CN115124874A - Back water surface anti-permeability coating and preparation method thereof - Google Patents
Back water surface anti-permeability coating and preparation method thereof Download PDFInfo
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- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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Abstract
The invention relates to the field of coatings, in particular to a back water surface anti-permeability coating and a preparation method thereof. The raw materials of the impervious coating on the back water surface comprise aqueous epoxy emulsion, modified filler and auxiliary agent. By adding the water-soluble epoxy resin, the chain acid and the chain ester and controlling the proportion of the water-soluble epoxy resin, the chain acid and the chain ester, the obtained water-soluble epoxy emulsion has excellent performance, the water solubility is obviously improved, and is not a gelatinous substance, and when the water-soluble epoxy emulsion is used in a coating system, the hardness is high, the impact toughness is good, and the water-soluble epoxy emulsion can be kept in a stable state for a long time; the performance and yield of a product system are improved, the GO and RGO are doped with Ce or Ti metal elements by a specific preparation method, the hardness and brittleness of the obtained coating can be further improved, the adhesion and corrosion resistance of the coating are improved, particularly the water resistance and the acid and alkali resistance are improved, and the corrosion resistance time of the coating is prolonged.
Description
Technical Field
The invention relates to the field of coatings, in particular to a back water surface anti-permeability coating and a preparation method thereof.
Background
Epoxy resins (EP) have been one of the most widely used coating substrates at present due to their excellent properties, but also suffer from disadvantages such as high brittleness, poor toughness and short corrosion protection time.
Patent No. CN108276737B provides a modified carbon nanotube toughened epoxy resin composite material and a preparation method thereof, which modifies the surface of carbon nanotubes and improves the tensile strength and flexural modulus of epoxy resin. The patent No. CN112980145B provides a thermosetting polyester amide modified nano CaCO 3 The toughened epoxy resin and the preparation method thereof graft nano calcium carbonate and polyesteramide, thereby improving the toughness of the epoxy resin.
In the prior art, epoxy resin is modified by nano-filler, and as a two-dimensional lamellar nano-material, Graphene Oxide (GO) has a large number of active functional groups on the surface, has good mechanical properties and chemical stability, and is paid much attention to in the field of composite materials. However, factors such as huge specific surface area and intermolecular van der waals forces reduce the dispersibility of GO, affecting its further applications.
Disclosure of Invention
In order to solve the above problems, a first aspect of the present invention provides a backside surface anti-permeation coating, which comprises raw materials including an aqueous epoxy emulsion, a modified filler and an auxiliary agent.
In a preferred embodiment of the present invention, the raw materials of the aqueous epoxy emulsion include water-soluble epoxy resin, chain acid, chain ester, and aromatic compound.
Preferably, the raw materials of the water-based epoxy emulsion comprise 55-67 parts by weight of water-soluble epoxy resin, 17-23 parts by weight of chain type acid, 8-11 parts by weight of chain type ester and 5-10 parts by weight of aromatic compound.
Further preferably, the raw materials of the aqueous epoxy emulsion comprise 63 parts of water-soluble epoxy resin, 20 parts of chain acid, 10 parts of chain ester and 7 parts of aromatic compound by weight.
Preferably, the water-soluble epoxy resin has an epoxy value of 0.15 to 0.23eq/100g and a softening point of 60 to 82 ℃.
As a preferable technical scheme of the invention, the water-soluble epoxy resin is selected from one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin and alicyclic polyepoxy compound.
As a preferable technical scheme of the invention, the molecular weight of the chain type acid is 70-110.
Preferably, the chain acids have a molecular weight of 80 to 90.
More preferably, the chain acid is methacrylic acid, molecular weight 86.
As a preferred technical scheme of the invention, the density of the chain ester is 0.7-1.1 g/mL.
Preferably, the chain ester has a density of 0.894g/mL and the chain ester is n-butyl acrylate.
In order to overcome the technical problem that bisphenol a epoxy resin is easily emulsified due to its low molecular weight when used in a coating material, and the resultant coating material has high hardness but high brittleness, the applicant has found through a large number of experiments that not only the aqueous epoxy emulsion obtained is excellent in performance and remarkably improved in water solubility, but also is not a gel-like substance, by adding a specific water-soluble epoxy resin, a chain acid and a chain ester and controlling the ratio thereof, but also when used in a coating material system, the hardness is high, the impact toughness is good, and a stable state can be maintained for a long period of time. The applicant conjectures that the carboxyl active site of the chain acid and the resin chain generate better crosslinking under the action of an initiator, and meanwhile, the chain ester with the density of 0.894g/mL has influence on the fluidity of the system, and the effect of free radical polymerization is improved, so that the crosslinking network is more compact.
Preferably, the raw materials of the aqueous epoxy emulsion further comprise an initiator.
Further preferably, the initiator is Benzoyl Peroxide (BPO).
Preferably, the weight of the initiator is 5.9% to 8.5% of the water-soluble epoxy resin.
In the preparation of aqueous epoxy emulsions, it is often necessary to add an initiator to increase the efficiency of the reaction, and then the resulting product may carry entangled initiator molecules due to the addition of the initiator, resulting in a decrease in the performance and yield of the product system. The problem is remarkably improved by controlling the adding weight of the initiator to be 5.9-8.5% of that of the water-soluble epoxy resin, and particularly, the effect is remarkable when the adding weight of the initiator is 7% of that of the water-soluble epoxy resin. The addition of a specific amount of initiator enables the density of the system to be improved, thus affecting the dispersibility, leading to a change in the cross-linked network, and at the same time interacting with the modified nanofiller, the entanglement carryover of the initiator is improved.
The aromatic compound is styrene.
As a preferable technical scheme of the invention, the modified filler is modified silica and/or modified carbon nano material.
As a preferable technical solution of the present invention, when the modified filler is a modified carbon nanomaterial, the modified carbon nanomaterial is Graphene Oxide (GO) or metal-doped Reduced Graphene Oxide (RGO), and the graphene oxide includes metal-doped graphene oxide.
Preferably, the metal is selected from one or more of titanium, cerium and calcium.
Preferably, the metal is titanium or cerium.
When the modified filler is a modified carbon nanomaterial, the modified carbon nanomaterial is titanium-doped graphene oxide (Ti-GO).
The preparation method of the titanium-doped graphene oxide comprises the following steps: (1) preparation of GO aqueous suspension: mixing GO powder with deionized water, and performing ultrasonic treatment for 20-30min to make the concentration of GO suspension water solution be 0.8-1.2 g/L; (2) preparation of precursor liquid: adding 1-2mL of butyl titanate into 15-25mL of absolute ethyl alcohol, and stirring for 15-25 min; (3) preparing a prefabricated liquid: the precursor liquid is dripped into 100-150mLGO suspension water solution, and the dripping speed is controlled to be 1-2 mL/min; (4) aging: aging at room temperature for 20-40min to obtain gel; (5) and (3) calcining: and drying the gel at 70-78 ℃ for 8-10h to obtain a solid, grinding the solid into powder, and calcining the powder at 355-370 ℃ for 1.5-2h to obtain the titanium-doped graphene oxide (Ti-GO).
When the modified filler is a modified carbon nano material, the modified carbon nano material is titanium-doped reduced graphene oxide (TiO) 2 -RGO）。
Titanium doped reduced graphene oxide (TiO) 2 -RGO) is prepared by: (1) preparation of a GO ethanol solution: taking 0.1-0.15g of GO powder, mixing with 120mL of 100-one-dose anhydrous ethanol, and carrying out ultrasonic treatment for 20-30 min; (2) preparing titanium sulfate alcoholic solution: adding 0.8-1.2g of titanium sulfate into 80-100mL of absolute ethyl alcohol, and carrying out ultrasonic treatment for 20-30 min; (3) hydrothermal reaction: adding a GO ethanol solution into a titanium sulfate alcohol solution, controlling the dropping speed of the GO ethanol solution to be 2-4mL/min, adding 0.8-1.5g of ascorbic acid, carrying out ultrasonic treatment for 30-50min to obtain a yellow-brown liquid, placing the yellow-brown liquid in a reaction kettle, reacting at the temperature of 190 ℃ for 240 ℃ for 1-7h, and cooling and taking out the yellow-brown liquid; (4) centrifugal filtration: centrifuging at 800r/min under 500 ℃ and filtering, washing filter residue with 300mL of anhydrous ethanol and 300mL of deionized water, and drying at 50-60 ℃ for 12-24h to obtain titanium-doped reduced graphene oxide (TiO) 2 -RGO）。
When the modified filler is a modified carbon nano material, the modified carbon nano material is reduced graphene oxide (CeO) doped with cerium 2 -RGO）。
Cerium doped reduced graphene oxide (CeO) 2 RGO) with TiO 2 Preparation of-RGO is the same as for TiO 2 The preparation method of the RGO is different in that titanium sulfate is replaced by cerium nitrate, and the temperature of the hydrothermal reaction is 740-760℃。
As a preferable technical scheme, when the modified filler is modified silicon dioxide and a modified carbon nano material, the modified carbon nano material is acidified graphene oxide.
Preferably, when the modified filler is modified silica and a modified carbon nanomaterial, the GO and the nano silica are simultaneously modified by a silane coupling agent and phosphoric acid.
The GO and the RGO are doped with Ce or Ti metal elements by a specific preparation method, so that the hardness and brittleness of the obtained coating can be further improved, the adhesion force and corrosion resistance of the coating are improved, particularly, the water resistance and the acid and alkali resistance are improved, and the corrosion resistance time of the coating is prolonged. The reason is probably that the specific metal is doped into the carbon network of GO and RGO, and when the aqueous epoxy emulsion provided by the invention is combined with epoxy resin, the agglomeration of the carbon nano material and the epoxy resin can be inhibited, so that the mixing of the two substances is enhanced, the mixed network is more compact, and the obtained coating is more stable and has better performance.
The preparation method of the acidified graphene oxide (PGO) comprises the following steps: adding 0.4-0.6gGO powder and 0.3-1g of silane coupling agent into 30-35mL of concentrated phosphoric acid, reacting at 45-50 ℃ for 60-80min, carrying out suction filtration on the reacted mixed liquid, washing the filter residue with deionized water until the pH of the washed washing liquid is =7, and drying the filter residue at 60 ℃ to obtain PGO.
The preparation method of the modified silicon dioxide is the same as that of PGO, and the difference is that GO powder is replaced by nano silicon dioxide powder.
When the modified filler is modified silicon dioxide and a modified carbon nano material, the weight ratio of the modified silicon dioxide to the modified carbon nano material in the modified filler is (1.8-2.4): (1.3-1.7).
More preferably, when the modified filler is modified silica and a modified carbon nanomaterial, the weight ratio of the modified silica to the modified carbon nanomaterial in the modified filler is 2: 1.5.
in graphene oxide/waterborne epoxy (GO/EP) composite coatings, GO is uniformly dispersed within the epoxy matrix and forms covalent crosslinks between the GO and EP matrices. Along with the increase of GO mass fraction, the wetting angle of the surface of the concrete test block coated with the composite coating is increased and then reduced.
As a preferable technical scheme, the auxiliary agent comprises a defoaming agent, a dispersing agent and a film-forming auxiliary agent.
Preferably, the weight ratio of the defoaming agent to the dispersing agent to the film-forming assistant is (1.7-3): (1.5-3): (4-8).
Further preferably, the weight ratio of the defoamer to the dispersant to the film-forming aid is 1.9: 1.8: 4.2.
preferably, the raw materials of the back water impervious coating comprise 24-28 parts of aqueous epoxy emulsion, 1-7 parts of modified filler and 12-18 parts of auxiliary agent in parts by weight.
The second aspect of the invention provides a preparation method of a back surface anti-permeability coating, which is used for preparing the back surface anti-permeability coating and comprises the following steps: (1) preparation of the aqueous epoxy emulsion: adding water-soluble epoxy resin into a mixed solution consisting of alcohol and ether, heating to 100 ℃, adding chain acid, chain ester and aromatic compound in a nitrogen atmosphere, and reacting for 5.8-6.3h to obtain a water-based epoxy emulsion; (2) preparing a modified filler; (3) preparing the water-based paint: stirring and mixing the water-based epoxy emulsion, the modified filler and the auxiliary agent to obtain the water-based paint.
The step (1) is specifically to add bisphenol A epoxy resin into a mixed solution composed of n-butyl alcohol and ethylene glycol butyl ether (the weight ratio of the n-butyl alcohol to the ethylene glycol butyl ether in the mixed solution is (0.9-1.2): 1), heat the mixed solution to 100 ℃, add methacrylic acid, n-butyl acrylate and styrene in the nitrogen atmosphere, and react for 5.8-6.3h to obtain the water-based epoxy emulsion.
Compared with the prior art, the invention has the following beneficial effects:
by adding the water-soluble epoxy resin, the chain acid and the chain ester and controlling the proportion of the water-soluble epoxy resin, the chain acid and the chain ester, the obtained water-soluble epoxy emulsion has excellent performance, the water solubility is obviously improved, and is not a gelatinous substance, and when the water-soluble epoxy emulsion is used in a coating system, the hardness is high, the impact toughness is good, and the water-soluble epoxy emulsion can be kept in a stable state for a long time; the addition weight of the initiator is controlled to be 5.9-8.5% of that of the water-soluble epoxy resin, so that the performance and yield of a product system are improved, the GO and the RGO are doped with Ce or Ti metal elements by a specific preparation method, the hardness and brittleness of the obtained coating can be further improved, the adhesion force and corrosion resistance of the coating are improved, particularly the water resistance and the acid and alkali resistance are improved, and the corrosion resistance time of the coating is prolonged. All substances of the whole system act together, so that the corrosion resistance and the impermeability of the coating are improved, and the performances are particularly obvious when the coating is applied to the surface of a concrete material.
Detailed Description
Examples
The raw materials for preparing the composition in the embodiment are all commercially available, wherein the bisphenol A type epoxy resin in the embodiment 1 and the embodiment 6 are different in source, the bisphenol A type epoxy resin in the embodiment 1 is purchased from Jining Baoyi chemical Co., Ltd, the mark is E-20, the epoxy value is 0.18-0.22eq/100g, and the softening point is 64-76 ℃; in example 6, bisphenol a epoxy resin was purchased from kning birch-yi chemical limited, trade name E-12, epoxy value 0.09-0.14eq/100g, softening point 85-95 ℃, defoamer was purchased from a new material of haideng, CAS number 126-73-8, dispersant was purchased from xin chemical, model number 5040, film forming aid was purchased from cheng rui, CAS number 5131-66-8, GO was purchased from hexagong graphite limited, absolute ethanol was purchased from langxiang chemical limited, nanchang city, ethanol content was 95wt%, nano silica was purchased from richly mineral products limited, east sea county, silane coupling agent was purchased from science and technology limited, dennan ying chemical, model number KH 550.
Example 1
The embodiment provides a back surface anti-permeability coating, and the raw materials of the back surface anti-permeability coating comprise 26 parts of aqueous epoxy emulsion, 6 parts of modified filler and 15 parts of auxiliary agent in parts by weight.
The raw materials of the water-based epoxy emulsion comprise water-soluble epoxy resin, chain acid, chain ester and aromatic compound.
The raw materials of the water-based epoxy emulsion comprise 63 parts of water-soluble epoxy resin, 20 parts of chain acid, 10 parts of chain ester and 7 parts of aromatic compound by weight.
The water-soluble epoxy resin is bisphenol A type epoxy resin. The chain acid was methacrylic acid, molecular weight 86. The chain ester had a density of 0.894g/mL and was n-butyl acrylate.
The raw materials of the aqueous epoxy emulsion also comprise an initiator.
The initiator is Benzoyl Peroxide (BPO).
The weight of the initiator is 7% of the water-soluble epoxy resin.
The modified filler is a modified carbon nanomaterial, and the modified carbon nanomaterial is titanium-doped graphene oxide (Ti-GO).
The preparation method of the titanium-doped graphene oxide comprises the following steps: (1) preparation of GO aqueous suspension: mixing GO powder with deionized water, and performing ultrasonic treatment for 25min to make the concentration of GO suspension water solution be 1 g/L; (2) preparation of precursor liquid: adding 1.5mL of butyl titanate into 25mL of absolute ethyl alcohol, and stirring for 20 min; (3) preparing a prefabricated liquid: the precursor liquid is dripped into 130mLGO suspension water solution, and the dripping speed is controlled to be 1 mL/min; (4) aging: aging at room temperature for 30min to obtain gel; (5) and (3) calcining: and drying the gel at 75 ℃ for 10h to obtain a solid, grinding the solid into powder, and calcining the powder at 360 ℃ for 1.8h to obtain the titanium-doped graphene oxide (Ti-GO).
The auxiliary agent comprises a defoaming agent, a dispersing agent and a film-forming auxiliary agent.
The weight ratio of the defoaming agent to the dispersing agent to the film-forming assistant is 1.9: 1.8: 4.2.
the embodiment also provides a preparation method of the impervious coating on the back water surface, which comprises the following steps: (1) preparation of aqueous epoxy emulsion: adding water-soluble epoxy resin into a mixed solution consisting of alcohol and ether, heating to 100 ℃, adding chain acid, chain ester and aromatic compound in a nitrogen atmosphere, and reacting for 5.8-6.3h to obtain a water-based epoxy emulsion; (2) preparing modified filler; (3) preparation of the water-based paint: stirring and mixing the water-based epoxy emulsion, the modified filler and the auxiliary agent to obtain the water-based paint.
Specifically, in the step (1), 5g of bisphenol A epoxy resin is added into 250mL of a mixed solution consisting of n-butyl alcohol and ethylene glycol butyl ether (the weight ratio of n-butyl alcohol to ethylene glycol butyl ether in the mixed solution is 0.9: 1), the temperature is raised to 100 ℃, methacrylic acid, n-butyl acrylate and styrene are added under the nitrogen atmosphere, and the reaction is carried out for 6 hours, so as to obtain the water-based epoxy emulsion.
Example 2
The embodiment provides a back water surface anti-permeability coating, which is different from the embodiment 1 in that the modified filler is a modified carbon nano material, and the modified carbon nano material is reduced graphene oxide (TiO) doped with titanium 2 -RGO）。
Titanium doped reduced graphene oxide (TiO) 2 -RGO) is prepared by: (1) preparing a GO ethanol solution: taking 0.13g of GO powder, mixing with 110mL of absolute ethyl alcohol, and carrying out ultrasonic treatment for 25 min; (2) preparing titanium sulfate alcoholic solution: adding 1.1g of titanium sulfate into 90mL of absolute ethyl alcohol, and carrying out ultrasonic treatment for 25 min; (3) hydrothermal reaction: adding a GO ethanol solution into a titanium sulfate alcohol solution, controlling the dropping speed of the GO ethanol solution to be 3mL/min, adding 1.1g of ascorbic acid, performing ultrasonic treatment for 50min to obtain a yellow-brown liquid, placing the yellow-brown liquid in a reaction kettle, reacting for 6h at 230 ℃, cooling and taking out; (4) centrifugal filtration: centrifuging at 600r/min, filtering, washing the filter residue with 300mL of anhydrous ethanol and 300mL of deionized water, and drying at 55 ℃ for 12h to obtain titanium-doped reduced graphene oxide (TiO) 2 -RGO）。
This example also provides a method of preparing an impervious coating on a backside surface, similar to example 1.
Example 3
The present example provides a back water anti-permeability coating, which is different from example 2 in that the modified filler is a modified carbon nanomaterial, and the modified carbon nanomaterial is reduced graphene oxide (CeO) doped with cerium 2 -RGO). Titanium sulfate is replaced by cerium nitrate, and the temperature of the hydrothermal reaction is 750 ℃.
This example also provides a method for preparing an impervious coating on a backside surface, similar to example 1.
Example 4
The embodiment provides a back water anti-permeability coating, and is different from embodiment 1 in that the modified filler is a modified carbon nano material, and the modified carbon nano material is Graphene Oxide (GO).
This example also provides a method for preparing an impervious coating on a backside surface, similar to example 1.
Example 5
The present example provides a backside surface anti-permeability coating, which is different from example 1 in that the raw materials of the backside surface anti-permeability coating comprise 25 parts of aqueous epoxy emulsion, 4 parts of modified filler and 15 parts of auxiliary agent.
The modified filler is modified silicon dioxide and a modified carbon nano material, and the modified carbon nano material is acidified graphene oxide.
The modified filler is modified silicon dioxide and a modified carbon nano material, and GO and the nano silicon dioxide are simultaneously modified by a silane coupling agent and phosphoric acid.
The preparation method of the acidified graphene oxide (PGO) comprises the following steps: adding 0.5gGO powder and 0.8g of silane coupling agent into 33mL of concentrated phosphoric acid, reacting at 48 ℃ for 70min, carrying out suction filtration on the mixed liquid after reaction, washing the filter residue with deionized water until the pH of the washing liquid is =7, and drying the filter residue at 60 ℃ to obtain PGO.
The preparation method of the modified silicon dioxide is the same as that of the PGO, except that GO powder is replaced by nano silicon dioxide powder.
In the modified filler, the weight ratio of the modified silicon dioxide to the modified carbon nano material is 2: 1.5.
this example also provides a method for preparing an impervious coating on a backside surface, similar to example 1.
Example 6
This example provides a backside water-barrier coating, which is different from example 1 in that the raw materials of the aqueous epoxy emulsion include 60 parts of water-soluble epoxy resin, 18 parts of chain acid, 9 parts of chain ester and 7 parts of aromatic compound.
The water-soluble epoxy resin is bisphenol A type epoxy resin. The origin of bisphenol a type epoxy resins varies.
This example also provides a method for preparing an impervious coating on a backside surface, similar to example 1.
Example 7
This example provides a backside anti-permeability coating that differs from example 1 in that the aqueous epoxy emulsion comprises 61 parts water-soluble epoxy resin, 20 parts chain acid, 11 parts chain ester, and 9 parts aromatic compound.
The raw materials of the water-based epoxy emulsion also comprise an initiator. The initiator is Benzoyl Peroxide (BPO). The weight of the initiator was 9% of the water-soluble epoxy resin.
This example also provides a method for preparing an impervious coating on a backside surface, similar to example 1.
Example 8
The embodiment provides a backside surface anti-permeability coating, which is different from the embodiment 5 in that in the modified filler, the weight ratio of the modified silicon dioxide to the modified carbon nano material is 4: 1.
this example also provides a method for preparing an impervious coating on a backside surface, similar to example 1.
Example 9
This example provides a backside anti-permeability coating that differs from example 3 in that the aqueous epoxy emulsion comprises 59 parts water soluble epoxy resin, 19 parts chain acid, 10 parts chain ester, and 8 parts aromatic compound.
When the filler is prepared, the temperature of the hydrothermal reaction is 600 ℃, and the reaction time is 10 hours.
And (3) performance testing:
1. atomic force microscopy test (AFM): Ti-GO prepared in example 1 and TiO prepared in example 2 2 AFM tests carried out on RGO show that the interlayer spacing of Ti-GO is increased to 1.02nm compared with that of GO with 0.81nm, and TiO is added 2 The sheet spacing of the RGO composite increased to 1.22nm, the state was more dispersed. The loading of the metal nanoparticles is shown to convert the multilayer close-packed structure of the graphene oxide into a thin-layer loose structure.
2. And (3) testing a settlement experiment: example 1-5g of each water-based paint obtained in the step 9 is put into 500mL of 4wt% NaCl solution, whether layering dispersion occurs or not is observed on the 7 th day and the 70 th day, the results are shown in the table 1, and when a sedimentation experiment is carried out to the 7 th day, GO/EP sedimentation layering dispersion is carried out, and Ti-GO/EP and TiO are carried out 2 RGO/EP remained without delamination and dispersion at 70 days of experiment. Combining the electron microscope scanning result of the fracture surface, Ti-GO and TiO can be obtained 2 RGO exhibits excellent dispersibility and compatibility in epoxy resins.
TABLE 1
3. Electrochemical workstation testing: electrochemical tests are carried out on the water-based paint obtained in the example 1 and the example 4 by using an electrochemical workstation, and the results show that after the soaking for 192 hours, the Ti-GO/EP reaches the middle corrosion stage, the impedance modulus value of the low-frequency region is higher than that of the GO/EP by one order of magnitude, and the water-based paint has excellent corrosion resistance.
4. Salt spray experiment test: salt spray tests were performed on the water-based paints obtained in examples 1-9 according to ISO9227-2012, and the water-based paints were tested for corrosion propagation after 168h of salt spray tests, the results are shown in Table 2, and Ti-GO/EP and TiO compounds after 168h of salt spray tests 2 The RGO/EP composite coating has only 1 mm of corrosion spread at the cross-cut, which is better than the GO/EP coating. This indicates that Ti-GO and TiO 2 The RGO/EP has good compatibility with epoxy resin, and can form a labyrinth effect to prevent the penetration of corrosive media, prolong the invasion path of the corrosive media and reduce the corrosion speed.
TABLE 2
5. And (3) testing mechanical properties: the water-based paint obtained in examples 1-9 was subjected to mechanical property test, friction coefficient test by a friction coefficient tester, adhesion test according to GB/T9286-88, impact resistance test according to GB/T1732-93, and hardness test according to GB/T6739-Test results are shown in Table 3, and mechanical property studies show that Ti-GO/EP and TiO 2 The RGO/EP composite coating can resist the impact of 30kg/cm compared with pure EP, Ti-GO/EP and TiO 2 The grade difference of the adhesion force of the RGO/EP composite coating before and after boiling is improved by 4 grades; the average friction coefficient of Ti-GO/EP is reduced by 0.34; the prepared modified GO compound effectively improves the mechanical property of the coating. This indicates that Ti-GO and TiO 2 The RGO can play a role in supporting, lubricating and heat conducting on the surface of the coating, and plays a role in matrix yield effect, pinning-crack effect and two-phase interface effect in the coating, so that the strength, toughness and wear resistance of the coating are improved.
TABLE 3
6. Water contact angle test: in graphene oxide/waterborne epoxy (GO/EP) composite coatings, GO is uniformly dispersed within the epoxy matrix and forms covalent crosslinks between the GO and EP matrices. The action mechanism of GO on the coating is to block the medium from invading the coating through the physical barrier effect, and simultaneously improve the wetting angle of the coating and the anti-permeability performance of the coating. The results showed that the wetting angle of the composite coating obtained in example 5 was 96.1 ° ± 0.3 °, exhibiting hydrophobic characteristics, while the saturated water absorption (1.28%) and the chloride ion diffusion coefficient (1.12 × 10) of the coated concrete -12 m 2 S) is also minimal. The aqueous coating materials obtained in examples 1 to 9 were subjected to mechanical property tests, and the results are shown in Table 4.
TABLE 4
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (10)
1. The impervious coating on the back surface is characterized in that the raw materials of the impervious coating on the back surface comprise aqueous epoxy emulsion, modified filler and auxiliary agent; the raw materials of the water-based epoxy emulsion comprise, by weight, 55-67 parts of water-soluble epoxy resin, 17-23 parts of chain acid, 8-11 parts of chain ester and 5-10 parts of aromatic compound; the water-soluble epoxy resin has an epoxy value of 0.15-0.23eq/100g and a softening point of 60-82 ℃; the raw material of the water-based epoxy emulsion also comprises an initiator, wherein the initiator is benzoyl peroxide, and the weight of the initiator is 5.9-8.5% of that of the water-soluble epoxy resin.
2. The backside water-barrier coating of claim 1, wherein the raw materials of the aqueous epoxy emulsion comprise 63 parts of water-soluble epoxy resin, 20 parts of chain acid, 10 parts of chain ester and 7 parts of aromatic compound.
3. The backside permeation resistant coating of claim 2, wherein the water soluble epoxy resin is selected from one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, alicyclic polyepoxy compound.
4. The backside water impervious coating of claim 2 wherein the chain acids have a molecular weight of 70 to 110.
5. The backside water impervious coating of claim 4 wherein the chain ester has a density of 0.7-1.1 g/mL.
6. The backside permeation resistant coating of any one of claims 1 to 5, wherein the modified filler is modified silica and/or modified carbon nanomaterial.
7. The backside surface anti-permeability coating of claim 6, wherein when the modified filler is a modified carbon nanomaterial, the modified carbon nanomaterial is graphene oxide or metal-doped reduced graphene oxide, and the graphene oxide comprises metal-doped graphene oxide.
8. The backside surface anti-permeability coating of claim 6, wherein when the modified filler is modified silica and modified carbon nanomaterial, the modified carbon nanomaterial is acidified graphene oxide.
9. The backside bleed resistant coating of claim 3 wherein the additives comprise defoamers, dispersants, and coalescents.
10. A method for preparing the back surface anti-permeability paint, which is characterized by being used for preparing the back surface anti-permeability paint as claimed in claim 9, and comprising the following steps: (1) preparation of aqueous epoxy emulsion: adding water-soluble epoxy resin into a mixed solution consisting of alcohol and ether, heating to 100 ℃, adding chain acid, chain ester and aromatic compound in a nitrogen atmosphere, and reacting for 5.8-6.3h to obtain water-based epoxy emulsion; (2) preparing modified filler; (3) preparation of the water-based paint: stirring and mixing the water-based epoxy emulsion, the modified filler and the auxiliary agent to obtain the water-based paint.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102161731A (en) * | 2010-09-30 | 2011-08-24 | 山东斯泰普力高新建材有限公司 | Preparation method and application method of water-based epoxy resin emulsion |
| CN107828313A (en) * | 2017-12-01 | 2018-03-23 | 安徽新大陆特种涂料有限责任公司 | A kind of epoxy coating containing modified graphene oxide and preparation method thereof |
| CN110218504A (en) * | 2019-06-25 | 2019-09-10 | 河南省宏瑞防腐安装有限公司 | A kind of steel structure anti-corrosion paint |
| CN114940851A (en) * | 2022-06-07 | 2022-08-26 | 西安理工大学 | Rare earth modified graphene/water-based epoxy resin coating and preparation and coating methods thereof |
-
2022
- 2022-09-01 CN CN202211060030.2A patent/CN115124874A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102161731A (en) * | 2010-09-30 | 2011-08-24 | 山东斯泰普力高新建材有限公司 | Preparation method and application method of water-based epoxy resin emulsion |
| CN107828313A (en) * | 2017-12-01 | 2018-03-23 | 安徽新大陆特种涂料有限责任公司 | A kind of epoxy coating containing modified graphene oxide and preparation method thereof |
| CN110218504A (en) * | 2019-06-25 | 2019-09-10 | 河南省宏瑞防腐安装有限公司 | A kind of steel structure anti-corrosion paint |
| CN114940851A (en) * | 2022-06-07 | 2022-08-26 | 西安理工大学 | Rare earth modified graphene/water-based epoxy resin coating and preparation and coating methods thereof |
Non-Patent Citations (2)
| Title |
|---|
| 刘乃亮等: "TiO2/RGO纳米复合光催化剂的制备及性能研究", 《化工新型材料》 * |
| 刘晓冬等: "单组分水性环氧乳液的合成研究", 《应用化工》 * |
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