CN111995307B - Preparation method of protective coating material for marine peripheral buildings - Google Patents

Preparation method of protective coating material for marine peripheral buildings Download PDF

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CN111995307B
CN111995307B CN202010895063.3A CN202010895063A CN111995307B CN 111995307 B CN111995307 B CN 111995307B CN 202010895063 A CN202010895063 A CN 202010895063A CN 111995307 B CN111995307 B CN 111995307B
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chitosan
sodium alginate
solution
marine
microemulsion
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CN111995307A (en
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陈顺
刘巧
谭梦曦
苏英
黄震宇
张路川
贺行洋
陈威
杨进
曾三海
熊潇
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Hubei University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24—Macromolecular compounds
    • C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2641—Polyacrylates; Polymethacrylates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00482—Coating or impregnation 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/24—Sea water resistance

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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

The invention discloses a preparation method of a protective coating material for marine peripheral buildings, which comprises the following steps: (1) preparing chitosan and sodium alginate solution; (2) preparing chitosan microemulsion and sodium alginate microemulsion; (3) mixing the sodium alginate microemulsion and the chitosan microemulsion to prepare chitosan-sodium alginate nano microspheres; (4) preparing cross-linked chitosan-sodium alginate particles; (5) preparing imprinted polymer microspheres rich in silver ions; (6) preparing hydrophobic modified acrylic copolymer emulsion; (7) preparing nano functionalized hydrophobic acrylic polymer emulsion; (8) mixing the nano functionalized hydrophobic acrylic polymer emulsion, cement and fine sand to obtain the protective coating material for the marine peripheral buildings. The protective coating material for the marine peripheral buildings, prepared by the method, can effectively reduce the deterioration and corrosion of seawater on the marine buildings and prolong the service life of the marine buildings in humid high-salt environments.

Description

Preparation method of protective coating material for marine peripheral buildings
Technical Field
The invention belongs to the field of marine building protective materials, and particularly relates to a preparation method of a marine surrounding building protective coating material.
Background
In a concrete building in the surrounding environment of the ocean, because of the complex corrosive environment of the ocean, the strength of a reinforced concrete structure is reduced due to the corrosion of concrete and reinforcing steel bars, the corrosion of the reinforcing steel bars is accelerated by the damage of the concrete structure, the durability of the structure is reduced, and the reliability is reduced. The economic loss caused by marine corrosion is very serious, and the countries spend huge expenses on the maintenance or reconstruction of buildings every year. Therefore, the protection problem of concrete engineering in marine environment is more and more concerned.
The humid and high-salt environment around the ocean can cause physical and chemical corrosion to the building structure, and the ocean salt fog contains a large amount of corrosive ions (such as sodium ions, chloride ions and the like), so that the corrosive ions permeate into the ocean salt fog to corrode the reinforcing steel bars, the surface of the concrete can be degraded, and even crystals are generated in the concrete to cause the building concrete to burst, so that the internal reinforcing steel bars are exposed outside, the corrosion of the reinforced concrete is accelerated, and the building structure is damaged.
In countries and regions such as japan, europe, etc., polymer mortar has been widely used as a building structure waterproof + protective material, a repair material, a decorative material, and in addition, has been widely used for a concrete structure waterproof system and an engineering having environmental adaptability requirements because it has good waterproof property, chloride ion permeation resistance, and carbonization resistance. Wuheil provides a preparation method for preparing thin flexible polymer mortar by using acrylic acid copolymer emulsion and the like as raw materials, and the prepared polymer mortar and alkali-resistant glass fiber mesh fabric are compounded and formed into a thin flexible polymer patch material during construction. The polymer emulsion mortar is utilized to help repair and maintain the structure.
On the other hand, with the development of advanced polymer technology, the molecular imprinting technology appears, which is a novel polymer preparation process with selective recognition capability for specific molecules. The polymer prepared by the technology has the characteristics of severe environment resistance, high selectivity, good stability, high mechanical strength and the like. The ion imprinting technology is a branch of the technology, and takes anions and cations as templates, and interacts with functional monomers through the actions of static electricity, coordination and the like, so that the template ions are removed after cross-linking polymerization to obtain a rigid polymer with specific group arrangement, fixed cavity size and shape, and the formed cavities have specific selectivity on target ions and can only combine specific ions.
Patent CN201811611491.8 discloses a method for preparing environment-friendly inorganic mineral polymer mortar by using solid waste, which has the characteristics of production cost, better working performance, durability and toughness resistance.
Patent CN200910196104.3 discloses a construction method of spraying polymer mortar for structural reinforcement, which optimizes the construction process of polymer mortar.
According to the patent CN201711136649.6 concrete thin layer repairing polymer mortar and the preparation method thereof, the prepared thin layer repairing polymer mortar has the advantages of good adhesive property, erosion resistance and abrasion resistance.
However, the polymer mortar is used for coating the surface of marine environmental building, and the application property, weather resistance and environment applicability of the polymer mortar are important considerations, and these problems are not well solved in these patents.
CN201810754720.5 discloses preparation and application of an amino-terminated hyperbranched polymer grafted graphene oxide magnetic anion adsorbent. The amino-terminated hyperbranched polymer is grafted to the magnetic graphene oxide under alkaline conditions, and the amino-terminated hyperbranched polymer-grafted graphene oxide magnetic anion adsorbent is obtained after washing and drying. The amino-terminated hyperbranched polymer grafted graphene oxide magnetic anion adsorbent prepared by the invention contains high-density amino functional groups, and the positively charged amino functional groups can realize high enrichment and rapid removal of negatively charged anion pollutants.
CN201710269729.2 discloses a magnetic hyperbranched polymer or a derivative thereof blood heavy metal ion adsorbent, and a preparation method and application thereof, and the magnetic hyperbranched polymer or the derivative thereof heavy metal ion adsorbent is prepared. The adsorbent can efficiently capture trace heavy metal ions in blood, has high biocompatibility and can realize selective adsorption of the heavy metal ions.
Therefore, the development of a high-performance, green and environment-friendly polymer emulsion mortar protective material is an extremely effective breakthrough for the scientific researchers in the industry to overcome the difficult problems of building structures at present.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a protective coating material for marine peripheral buildings, and particularly provides a method for preventing corrosion of the marine peripheral buildings by using polymer emulsion mortar.
The invention utilizes the acrylic polymer to functionalize the mortar material to prepare the coating on the surface of the marine environmental building. The mortar is prepared by the cyclohexasilane modified acrylic acid copolymer emulsion, in the process of slurry solidification, the wettability of an inorganic material can be increased by utilizing the action of an acrylic acid group, a film is formed in the slurry after the slurry is solidified, the film interacts with the inorganic material tightly, a communicating pore channel in the slurry is blocked, and the invasion of moisture is blocked well. Meanwhile, after the cyclohexasilane modified acrylic copolymer emulsion is formed into a film, the surface of the emulsion can show microphase separation, the hydrophobic property of the emulsion is improved, the problem that water is gradually immersed in a long-time humid environment can be effectively solved, and the permeation of chloride ions is effectively inhibited by blocking a water channel. In addition, due to the presence of the silver ion-rich imprinted polymeric microspheres, chloride ions react with silver ions at the contact surface to form a passivation layer, further preventing chloride ions from soaking in. Therefore, the modified polymer emulsion mortar can effectively block internal pores and ducts, increase the isolation effect on chloride ions through point position adsorption and passivation reaction, effectively overcome the problem of chloride ion permeation, and solve the problems of concrete deterioration, corrosion, easy corrosion of internal steel bars and the like when the marine surrounding buildings are in a humid high-salt environment for a long time, so that the marine buildings can be effectively protected, and the service life of the marine buildings is prolonged.
The technical scheme provided by the invention is as follows:
a preparation method of a protective coating material for marine surrounding buildings comprises the following steps:
(1) preparing chitosan and sodium alginate solution;
(2) respectively adding a surfactant and an organic solvent into chitosan solution and sodium alginate solution, and uniformly mixing to form chitosan microemulsion and sodium alginate microemulsion respectively;
(3) dropwise adding the sodium alginate microemulsion into the chitosan microemulsion, reacting fully, centrifuging, washing, and freeze-drying to obtain chitosan-sodium alginate nano microspheres; preferably, the mass ratio of the sodium alginate microemulsion to the chitosan microemulsion is 50-100: 100, respectively;
(4) adding chitosan-sodium alginate nano microspheres into an ethanol solution of monocyclohexyl maleate, adding an aldehyde solution, after complete reaction, centrifuging, washing and drying to obtain chitosan-sodium alginate particles;
(5) adding chitosan-sodium alginate particles into an ethanol dilute solution of silver acetate, and reacting fully to obtain imprinted polymer microspheres rich in silver ions;
(6) preparing modified acrylic copolymer emulsion;
(7) adding the imprinted polymer microspheres rich in silver ions into the modified acrylic copolymer emulsion to obtain a nano functionalized hydrophobic acrylic polymer emulsion;
(8) mixing the nano functionalized hydrophobic acrylic polymer emulsion, cement and fine sand to obtain a protective coating material for marine peripheral buildings; preferably, the mass ratio of the polymer emulsion to the cement to the fine sand is 1:3:1, and the fine sand is selected from natural river sand, washed sand or quartz sand.
Further, in the present invention,
the preparation method of the chitosan solution comprises the following steps: dissolving chitosan in water, adding a solvent, dissolving, and centrifuging to remove insoluble substances, wherein the mass ratio of the chitosan to the water to the glacial acetic acid is (0.5-1): 100: 1.75; the solvent is selected from one of glacial acetic acid, ethanol, ethyl acetate, sec-butyl acetate and acetic anhydride;
the preparation method of the sodium alginate solution comprises the following steps: dissolving sodium alginate in water, centrifuging to remove insoluble substances after dissolving, and adjusting pH to 5-6 with acetic acid, wherein the mass ratio of sodium alginate to water is 0.5-1: 100.
further, in the step (2), the surfactant is selected from one of phospholipid, choline, protein, sodium stearyl sulfate and sodium stearate.
Further, the organic solvent in the step (2) is one or more selected from n-hexane, cyclohexane, chloroform and ethyl acetate.
Further, in the step (2), the mass ratio of the chitosan/sodium alginate solution to the surfactant to the organic solvent is 100: 2-10: 30-50.
Further, in the step (4), the mass ratio of the chitosan-sodium alginate nano microspheres to the ethanol solution of the fumaric acid monocyclohexyl ester to the aldehyde solution is 50-100: 100: 5-10; the aldehyde is selected from one of formaldehyde, glutaraldehyde and glyoxal. Preferably, the aldehyde solution has a concentration of 1% and the reaction time is 4 hours.
Further, in the step (5), the mass ratio of the chitosan-sodium alginate particles to the ethanol solution of silver acetate is 50-100: 100.
further, in the step (6), the preparation method of the hydrophobically modified acrylic copolymer emulsion is as follows: adding 10-20 parts by mass of cyclohexasilane into 100 parts by mass of acrylic copolymer emulsion for reaction, and obtaining modified acrylic copolymer emulsion after full reaction; the acrylic copolymer emulsion is one of methacrylic acid, methyl methacrylate, ethyl methacrylate or butyl methacrylate emulsion.
Further, in the step (7), the mass ratio of the silver ion-rich imprinted polymer microspheres to the modified acrylic copolymer emulsion is 5-10: 110-120.
The invention also aims to provide a protective coating material for marine surrounding buildings, which is prepared by the method.
The invention has the beneficial effects that:
(1) the nano-functionalized hydrophobic acrylic polymer is utilized to promote the generation of hydration products of cement slurry in the coating material and reduce the breeding pores and pore channels; meanwhile, a cross-linking network is formed after the polymer film is formed, so that pore channels are further isolated, the penetration of water into the interior is reduced, the barrier property to chloride ions is improved, and the corrosion of the chloride ions to buildings is greatly reduced;
(2) the silver ion-rich imprinted polymer is added in the material, and can generate a silver chloride passivation substance through reaction with contacted chloride ions, so that the permeation of the chloride ions is further blocked, the curing effect on the immersed chloride ions is realized, and the corrosion effect of the chloride ions on building materials is reduced;
(3) the nano functionalized hydrophobic acrylic polymer is well combined with mortar, has good wettability to inorganic materials, can be directly constructed on marine buildings as a coating, and has strong applicability;
(4) the nano functionalized hydrophobic modified polymer emulsion mortar prepared by the invention can effectively reduce the deterioration and corrosion of seawater or marine climate to the marine surrounding buildings, and prolong the service life of the nano functionalized hydrophobic modified polymer emulsion mortar in a humid high-salt environment.
Drawings
FIG. 1 is a transmission electron micrograph of imprinted polymeric microspheres rich in silver ions;
FIG. 2 is a microphase separation diagram of a nano-functionalized hydrophobic acrylic polymer membrane.
Detailed Description
The present invention will be further described with reference to specific examples, which are not intended to limit the scope of the present invention.
A preparation method of a protective coating material for marine surrounding buildings comprises the following steps:
(1) preparing chitosan and sodium alginate solution;
(2) respectively adding a surfactant and an organic solvent into chitosan solution and sodium alginate solution, and uniformly mixing to form chitosan microemulsion and sodium alginate microemulsion respectively;
(3) dropwise adding the sodium alginate microemulsion into the chitosan microemulsion, reacting fully, centrifuging, washing, and freeze-drying to obtain chitosan-sodium alginate nano microspheres; preferably, the mass ratio of the sodium alginate microemulsion to the chitosan microemulsion is 50-100: 100, respectively;
(4) adding chitosan-sodium alginate nano microspheres into an ethanol solution of monocyclohexyl maleate, adding an aldehyde solution, after complete reaction, centrifuging, washing and drying to obtain chitosan-sodium alginate particles;
(5) adding chitosan-sodium alginate particles into an ethanol dilute solution of silver acetate, and reacting fully to obtain imprinted polymer microspheres rich in silver ions;
(6) preparing modified acrylic copolymer emulsion;
(7) adding the imprinted polymer microspheres rich in silver ions into the modified acrylic copolymer emulsion to obtain a nano functionalized hydrophobic acrylic polymer emulsion;
(8) mixing the nano functionalized hydrophobic acrylic polymer emulsion, cement and fine sand to obtain a protective coating material for marine peripheral buildings; preferably, the mass ratio of the polymer emulsion to the cement to the fine sand is 1:3:1, and the fine sand is selected from natural river sand, washed sand or quartz sand.
Further, in the present invention,
the preparation method of the chitosan solution comprises the following steps: dissolving chitosan in water, adding a solvent, dissolving, and centrifuging to remove insoluble substances, wherein the mass ratio of the chitosan to the water to the glacial acetic acid is (0.5-1): 100: 1.75; the solvent is selected from one of glacial acetic acid, ethanol, ethyl acetate, sec-butyl acetate and acetic anhydride;
the preparation method of the sodium alginate solution comprises the following steps: dissolving sodium alginate in water, centrifuging to remove insoluble substances after dissolving, and adjusting pH to 5-6 with acetic acid, wherein the mass ratio of sodium alginate to water is 0.5-1: 100.
further, in the step (2), the surfactant is selected from one of phospholipid, choline, protein, sodium stearyl sulfate and sodium stearate.
Further, the organic solvent in the step (2) is selected from one of n-hexane, cyclohexane, chloroform and ethyl acetate.
Further, in the step (2), the mass ratio of the chitosan/sodium alginate solution to the surfactant to the organic solvent is 100: 2-10: 30-50.
Further, in the step (4), the mass ratio of the chitosan-sodium alginate nano microspheres to the ethanol solution of the fumaric acid monocyclohexyl ester to the aldehyde solution is 50-100: 100: 5-10; the aldehyde is selected from one of formaldehyde, glutaraldehyde and glyoxal. Preferably, the aldehyde solution has a concentration of 1% and the reaction time is 4 hours.
Further, in the step (5), the mass ratio of the chitosan-sodium alginate particles to the ethanol solution of silver acetate is 50-100: 100.
further, in the step (6), the preparation method of the hydrophobically modified acrylic copolymer emulsion is as follows: adding 10-20 parts by mass of cyclohexasilane into 100 parts by mass of acrylic copolymer emulsion for reaction, and obtaining modified acrylic copolymer emulsion after full reaction; the acrylic copolymer emulsion is one of methacrylic acid, methyl methacrylate, ethyl methacrylate or butyl methacrylate emulsion.
Further, in the step (7), the mass ratio of the silver ion-rich imprinted polymer microspheres to the modified acrylic copolymer emulsion is 5-10: 110-120.
The following examples are not specifically described, and the parts are parts by mass.
Example 1
(1) Weighing 0.5 part of chitosan, dissolving in 100 parts of water, adding 1.75 parts of glacial acetic acid, and removing insoluble substances through centrifugation after dissolving to obtain a chitosan solution;
0.5 part of sodium alginate is weighed and dissolved in 100 parts of water, after dissolution, insoluble substances are removed by centrifugation, and the pH is adjusted to 5-6 by acetic acid, thus obtaining a sodium alginate solution.
(2) Mixing 100 parts of chitosan solution, 2 parts of phospholipid and 30 parts of n-hexane, and stirring at room temperature to form the chitosan microemulsion. And preparing the sodium alginate microemulsion in the same way.
(3) Gradually dripping 50 parts of sodium alginate microemulsion into 100 parts of chitosan microemulsion, reacting for 4 hours, centrifuging, washing with deionized water, and freeze-drying to obtain the chitosan-sodium alginate nano microsphere.
(4) Adding 50 parts of chitosan-sodium alginate nano microspheres into 100 parts of ethanol solution of monocyclohexyl fumarate, adding 5 parts of 1% glutaraldehyde solution, treating for 4 hours, centrifuging, washing with ethanol, and drying to obtain chitosan-sodium alginate particles.
(5) 50 parts of the particles are added into 100 parts by weight of ethanol diluted solution of silver acetate, and the mixture is treated for 12 hours to obtain the imprinted polymer microspheres rich in silver ions.
(6) And adding 10 parts of cyclohexasilane into 100 parts of acrylic acid copolymer emulsion for modification to prepare the modified acrylic acid copolymer emulsion.
(7) And adding 5 parts of silver ion-rich imprinted polymer microspheres into the modified acrylic copolymer emulsion to obtain the nano functionalized hydrophobic acrylic polymer emulsion.
(8) Mixing nano functionalized hydrophobic acrylic polymer emulsion, cement and fine sand according to the weight ratio of 1:3:1, and obtaining the protective coating material for the marine peripheral buildings.
Example 2
(1) Weighing 0.6 part of chitosan, dissolving in 100 parts of water, adding 1.75 parts of glacial acetic acid by weight, and removing insoluble substances through centrifugation after dissolving to obtain a chitosan solution;
0.6 part of sodium alginate is weighed and dissolved in 100 parts of water, after dissolution, insoluble substances are removed by centrifugation, and the pH is adjusted to 5-6 by acetic acid, thus obtaining a sodium alginate solution.
(2) Mixing 100 parts of chitosan solution, 3 parts of choline and 35 parts of cyclohexane, and stirring at room temperature to form the chitosan microemulsion. And preparing the sodium alginate microemulsion in the same way.
(3) Gradually dripping 60 parts of sodium alginate microemulsion into 100 parts of chitosan microemulsion, reacting for 4 hours, centrifuging, washing with deionized water, and freeze-drying to obtain the chitosan-sodium alginate nano microsphere.
(4) Adding 60 parts of chitosan-sodium alginate sodium microspheres into 100 parts of ethanol solution of monocyclohexyl fumarate, adding 6 parts of 1% glutaraldehyde solution, treating for 4 hours, centrifuging, washing with ethanol, and drying.
(5) 60 parts of the particles are added into 100 parts of ethanol diluted solution of silver acetate, and the mixture is treated for 12 hours to obtain the imprinted polymer microspheres rich in silver ions.
(6) Adding 12 parts of cyclohexasilane into 100 parts of acrylic acid copolymer emulsion for modification to prepare the modified acrylic acid copolymer emulsion.
(7) And adding 6 parts of silver ion-rich imprinted polymer microspheres into the modified acrylic copolymer emulsion to obtain the nano functionalized hydrophobic acrylic polymer emulsion.
(8) Mixing nano functionalized hydrophobic acrylic polymer emulsion, cement and fine sand according to the weight ratio of 1:3:1, and obtaining the protective coating material for the marine peripheral buildings.
Example 3
(1) Weighing 0.7 part of chitosan, dissolving in 100 parts of water, adding 1.75 parts of glacial acetic acid, and removing insoluble substances through centrifugation after dissolving to obtain a chitosan solution;
0.7 part of sodium alginate is weighed and dissolved in 100 parts of water, after dissolution, insoluble substances are removed by centrifugation, and the pH is adjusted to 5-6 by acetic acid, thus obtaining a sodium alginate solution.
(2) Mixing 100 parts of chitosan solution, 5 parts of protein and 40 parts of chloroform, and stirring at room temperature to form the chitosan microemulsion. And preparing the sodium alginate microemulsion in the same way.
(3) Gradually dripping 70 parts of sodium alginate microemulsion into 100 parts of chitosan microemulsion, reacting for 4 hours, centrifuging, washing with deionized water, and freeze-drying to obtain the chitosan-sodium alginate nano microsphere.
(4) Adding 70 parts of chitosan-sodium alginate sodium microspheres into 100 parts of ethanol solution of monocyclohexyl fumarate, adding 7 parts of 1% glutaraldehyde solution by weight, treating for 4 hours, centrifuging, washing with ethanol, and drying.
(5) 70 parts of the particles are added into 100 parts of ethanol diluted solution of silver acetate, and the mixture is treated for 12 hours to obtain the imprinted polymer microspheres rich in silver ions.
(6) Adding 15 parts of cyclohexasilane into 100 parts of acrylic acid copolymer emulsion for modification to prepare the modified acrylic acid copolymer emulsion.
(7) And adding 7 parts of silver ion-rich imprinted polymer microspheres into the modified acrylic copolymer emulsion to obtain the nano functionalized hydrophobic acrylic polymer emulsion.
(8) Mixing nano functionalized hydrophobic acrylic polymer emulsion, cement and fine sand according to the weight ratio of 1:3:1, and obtaining the protective coating material for the marine peripheral buildings.
Example 4
(1) Weighing 0.8 part of chitosan, dissolving in 100 parts of water, adding 1.75 parts of glacial acetic acid by weight, and removing insoluble substances through centrifugation after dissolving to obtain a chitosan solution;
weighing 0.8 part of sodium alginate, dissolving in 100 parts of water, removing insoluble substances by centrifugation after dissolving, and adjusting pH to 5-6 with acetic acid to obtain sodium alginate solution.
(2) 100 parts of chitosan solution, 7 parts of sodium stearyl sulfate and 45 parts of ethyl acetate are mixed and stirred at room temperature to form the chitosan microemulsion. And preparing the sodium alginate microemulsion in the same way.
(3) Gradually dripping 90 parts of sodium alginate microemulsion into 100 parts of chitosan microemulsion, reacting for 4 hours, centrifuging, washing with deionized water, and freeze-drying to obtain the chitosan-sodium alginate nano microsphere.
(4) Adding 90 parts of chitosan-sodium alginate sodium microspheres into 100 parts of ethanol solution of monocyclohexyl fumarate, adding 9 parts of 1% glutaraldehyde solution, treating for 4 hours, centrifuging, washing with ethanol, and drying.
(5) 90 parts of the particles are added into 100 parts of ethanol diluted solution of silver acetate, and the mixture is treated for 12 hours to obtain the imprinted polymer microspheres rich in silver ions.
(6) Adding 18 parts of cyclohexasilane into 100 parts of acrylic acid copolymer emulsion for modification to prepare the modified acrylic acid copolymer emulsion.
(7) And adding 9 parts of silver ion-rich imprinted polymer microspheres into the modified acrylic copolymer emulsion to obtain the nano functionalized hydrophobic acrylic polymer emulsion.
(8) Mixing nano functionalized hydrophobic acrylic polymer emulsion, cement and fine sand according to the weight ratio of 1:3:1, and obtaining the protective coating material for the marine peripheral buildings.
Example 5
(1) Weighing 1 part of chitosan, dissolving in 100 parts of water, adding 1.75 parts of glacial acetic acid by weight, and removing insoluble substances through centrifugation after dissolving to obtain a chitosan solution;
weighing 1 part of sodium alginate, dissolving in 100 parts of water, removing insoluble substances by centrifugation after dissolving, and adjusting pH to 5-6 with acetic acid to obtain sodium alginate solution.
(2) 100 parts of chitosan solution, 10 parts of sodium stearate and 50 parts of ethyl acetate are mixed and stirred at room temperature to form the chitosan microemulsion. And preparing the sodium alginate microemulsion in the same way.
(3) Gradually dripping 100 parts of sodium alginate microemulsion into 100 parts of chitosan microemulsion, reacting for 4 hours, centrifuging, washing with deionized water, and freeze-drying to obtain the chitosan-sodium alginate nano microsphere.
(4) Adding 100 parts of chitosan-sodium alginate sodium microspheres into 100 parts of ethanol solution of monocyclohexyl fumarate, adding 10 parts of 1% glutaraldehyde solution, treating for 4 hours, centrifuging, washing with ethanol, and drying.
(5) 100 parts of the particles are added into 100 parts of ethanol diluted solution of silver acetate, and the mixture is treated for 12 hours to obtain the imprinted polymer microspheres rich in silver ions.
(6) Adding 20 parts of cyclohexasilane into 100 parts of acrylic acid copolymer emulsion for modification to prepare the modified acrylic acid copolymer emulsion.
(7) And adding 10 parts of silver ion-rich imprinted polymer microspheres into the modified acrylic copolymer emulsion to obtain the nano functionalized hydrophobic acrylic polymer emulsion.
(8) Mixing nano functionalized hydrophobic acrylic polymer emulsion, cement and fine sand according to the weight ratio of 1:3:1, and obtaining the protective coating material for the marine peripheral buildings.
The performance test of the building protective coating material prepared by each example is shown in the table 1:
TABLE 1
Figure GDA0003496550790000091
Figure GDA0003496550790000101
As can be seen from the data for each example in table 1: the building protective coating material provided by the invention has good sulfate corrosion resistance, good chloride ion adsorption capacity, good bonding performance and excellent comprehensive performance. Fig. 1 shows transmission electron micrographs of imprinted polymeric microspheres rich in silver ions. FIG. 2 is a microphase separation diagram of a nano-functionalized hydrophobic acrylic polymer membrane.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any modification, equivalent replacement, and improvement made by those skilled in the art within the technical scope of the present invention should be included in the scope of the present invention.

Claims (10)

1. A preparation method of a protective coating material for marine surrounding buildings is characterized by comprising the following steps:
(1) preparing chitosan and sodium alginate solution;
(2) respectively adding a surfactant and an organic solvent into chitosan solution and sodium alginate solution, and uniformly mixing to form chitosan microemulsion and sodium alginate microemulsion respectively;
(3) dropwise adding the sodium alginate microemulsion into the chitosan microemulsion, reacting fully, centrifuging, washing, and freeze-drying to obtain chitosan-sodium alginate nano microspheres;
(4) adding chitosan-sodium alginate nano microspheres into an ethanol solution of monocyclohexyl maleate, adding an aldehyde solution, after complete reaction, centrifuging, washing and drying to obtain crosslinked chitosan-sodium alginate particles;
(5) adding chitosan-sodium alginate particles into an ethanol dilute solution of silver acetate, and reacting fully to obtain imprinted polymer microspheres rich in silver ions;
(6) preparing hydrophobic modified acrylic copolymer emulsion;
(7) adding the imprinted polymer microspheres rich in silver ions into the modified acrylic copolymer emulsion to obtain a nano functionalized hydrophobic acrylic polymer emulsion;
(8) mixing the nano functionalized hydrophobic acrylic polymer emulsion, cement and fine sand to obtain the protective coating material for the marine peripheral buildings.
2. The method of claim 1, wherein:
the preparation method of the chitosan solution comprises the following steps: dissolving chitosan in water, adding a solvent, dissolving, and centrifuging to remove insoluble substances, wherein the mass ratio of the chitosan to the water to the glacial acetic acid is (0.5-1): 100: 1.75; the solvent is selected from one of glacial acetic acid, ethanol, ethyl acetate, sec-butyl acetate and acetic anhydride;
the preparation method of the sodium alginate solution comprises the following steps: dissolving sodium alginate in water, centrifuging to remove insoluble substances after dissolving, and adjusting pH to 5-6 with acetic acid, wherein the mass ratio of sodium alginate to water is 0.5-1: 100.
3. the method of claim 1, wherein: the surfactant in the step (2) is selected from one of phospholipid, choline, protein, sodium stearyl sulfate and sodium stearate.
4. The method of claim 1, wherein: the organic solvent in the step (2) is one or more of n-hexane, cyclohexane, chloroform and ethyl acetate.
5. The method of claim 1, wherein: in the step (2), the mass ratio of the chitosan/sodium alginate solution to the surfactant to the organic solvent is 100: 2-10: 30-50.
6. The method of claim 1, wherein: in the step (4), the mass ratio of the chitosan-sodium alginate nano microspheres to the ethanol solution of the fumaric acid monocyclohexyl ester to the aldehyde solution is 50-100: 100: 5-10; the aldehyde is selected from one of formaldehyde, glutaraldehyde and glyoxal.
7. The method of claim 1, wherein: in the step (5), the mass ratio of the chitosan-sodium alginate particles to the ethanol solution of silver acetate is 50-100: 100.
8. the method of claim 1, wherein: in the step (6), the preparation method of the hydrophobically modified acrylic copolymer emulsion comprises the following steps: adding 10-20 parts by mass of cyclohexasilane into 100 parts by mass of acrylic copolymer emulsion for reaction, and obtaining modified acrylic copolymer emulsion after full reaction; the acrylic copolymer emulsion is one of methacrylic acid, methyl methacrylate, ethyl methacrylate or butyl methacrylate emulsion.
9. The method of claim 1, wherein in the step (7), the mass ratio of the silver ion-rich imprinted polymer microspheres to the modified acrylic copolymer emulsion is 5-10: 110-120.
10. A protective coating material for marine peripheral buildings is characterized in that: prepared by the method of any one of claims 1 to 9.
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