Aryl-containing asymmetric polytelluroxane as well as preparation method and application of aryl-containing asymmetric polytelluroxane

Abstract

The invention belongs to the field of polymer chemistry, and particularly discloses aryl-containing asymmetric poly (tellurium oxyalkane) and a preparation method and application thereof.The aryl-containing asymmetric poly (tellurium oxyalkane) has the structure shown in the formula (I), # imgabs0 #, Z1-Z5 are independently selected from hydrogen, halogen, nitryl, hydroxyl, substituted or unsubstituted C1-C12 alkyl, C1-C12 alkoxy and C1-C12 sulfenyl, and the aryl-containing asymmetric poly (tellurium oxyalkane) has the structure shown in the formula (I), # imgabs0 #, r1 is selected from substituted or unsubstituted C1-C20 alkyl groups; and n is any integer between 2 and 5000. According to the aryl-containing asymmetric poly (tellurium oxyalkane), the aryl is directly introduced to a tellurium atom, so that the flexibility and the electronic structure of a tellurium-oxygen main chain are effectively changed, and good properties are provided for the poly (tellurium oxyalkane) to play a role in the fields of photocatalysis, semiconductors, photoetching and the like.

Description

Technical Field

[0001] The present application belongs to the field of polymer chemistry, and specifically relates to an asymmetric polytelluroxide containing an aromatic group and a preparation method and application thereof. Background Art

[0002] Since the concept of polymers was proposed, scientists have focused their research on polymers with carbon as the main chain. The most common polymer materials in life, such as polyethylene, polypropylene, polyvinyl chloride, etc., are all polymers with carbon atoms as the main chain. With the development of polymer science, many polymers with heteroatoms in the main chain have been gradually applied to actual life production, such as polycarbonate, polyurethane, etc. In addition, more and more high-performance rubbers, engineering plastics, and special plastics have been commercialized. The main chains of these polymers also contain heteroatoms other than carbon, such as polyamide, polyimide, and polysulfone, etc. It is the diversity and designability of the polymer main chain structure that allows polymer materials to have a variety of excellent properties and are suitable for various scenarios and extreme conditions.

[0003] In addition, there is a class of polymers whose main chains are completely composed of elements other than carbon, which have special properties different from the above-mentioned traditional polymers. For example, polysiloxanes and polyphosphazenes are called non-carbon main-chain polymers. Polysiloxanes are widely used in flexible electronics, lubricants and other fields due to the flexibility of their Si-O main chains; polyphosphazenes are widely used in the field of biomedical materials due to the good biocompatibility of their main chain P and N atoms. Although non-carbon main-chain polymers have shown significant advantages in some specific applications due to their unique chemical structure and properties, there are still few known non-carbon main-chain polymers. This is because the main chain structure of most of these polymers is unstable, the application range is narrow, and the research and development is difficult. With the advancement of science and technology and changes in application needs, non-carbon main-chain polymers will continue to play an important role in various high-tech fields and bring new development opportunities for future materials science and engineering. The research and development of non-carbon main-chain polymers provides an important scientific basis and technical support for the innovation and application of new materials.

[0004] A new type of non-carbon main chain polymer with a Te-O main chain, polytelluroxane, has been published in the related technology. Studies have shown that polytelluroxane has the properties of simple preparation, economical raw material price, and good molding and processing performance. At the same time, polytelluroxane has application potential in ultraviolet light protection and organic catalysis, and the special Te-O main chain structure brings closed-loop degradable properties to polytelluroxane, which has good economic benefits and prospects for industrial application. Polytelluroxane is used as a UV protection layer to inhibit the degradation and oxidation of perovskite active materials by ultraviolet rays, inhibit phase separation and the increase of grain boundary defects, and can extend the life of solar cells and improve their photoelectric conversion efficiency.

[0005] However, the polytelluroxane synthesized by current technology can only have a symmetrical structure, which limits its chemical design and functionality. Therefore, the development of a new synthesis route for polytelluroxane is of great significance for expanding the scope of non-carbon backbone polymers and exploring their potential applications. Summary of the invention

[0006] This application is based on the inventor's discovery and understanding of the following facts and problems:

[0007] Polytelluroxane is a new type of non-carbon main-chain polymer with great application potential in biodegradability, photocatalysis, radiation protection, etc. The Te-O main chain of polytelluroxane provides it with special uses that are different from ordinary polymers, and the two organic side chains R on each tellurium atom provide polytelluroxane with good solubility and hydrophilic and hydrophobic properties. However, the synthesis route of polytelluroxane with current technology is single, because the synthesis route of tellurium-containing small molecule monomers is based on sodium telluride and halogenated hydrocarbon S. N 2 reactions, so sp 2 Hybridized carbon atoms (such as aromatic groups) cannot be directly connected to tellurium atoms, and the organic tellurium ethers prepared can only have symmetrical structures (i.e., R-Te-R), and the synthesized polytelluroxanes also have symmetrical -[Te(R) 2 -O]- structure, which limits its chemical design and functionality. Therefore, the preparation method of asymmetric polytelluroxane containing aromatic groups needs to be further improved.

[0008] The present application aims to solve at least one of the technical problems in the related art to a certain extent. To this end, the present application proposes an asymmetric polytelluroxane containing an aromatic group and a preparation method and application thereof, and directly introduces an aromatic group into the tellurium atom of the polytelluroxane to expand the side chain structure of the non-carbon main chain polytelluroxane and explore potential application scenarios.

[0009] In the first aspect of the present application, an aromatic-containing asymmetric polytelluroxane is proposed, which has a structure shown in formula (I):

[0010]

[0011] Among them, Z 1 -Z 5 are independently selected from hydrogen, halogen, nitro, hydroxyl, substituted or unsubstituted C 1 -C 12 Hydrocarbon, C 1 -C 12 Hydroxyl, C 1 -C 12 Hydrocarbon thio group; R 1 Selected from substituted or unsubstituted C 1 -C 20 Hydrocarbyl; n is any integer between 2 and 5000.

[0012] The above-mentioned asymmetric polytelluroxane containing aromatic groups has the following beneficial effects:

[0013] First, compared with common non-carbon main chain polymers such as polysiloxane and polyphosphazene, the main chain of polytelluroxane has tellurium atoms with higher atomic numbers and larger radii. High-period elements can give polymer materials more special thermal, optical and electrical properties. In addition, the introduction of aromatic groups can provide a means of regulating the electronic structure of the Te-O main chain of polytelluroxane. The electronic effect of different substituted aromatic groups will affect the electron cloud density of the Te-O main chain of polytelluroxane, and thus the energy level structure of polytelluroxane can be regulated. At the same time, aromatic groups, as rigid groups, can regulate the flexibility of the polytelluroxane chain. The π-π interaction between aromatic groups can also regulate the interaction between polymers, thereby achieving the performance regulation of polytelluroxane macroscopic materials and making them have richer physical and chemical properties. In addition, the other half of the alkyl part of the asymmetric polytelluroxane, except for the aromatic group, still has structural adjustability, and different functional groups can be introduced as needed to achieve different functions.

[0014] In some embodiments, the substituted or unsubstituted C 1 -C 20 The substituents in the hydrocarbon group include hydroxyl, substituted or unsubstituted amino, cyano and aryl. Thus, the asymmetric polytelluroxane containing aromatic groups has rich structures and physical and chemical properties.

[0015] In some embodiments, R 1 It has the structure shown in general formula (II):

[0016]

[0017] Among them, R 2 is selected from hydrogen, hydroxy, substituted or unsubstituted amino, cyano and aryl, and x is any integer between 1 and 20.

[0018] In some embodiments, R 1 Selected from substituted or unsubstituted C 1 -C 12 In some other embodiments, R 1 Selected from C 1 -C 5 The hydrocarbon group may be, for example, ethyl, propyl or butyl.

[0019] In some embodiments, Z 1 -Z 5 are independently selected from hydrogen, chlorine, bromine, iodine, nitro, hydroxyl, substituted or unsubstituted C 1 -C 8 Hydrocarbon, C 1 -C 8Hydroxyl, C 1 -C 8 and n is any integer between 2 and 3000. In some other embodiments, Z 1 -Z 5 independently selected from hydrogen, C 1 ~C 5 Alkoxy group; and n is any integer between 2 and 250. Thus, the asymmetric polytelluroxane containing aromatic groups has structural adjustability, thereby achieving different functions.

[0020] The second aspect of the present application provides a method for preparing an aromatic-containing asymmetric polytelluroxane, comprising:

[0021] Magnesium and an aryl halide as shown in Formula 1 are reacted in a first solvent to obtain an aryl Grignard reagent, which is then reacted with tellurium powder to obtain an aryl ditelluride as shown in Formula 2; the aryl ditelluride is reacted with sodium borohydride in a second solvent, which is then further reacted with a halogenated hydrocarbon as shown in Formula 3 to obtain an asymmetric organic tellurium ether containing an aromatic group as shown in Formula 4; the asymmetric organic tellurium ether containing an aromatic group is dissolved in a third solvent, and subjected to an interfacial oxidative polymerization reaction with an aqueous hydrogen peroxide solution to obtain an asymmetric polytelluroxide containing an aromatic group as shown in Formula (I).

[0022]

[0023] R 1 -X-style 3

[0024]

[0025] wherein X is selected from chlorine, bromine and iodine.

[0026] In the present application, the preparation method is easy to operate and has not only higher yield and conversion rate, but also higher safety and economy.

[0027] In some embodiments, the molar ratio of magnesium, aryl halide and tellurium powder is 1:(0.9-1):(0.9-1). This can make the reaction more complete, avoid the waste of raw materials, and better synthesize the aryl Grignard reagent.

[0028] In some embodiments, the first solvent comprises at least one of anhydrous tetrahydrofuran or anhydrous ether.

[0029] In some embodiments, the reaction temperature for preparing the aryl Grignard reagent is 0° C. to 70° C., and the reaction time is 0.5 hour to 2 hours, thereby promoting the reaction and making the reaction more complete.

[0030] In some embodiments, the reaction temperature of the aryl Grignard reagent and tellurium powder is 0° C. to 50° C., and the reaction time is 0.5 hour to 2 hours, thereby promoting the reaction and improving the reaction efficiency.

[0031] In some embodiments, the molar ratio of the aryl ditelluride, sodium borohydride, and halogenated hydrocarbon is 1:(4-10):(1.9-2). This can make the reaction more complete, avoid waste of raw materials, and better synthesize the asymmetric organic tellurium ether containing aromatic groups.

[0032] In some embodiments, the second solvent includes at least one of a mixed solvent of water and tetrahydrofuran, a mixed solvent of acetonitrile and water, and N,N-dimethylacetamide.

[0033] In some embodiments, the volume ratio of water to tetrahydrofuran in the mixed solvent of water and tetrahydrofuran is 1:(0.5-2).

[0034] In some embodiments, the reaction temperature of the arylditellurium and sodium borohydride is 0°C to 25°C, and the reaction time is 0.5 hours to 2 hours. The reaction temperature after adding the halogenated hydrocarbon is 0°C to 50°C, and the reaction time is 0.5 hours to 12 hours. This can promote the reaction, make the reaction more complete, and improve the reaction efficiency.

[0035] In some embodiments, the third solvent includes at least one of ethyl acetate, dichloromethane, chloroform, and tetrahydrofuran, so that the solvent has a wide source and is conducive to the smooth progress of the reaction.

[0036] In some embodiments, the concentration of the asymmetric organotelluride ether containing an aromatic group in the third solvent is 0.1 mol / L to 2 mol / L, thereby making the reaction more complete and avoiding the waste of raw materials.

[0037] In some embodiments, the concentration of the aqueous hydrogen peroxide solution is 0.1 mol / L to 5 mol / L, which is conducive to the smooth progress of the interfacial oxidative polymerization reaction and improves the reaction efficiency.

[0038] In some embodiments, the interfacial oxidative polymerization reaction temperature is 0° C. to 40° C., and the reaction time is 0.5 day to 7 days, thereby making the reaction more complete and accelerating the reaction rate.

[0039] In some embodiments, the aromatic-containing asymmetric polytelluroxane can be used in fields such as extreme ultraviolet photoresist.

[0040] The method for preparing the above-mentioned asymmetric polytelluroxane containing aromatic groups has the following beneficial effects:

[0041] First, compared with the traditional symmetrical polytelluroxide synthesis route, the preparation method of asymmetric polytelluroxide containing aromatic groups can introduce aromatic groups with rich structures and high controllability into polytelluroxide, which greatly increases the diversity of the side chain structure of polytelluroxide and can achieve more functions and applications. In addition, compared with the solid-liquid phase preparation method of symmetrical organic tellurium ethers, the reaction conditions of the asymmetric monomer preparation step are milder and more controllable, and the reaction rate is faster. This is because the step is a liquid-liquid phase reaction, and the contact area between the reactants is larger. And this step has a high atomic utilization rate, and almost no by-products such as organic ditellurium and organic tritellurium are produced. Compared with the symmetrical tellurium ether monomer preparation method that is easy to produce organic polytellurium, it has a higher yield and conversion rate. In addition, the amount of sodium borohydride required in this preparation method is less, and it has higher safety and economy. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 The synthetic route of the aromatic-containing asymmetric polytelluroxane of the embodiments of the present application is shown in FIG.

[0043] Figure 2 is the hydrogen nuclear magnetic resonance spectrum of diphenyl ditelluride in Example 1 of the present application ( Figure 2 (a)) and C NMR spectra ( Figure 2 (b)).

[0044] Figure 3 is the hydrogen nuclear magnetic resonance spectrum of phenyl n-butyl telluride in Example 1 of the present application ( Figure 3 (a)), C NMR spectrum ( Figure 3 (b)) and NMR tellurium spectra ( Figure 3 (c)).

[0045] Figure 4 The mass spectrum (a) and (b) isotope simulated mass spectrum of phenyl n-butyl telluride in Example 1 of the present application.

[0046] Figure 5 Comparative H NMR spectra of polyphenyl n-butyl telluroxide and phenyl n-butyl telluride in Example 1 of the present application.

[0047] Figure 6 This is the Raman spectrum of polyphenyl n-butyltelluroxane in Example 1 of the present application.

[0048] Figure 7 This is the X-ray photoelectron spectrum of polyphenyl n-butyltelluroxane in Example 1 of the present application.

[0049] Figure 8 This is a differential scanning calorimetry analysis diagram of polyphenyl n-butyltelluroxide in Example 1 of the present application.

[0050] Fig. 9This is an analysis chart of the gel permeation chromatography of polyphenyl n-butyl telluroxane in Example 1 of the present application changing with time. DETAILED DESCRIPTION

[0051] The embodiments of the present application are described in detail below, and examples of the embodiments are shown in the accompanying drawings. The embodiments described below with reference to the accompanying drawings are exemplary and are intended to be used to explain the present application, but cannot be understood as limiting the present application.

[0052] In the first aspect of the present application, an aromatic-containing asymmetric polytelluroxane is proposed, which has a structure shown in the general formula (I):

[0053]

[0054] Among them, Z 1 -Z 5 are independently selected from hydrogen, halogen, nitro, hydroxyl, substituted or unsubstituted C 1 -C 12 Hydrocarbon, C 1 -C 12 Hydroxyl, C 1 -C 12 Hydrocarbon thio group; R 1 Selected from substituted or unsubstituted C 1 -C 20 Hydrocarbyl; n is any integer between 2 and 5000.

[0055] The aromatic-containing asymmetric polytelluroxane described in the present application directly connects structurally diverse and electrically adjustable aromatic groups to the tellurium atoms of the polytelluroxane, and the side chain structure is controllable, thereby enabling the performance of the polytelluroxane macroscopic material to be controlled to expand its application scenarios.

[0056] In some embodiments, substituted or unsubstituted C 1 -C 20 The substituents in the hydrocarbon group include hydroxyl, substituted or unsubstituted amino, cyano and aryl. Thus, the asymmetric polytelluroxane containing aromatic groups has rich structures and physical and chemical properties.

[0057] In some embodiments, R 1 It has the structure shown in general formula (II):

[0058]

[0059] Among them, R 2 is selected from hydrogen, hydroxy, substituted or unsubstituted amino, cyano and aryl, and x is any integer between 1 and 20.

[0060] In some embodiments, R 1 Selected from substituted or unsubstituted C 1 -C12 In some other embodiments, R 1 Selected from C 1 -C 5 The hydrocarbon group may be, for example, ethyl, propyl or butyl.

[0061] In some embodiments, Z 1 -Z 5 are independently selected from hydrogen, chlorine, bromine, iodine, nitro, hydroxyl, substituted or unsubstituted C 1 -C 8 Hydrocarbon, C 1 -C 8 Hydroxyl, C 1 -C 8 and n is any integer between 2 and 3000. In some other embodiments, Z 1 -Z 5 independently selected from hydrogen, C 1 ~C 5 Alkoxy; and n is any integer between 2 and 250.

[0062] As an example, the polytelluroxane may be at least one of the following compounds:

[0063]

[0064] The second aspect of the present application provides a method for preparing an aromatic-containing asymmetric polytelluroxane, comprising:

[0065] S10: reacting magnesium and an aryl halide in a first solvent to obtain an aryl Grignard reagent, and then reacting the aryl Grignard reagent with tellurium powder to obtain an aryl ditellurium.

[0066] It should be noted that Grignard reagent is referred to as "Grignard reagent". It is an organometallic compound containing magnesium halide. Since it contains carbon anions, it is a nucleophilic reagent. In this step, the shape of magnesium is not specifically limited, for example, it can be magnesium chips or magnesium powder, as long as it can react with aryl halides. Using aryl bromide as a substrate can better initiate the reaction, and there are fewer side reactions, which is conducive to obtaining aryl ditellurides.

[0067] In some embodiments, the molar ratio of magnesium, aryl halide, and tellurium powder is 1:(0.9-1):(0.9-1), for example, 1:0.9:0.9, 1:0.9:1, 1:1:0.9, or 1:1:1, etc. This ratio range is conducive to the full reaction and will not cause waste of raw materials.

[0068] In some embodiments, the first solvent includes at least one of anhydrous tetrahydrofuran or anhydrous ether. This allows the reaction to proceed smoothly and is conducive to obtaining an aryl Grignard reagent.

[0069] In some embodiments, the reaction temperature for preparing the aryl Grignard reagent is 0°C to 70°C (such as 10°C, 20°C, 30°C, 40°C, 50°C, 60°C or 70°C, etc.), and the reaction time is 0.5 hours to 2 hours (such as 0.5 hours, 0.6 hours, 0.7 hours, 0.8 hours, 0.9 hours, 1 hour, 1.1 hours, 1.2 hours, 1.3 hours, 1.4 hours, 1.5 hours, 1.6 hours, 1.7 hours, 1.8 hours, 1.9 hours or 2 hours, etc.). At the above reaction temperature and reaction time, the reaction can be promoted, so that the magnesium and aryl halide react more fully, and the reaction efficiency can be improved.

[0070] In some embodiments, the reaction temperature of the aryl Grignard reagent and tellurium powder is 0°C to 50°C (such as 10°C, 20°C, 30°C, 40°C or 50°C, etc.), and the reaction time is 0.5 hours to 2 hours (such as 0.5 hours, 0.6 hours, 0.7 hours, 0.8 hours, 0.9 hours, 1 hour, 1.1 hours, 1.2 hours, 1.3 hours, 1.4 hours, 1.5 hours, 1.6 hours, 1.7 hours, 1.8 hours, 1.9 hours or 2 hours, etc.). At the above reaction temperature and reaction time, the reaction of the aryl Grignard reagent and tellurium powder can be promoted to improve the reaction efficiency.

[0071] In some embodiments, after the aryl Grignard reagent reacts with tellurium powder, a step of separating aryl ditellurium from the reaction system may be included, which may specifically include extraction, drying, concentration, and crystallization steps, thereby effectively separating and obtaining aryl ditellurium with higher purity.

[0072] In some embodiments, the extraction can be performed using 100 mL of one or more mixed solvents of ethyl acetate, ethyl ether, dichloromethane, and petroleum ether for three extractions. This provides a wide range of material sources and is beneficial for extracting aryl ditelluride from the solvent.

[0073] In some embodiments, the drying may use a commonly used desiccant, such as sodium sulfate, calcium sulfate, magnesium sulfate, calcium chloride, etc. Thus, the material source is wide, no impurities are introduced, and the water absorption effect is good.

[0074] In some embodiments, the concentration can be performed by removing the organic solvent using a rotary evaporator.

[0075] In some embodiments, the crystallization can be performed by cooling at -20°C to room temperature, such as in a 4°C freezer.

[0076] In some embodiments, after separating the aryl ditelluride from the reaction system, the process further includes a step of purifying the aryl ditelluride. For example, the product aryl ditelluride may be purified by recrystallization, and the purification solvent may be ethanol, isopropanol, methanol, or the like.

[0077] S20: reacting the aryl ditelluride with sodium borohydride in a second solvent, reducing the Te-Te bond by sodium borohydride, and generating aryl tellurol sodium salt in situ, which then undergoes a nucleophilic substitution reaction with a halogenated hydrocarbon to obtain an asymmetric organic tellurium ether containing an aromatic group.

[0078] In some embodiments, the molar ratio of the aryl ditelluride, sodium borohydride, and halogenated hydrocarbon is 1:(4-10):(1.9-2), for example, 1:10:2, 1:8:2, 1:4:2, 1:4:1.9, 1:8:1.9, or 1:10:1.9, etc. This can make the reaction more complete, avoid the waste of raw materials, and better synthesize the asymmetric organic tellurium ether containing aromatic groups.

[0079] In some embodiments, the second solvent includes at least one of a water / tetrahydrofuran mixed solvent, a mixed solvent of acetonitrile and water, and N,N-dimethylacetamide. In other embodiments, the volume ratio of water to tetrahydrofuran in the mixed solvent of water and tetrahydrofuran is 1:(0.5-2), for example, 1:0.5, 1:1, 1:1.5 or 1:2. Within the above ratio range, the reaction of aryl ditelluride and sodium borohydride is favorable, and the reaction efficiency is improved.

[0080] In some embodiments, the reaction temperature of the arylditellurium and sodium borohydride is 0°C to 25°C (such as 5°C, 10°C, 15°C, 20°C or 25°C, etc.), and the reaction time is 0.5 hours to 2 hours (such as 0.5 hours, 1 hour, 1.5 hours or 2 hours, etc.). The reaction temperature after adding the halogenated hydrocarbon is 0°C to 50°C (such as 10°C, 20°C, 30°C, 40°C or 50°C, etc.), and the reaction time is 0.5 hours to 12 hours (such as 0.5 hours, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours or 12 hours, etc.). At the above reaction temperature and reaction time, the reaction is more complete and the reaction efficiency is higher.

[0081] In some embodiments, after reacting with the halogenated hydrocarbon, a step of separating the asymmetric organic tellurium ether containing an aromatic group from the reaction system may be further included, which may specifically include extraction, drying, and concentration steps, thereby effectively separating and obtaining an asymmetric organic tellurium ether containing an aromatic group with a high purity. The specific operations of the extraction, drying, and concentration steps may be consistent with the operations of separating the aromatic ditellurium in step S10, and will not be described in detail here.

[0082] In some embodiments, in step S20, silica gel column chromatography is used to separate and purify the product asymmetric organic tellurium ether containing an aromatic group, and the eluent can be a mixed solvent of ethyl acetate and petroleum ether. Specifically, the volume ratio of ethyl acetate to petroleum ether is 1: (1-5), for example, it can be 1: 2, 1: 3, 1: 4 or 1: 5. Within the above ratio range, it is beneficial to improve the purity of the asymmetric organic tellurium ether containing an aromatic group.

[0083] S30: dissolving the aromatic-containing asymmetric organic tellurium ether in a third solvent, and reacting the solvent with an aqueous hydrogen peroxide solution to perform interfacial oxidative polymerization to obtain an aromatic-containing asymmetric polytelluroxide.

[0084] During this step, the reaction will release a large amount of heat and the organic phase will turn from yellow to colorless.

[0085] In some embodiments, the third solvent includes at least one of ethyl acetate, dichloromethane, chloroform, and tetrahydrofuran. Thus, the source of materials is wide, the cost is low, and the reaction is conducive to proceed.

[0086] In some embodiments, the concentration of the asymmetric organotelluride ether containing an aromatic group in the third solvent is 0.1 mol / L to 2 mol / L, for example, 0.1 mol / L, 0.2 mol / L, 0.4 mol / L, 0.6 mol / L, 0.8 mol / L, 1 mol / L, 1.2 mol / L, 1.4 mol / L, 1.6 mol / L, 1.8 mol / L or 2 mol / L, etc. Within the above concentration range, the reaction is facilitated to proceed smoothly and the reaction rate is increased.

[0087] In some embodiments, the concentration of the aqueous hydrogen peroxide solution is 0.1 mol / L to 5 mol / L, for example, 0.1 mol / L, 0.5 mol / L, 1 mol / L, 1.5 mol / L, 2 mol / L, 2.5 mol / L, 3 mol / L, 3.5 mol / L, 4 mol / L, 4.5 mol / L or 5 mol / L, etc. Within the above concentration range, the reaction can proceed smoothly and the waste of raw materials can be avoided.

[0088] In some embodiments, the interfacial oxidative polymerization reaction temperature is 0°C to 40°C (such as 10°C, 20°C, 30°C or 40°C, etc.), and the reaction time is 0.5 day to 7 days (such as 0.5 day, 1 day, 2 days, 3 days, 4 days, 5 days, 6 days or 7 days, etc.), thereby making the reaction more complete and accelerating the reaction rate.

[0089] In some embodiments, after the interfacial oxidative polymerization reaction is completed, the organic solution containing the asymmetric polytelluroxane containing an aromatic group obtained by the reaction is added dropwise to a large amount of methanol to separate the asymmetric polytelluroxane containing an aromatic group by precipitation, and the precipitate is collected and washed with methanol as a detergent to obtain the asymmetric polytelluroxane containing an aromatic group with a higher purity. In this way, the purity of the asymmetric polytelluroxane containing an aromatic group can be improved.

[0090] In some specific embodiments of the present application, the method for preparing an asymmetric polytelluroxane containing an aromatic group may include:

[0091] S1. Preparation of aryl ditellurides

[0092] First, an aryl Grignard reagent is prepared in situ using magnesium chips and aryl halides in an organic solvent, and then reacted with tellurium powder in air, followed by extraction, drying, concentration and crystallization to obtain aryl ditelluride.

[0093] S2. Preparation of Asymmetric Organotelluryl Ethers Containing Aromatic Groups

[0094] The aryl ditelluride prepared in S1 is mixed with sodium borohydride, reacted in a mixed solvent of water and tetrahydrofuran, and then a halogenated hydrocarbon is added, the reaction is continued, and an asymmetric organic tellurium ether containing an aromatic group is obtained after extraction, drying and concentration;

[0095] S3. Preparation of Asymmetric Polytelluroxide Containing Aromatic Groups

[0096] The aromatic asymmetric organic tellurium ether prepared in S2 is dissolved in an organic solvent, an aqueous hydrogen peroxide solution is added and stirred to carry out interfacial oxidative polymerization, the organic solution of the product is dropped into methanol for precipitation to separate the product, and methanol is used as a washing agent to obtain an aromatic asymmetric polytelluroxide.

[0097] In general, the method for preparing the aromatic-containing asymmetric polytelluroxane provided in the present application is easy to operate, and has higher yield and efficiency while ensuring safety and economy.

[0098] In some embodiments, the aromatic-containing asymmetric polytelluroxane can be used in fields such as extreme ultraviolet photoresist.

[0099] The embodiments of the present application are described in detail below.

[0100] Example 1

[0101] 1. Preparation of diphenyl ditelluride

[0102] Magnesium powder (0.535g, 22.0mmol) and a small particle of iodine were added to an eggplant-shaped flask, and 20mL of anhydrous tetrahydrofuran was added. Bromobenzene (3.14g, 20.0mmol) was dissolved in 20mL of anhydrous tetrahydrofuran, and slowly dripped into the eggplant-shaped flask with a syringe under slow stirring. After the addition was completed, it was refluxed for 1 hour to obtain an aromatic Grignard reagent. The reaction solution was cooled to room temperature, tellurium powder (2.55g, 20.0mmol) was added, and the mixture continued to react in an open system for 1 hour, and the reaction was completed. After the reaction was completed, the mixture was extracted with 100mL of ethyl acetate three times, the organic phases were combined, dried with magnesium sulfate, and filtered. The obtained organic solution was desolventized by a rotary evaporator, and the crude product was obtained after cooling to 4°C. The crude product was recrystallized in ethanol to obtain red needle-shaped crystals of diphenylditelluride.

[0103] 2. Preparation of phenyl n-butyl telluride

[0104] Diphenylditellurium (819 mg, 2.00 mmol) and sodium borohydride (757 mg, 20.0 mmol) were added to an eggplant-shaped flask, 10 mL of tetrahydrofuran was added in a nitrogen atmosphere, 20 mL of deionized water was slowly added dropwise with a syringe, and the reaction was stirred for 20 minutes. After the reaction solution turned light yellow, a solution of n-butyl bromide (548 mg, 4.00 mmol) dissolved in 10 mL of tetrahydrofuran was slowly added dropwise to the reaction flask, and the mixture was stirred vigorously at 50 ° C overnight to complete the reaction. After the reaction, the mixture was extracted three times with 60 mL of ethyl acetate, the organic phases were combined, dried with magnesium sulfate, and filtered. The obtained organic solution was used to remove the solvent using a rotary evaporator to obtain a yellow asymmetric aryl alkyl telluride ether liquid. The purer product phenyl n-butyl telluride ether can be obtained by separation and purification using silica gel column chromatography.

[0105] 3. Preparation of polyphenyl n-butyl telluroxane

[0106] Dissolve phenyl n-butyl telluride (200 mg, 0.766 mmol) in 1 mL of dichloromethane to obtain component A, and dilute 0.5 mL of 30% hydrogen peroxide solution to obtain component B. Mix component A and component B fully in a reaction bottle, the reaction releases a large amount of heat, and the organic phase changes from yellow to colorless, and the reaction is continued for 7 days. After the reaction is completed, the organic phase is separated and added dropwise to 40 mL of methanol to produce a white precipitate. The product is washed with 10 mL of methanol and dried in an oven at 60°C to obtain polyphenyl n-butyl telluride as a white solid.

[0107] Example 2

[0108] 1. Preparation of diphenyl ditelluride

[0109] Add magnesium powder (0.267g, 11.0mmol) and a small particle of iodine to an eggplant-shaped flask, and add 10mL of anhydrous tetrahydrofuran. Dissolve bromobenzene (1.57g, 10.0mmol) in 8mL of anhydrous tetrahydrofuran, slowly drip into the eggplant-shaped flask with a syringe under slow stirring, and reflux for 40 minutes after the addition is completed to obtain an aryl Grignard reagent. The reaction solution is cooled to room temperature, tellurium powder (1.28g, 10.0mmol) is added, and the mixture continues to react in an open system for 40 minutes, and the reaction is completed. After the reaction is completed, the mixture is extracted three times with 60mL of ether, the organic phases are combined, dried with sodium sulfate, and filtered. The obtained organic solution is used to remove the solvent using a rotary evaporator, and the crude product can be obtained after cooling to 0°C. The crude product is recrystallized in ethanol to obtain red needle-shaped crystals of diphenylditelluride.

[0110] 2. Preparation of phenyl n-propyl telluride

[0111] Diphenylditellurium (819 mg, 2.00 mmol) and sodium borohydride (605 mg, 16.0 mmol) were added to an eggplant-shaped flask, 10 mL of tetrahydrofuran was added in a nitrogen atmosphere, 20 mL of deionized water was slowly added dropwise with a syringe, and the reaction was stirred for 20 minutes. After the reaction solution turned light yellow, a solution of n-propyl bromide (492 mg, 4.00 mmol) dissolved in 10 mL of tetrahydrofuran was slowly added dropwise to the reaction flask, and the mixture was stirred vigorously at 50 ° C for 4 hours to complete the reaction. After the reaction, the mixture was extracted three times with 120 mL of ether, the organic phases were combined, dried with sodium sulfate, and filtered. The obtained organic solution was desolventized by a rotary evaporator to obtain a yellow phenyl n-propyl telluride ether liquid.

[0112] 3. Preparation of polyphenyl n-propyl telluroxane

[0113] Dissolve phenyl n-propyl telluride (250 mg, 1.01 mmol) in 1 mL of ethyl acetate to obtain component A, and dilute 0.5 mL of 30% aqueous hydrogen peroxide solution to obtain component B. Mix component A and component B fully in a reaction bottle, the reaction releases a large amount of heat, and the organic phase changes from yellow to colorless, and the reaction is continued for 7 days. After the reaction is completed, the organic phase is collected by liquid separation and added dropwise to 100 mL of methanol to produce a white precipitate. The product is washed with 10 mL of methanol and dried in an oven at 60°C to obtain polyphenyl n-propyl telluride as a white solid.

[0114] Example 3

[0115] 1. Preparation of diphenyl ditelluride

[0116] Add magnesium powder (0.267g, 11.0mmol) and a small particle of iodine to an eggplant-shaped flask, and add 10mL of anhydrous tetrahydrofuran. Dissolve bromobenzene (1.57g, 10.0mmol) in 8mL of anhydrous tetrahydrofuran, slowly drip into the eggplant-shaped flask with a syringe under slow stirring, and reflux for 40 minutes after the addition is completed to obtain an aryl Grignard reagent. The reaction solution is cooled to room temperature, tellurium powder (1.28g, 10.0mmol) is added, and the mixture continues to react in an open system for 40 minutes, and the reaction is completed. After the reaction is completed, the mixture is extracted three times with 60mL of ether, the organic phases are combined, dried with sodium sulfate, and filtered. The obtained organic solution is used to remove the solvent using a rotary evaporator, and the crude product can be obtained after cooling to 0°C. The crude product is recrystallized in ethanol to obtain red needle-shaped crystals of diphenylditelluride.

[0117] 2. Preparation of phenyl ethyl telluride

[0118] Diphenylditellurium (819 mg, 2.00 mmol) and sodium borohydride (605 mg, 16.0 mmol) were added to an eggplant-shaped flask, 10 mL of tetrahydrofuran was added in a nitrogen atmosphere, 20 mL of deionized water was slowly added dropwise with a syringe, and the reaction was stirred for 20 minutes. After the reaction solution turned light yellow, ethyl iodide (624 mg, 4.00 mmol) dissolved in 10 mL of tetrahydrofuran was slowly added dropwise to the reaction flask, and the mixture was stirred vigorously at 50 ° C for 2 hours, and the reaction was completed. After the reaction, the mixture was extracted three times with 120 mL of ethyl acetate, the organic phases were combined, dried with magnesium sulfate, and filtered. The obtained organic solution was used to remove the solvent using a rotary evaporator to obtain a yellow phenylethyl telluride ether liquid. The purer product phenylethyl telluride ether can be obtained by separation and purification using silica gel column chromatography.

[0119] 3. Preparation of polyphenylethyltelluroxide

[0120] Dissolve phenylethyl telluride (250 mg, 1.07 mmol) in 1 mL of chloroform to obtain component A, and dilute 0.5 mL of 30% hydrogen peroxide solution to obtain component B. Mix component A and component B fully in a reaction bottle, the reaction releases a large amount of heat, and the organic phase changes from yellow to colorless, and the reaction is continued for 7 days. After the reaction is completed, the organic phase is collected by liquid separation and added dropwise to 100 mL of methanol to produce a white precipitate. The product is washed with 10 mL of methanol and dried in an oven at 60°C to obtain polyphenylethyl telluride as a white solid.

[0121] Example 4

[0122] 1. Preparation of diphenyl ditelluride

[0123] Magnesium powder (0.535g, 22.0mmol) and a small particle of iodine were added to an eggplant-shaped flask, and 20mL of anhydrous tetrahydrofuran was added. Bromobenzene (3.14g, 20.0mmol) was dissolved in 20mL of anhydrous tetrahydrofuran, and slowly dripped into the eggplant-shaped flask with a syringe under slow stirring. After the addition was completed, it was refluxed for 1 hour to obtain an aromatic Grignard reagent. The reaction solution was cooled to room temperature, tellurium powder (2.55g, 20.0mmol) was added, and the mixture continued to react in an open system for 1 hour, and the reaction was completed. After the reaction was completed, the mixture was extracted with 100mL of ethyl acetate three times, the organic phases were combined, dried with magnesium sulfate, and filtered. The obtained organic solution was desolventized by a rotary evaporator, and the crude product was obtained after cooling to 4°C. The crude product was recrystallized in ethanol to obtain red needle-shaped crystals of diphenylditelluride.

[0124] 2. Preparation of phenyl (3-hydroxypropyl) telluride ether

[0125] Diphenylditellurium (819 mg, 2.00 mmol) and sodium borohydride (757 mg, 20.0 mmol) were added to an eggplant-shaped flask, 10 mL of tetrahydrofuran was added in a nitrogen atmosphere, 20 mL of deionized water was slowly added dropwise with a syringe, and the reaction was stirred for 20 minutes. After the reaction solution turned light yellow, a solution of 3-bromo-1-propanol (556 mg, 4.00 mmol) dissolved in 10 mL of tetrahydrofuran was slowly added dropwise to the reaction flask, and the mixture was stirred vigorously at 50 ° C overnight to complete the reaction. After the reaction, the mixture was extracted three times with 60 mL of ethyl acetate, the organic phases were combined, dried with magnesium sulfate, and filtered. The obtained organic solution was used to remove the solvent using a rotary evaporator to obtain a yellow asymmetric aryl alkyl telluride ether liquid. The purer product phenyl (3-hydroxypropyl) telluride ether can be obtained by separation and purification using silica gel column chromatography.

[0126] 3. Preparation of polyphenyl (3-hydroxypropyl) telluroxane

[0127] Phenyl (3-hydroxypropyl) telluride (250 mg, 0.948 mmol) was dissolved in 1 mL of chloroform to obtain component A, and 0.5 mL of 30% aqueous hydrogen peroxide solution was diluted by half to obtain component B. Component A and component B were fully mixed in a reaction bottle, and the reaction released a large amount of heat, and the organic phase changed from yellow to colorless, and the reaction was continued for 7 days. After the reaction was completed, the organic phase was collected by liquid separation and added dropwise to 100 mL of methanol to produce a white precipitate. The product was washed with 10 mL of methanol and dried in an oven at 60°C to obtain polyphenyl (3-hydroxypropyl) telluride as a white solid.

[0128] Example 5

[0129] 1. Preparation of diphenyl ditelluride

[0130] Magnesium powder (0.535g, 22.0mmol) and a small particle of iodine were added to an eggplant-shaped flask, and 20mL of anhydrous tetrahydrofuran was added. Bromobenzene (3.14g, 20.0mmol) was dissolved in 20mL of anhydrous tetrahydrofuran, and slowly dripped into the eggplant-shaped flask with a syringe under slow stirring. After the addition was completed, it was refluxed for 1 hour to obtain an aromatic Grignard reagent. The reaction solution was cooled to room temperature, tellurium powder (2.55g, 20.0mmol) was added, and the mixture continued to react in an open system for 1 hour, and the reaction was completed. After the reaction was completed, the mixture was extracted with 100mL of ethyl acetate three times, the organic phases were combined, dried with magnesium sulfate, and filtered. The obtained organic solution was desolventized by a rotary evaporator, and the crude product was obtained after cooling to 4°C. The crude product was recrystallized in ethanol to obtain red needle-shaped crystals of diphenylditelluride.

[0131] 2. Preparation of phenyl (3-phenylpropyl) telluride ether

[0132] Diphenylditellurium (819 mg, 2.00 mmol) and sodium borohydride (757 mg, 20.0 mmol) were added to an eggplant-shaped flask, 10 mL of tetrahydrofuran was added in a nitrogen atmosphere, 20 mL of deionized water was slowly added dropwise with a syringe, and the reaction was stirred for 20 minutes. After the reaction solution turned light yellow, a solution of 1-bromo-3-phenylpropane (796 mg, 4.00 mmol) dissolved in 10 mL of tetrahydrofuran was slowly added dropwise to the reaction flask, and the mixture was stirred vigorously at 50 ° C overnight to complete the reaction. After the reaction, the mixture was extracted three times with 60 mL of ethyl acetate, the organic phases were combined, dried with magnesium sulfate, and filtered. The obtained organic solution was used to remove the solvent using a rotary evaporator to obtain a yellow asymmetric aryl alkyl telluride ether liquid. The purer product phenyl (3-phenylpropyl) telluride ether can be obtained by separation and purification using silica gel column chromatography.

[0133] 3. Preparation of polyphenyl (3-phenylpropyl) telluroxane

[0134] Dissolve phenyl (3-phenylpropyl) telluride (250mg, 0.772mmol) in 1mL chloroform to obtain component A, and dilute 0.5mL 30% hydrogen peroxide solution to obtain component B. Mix component A and component B fully in a reaction bottle, the reaction releases a large amount of heat, the organic phase changes from yellow to colorless, and the reaction is continued for 7 days. After the reaction is completed, the organic phase is collected by liquid separation and added dropwise to 100mL methanol to produce a white precipitate. The product is washed with 10mL methanol and dried in an oven at 60°C to obtain polyphenyl (3-phenylpropyl) telluride as a white solid.

[0135] Example 6

[0136] 1. Preparation of bis(p-methoxyphenyl)ditellurium

[0137] Magnesium powder (0.511g, 21.0mmol) and a small particle of iodine were added to an eggplant-shaped flask, and 20mL of anhydrous tetrahydrofuran was added. p-Methoxybromobenzene (3.74g, 20.0mmol) was dissolved in 10mL of anhydrous tetrahydrofuran, and slowly dripped into the eggplant-shaped flask with a syringe under slow stirring. After the addition was completed, it was refluxed for 1 hour to obtain an aromatic Grignard reagent. The reaction solution was cooled to room temperature, tellurium powder (2.55g, 20.0mmol) was added, and the mixture continued to react in an open system for 2 hours, and the reaction was completed. After the reaction was completed, the mixture was extracted three times with 120mL of ethyl acetate, the organic phases were combined, dried with magnesium sulfate, and filtered. The obtained organic solution was used to remove the solvent using a rotary evaporator, and the crude product was obtained after cooling to 0°C. The crude product was recrystallized in methanol to obtain red needle-shaped crystals of di(p-methoxyphenyl)ditellurium.

[0138] 2. Preparation of (p-methoxyphenyl) n-butyl telluride

[0139] Add di(p-methoxyphenyl)ditellurium (938mg, 2.00mmol) and sodium borohydride (757mg, 20.0mmol) to an eggplant-shaped flask, add 15mL of tetrahydrofuran in a nitrogen atmosphere, slowly drop 30mL of deionized water with a syringe, and stir the reaction for 30 minutes. After the reaction solution turns light yellow, slowly drop a solution of n-butyl bromide (548mg, 4.00mmol) dissolved in 15mL of tetrahydrofuran into the reaction flask, and the mixture continues to react at 50°C for 12 hours under vigorous stirring until the reaction is complete. After the reaction, the mixture is extracted three times with 120mL of ethyl acetate, the organic phases are combined, dried with magnesium sulfate, and filtered. The obtained organic solution is desolventized by a rotary evaporator to obtain a yellow (p-methoxyphenyl) n-butyl tellurium ether liquid.

[0140] 3. Preparation of poly(p-methoxyphenyl) n-butyltelluroxide

[0141] Dissolve (p-methoxyphenyl) n-butyl telluride (250 mg, 0.857 mmol) in 1 mL of ethyl acetate to obtain component A, and dilute 0.5 mL of 30% aqueous hydrogen peroxide solution to obtain component B. Mix component A and component B fully in a reaction bottle, the reaction releases a large amount of heat, the organic phase changes from yellow to colorless, and the reaction is continued for 7 days. After the reaction is completed, the organic phase is collected by liquid separation and added dropwise to 100 mL of methanol to produce a white precipitate. The product is washed with 10 mL of methanol and dried in an oven at 60°C to obtain poly (p-methoxyphenyl) n-butyl telluride as a white solid.

[0142] Example 7

[0143] 1. Preparation of bis(pentafluorophenyl)ditellurium

[0144] Magnesium powder (0.511g, 21.0mmol) and a small particle of iodine were added to an eggplant-shaped flask, and 20mL of anhydrous tetrahydrofuran was added. Pentafluorobromobenzene (4.94g, 20.0mmol) was dissolved in 10mL of anhydrous tetrahydrofuran, and slowly dripped into the eggplant-shaped flask with a syringe under slow stirring. After the addition was completed, it was refluxed for 1 hour to obtain an aromatic Grignard reagent. The reaction solution was cooled to room temperature, tellurium powder (2.55g, 20.0mmol) was added, and the mixture continued to react in an open system for 2 hours, and the reaction was completed. After the reaction was completed, the mixture was extracted three times with 120mL of ethyl acetate, the organic phases were combined, dried with magnesium sulfate, and filtered. The obtained organic solution was desolventized by a rotary evaporator, and the crude product was obtained after cooling to 0°C. The crude product was recrystallized in methanol to obtain red crystals of di(pentafluorophenyl)ditellurium.

[0145] 2. Preparation of (pentafluorophenyl) n-butyl telluride

[0146] Add di(pentafluorophenyl)ditellurium (1.18g, 2.00mmol) and sodium borohydride (757mg, 20.0mmol) to an eggplant-shaped flask, add 15mL of tetrahydrofuran in a nitrogen atmosphere, slowly drop 30mL of deionized water with a syringe, and stir the reaction for 30 minutes. After the reaction solution turns light yellow, slowly drop a solution of n-butyl bromide (548mg, 4.00mmol) dissolved in 15mL of tetrahydrofuran into the reaction flask, and the mixture continues to react at 50°C for 12 hours under vigorous stirring until the reaction is complete. After the reaction, the mixture is extracted three times with 120mL of ethyl acetate, the organic phases are combined, dried with magnesium sulfate, and filtered. The obtained organic solution is desolventized by a rotary evaporator to obtain a yellow (pentafluorophenyl) n-butyl tellurium ether liquid.

[0147] 3. Preparation of poly(pentafluorophenyl) n-butyltelluroxane

[0148] Dissolve (pentafluorophenyl) n-butyl telluride (250 mg, 0.711 mmol) in 1 mL of chloroform to obtain component A, and dilute 0.5 mL of 30% aqueous hydrogen peroxide solution to obtain component B. Mix component A and component B fully in a reaction bottle, the reaction releases a large amount of heat, the organic phase changes from yellow to colorless, and the reaction is continued for 7 days. After the reaction is completed, the organic phase is collected by liquid separation and added dropwise to 100 mL of methanol to produce a white precipitate. The product is washed with 10 mL of methanol and dried in an oven at 60°C to obtain poly (pentafluorophenyl) n-butyl telluride as a white solid.

[0149] Example 8

[0150] 1. Preparation of di(o-methylphenyl)ditellurium

[0151] Magnesium powder (0.511g, 21.0mmol) and a small particle of iodine were added to an eggplant-shaped flask, and 20mL of anhydrous tetrahydrofuran was added. Ortho-methyl bromobenzene (3.42g, 20.0mmol) was dissolved in 10mL of anhydrous tetrahydrofuran, and slowly dripped into the eggplant-shaped flask with a syringe under slow stirring. After the addition was completed, it was refluxed for 1 hour to obtain an aromatic Grignard reagent. The reaction solution was cooled to room temperature, tellurium powder (2.55g, 20.0mmol) was added, and the mixture continued to react in an open system for 2 hours, and the reaction was completed. After the reaction was completed, the mixture was extracted three times with 120mL of ethyl acetate, the organic phases were combined, dried with magnesium sulfate, and filtered. The obtained organic solution was desolventized by a rotary evaporator, and the crude product was obtained after cooling to 0°C. The crude product was recrystallized in methanol to obtain red crystals of di(o-methylphenyl)ditellurium.

[0152] 2. Preparation of (o-methylphenyl) n-butyl telluride

[0153] Add di(o-methylphenyl)ditellurium (875mg, 2.00mmol) and sodium borohydride (757mg, 20.0mmol) to an eggplant-shaped flask, add 15mL of tetrahydrofuran in a nitrogen atmosphere, slowly drop 30mL of deionized water with a syringe, and stir the reaction for 30 minutes. After the reaction solution turns light yellow, slowly drop a solution of n-butyl bromide (548mg, 4.00mmol) dissolved in 15mL of tetrahydrofuran into the reaction flask, and the mixture continues to react at 50°C for 12 hours under vigorous stirring until the reaction is complete. After the reaction, the mixture is extracted three times with 120mL of ethyl acetate, the organic phases are combined, dried with magnesium sulfate, and filtered. The obtained organic solution is desolventized by a rotary evaporator to obtain a yellow (o-methylphenyl) n-butyl tellurium ether liquid.

[0154] 3. Preparation of poly(o-methylphenyl) n-butyl telluroxane

[0155] Dissolve (o-methylphenyl) n-butyl telluride (250 mg, 0.906 mmol) in 1 mL of chloroform to obtain component A, and dilute 0.5 mL of 30% aqueous hydrogen peroxide solution to obtain component B. Mix component A and component B fully in a reaction bottle, the reaction releases a large amount of heat, the organic phase changes from yellow to colorless, and the reaction is continued for 7 days. After the reaction is completed, the organic phase is collected by liquid separation and added dropwise to 100 mL of methanol to produce a white precipitate. The product is washed with 10 mL of methanol and dried in an oven at 60°C to obtain poly (o-methylphenyl) n-butyl telluride as a white solid.

[0156] Example 9

[0157] 1. Preparation of di(p-chlorophenyl)ditellurium

[0158] Magnesium powder (0.511g, 21.0mmol) and a small particle of iodine were added to an eggplant-shaped flask, and 20mL of anhydrous tetrahydrofuran was added. p-Chlorobromobenzene (3.83g, 20.0mmol) was dissolved in 10mL of anhydrous tetrahydrofuran, and slowly dripped into the eggplant-shaped flask with a syringe under slow stirring. After the addition was completed, it was refluxed for 1 hour to obtain an aromatic Grignard reagent. The reaction solution was cooled to room temperature, tellurium powder (2.55g, 20.0mmol) was added, and the mixture continued to react in an open system for 2 hours, and the reaction was completed. After the reaction was completed, the mixture was extracted with 120mL of ethyl acetate three times, the organic phases were combined, dried with magnesium sulfate, and filtered. The obtained organic solution was used to remove the solvent using a rotary evaporator, and the crude product was obtained after cooling to 0°C. The crude product was recrystallized in methanol to obtain red crystals of di(p-chlorophenyl)ditellurium.

[0159] 2. Preparation of (p-chlorophenyl) n-butyl telluride

[0160] Add di(p-chlorophenyl)ditellurium (957mg, 2.00mmol) and sodium borohydride (757mg, 20.0mmol) to an eggplant-shaped flask, add 15mL of tetrahydrofuran in a nitrogen atmosphere, slowly drop 30mL of deionized water with a syringe, and stir the reaction for 30 minutes. After the reaction solution turns light yellow, slowly drop a solution of n-butyl bromide (548mg, 4.00mmol) dissolved in 15mL of tetrahydrofuran into the reaction flask, and the mixture continues to react at 50°C for 12 hours under vigorous stirring until the reaction is complete. After the reaction, the mixture is extracted three times with 120mL of ethyl acetate, the organic phases are combined, dried with magnesium sulfate, and filtered. The obtained organic solution is desolventized by a rotary evaporator to obtain a yellow (p-chlorophenyl) n-butyl tellurium ether liquid.

[0161] 3. Preparation of poly (p-chlorophenyl) n-butyl telluroxane

[0162] Dissolve (p-chlorophenyl) n-butyl telluride (250 mg, 0.843 mmol) in 1 mL of chloroform to obtain component A, and dilute 0.5 mL of 30% aqueous hydrogen peroxide solution to obtain component B. Mix component A and component B fully in a reaction bottle, the reaction releases a large amount of heat, the organic phase changes from yellow to colorless, and the reaction is continued for 7 days. After the reaction is completed, the organic phase is collected by liquid separation and added dropwise to 100 mL of methanol to produce a white precipitate. The product is washed with 10 mL of methanol and dried in an oven at 60°C to obtain poly (o-methylphenyl) n-butyl telluride as a white solid.

[0163] The validity of the embodiments of the present application is verified as follows:

[0164] 1. Structural characterization of intermediates in the synthetic route

[0165] The diphenyl ditelluride prepared in Example 1 (Preparation of diphenyl ditelluride) was dissolved in deuterated chloroform and analyzed by hydrogen nuclear magnetic resonance spectrum and carbon nuclear magnetic resonance spectrum. Figure 2 As shown, Figure 2 (a) is the hydrogen nuclear magnetic resonance spectrum of diphenyl ditelluride, and (b) is the carbon nuclear magnetic resonance spectrum of diphenyl ditelluride. The phenyl n-butyl telluride prepared in Example 1 (preparation of phenyl n-butyl telluride) was dissolved in deuterated chloroform, and the hydrogen nuclear magnetic resonance spectrum, carbon nuclear magnetic resonance spectrum and tellurium nuclear magnetic resonance spectrum were analyzed. The characterization results are shown in FIG. Figure 3 As shown in (a) (H NMR spectrum of phenyl n-butyl telluride), (b) (C NMR spectrum of phenyl n-butyl telluride), and (c) (T NMR spectrum of phenyl n-butyl telluride). The phenyl n-butyl telluride prepared in Example 1 (Preparation of phenyl n-butyl telluride) was dissolved in dichloromethane, a small amount of silver nitrate solid was added, and the mixture was filtered and then analyzed by liquid phase mass spectrometry. Figure 4 As shown in the mass spectrum of (a), Figure 4 The results of the isotope simulation mass spectrometry in (b) are basically consistent. The above characterization results prove that aryl ditellurides and asymmetric organic tellurium ethers containing aromatic groups can be prepared by the preparation method provided in the present application.

[0166] 2. Structural characterization of asymmetric polytelluroxanes containing aromatic groups

[0167] The polyphenyl n-butyl telluroxane prepared in Example 1 (Preparation of polyphenyl n-butyl telluroxane) was dissolved in deuterated chloroform and subjected to H NMR spectrum analysis. Figure 5 (NMR hydrogen spectrum of diphenyl ditelluride). The results show that the NMR peak of the telluride ether monomer broadens after oxidative polymerization, which effectively proves that the preparation method provided by the present application can prepare an asymmetric polytellurone containing an aromatic group. At the same time, the polyphenyl n-butyl tellurone prepared in Example 1 (Preparation of polyphenyl n-butyl tellurone) was subjected to Raman spectroscopy analysis, and the relevant results are as follows Figure 6 As shown. Among them, 500cm -1 The peak at 600 cm is the stretching vibration of the Te-O long chain. -1 The peak at 1000 cm is the stretching vibration of Te-C bond. -1 The peak at 2800-3000cm is the breathing peak of the benzene ring. -1 The peak is sp 3 CH stretching vibration peak, 3000-3100cm -1 The peak is sp 2 In addition, the polyphenyl n-butyl telluroxane prepared in Example 1 (Preparation of polyphenyl n-butyl telluroxane) was subjected to X-ray photoelectron spectroscopy analysis, and the relevant results are as follows: Figure 7(a) Tellurium spectrum, (b) oxygen spectrum, (c) carbon spectrum. The above experimental results all prove that the asymmetric polytelluroxane containing phenyl groups was successfully prepared.

[0168] 3. Characterization of thermodynamic properties of asymmetric polytelluroxanes containing aromatic groups

[0169] The polyphenyl n-butyl telluroxane prepared in Example 1 (Preparation of polyphenyl n-butyl telluroxane) was subjected to scanning differential calorimetry analysis. The relevant results are as follows: Figure 8 The results show that poly(phenyl n-butyl telluroxane) has obvious decomposition phenomenon after exceeding 100℃, and no T g platform, indicating the T g The decomposition temperature may have been exceeded.

[0170] 4. Polymerization kinetics of asymmetric polytelluroxanes containing aromatic groups

[0171] During the polymerization process, samples were taken at intervals for gel permeation chromatography analysis. The test results were as follows: Fig. 9 As shown. The results show that polyphenyl n-butyl telluroxane will only obtain a higher number average molecular weight after the polymerization time is greater than 7 days, and a large number of oligomers will remain within 7 days. This may be due to the introduction of phenyl groups causing a large steric hindrance, which makes the polymerization process rate lower. After the polymerization is completed, polyphenyl n-butyl telluroxane with a molecular weight of 16.7 kDa, corresponding to n of approximately 60, and a polydispersity coefficient of 2.11 can be obtained.

[0172] In the description of the present application, it should be understood that the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one of the features. In the description of the present application, "plurality" means at least two, such as two, three, etc., unless otherwise clearly and specifically defined.

[0173] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example" or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present application. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, without contradiction.

[0174] Although the embodiments of the present application have been shown and described above, it can be understood that the above embodiments are exemplary and cannot be understood as limitations on the present application. Ordinary technicians in the field can change, modify, replace and modify the above embodiments within the scope of the present application.

Claims

1. An asymmetric polytelluroxane containing an aromatic group, characterized in that: It has the structure shown in formula (I): wherein Z1-Z5 are independently selected from hydrogen, halogen, nitro, hydroxyl, substituted or unsubstituted C1-C 12 Hydrocarbon, C1-C 12 Alkyloxy, C1-C 12 alkylthio; R1 is selected from substituted or unsubstituted C1-C 20 Hydrocarbon; n is any integer between 2 and 5000.

2. The aromatic-containing asymmetric polytelluroxane according to claim 1, characterized in that: The substituted or unsubstituted C1-C 20 The substituent in the hydrocarbon group includes at least one of a hydroxyl group, a substituted or unsubstituted amino group, a cyano group and an aryl group.

3. The aromatic-containing asymmetric polytelluroxane according to claim 1, characterized in that: R1 has the structure shown in general formula (II): Wherein, R2 is selected from hydrogen, hydroxyl, substituted or unsubstituted amino, cyano and aryl, and x is any integer between 1-20.

4. The aromatic-containing asymmetric polytelluroxane according to any one of claims 1 to 3, characterized in that: R1 is selected from substituted or unsubstituted C1-C 12 Hydrocarbyl; preferably C1 to C5 hydrocarbon group.

5. The aromatic-containing asymmetric polytelluroxane according to claim 1 or 2, characterized in that: Z1-Z5 are independently selected from hydrogen, chlorine, bromine, iodine, nitro, hydroxyl, substituted or unsubstituted C1-C8 hydrocarbon group, C1-C8 hydrocarbonoxy group, C1-C8 hydrocarbonthio group; and n is any integer between 2 and 3000; or Z1-Z5 are independently selected from hydrogen and C1-C5 alkoxy; and n is any integer between 2-250.

6. A method for preparing the aromatic-containing asymmetric polytelluroxane according to any one of claims 1 to 5, characterized in that: include: Allowing magnesium and an aryl halide compound of Formula 1 to react in a first solvent to obtain an aryl Grignard reagent, which is then reacted with tellurium powder to obtain an aryl ditellurium of Formula 2; The aryl ditelluride is reacted with sodium borohydride in a second solvent, and then further reacted with a halogenated hydrocarbon represented by Formula 3 to obtain an asymmetric organic tellurium ether containing an aromatic group represented by Formula 4; Dissolving the aromatic-containing asymmetric organic tellurium ether in a third solvent and subjecting it to an interfacial oxidative polymerization reaction with an aqueous hydrogen peroxide solution to obtain an aromatic-containing asymmetric polytelluroxide represented by formula (I); R1-X Type 3 wherein X is selected from chlorine, bromine and iodine.

7. The method according to claim 6, characterized in that The molar ratio of the magnesium, the aryl halide represented by Formula 1 and the tellurium powder is 1:(0.9-1):(0.9-1); and / or The first solvent comprises at least one of anhydrous tetrahydrofuran or anhydrous ether; and / or The reaction temperature for preparing the aryl Grignard reagent is 0°C to 70°C, and the reaction time is 0.5 hour to 2 hours; and / or The reaction temperature of the aryl Grignard reagent and tellurium powder is 0° C. to 50° C., and the reaction time is 0.5 hour to 2 hours.

8. The method according to claim 6, characterized in that The molar ratio of the arylditellurium, sodium borohydride and halogenated hydrocarbon is 1:(4-10):(1.9-2); and / or The second solvent comprises at least one of a mixed solvent of water and tetrahydrofuran, a mixed solvent of acetonitrile and water, and N,N-dimethylacetamide; and / or The reaction temperature of the arylditellurium and sodium borohydride is 0°C to 25°C, and the reaction time is 0.5 hours to 2 hours; and / or The reaction temperature with the halogenated hydrocarbon is 0°C to 50°C, and the reaction time is 0.5 hours to 12 hours; and / or The third solvent comprises at least one of ethyl acetate, dichloromethane, chloroform and tetrahydrofuran; and / or The concentration of the aromatic-containing asymmetric organic tellurium ether in the third solvent is 0.1 mol / L to 2 mol / L; and / or The concentration of the aqueous hydrogen peroxide solution is 0.1 mol / L to 5 mol / L; and / or The temperature of the interfacial oxidative polymerization reaction is 0° C. to 40° C., and the reaction time is 0.5 day to 7 days.

9. The method according to claim 8, characterized in that The volume ratio of water to tetrahydrofuran in the mixed solvent of water and tetrahydrofuran is 1:(0.5-2).

10. Use of the aromatic-containing asymmetric polytelluroxane according to any one of claims 1 to 5 in the field of extreme ultraviolet photoresists.

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