CN113429857A - High molecular nano microgranule and preparation method thereof - Google Patents
High molecular nano microgranule and preparation method thereof Download PDFInfo
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- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The invention discloses a preparation method of a high-molecular nano particle agent, which is prepared from the following raw materials: the paint comprises dihydroxy functional group organic silicon modified acrylic resin, silane coupling agent modified nano silicon dioxide, absolute ethyl alcohol, water-soluble hydrogen-containing silicone oil, a dispersing agent, a flatting agent, a film forming agent, a stabilizing agent, acetic acid, ammonia water and water. The high molecular nanometer particle agent can enhance the corrosion resistance, the anti-staining performance, the self-cleaning performance, the high conductivity and the coating performance of the metal surface after being solidified.
Description
Technical Field
The invention relates to the field of polymer coatings, in particular to a preparation method of a polymer nanometer particle agent.
Technical Field
In recent years, with the continuous improvement of living standard of people, the popularity of electronic products such as computers, liquid crystal televisions, smart phones and the like is increasing, and the requirements of people on the performance and the appearance are also increasing. In the use process of electronic products, the problem of signal transmission cannot be solved, the phenomena of rusting, candle corrosion and the like are easy to occur when common metal is exposed in the air, so that the performance of the product is influenced, early signal transmission equipment generally adopts a surface coating material to achieve the effects of attractiveness and protection, but the coating material has a shielding effect on signals, so that the attenuation of the signals in the transmission process is caused, and the performance of the product is influenced. The issue is well solved by the advent of polymer nanoparticles. The polymer nanoparticles are a process for imparting high conductivity and high corrosion resistance to the surface of a metal plate after chemical and inorganic chemical treatments are performed on the surface. Developed by japan corporation the earliest 70 s in the 20 th century. Its original idea was to make the galvanized sheet non-stick by treating it. Subsequently, people change the idea and turn to searching for a special substance, and after the substance is coated on the surfaces of other metals, the optical properties of the metal before and after the substance is attached are not obviously changed, so that the corrosion resistance effect is achieved.
The inorganic fine particles have high strength, high hardness, thermal stability and chemical stability, are mixed and compounded with a tough organic polymer, can fully exert the respective advantages, and can obtain characteristics which are not possessed by the both. After the nano composite particle-organic polymer mixed system is formed into a film, the performances of the film, such as hardness, wear resistance, scratch resistance, heat resistance, water resistance, weather resistance, conductivity and the like, are greatly improved, and the cost and the lowest film forming temperature can be reduced.
The Chinese invention patent CN1431234A relates to a preparation method of soap-free nano core-shell silicone-acrylate emulsion. The preparation method comprises the steps of firstly preparing nano-grade pure acrylic core emulsion with good film-forming property by using an emulsifier, then adding active organic silicide and (methyl) acrylate to generate shell emulsion, and then completing silanol-based three-way chemical bonding in the presence of organic tin compound or titanate. The emulsion prepared by the preparation method has the characteristics of nano-scale particle size and specific core-shell structure, is used for manufacturing environment-friendly water-based emulsion paint, and has better water resistance, weather resistance, stain resistance and color retention compared with the common silicone-acrylate emulsion. Is especially suitable for manufacturing high-grade indoor and outdoor wall latex paint.
Chinese invention patent CN1424353A discloses an organosilicon modified acrylic ester/inorganic nano composite emulsion and a preparation method thereof, wherein the emulsion contains nano SiO in silicone-acrylate emulsion particles2、TiO2、ZnO、CaCO3The inorganic phase is prepared by adopting a two-step polymerization method of inverse emulsion polymerization/emulsion polymerization. The inorganic nano particles have full size effect, surface effect, quantum effect, filling effect and catalytic property, so that the mechanical property, the anti-staining property, the self-cleaning property, the antistatic property and the like of the silicone-acrylate emulsion coating can be effectively improved. By adopting an in-situ polymerization technology, grafting polymerization is carried out on the surfaces of the inorganic nanoparticles, so that the interaction between the polymer and the inorganic nanoparticles is enhanced. Compared with physical blending, the silicone-acrylate emulsion not only improves the stability of the emulsion, but also endows the silicone-acrylate emulsion with excellent performance. The emulsion can be used as coating, adhesive, glazing agent and cement modifier, and can be especially used as high-performance water-based coating.
A fingerprint-resistant liquid is described in chinese patent application No. 201310736954.4. The product uses crosslinking agents such as aziridine, polycarbodiimide and the like, the crosslinking agents have good reactivity with resin in a system and can improve the crosslinking strength of a coating, but the crosslinking reaction can be carried out at room temperature, so that the storage stability of the product is influenced and the gel phenomenon is easy to occur.
The chinese patent application No. 201510507320.0 describes an aluminum-zinc plating fingerprint-resistant liquid with a corrosion resistance of 120 hours, but the experimental results do not mention the problems of alkali resistance and blackening. In addition, the product contains nitrite with high toxicity.
The invention provides a simple and feasible preparation method, aiming at the current situation that the selected dihydroxy functional group organic silicon modified acrylic resin and silane coupling agent modified nano-silica can overcome the defect, and the storage period can reach more than one year by compounding ethanol, water-soluble hydrogen-containing silicone oil crosslinking and emulsifying agents (polyacrylic acid, sodium dodecyl benzene sulfonate, sulfuric ester, carboxymethyl cellulose and the like), flatting agents (acrylic acids, fluorine flatting agents and the like), film forming additives (potassium fluotitanate, malonic acid, copper sulfate, maleic acid dispersing agents and the like), stabilizing agents (hydrogen peroxide, potassium pyrophosphate and sodium metasilicate) and taking out for use, thereby being more convenient to operate and use.
Disclosure of Invention
The invention discloses a high-molecular nanometer particle agent and a preparation method thereof.
A high molecular nanometer microgranule is composed of the following raw materials: 150-250g of dihydroxy functional group organic silicon modified acrylic resin, 50-150g of silane coupling agent modified nano silicon dioxide, 10-100g of absolute ethyl alcohol, 25-75g of water-soluble hydrogen-containing silicone oil, 0.01-5g of dispersing agent, 0.1-10g of flatting agent, 0.1-20g of film forming agent, 0.5-35g of stabilizing agent, 4-6g of acetic acid, 6-8g of ammonia water and 600g of water 500-.
The dispersant is one or a mixture of two or more of polyacrylic acid, sulfuric ester, carboxymethyl cellulose and sodium dodecyl benzene sulfonate; preferably, the dispersant is sodium dodecyl benzene sulfonate.
The flatting agent is one of an acrylic flatting agent, a fluorine flatting agent and a fluorine modified acrylic flatting agent; preferably, the leveling agent is a fluorine modified polyacrylate leveling agent.
The film forming agent is one or a mixture of two or more of potassium fluotitanate, malonic acid, copper sulfate and maleic acid; preferably, the film forming agent is prepared by mixing potassium fluotitanate and maleic acid according to the mass ratio of (15-17) to (2-4).
The stabilizer is one or a mixture of two or more of hydrogen peroxide, potassium pyrophosphate and sodium metasilicate; preferably, the stabilizer is hydrogen peroxide.
The preparation method of the silane coupling agent modified nano silicon dioxide comprises the following steps: mixing nano-silica, R-8204 functional polysiloxane and toluene according to the mass ratio of (20-40): 6-12): 90-110, stirring at the rotating speed of 12000R/min of 8000-.
The preparation method of the dihydroxy functional group organic silicon modified acrylic resin comprises the following steps: adding 6-7g of dihydroxy functional group organic silicon and 0.1-0.5g of initiator into 18-22g of butyl acetate, uniformly mixing, stirring at 65-75 ℃ at a rotating speed of 200r/min for 4-8min, then adding 24-28g of acrylate and 4-6g of acrylic acid, reacting at 75-85 ℃ for 0.5-1.5h, filtering, taking precipitate, washing and drying to obtain the dihydroxy functional group organic silicon modified acrylic resin.
The acrylate is one or a mixture of two of hydroxypropyl acrylate and n-butyl methacrylate, preferably the mixture of hydroxypropyl acrylate and n-butyl methacrylate according to the mass ratio of (8-10) to (5-6).
The initiator is one of ZIF-5, ZnGGH-9 and ZIF-8; preferably, the initiator is ZIF-8.
A preparation method of a high-molecular nanometer particle agent comprises the following steps:
s1 mixing 150-150 g of dihydroxy functional group organic silicon modified acrylic resin, 50-150g of silane coupling agent modified nano silicon dioxide, 10-100g of absolute ethyl alcohol and 600g of water, and then adding 4-6g of acetic acid to adjust the pH value to 3-4 to obtain the acidic precursor.
S2 adding 25-75g of water-soluble hydrogen-containing silicone oil, 0.01-5g of dispersant, 0.1-10g of flatting agent, 0.1-20g of film-forming agent and 0.5-35g of stabilizer into the acidic precursor prepared in S1, uniformly mixing, and then adding 6-8g of ammonia water to adjust the pH value to 7-8, thereby obtaining the polymer nano particle agent.
Most of the traditional high-molecular nano-particles adopt a physical mixing method to directly mix and dissolve all components, and the obtained product has poor crosslinking capability. According to the invention, firstly, the acrylic resin modified by the organic silicon with the dihydroxy functional group and the nano silicon dioxide modified by the silane coupling agent are grafted on the acrylic resin by virtue of the organic silicon with the dihydroxy functional group, so that the conductivity, corrosion resistance, anti-sticking performance and anti-fouling performance of the acrylic resin after film formation are improved; in addition, since the dihydroxy functional group organosilicon has the reaction activity similar to that of polyol and can generate copolymerization reaction with-NCO and-COOH, the dihydroxy functional group organosilicon is selected for copolymerization with acrylic resin, compared with common organosilicon modified acrylic resin, the dihydroxy functional group organosilicon has lower reaction conditions and easier reaction. The method adopts a copolymerization mode of the double-hydroxyl functional group organic silicon and the acrylic ester for production, and the double-hydroxyl functional group organic silicon and the acrylic ester are easier to polymerize, so that the double-hydroxyl functional group organic silicon is firstly polymerized with the acrylic ester in the reaction to form the double-hydroxyl functional group organic silicon modified acrylic ester, and when the double-hydroxyl functional group organic silicon is reacted, the acrylic ester and the double-hydroxyl functional group organic silicon modified acrylic ester begin to polymerize, and finally the double-hydroxyl functional group organic silicon modified acrylic resin is obtained. The performance of the reaction process can be regulated and controlled by adjusting the proportion of the dihydroxy functional group organosilicon and the acrylate, and the prepared product has higher pertinence and saves energy.
At the same time, we have adopted a new acrylate combination: the hydroxypropyl acrylate and the n-butyl methacrylate are mixed according to the mass ratio of (8-10) to (5-6), and the combination of the acrylate is more beneficial to grafting of the double-hydroxyl functional group organosilicon, and simultaneously, the property of the acrylate is kept. In addition, due to the existence of hydroxyl and carboxyl functional groups in the hydroxypropyl acrylate, the hydroxypropyl acrylate is easier to crosslink with MOFs initiators to form ester bonds and coordination bonds, and the bond strength is higher, so that the film is more stable after being formed and is not easy to corrode. The acrylic resin obtained after the polymerization of n-butyl methacrylate forms a film, has the best corrosion resistance and mechanical properties, but has high polymerization difficulty and high reaction requirement; the polymerization requirement can be reduced by mixing the acrylic acid with ethyl acrylate and acrylic acid. Meanwhile, compared with ethyl acrylate and n-butyl methacrylate, acrylic acid is easier to react with the dihydroxy functional group organosilicon, acrylic acid preferentially reacts with the dihydroxy functional group organosilicon at the initial reaction, the requirement on the reaction temperature is low, an initiator is not needed, and the dihydroxy functional group organosilicon modified acrylic acid obtained by the reaction has physical properties which are not inferior to n-butyl methacrylate.
The biggest bright point of the invention is that the initiator of the polymerization reaction adopted by the invention is not the traditional azo initiator or peroxy initiator, but is replaced by MOFs material, and the Metal-organic Framework compound (MOFs for short) is a novel functional material developed in recent years and is a crystalline porous material with a periodic network structure formed by connecting an inorganic Metal center (Metal ion or Metal cluster) and a bridged organic ligand through self-assembly. MOFs are an organic-inorganic hybrid material, also called coordination polymer, which is different from inorganic porous materials and from general organic complexes. Combines the rigidity of inorganic materials with the flexibility of organic materials. The method has great development potential and attractive development prospect in the aspect of modern material research. A large number of unsaturated metal sites exist on the surface of the MOFs material and are used as Lewis acid sites, can be used as catalytic centers, are used for various reactions such as cyanation reaction, oxidation reaction of hydrocarbons and alcohols, esterification reaction, Diels-Alder reaction and the like, and have higher activity; however, it has been found for the first time that it can be used for organosilicon-modified acrylic acids and initiators for the polymerization of acrylic acids. First, unlike conventional initiators, the surface of the initiator is not heated to self-generate radicals by decomposition, but generates electron transitions under photoexcited or thermally excited conditions to generate radicals without self-decomposition. Compared with the conventional initiator, the reaction rate is more stable because it is not decomposed, and the disadvantage is that it is not easy to separate out. However, in the polymerization reaction of organosilicon modified acrylic acid and acrylic acid, ZIF-8 is selected, can be used as an initiator, and can also be used as a bridge for polymerization of organosilicon modified acrylic acid and acrylic acid due to the larger surface area and the polyhydroxy and carboxyl structures to form an organosilicon-MOFs-acrylate or acrylate-MOFs-acrylate structure, so that the organosilicon-MOFs-acrylate or acrylate-MOFs-acrylate structure has more excellent performance.
R-8204 functional polysiloxane modified nano-silica produced by Zhejiang boiling point chemical industry is adopted, so that the dispersibility of the nano-silica in aqueous solution is enhanced, the nano-silica is not easy to agglomerate, the transparency of the high-molecular nano-microparticle agent is influenced, and meanwhile, the surface of the modified nano-silica contains more hydroxyl groups, so that the improvement of the integral conductivity of a paint film is facilitated.
In conclusion, the invention adopts the dihydroxy functional group organosilicon modified acrylic resin, and simultaneously prepares the most suitable acrylate combination, thereby reducing the reaction requirement and the cost; meanwhile, the MOFs material is creatively adopted as an initiator and a reaction raw material of the reaction, so that the organosilicon-MOFs-acrylate material with more excellent performance is obtained.
The invention has the beneficial effects that:
1. according to the invention, the acrylic resin is modified by adopting the double-hydroxyl functional group organic silicon, and the modification reaction condition is reduced by utilizing the property of the double-hydroxyl functional group organic silicon polyhydroxy; the polyhydroxy group also facilitates charge transport, enhancing electrical conductivity.
2. In the process of modifying acrylic resin by using double-hydroxyl functional group organic silicon, the invention adopts the MOFs initiator which not only has the function of the initiator, but also can participate in the reaction to form an organic silicon-MOFs-acrylate or acrylate-MOFs-acrylate structure, and an ester bond and a coordination bond are formed, so that the organic silicon-MOFs-acrylate or acrylate-MOFs-acrylate structure has stronger bond energy and is more corrosion-resistant; the electrons of the MOFs are still easier to be excited to generate movable electrons, and in addition, a large number of hydroxyl groups exist in a cross-linked network, so that the electron transport is facilitated, and the excellent conductivity is shown.
3. The invention discloses a high-molecular nano particle agent, which adopts the organic silicon-MOFs-acrylate material as a main substance, has high conductivity, can be cured at a lower temperature, and can enhance the corrosion resistance, the anti-staining property, the self-cleaning property, the high conductivity and the coatability of the metal surface after being cured.
Detailed Description
The dihydroxy functional group organosilicon in the embodiment is dihydroxy functional group organosilicon oligomer 8865H, the dihydroxy functional group organosilicon oligomer 8865H is produced by Shanghai spectral vibration biotechnology limited, has an average molecular weight of 4000, has dihydroxy functional groups, has a hydroxyl content of 0.8 percent, has high reactivity with-NCO and-COOH, and has good resin compatibility.
Nano-silica, particle size: 20nm, CAS number: 7631-86-9, cat #: NM000840, Beijing Sorley technologies, Inc.
R-8204 functional polysiloxane, type: r-8204, purchased from Zhejiang boiling point chemical Co., Ltd, has better water solubility, contains more functional groups and has better coupling effect.
The water-soluble hydrogen-containing silicone oil has the following types: HY-6, Hongyejie technologies, Inc.
Fluorine modified polyacrylate flatting agent, type: shanheTM-870, Whitman Sandy Polymer technology, Inc.
Acrylic resin, type: r010670, average molecular mass: 3000, Shanghai Yien chemical technology, Inc.
Hydroxypropyl acrylate, CAS No.: 25584-83-2.
N-butyl methacrylate, CAS No.: 97-88-1.
Vinyltrimethoxysilane, CAS No.: 2768-02-7.
Azobisisobutyronitrile, CAS number: 78-67-1.
Benzoyl peroxide, CAS number: 94-36-0.
ZIF-8, cat # C: 59061-53-9, particle size: 4.9 μm, surface area: 1300-1800m2G, sigma aldrich trade ltd.
Hydrogen peroxide, CAS No.: 7722-84-1, concentration: 20 wt%.
Acetic acid, CAS No.: 64-19-7 and the concentration is 30 wt%.
Ammonia, CAS No.: 1336-21-6, concentration 27 wt%.
Example 1
A high molecular nanometer microgranule is composed of the following raw materials: 200g of dihydroxy functional group organic silicon modified acrylic resin, 120g of silane coupling agent modified nano silicon dioxide, 38g of absolute ethyl alcohol, 45g of water-soluble hydrogen-containing silicone oil, 4g of sodium dodecyl benzene sulfonate, 5g of fluorine modified polyacrylate flatting agent, 19g of film forming agent, 7g of hydrogen peroxide, 5g of acetic acid, 7g of ammonia water and 550g of water.
The film forming agent is prepared from potassium fluotitanate and maleic acid according to a mass ratio of 16: 3, mixing.
The preparation method of the silane coupling agent modified nano silicon dioxide comprises the following steps: mixing nano-silica, R-8204 functional polysiloxane and toluene according to the mass ratio of 30:9:100, stirring at the rotating speed of 10000R/min for 2min, refluxing at 150 ℃ for 24h, cooling, washing and drying to obtain the silane coupling agent modified nano-silica.
The preparation method of the dihydroxy functional group organic silicon modified acrylic resin comprises the following steps: adding 6.25g of dihydroxy functional group organic silicon and 0.25g of initiator into 20g of butyl acetate, uniformly mixing, stirring at the rotating speed of 160r/min for 5min at 70 ℃, then adding 25.6g of acrylate and 5g of acrylic acid, reacting at the constant temperature of 80 ℃ for 1h, filtering, taking precipitate, washing and drying to obtain the dihydroxy functional group organic silicon modified acrylic resin.
The acrylate is prepared by mixing hydroxypropyl acrylate and n-butyl methacrylate according to a mass ratio of 9: 5.5.
The initiator is ZIF-8.
A preparation method of a high-molecular nanometer particle agent comprises the following steps:
s1 mixing 200g of dihydroxy functional group organic silicon modified acrylic resin, 120g of silane coupling agent modified nano-silica, 38g of absolute ethyl alcohol and 550g of water, and then adding 5g of acetic acid to obtain the acidic precursor.
S2 adding 45g of water-soluble hydrogen-containing silicone oil, 4g of sodium dodecyl benzene sulfonate, 5g of fluorine modified polyacrylate flatting agent, 19g of film-forming agent and 7g of hydrogen peroxide into the acidic precursor prepared in the S1, uniformly mixing, and then adding 7g of ammonia water to obtain the polymer nano particle agent.
Example 2
Essentially the same as example 1, except that:
the preparation method of the organic silicon modified acrylic resin comprises the following steps: adding 6.25g of organic silicon and 0.25g of initiator into 20g of butyl acetate, uniformly mixing, and stirring at the rotating speed of 160r/min for 5min at 70 ℃; then adding 25.6g of acrylic ester and 5g of acrylic acid, reacting for 1h at the constant temperature of 80 ℃, filtering, taking the precipitate, washing and drying to obtain the organic silicon modified acrylic resin.
The organic silicon is vinyl trimethoxy silane
The acrylate is prepared by mixing hydroxypropyl acrylate and n-butyl methacrylate according to a mass ratio of 9: 5.5.
The initiator is ZIF-8.
Example 3
Essentially the same as example 1, except that:
the preparation method of the dihydroxy functional group organic silicon modified acrylic resin comprises the following steps: adding 6.25g of dihydroxy functional group organic silicon and 0.25g of initiator into 20g of butyl acetate, uniformly mixing, and stirring at 70 ℃ at the rotating speed of 160r/min for 5 min; then adding 25.6g of acrylic ester and 5g of acrylic acid, reacting for 1h at the constant temperature of 80 ℃, filtering, taking the precipitate, washing and drying to obtain the dihydroxy functional group organic silicon modified acrylic resin.
The acrylate is hydroxypropyl acrylate.
The initiator is ZIF-8.
Example 4
Essentially the same as example 1, except that:
the preparation method of the dihydroxy functional group organic silicon modified acrylic resin comprises the following steps:
adding 6.25g of dihydroxy functional group organic silicon and 0.25g of initiator into 20g of butyl acetate, uniformly mixing, stirring at the rotating speed of 160r/min for 5min, heating to 70 ℃, then adding 25.6g of acrylate and 5g of acrylic acid, heating to 80 ℃, reacting at constant temperature for 1h, filtering, taking precipitate, washing and drying to obtain the dihydroxy functional group organic silicon modified acrylic resin.
The acrylate is n-butyl methacrylate.
The initiator is ZIF-8.
Example 5
Essentially the same as example 1, except that:
replacing the silane coupling agent modified nano silicon dioxide with nano silicon dioxide.
Comparative example 1
Essentially the same as example 1, except that:
the preparation method of the dihydroxy functional group organic silicon modified acrylic resin comprises the following steps: adding 6.25g of dihydroxy functional group organic silicon and 0.25g of initiator into 20g of butyl acetate, uniformly mixing, stirring at the rotating speed of 160r/min for 5min, heating to 70 ℃, then adding 25.6g of acrylate and 5g of acrylic acid, heating to 80 ℃, reacting at constant temperature for 1h, filtering to obtain a precipitate, washing and drying to obtain the dihydroxy functional group organic silicon modified acrylic resin.
The acrylate is a mixture of hydroxypropyl acrylate and n-butyl methacrylate according to a mass ratio of 9: 5.5.
The initiator is azobisisobutyronitrile.
Comparative example 2
Essentially the same as example 1, except that:
the dihydroxy functional group organosilicon modified acrylic resin is replaced by acrylic resin.
Test example 1
Preparation of a sample plate: the high molecular nanometer particle agent prepared in the examples and the comparative examples is sprayed on the hot galvanizing substrate by a spraying method for 150X 200mm hot galvanizing substrate, and is baked for 30 minutes at 90 ℃ to obtain a test sample with a paint film thickness of 20 mu m.
The test sample is detected as follows:
(1) salt spray resistance test:
the test panels were placed in a salt spray test box and tested continuously for 72 hours, expressed as panel rust area/test panel area (expressed as%). The salt spray test was performed according to astm b117-03 standard, with the set conditions of 35 ℃ temperature, 47P saturated air, 5% salt water concentration, pH =6.9, spray volume 1.6 ml/80 cm/h. The lost quality of the plate is measured.
(2) Solvent resistance test:
the test sample was repeatedly wiped with a cotton yarn rod (diameter of the cotton yarn rod is 10 mm) soaked with alcohol 20 times under a pressure of 5N, and the change Δ E of the color difference before and after the test was measured with a color difference meter.
(3) And (3) stability testing:
the stability test of the examples and comparative products of the invention is carried out by placing the prepared polymer nano microgranule liquid medicine in a 40 ℃ oven and observing the occurrence of precipitation or gel after 15 days.
(4) And (3) conductivity test:
and measuring the surface contact resistance of the test sample plate, using a microohm meter to enable the two electrodes to be in contact with the measured surface, measuring at any two points on the surface of the test sample plate by using the electrode area of 1 cm 2 and the electrode pressure of 1.4MPa, and measuring for 3 times to obtain an average value (not more than 15m omega).
The results of salt spray resistance, solvent resistance, stability, conductivity tests are shown in Table 1.
Table 1: salt spray resistance, solvent resistance, stability, conductivity test results
From table 1, it can be seen that the MOFs initiator and the acrylate have a great influence on the salt spray resistance, i.e., the corrosion resistance, of the product, and the dihydroxy functional group and the MOFs initiator have a great influence. The hydroxyl and carboxyl functional groups exist in the hydroxypropyl acrylate, so that the hydroxypropyl acrylate is easy to crosslink with an MOFs initiator to form ester bonds and coordination bonds, and the bond strength is higher, so that the hydroxypropyl acrylate is more stable after film formation and is not easy to corrode. N-butyl methacrylate. In addition, the conductivity of the polymer nanoparticle prepared by the MOFs initiator in the example 1 is obviously better than that of the polymer nanoparticle prepared by the traditional initiator in the comparative example 1. The reason why the MOFs material can greatly improve the performance of the organosilicon modified acrylic resin as the initiator is presumed to be that the MOFs material has larger surface area and multiple reaction sites, can be polymerized into a more compact network by taking the MOFs material as a center, and shows better salt spray resistance and stability. Example 5 shows that the nano-silica which is not modified by the R-8204 functional polysiloxane is more easily agglomerated and affects the storage time, and the unmodified nano-silica has slightly less hydroxyl content on the surface and hindered charge transfer, so that the overall conductivity of the paint film is reduced.
Undeniably, the polymer nano particle agent prepared by the invention has excellent performances in the aspects of conductivity, salt mist resistance, solvent resistance, stability and the like, and particularly has the most prominent conductivity.
Test example 2
(1) And (3) testing the scribing of paint films:
reference is made to GB/T9286-1998 test for the test of the marking of paint films of paints and varnishes.
(2) Paint film impact test (50 kg. cm)
Refer to GB/T1732-1993 'determination of paint film impact resistance'. The bottom plate is made of a tin plate, and the size of the bottom plate is 50mm multiplied by 120mm multiplied by 0.3 mm.
Table 2: results of paint film scratching test and paint film impact test
It can be seen from table 2 that the polymer nanoparticles prepared by the present invention have excellent physical properties, and the MOFs further enhances the strength of the cross-linked network, thereby enhancing the impact resistance and the anti-peeling property of the paint film. The physical properties of the acrylic resin are not obviously optimized by the conventional initiator azobisisobutyronitrile adopted by the comparative example, which highlights the superiority of MOFs materials.
Test example 3
The hot dip galvanized substrate was immersed in the polymeric nanoparticle prepared in example 1, and then comparative tests were performed on the bake-cure temperature and time effect.
Table 3: example 1 thermosetting film formation test of Polymer nanoparticles
The polymer nanometer particle agent prepared by the embodiment of the invention has the property of forming a film at a lower temperature, and the film is formed mainly by the evaporation of water in the polymer nanometer particle agent, and under the action of a film forming agent and a dispersing agent, the dihydroxy functional group organic silicon modified acrylic resin and the silane coupling agent modified nanometer silicon dioxide form a firm cross-linked network. Because the modified acrylic resin and the modified silicon dioxide contain more hydroxyl, carboxyl and other groups, the physical crosslinking capacity and the chemical crosslinking capacity of the modified acrylic resin and the modified silicon dioxide are greatly improved.
Compared with the corresponding products commonly used in the market, the polymer nano particle agent can ensure the performance of the product at lower curing temperature, breaks through the mode that the traditional process needs curing for 20-30 minutes at 180-220 ℃, and meets the performance requirement in a mode of saving more energy.
Claims (9)
1. A preparation method of a high-molecular nano particle agent is characterized by comprising the following steps: and mixing the dihydroxy functional group organic silicon modified acrylic resin, the silane coupling agent modified nano silicon dioxide, a dispersing agent, a flatting agent, a film forming agent, a stabilizing agent, absolute ethyl alcohol and water to obtain the macromolecular nano particle agent.
2. A preparation method of a high-molecular nano particle agent is characterized by comprising the following steps:
s1, mixing 150-150 g of dihydroxy functional group organic silicon modified acrylic resin, 50-150g of silane coupling agent modified nano silicon dioxide, 10-100g of absolute ethyl alcohol and 600g of water, and adding 4-6g of acetic acid to adjust the pH value to 3-4 to obtain an acidic precursor;
s2 adding 25-75g of water-soluble hydrogen-containing silicone oil, 0.01-5g of dispersant, 0.1-10g of flatting agent, 0.1-20g of film-forming agent and 0.5-35g of stabilizer into the acidic precursor prepared in S1, uniformly mixing, adding 6-8g of ammonia water, and adjusting the pH value to 7-8 to obtain the high-molecular nano particle agent.
3. The method for preparing polymeric nanoparticles of claim 1 or 2, wherein the film-forming agent is one or two or more of potassium fluotitanate, malonic acid, copper sulfate, and maleic acid.
4. The method for preparing polymer nanoparticles of claim 1 or 2, wherein the stabilizer is one or a mixture of two or more of hydrogen peroxide, potassium pyrophosphate and sodium metasilicate.
5. The method for preparing polymeric nanoparticle agent according to claim 1 or 2, wherein the method for preparing silane coupling agent modified nanosilicon dioxide comprises the following steps: mixing nano-silica, R-8204 functional polysiloxane and toluene according to the mass ratio of (20-40): 6-12): 90-110, stirring at the rotating speed of 12000R/min of 8000-.
6. The method for preparing polymeric nanoparticles of claim 1 or 2, wherein the method for preparing the dihydroxy functional silicone modified acrylic resin comprises the following steps:
adding 6-7g of dihydroxy functional group organic silicon and 0.1-0.5g of initiator into 18-22g of butyl acetate, uniformly mixing, stirring at 65-75 ℃ at the rotating speed of 120-200r/min for 4-8min, then adding 24-28g of acrylate and 4-6g of acrylic acid, reacting at 75-85 ℃ for 0.5-1.5h, filtering, taking precipitate, washing and drying to obtain the dihydroxy functional group organic silicon modified acrylic resin.
7. The method for preparing polymeric nanoparticles of claim 6, wherein the acrylate is one or both of hydroxypropyl acrylate and n-butyl methacrylate.
8. The method for preparing polymer nanoparticles of claim 6, wherein the initiator is any one of ZIF-5, ZnGGH-9 and ZIF-8.
9. A polymeric nanoparticle formulation prepared by the method of any one of claims 1 to 8.
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