activated processing in organic solvent J, stirred at 30-50 DEG C after 5-12 h,
In ultrasound 8-12 h at 60-80 DEG C in 20 kHz, 100 KW supersonic wave cleaning machine, then with 3500-5000 rpm turn
Speed centrifugation 20-30 min, after separating solid and being cleaned through organic solvent K, then the vacuum drying 24-48 h at 30-40 DEG C；
（2）By above-mentioned steps（1）Galapectite, difunctional organic compound and the 3- picolines of processing are in organic solvent J
Mixing, is stirred after 3-12 h at 40-50 DEG C, under nitrogen protection, in 20 kHz, 100 KW supersonic wave cleaning machine in
At 80-90 DEG C after ultrasonic reaction 5-8 h, 3- picolines and organic solvent J are evaporated off, then after blended solvent L is cleaned, in 10-
24-36 h are dried in vacuo at 20 DEG C；
（3）By above-mentioned steps（2）The galapectite and Cyanuric Chloride of processing are mixed in tetrahydrofuran, and 12- is stirred at 0-10 DEG C
24 h, in after ultrasound 2-6 h at 0-10 DEG C in 20 kHz, 100 KW supersonic wave cleaning machine, then react at 0-10 DEG C
After 30-72 h, cleaned through tetrahydrofuran, 24-48 h are dried in vacuo at 10-15 DEG C；
（4）By above-mentioned steps（3）After the galapectite of processing dissolves in 1-METHYLPYRROLIDONE, it is added to and is dissolved with ethoxy fibre
In the pyridine solution for tieing up element, 3-10 h are stirred at 10-20 DEG C, in 10-20 in 40 kHz, 200 KW supersonic wave cleaning machine
Ultrasound 1-3 h at DEG C, are warming up to after 40-60 DEG C of isothermal reaction 24-48 h, then be warming up to 83-95 DEG C of constant temperature under nitrogen protection
24-48 h are reacted, solvent is evaporated off, after being eluted with water, obtain being modified galapectite product after being dried in vacuo 24-48 h at 50 DEG C.
4. the concrete toughness reinforcing according to claim 3 preparation method of modified galapectite, it is characterised in that：The step
Suddenly（1）In activated processing galapectite be 1-20 kg, thionyl chloride be 5-50 kg；Organic solvent J is 30-200 L；It is organic
Solvent K is tetrahydrofuran or acetone.
5. the concrete toughness reinforcing according to claim 3 preparation method of modified galapectite, it is characterised in that：The step
Suddenly（2）In galapectite be 3-20 kg；Difunctional organic compound is 1-5 kg；3- picolines are 1-5 L；It is organic molten
Agent J is 50-200 L；Organic solvent J is any one in dimethylbenzene, 1-METHYLPYRROLIDONE, N, N '-dimethyl formamide；
Difunctional organic compound is one kind in ethylene glycol and 1,3- propane diols.
6. the concrete toughness reinforcing according to claim 3 preparation method of modified galapectite, it is characterised in that：The step
（2）In mixed solvent L be made up of ethanol, acetone and water, wherein the volume ratio of ethanol, acetone and water be 3:1:6.
7. the concrete toughness reinforcing according to claim 3 preparation method of modified galapectite, it is characterised in that：The step
Suddenly（3）In galapectite be 2-18 kg；Cyanuric Chloride is 0.5-5 kg；Tetrahydrofuran is 50-200 L.
8. the concrete toughness reinforcing according to claim 3 preparation method of modified galapectite, it is characterised in that：
The step（4）In galapectite be 2-15 kg；1-METHYLPYRROLIDONE is 50-260 L；Hydroxyethyl cellulose is 1-5
kg；Pyridine is 20-80 L；The viscosity average molecular weigh of hydroxyethyl cellulose is 5000-30000, and substitution value is 0.5-2.5.
9. the concrete toughness reinforcing according to claim 3 preparation method of modified galapectite, it is characterised in that：
The galapectite of the activated processing, its activation process is concretely comprised the following steps：
（1）Galapectite is taken, is handled through mechanical crushing and uses 400 mesh sieves stand-by after selecting；
（2）Each stainless steel ball for loading 55 a diameter of 5 mm and 50 a diameter of 10 in two L nylon tanks of identical 12
Mm stainless steel ball, is then respectively adding the kg of the galapectite after being handled through previous step 5, then that 500 ml are added dropwise respectively is anhydrous
Ethanol, and sealed with nylon lid, two ball grinders are symmetrically put into planetary ball mill, are 300 rpm in rotating speed, and often
Under conditions of 60 minutes automatic conversion direction of rotation after ball milling 45-50 h, obtain average length for 180-200 nm be chopped angstrom
Lip river stone；
（3）It is the water-soluble of the Tween 40 that 8, concentration is 12 wt% to take the galapectite after the chopped processing of previous step to be added to pH
Ultrasonic 20 h in liquid, filtering is stand-by after 24 h in being dried in vacuo at 65-67 DEG C after being eluted with water.
10. a kind of modified galapectite of concrete toughness reinforcing made from preparation method as described in claim 1-9.
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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 |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119704A (en) * | 2013-04-27 | 2014-10-29 | 中国科学院化学研究所 | Surface modification treatment method of halloysite nanotube |
| CN105541212A (en) * | 2015-12-30 | 2016-05-04 | 福建江夏学院 | Composite material toughened ceramisite concrete and preparation method thereof |
| CN105619916A (en) * | 2015-12-25 | 2016-06-01 | 北京化工大学 | Nano-toughened carbon fiber composite material and preparation method thereof |
| CN106045404A (en) * | 2016-06-08 | 2016-10-26 | 福建江夏学院 | Environment-friendly pervious recycled aggregate concrete and preparation method thereof |
| CN106082799A (en) * | 2016-06-08 | 2016-11-09 | 福建江夏学院 | A kind of anti-crack concrete with anti-electromagnetic radiation and preparation method thereof |
| CN106082800A (en) * | 2016-06-08 | 2016-11-09 | 福建江夏学院 | A kind of have anti-crack concrete inhaling wave energy and preparation method thereof |
-
2017
- 2017-05-31 CN CN201710399026.1A patent/CN107200491A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119704A (en) * | 2013-04-27 | 2014-10-29 | 中国科学院化学研究所 | Surface modification treatment method of halloysite nanotube |
| CN105619916A (en) * | 2015-12-25 | 2016-06-01 | 北京化工大学 | Nano-toughened carbon fiber composite material and preparation method thereof |
| CN105541212A (en) * | 2015-12-30 | 2016-05-04 | 福建江夏学院 | Composite material toughened ceramisite concrete and preparation method thereof |
| CN106045404A (en) * | 2016-06-08 | 2016-10-26 | 福建江夏学院 | Environment-friendly pervious recycled aggregate concrete and preparation method thereof |
| CN106082799A (en) * | 2016-06-08 | 2016-11-09 | 福建江夏学院 | A kind of anti-crack concrete with anti-electromagnetic radiation and preparation method thereof |
| CN106082800A (en) * | 2016-06-08 | 2016-11-09 | 福建江夏学院 | A kind of have anti-crack concrete inhaling wave energy and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111233362A (en) * | 2020-03-25 | 2020-06-05 | 福建江夏学院 | Preparation method and application of concrete toughening material |
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