X-shaped parent diene monomer, polymer hollow sphere, polymer@siO2 sphere, double-layer hollow sphere sol, antireflection film, antireflection material and preparation method thereof

Abstract

The application belongs to the field of functional coating, and particularly relates to a X type amphiphilic diene monomer, a polymer hollow sphere, a polymer@SiO2 sphere, a double-layer hollow sphere sol, an anti-reflective film, an anti-reflective material and a preparation method thereof, wherein the X type amphiphilic diene monomer is a compound of formula 1. The application provides a multi-aromatic para-bis-carboxyl-diene X type structure monomer, which can be polymerized and assembled to form a hollow microsphere structure with excellent thermodynamic stability under a template-free condition based on the combination of structure and groups, and the polymer hollow sphere can exhibit excellent performance when applied in the field of anti-reflective film.

Description

Technical Field

[0001] This invention relates to the field of functional coatings, and more specifically to the field of antireflective film materials. Background Technology

[0002] Depositing antireflective films on the surface of solar cells can significantly reduce reflectivity, thereby improving cell efficiency. While wavelength destructive interference and "moth-eye" array structures can achieve small-scale, extremely high antireflection effects in some precision instruments, the fabrication of these two types of films requires extremely high control precision, resulting in high costs and relatively harsh fabrication conditions. Compared to traditional vacuum sputtering technology used in optical lenses and precision industries, or novel ion etching and nanoprinting technologies, products obtained solely through the sol-gel method currently cannot match their performance.

[0003] However, for antireflective films with porous graded refractive indices, the sol-gel method has inherent advantages such as uniform product preparation, controllable film pore size, and low cost. The rapid development of the solar energy industry, in particular, has brought opportunities to the sol-gel method. Especially in the field of coating large solar glass covers, sol-gel technology has an absolute advantage over other technologies, indicating its promising industrialization prospects in the preparation of multifunctional composite films on solar silicon substrates. However, the sol-gel method also has some unresolved issues, such as the poor outdoor mechanical properties of the films. For antireflective films used in solar cells, mechanical wear under various environments can easily damage the film's microstructure, thus affecting its function. Therefore, achieving sufficient mechanical strength is a significant challenge for the practical application of this technology.

[0004] Furthermore, the sacrificial template method is currently the primary method for preparing porous materials. This method involves adding a template to a precursor solution of the target product, using a specific process to transform the precursor solution into the target product, and finally removing the template to obtain a porous aerogel. However, removing the polymer template using high-temperature calcination has significant drawbacks; for example, most of the shell layers of the calcined silica hollow spheres crack or collapse. Therefore, developing a method to prepare organic-inorganic bilayer hollow spheres with excellent mechanical properties without template removal is of significant practical value. Summary of the Invention

[0005] To address the problems existing in the prior art, the primary objective of this invention is to provide an X-type amphiphilic diene monomer and its preparation method, aiming to provide a monomer that can be polymerized to form hollow polymer spheres without the need for a template, and which is beneficial for improving the performance of antireflective films.

[0006] A second objective of this invention is to provide polymer hollow spheres and a method for their preparation via emulsion polymerization of the aforementioned X-type amphiphilic diene monomers.

[0007] A third objective of this invention is to provide polymer@SiO2 spheres with silica composited on the polymer hollow spheres and a method for preparing the same.

[0008] The fourth objective of this invention is to provide a double-layer hollow spherical sol containing the polymer@SiO2 spheres and a method for preparing the same.

[0009] The fifth objective of this invention is to provide an antireflective film comprising the aforementioned double-layer hollow sphere and a method for preparing the same.

[0010] The sixth objective of this invention is to provide an antireflective material comprising the aforementioned antireflective film.

[0011] Most existing methods for preparing porous silica thin films using sol-gel techniques require template methods and high-temperature calcination, which can easily lead to hollow sphere breakage or structural collapse, negatively impacting mechanical properties and antireflective performance. To address this problem, this invention provides the following improvement:

[0012] An X-type amphiphilic diene monomer, which is a compound having the structure of Formula 1;

[0013] Formula 1;

[0014] In Formula 1, M is H, Na, K or NH4; Ar is a five- or six-membered aromatic ring or an aromatic ring with substituents; the substituents include at least one of hydroxyl, C1-C4 alkoxy, halogen, nitro, and trifluoromethyl.

[0015] This invention provides a multi-aromatic meta-dicarboxylic acid-diene X-type structure monomer. Based on the combination of structure and groups, it can be polymerized and assembled into polymer hollow spheres with excellent thermodynamic stability by means of the synergistic effect of π-π stacking in the molecular structure, hydrophobicity and structural rigidity. Furthermore, the polymer hollow spheres exhibit excellent performance when applied in the field of antireflective coatings.

[0016] In this invention, the aromatic rings include, for example, five-membered aromatic rings such as thiophene rings, pyran rings, thiazole rings, and imidazole rings. Hexacyclic aromatic rings include, for example, benzene rings or six-membered heterocyclic aromatic rings. The six-membered heterocyclic aromatic rings include, for example, pyridine and pyrimidine.

[0017] In this invention, the Ar can further be a benzene ring.

[0018] In this invention, the olefin can be used in any position on the benzene ring without particular requirements; for example, it can be para-positioned.

[0019] Furthermore, the X-type amphiphilic diene monomer is a compound having the structure of formula 1A;

[0020] Formula 1A.

[0021] The present invention also provides a method for preparing the X-type amphiphilic diene monomer, wherein a substitution reaction (ammoniation reaction) is carried out by formula 2, formula 3, activator and acid-binding agent to obtain intermediate of formula 4, and intermediate of formula 4 is subjected to ester hydrolysis to obtain formula 1 in which M is Na, K or NH4; or, formula 1 in which M is Na, K or NH4 is subjected to acidification to obtain formula 1 in which M is H.

[0022] Formula 2;

[0023] Formula 3;

[0024] Equation 4;

[0025] In Formula 2, R1 is a C1~C4 alkyl group;

[0026] In Equation 3, Ar is the same as Ar in Equation 1, and X is Cl, Br, or I;

[0027] The molar ratio of Equation 3 to Equation 2 is 2~3:1.

[0028] In this invention, Formulas 2 and 3 can be subjected to the aforementioned substitution reaction and ester hydrolysis to obtain salt form 1 (Formula 1 where M is Na, K, or NH4). If it is necessary to prepare acid form 1 (Formula 1 where M is H), salt form 1 can be acidified. In addition, to further obtain purified salt form 1, pure acid form 1 can also be prepared in advance, and the corresponding salt form 1 can be obtained by exchanging acid form 1 with a base.

[0029] In this invention, the activator can be an alkali metal iodide, such as at least one of sodium iodide and potassium iodide.

[0030] Preferably, the activator is 0.1 to 0.3 times the molar amount of Formula 2; more preferably, it can be 0.15 to 0.25 times.

[0031] In this invention, the acid-binding agent is a conventional component capable of neutralizing HX, such as at least one of sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, and ammonia water.

[0032] In this invention, the amount of acid-binding agent can be adjusted as needed. For example, it can be 1 to 5 times the theoretical reaction amount, or 2 to 4 times the molar amount of Formula 2.

[0033] In this invention, the molar ratio of Formula 3 and Formula 2 is 2.2~2.6:1.

[0034] In this invention, there are no special requirements for the temperature of the substitution reaction, for example, it can be 30~60℃, or 35~45℃, and the reaction time can be adjusted as needed, for example, it can be 5~20h, or even 12~16h.

[0035] In this invention, the solvent for the substitution reaction can be DMF, DMSO, NMP, etc. The amount used can be adjusted reasonably as needed; for example, the concentration of Formula 2 in the solvent can be 0.5~5 mmol / mL; further, it can be 1~2 mmol / mL.

[0036] In this invention, after the substitution reaction, an organic solvent can be used for extraction to obtain the intermediate of Formula 4.

[0037] The organic solvent used in the extraction process can be components such as EA and DCM.

[0038] In this invention, Formula 4 can be prepared by ester hydrolysis using conventional methods to obtain Formula 1.

[0039] For example, an alkaline component is added during the ester hydrolysis process, and the alkaline component can be a hydroxide of M.

[0040] In this invention, the molar ratio of Formula 4 and the alkaline component can be 1:2~5; more specifically, it can be 1:3~4.

[0041] In this invention, the solvent for ester hydrolysis can be a mixture of alcohol and water, or more specifically, an alcohol-water solvent with a volume ratio of 1 to 3:1.

[0042] In this invention, the temperature of the ester hydrolysis process can be 50~100℃, and more specifically 75~85℃.

[0043] In this invention, the ester hydrolysis time can be adjusted reasonably as needed. For example, the reaction process can be monitored by thin-layer chromatography.

[0044] In this invention, after ester hydrolysis, products in Formula 1 where M is Na, K, or NH4 can be separated. Alternatively, acidification can be performed to collect products in Formula 1 where M is H.

[0045] The present invention also provides a method for preparing polymer hollow spheres, wherein the X-type amphiphilic diene monomer and the counterion agent are dispersed in water to form an aqueous phase, which is then mixed with an oil phase, and subsequently a reducing agent and an oxidizing agent are added to carry out emulsion polymerization to obtain the polymer hollow spheres.

[0046] In this invention, thanks to the special structure of the X-type amphiphilic diene monomer, it is possible to unexpectedly polymerize high-stability polymer hollow spheres that are conducive to the preparation of high antireflection film performance under template-free conditions.

[0047] In this invention, the counterion agent includes at least one of tetramethylguanidine, sodium hydroxide, potassium hydroxide, and tetraethylammonium hydroxide;

[0048] The molar ratio of the X-type amphiphilic diene monomer to the counterionizing agent is 1:1 to 5; more specifically, it can be 1:2 to 3.

[0049] In the aqueous phase, the concentration of the X-type amphiphilic diene monomer is 0.005~0.02 mmol / mL, and can be further 0.01~0.015 mmol / mL;

[0050] The oil phase is a hydrophobic solvent with a boiling point of 60-120℃; further, it can be at least one of n-heptane and n-hexane.

[0051] The volume ratio of oil phase to water phase is (0.002~0.03):1, preferably (0.004~0.006):1; more preferably (0.005~0.0055):1; the preferred ratio helps to further optimize the particle structure formed by polymerization of formula 1 and helps to further enhance the performance of the antireflective film prepared subsequently.

[0052] The reducing agent includes at least one of sodium thiosulfate and sodium sulfite;

[0053] Oxidizing agents include at least one of potassium persulfate, ammonium persulfate, and sodium persulfate;

[0054] The molar ratio of the X-type amphiphilic diene monomer, reducing agent, and oxidizing agent is 1:0.04~0.06:0.05~0.07.

[0055] In this invention, the emulsion polymerization temperature is 20~40℃ and the time is 16~36h.

[0056] The present invention also provides a polymer hollow sphere prepared by the aforementioned preparation method.

[0057] In this invention, the preparation method can endow the polymer hollow spheres with special physicochemical properties, and the polymer hollow spheres prepared by the preparation method can be prepared without a template at low temperature, and have excellent application advantages in antireflection films.

[0058] The present invention also provides a polymer@SiO2 sphere (also referred to as a double-layer hollow sphere), which includes the polymer hollow sphere described in the present invention and a silicon dioxide shell layer composite on its surface.

[0059] The present invention also provides a method for preparing the polymer@SiO2 spheres, wherein the polymer hollow spheres and silicate are mixed and hydrolyzed under alkaline conditions to deposit a silica layer on the polymer hollow spheres, followed by solid-liquid separation and drying to obtain the polymer@SiO2 spheres.

[0060] In this invention, the silicate ester is, for example, a tetraester of orthosilicate formed from orthosilicic acid and C1-C4 alcohols.

[0061] In this invention, the weight-to-volume ratio of water to polymer hollow spheres during the hydrolysis process can be 10-30 mL / g, and more specifically 15-25 mL / g.

[0062] In this invention, the alkaline condition can be, for example, ammonia water. The ammonia water can be saturated ammonia water.

[0063] In this invention, the volume ratio of ammonia to water is 1:5~20, and can be further 1:10~15.

[0064] In this invention, the weight ratio of polymer hollow spheres to silicate is 1:1 to 3; more specifically, it is 1:1.5 to 2.5.

[0065] In this invention, the hydrolysis reaction is carried out at 15-45°C. The hydrolysis time can be 1-5 hours.

[0066] The present invention also provides a double-layer hollow spherical sol, which is a gel in which the polymer@SiO2 spheres described in the present invention are dispersed.

[0067] The present invention also provides a method for preparing the aforementioned double-layer hollow sphere sol, wherein the polymer hollow spheres and silicate are mixed and hydrolyzed under alkaline conditions to deposit a silica layer on the polymer hollow spheres, followed by aging treatment to obtain the aforementioned double-layer hollow sphere sol.

[0068] In this invention, the difference between the sol preparation process and the preparation process of polymer@SiO2 spheres lies in the fact that after hydrolysis, solid-liquid separation is not performed, but aging treatment is carried out directly.

[0069] In this invention, the aging time can be 1 to 5 days.

[0070] The present invention also provides an antireflective film comprising the polymer@SiO2 spheres described in the present invention.

[0071] The present invention demonstrates that the polymer@SiO2 spheres used to form an antireflective film exhibit excellent light transmittance and stability.

[0072] The present invention also provides a method for preparing the antireflective film, which is obtained by drying the double-layer hollow spherical sol described in the present invention.

[0073] The present invention also provides an antireflective material, comprising a substrate and an antireflective film composited thereon, wherein the antireflective film is the antireflective film described in the present invention.

[0074] In this invention, the substrate can be any substrate that requires anti-reflection treatment.

[0075] As an example, the antireflective material described in this invention can be a solar panel.

[0076] Beneficial effects

[0077] 1) This invention provides an X-type amphiphilic diene monomer, which, based on the combination of structure and groups, is advantageous for assembling thermodynamically stable hollow microsphere structures without a template.

[0078] 2) The present invention can deposit silicon dioxide on a polymer hollow microsphere substrate, thus obtaining an antireflection film with excellent antireflection performance and stability under mild conditions. Attached Figure Description

[0079] Figure 1 The figures are 1H NMR spectra of the products prepared in Example 1, where a is the 1H NMR spectrum of the intermediate of Formula 4A; and b is the 1H NMR spectrum of the X-type amphiphilic diene monomer.

[0080] Figure 2 The images show the 1H NMR spectra of the X-type amphiphilic diene monomer prepared in Example 1 before and after polymerization.

[0081] Figure 3 The images show the microstructure of the polymer hollow spheres prepared in Example 2. Images a and b are TEM images of the polymer solution after acidification. Images c and d are SEM images of the polymer solution after acidification.

[0082] Figure 4 This is a TEM image of the polymer / SiO2 double-layer hollow sphere antireflection film prepared in Example 2. Detailed Implementation

[0083] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0084] Example 1

[0085] Step (1): Synthesis of intermediates

[0086] ;

[0087] Weigh 10 mmol of Formula 2A and 2 mmol of potassium iodide into a reaction flask, add 24 mmol of Formula 3A, and finally add 10 mL of DMF. Slowly add 24 mmol of potassium carbonate while stirring, and heat to 40 °C overnight (10–14 h). After the reaction, add 20 mL of dichloromethane and extract three times with distilled water. Dry the organic layer with anhydrous sodium sulfate. Remove the solvent by rotary evaporation under reduced pressure. Wash the resulting yellow solid (Formula 4A) ultrasonically with methanol, filter, repeat several times to obtain a white solid, and dry under vacuum. Yield: 70%.

[0088] Step (2): Synthesis of X-type amphiphilic diene monomers

[0089] ;

[0090] The intermediate 4A (12.3 mmol) was weighed into a reaction flask and dissolved by heating with ethanol (20 mL). Then, a solution of sodium hydroxide (36.9 mmol) in water (10 mL) was added and stirred, and the mixture was refluxed at 80 °C. A yellow, transparent solution was obtained after the reaction. The ethanol was evaporated under reduced pressure, acidified with dilute hydrochloric acid, filtered to collect the precipitate, and washed thoroughly with plenty of water and ethanol to give monomer X, 1A. Yield: 92%.

[0091] Step (3): Preparation of polymer hollow nanospheres

[0092] Weigh 0.1211 mmol of monomer X (Formula 1A) and add it to 10 g of water containing TMG (tetramethylguanidine, 0.2422 mmol). Stir to dissolve and obtain a clear solution. After three gas exchange cycles of freezing-evacuation-thawing-nitrogen purging, add 20 μL of n-heptane and stir at room temperature. Then add sodium thiosulfate pentahydrate (0.0051 mmol) as a reducing agent and potassium persulfate (0.0061 mmol) as an oxidizing agent. React at 30 °C and 500 r / min with a magnetic stirrer for 24 hours. After polymerization, acidify with dilute hydrochloric acid to pH 3-4, then transfer to a dialysis bag with a molecular weight cutoff of 8000 and dialyze for one week using water as the dialysis solvent, changing the solution 5 times a day. Freeze with liquid nitrogen and then freeze-dry under vacuum to obtain hollow polymer spheres.

[0093] Step (4): Preparation of polymer / SiO2 bilayer hollow spherical sol

[0094] 0.5 g of the polymer hollow spheres obtained in step 3 were re-ultrasonically dispersed in 10 mL of deionized water to form a homogeneous suspension. 1 g of tetraethyl orthosilicate was added to this suspension and stirred for ten minutes. Then, 1 mL of ammonia (saturated ammonia) was slowly added under vigorous stirring, and the reaction was continued at room temperature for 4 hours to allow the tetraethyl orthosilicate to hydrolyze and condense under alkaline conditions, depositing a silica layer on the surface of the polymer hollow spheres. The resulting product was allowed to stand and age for 2–3 days to obtain a stable bilayer hollow sphere sol.

[0095] Examples 2-5

[0096] Compared with Example 1, the only difference is that in step 3, the volume of n-heptane is changed as shown in Table 1; all other operations and parameters are the same as in Example 1.

[0097] Table 1. Volume of different n-heptanes

[0098] ;

[0099] Example 6

[0100] Compared with Example 1, the only difference is that the conditions of steps (3) and (4) are changed. The specific difference is as follows:

[0101] Step (3): Preparation of polymer hollow nanospheres

[0102] Weigh out monomer X (Formula 1A, 0.1211 mmol) and add it to 10 g of water containing tetramethylguanidine (TMG, 0.3633 mmol). Stir to dissolve and obtain a clear aqueous phase. Then, perform a freeze-evacuation-thawing-nitrogen purging cycle three times to remove oxygen.

[0103] Add 55 μL of n-heptane to the above aqueous phase as the oil phase, and stir at room temperature to disperse it evenly.

[0104] Then, sodium thiosulfate pentahydrate (0.0055 mmol) and potassium persulfate (0.0065 mmol) were added sequentially. The reaction system was placed in a constant temperature environment of 25 °C and reacted for 30 hours with magnetic stirring at 500 r / min.

[0105] After the reaction, the pH of the resulting polymer emulsion was adjusted to 3-4 with dilute hydrochloric acid. The solution changed from clear to milky white, indicating the formation of hollow spheres. This acidified emulsion was then transferred to a dialysis bag with a molecular weight cutoff of 8000 and dialyzed with deionized water for 5 days, changing the water three times a day, to obtain a stable aqueous dispersion of polymer hollow spheres (solid content approximately 0.5 wt%). A portion of the dispersion was freeze-dried to obtain a solid powder.

[0106] Step (4): Preparation of polymer / SiO2 bilayer hollow spherical sol

[0107] Approximately 0.5 g of the above-mentioned polymer hollow spheres were re-dispersed ultrasonically in 12 mL of deionized water. 1.5 g of tetraethyl orthosilicate (TEOS) was added, and the mixture was stirred for 10 minutes to ensure thorough premixing. Subsequently, 1.5 mL of ammonia water was rapidly added under vigorous stirring. The reaction was carried out at room temperature with continuous stirring for 4 hours. After stopping stirring, the mixed sol was allowed to stand at 25°C for 3 days to age, yielding a double-layered hollow sphere sol.

[0108] All other operations and parameters are the same as in Example 1.

[0109] Comparative Example 1

[0110] Compared with Example 1, the only difference is that the preparation method of the hollow polymer spheres in step 3 is changed. The difference is that traditional polystyrene microspheres are used as templates, silica is deposited by sol-gel method, and then the template is removed by high-temperature calcination (500°C). The specific steps and conditions for its preparation are as follows:

[0111] Specific preparation steps and conditions:

[0112] Silica shell coating (sol-gel method):

[0113] Take 10 g of polystyrene (PS) microsphere emulsion (containing approximately 1 g of PS) and dilute it to 100 mL with deionized water. Add 20 mL of anhydrous ethanol and 2 mL of concentrated ammonia (28 wt%), and stir at a constant speed at 30°C for 30 minutes. Mix 2 mL of tetraethyl orthosilicate (TEOS) with 10 mL of anhydrous ethanol, and slowly add it dropwise to the above mixture using a constant pressure dropping funnel, controlling the dropping time to exceed 2 hours. After the addition is complete, continue stirring at 30°C for 12 hours to allow TEOS to fully hydrolyze and condense, depositing a silica (SiO2) shell layer on the surface of the PS microspheres to obtain a PS@SiO2 core-shell structured microsphere suspension.

[0114] High-temperature calcination to remove the template:

[0115] The above PS@SiO2 suspension was collected by centrifugation and washed three times alternately with ethanol and deionized water to obtain a white precipitate. The precipitate was dried in a forced-air drying oven at 60°C for 12 hours to obtain PS@SiO2 core-shell powder. The dried powder was placed in a muffle furnace and heated to 500°C at a rate of 2°C / min under air atmosphere, and then calcined at 500°C for 4 hours to completely remove the internal polystyrene template.

[0116] After natural cooling to room temperature, pure silica (SiO2) hollow sphere powder was obtained. Preparation of silica hollow sphere sol and antireflective film: 0.5 g of the above calcined SiO2 hollow sphere powder was dispersed in 10 mL of anhydrous ethanol and ultrasonically treated for 1 hour to obtain SiO2 hollow sphere ethanol dispersion.

[0117] Comparative Example 2

[0118] Compared with Example 2, the only difference is that in step 4, no silicate ester was added and no silica layer was formed on the surface of the hollow polymer spheres. All other operations and parameters are the same as in Example 2.

[0119] Comparative Example 3

[0120] Compared with Example 2, the only difference is that in step 3, comparative formula A is used. Replace the X-type monomer, and all other operations and parameters are the same as in Example 2.

[0121] Comparative Example 4

[0122] Compared with Example 2, the only difference is that in step 3, comparative formula B is used. Replace the X-type monomer, and all other operations and parameters are the same as in Example 2.

[0123] Comparative Example 5

[0124] Compared with Example 2, the only difference is that in step 3, comparative formula C is used. Replace the X-type monomer, and all other operations and parameters are the same as in Example 2.

[0125] Comparative Example 6

[0126] Compared with Example 2, the only difference is that in step 3, TMG counterion agent is not added; all other operations and parameters are the same as in Example 2.

[0127] Comparative Examples 3 to 6 were unable to form a hollow sphere structure.

[0128] Comparative formulas A through C are all derived from known products, or prepared based on ammonia substitution and alkali ester hydrolysis reactions similar to those in Formula 1. For example, the amine raw materials for comparative formulas A through C are respectively... , or .

[0129] Application example (test)

[0130] The polymer / SiO2 bilayer hollow spherical sols prepared in Examples 1-6 and each comparative example were used to prepare organic-inorganic composite reflective films. The specific steps are as follows:

[0131] The substrate (which can be glass in this case) is immersed at a constant speed into a beaker containing a polymer / SiO2 double-layer hollow sphere sol. After standing in the sol for 10 minutes, it is pulled out at a constant speed of 50 mm / min. Once the substrate is completely removed from the SiO2 sol mixture, the pulling is stopped, and the substrate is allowed to stand for about 5 minutes to allow the solution on the substrate surface to evaporate fully, resulting in a relatively stable gel film. Finally, the gel film is dried in a 70°C forced-air drying oven for 30 minutes to obtain the composite antireflective film.

[0132] The transmittance of the antireflective films prepared in each case was tested according to GB / T 2410-2008. The test structures are shown in Tables 2 and 3.

[0133] Table 2. Transmittance results of antireflective films prepared in each embodiment.

[0134] ;

[0135] Table 3. Transmittance results of antireflective films prepared in each comparative example.

[0136] ;

[0137] The antireflective coating performance of Examples 2, 6 and Comparative Example 1 is shown in Table 4.

[0138] Table 4: Performance results of antireflective films in Examples 2, 6 and Comparative Example 1

[0139] ;

[0140] In summary, the antireflective film of the present invention does not require high-temperature calcination, has a complete hollow spherical structure, and its organic-inorganic composite structure endows the film with good mechanical properties and durability.

Claims

1. An X-type amphiphilic diene monomer, characterized in that, It is a compound having the structure of Formula 1; Formula 1; In Formula 1, M is H, Na, K or NH4; Ar is a six-membered aromatic ring.

2. The X-type amphiphilic diene monomer as described in claim 1, characterized in that, X-type amphiphilic diene monomers are compounds having the structure of formula 1A; Formula 1A.

3. A method for preparing the X-type amphiphilic diene monomer according to claim 1 or 2, characterized in that, The intermediate of formula 4 is prepared by substitution reaction of formula 2, formula 3, activator and acid-binding agent. The intermediate of formula 4 is then subjected to ester hydrolysis to obtain formula 1 with M being Na, K or NH4; or, formula 1 with M being Na, K or NH4 is subjected to acidification to obtain formula 1 with M being H. Formula 2; Formula 3; Equation 4; In Formula 2, R1 is a C1~C4 alkyl group; In Equation 3, Ar is the same as Ar in Equation 1, and X is Cl, Br, or I; The molar ratio of Equation 3 to Equation 2 is 2~3:

1.

4. A method for preparing polymer hollow spheres, characterized in that, The X-type amphiphilic diene monomer and the counterion agent described in any one of claims 1 to 2 are dispersed in water to form an aqueous phase, which is then mixed with an oil phase. Subsequently, a reducing agent and an oxidizing agent are added to carry out emulsion polymerization to obtain the polymer hollow spheres.

5. The method for preparing polymer hollow spheres as described in claim 4, characterized in that, The counterion agent includes at least one of tetramethylguanidine, sodium hydroxide, potassium hydroxide, and tetraethylammonium hydroxide; The molar ratio of the X-type amphiphilic diene monomer to the counterionizing agent is 1:1~5; In the aqueous phase, the concentration of type X amphiphilic diene monomer is 0.005~0.02 mmol / mL; The oil phase is a hydrophobic solvent with a boiling point of 60~120℃; The volume ratio of the oil phase to the water phase is (0.002~0.03):1; The reducing agent includes at least one of sodium thiosulfate and sodium sulfite; Oxidizing agents include at least one of potassium persulfate, ammonium persulfate, and sodium persulfate; The molar ratio of the X-type amphiphilic diene monomer, reducing agent, and oxidizing agent is 1:0.04~0.06:0.05~0.

07.

6. A polymer hollow sphere prepared by the preparation method according to claim 4 or 5.

7. A polymer@SiO2 sphere, characterized in that, It includes the polymer hollow sphere as described in claim 6 and a silica shell layer composited on its surface.

8. A method for preparing polymer@SiO2 spheres according to claim 7, characterized in that, The polymer hollow spheres of claim 6 are mixed with silicate and hydrolyzed under alkaline conditions to deposit a silica layer on the polymer hollow spheres. Subsequently, solid-liquid separation and drying are performed to obtain the polymer@SiO2 spheres.

9. A double-layer hollow spherical sol, characterized in that, To disperse the sol containing the polymer@SiO2 spheres of claim 7.

10. A method for preparing the double-layer hollow spherical sol according to claim 9, characterized in that, The polymer hollow spheres of claim 6 are mixed with silicate ester and hydrolyzed under alkaline conditions to deposit a silica layer on the polymer hollow spheres. Then, the mixture is aged to obtain the double-layer hollow sphere sol.

11. An antireflective film, characterized in that, Includes the polymer@SiO2 spheres as described in claim 7.

12. A method for preparing the antireflective film according to claim 11, characterized in that, It is obtained by drying the double-layer hollow sphere sol as described in claim 9.

13. An antireflective material, characterized in that, It includes a substrate and an antireflective film composited thereon, wherein the antireflective film is the antireflective film of claim 11.

Images