Disclosure of Invention
The invention aims to provide a high-permeability flexible self-crosslinking waterproof material and application thereof, wherein the waterproof material can be used for micro-crack seepage prevention and leakage prevention.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a high-permeability flexible self-crosslinking waterproof material which comprises a first component, a second component and a third component which are independently subpackaged in parts by mass, wherein the first component comprises 25-150 parts of fly ash, 5-25 parts of a hydrophilic high polymer, 2-30 parts of a mineral filler, 30-200 parts of water and 0.1-5.0 parts of an auxiliary agent;
the second component comprises 2-50 parts of an exciting agent and 10-100 parts of water;
the third component comprises 2-15 parts of a cross-linking agent and 5-60 parts of a diluent.
Preferably, the particle size of the fly ash is less than 45 μm.
Preferably, the hydrophilic high molecular polymer comprises one or more of polyacrylate polymer containing a plurality of hydroxyl groups, polyurethane containing a plurality of hydroxyl groups, polyvinyl alcohol, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and starch; the molecular weight of the hydrophilic high molecular polymer is 5-100 ten thousand.
Preferably, the mineral filler comprises one or more of mica powder, kaolin, silica powder, barium sulfate and titanium dioxide, and the particle size of the mineral filler is 800-4000 meshes.
Preferably, the auxiliaries comprise wetting dispersants and/or defoamers.
Preferably, the activator comprises an alkaline activator and/or an acidic activator, the alkaline activator comprises one or more of sodium hydroxide, sodium bicarbonate, sodium silicate, sodium sulfate, potassium hydroxide, calcium oxide and calcium sulfate, and the acidic activator comprises one or more of sulfuric acid, hydrochloric acid, phosphoric acid and acetic acid.
Preferably, the cross-linking agent comprises one or more of sodium trimetaphosphate, sodium tripolyphosphate, formaldehyde, glutaraldehyde, epichlorohydrin and phosphorus oxychloride.
Preferably, the diluent comprises one or more of water, ethanol and ethyl acetate.
Preferably, the mass ratio of the first component to the second component to the third component is 100 (0.05-30) to (0.001-1.0).
The invention provides application of the high-permeability flexible self-crosslinking waterproof material in the technical scheme in the field of microcrack seepage prevention and leakage prevention.
The invention provides a high-permeability flexible self-crosslinking waterproof material which comprises a first component, a second component and a third component which are independently subpackaged in parts by mass, wherein the first component comprises 25-150 parts of fly ash, 5-25 parts of a hydrophilic high polymer, 2-30 parts of a mineral filler, 30-200 parts of water and 0.1-5.0 parts of an auxiliary agent; the second component comprises 2-50 parts of an exciting agent and 10-100 parts of water; the third component comprises 2-15 parts of a cross-linking agent and 5-60 parts of a diluent. The high-permeability flexible self-crosslinking waterproof material provided by the invention takes the fly ash as a main filling and reinforcing component, takes a reactive hydrophilic high polymer material as a flexible bonding phase, has the characteristics of low viscosity and high permeability before curing, and is cured and formed in situ under the combined action of crosslinking curing of the hydrophilic high polymer and hydration of the fly ash after the waterproof material reaches a protection and repair part to form a solid network-shaped high polymer-fly ash composite waterproof material, and the fly ash is hydrated to form a bonding phase to be effectively bonded with a base material. Therefore, the curing and forming of the waterproof material provided by the invention take the cross-linking polymerization reaction of the hydrophilic high-molecular polymer as a mechanism, and the first component, the second component and the third component are cross-linked and cured in situ at the water leakage part and form the water-based composite material with an organic-inorganic double cross-linked network structure with the fly ash, so that the effect of rapid waterproof and leakage stoppage is achieved, and the water is not required to be evaporated and dried.
The waterproof material provided by the invention obtains good mechanical strength by forming an organic-inorganic double-crosslinking network structure, achieves the filling purpose by water absorption expansion, is different from the traditional material taking physical filling as a waterproof plugging principle, reduces the dependence on solid content, can be prepared into a low-viscosity system (20-800 mPa & s) by taking water as a solvent, has excellent fluidity and high permeability, is suitable for a grouting process, can permeate into deep fine cracks, has remarkable advantages in repairing micro cracks and internal cracks, and has remarkable waterproof and repairing effects on the water seepage problem which is difficult to repair by the traditional material and is formed by microcracks.
The waterproof material provided by the invention has the advantages that the waterproof material has high strength, ageing resistance, corrosion resistance and cracking resistance, good flexibility and long waterproof effective period due to the double network structure formed by the polymer-based binding phase and the inorganic phase.
The organic component in the waterproof material provided by the invention expands in volume after absorbing water, and the elastic property is improved, so that the waterproof material shows good flexibility; and can form effective filling to the crack through expansion and deformation, and show good shape adaptability, thereby having outstanding advantages in the aspects of shrinkage resistance, cracking resistance and the like.
The waterproof material disclosed by the invention takes water as a dispersing agent and a diluting agent, so that the harm of the material to the environment and human bodies is reduced, and the safety of the waterproof material in the processes of production, transportation, storage and use is guaranteed.
The invention takes the solid waste fly ash as a main reinforcing and filling component, the hydration reaction activity of the fly ash endows the material with better strength advantage, has outstanding environmental benefit and cost advantage, realizes high-value utilization of the solid waste, and has positive significance to the environment and resources. Meanwhile, the fly ash has wide source and low price, and can obviously reduce the cost of the materials when being widely applied to waterproof materials.
The waterproof paint can be widely used for waterproofing of tunnels, bridges and the like in highway engineering construction by adjusting the proportion of the first component, the second component and the third component, and can also be used for construction and repair of waterproofing engineering of basements, roofs and the like of buildings. The system viscosity, the crosslinking speed and the material strength of the waterproof material provided by the invention can be adjusted according to the requirements through the component proportion ratio, so that a waterproof material system with good applicability is obtained.
Detailed Description
The invention provides a high-permeability flexible self-crosslinking waterproof material which comprises a first component, a second component and a third component which are independently packaged in parts by mass, wherein the first component comprises 25-150 parts of fly ash, 5-25 parts of a hydrophilic high polymer, 2-30 parts of a mineral filler, 30-200 parts of water and 0.1-5.0 parts of an auxiliary agent;
the second component comprises 2-50 parts of an exciting agent and 10-100 parts of water;
the third component comprises 2-15 parts of a cross-linking agent and 5-60 parts of a diluent.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
The high-permeability flexible self-crosslinking waterproof material comprises a first component which is independently packaged, wherein the first component comprises 25-150 parts of fly ash, and more preferably 75-100 parts. In the present invention, the fly ash preferably has a particle size of < 45 μm, more preferably < 30 μm. The invention preferably carries out crushing treatment on the solid waste fly ash, and the fly ash is sieved after being ground to obtain the fly ash with the grain diameter less than 45 mu m; the pulverization is preferably carried out by adopting a ball mill, a vibration mill pulverizer, a jaw crusher or a steam power grinder; the invention has no special limitation on the specific conditions of the pulverization, and the pulverization is carried out according to the process well known in the field; in the embodiment of the invention, the solid waste fly ash and the equal mass agate beads are mixed uniformly and then put into a ball mill for crushing for 4 hours. The process of grinding and sieving is not particularly limited in the present invention, and the fly ash with the above particle size requirement can be obtained according to the process well known in the art. The invention uses the fly ash as a main filling and reinforcing component, and realizes high-value utilization of solid waste.
Based on the mass parts of the fly ash, the first component of the high-permeability flexible self-crosslinking waterproof material provided by the invention comprises 5-25 parts of hydrophilic high-molecular polymer, and more preferably 10-15 parts. In the present invention, the hydrophilic high molecular polymer preferably includes one or more of polyacrylate polymer having a plurality of hydroxyl groups, polyurethane having a plurality of hydroxyl groups, polyvinyl alcohol, hydroxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and starch; the molecular weight of the hydrophilic high molecular polymer is preferably 5 to 100 ten thousand; the polyacrylate polymer containing a plurality of hydroxyl groups is preferably an aqueous hydroxy acrylic resin; the polyurethane containing a plurality of hydroxyl groups is preferably a hydroxyl polyurethane polymer. When the hydrophilic high molecular polymers are more than two of the above, the proportion of the hydrophilic high molecular polymers of different types is not particularly limited, and the proportion can be any. The invention takes reactive water-soluble high molecular polymer material as a flexible bonding component, and forms a cross-linked network structure through in-situ cross-linking reaction, thereby improving the flexibility and permeability of the waterproof material.
Based on the mass parts of the fly ash, the first component of the high-permeability flexible self-crosslinking waterproof material provided by the invention comprises 2-30 parts of mineral filler, and more preferably 10-20 parts. In the invention, the mineral filler preferably comprises one or more of mica powder, kaolin, silica powder, barium sulfate and titanium dioxide, and the particle size of the mineral filler is preferably 800-4000 meshes. When the mineral fillers are more than two of the mineral fillers, the proportion of different mineral fillers is not specially limited, and the mineral fillers can be mixed at any proportion. The invention utilizes mineral filler to play the roles of filling and reinforcing.
Based on the mass parts of the fly ash, the first component of the high-permeability flexible self-crosslinking waterproof material provided by the invention comprises 30-200 parts of water, and more preferably 100-150 parts of water. The present invention utilizes water as the diluent for the first component.
Based on the mass parts of the fly ash, the first component of the high-permeability flexible self-crosslinking waterproof material provided by the invention comprises 0.1-5.0 parts of an auxiliary agent, and more preferably 2-4 parts; in the present invention, the auxiliary preferably includes a wetting dispersant and/or a defoaming agent; when the auxiliary agent is a wetting dispersant and a defoaming agent, the proportion of the wetting dispersant and the defoaming agent is not specially limited, and the auxiliary agent can be adjusted according to actual requirements.
In the present invention, the wetting dispersant preferably comprises one or more of TEGO Dispers 655, TEGO Dispers 735W, TEGO Dispers 740W, TEGO Dispers 750W, TEGO Dispers755W, TEGO Dispers 760W, ZetaSperse 2500, ZetaSperse 3100, ZetaSperse3400, ZetaSperse 3600, DisperbYK-180, DisperbYK-190, Disper BYK-191, Disper BK-23160, Disper BYK-2010, Triton CF-10, Triton X-405, Triton OT-75, Triton X-100, OROTAN 731A, SN 5040 and Additol VXW 6208/60; when the wetting dispersant is more than two of the wetting dispersants, the proportion of different wetting dispersants is not specially limited, and any proportion can be adopted. In the present invention, the antifoaming agent preferably comprises one or more of BYK-019, BYK-023, BYK-024, BYK-034, BYK 1780, TEGO FOAMEX 810, Tego Foamex 825, TEGO FOAMEX 920, TEGO FOAMEX1488, TEGO Airex 904W, FoamStar 2410AC, FOAMSTAR SI 2250 and Foamaster 328; when the defoaming agents are more than two of the defoaming agents, the types of the defoaming agents in different types are not particularly limited, and the defoaming agents can be prepared in any proportion. The invention utilizes wetting dispersant to disperse and stabilize the fly ash and mineral filler; the defoaming agent is used for inhibiting the system from generating bubbles and helping to eliminate the bubbles.
In the present invention, the method for preparing the first component preferably comprises the steps of: carrying out first stirring and mixing on a hydrophilic high molecular polymer and water to obtain a polymer solution, adding an auxiliary agent into the polymer solution, and carrying out second stirring and mixing to obtain precursor mother liquor; and (3) performing third stirring and mixing on the fly ash, the mineral filler and the precursor mother liquor to obtain a first component. In the invention, the first stirring mixing, the second stirring mixing and the third stirring mixing are preferably carried out under normal temperature and normal pressure, and the speed of the first stirring mixing, the speed of the second stirring mixing and the speed of the third stirring mixing are independently preferably 400-2000 r/min, and more preferably 600-1200 r/min; the first stirring and mixing time is preferably 1-4 h, and more preferably 2 h; the time for the second stirring and mixing is preferably 10 min; the time for the third stirring and mixing is preferably 60 min.
The high-permeability flexible self-crosslinking waterproof material comprises a second component which is independently packaged, wherein the second component comprises 2-50 parts of an exciting agent, and more preferably 10 parts. The activator preferably comprises an alkaline activator and/or an acidic activator, the alkaline activator preferably comprises one or more of sodium hydroxide, sodium bicarbonate, sodium silicate, sodium sulfate, potassium hydroxide, calcium oxide and calcium sulfate, and the acidic activator preferably comprises one or more of sulfuric acid, hydrochloric acid, phosphoric acid and acetic acid. When the number of the exciting agents is more than two, the proportion of different exciting agents is not specially limited, and the exciting agents can be mixed at any proportion. Under the action of an activator, a high molecular polymer containing active hydroxyl (-OH) and a cross-linking agent are subjected to a cross-linking reaction to form a polymer cross-linking structure, when an alkaline activator is selected, the polymer cross-linking structure is used as an elastic bonding component under an alkaline condition, the fly ash forms a more effective inorganic bonding phase reinforced structure under the action of hydration, and the polymer cross-linking structure and the fly ash hydration reinforced structure form a composite interpenetrating network structure, so that the permeability and the flexibility of the waterproof material are improved.
Based on the parts by weight of the excitant, the second component of the high-permeability flexible self-crosslinking waterproof material provided by the invention comprises 10-100 parts of water. The present invention utilizes water as the diluent for the second component.
The high-permeability flexible self-crosslinking waterproof material comprises a third component which is independently packaged, wherein the third component comprises 2-15 parts of a crosslinking agent, and more preferably 5-10 parts; the cross-linking agent preferably comprises one or more of sodium trimetaphosphate, sodium tripolyphosphate, formaldehyde, glutaraldehyde, epichlorohydrin and phosphorus oxychloride. When the cross-linking agents are more than two of the cross-linking agents, the proportion of the cross-linking agents of different types is not particularly limited, and the cross-linking agents can be mixed at any proportion. The invention uses the cross-linking agent to promote the hydrophilic high molecular polymer to generate cross-linking reaction to form a cross-linked network structure.
Based on the mass parts of the cross-linking agent, the third component of the high-permeability flexible self-crosslinking waterproof material provided by the invention comprises 5-60 parts of a diluent, and more preferably 40-50 parts. In the present invention, the diluent preferably comprises one or more of water, ethanol and ethyl acetate; when the diluent is more than two of the above, the proportion of different diluents is not particularly limited, and any proportion can be adopted.
In the invention, the mass ratio of the first component, the second component and the third component is preferably 100 (0.05-30): (0.001-1.0), more preferably 100 (0.15-5): 0.0015-0.5).
The preparation method of the second component and the third component is not specially limited, and the materials corresponding to the second component and the third component are uniformly mixed.
The invention provides application of the high-permeability flexible self-crosslinking waterproof material in the technical scheme in the field of microcrack seepage prevention and leakage prevention. The method of the present invention is not particularly limited, and the method may be applied according to a method known in the art.
In the invention, when the high-permeability flexible self-crosslinking waterproof material is used, the independently subpackaged first component is mixed with water and diluted to the required viscosity; and then adding the second component and the third component, and uniformly mixing to obtain the waterproof material. In the invention, the mass ratio of the water used for dilution to the first component is preferably (15-100): 100, more preferably (20-50): 100, and the invention is preferably adjusted to the required viscosity according to the size of cracks, and the first component can penetrate into the base material after dilution as a judgment standard.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1
Taking 200g of solid waste fly ash, uniformly mixing the solid waste fly ash with agate beads with equal mass, putting the mixture into a star-type ball mill, crushing the mixture for 4 hours, taking out the mixture, sieving the mixture, and collecting the part with the particle size of less than 45 mu m to obtain the fly ash;
weighing 1.5g of starch and 8.5g of polyvinyl alcohol, dissolving in 100g of water under the stirring condition, stirring for 2 hours at a speed of 600r/min, uniformly dispersing, adding 1.0g of BYK 1780 as an auxiliary agent, 1.0g of TEGO FOAMEX 810 and 2.0g of OROTAN 731A into the polymer solution, and continuously dispersing for 10 minutes; taking 75g of fly ash and 10g of mica powder, and adding and dispersing for 60min to be uniform under the mechanical stirring condition of 1200r/min to obtain a first component;
weighing 10g of exciting agent phosphoric acid and water to prepare a 50% phosphoric acid water solution to obtain a second component;
weighing 10g of cross-linking agent glutaraldehyde, dissolving in a mixed solvent of 30g of ethanol and 30g of ethyl acetate, and stirring uniformly to obtain a third component;
and (3) diluting the first component by adding water, taking 100g of the first component, adding 20g of water for dilution, adding 5g of the second component and 0.5g of the third component under the stirring condition, and stirring for 10min till the mixture is uniform to obtain the waterproof material.
Examples 2 to 5
Taking 200g of solid waste fly ash, uniformly mixing the solid waste fly ash with agate beads with equal mass, putting the mixture into a star-type ball mill, crushing the mixture for 4 hours, taking out the mixture, sieving the mixture, and collecting the part with the particle size smaller than 30 mu m to obtain the fly ash;
weighing 10g of polyvinyl alcohol quantitatively, dissolving the polyvinyl alcohol in 100g of water under stirring, stirring for 2 hours at 600r/min, dispersing uniformly to obtain a polymer solution, adding 2.0g of BYK 1780 of an auxiliary agent into the polymer solution, continuously dispersing for 10 minutes, adding 100g of fly ash and 5g of barium sulfate under mechanical stirring at 1200r/min, and dispersing for 60 minutes to be uniform to obtain a first component;
weighing 10g of exciting agent sodium hydroxide and water to prepare 10% aqueous solution to obtain a second component;
weighing 10g of cross-linking agent glutaraldehyde, dissolving in a mixed solution of 20g of water and 20g of ethanol, and stirring uniformly to obtain a third component;
diluting the first component with water, taking the first component, adding 20g of water for dilution, adding the second component and the third component under the stirring condition, and stirring for 10min till the mixture is uniform to obtain the waterproof material, wherein the specific ratio of the first component, the second component and the third component is shown in table 1.
Comparative example 1
The only difference from example 2 is: the masses of the first component, the second component and the third component were 40g, 0.0g and 0.06g, respectively.
Performance testing
1) The waterproof material prepared in example 1 was released after extrusion and the rebound was observed, and the results are shown in FIG. 1; as can be seen from the figure, the waterproof material can rebound to the original shape, which shows that the elasticity is excellent.
The waterproof material prepared in example 1 was cut to a length of 1.5cm, stretched to a length of > 3cm and then released, and the rebound was observed, and the results are shown in FIG. 1; as can be seen from fig. 1, the waterproof material can rebound to its original length after being stretched, indicating that it is excellent in elasticity.
2) Micrographs of the waterproof material prepared in example 1 are shown in FIG. 2; as can be seen from fig. 2, the pelletized fly ash is dispersed in the polymer phase as a reinforcing and filling component.
3) The waterproof materials prepared in examples 2-5 and comparative example 1 were subjected to a curing time test, which was carried out by the following method: at 23 +/-2 ℃, the components after constant temperature are mixed uniformly, counting is started, the recording time is the curing time when the material loses fluidity and is in a solid state, and the obtained result is shown in table 1.
TABLE 1 results of the effect of different ratios of the first, second and third components on the curing time in examples 2 to 5 and comparative example 1
|
First component
|
Second component
|
Third component
|
Curing time
|
Comparative example 1
|
40g
|
0.0
|
0.06
|
1.0h
|
Example 2
|
40g
|
2.0
|
0.06
|
31min
|
Example 3
|
40g
|
4.0
|
0.06
|
16min
|
Example 4
|
40g
|
6.0
|
0.06
|
5min
|
Example 5
|
40g
|
4.0
|
0.12
|
24min |
As can be seen from Table 1, the waterproof material provided by the invention has short curing time, which indicates that the curing speed is high.
4) The waterproof materials prepared in examples 1 and 3 were subjected to a performance test, wherein the viscosity test method was a rotational viscometer method; the test method of tensile strength and elongation at break comprises the following steps: preparing a sample into a dumbbell-shaped sample strip, and testing by adopting a universal mechanical testing machine; the water-swelling rate test method is carried out according to JC 2041-2010; the method for testing the compressive strength is carried out according to JC 2041-; the water impermeability test method is carried out according to the regulation of GB/T16777-; the elastic recovery rate test method is carried out according to 6.10 in GB/T23457-2008;
permeability test method: taking sandy soil with the particle size range of 20-30 meshes, and drying at 50 ℃ for 8 hours; diluting the waterproof material with 20% water, and uniformly stirring for later use; filling the dried sand into a transparent glass tube, and diluting the waterproof material at 5.0kg/m 2 The amount of (A) is injected into a glass tube, and the permeation thickness is measured after natural permeation for 2 hours.
Acid resistance: preparing and curing the waterproof material into a cuboid sample bar, soaking the cuboid sample bar in a sulfuric acid solution with the mass concentration of 2% for 24 hours, observing the appearance, and measuring the elastic shape recovery rate according to the method recorded in GB/T23457-2008 6.10;
alkali resistance: preparing and curing the waterproof material into a cuboid sample bar, soaking the cuboid sample bar in a mixed solution of 0.1% sodium hydroxide and 0.1% calcium hydroxide for 24 hours, observing the appearance, and measuring the elastic shape recovery rate according to 6.10 in GB/T23457-2008; the results are shown in tables 2 and 3.
Table 2 results of performance test of the waterproof material prepared in example 1
Serial number
|
Item
|
Test results
|
1
|
Appearance of the product
|
Liquid of grey and black color
|
2
|
Viscosity of the oil
|
102mPa.s
|
3
|
Curing time
|
30min
|
4
|
Tensile strength
|
1.1/MPa
|
5
|
Elongation at break
|
>120%
|
6
|
Rate of swelling with water
|
≥45%
|
7
|
Compressive strength
|
0.30MPa
|
8
|
Water impermeability
|
0.2MPa, 30min no water seepage
|
9
|
Elastic recovery rate/%)
|
>85%
|
10
|
Thickness of penetration
|
5cm
|
11
|
Alkali resistance
|
The appearance is normal; the elastic recovery rate is more than 60 percent
|
12
|
Acid resistance
|
The appearance is normal; the elastic recovery rate is more than 65 percent |
Table 3 results of performance test of waterproof material prepared in example 3
Serial number
|
Item
|
Test results
|
1
|
Appearance of the product
|
Liquid of grey and black color
|
2
|
Viscosity of the oil
|
169mPa.s
|
3
|
Tensile strength
|
1.7MPa
|
4
|
Elongation at break
|
85%
|
5
|
Water-swelling rate/%)
|
≥30%
|
6
|
Compressive strength/MPa
|
0.33MPa
|
7
|
Water impermeability
|
0.2MPa, 30min no water seepage
|
8
|
Elastic recovery rate/%)
|
>75%
|
9
|
Thickness of penetration
|
3.5cm
|
10
|
Alkali resistance
|
The appearance is normal; the elastic recovery rate is more than 50 percent
|
11
|
Acid resistance
|
The appearance is normal; the elastic recovery rate is more than 55 percent |
As can be seen from tables 2 and 3, the waterproof material provided by the invention has the characteristics of low viscosity, high elasticity and water swelling, and is high in material strength, elastic elongation, rebound resilience, permeability and corrosion resistance (acid and alkali resistance).
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.