CN116716022A - High-permeability concrete protective material imitating shell structure vinyl resin and preparation method thereof - Google Patents
High-permeability concrete protective material imitating shell structure vinyl resin and preparation method thereof Download PDFInfo
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- CN116716022A CN116716022A CN202310486064.6A CN202310486064A CN116716022A CN 116716022 A CN116716022 A CN 116716022A CN 202310486064 A CN202310486064 A CN 202310486064A CN 116716022 A CN116716022 A CN 116716022A
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- vinyl resin
- mxene
- coupling agent
- silane coupling
- protective material
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- 239000000463 material Substances 0.000 title claims abstract description 95
- 229920005989 resin Polymers 0.000 title claims abstract description 84
- 239000011347 resin Substances 0.000 title claims abstract description 84
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 53
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims abstract description 51
- 239000004567 concrete Substances 0.000 title claims abstract description 39
- 230000001681 protective effect Effects 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title abstract description 9
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910000077 silane Inorganic materials 0.000 claims abstract description 26
- 238000001746 injection moulding Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 41
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000011259 mixed solution Substances 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000013049 sediment Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 238000006460 hydrolysis reaction Methods 0.000 claims description 17
- 239000006185 dispersion Substances 0.000 claims description 16
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 14
- 239000011159 matrix material Substances 0.000 claims description 14
- 239000003085 diluting agent Substances 0.000 claims description 12
- 229910052723 transition metal Inorganic materials 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 150000003624 transition metals Chemical class 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 7
- 239000012530 fluid Substances 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000413 hydrolysate Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 4
- -1 transition metal nitride Chemical class 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 claims description 3
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 3
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 claims description 3
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 claims description 3
- 238000003828 vacuum filtration Methods 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 13
- 239000000203 mixture Substances 0.000 abstract description 9
- 239000002344 surface layer Substances 0.000 abstract description 5
- 230000035699 permeability Effects 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000010354 integration Effects 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- 230000002265 prevention Effects 0.000 abstract 1
- 239000007921 spray Substances 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 22
- 239000004744 fabric Substances 0.000 description 10
- 230000007062 hydrolysis Effects 0.000 description 10
- 238000002347 injection Methods 0.000 description 10
- 239000007924 injection Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000000565 sealant Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 238000009777 vacuum freeze-drying Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000002135 nanosheet Substances 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 3
- RZXMPPFPUUCRFN-UHFFFAOYSA-N para-methylaniline Natural products CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 229920006337 unsaturated polyester resin Polymers 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 210000000795 conjunctiva Anatomy 0.000 description 1
- 238000007596 consolidation process Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010125 resin casting Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
-
- 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
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
- C04B41/61—Coating or impregnation
- C04B41/65—Coating or impregnation with inorganic materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Structural Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Producing Shaped Articles From Materials (AREA)
Abstract
The invention discloses a high-permeability concrete protective material imitating shell structure vinyl resin and a preparation method thereof, belonging to the technical field of compositions of high molecular compounds. The silane modified MXene material is combined with vinyl resin through injection molding, so that the high-permeability concrete protective material with the shell-like layered structure is prepared. The protective material has the characteristics of strong permeability, good flexibility, good compactness and ion permeation prevention, can be deeply solidified in a concrete material, and greatly improves the strength, toughness and compactness of the material, so that a concrete surface layer forms a sealed integral protective structure layer. Even if the surface film forming substance is destroyed, the concrete surface layer can be closed by the protective material to achieve a compact waterproof structure layer, thereby playing a permanent protective role. The invention adopts the spray molding mode, can realize the integration of the waterproof layer concrete base layer and form a shell-like structure, and enhances the strength and toughness of the protective material.
Description
Technical Field
The invention relates to the technical field of high molecular compound compositions, in particular to a high-permeability concrete protective material imitating shell structure vinyl resin and a preparation method thereof.
Background
Most of the structures of the current concrete buildings adopt a mode of combining reinforced steel bars and concrete, and cracks exist in the concrete due to long-term action. The traditional waterproof materials such as emulsified asphalt, polyurethane and the like form a layer of waterproof film on the surface of a concrete structure, and can play a good waterproof role on the concrete surface layer. Due to the stress, the waterproof conjunctiva of the concrete surface layer is extremely easy to break, and the concrete structure can be again subjected to corrosion threat. Vinyl resin (VER) is a thermosetting resin synthesized by the reaction of methacrylic acid and bisphenol A epoxy resin, can be quickly cured at normal temperature, and has good mechanical properties of the epoxy resin. Unsaturated Polyester Resins (UPR) and vinyl resins (VER) are commonly used in the fields of automobiles, ships, chemical storage tank facilities, buildings, and the like. In addition, they are also often used for preparing resin-based composite materials, and have good application prospects. When the resin is applied to the fields of building materials and the like or used for preparing composite materials, the mechanical properties, particularly the fracture toughness such as stretching, bending and the like, are particularly important, and the application range of the resin is greatly widened by improving the mechanical properties of the resin. Therefore, resins are often modified by various means to improve their mechanical properties.
Building leakage not only disturbs people's normal life, work and production order, but also causes great economic loss. Firstly, the damage to the structure of the building directly affects the service function and service life of the building; secondly, every day and again, the housing is mildewed and tasty due to long-term leakage to influence the health of the housing, so that the life quality of people is reduced; again, damage to the product materials and even serious accidents are caused, and moreover, a great deal of funds and labor are spent for repairing the leakage phenomenon every several years, so that resource waste is caused. Therefore, waterproof materials with high performance and high durability are a trend of market development in the future. Therefore, the modification method which has the advantages of simple preparation method and small addition amount of the modification material and can greatly improve the performance of the vinyl resin is of great significance to the modification of the vinyl resin.
Chinese patent CN114316520A discloses a two-dimensional MXene nano-sheet vinyl resin composite material and a preparation method thereof, wherein the composite material is obtained by modifying vinyl resin by two-dimensional MXene nano-sheets and a coupling agent, and comprises the following steps: mixing the two-dimensional MXene nano-sheets with a coupling agent in ethanol to obtain an ethanol solution of the MXene nano-sheets coated with the coupling agent on the surface, then mixing and dispersing the ethanol solution with vinyl resin, removing ethanol of a reaction system, sequentially adding an accelerator and an initiator, and carrying out vacuum defoamation, casting, standing and heating treatment on the obtained resin mixture to obtain the composite material. However, the composite material has loose structure and poor mechanical property, and further application of the composite material is limited.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, in a first aspect of the present invention, there is provided a high-permeability concrete protective material of shell-like vinyl resin having excellent mechanical properties and strong permeability, the protective material comprising the following components: vinyl resin, reactive diluent, curing agent, accelerator, silane modified MXene material; the protective material has a shell-like layered structure formed by alternately superposing and solidifying vinyl resin and a silane modified MXene material, wherein the silane modified MXene material is prepared by grafting a silane coupling agent on the MXene material.
In the high-permeability concrete protective material of the shell-like vinyl resin, the cured vinyl resin and the silane modified MXene material form a shell-like layered hierarchical structure with alternating soft and hard phases, so that the material is endowed with excellent mechanical properties, and the combination of strength and toughness is realized.
Preferably, the vinyl resin is 90-100 parts by weight, the reactive diluent is 20-50 parts by weight, the curing agent is 1-5 parts by weight, the accelerator is 0.1-3 parts by weight, and the silane modified MXene material is 1-10 parts by weight.
Preferably, the vinyl resin is bisphenol a type vinyl resin.
Preferably, in the MXene material, the MAX phase material is at least one of a two-dimensional transition metal carbide, a transition metal nitride, and a transition metal carbonitride.
Preferably, the silane coupling agent is at least one of a silane coupling agent KH550 and a silane coupling agent KH 560.
Preferably, the reactive diluent is at least one of vinyl ether, styrene, alpha-methylstyrene, methyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and trimethylolpropane triacrylate.
Preferably, the curing agent is at least one of methyl ethyl ketone peroxide, dibenzoyl peroxide and cyclohexanone peroxide.
Preferably, the accelerator is at least one of dimethylaniline, diethylaniline and dimethyl p-methylaniline.
In a second aspect of the invention, a preparation method of a high-permeability concrete protective material with a shell-like vinyl resin with a simple technological process is provided, which comprises the following steps:
(1) Uniformly dispersing an MXene material in a solvent to obtain an MXene dispersion liquid; regulating the MXene dispersion liquid to be acidic to obtain a mixed phase solution;
(2) Adding a silane coupling agent hydrolysate into the mixed phase solution, and reacting to obtain an MXene reaction solution after the reaction is finished;
(3) Collecting lower-layer sediment and washing sediment of the MXene reaction liquid through centrifugal treatment, circularly operating until supernatant fluid is neutral after centrifugation, collecting final sediment and drying to obtain silane modified MXene material;
(4) Uniformly mixing vinyl resin with a reactive diluent, a curing agent and an accelerator to obtain a resin mixed solution;
(5) Adopting an injection molding process, alternately injecting the resin mixed solution and the silane modified MXene material to the surface of the matrix, and superposing to form a layered structure; the laminated structure is compacted, superfluous resin on the surface of the matrix is removed, and the laminated structure is solidified, so that the high-permeability concrete protective material imitating the vinyl resin with the shell structure is obtained.
Preferably, in the step (1), uniform dispersion of the MXene material in the solvent is achieved by ultrasonic treatment; the temperature of the ultrasonic treatment is 40-60 ℃ and the treatment time is 0.5-2 h.
Preferably, in the step (1), the solvent is an alcohol-water mixture formed by deionized water and absolute ethyl alcohol.
Further preferably, the volume ratio of the ionized water to the absolute ethyl alcohol in the alcohol-water mixed solution is 9:1.
preferably, in the step (1), the pH of the mixed phase solution is 3 to 4.
Preferably, in the step (2), the silane coupling agent hydrolysate is prepared by the following method: adding a silane coupling agent into deionized water and absolute ethyl alcohol according to the volume ratio of 9: in the alcohol-water mixed solution formed by the method 1, the mass ratio of the silane coupling agent to the alcohol-water mixed solution is 1: 1-10, then adjusting the pH value to 3-4, and carrying out hydrolysis reaction for 1-2 h at normal temperature to obtain the silane coupling agent hydrolysate.
Further preferably, the mass ratio of the MXene material to the silane coupling agent is 1:1 to 100.
Preferably, in the step (2), the reaction temperature is 60-100 ℃ and the reaction time is 3-8 h.
Preferably, in the step (5), the layered structure is compacted by vacuum filtration, and the superfluous resin on the surface of the substrate is removed.
The vacuum suction filtration technology is quicker, and can be used for quickly assembling the protective material with a large-area shell-like layered structure. The vacuum filtration can form uniform pressure difference, and the liquid flow is driven to facilitate the layer-by-layer orderly arrangement of the assembled units.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the invention provides a high-permeability concrete protective material imitating shell structure vinyl resin, which has a shell-imitating layered structure and excellent mechanical properties. Meanwhile, the material of the protective material has strong permeability, can penetrate into the concrete to achieve the effect of root planting type deep consolidation, greatly improves the strength, toughness and compactness of the material, and enables the concrete surface layer to form a sealed integral waterproof structure layer.
2. The invention provides a preparation method of a shell-structure-imitated vinyl resin high-permeability concrete protective material, which has the advantages of simple technical process and less addition of silane modified MXene material, and can not have obvious negative influence on the elastic modulus of the cured resin.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
In the following examples, the molar concentration of hydrochloric acid was 1mol/L.
Example 1
A high-permeability concrete protective material imitating shell structure vinyl resin is prepared by the following method:
(1) Ultrasonic treatment is carried out for 1h at 45 ℃ to uniformly disperse 0.3gMAX phase material which is MXene material of two-dimensional transition metal carbide in deionized water and absolute ethyl alcohol according to the volume ratio of 9:1 to obtain an MXene dispersion liquid in 10mL of alcohol-water mixed liquid; adjusting the pH value of the MXene dispersion liquid to 3 by hydrochloric acid to obtain a mixed phase solution;
(2) 30g of silane coupling agent KH550 was added to a mixture of deionized water and absolute ethanol in a volume ratio of 9: in the alcohol-water mixed solution formed by the method 1, the mass ratio of the silane coupling agent to the alcohol-water mixed solution is 1:10, then adjusting the pH value to 3 by hydrochloric acid, carrying out hydrolysis reaction for 1h at normal temperature to obtain silane coupling agent hydrolysis solution, adding the silane coupling agent hydrolysis solution into the mixed phase solution, and reacting at 75 ℃ for 5h to obtain MXene reaction solution after the reaction is finished;
(3) Centrifuging the MXene reaction solution at 4500rpm for 10min, collecting the lower-layer sediment, washing the sediment with absolute ethyl alcohol and deionized water in sequence, circularly operating until the supernatant fluid is neutral after centrifugation, collecting the final sediment, and performing vacuum freeze drying to obtain the silane modified MXene material;
(4) Uniformly mixing 50g of bisphenol A type vinyl resin, 20g of vinyl ether, 2g of methyl ethyl ketone peroxide and 1g of dimethylaniline to obtain a resin mixed solution;
(5) Adopting an injection molding process to alternately inject the resin mixed solution and 3g of silane modified MXene material onto the surface of a substrate, and superposing to form a layered structure, wherein the injection pressure is 0.20MPa, and the injection distance is 3mm; and sequentially laying a demolding cloth, a diversion net, a diversion pipe, a rubber inlet pipe and a vacuum bag on the surface of the matrix after injection molding, sealing the vacuum bag by using sealant, vacuumizing until the pressure in the vacuum bag is minus 0.1MPa, compacting the layered structure, removing redundant resin mixed liquid on the surface of the matrix, and removing the diversion pipe, the diversion net and the vacuum bag by using the demolding cloth after curing at room temperature to obtain the shell-like vinyl resin high-permeability concrete protective material.
Example 2
(1) 1.2g of MXene material of which the MAX phase material is two-dimensional transition metal carbide is uniformly dispersed in deionized water and absolute ethyl alcohol in a volume ratio of 9:1 to obtain an MXene dispersion liquid in 10mL of alcohol-water mixed liquid; adjusting the pH value of the MXene dispersion liquid to 4 by hydrochloric acid to obtain a mixed phase solution;
(2) 30g of silane coupling agent KH550 was added to a mixture of deionized water and absolute ethanol in a volume ratio of 9: in the alcohol-water mixed solution formed by the method 1, the mass ratio of the silane coupling agent to the alcohol-water mixed solution is 1:10, then adjusting the pH value to 4 by hydrochloric acid, carrying out hydrolysis reaction for 1h at normal temperature to obtain silane coupling agent hydrolysis solution, adding the silane coupling agent hydrolysis solution into the mixed phase solution, and reacting at 80 ℃ for 5h to obtain MXene reaction solution after the reaction is finished;
(3) Centrifuging the MXene reaction solution at 4500rpm for 10min, collecting the lower-layer sediment, washing the sediment with absolute ethyl alcohol and deionized water in sequence, circularly operating until the supernatant fluid is neutral after centrifugation, collecting the final sediment, and performing vacuum freeze drying to obtain the silane modified MXene material;
(4) Uniformly mixing 100g of bisphenol A type vinyl resin, 30g of vinyl ether, 3g of methyl ethyl ketone peroxide and 2g of dimethylaniline to obtain a resin mixed solution;
(5) Adopting an injection molding process to alternately inject the resin mixed solution and 5g of silane modified MXene material onto the surface of a substrate, and superposing to form a layered structure, wherein the injection pressure is 0.20MPa, and the injection distance is 3mm; and sequentially laying a demolding cloth, a diversion net, a diversion pipe, a rubber inlet pipe and a vacuum bag on the surface of the matrix after injection molding, sealing the vacuum bag by using sealant, vacuumizing until the pressure in the vacuum bag is minus 0.1MPa, compacting the layered structure, removing redundant resin mixed liquid on the surface of the matrix, and removing the diversion pipe, the diversion net and the vacuum bag by using the demolding cloth after curing at room temperature to obtain the shell-like vinyl resin high-permeability concrete protective material.
Example 3
(1) Ultrasonic treatment is carried out for 1h at 45 ℃ to uniformly disperse 2.5g of MXene material of which the MAX phase material is two-dimensional transition metal carbide in deionized water and absolute ethyl alcohol according to the volume ratio of 9:1 to obtain an MXene dispersion liquid in 10mL of alcohol-water mixed liquid; adjusting the pH value of the MXene dispersion liquid to 4 by hydrochloric acid to obtain a mixed phase solution;
(2) 30g of silane coupling agent KH550 was added to a mixture of deionized water and absolute ethanol in a volume ratio of 9: in the alcohol-water mixed solution formed by the method 1, the mass ratio of the silane coupling agent to the alcohol-water mixed solution is 1:10, then adjusting the pH value to 4 by hydrochloric acid, carrying out hydrolysis reaction for 1h at normal temperature to obtain silane coupling agent hydrolysis solution, adding the silane coupling agent hydrolysis solution into the mixed phase solution, and reacting at 80 ℃ for 5h to obtain MXene reaction solution after the reaction is finished;
(3) Centrifuging the MXene reaction solution at 4500rpm for 10min, collecting the lower-layer sediment, washing the sediment with absolute ethyl alcohol and deionized water in sequence, circularly operating until the supernatant fluid is neutral after centrifugation, collecting the final sediment, and performing vacuum freeze drying to obtain the silane modified MXene material;
(4) Uniformly mixing 140g of bisphenol A type vinyl resin, 40g of vinyl ether, 4g of methyl ethyl ketone peroxide and 2g of dimethyl p-toluidine to obtain a resin mixed solution;
(5) Adopting an injection molding process to alternately inject the resin mixed solution and 5g of silane modified MXene material onto the surface of a substrate, and superposing to form a layered structure, wherein the injection pressure is 0.20MPa, and the injection distance is 3mm; and sequentially laying a demolding cloth, a diversion net, a diversion pipe, a rubber inlet pipe and a vacuum bag on the surface of the matrix after injection molding, sealing the vacuum bag by using sealant, vacuumizing until the pressure in the vacuum bag is minus 0.1MPa, compacting the layered structure, removing redundant resin mixed liquid on the surface of the matrix, and removing the diversion pipe, the diversion net and the vacuum bag by using the demolding cloth after curing at room temperature to obtain the shell-like vinyl resin high-permeability concrete protective material.
Example 4
A high-permeability concrete protective material imitating shell structure vinyl resin is prepared by the following method:
(1) Uniformly dispersing 0.3gMAX phase material which is MXene material of two-dimensional transition metal nitride in deionized water and absolute ethyl alcohol in a volume ratio of 9:1 to obtain an MXene dispersion liquid in 10mL of alcohol-water mixed liquid; adjusting the pH value of the MXene dispersion liquid to 3 by hydrochloric acid to obtain a mixed phase solution;
(2) 0.3g of silane coupling agent KH560 was added to a mixture of deionized water and absolute ethanol in a volume ratio of 9: in the alcohol-water mixed solution formed by the method 1, the mass ratio of the silane coupling agent to the alcohol-water mixed solution is 1:1, then adjusting the pH value to 3 by hydrochloric acid, and carrying out hydrolysis reaction for 2 hours at normal temperature to obtain silane coupling agent hydrolysis solution, adding the silane coupling agent hydrolysis solution into the mixed phase solution, and reacting at 60 ℃ for 8 hours to obtain MXene reaction solution after the reaction is finished;
(3) Centrifuging the MXene reaction solution at 4500rpm for 10min, collecting the lower-layer sediment, washing the sediment with absolute ethyl alcohol and deionized water in sequence, circularly operating until the supernatant fluid is neutral after centrifugation, collecting the final sediment, and performing vacuum freeze drying to obtain the silane modified MXene material;
(4) Uniformly mixing 90g of bisphenol A type vinyl resin with 20g of styrene, 1g of dibenzoyl peroxide and 0.1g of diethylaniline to obtain a resin mixed solution;
(5) Adopting an injection molding process to alternately inject the resin mixed solution and 1g of silane modified MXene material onto the surface of a substrate, and superposing to form a layered structure, wherein the injection pressure is 0.20MPa, and the injection distance is 3mm; and sequentially laying a demolding cloth, a diversion net, a diversion pipe, a rubber inlet pipe and a vacuum bag on the surface of the matrix after injection molding, sealing the vacuum bag by using sealant, vacuumizing until the pressure in the vacuum bag is minus 0.1MPa, compacting the layered structure, removing redundant resin mixed liquid on the surface of the matrix, and removing the diversion pipe, the diversion net and the vacuum bag by using the demolding cloth after curing at room temperature to obtain the shell-like vinyl resin high-permeability concrete protective material.
Example 5
A high-permeability concrete protective material imitating shell structure vinyl resin is prepared by the following method:
(1) Ultrasonic treatment is carried out for 0.5h at 60 ℃ to uniformly disperse 0.3g of MXene material of which the MAX phase material is two-dimensional transition metal carbonitride in deionized water and absolute ethyl alcohol according to the volume ratio of 9:1 to obtain an MXene dispersion liquid in 10mL of alcohol-water mixed liquid; adjusting the pH value of the MXene dispersion liquid to 3 by hydrochloric acid to obtain a mixed phase solution;
(2) 30g of silane coupling agent KH550 was added to a mixture of deionized water and absolute ethanol in a volume ratio of 9: in the alcohol-water mixed solution formed by the method 1, the mass ratio of the silane coupling agent to the alcohol-water mixed solution is 1:1, then adjusting the pH value to 3 by hydrochloric acid, carrying out hydrolysis reaction for 2 hours at normal temperature to obtain silane coupling agent hydrolysis solution, adding the silane coupling agent hydrolysis solution into the mixed phase solution, and reacting at 100 ℃ for 3 hours to obtain MXene reaction solution after the reaction is finished;
(3) Centrifuging the MXene reaction solution at 4500rpm for 10min, collecting the lower-layer sediment, washing the sediment with absolute ethyl alcohol and deionized water in sequence, circularly operating until the supernatant fluid is neutral after centrifugation, collecting the final sediment, and performing vacuum freeze drying to obtain the silane modified MXene material;
(4) Uniformly mixing 100g of bisphenol A type vinyl resin with 50g of alpha-methylstyrene, 5g of cyclohexanone peroxide and 3g of dimethyl para-methylaniline to obtain a resin mixed solution;
(5) Adopting an injection molding process to alternately inject the resin mixed solution and 10g of silane modified MXene material onto the surface of a substrate, and superposing to form a layered structure, wherein the injection pressure is 0.20MPa, and the injection distance is 3mm; and sequentially laying a demolding cloth, a diversion net, a diversion pipe, a rubber inlet pipe and a vacuum bag on the surface of the matrix after injection molding, sealing the vacuum bag by using sealant, vacuumizing until the pressure in the vacuum bag is minus 0.1MPa, compacting the layered structure, removing redundant resin mixed liquid on the surface of the matrix, and removing the diversion pipe, the diversion net and the vacuum bag by using the demolding cloth after curing at room temperature to obtain the shell-like vinyl resin high-permeability concrete protective material.
Example 6
This example is substantially identical to example 1, except that the reactive diluent employed in this example is methyl methacrylate.
Example 7
This example is substantially identical to example 1, except that the reactive diluent used in this example is hydroxyethyl methacrylate.
Example 8
This example is substantially identical to example 1, except that the reactive diluent employed in this example is hydroxypropyl methacrylate.
Example 9
This example is substantially identical to example 1 except that the reactive diluent employed in this example is trimethylolpropane triacrylate.
Test example 1
According to GB/T2567-2021 method for testing the performance of a resin casting body, the mechanical properties of a high-permeability concrete protective material imitating vinyl resin with a shell structure are tested; in the penetration depth test, a sample block is cut, and the sample block is observed and measured under a microscope to obtain the penetration depth. The processes of examples 1-3 were used for sample preparation and testing according to the standard or method described above. Bisphenol A vinyl resin without silane modified MXene material is used as blank control, the blank control is prepared by mixing and curing 100g bisphenol A vinyl resin with 30g vinyl ether, 2g methyl ethyl ketone peroxide and 1g dimethylbenzene para-methylaniline, and the corresponding test results are shown in table 1.
As can be seen from the test results in Table 1, the mechanical properties and the permeability of the examples of the present invention are superior to those of the blank. The high-permeability concrete protective material of the shell-like vinyl resin has excellent mechanical properties, and the MXene material can realize the mechanical property modification of the resin under the condition of low addition due to the unique high specific surface area, good mechanical properties and other factors, so that the prepared protective material has better mechanical properties compared with common resin. The shell-like layered structure is formed, so that the mechanical property is further improved, and the method has a good application prospect.
The foregoing describes in detail preferred embodiments of the present invention. It should be understood that numerous modifications and variations can be made in accordance with the concepts of the invention by one of ordinary skill in the art without undue burden. Therefore, all technical solutions which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the person skilled in the art according to the inventive concept shall be within the scope of protection defined by the claims.
Claims (10)
1. The shell-structure-imitated vinyl resin high-permeability concrete protective material is characterized by comprising the following raw materials: vinyl resin, reactive diluent, curing agent, accelerator, silane modified MXene material; the protective material has a shell-like layered structure formed by alternately superposing and solidifying vinyl resin and a silane modified MXene material, wherein the silane modified MXene material is prepared by grafting a silane coupling agent on the MXene material.
2. The high-permeability concrete protective material of shell-like vinyl resin according to claim 1, wherein: 90-100 parts of vinyl resin, 20-50 parts of reactive diluent, 1-5 parts of curing agent, 0.1-3 parts of accelerator and 1-10 parts of silane modified MXene material.
3. The high-permeability concrete protective material of shell-like vinyl resin according to claim 1, wherein: the vinyl resin is bisphenol A type vinyl resin; in the MXene material, the MAX phase material is at least one of two-dimensional transition metal carbide, transition metal nitride and transition metal carbonitride; the silane coupling agent is at least one of a silane coupling agent KH550 and a silane coupling agent KH 560; the reactive diluent is at least one of vinyl ether, styrene, alpha-methylstyrene, methyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and trimethylolpropane triacrylate; the curing agent is at least one of methyl ethyl ketone peroxide, dibenzoyl peroxide and cyclohexanone peroxide; the accelerator is at least one of dimethylaniline, diethylaniline and dimethyl-p-methylaniline.
4. A method for preparing the shell-like vinyl resin-based high-permeability concrete protective material according to claim 1, comprising the steps of:
(1) Uniformly dispersing an MXene material in a solvent to obtain an MXene dispersion liquid; regulating the MXene dispersion liquid to be acidic to obtain a mixed phase solution;
(2) Adding a silane coupling agent hydrolysate into the mixed phase solution, and reacting to obtain an MXene reaction solution after the reaction is finished;
(3) Collecting lower-layer sediment and washing sediment of the MXene reaction liquid through centrifugal treatment, circularly operating until supernatant fluid is neutral after centrifugation, collecting final sediment and drying to obtain silane modified MXene material;
(4) Uniformly mixing vinyl resin with a reactive diluent, a curing agent and an accelerator to obtain a resin mixed solution;
(5) Adopting an injection molding process, alternately injecting the resin mixed solution and the silane modified MXene material to the surface of the matrix, and superposing to form a layered structure; the laminated structure is compacted, superfluous resin on the surface of the matrix is removed, and the laminated structure is solidified, so that the high-permeability concrete protective material imitating the vinyl resin with the shell structure is obtained.
5. The method of manufacturing according to claim 4, wherein: in the step (1), uniform dispersion of the MXene material in the solvent is realized by ultrasonic treatment; the temperature of the ultrasonic treatment is 40-60 ℃ and the treatment time is 0.5-2 h.
6. The method of manufacturing according to claim 4, wherein: in the step (1), the solvent is an alcohol-water mixed solution formed by deionized water and absolute ethyl alcohol; the pH of the mixed phase solution is 3-4.
7. The method according to claim 4, wherein in the step (2), the silane coupling agent hydrolysate is prepared by the following method: adding a silane coupling agent into deionized water and absolute ethyl alcohol according to the volume ratio of 9: in the alcohol-water mixed solution formed by the method 1, the mass ratio of the silane coupling agent to the alcohol-water mixed solution is 1: 1-10, then adjusting the pH value to 3-4, and carrying out hydrolysis reaction for 1-2 h at normal temperature to obtain the silane coupling agent hydrolysate.
8. The method of manufacturing according to claim 7, wherein: the mass ratio of the MXene material to the silane coupling agent is 1:1 to 100.
9. The method of manufacturing according to claim 4, wherein: in the step (2), the reaction temperature is 60-100 ℃ and the reaction time is 3-8 h.
10. The method of manufacturing according to claim 4, wherein: in the step (5), the layered structure is compacted by vacuum filtration, and the superfluous resin on the surface of the substrate is removed.
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