CN109627826B - Composite shell material microcapsule with double anti-corrosion functions and preparation method thereof - Google Patents
Composite shell material microcapsule with double anti-corrosion functions and preparation method thereof Download PDFInfo
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
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- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
Abstract
The invention discloses a composite shell material microcapsule with double anti-corrosion functions, wherein the shell material of the microcapsule is formed by polyaniline, vinyl polymer and nano SiO2Composition is carried out; the core material of the microcapsule is a metal corrosion inhibitor; the size of the microcapsule is 5-100 mu m, and the shell thickness of the microcapsule is 100 nm-2 mu m; the monomer of the vinyl polymer is the mixture of a single-functionality vinyl monomer and a double-functionality vinyl monomer; the metal corrosion inhibitor is one or more of benzotriazole, methylbenzotriazole, nitrobenzotriazole, hydroxybenzotriazole, 2-mercaptobenzothiazole and 8-hydroxyquinoline. The invention takes polyaniline with anti-corrosion function and vinyl polymer with better compatibility with matrix resin as shell material of the microcapsule to load anti-corrosion functional substances, and prepares the composite shell material microcapsule with double anti-corrosion function.
Description
Technical Field
The invention relates to the technical field of high polymer materials and anti-corrosion microcapsules, in particular to a composite shell material microcapsule with double anti-corrosion functions and a preparation method thereof.
Background
Microcapsule technology is the most commonly used method for loading functional substances at present, and has the advantages that the microcapsule technology is an effective substance immobilization technology, molecules can be encapsulated by a capsule wall to be isolated from the external environment, the property of the capsule core is protected from being influenced, and meanwhile, the capsule wall is damaged under proper conditions such as pressurization, temperature rise or radiation, or the capsule core substance is diffused outwards through the capsule wall to realize controlled release. At present, a plurality of methods for preparing microcapsules are available, such as a template method, an interfacial polycondensation method, an in-situ polymerization method and the like, wherein a Pickering emulsion template method provides a simple and effective preparation approach for preparing the microcapsules, and a Pickering emulsion is an emulsion stabilized by replacing a traditional surfactant with fine solid particles (such as silicon dioxide, lignin, barium sulfate and kaolin), and has the advantages of super stability, low foamability and no toxicity problem caused by molecular migration compared with the traditional emulsion.
The addition of microcapsules with corrosion prevention or inhibition functions in the coating is an effective metal corrosion prevention means. The metal corrosion inhibitor is loaded in the microcapsule, and when the microcapsule breaks along with the coating, the loaded substance interacts or reacts with the metal to form a barrier film, so that the metal is passivated.
Various polymers (such as polystyrene, polyurethane, polyurea and the like) are reported to be used as shell materials to prepare the anti-corrosion microcapsule, but most shell materials mainly play a role in coating and providing mechanical support, but have no inhibition effect on corrosion per se, and the main problem is that the compatibility of the microcapsule and a matrix is poor. Therefore, the development and research of the anti-corrosion microcapsule with multifunctional shell layer and excellent compatibility with the coating matrix are urgently needed to meet the wider application requirements.
Disclosure of Invention
In order to solve the problems in the prior art, the applicant of the present invention provides a composite shell microcapsule with dual anti-corrosion functions and a preparation method thereof. The invention takes polyaniline with anti-corrosion function and vinyl polymer with better compatibility with matrix resin as shell material of the microcapsule to load anti-corrosion functional substances, and prepares the composite shell material microcapsule with double anti-corrosion function.
The technical scheme of the invention is as follows:
a composite shell material microcapsule with dual anticorrosion functions is prepared from polyaniline, vinyl polymer and nano SiO2Composition is carried out; the core material of the microcapsule is a metal corrosion inhibitor; the size of the microcapsule is 5-100 mu m, and the shell thickness of the microcapsule is 100 nm-2 mu m;
the monomer of the vinyl polymer is the mixture of a single-functionality vinyl monomer and a double-functionality vinyl monomer;
the metal corrosion inhibitor is one or more of benzotriazole, methylbenzotriazole, nitrobenzotriazole, hydroxybenzotriazole, 2-mercaptobenzothiazole and 8-hydroxyquinoline.
The monofunctional alkene monomer is one or more of glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isooctyl (meth) acrylate, hydroxyethyl (meth) acrylate, ethylhexyl (meth) acrylate, (meth) acrylic acid, tert-butyl (meth) acrylate, methoxy polyethylene glycol acrylate, ethoxy ethyl acrylate, styrene, N-isopropyl acrylamide, acrylamide and 2-butene amide.
The difunctional alkene monomer is one or more of 1, 6-hexanediol acrylate, 1, 6-hexanediol di (methyl) acrylate, tripropylene glycol diacrylate, N-methylene bisacrylamide, ethylene glycol di (methyl) acrylate, diethylene glycol diacrylate, neopentyl glycol diethoxy acrylate, diethylene glycol diacrylate phthalate, dipropylene glycol diacrylate and divinyl benzene.
A preparation method of the composite shell material microcapsule with the double anti-corrosion function comprises the following steps:
(1) mixing nano SiO2Uniformly dispersing in ultrapure water as waterSimultaneously, dissolving a monomer of an olefin polymer, aniline and a photoinitiator in an organic solvent to be used as an oil phase, mixing the oil phase and the water phase, and forming a stable oil-in-water emulsion under the action of an emulsifying machine;
(2) placing the emulsion prepared in the step (1) under ultraviolet light for illumination for 2-5 min, then dropwise adding an aqueous solution containing a phenylamine initiator, standing, and reacting for 8-24 h at the temperature of 0-20 ℃; then, alternately washing and drying by adopting water and ethanol to obtain the composite shell material microcapsule;
(3) dissolving a metal corrosion inhibitor in a solvent, soaking the microcapsule prepared in the step (2) in a metal corrosion inhibitor solution, stirring for 1-5 h, washing with water and ethanol to remove unsupported objects, and drying to obtain the composite shell material microcapsule with the double anti-corrosion function.
The nano SiO in the step (1)2Is commercially available gas-phase nano SiO2Nano SiO synthesized by sol-gel method2Gas-phase nano SiO hydrophobically modified by silane coupling agent2One of (1); the nano SiO2The particle size of (A) is 10 to 100 nm.
The silane coupling agent for hydrophobic modification is one or more of diphenyldimethoxysilane, (3-mercaptopropyl) trimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane; the method for hydrophobic modification comprises the following steps: the commercially available gas-phase nano SiO2Dispersing in ethanol, adding SiO22-10% of silane coupling agent by mass, then adjusting the pH value to 8-10 with ammonia water, reacting for 8-16 h at 50-70 ℃, alternately washing and drying with ethanol and ultrapure water after reaction to prepare the gas-phase nano SiO modified by the silane coupling agent through hydrophobic modification2。
The nano SiO in the step (1)2The concentration of the product in the ultrapure water is 3-5 wt%; the aniline accounts for 5-20 vol% of the oil phase; the volume ratio of the bifunctional monomer to the alkene monofunctional monomer in the alkene polymer monomer is 1: 1-4, and the total amount of the added bifunctional monomer accounts for 30-60 vol% of the oil phase; the amount of the photoinitiator is 2-5 wt% of the vinyl polymer monomer; the oil phase is mixed withThe volume ratio of the water phase is 1: 1-4.
The organic solvent in the step (1) is one or more of benzene, toluene, xylene, chloroform, diethyl ether, white oil, hexane, bromopropane, dichloroethane, chloroform, ethyl acetate, n-pentane and n-butanol; the photoinitiator is one or more of a photoinitiator 1173, a photoinitiator 369, a photoinitiator 2959, a photoinitiator 184, a photoinitiator 907, a photoinitiator 651, a photoinitiator 127 and a photoinitiator 819.
The aniline initiator in the step (2) is ammonium persulfate, potassium persulfate or ferric trichloride; the molar ratio of the dosage of the aniline initiator to the aniline is 1: 1-4.
The beneficial technical effects of the invention are as follows:
the invention adopts a Pickering emulsion template method to prepare the microcapsule, and the granular emulsifier SiO can be changed2The particle size of the emulsion drop is adjusted by using the amount so as to control the size of the obtained microcapsule, meanwhile, compared with the traditional surfactant, the amount of the particle emulsifier is less, the particle size distribution of the prepared emulsion is more uniform, the stability is higher, and the hydrophilicity and the hydrophobicity of the emulsion can be adjusted according to the needs so as to meet the needs of different oil-water phase polarities. In addition, the process for preparing the microcapsule by the Pickering emulsion template method is simple, economic and environment-friendly, and the pollution problem caused by excessive use of the surfactant is reduced.
The shell material of the microcapsule contains polyaniline with an anti-corrosion function, and the inner core is loaded with the corrosion inhibitor which interacts with the surface of metal to passivate the metal and form a film for blocking corrosion factors, so that pitting corrosion of the metal can be effectively inhibited.
The shell material of the microcapsule contains the vinyl polymer, so that the compatibility of the microcapsule in a coating can be effectively improved, and meanwhile, the vinyl polymer can improve the toughness and mechanical strength of the microcapsule and make up for the defects of high rigidity and brittle quality of polyaniline.
Drawings
Fig. 1 is a schematic structural diagram of a composite shell microcapsule with dual anticorrosion effects synthesized in example 1.
FIG. 2 is an SEM photograph of the composite shell microcapsules with dual corrosion protection effects synthesized in examples 1-3; in the figure, A is example 1; b, example 2; c, example 3.
FIG. 3 is an infrared spectrum of the composite shell microcapsule (A) synthesized in example 1 and the composite shell microcapsule (B) loaded with a corrosion inhibitor and having dual corrosion protection effects;
in the figure A, PANI HS is a microcapsule synthesized by taking polyaniline as a shell material alone; p (GMA-co-HDDA) HS is a microcapsule which takes vinyl polymer as shell material; p (GMA-co-HDDA) -PANI HS is the composite shell material microcapsule synthesized by the invention; in the diagram B, P (GMA-co-HDDA) -PANI HS @ MBT is the composite shell material microcapsule which loads the dual anti-corrosion efficacy of the corrosion inhibitor MBT.
Fig. 4 is an ultra-deep field and digital photograph of the dispersion of the composite shell microcapsules with dual corrosion protection effects synthesized in example 1 in an epoxy resin coating.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings and examples.
Example 1
A preparation method of a composite shell material microcapsule with double anti-corrosion effects comprises the following steps:
(1) firstly, 6g of nano SiO is weighed2(50nm) is dispersed in 50mL solvent ethanol, then 120mg of diphenyldimethoxysilane is added, ammonia water is added to adjust the pH value to 10, the reaction is carried out for 8h at 50 ℃, and after the reaction, ethanol and water are used for alternative washing to obtain the modified nano SiO2；
(2) Subjecting 180mg of the modified SiO prepared in step (1) to ultrasonic treatment2Uniformly dispersing the mixture in 6mL of ultrapure water as a water phase, simultaneously dissolving 0.3mL of aniline, 0.9mL of Glycidyl Methacrylate (GMA) and 0.9mL of 1, 6-hexanediol acrylate (HDDA) in 3.9mL of oil phase toluene, and simultaneously adding 36mg of photoinitiator 369 as an oil phase; mixing oil and water phases, and emulsifying for 2min by 8000rmp emulsifying machine to obtain stable oil-in-water (O/W) emulsion;
(3) placing the emulsion prepared in the step (2) in an ultraviolet curing machine for illumination for 3min to polymerize an alkene monomer, dropwise adding 2mL of aqueous solution containing 750mg of ammonium persulfate and 50 mu L of HCl (1M) after illumination to polymerize aniline, reacting for 10h at 0 ℃ without any stirring, alternately washing with ultrapure water and ethanol, and drying to obtain a composite shell material microcapsule;
(4) and (3) placing the dried microcapsule into a flask, adding a saturated ethanol solution of 2-Mercaptobenzothiazole (MBT), stirring for 6 hours to increase the loading capacity, washing with water and ethanol to remove the unloaded substances, and drying to obtain the composite shell material microcapsule with the double anti-corrosion effect.
An SEM photograph of the composite shell material microcapsule synthesized in this example is shown in fig. 2, from which it can be seen that the microsphere is in a regular spherical shape, and from the damaged portion, it can be seen that the interior of the microsphere is a hollow structure.
The infrared spectrum of the composite shell microcapsule synthesized in this example is shown in fig. 3A, and it can be seen from the graph that, compared with the microcapsule (PANI HS) synthesized by using polyaniline alone as the shell material and the microcapsule (P (GMA-co-HDDA) HS) synthesized by using vinyl polymer alone as the shell material, the composite shell microcapsule (P (GMA-co-HDDA) -PANI HS) synthesized by the present invention has the characteristic absorption peaks of the former two, which proves that it is successfully prepared, the infrared spectrum of the composite shell microcapsule loaded with the dual corrosion protection efficacy of the corrosion inhibitor MBT is shown in fig. 3B, and it can be seen from the graph that the microcapsule P (GMA-co-HDDA) -PANI @ HS MBT loaded with the corrosion inhibitor has the characteristic absorption peak of the corrosion inhibitor MBT compared with the microcapsule (P (GMA-co-HDDA) -PANI HS) unloaded, the successful preparation of the composite shell material microcapsule with double anti-corrosion effects is demonstrated.
The super-depth of field and digital photograph of the dispersion condition of the composite shell microcapsule with double anti-corrosion effect synthesized in this example in the epoxy resin coating are shown in fig. 4, before the epoxy resin is cured, the composite shell microcapsule with double anti-corrosion effect accounting for 2% of the resin mass is dispersed in the epoxy resin coating by stirring, and is coated on the metal surface by a roller coating method, and then is heated and cured to form the epoxy resin coating dispersed with the composite shell microcapsule with double anti-corrosion effect. The figure is a photograph of the cured resin, from which it can be seen that the microcapsules can be uniformly dispersed in the coating without significant aggregation.
Example 2
A preparation method of a composite shell material microcapsule with double anti-corrosion effects comprises the following steps:
(1) firstly, 6g of nano SiO is weighed2(100nm) is dispersed in 50mL of solvent ethanol, then 300mg of 3-methoxy acryloxy propyl trimethoxy silane is added, ammonia water is added to adjust the pH value to 8, the mixture reacts for 12h at the temperature of 60 ℃, and after the reaction, the mixture is washed by ethanol and water alternately to obtain the product.
(2) Performing ultrasonic treatment on 240mg of modified nano SiO prepared in the step (1)2Uniformly dispersed in 6mL of ultrapure water, while dissolving 0.3mL of aniline, 0.75mL of dimethylaminoethyl methacrylate (DMAEMA), 0.75mL of Divinylbenzene (DVB) in 1.2mL of oily phase ethyl acetate, 54mg of photoinitiator 1173 was added. Mixing oil and water phases, and emulsifying for 5min by 10000rmp emulsifying machine to obtain stable oil-in-water (O/W) emulsion.
(3) And (3) placing the emulsion prepared in the step (2) in an ultraviolet curing machine for illumination for 4min to polymerize the vinyl monomer. After the light irradiation, 2mL of an aqueous solution containing 375mg of ammonium persulfate and 100. mu.L of HCl (1M) was added dropwise to polymerize aniline, the reaction was carried out at 10 ℃ for 16 hours without any stirring, and the composite shell material microcapsules were obtained by alternately washing with water and ethanol and drying.
(4) And (3) placing the dried microcapsule into a flask, adding a saturated ethanol solution of Benzotriazole (BTA), stirring for 12 hours to increase the loading capacity, washing with water and ethanol to remove the unloaded substances, and drying to obtain the composite shell material microcapsule with the double anti-corrosion effect. An SEM photograph of the composite shell material microcapsule synthesized in this example is shown in fig. 2, from which it can be seen that the microsphere is in a regular spherical shape, and from the damaged portion, it can be seen that the interior of the microsphere is a hollow structure.
Example 3
A preparation method of a composite shell material microcapsule with double anti-corrosion effects comprises the following steps:
(1) 300mg of commercially available gas-phase SiO are introduced by sonication2(15nm) was uniformly dispersed in 6mL of ultrapure water, as was0.3mL of aniline, 0.72mL of styrene (St), and 0.18mL of dipropylene glycol diacrylate (DPGDA) were dissolved in 0.3mL of oil-phase dichloroethane, and 41mg of photoinitiator 907 was added. Mixing the oil and water phases, and emulsifying with 12500rmp emulsifier for 10min to obtain stable oil-in-water (O/W) emulsion.
(2) And (2) pouring the emulsion prepared in the step (1) into an ultraviolet curing machine, irradiating for 5min to polymerize an alkene monomer, dropwise adding 2mL of aqueous solution containing 250mg of ammonium persulfate and 50 mu L of HCl (1M) after irradiation to polymerize aniline, reacting for 24h at 20 ℃ without any stirring, alternately washing with water and ethanol, and drying to obtain the composite shell material microcapsule.
(3) And (3) placing the dried microcapsules into a flask, adding an ethanol solution of 8-Hydroxyquinoline (HQ), stirring for 24 hours to increase the loading capacity, washing with water and ethanol to remove unloaded substances, and drying to obtain the composite shell material microcapsules with double anti-corrosion effects. An SEM photograph of the composite shell material microcapsule synthesized in this example is shown in fig. 2, from which it can be seen that the microsphere is in a regular spherical shape, and from the damaged portion, it can be seen that the interior of the microsphere is a hollow structure.
Claims (8)
1. The composite shell material microcapsule with double anti-corrosion functions is characterized in that shell materials of the microcapsule are polyaniline, vinyl polymer and nano SiO2Composition is carried out; the core material of the microcapsule is a metal corrosion inhibitor; the size of the microcapsule is 5-100 mu m, and the shell thickness of the microcapsule is 100 nm-2 mu m;
the monomer of the vinyl polymer is the mixture of a single-functionality vinyl monomer and a double-functionality vinyl monomer;
the metal corrosion inhibitor is one or more of benzotriazole, methylbenzotriazole, nitrobenzotriazole, hydroxybenzotriazole, 2-mercaptobenzothiazole and 8-hydroxyquinoline;
the preparation method of the composite shell material microcapsule with the double anti-corrosion function comprises the following steps:
(1) mixing nano SiO2Uniformly dispersing in ultrapure water as water phase, and simultaneously initiating monomer, aniline and light of vinyl polymerDissolving the agent in an organic solvent to serve as an oil phase, mixing the oil phase and the water phase, and forming a stable oil-in-water type emulsion under the action of an emulsifying machine;
(2) placing the emulsion prepared in the step (1) under ultraviolet light for illumination for 2-5 min, then dropwise adding an aqueous solution containing a phenylamine initiator, standing, and reacting for 8-24 h at the temperature of 0-20 ℃; then, alternately washing and drying by adopting water and ethanol to obtain the composite shell material microcapsule;
(3) dissolving a metal corrosion inhibitor in a solvent, soaking the microcapsule prepared in the step (2) in a metal corrosion inhibitor solution, stirring for 1-5 h, washing with water and ethanol to remove unsupported objects, and drying to obtain the composite shell material microcapsule with the double anti-corrosion function.
2. The composite shell microcapsule of claim 1, wherein the monofunctional vinyl monomer is one or more of glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isooctyl (meth) acrylate, hydroxyethyl (meth) acrylate, ethylhexyl (meth) acrylate, (meth) acrylic acid, t-butyl (meth) acrylate, methoxypolyethylene glycol acrylate, ethoxyethoxyethyl acrylate, styrene, N-isopropylacrylamide, acrylamide, and 2-butenamide.
3. The composite shell material microcapsule of claim 1, wherein the difunctional vinyl monomer is one or more of 1, 6-hexanediol diacrylate, 1, 6-hexanediol di (meth) acrylate, tripropylene glycol diacrylate, N-methylene bisacrylamide, ethylene glycol di (meth) acrylate, diethylene glycol diacrylate, neopentyl glycol diethoxy acrylate, diethylene glycol diacrylate phthalate, dipropylene glycol diacrylate, and divinylbenzene.
4. The composite shell microcapsule of claim 1Characterized in that the nano SiO in the step (1)2Is commercially available gas-phase nano SiO2Nano SiO synthesized by sol-gel method2Gas-phase nano SiO hydrophobically modified by silane coupling agent2One of (1); the nano SiO2The particle size of (A) is 10 to 100 nm.
5. The composite shell microcapsule according to claim 4, wherein the silane coupling agent for hydrophobic modification is one or more of diphenyldimethoxysilane, (3-mercaptopropyl) trimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, and 3-methoxypropenoxypropyltrimethoxysilane; the method for hydrophobic modification comprises the following steps: the commercially available gas-phase nano SiO2Dispersing in ethanol, adding SiO22-10% of silane coupling agent by mass, then adjusting the pH value to 8-10 with ammonia water, reacting for 8-16 h at 50-70 ℃, alternately washing and drying with ethanol and ultrapure water after reaction to prepare the gas-phase nano SiO with hydrophobic modification of the silane coupling agent2。
6. A composite shell microcapsule according to claim 1, wherein said nanosio is present in step (1)2The concentration of the product in the ultrapure water is 3-5 wt%; the aniline accounts for 5-20 vol% of the oil phase; the volume ratio of the bifunctional monomer to the alkene monofunctional monomer in the alkene polymer monomer is 1: 1-4, and the total amount of the added bifunctional monomer accounts for 30-60 vol% of the oil phase; the amount of the photoinitiator is 2-5 wt% of the vinyl polymer monomer; the volume ratio of the oil phase to the water phase is 1: 1-4.
7. A composite shell material microcapsule according to claim 1, wherein the organic solvent in step (1) is one or more of benzene, toluene, xylene, chloroform, diethyl ether, white oil, hexane, bromopropane, dichloroethane, chloroform, ethyl acetate, n-pentane, and n-butanol; the photoinitiator is one or more of a photoinitiator 1173, a photoinitiator 369, a photoinitiator 2959, a photoinitiator 184, a photoinitiator 907, a photoinitiator 651, a photoinitiator 127 and a photoinitiator 819.
8. A composite shell microcapsule according to claim 1, wherein the aniline initiator in step (2) is ammonium persulfate, potassium persulfate or ferric trichloride; the molar ratio of the dosage of the aniline initiator to the aniline is 1: 1-4.
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