CN114085384A - Polysulfide oligomer modified acrylic resin and preparation method and application thereof - Google Patents
Polysulfide oligomer modified acrylic resin and preparation method and application thereof Download PDFInfo
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- CN114085384A CN114085384A CN202111286512.5A CN202111286512A CN114085384A CN 114085384 A CN114085384 A CN 114085384A CN 202111286512 A CN202111286512 A CN 202111286512A CN 114085384 A CN114085384 A CN 114085384A
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Abstract
The invention belongs to the field of metal organic anticorrosive coatings, and discloses a polysulfide oligomer modified acrylic resin, and a preparation method and application thereof. The invention uses polysulfide oligomer to modify acrylic resin to increase the corrosion resistance of the resin on the metal surface. The polysulfide oligomer is an elemental sulfur/terpene copolymer with sulfydryl, latex particles in the acrylic resin emulsion have a core-shell structure, the mesoporous size is achieved, a resin coating can form a compact and continuous film, the shell layer of the polysulfide oligomer contains abundant epoxy groups, crosslinking sites can be provided, and the polysulfide oligomer reacts with sulfydryl in a chain segment, so that the crosslinking density of the coating is uniformly distributed, the internal crosslinking density of the coating is increased, the density of the coating is improved, the hydrophobic performance of the coating can be greatly increased, the anticorrosion effect of the composite coating on the metal surface is increased, and the electrochemical corrosion of the metal surface is delayed.
Description
Technical Field
The invention belongs to the field of metal organic anticorrosive coatings, and particularly relates to polysulfide oligomer modified acrylic resin and a preparation method and application thereof.
Background
The corrosion prevention of metal is a great problem all the time, particularly in coastal areas, in damp and hot areas, and with salt fog all the year round, ships entering and leaving the sea are soaked in seawater to aggravate the corrosion of metal materials of ship bodies. The electrochemical corrosion of metals is aggravated by the presence of electrolytes such as brine, and once the metal surface is damaged, the brine environment accelerates corrosion, which severely can cause machine waste. To slow down the corrosion of metal surfaces by seawater, organic anti-corrosive coatings have been developed. Organic coatings have been of early origin, but early organic anti-corrosive coatings were solvent-based, and organic volatilization not only affected the environment, but also physically damaged people working in the environment. Waterborne coatings should work against this background. The water-based paint comprises water-based polyurethane, water-based epoxy resin, water-based acrylic resin and the like. The water-based acrylic resin has good weather resistance, water resistance and glossiness, and is a coating film forming material with excellent performance. However, the latex particles in the conventional production method have a very large particle size, which may cause large gaps in the coating layer, thereby affecting the water resistance and corrosion resistance of the film.
Elemental sulfur in petrochemical products is often a waste in petroleum production, so that not only is environmental pollution caused, but also great resource waste is caused, and the development and application of the waste sulfur become problems which need to be solved urgently.
Disclosure of Invention
In order to overcome the disadvantages and shortcomings of the prior art, the present invention provides a method for preparing a polysulfide oligomer-modified acrylic resin.
Another object of the present invention is to provide a polysulfide oligomer-modified acrylic resin prepared by the above process.
The invention further aims to provide application of the polysulfide oligomer modified acrylic resin in the field of metal organic anticorrosive coatings.
The purpose of the invention is realized by the following scheme:
a method for preparing a polysulfide oligomer-modified acrylic resin, comprising the steps of:
(1) preparing acrylic resin emulsion with a core-shell structure: selecting an acrylic acid derivative as a nuclear layer monomer for pre-emulsification, and then adding a nuclear layer initiator to initiate the polymerization of the nuclear layer monomer to obtain a nuclear structure; and then, taking an acrylic acid derivative as a shell monomer for pre-emulsification, respectively adding the shell monomer and a shell initiator, and carrying out shell polymerization on the basis of the core structure to obtain the acrylic resin emulsion with the core-shell structure.
(2) Preparation of polysulfide emulsion: firstly, emulsifying polysulfide oligomer by using an emulsifier to obtain polysulfide oligomer emulsion, and then carrying out phase inversion on the polysulfide oligomer emulsion by using water to obtain the polysulfide emulsion.
(3) And (3) uniformly mixing the acrylic resin emulsion with the core-shell structure and the polysulfide emulsion, and crosslinking to obtain the polysulfide oligomer modified acrylic resin.
The reaction temperature of the nuclear layer monomer polymerization in the step (1) is 70-90 ℃, and the reaction time is 1-3 hours; the reaction temperature of the shell polymerization is 75-95 ℃, and the reaction time is 3-5 hours.
In the step (1), the dosage of the core layer monomer, the core layer initiator, the shell layer monomer and the shell layer initiator meets the following requirements: the core layer monomer accounts for 35-55% of the mass of the shell layer monomer; the nuclear layer initiator accounts for 0.1 to 3 percent of the mass of the nuclear monomer; the shell initiator accounts for 0.5-2.3% of the mass of the shell monomer.
The core layer monomer in the step (1) comprises at least two of butyl acrylate, cetyl methacrylate, methyl methacrylate, tert-butyl methacrylate, lauryl methacrylate and styrene.
The shell layer monomer in the step (1) comprises a shell layer conventional monomer and a shell layer functional monomer; the shell layer conventional monomer comprises at least three of butyl acrylate, cyclohexyl methacrylate, hexadecyl methacrylate, methyl methacrylate, tert-butyl methacrylate and dodecyl methacrylate; the shell layer functional monomer comprises at least one of glycidyl methacrylate, glycidyl acrylate, glycidyl n-butyrate and 2, 3-epoxypropyl acrylate.
The nuclear layer initiator in the step (1) comprises at least one of ammonium persulfate, azo thioether, hydrogen peroxide, ferric persulfate-ferrous oxide and potassium persulfate; the shell initiator comprises at least one of ammonium persulfate, azo thioether, hydrogen peroxide, ferric persulfate-ferrous oxide and potassium persulfate.
The pre-emulsification of the core layer monomer in the step (1) is to add an emulsifier and water into the core layer monomer, and stir at normal temperature to achieve the emulsification effect; the emulsifier comprises at least one of span 60, span 80, OP-10, se-10 and PCA; the dosage of the emulsifier is 0.5 to 7.5 percent of the mass of the core layer monomer.
The pre-emulsification of the shell monomer in the step (1) is to add an emulsifier and water into the shell monomer and stir at normal temperature to achieve the emulsification effect; the emulsifier comprises at least one of span 60, span 80, OP-10, se-10 and PCA; the dosage of the emulsifier is 0.5 to 9 percent of the dosage of the shell layer monomer.
The average particle size of latex particles in the acrylic resin emulsion with the core-shell structure in the step (1) is about 58nm, the size is very small, and the resin coating can form a compact continuous coating.
In the step (2), the polysulfide oligomer is an elemental sulfur/terpene copolymer with sulfydryl.
In the emulsification in the step (2), the polysulfide oligomer and the emulsifier are mixed and stirred uniformly at the temperature of 25-55 ℃ to obtain polysulfide oligomer emulsion; the emulsifier comprises at least two of (sodium dodecyl benzene sulfonate) SDBS, span 60, span 80, tween 80, OP-10 and L-pyrrolidone-5-sodium carboxylate, wherein the dosage of the emulsifier accounts for 2 to 7 percent of the total mass of the core layer monomer and the shell layer monomer
In the step (2), the phase inversion is carried out by dripping water into the polysulfide oligomer emulsion at the temperature of between 50 and 80 ℃ and stirring the mixture to carry out phase inversion, and the color of the emulsion is changed into light yellow from dark red to obtain polysulfide emulsion; the solid content of the polysulfide emulsion is 5-30%.
In the step (3), the polysulfide emulsion and the acrylic resin emulsion are mixed at room temperature to form a mixed solution, and the mass of the polysulfide emulsion is 0.5-10% of the mass of the mixed solution; the crosslinking is the crosslinking of the mixed solution at the temperature of 55-80 ℃ for 10-30 minutes.
A polysulfide oligomer-modified acrylic resin prepared by the above method.
The acrylic resin is of a core-shell structure, and the acrylic resin shell structure is composed of a shell layer conventional monomer and a shell layer functional monomer; the conventional monomer comprises at least three of butyl acrylate, cyclohexyl methacrylate, hexadecyl methacrylate, methyl methacrylate, tert-butyl methacrylate and dodecyl methacrylate; the functional monomer comprises at least one of glycidyl methacrylate, glycidyl acrylate, glycidyl n-butyrate and 2, 3-epoxypropyl acrylate.
On one hand, the conventional monomer of the shell layer increases the monomer compatibility of the shell layer and the core layer, and better forms acrylic latex particles with a core-shell structure; on the other hand, the acrylic latex particles form a polymer chain segment with a cross-linked network, and the cross-linking density of the shell layer and the core layer is increased; the shell layer functional monomer contains epoxy groups, and the epoxy groups react with sulfydryl in polysulfide oligomer to increase the crosslinking density of modified acrylic resin particles; the increase of the crosslinking density can increase the capillary force action among latex particles in the film forming process of the acrylic resin, and better exclude particles such as water and the like in an acrylic polymer chain segment to form a more compact continuous film layer.
The polysulfide oligomer is an elemental sulfur/terpene copolymer with mercapto groups. The addition of the polysulfide oligomer can not only provide sulfydryl as a crosslinking site with an epoxy group in an acrylic resin shell structure, thereby improving the compactness of latex particles, but also increase the stability of the acrylic resin emulsion and enable the acrylic resin emulsion to exist stably for a long time. The acrylic resin emulsion is very convenient to use, the acrylic resin emulsion is only required to be coated on the surface of a matrix, the crosslinking temperature is not additionally provided, a film can be formed after moisture in the composite emulsion is volatilized, and the operation is convenient.
The application of the multi-sulfur oligomer modified acrylic resin in the field of metal organic anticorrosive coatings.
The acrylic resin introduced by the polysulfide oligomer prepared by the invention is coated on the surface of a metal matrix, and through the test of a saline water immersion experiment, the modified resin can obviously improve the corrosion resistance of the metal surface. After the acrylic coating without the polysulfide emulsion is corroded, the corrosion phenomenon can be rapidly deepened, and the damage of the film layer also aggravates the electrochemical corrosion process, so that the coating loses the corrosion resistance. After the composite coating added with the polysulfide emulsion is corroded, the accumulation of corrosive substances such as rusty spots and the like does not occur on the surface of the coating, and obvious convolution of a curve in a high-frequency part (representing the substance transfer condition in the interface between the composite coating and metal) can be observed from an impedance spectrum, and the substance transfer is also verified to be generated after the composite coating is subjected to electrochemical corrosion, and the generated corrosive substances such as polysulfide-iron and other complexes can block a substance transfer channel, namely an ion channel, so that the entry of external electrolyte ions, water, oxygen and other ions is prevented, and the corrosion process is slowed down.
The mechanism of the invention is as follows:
according to the invention, the acrylic resin emulsion is prepared by adopting a core-shell emulsion polymerization method, the size of latex particles in the acrylic resin emulsion is very small and reaches the size of a mesopore, so that a resin coating can form a compact and continuous film, a good capillary acting force is generated in the film forming process, and the invasion of media such as extrusion water and the like to the metal surface can be better eliminated; the latex particles are of a spherical structure with interpenetrating networks, the shell layers of the latex particles contain abundant epoxy groups, can provide crosslinking sites, and react with sulfydryl in a polysulfide oligomer chain segment to prepare the composite coating with the anticorrosion performance. The polysulfide oligomer has excellent dispersing power, can be uniformly distributed in the emulsion, can ensure that a system is more uniform during crosslinking, ensures that the crosslinking density of the coating is uniformly distributed, can greatly increase the hydrophobic property of the coating while increasing the crosslinking density in the coating and improving the density of the coating, increases the anticorrosion effect of the composite coating on the metal surface, and delays the electrochemical corrosion of the metal surface. Corrosive substances generated in the electrochemical corrosion process of the acrylic acid coating added with the polysulfide emulsion can block an ion channel, so that the entry of water molecules and oxygen molecules is blocked, and the corrosion is delayed. Compared with an acrylic coating without the addition of the polysulfide emulsion, the corrosion is continuously deepened after the coating is corroded due to the entrance of water vapor and oxygen until the corrosion resistance is lost.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention adopts a core-shell emulsion polymerization method to prepare the acrylic resin emulsion, the size of latex particles in the acrylic resin emulsion is distributed in a nanometer level, and the average particle size is about 58nm, thereby being beneficial to forming a compact continuous coating on a resin coating. Polysulfide oligomer is introduced into acrylic resin to be used as an external crosslinking agent to prepare the composite coating, so that the internal crosslinking density of the coating is increased, meanwhile, the hydrophobicity is increased, and the anticorrosion effect is improved. The results of soaking in 40 ℃ saline showed that the samples coated with the composite coating started to rust 24 hours after the samples coated with the acrylic resin coating not modified with polysulfide oligomer had been rust-inhibited and were more corrosion resistant. Compared with other external crosslinking agents, the polysulfide oligomer and the acrylic resin emulsion used in the invention can be crosslinked at normal temperature to save energy, and the polysulfide oligomer can be prepared by using waste elemental sulfur in petroleum production as a substrate, so that the environmental problem caused by waste sulfur accumulation is solved.
Drawings
FIG. 1 is an infrared spectrum of a coating formed by reacting the polythiooligomer prepared in example 8 with an acrylic resin emulsion.
FIG. 2 is a graph showing an average particle diameter distribution of acrylic latex particles having a core-shell structure in the acrylic resin emulsion prepared in example 8.
FIG. 3 shows the corrosion resistance of the coating prepared in example 9 in the salt water test, the control group on the left and the experimental group on the right.
FIG. 4 is a chart of the infrared spectra of polythiooligomers used in various examples of the invention.
FIG. 5 is an impedance plot of the coating prepared in example 10 soaked in saline for 7 days.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. The polysulfide oligomers used in the examples were elemental sulfur/terpene copolymers (PST) prepared by the method of example 1 of chinese patent publication 201710617001.4. Wherein the beta-pinene accounts for 40 percent of the total mass of the elemental sulfur and the terpene. The desired compound was identified by measuring the infrared spectrum (i.e., FIG. 4) and comparing it to the infrared spectrum data in the article L.Sun, et al.European Polymer Journal 123(2020) 109440. It is also clear from the published article L.Sun, et al.European Polymer Journal 123(2020)109440 that the PST molecule segment contains a large number of thiol groups.
The reagents used in the examples are commercially available without specific reference.
Example 1
(1) Preparation of acrylic resin emulsion with core-shell structure
Firstly, emulsifying a nuclear monomer: core monomers of hexadecyl methacrylate, dodecyl methacrylate and styrene are added into a 250ml four-neck flask according to the mass ratio of 1:1:3, the total mass of the core monomers is 30g, then emulsifier span 80 and op-10 are added, the total mass is 1.5g, water is added into the flask 40g, mechanical stirring is adopted at normal temperature for one hour, and the rotating speed is 600 r/min. After emulsification, a reaction device is arranged. Mechanically stirring for 140r/min, introducing nitrogen, condensing water, and keeping the temperature of an oil bath kettle at 70 ℃. 0.4g of ammonium persulfate initiator is dissolved in 10g of water and slowly dropped at the dropping speed of 0.5g/min by adopting a peristaltic pump. Until a significant blue light appeared in the four-necked flask, 1.2g of the emulsified shell monomer and the initiator potassium persulfate dissolved in 20g of water were added dropwise at a rate of 0.4g/min at 8 g/min. Then keeping the temperature at 80 ℃ for 1 hour after the shell monomer is dripped, and taking out the emulsion. The shell monomer is prepared by taking 70g of shell monomer of cyclohexyl methacrylate, methyl methacrylate, styrene and glycidyl methacrylate in a mass ratio of 10:7:7:1.5, adding the shell monomer, 150g of water and 3g of op-10 emulsifier into a beaker, and mechanically stirring for 1 hour at normal temperature at the rotating speed of 1000 r/min.
(2) Emulsification of elemental sulfur/terpene copolymers
Preparing polysulfide emulsion of elementary sulfur/terpene copolymer according to phase inversion method: 5g of emulsifier (sodium dodecyl benzene sulfonate) SDBS and 5g of elemental sulfur/terpene copolymer are added into a four-mouth flask, the mixture is stirred and mixed evenly at 50 ℃ to obtain elemental sulfur/terpene copolymer emulsion, then the temperature is raised to 65 ℃, 95g of water is dripped in at 3g/min for phase inversion. The dark red color in the flask turned to light yellow and the reaction was complete. Obtain the polysulfide emulsion with the solid content of 5 percent.
(3) And (2) blending the polysulfide emulsion and the acrylic resin emulsion at room temperature to form a mixed solution, wherein the mass of the polysulfide emulsion is 0.5 percent of the mass of the mixed solution, and crosslinking the polysulfide emulsion for 10min at 60 ℃ to obtain the elemental sulfur/terpene copolymer modified acrylic resin. And then carrying out an anti-corrosion performance test.
Example 2
(1) Preparation of acrylic resin emulsion with core-shell structure
Firstly, emulsifying a nuclear monomer: core monomers of hexadecyl methacrylate, dodecyl methacrylate and styrene are added into a 250ml four-neck flask according to the mass ratio of 1:1:3, the total mass of the core monomers is 30g, then emulsifier span 80 and op-10 are added, the total mass is 1.5g, water is added into the flask for 40g, mechanical stirring is adopted at normal temperature for one hour, and the rotating speed is 600 r/min. After emulsification, a reaction device is arranged. Mechanically stirring for 140r/min, introducing nitrogen, condensing water, and keeping the temperature of an oil bath kettle at 74 ℃. 0.4g of ammonium persulfate initiator is dissolved in 10g of water, and the dropping speed is 0.5g/min by adopting a peristaltic pump. Until a noticeable blue light appeared in the four-necked flask. 1.2g of the emulsified shell monomer and 1.2g of the initiator potassium persulfate dissolved in 20g of water were initially added dropwise at a rate of 0.4 g/min. Then keeping the temperature at 80 ℃ for 1 hour after the shell monomer is dripped, and taking out the emulsion. The shell monomer is prepared by taking 70g of shell monomer of cyclohexyl methacrylate, methyl methacrylate, styrene and glycidyl methacrylate in a mass ratio of 10:7:7:1.5, adding the shell monomer, 150g of water and 3g of op-10 emulsifier into a beaker, and mechanically stirring for 1 hour at normal temperature at the rotating speed of 1000 r/min.
(2) Emulsification of elemental sulfur/terpene copolymers
Preparing polysulfide emulsion of elementary sulfur/terpene copolymer according to phase inversion method: 5g of emulsifier (sodium dodecyl benzene sulfonate) SDBS and 8g of elemental sulfur/terpene copolymer are added into a four-mouth flask, the mixture is stirred and mixed uniformly at 50 ℃ to obtain elemental sulfur/terpene copolymer emulsion, then the temperature is raised to 65 ℃, and 92g of water is dripped at 3g/min for phase inversion. The dark red color in the flask turned to light yellow and the reaction was complete. Obtain the polysulfide emulsion with the solid content of 8 percent.
(3) And (2) blending the polysulfide emulsion and the acrylic resin emulsion at room temperature to form a mixed solution, wherein the mass of the polysulfide emulsion is 1% of that of the mixed solution, and crosslinking the polysulfide emulsion for 20min at 70 ℃ to obtain the elemental sulfur/terpene copolymer modified acrylic resin. And then carrying out an anti-corrosion performance test.
Example 3
(1) Preparation of acrylic resin emulsion with core-shell structure
Firstly, emulsifying a nuclear monomer: core monomers of hexadecyl methacrylate, dodecyl methacrylate and styrene are added into a 250ml four-neck flask according to the mass ratio of 1:1:3, the total mass of the core monomers is 40g, then emulsifier span 80 and op-10 are added, the total mass is 1.5g, water is added into the flask 40g, mechanical stirring is adopted at normal temperature for one hour, and the rotating speed is 600 r/min. After emulsification, a reaction device is arranged. Mechanically stirring for 220r/min, introducing nitrogen, condensing water, and keeping the temperature of an oil bath kettle at 78 ℃. 0.4g of ammonium persulfate initiator is dissolved in 10g of water, and the dropping speed is 0.5g/min by adopting a peristaltic pump. Until a noticeable blue light appeared in the four-necked flask. 1.2g of the emulsified shell monomer and 1.2g of the initiator potassium persulfate dissolved in 20g of water were initially added dropwise at a rate of 0.4 g/min. Then keeping the temperature at 80 ℃ for 1 hour after the shell monomer is dripped, and taking out the emulsion. The shell monomer emulsifying process comprises the following steps of taking 60g of shell monomer cyclohexyl methacrylate, methyl methacrylate, styrene and glycidyl methacrylate in a mass ratio of 10:7:7:1.5, adding the shell monomer cyclohexyl methacrylate, methyl methacrylate, styrene and glycidyl methacrylate into a beaker together with 150g of water and 3g of op-10 emulsifier, and mechanically stirring for 1 hour at normal temperature at the rotating speed of 1000 r/min.
(2) Emulsification of elemental sulfur/terpene copolymers
Preparing polysulfide emulsion of elementary sulfur/terpene copolymer according to phase inversion method: 5g of emulsifier (sodium dodecyl benzene sulfonate) SDBS and 12g of elemental sulfur/terpene copolymer are added into a four-neck flask, the mixture is stirred and mixed evenly at 25 ℃ to obtain elemental sulfur/terpene copolymer emulsion, then the temperature is raised to 65 ℃, 88g of water is dripped in 3g/min for phase inversion. The dark red color in the flask turned to light yellow and the reaction was complete. A polysulfide emulsion with a solid content of 12% is obtained.
(3) And (2) blending the polysulfide emulsion and the acrylic resin emulsion at room temperature to form a mixed solution, wherein the mass of the polysulfide emulsion is 2% of that of the mixed solution, and crosslinking the polysulfide emulsion for 10min at 65 ℃ to obtain the elemental sulfur/terpene copolymer modified acrylic resin. And then carrying out an anti-corrosion performance test.
Example 4
(1) Preparation of acrylic resin emulsion with core-shell structure
Firstly, emulsifying a nuclear monomer: core monomers of hexadecyl methacrylate, dodecyl methacrylate and styrene are added into a 250ml four-neck flask according to the mass ratio of 1:1:3, the total mass of the core monomers is 35g, then emulsifier span 80 and op-10 are added, the total mass is 1.5g, water is added into the flask for 40g, mechanical stirring is adopted at normal temperature for one hour, and the rotating speed is 600 r/min. After emulsification, a reaction device is arranged. Mechanically stirring at 260r/min, introducing nitrogen, condensing water, and keeping the temperature of an oil bath kettle at 80 ℃. 0.4g of ammonium persulfate initiator is dissolved in 10g of water, and the dropping speed is 0.5g/min by adopting a peristaltic pump. Until a noticeable blue light appeared in the four-necked flask. 1.2g of the emulsified shell monomer and 1.2g of the initiator potassium persulfate dissolved in 20g of water were initially added dropwise at a rate of 0.4 g/min. Then keeping the temperature at 80 ℃ for 1 hour after the shell monomer is dripped, and taking out the emulsion. The shell monomer is prepared by taking 65g of shell monomer of cyclohexyl methacrylate, methyl methacrylate, styrene and glycidyl methacrylate in a mass ratio of 10:7:7:1.5, adding 150g of water and 3g of op-10 emulsifier into a beaker, and mechanically stirring for 1 hour at normal temperature at the rotating speed of 1000 r/min.
(2) Emulsification of elemental sulfur/terpene copolymers
Preparing polysulfide emulsion of elementary sulfur/terpene copolymer according to phase inversion method: 5g of emulsifier (sodium dodecyl benzene sulfonate) SDBS and 16g of elemental sulfur/terpene copolymer are added into a four-mouth flask, the mixture is stirred and mixed evenly at 45 ℃ to obtain elemental sulfur/terpene copolymer emulsion, then the temperature is raised to 70 ℃, 84g of water is dripped in at 3g/min for phase inversion. The dark red color in the flask turned to light yellow and the reaction was complete. A polysulfide emulsion with a solid content of 16% is obtained.
(3) And (2) blending the polysulfide emulsion and the acrylic resin emulsion at room temperature to form a mixed solution, wherein the mass of the polysulfide emulsion is 3% of that of the mixed solution, and crosslinking the polysulfide emulsion for 20min at 70 ℃ to obtain the elemental sulfur/terpene copolymer modified acrylic resin. And then carrying out an anti-corrosion performance test.
Example 5
(1) Preparation of acrylic resin emulsion with core-shell structure
Firstly, emulsifying a nuclear monomer: core monomers of hexadecyl methacrylate, dodecyl methacrylate and styrene are added into a 250ml four-neck flask according to the mass ratio of 1:1:3, the total mass of the core monomers is 30g, then emulsifier span 80 and op-10 are added, the total mass is 1.5g, water is added into the flask for 40g, mechanical stirring is adopted at normal temperature for one hour, and the rotating speed is 600 r/min. After emulsification, a reaction device is arranged. Mechanically stirring for 180r/min, introducing nitrogen, condensing water, and carrying out oil bath at the constant temperature of 75 ℃. 0.4g of ammonium persulfate initiator is dissolved in 10g of water, and the dropping speed is 0.5g/min by adopting a peristaltic pump. Until a noticeable blue light appeared in the four-necked flask. 1.2g of the emulsified shell monomer and 1.2g of the initiator potassium persulfate dissolved in 20g of water were initially added dropwise at a rate of 0.4 g/min. And then keeping the temperature for 1 hour after the shell monomer is dripped, and taking out the emulsion. The shell monomer is prepared by taking 70g of shell monomer of cyclohexyl methacrylate, methyl methacrylate, styrene and glycidyl methacrylate in a mass ratio of 10:7:7:1.5, adding the shell monomer, 150g of water and 3g of op-10 emulsifier into a beaker, and mechanically stirring for 1 hour at normal temperature at the rotating speed of 1000 r/min.
(2) Emulsification of elemental sulfur/terpene copolymers
Preparing polysulfide emulsion of elementary sulfur/terpene copolymer according to phase inversion method: 5g of emulsifier (sodium dodecyl benzene sulfonate) SDBS and 5g of elemental sulfur/terpene copolymer are added into a four-mouth flask, the mixture is stirred and mixed evenly at 50 ℃ to obtain elemental sulfur/terpene copolymer emulsion, then the temperature is raised to 65 ℃, 80g of water is dripped in at 3g/min for phase inversion. The dark red color in the flask turned to light yellow and the reaction was complete. Obtain the polysulfide emulsion with the solid content of 6 percent.
(3) And (2) blending the polysulfide emulsion and the acrylic resin emulsion at room temperature to form a mixed solution, wherein the mass of the polysulfide emulsion is 0.5 percent of the mass of the mixed solution, and crosslinking the polysulfide emulsion for 20min at 80 ℃ to obtain the elemental sulfur/terpene copolymer modified acrylic resin. And then carrying out an anti-corrosion performance test.
Example 6
(1) Preparation of acrylic resin emulsion with core-shell structure
Firstly, emulsifying a nuclear monomer: sixteen-methyl acrylate and twelve-methyl acrylate) with the mass ratio of 1:1:3 and nuclear monomer of styrene are added into a 250ml four-neck flask, the total mass of the nuclear monomer is 30g, then span 80 and op-10 which are emulsifying agents are added, the total mass is 1.5g, 40g of water is added, mechanical stirring is adopted at normal temperature for one hour, and the rotating speed is 700 r/min. After emulsification, a reaction device is arranged. Mechanically stirring for 140r/min, introducing nitrogen, condensing water, and keeping the temperature of an oil bath kettle at 80 ℃. 0.4g of ammonium persulfate initiator is dissolved in 10g of water, and the dropping speed is 0.5g/min by adopting a peristaltic pump. Until a noticeable blue light appeared in the four-necked flask. 1.2g of the emulsified shell monomer and 1.2g of the initiator potassium persulfate dissolved in 20g of water were initially added dropwise at a rate of 0.4 g/min. And then keeping the temperature for 1 hour after the shell monomer is dripped, and taking out the emulsion. The shell monomer is prepared by taking 70g of shell monomer of cyclohexyl methacrylate, methyl methacrylate, styrene and glycidyl methacrylate in a mass ratio of 10:7:7:1.5, adding the shell monomer, 150g of water and 3g of op-10 emulsifier into a beaker, and mechanically stirring for 1 hour at normal temperature at the rotating speed of 1000 r/min.
(2) Emulsification of elemental sulfur/terpene copolymers
Preparing polysulfide emulsion of elementary sulfur/terpene copolymer according to phase inversion method: 5g of emulsifier (sodium dodecyl benzene sulfonate) SDBS and 10g of elemental sulfur/terpene copolymer are added into a four-mouth flask, the mixture is stirred and mixed evenly at the temperature of 40 ℃ to obtain elemental sulfur/terpene copolymer emulsion, then the temperature is raised to 65 ℃, and 90g of water is dripped in at the speed of 3g/min for phase inversion. The dark red color in the flask turned to light yellow and the reaction was complete. A polysulfide emulsion with a solid content of 10% is obtained.
(3) And (2) blending the polysulfide emulsion and the acrylic resin emulsion at room temperature to form a mixed solution, wherein the mass of the polysulfide emulsion is 2% of that of the mixed solution, and crosslinking the polysulfide emulsion for 10min at 80 ℃ to obtain the elemental sulfur/terpene copolymer modified acrylic resin. And then carrying out an anti-corrosion performance test.
Example 7
(1) Preparation of acrylic resin emulsion with core-shell structure
Firstly, emulsifying a nuclear monomer: core monomers of hexadecyl methacrylate, dodecyl methacrylate and styrene are added into a 250ml four-neck flask according to the mass ratio of 1:1:3, the total mass of the core monomers is 20g, then emulsifier span 80 and op-10 are added, the total mass is 1.5g, water is added into the flask for 40g, mechanical stirring is adopted at normal temperature for one hour, and the rotating speed is 600 r/min. After emulsification, a reaction device is arranged. Mechanically stirring for 240r/min, introducing nitrogen, condensing water, and keeping the temperature of an oil bath kettle at 80 ℃. 0.4g of ammonium persulfate initiator is dissolved in 10g of water, and the dropping speed is 0.5g/min by adopting a peristaltic pump. Until a noticeable blue light appeared in the four-necked flask. 1.2g of the emulsified shell monomer and 1.2g of the initiator potassium persulfate dissolved in 20g of water were initially added dropwise at a rate of 0.4 g/min. Then keeping the temperature at 80 ℃ for 1 hour after the shell monomer is dripped, and taking out the emulsion. The shell monomer is prepared by taking 80g of shell monomer of cyclohexyl methacrylate, methyl methacrylate, styrene and glycidyl methacrylate in a mass ratio of 10:7:7:1.5, adding the shell monomer, 150g of water and 3g of op-10 emulsifier into a beaker, and mechanically stirring for 1 hour at normal temperature at the rotating speed of 1000 r/min.
(2) Emulsification of elemental sulfur/terpene copolymers
Preparing polysulfide emulsion of elementary sulfur/terpene copolymer according to phase inversion method: 5g of emulsifier (sodium dodecyl benzene sulfonate) SDBS and 7g of elemental sulfur/terpene copolymer are added into a four-mouth flask, the mixture is stirred and mixed evenly at 50 ℃ to obtain elemental sulfur/terpene copolymer emulsion, then the temperature is raised to 65 ℃, 93g of water is dripped in at 3g/min for phase inversion. The dark red color in the flask turned to light yellow and the reaction was complete. A polysulfide emulsion with a solid content of 7% is obtained.
(3) And (2) blending the polysulfide emulsion and the acrylic resin emulsion at room temperature to form a mixed solution, wherein the mass of the polysulfide emulsion is 1.5% of that of the mixed solution, and crosslinking the polysulfide emulsion for 10min at 80 ℃ to obtain the elemental sulfur/terpene copolymer modified acrylic resin. And then carrying out an anti-corrosion performance test.
Example 8
(1) Preparation of acrylic resin emulsion with core-shell structure
Firstly, emulsifying a nuclear monomer: core monomers of hexadecyl methacrylate, dodecyl methacrylate and styrene are added into a 250ml four-neck flask according to the mass ratio of 1:1:3, the total mass of the core monomers is 25g, then emulsifier span 80 and op-10 are added, the total mass is 1.5g, water is added into the flask for 40g, mechanical stirring is adopted at normal temperature for one hour, and the rotating speed is 600 r/min. After emulsification, a reaction device is arranged. Mechanically stirring for 190r/min, introducing nitrogen, condensing water, and keeping the temperature of an oil bath kettle at 78 ℃. 0.4g of ammonium persulfate initiator is dissolved in 10g of water, and the dropping speed is 0.5g/min by adopting a peristaltic pump. Until a noticeable blue light appeared in the four-necked flask. 1.2g of the emulsified shell monomer and 1.2g of the initiator potassium persulfate dissolved in 20g of water were initially added dropwise at a rate of 0.4 g/min. And then keeping the temperature for 1 hour after the shell monomer is dripped, and taking out the emulsion. The shell monomer is prepared by taking 75g of shell monomer of cyclohexyl methacrylate, methyl methacrylate, styrene and glycidyl methacrylate in a mass ratio of 10:7:7:1.5, adding the shell monomer, 150g of water and 3g of op-10 emulsifier into a beaker, and mechanically stirring for 1 hour at normal temperature at the rotating speed of 1000 r/min. The average particle size of the acrylic latex particles obtained by the particle size analyzer is shown in FIG. 2, the average particle size is 58.77nm, and is below 100nm, which meets the requirement of preparing acrylic latex with small dispersed particle size.
(2) Emulsification of elemental sulfur/terpene copolymers
Preparing polysulfide emulsion of elementary sulfur/terpene copolymer according to phase inversion method: 5g of emulsifier (sodium dodecyl benzene sulfonate) SDBS and 5g of elemental sulfur/terpene copolymer are added into a four-mouth flask, the mixture is stirred and mixed evenly at 50 ℃ to obtain elemental sulfur/terpene copolymer emulsion, then the temperature is raised to 65 ℃, 95g of water is dripped in at 3g/min for phase inversion. The dark red color in the flask turned to light yellow and the reaction was complete. Obtain the polysulfide emulsion with the solid content of 5 percent.
(3) And (2) blending the polysulfide emulsion and the acrylic resin emulsion at room temperature to form a mixed solution, wherein the mass of the polysulfide emulsion is 3% of that of the mixed solution, and crosslinking the polysulfide emulsion for 10min at 80 ℃ to obtain the elemental sulfur/terpene copolymer modified acrylic resin. And then carrying out an anti-corrosion performance test. Wherein the infrared spectrum of the resin sample after film formation is shown in FIG. 1. By comparing fig. 1 and fig. 4, the ring-opened epoxy group in the shell monomer is crosslinked with the mercapto group in the polysulfide emulsion, so the generated hydroxyl group is 3200cm in fig. 1-1-3600cm-1The occurrence of a distinct absorption peak indicates the successful preparation of the polysulfide oligomer-modified acrylic resin of the present invention.
Example 9
The acrylic resin introduced with polysulfide oligomer prepared in embodiment 8 of the present invention was coated on the surface of a tinplate metal substrate from which a zinc coating and dust were removed by 1.4g of the resin, and after the surface of the substrate was dried, the substrate was placed in an oven maintained at a constant temperature of 80 ℃ for 3 hours to obtain a metal substrate coated with a modified coating, which was used as an experimental group. The unmodified acrylic resin prepared in step (1) of example 8 was coated on the surface of a metal substrate as a control. The test group and the control group were immersed in 3.5 wt% saline at 40 c to perform the corrosion prevention performance test, and the results are shown in fig. 3, in which the left side is the unmodified acrylic resin coating layer prepared in step (1) of example 8, which is the control group, and the right side is the acrylic resin coating layer with the introduction of the polysulfide oligomer, which is prepared in example 8, which is the test group. The rusted substrate coated with the modified resin disclosed by the invention starts to rust after being rusted for 24 hours, so that the modified resin disclosed by the invention can obviously improve the corrosion resistance of the metal surface.
Example 10
1.4g of acrylic resin introduced by the polysulfide oligomer prepared in the embodiment 1 of the invention is coated on the surface of the tinplate metal matrix from which the zinc coating, dust and the like are removed, and after the surface of the base material is dried, the base material is placed in an oven with the constant temperature of 80 ℃ for 3 hours, so that the metal base material coated with the modified coating is obtained. The substrate was immersed in 3.5 wt% saline at 40 ℃ for 7 days to test the impedance profile. As shown in fig. 5, a significant convolution of the curve in the high frequency region (representing the material transfer condition in the interface between the composite coating and the metal) can be observed from the impedance spectrum, which confirms that the material transfer is generated after the composite coating is subjected to electrochemical corrosion, and the generated corrosion substance, such as a polysulfide-iron complex, can block a material transfer channel, i.e., an ion channel, so as to prevent the entry of external electrolyte ions, water, oxygen and other ions and slow down the corrosion process.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for preparing a polysulfide oligomer-modified acrylic resin, comprising the steps of:
(1) preparing acrylic resin emulsion with a core-shell structure: selecting an acrylic acid derivative as a nuclear layer monomer for pre-emulsification, and then adding a nuclear layer initiator to initiate the polymerization of the nuclear layer monomer to obtain a nuclear structure; then, taking an acrylic acid derivative as a shell monomer for pre-emulsification, respectively adding the shell monomer and a shell initiator, and carrying out shell polymerization on the basis of a core structure to obtain an acrylic resin emulsion with a core-shell structure;
(2) preparation of polysulfide emulsion: emulsifying polysulfide oligomer by using an emulsifier to obtain polysulfide oligomer emulsion, and then performing phase inversion on the polysulfide oligomer emulsion by using water to obtain polysulfide emulsion;
(3) and (3) uniformly mixing the acrylic resin emulsion with the core-shell structure and the polysulfide emulsion, and crosslinking to obtain the polysulfide oligomer modified acrylic resin.
2. The method of claim 1, wherein the acrylic resin modified with polysulfide oligomer is prepared by the following steps:
the core layer monomer in the step (1) comprises at least two of butyl acrylate, cetyl methacrylate, methyl methacrylate, tert-butyl methacrylate, lauryl methacrylate and styrene;
the shell layer monomer in the step (1) comprises a shell layer conventional monomer and a shell layer functional monomer; the shell layer conventional monomer comprises at least three of butyl acrylate, cyclohexyl methacrylate, hexadecyl methacrylate, methyl methacrylate, tert-butyl methacrylate and dodecyl methacrylate; the shell layer functional monomer comprises at least one of glycidyl methacrylate, glycidyl acrylate, glycidyl n-butyrate and 2, 3-epoxypropyl acrylate.
3. The method of claim 1, wherein the acrylic resin modified with polysulfide oligomer is prepared by the following steps:
in the step (1), the dosage of the core layer monomer, the core layer initiator, the shell layer monomer and the shell layer initiator meets the following requirements: the core layer monomer accounts for 35-55% of the mass of the shell layer monomer; the nuclear layer initiator accounts for 0.1 to 3 percent of the mass of the nuclear monomer; the shell initiator accounts for 0.5 to 2.3 percent of the mass of the shell monomer;
the nuclear layer initiator in the step (1) comprises at least one of ammonium persulfate, azo thioether, hydrogen peroxide, ferric persulfate-ferrous oxide and potassium persulfate; the shell initiator comprises at least one of ammonium persulfate, azo thioether, hydrogen peroxide, ferric persulfate-ferrous oxide and potassium persulfate.
4. The method of claim 1, wherein the acrylic resin modified with polysulfide oligomer is prepared by the following steps:
the reaction temperature of the nuclear layer monomer polymerization in the step (1) is 70-90 ℃, and the reaction time is 1-3 hours; the reaction temperature of the shell polymerization is 75-95 ℃, and the reaction time is 3-5 hours.
5. The method of claim 1, wherein the acrylic resin modified with polysulfide oligomer is prepared by the following steps:
the pre-emulsification of the core layer monomer in the step (1) is to add an emulsifier and water into the core layer monomer, and stir at normal temperature to achieve the emulsification effect; the emulsifier comprises at least one of span 60, span 80, OP-10, se-10 and PCA; the dosage of the emulsifier is 0.5 to 7.5 percent of the mass of the core layer monomer;
the pre-emulsification of the shell monomer in the step (1) is to add an emulsifier and water into the shell monomer and stir at normal temperature to achieve the emulsification effect; the emulsifier comprises at least one of span 60, span 80, OP-10, se-10 and PCA; the dosage of the emulsifier is 0.5 to 9 percent of the dosage of the shell layer monomer.
6. The method of claim 1, wherein the acrylic resin modified with polysulfide oligomer is prepared by the following steps:
in the step (2), the polysulfide oligomer is an elemental sulfur/terpene copolymer with sulfydryl.
7. The method of claim 1, wherein the acrylic resin modified with polysulfide oligomer is prepared by the following steps:
in the emulsification in the step (2), the polysulfide oligomer and the emulsifier are mixed and stirred uniformly at the temperature of 25-55 ℃ to obtain polysulfide oligomer emulsion; the emulsifier comprises at least two of (sodium dodecyl benzene sulfonate) SDBS, span 60, span 80, Tween 80, OP-10 and L-pyrrolidone-5-sodium carboxylate, wherein the using amount of the emulsifier accounts for 2% -7% of the total mass of the core layer monomer and the shell layer monomer;
in the step (2), the phase inversion is carried out by dripping water into the polysulfide oligomer emulsion at the temperature of between 50 and 80 ℃ and stirring the mixture to carry out phase inversion, and the color of the emulsion is changed into light yellow from dark red to obtain polysulfide emulsion; the solid content of the polysulfide emulsion is 5-30%.
8. The method of claim 1, wherein the acrylic resin modified with polysulfide oligomer is prepared by the following steps:
in the step (3), the polysulfide emulsion and the acrylic resin emulsion are mixed at room temperature to form a mixed solution, and the mass of the polysulfide emulsion is 0.5-10% of the mass of the mixed solution; the crosslinking is the crosslinking of the mixed solution at the temperature of 55-80 ℃ for 10-30 minutes.
9. A polysulfide oligomer-modified acrylic resin prepared by the process of any one of claims 1-8.
10. The use of the polythio oligomer-modified acrylic resin of claim 9 in the field of metal organic anticorrosive coatings.
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