CN115322383A

CN115322383A - Polytelluroxane and preparation method thereof

Info

Publication number: CN115322383A
Application number: CN202210768087.1A
Authority: CN
Inventors: 许华平; 戴以恒; 张之恒
Original assignee: Tsinghua University
Current assignee: Tsinghua University
Priority date: 2022-07-01
Filing date: 2022-07-01
Publication date: 2022-11-11
Anticipated expiration: 2042-07-01
Also published as: CN115322383B

Abstract

The disclosure provides a polytelluroxane and a preparation method thereof, wherein the structural formula of the polytelluroxane is shown as- [ Te (R) ₂ )‑O] _n -, n is not less than 2; r-is any one or more of the following organic side chains: hydrophobic chain segment- (CH) ₂ ) X-, X is 1 to 16; hydrophilic chain segment- (CH) ₂ CH ₂ O) _Y ‑CH ₃ Or- (CH) ₂ CH ₂ O) _Y -H, Y is 1 to 6; proton chain segment- (CH) ₂ ) _Z -COOH, Z is 1 to 10. The preparation method of the polytelluroxane provided by the disclosure comprises the following steps: preparing the polytelluroxane from tellurium-containing monomers by interfacial polymerization, hydrolytic polymerization or electrochemical polymerization. The present disclosure provides a novel class of backbone non-carbon organic polymers based on their backboneThe oxidation-reduction responsiveness and the photoelectric property of tellurium elements with chain core structures, and the polyterexaxane have various synthetic paths and rich chemical structures, and have potential application in the fields of degradable plastics, radiation-proof materials, organic polymer photoelectric materials and the like.

Description

Polytelluroxane and preparation method thereof

Technical Field

The disclosure relates to the field of polymer chemistry, in particular to polytelluroxane and a preparation method thereof.

Background

The synthesis and performance exploration of the novel polymer material play an important role in promoting the development of basic scientific research and engineering technology. Compared with small molecular compounds, polymer molecules have various sequence structures and rich secondary interaction, the synthesis of novel polymers brings a brand-new research object in the fields of chemistry and materials, the breaking and generating rule of chemical bonds can be further disclosed, and the correlation between the micro molecular interaction and the performance of macro materials is clarified. Meanwhile, the novel polymer can bring brand new possibility to the engineering technical field, the novel material with degradable, photoelectric and catalytic properties is helpful to provide material basis for important fields such as carbon neutralization and chips, and the application layout of the advanced innovation technology development and the advanced industry is promoted while interdisciplinary, scale-span, deep level and large cross are promoted.

The polymers can be classified into three groups according to the composition of the polymer backbone: carbon chain polymers, heterochain polymers and organic polymers with main chains not containing carbon elements. Most of the common polymers have a main chain of carbon atoms and are carbon chain polymers. The main chain of the heterochain polymer contains nitrogen, oxygen, sulfur, selenium or tellurium, etc. in addition to carbon atoms. The main chain of the organic polymer of non-carbon elements has no carbon atoms and is completely composed of silicon, oxygen, nitrogen, phosphorus, boron or sulfur. The types of common organic polymers with main chain non-carbon elements are few, and only polysiloxane, polyphosphazene, polysulfide and the like are reported at present. The above elements generally have a larger atomic radius than carbon atoms, thereby providing good segment mobility to the polymer backbone. Meanwhile, the unique bonding configuration, such as a non-carbon element bond or a non-carbon element-non-carbon element bond in the main chain brings different electronic structures and chemical reaction sites for the main chain of the polymer, and the polymer has wide potential application in multiple fields of high mechanical property materials, biomedicine, photoelectric organic devices and the like. However, the development of the main chain non-carbon element organic polymer still has many challenges — firstly, most of the existing synthetic methods of the main chain non-carbon element organic polymer are ring-opening polymerization, and the synthetic method is single and is difficult to meet the practical application requirements of various situations; secondly, in recent years, the research center of gravity of the main chain non-carbon organic polymer in the scientific research field is still limited to polysiloxane, polyphosphazene, polysulfide and the like, and the development of the novel main chain non-carbon organic polymer is always a great challenge. Therefore, the method has important significance for constructing a polymer molecular framework by adopting new elements, developing a novel main chain non-carbon element organic polymer and preparing a simple and diversified preparation method.

Disclosure of Invention

The present disclosure is directed to solving, at least in part, one of the technical problems in the related art.

Therefore, the Polytelluroxane (PTO) provided in the embodiment of the first aspect of the disclosure is a brand new class of organic polymers with main chain non-carbon elements, and based on the unique redox responsiveness and photoelectric property of tellurium element in the core structure of the main chain, the polytelluroxane has diverse synthetic routes, abundant chemical structures and potential applications in multiple fields of degradable plastics, radiation-proof materials, organic polymer photoelectric materials and the like.

According to a first aspect of the disclosure there is provided a polytelluloxane of the formula [ Te (R) ₂ )-O] _n -, wherein:

the repeating unit is-Te (R) ₂ ) -O-, n is the number of repeating units, n is an integer greater than or equal to 2 (alternatively, n is a positive integer from 2 to 10000);

r-is any one or more of the following organic side chains:

hydrophobic segment- (CH) ₂ ) X-, X is the number of repeating units, and X is an integer of 1 to 16;

hydrophilic chain segment- (CH) ₂ CH ₂ O) _Y -CH ₃ Or- (CH) ₂ CH ₂ O) _Y -H, Y is the number of repeating units, Y is an integer from 1 to 6;

proton chain segment- (CH) ₂ ) _Z -COOH, Z is the number of repeating units and Z is an integer from 1 to 10.

The polytelluroxane provided by the embodiment of the first aspect of the disclosure has the following characteristics and beneficial effects:

firstly, compared with silicon, nitrogen, sulfur and other elements in common polysiloxane, polyphosphazene, polysulfide and other organic polymers with non-carbon elements in the main chain, tellurium elements have larger atomic radius, and further the polymer chain segments have better flexibility. And secondly, the organic side chain of the poly-telluroxane can be a hydrophobic chain segment, a hydrophilic chain segment or a proton chain segment, and has rich selectivity and good adjustability compared with the traditional main chain non-carbon element organic polymer, and particularly, the poly-telluroxane has various physicochemical properties in a mode of adjusting the chemical structure of the side chain. In addition, the reaction active site for synthesizing the polytereoxole is a tellurium ether structure in the monomer, and the rest chain segments have no obvious influence on the reaction process, so that the high-efficiency synthesis of the block polymer can be realized by mixing various tellurium-containing monomers with different side chain chemical structures. Besides, tellurium has sensitive redox stimulus responsiveness and a series of oxidation states of-2, 0, +2, +4, +6 and the like, and diversified and adjustable bonding modes and spatial structures are endowed to the polyterebrane. Moreover, compared with other miscellaneous elements, tellurium has unique electronic structure and optical properties, for example, inorganic telluride is a common chemical raw material in the field of thin film solar cells, and the characteristic endows the poly-tellurium-oxoalkane with potential application in the fields of photocatalysis and organic semiconductors.

A second aspect of the present disclosure provides a method of preparing a polytelluroxane, comprising:

dissolving a tellurium-containing monomer in an organic solvent to obtain a tellurium-containing organic solution system, mixing the tellurium-containing organic solution system with an aqueous hydrogen peroxide solution, carrying out interfacial polymerization reaction to obtain a reactant, and drying the reactant to obtain the polytereoxoalkane.

The preparation method of the polytelluroxane provided by the embodiment of the second aspect of the disclosure has the following characteristics and beneficial effects:

the preparation method of the polyterel siloxane provided by the embodiment of the second aspect of the disclosure is an interfacial polymerization method, wherein a tellurium-containing monomer is dissolved in an organic solvent to form an organic phase component, an oxidant is dissolved in deionized water to form an aqueous phase component, and the organic phase component and the oxidant are contacted to generate a chemical reaction at an interface. In the reaction process, the tellurium ether structure at the reaction site in the tellurium-containing monomer has stronger electronegativity and tends to be assembled into a Langmuir-Blodgett film structure at a two-phase interface, so that the reaction density of the tellurium ether structure is effectively increased, and a good dynamic environment is provided for the oxidative polymerization process. In the reaction process, the tellurium element in the tellurium-containing monomer loses electrons and is oxidized to a high valence state, and the oxygen element in the hydrogen peroxide obtains electrons and is reduced to a low valence state. Meanwhile, tellurium element in the tellurium-containing monomer is combined with oxygen element in hydrogen peroxide to form a main chain structure of the polymer, and then the poly-tellurium-oxoalkane is prepared. Compared with the traditional macromolecule preparation method, the interfacial polymerization reaction of the polytelluroxane has the following advantages: 1. the preparation method can be carried out in a room temperature environment, the reaction condition is mild and simple, and common polymerization conditions such as high temperature and high pressure, strong acid and strong base, metal catalyst, ultraviolet irradiation and the like are not needed; 2. the preparation method has remarkable kinetic advantages and has the potential of industrial high-efficiency production; 3. the preparation method does not need to strictly control the stoichiometric ratio of the reaction monomer to the catalyst, and the reaction process is not interfered by common polymerization inhibitors such as oxygen, metal ions and the like; 4. the preparation method has good adjustability, and the molecular weight of the polytelluroxane obtained by the reaction can be controlled by adjusting the concentration of the organic phase tellurium-containing monomer.

In some embodiments, the tellurium-containing monomer is any one or more of dimethyl tellurium, diethyl tellurium, dipropyl tellurium, dibutyl tellurium, diamyl tellurium, dihexyl tellurium, diheptyl tellurium, dioctyl tellurium, dinonyl tellurium, didecyl tellurium, diundecyl tellurium, didodecyl tellurium, ditridecyl tellurium, ditetradecyl tellurium, dipentadecyl tellurium, dihexadecyl tellurium, diethanol tellurium, bis-diethylene glycol tellurium, bis-triethylene glycol tellurium, bis-tetraethylene glycol tellurium, bis-pentaethylene glycol tellurium, bis-hexaethylene glycol tellurium, bis-methyl ethanol tellurium, bis-methyl diethylene glycol tellurium, bis-methyl triethylene glycol tellurium, bis-methyl tetraethylene glycol tellurium, bis-methyl pentaethylene glycol tellurium, bis-methyl hexaethylene glycol tellurium, diacetic acid tellurium, dipropionic acid tellurium, dibutylic acid tellurium, dipentanoic acid tellurium, dihexanoic acid tellurium, diheptanoic acid tellurium, dioctoic acid tellurium, dinonoic acid tellurium, didecanoic acid tellurium, and diundecyl acid tellurium.

In some embodiments, the organic solvent is any one or more of dichloromethane, ethyl acetate, toluene, chloroform, acetonitrile, dimethylformamide, dimethylsulfoxide, and tetrahydrofuran.

In some embodiments, the molar concentration of the tellurium-containing organic solution system is in the range of 0.1mol/L to 2mol/L.

In some embodiments, the aqueous hydrogen peroxide solution has a molar concentration of 0.1 to 5mol/L.

In some embodiments, the volume ratio of the tellurium-containing organic solution system to the aqueous hydrogen peroxide solution is from 0.1 to 10.

In some embodiments, the drying is done by lyophilization, oven drying under vacuum, removal of solvent by rotary evaporation, or blow drying with an inert gas.

A method of preparing a polytelluroxane according to an embodiment of the third aspect of the disclosure comprises:

mixing a tellurium-containing dihalogen compound with deionized water in any proportion, carrying out hydrolytic polymerization reaction to obtain a reactant, and drying the reactant to obtain the polytelluroxane.

The preparation method of the polytelluroxane provided by the embodiment of the third aspect of the disclosure has the following characteristics and beneficial effects:

the preparation method of the polytereoloxane provided by the embodiment of the third aspect of the disclosure is a hydrolysis polymerization method, which takes a tellurium-containing dihalogen compound and deionized water as raw materials, wherein the tellurium-containing dihalogen compound provides a tellurium element, and water molecules provide an oxygen element, and a tellurium-oxygen chemical bond is constructed while a tellurium-halogen single bond is destroyed through hydrolysis reaction, so that a high-molecular main chain structure is generated, and the polytereoloxane is obtained. Compared with the traditional macromolecule preparation method, the hydrolysis polymerization reaction of the polytelluroxane has the following advantages: 1. the oxygen element source of the preparation method is the most common water molecule, and the source is wide and environment-friendly; 2. the preparation method does not need to use organic solvent, and reduces the harm to operators and ecological environment.

<xnotran> , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , </xnotran> Dibromo-dimethyltetraglycol tellurium, dibromo-dimethylpentaglycol tellurium, dibromo-dimethylhexaglycol tellurium, dibromo-diacetic acid tellurium, dibromo-dipropionic acid tellurium, dibromo-dibutyric acid tellurium, dibromo-dihexanoic acid tellurium, dibromo-diheptanoic acid tellurium, dibromo-dioctanoic acid tellurium, dibromo-didecyl acid tellurium, dibromo-diundecylic acid tellurium, diiododimethyl tellurium, diiododiethyl tellurium, diiododipropyl tellurium, diiododibutyl tellurium, diiododipentyl tellurium, diiododihexyl tellurium, diiododiheptyl tellurium, diiododioctyl tellurium, diiododinononyl tellurium, diiododidecyl tellurium, diiododiundecylic tellurium, diiododidodecyl tellurium, diiododitridecyl tellurium, diiododitetradecyl tellurium, di-tetradecyl tellurium, di-iododitetradecyl tellurium, di-iododitridecyl tellurium, and mixtures thereof dipentadecyl tellurium, dihexadecyl tellurium, diiododiethanol tellurium, diiodobis-diethylene glycol tellurium, diiodobis-triethylene glycol tellurium, diiodobis-tetraethylene glycol tellurium, diiodobis-pentaethylene glycol tellurium, diiodobis-hexaethylene glycol tellurium, diiodobis-methyl ethanol tellurium, diiodobis-methyl diethylene glycol tellurium, diiodobis-methyl triethylene glycol tellurium, diiodobis-methyl tetraethylene glycol tellurium, diiodobis-methyl pentaethylene glycol tellurium, diiodobis-methyl hexaethylene glycol tellurium, diiododiacetic acid tellurium, diiododipropionic acid tellurium, diiododibutyric acid tellurium, diiododipentavaleric acid tellurium, diiododiheptanic acid tellurium, diiododioctoate tellurium, diiododinononanoate tellurium, diiododidecyl tellurium and diiodobisundecanoate tellurium.

In some embodiments, the tellurium-containing dihalogen compound is prepared according to the following steps: dissolving a tellurium-containing monomer in an organic solvent to obtain a tellurium-containing organic solution system, and adding a halogen simple substance into the tellurium-containing organic solution system to obtain the tellurium-containing dihalogen compound.

Further, the tellurium-containing monomer is any one or a mixture of more than one of dimethyl tellurium, diethyl tellurium, dipropyl tellurium, dibutyl tellurium, dipentyl tellurium, dihexyl tellurium, diheptyl tellurium, dioctyl tellurium, dinonyl tellurium, didecyl tellurium, diundecyl tellurium, didodecyl tellurium, ditridecyl tellurium, ditetradecyl tellurium, dipentadecyl tellurium, dihexadecyl tellurium, diethanol tellurium, bis diethylene glycol tellurium, bis triethylene glycol tellurium, bis tetraethylene glycol tellurium, bis pentaethylene glycol tellurium, bis hexaethylene glycol tellurium, bis methyl ethanol tellurium, bis methyl diethylene glycol tellurium, bis methyl triethylene glycol tellurium, bis methyl tetraethylene glycol tellurium, bis methyl pentaethylene glycol tellurium, bis methyl hexaethylene glycol tellurium, diacetic acid tellurium, dipropionic acid tellurium, dibutylic acid tellurium, diamic acid tellurium, dihexanoic acid tellurium, dioctoic acid tellurium, dinonylic acid tellurium, didecanoic acid tellurium and diundecyl tellurium.

Further, the organic solvent is any one or more of dichloromethane, ethyl acetate, toluene, chloroform, acetonitrile, dimethylformamide, dimethylsulfoxide and tetrahydrofuran.

Further, 1-5 times of molar equivalent of the halogen simple substance is added into the tellurium-containing organic solution system.

In some embodiments, the molar concentration of the tellurium-containing organic solution system is from 0.1mol/L to 10mol/L.

In some embodiments, the drying is done by lyophilization, oven drying under vacuum, rotary evaporation to remove solvent, or blow drying with an inert gas.

A fourth aspect of the present disclosure provides a method of preparing a polytelluroxane, comprising:

dissolving a tellurium-containing monomer in an organic solvent to obtain a tellurium-containing organic solution system, adding an organic electrolyte into the tellurium-containing organic solution system, applying voltage, carrying out electrochemical polymerization reaction to obtain a reactant, and drying the reactant to obtain the polyteremoxane.

The preparation method of the polytelluroxane provided by the embodiment of the fourth aspect of the disclosure has the following characteristics and beneficial effects:

the preparation method of the telluroxane provided by the embodiment of the fourth aspect of the disclosure is an electrochemical polymerization method, and the telluroxane is obtained by taking a tellurium-containing monomer as a raw material, converting the tellurium-containing monomer into a high valence state by losing electrons through a method of adding an external power supply, converting oxygen dissolved in a system into a low valence state by losing electrons, and constructing a high molecular main chain structure by combining the tellurium-containing monomer and the oxygen. Compared with the traditional macromolecule preparation method, the electrochemical polymerization reaction of the polytelluroxane has the following advantages: 1. in the preparation method, the transfer of electrons is controlled by an electrochemical process, and the reaction time, the reaction rate and the molecular weight of a product can be accurately regulated and controlled by the magnitude of an external voltage and current; 2. the electrochemical reaction raw materials of the preparation method are tellurium-containing monomers and dissolved oxygen, and the reaction process has the advantages of less side reactions and high atom economy. 3. The preparation method can generate the poly-telluroxane film material on the surface of the electrode in situ without further post-treatment processing, and the physical properties of the poly-telluroxane film material can be effectively regulated and controlled by the factors of the magnitude of the applied voltage and current, the concentration of the tellurium-containing monomer solution, the type of the electrode material and the like.

In some embodiments, the organic solvent employs a mixture of any one or more of dichloromethane, ethyl acetate, toluene, chloroform, acetonitrile, dimethylformamide, dimethylsulfoxide, and tetrahydrofuran.

In some embodiments, the organic solution system has a molar concentration of 0.1mol/L to 10mol/L.

In some embodiments, the organic electrolyte employs a mixture of any one or more of tetrabutylammonium tetrafluoroborate and tetrabutylammonium hexafluorophosphate.

In some embodiments, the organic electrolyte has a molar concentration in the organic solvent system of 0.1mol/L to 10mol/L.

In some embodiments, the voltage applied is between 0.5V and 2.0V.

Drawings

FIG. 1 is a schematic diagram of a polytelluroxane and a method for preparing the same by an interfacial polymerization method according to an embodiment of the disclosure.

FIG. 2 is a schematic view of a polytelluloxane and a polytelluloxane prepared by a hydrolytic polymerization method according to an embodiment of the disclosure.

FIG. 3 is a schematic diagram of a polytelluloxane and a process for preparing the polytelluloxane by an electrochemical polymerization method according to an embodiment of the disclosure.

FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of tellurium-containing monomers dibutyl tellurium and polydibutyl telluroxane (PTOC 4) in an example of the present disclosure.

FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of the tellurium-containing monomers dihexyltellurium and polydihexyltelluroxane (PTOC 6) in an embodiment of the present disclosure.

FIG. 6 is a NMR spectrum of tellurium-containing monomers dioctyltellurium and polydioctyltelluroxane (PTOC 8) in an example of the present disclosure.

Fig. 7 (a) - (c) are fourier transform infrared absorption spectroscopy (FTIR) tests of polydibutyltelluroxane (PTOC 4), polydihexyltelluroxane (PTOC 6), and polydioctyltelluroxane (PTOC 8) in examples of the present disclosure.

FIG. 8 is an energy dispersive X-ray spectroscopy (EDS) characterization of polytereoloxanes in an example of the present disclosure.

Fig. 9 (a), (b) are X-ray photoelectron spectroscopy (XPS) analyses of tellurium-containing monomers and polytelluroxanes in the examples of the present disclosure.

FIG. 10 is a Transmission Electron Microscopy (TEM) characterization of polyterefoloxane in examples of the disclosure.

FIGS. 11 (a), (b) are Scanning Transmission Electron Microscope (STEM) characterization and scanning transmission electron microscopy mirror scanning elemental analysis (STEM-Mapping) of polyterefuloxanes in examples of the present disclosure.

Fig. 12 (a) - (c) are thermogravimetric analyses (TGA) of polydibutyltelluroxane (PTOC 4), polydihexyltelluroxane (PTOC 6), and polydioctyltelluroxane (PTOC 8) in examples of the present disclosure.

FIG. 13 shows the molecular weights and molecular weight distributions of dimethyltriglycoltelluriloxane (PTOEG 3 Me) at different polymerization times in the examples of the present disclosure.

Fig. 14 is a polyteredosulfoxane glass prepared based on polydidodecyltelluroxane (PTOC 12) provided in an example of the present disclosure.

Fig. 15 is a high viscosity fluid of polytereoloxane prepared based on polybismethyltetraglyeloxane (PTOEG 4 Me) provided in an example of the present disclosure.

Fig. 16 is a polytelluroxane plastic prepared based on polytelluroxane dibutyrate (PTOC 3 COOH) provided in an example of the present disclosure.

Detailed Description

Reference will now be made in detail to embodiments of the present application, examples of which are illustrated in the accompanying drawings. The embodiments described below with reference to the drawings are exemplary and intended to be used for explaining the present application and should not be construed as limiting the present application. In addition, all reagents used in the following examples are commercially available or can be synthesized according to methods herein or known, and are readily available to those skilled in the art for reaction conditions not listed, if not explicitly stated.

Example 1: interfacial polymerization preparation method of polydimethyl tellurium siloxane (PTOC 1) based on dimethyl tellurium

15.77mg of dimethyl tellurium was dissolved in 1mL of dichloromethane to give component A, and 30% aqueous hydrogen peroxide was diluted to 5mol/L to give component B. 1mL of component A was mixed well with 0.1mL of component B in a reaction flask. The reaction is heated, the organic phase is changed from yellow to colorless, and a large amount of white solid can be observed at the interface of the solvent in the reaction system. And filtering the system, and drying in a vacuum oven to obtain the polydimethyl telluroxane.

Example 2: preparation of polydibutyltelluroxane (PTOC 4) by interfacial polymerization method based on dibutyltellurium

120.92mg of dibutyltellurium was dissolved in 1mL of ethyl acetate to obtain component A, and a 30% aqueous hydrogen peroxide solution was diluted to 2mol/L to obtain component B. 1mL of component A was mixed well with 1mL of component B in a reaction flask. The reaction is heated, the organic phase is changed from yellow to colorless, and a large amount of white solid can be observed at the interface of the solvent in the reaction system. And (3) freeze-drying the system to obtain the polydibutyltellurium siloxane.

Example 3: interfacial polymerization process for preparing polydihexyltelloxanes (PTOC 6) based on dihexyltellurium

354.05mg of dihexyltellurium was dissolved in 1mL of toluene to obtain component A, and a 30% aqueous hydrogen peroxide solution was diluted to 1mol/L to obtain component B. 1mL of component A was mixed well with 2mL of component B in a reaction flask. The reaction is heated, the organic phase is changed from yellow to colorless, and a large amount of white solid is observed at the interface of the solvent in the reaction system. And (3) carrying out rotary evaporation on the system to obtain the polyhexamethylene telluroxane.

Example 4: preparation of Polydioctyltelluroxane (PTOC 8) by interfacial polymerization based on dioctyltelluro

699.39mg of didodecyltellurium was dissolved in 1mL of chloroform to give component A, and 30% aqueous hydrogen peroxide was diluted to 0.5mol/L to give component B. Mix 1mL of component A well with 4mL of component B in a reaction flask. The reaction is heated, the organic phase is changed from yellow to colorless, and a large amount of white solid can be observed at the interface of the solvent in the reaction system. And (3) carrying out rotary evaporation on the system to obtain the poly dioctyl tellurium siloxane.

Example 5: preparation of polydidodecyl tellurium oxoalkane (PTOC 12) based on interface polymerization method of didodecyl tellurium

1156.96mg of didodecyltellurium was dissolved in 1mL of tetrahydrofuran to obtain component A, and 30% aqueous hydrogen peroxide was diluted to 0.2mol/L to obtain component B. 1mL of component A was mixed well with 10mL of component B in a reaction flask. The reaction is heated, the organic phase is changed from yellow to colorless, and a large amount of white solid can be observed at the interface of the solvent in the reaction system. And (3) drying the solvent by using nitrogen in the system to obtain the poly-didodecyltelluroxane.

Example 6: interfacial polymerization method for preparing polydiethylene glycol tellurium alkyl (PTOEGOH) based on diethene glycol tellurium

43.544mg of diethanoltellurium was dissolved in 1mL of acetonitrile to obtain component A, and a 30% aqueous hydrogen peroxide solution was diluted to 0.1mol/L to obtain component B. 1mL of component A was mixed well with 10mL of component B in a reaction flask. The reaction is heated, the organic phase is changed from yellow to colorless, and a large amount of white solid can be observed at the interface of the solvent in the reaction system. And drying the system in a vacuum oven to obtain the polydiethylol telluroxane.

Example 7: preparation of Polybistetraglycol telluroxane (PTOEG 3 OH) by interfacial polymerization method based on bistetraglycol tellurium

196.97mg of ditrimethyleneglycol tellurium were dissolved in 1mL of dimethylformamide to give component A, and 30% aqueous hydrogen peroxide was diluted to 5mol/L to give component B. 1mL of component A was mixed well with 0.2mL of component B in a reaction flask. The reaction is heated, the organic phase is changed from yellow to colorless, and a large amount of white solid can be observed at the interface of the solvent in the reaction system. And (4) freeze-drying the system to obtain the polytetraethylene glycol tellurium.

Example 8: preparation of Polybishexaethylene glycol telluroxane (PTOEG 6 OH) by interfacial polymerization method based on bishexaethylene glycol tellurium

658.25mg of bis-hexaethyleneglycol tellurium was dissolved in 1mL of dimethyl sulfoxide to obtain component A, and 30% aqueous hydrogen peroxide was diluted to 2mol/L to obtain component B. Mix 1mL of component A well with 4mL of component B in a reaction flask. The reaction is heated, the organic phase is changed from yellow to colorless, and a large amount of white solid is observed at the interface of the solvent in the reaction system. And (3) carrying out rotary evaporation on the system to obtain the polyhexamethylene glycol tellurium.

Example 9: preparation of poly (PTOEGMe) based on interface polymerization of bis (methylethanol) tellurium

24.58mg of tellurium bismethylethoxide was dissolved in 1mL of a mixed solvent of dichloromethane and dimethylformamide to obtain a component A, and a 30% aqueous hydrogen peroxide solution was diluted to 5mol/L to obtain a component B. 1mL of component A was mixed well with 0.1mL of component B in a reaction flask. The reaction is heated, the organic phase is changed from yellow to colorless, and a large amount of white solid can be observed at the interface of the solvent in the reaction system. And drying the system in a vacuum oven to obtain the poly (dimethyl ethyl alcohol tellurium-alkyl oxide).

Example 10: preparation of Poly (bis-methyl triethylene glycol tellurium-alkyl) siloxane (PTOEG 3 Me) based on interfacial polymerization method of bis-methyl triethylene glycol tellurium

421.99mg of bis-methyltriglycol was dissolved in 1mL of a mixed solvent of dichloromethane and dimethylformamide to obtain component A, and 30% aqueous hydrogen peroxide was diluted to 5mol/L to obtain component B. 1mL of component A was mixed well with 0.5mL of component B in a reaction flask. The reaction is heated, the organic phase is changed from yellow to colorless, and a large amount of white solid can be observed at the interface of the solvent in the reaction system. And drying the system in a vacuum oven to obtain the poly (dimethyl triethylene glycol tellurium-alkyl).

Example 11: preparation of Poly (dimethylhexaethyleneglycol) telluroxane (PTOEG 6 Me) by interfacial polymerization method based on dimethylhexaethyleneglycol tellurium

1372.62mg of tellurium bis-methylhexaglycol was dissolved in 1mL of a mixed solvent of toluene and dimethyl sulfoxide to obtain component A, and a 30% aqueous hydrogen peroxide solution was diluted to 2mol/L to obtain component B. 1mL of component A was mixed well with 5mL of component B in a reaction flask. The reaction is heated, the organic phase is changed from yellow to colorless, and a large amount of white solid can be observed at the interface of the solvent in the reaction system. And (3) drying the system in a vacuum oven to obtain the dimethyl hexaethylene glycol telluroxane.

Example 12: interfacial polymerization method for preparing telluroxane diacetate (PTOC 1 COOH) based on tellurium diacetate

245.69mg of tellurium diacetate was dissolved in 1mL of a mixed solvent of dimethylformamide and acetonitrile to obtain component A, and 30% aqueous hydrogen peroxide was diluted to 1mol/L to obtain component B. 1mL of component A was mixed well with 10mL of component B in a reaction flask. The reaction is heated, the organic phase is changed from yellow to colorless, and a large amount of white solid is observed at the interface of the solvent in the reaction system. And (3) freeze-drying the system to obtain the telluroxane diacetate.

Example 13: preparation of Polytelluroxane dibutyrate (PTOC 3 COOH) based on interfacial polymerization of tellurium dibutyrate

603.60mg of tellurium dibutyrate is dissolved in 1mL of a mixed solvent of toluene and acetonitrile to obtain a component A, and a 30% aqueous hydrogen peroxide solution is diluted to 2mol/L to obtain a component B. Mix 1mL of component A well with 4mL of component B in a reaction flask. The reaction is heated, the organic phase is changed from yellow to colorless, and a large amount of white solid is observed at the interface of the solvent in the reaction system. And (3) carrying out rotary evaporation on the system to obtain the poly-tellurium alkyl dibutyrate.

Example 14: interfacial polymerization method for preparing poly (tellurium dioctoate) (PTOC 7 COOH) based on tellurium dioctoate

621.02mg of tellurium dioctoate was dissolved in 1mL of a mixed solvent of toluene, acetonitrile, and dimethylformamide to obtain component A, and 30% aqueous hydrogen peroxide was diluted to 4mol/L to obtain component B. 1mL of component A was mixed well with 3mL of component B in a reaction flask. The reaction is heated, the organic phase is changed from yellow to colorless, and a large amount of white solid can be observed at the interface of the solvent in the reaction system. And drying the system by nitrogen to obtain the poly (tellurium dioctoate siloxane).

Example 15: interfacial polymerization method for preparing poly tellurium diundecate siloxane (PTOC 11 COOH) based on tellurium diundecate

996.34mg of tellurium diundecanoate was dissolved in 1mL of a mixed solvent of dichloromethane, ethyl acetate, toluene, chloroform, acetonitrile, dimethylformamide, dimethyl sulfoxide, and tetrahydrofuran to obtain a component A, and a 30% aqueous hydrogen peroxide solution was diluted to 5mol/L to obtain a component B. 1mL of component A was mixed well with 10mL of component B in a reaction flask. The reaction is heated, the organic phase is changed from yellow to colorless, and a large amount of white solid is observed at the interface of the solvent in the reaction system. And (3) carrying out rotary evaporation on the system to obtain the polydiundecylate telluroxane.

Example 16: preparation of poly dipropyl diamyl telluroxane (PTOC 3-C5) based on interfacial polymerization method of dipropyl tellurium and diamyl tellurium

150.02mg of dipropyltellurium and 182.60mg of dipentyltelliumhloride were dissolved in 1mL of toluene to obtain component A, and a 30% aqueous hydrogen peroxide solution was diluted to 1mol/L to obtain component B. Mix 1mL of component A well with 2mL of component B in a reaction flask. The reaction is heated, the organic phase is changed from yellow to colorless, and a large amount of white solid can be observed at the interface of the solvent in the reaction system. And (3) carrying out rotary evaporation on the system to obtain the poly dipropyl dipentyl telluroxane.

Example 17: preparation of polybisdiglycol bis-hexaglycol telluroxane (PTOEG 2OH-EG6 OH) based on interfacial polymerization method of bis-diglycol tellurium and bis-hexaglycol tellurium

212.56mg of tellurium bisdiethylene glycol and 308.01mg of tellurium bishexaethylene glycol were dissolved in 1mL of dimethyl sulfoxide to obtain component A, and 30% aqueous hydrogen peroxide was diluted to 2mol/L to obtain component B. 1mL of component A was mixed well with 4mL of component B in a reaction flask. The reaction is heated, the organic phase is changed from yellow to colorless, and a large amount of white solid can be observed at the interface of the solvent in the reaction system. And (3) carrying out rotary evaporation on the system to obtain the polybis-diethylene glycol bis-hexaethylene glycol telluroxane.

Example 18: preparation of poly (dimethyltriethylene glycol) dimethylpentaethylene glycol telluroxane (PTOEG 3Me-EG5 Me) based on interface polymerization method of dimethyltriethylene glycol tellurium and dimethylpentaethylene glycol tellurium

210.44mg of dimethyltriethylene glycol and 294.86mg of dimethylpentaethylene glycol tellurium were dissolved in 1mL of a mixed solvent of methylene chloride and dimethylformamide to obtain component A, and a 30% aqueous hydrogen peroxide solution was diluted to 5mol/L to obtain component B. 1mL of component A was mixed well with 0.5mL of component B in a reaction flask. The reaction is heated, the organic phase is changed from yellow to colorless, and a large amount of white solid is observed at the interface of the solvent in the reaction system. And drying the system in a vacuum oven to obtain the poly-bis-methyl triethylene glycol-bis-methyl pentaglycol tellurium alkyl.

Example 19: interfacial polymerization method for preparing poly (tellurium dicaprylate-C9 COOH) based on tellurium dicaprylate and tellurium dicaprate

315.02mg of tellurium dioctoate and 462.40mg of tellurium didecanoate were dissolved in 1mL of a mixed solvent of toluene, acetonitrile and dimethylformamide to obtain component A, and 30% aqueous hydrogen peroxide was diluted to 4mol/L to obtain component B. 1mL of component A was mixed well with 3mL of component B in a reaction flask. The reaction is heated, the organic phase is changed from yellow to colorless, and a large amount of white solid can be observed at the interface of the solvent in the reaction system. And drying the system by nitrogen to obtain the poly-dioctanoate-dicaprate-telluroxane.

Example 20: preparation of Polydibutylbis-hexaethylene glycol-bis-methyl-tetraethylene glycol-bis-hexanoate telluroxane (PTOC 4-EG6OH-EG4Me-C5 COOH) by interfacial polymerization based on dibutyltellurium, bis-hexaethylene glycol-tellurium, bis-methyl-tetraethylene glycol-tellurium and bis-hexanoate tellurium

232.10mg of dibutyltellurium, 148.30mg of dihexaethyleneglycol tellurium, 320.80mg of dimethyltetraethyleneglycol tellurium and 279.31mg of tellurium dihexanoate were dissolved in 1mL of tetrahydrofuran to give component A, and 30% aqueous hydrogen peroxide was diluted to 0.2mol/L to give component B. 1mL of component A was mixed well with 10mL of component B in a reaction flask. The reaction is heated, the organic phase is changed from yellow to colorless, and a large amount of white solid is observed at the interface of the solvent in the reaction system. And blowing the solvent by using nitrogen of the system to obtain the poly-dibutyl-bis-hexa-glycol-bis-methyl-tetra-glycol-di-tellurium alkyl caproate.

Example 21: preparation of Polydimethyltelluroxane (PTOC 1) by hydrolysis polymerization method based on dimethyl tellurium

15.77mg of dimethyl tellurium was dissolved in 1mL of methylene chloride to give fraction A, and 25.38mg of elemental iodine was added to fraction A to give fraction B. And drying the mixture in a vacuum oven to remove the solvent and unreacted elemental iodine to obtain the component C. And fully mixing and stirring the component C and the deionized water. The reaction system produced a large amount of white solid. And filtering the system, and drying in a vacuum oven to obtain the polydimethyl telluroxane.

Example 22: preparation of polydibutyltelluroxane (PTOC 4) based on a method of hydrolytic polymerization of dibutyltellurium

120.92mg of dibutyltellurium was dissolved in 1mL of ethyl acetate to obtain component A, and 65.00mg of elemental iodine was added to component A to obtain component B. And drying the mixture in a vacuum oven to remove the solvent and unreacted elemental iodine to obtain the component C. And fully mixing and stirring the component C and the deionized water. The reaction system produced a large amount of white solid. And (3) freeze-drying the system to obtain the polydibutyltellurium siloxane.

Example 23: preparation of Polydioctyltelluroxane (PTOC 6) based on hydrolytic polymerization of dihexyltellurium

265.54mg of dihexyltellurium was dissolved in 1mL of toluene to give fraction A, and 159.81mg of liquid bromine was added to fraction A to give fraction B. The solvent and unreacted liquid bromine were removed by rotary evaporation to give component C. And fully mixing and stirring the component C and the deionized water. The reaction system produced a large amount of white solid. And (3) carrying out rotary evaporation on the system to obtain the polyhexamethylene telluroxane.

Example 24: preparation of Polydidodecyltelluroxane (PTOC 12) based on Didodecyltellurium hydrolytic polymerization method

699.39mg of didodecyltellurium was dissolved in 1mL of chloroform to give component A, and 709.00mg of chlorine gas was added to component A to give component B. The solvent and unreacted chlorine were removed by blowing dry with nitrogen to give component C. And fully mixing and stirring the component C and the deionized water. And (3) carrying out rotary evaporation on the system to obtain the polydidodecyl tellurium oxoalkane.

Example 25: preparation of Polydicetyl telluroxane (PTOC 16) by hydrolytic polymerization method based on dicetyl telluro

1156.96mg of dihexadecyl tellurium was dissolved in 1mL of tetrahydrofuran to obtain component A, and 1015.24mg of elemental iodine was added to component A to obtain component B. And drying the mixture in a vacuum oven to remove the solvent and unreacted elemental iodine to obtain the component C. And fully mixing and stirring the component C and the deionized water. The reaction system produced a large amount of white solid. And blowing the solvent by using nitrogen of the system to obtain the poly-dihexadecyl tellurium alkyl.

Example 26: preparation of Polydiethanoltelluroxane (PTOEGOH) based on hydrolytic polymerization method of diethanoltelluroxide

43.544mg of diethanoltellurium was dissolved in 1mL of acetonitrile to obtain component A, and 534.18mg of liquid bromine was added to component A to obtain component B. And drying the mixture by a vacuum oven to remove the solvent and the unreacted liquid bromine to obtain the component C. And fully mixing and stirring the component C and the deionized water. And drying the system in a vacuum oven to obtain the polydiethylol telluroxane.

Example 27: preparation of Polybistetraglycol telluroxanes (PTOEG 3 OH) based on hydrolytic polymerization of bistetraglycol tellurium

196.97mg of ditrimethyleneglycol tellurium was dissolved in 1mL of dimethylformamide to give component A, and 924.33mg of chlorine gas was added to component A to give component B. The solvent and unreacted chlorine were removed by blowing dry with nitrogen to give component C. And fully mixing and stirring the component C and the deionized water. The reaction system produced a large amount of white solid. And (3) freeze-drying the system to obtain the polybistetraglycol telluroxane.

Example 28: preparation of Polybishexaethylene glycol telluroxane (PTOEG 6 OH) by hydrolysis polymerization method based on bishexaethylene glycol tellurium

658.25mg of bis-hexaethyleneglycol tellurium were dissolved in 1mL of dimethyl sulfoxide to obtain fraction A, and 640.86mg of liquid bromine was added to fraction A to obtain fraction B. The solvent and unreacted liquid bromine were removed by rotary evaporation to give component C. And fully mixing and stirring the component C and the deionized water. The reaction system produced a large amount of white solid. And (3) carrying out rotary evaporation on the system to obtain the poly-bis-hexaethyleneglycol telluroxane.

Example 29: preparation of Polybismethylethanoltetralkyloxanes (PTOEGMe) based on the hydrolytic polymerization of Dimethylethanoltetralkylenes

24.58mg of tellurium bismethylethoxide was dissolved in 1mL of a mixed solvent of methylene chloride and dimethylformamide to give a component A, and 18.33mg of chlorine gas was added to the component A to give a component B. The solvent and unreacted chlorine were removed by rotary evaporation to give component C. And fully mixing and stirring the component C and the deionized water. The reaction system produced a large amount of white solid. And drying the system in a vacuum oven to obtain the poly (dimethyl ethyl alcohol tellurium-alkyl oxide).

Example 30: preparation of Poly (bis-methyl triethylene glycol tellurium-siloxane) (PTOEG 3 Me) based on hydrolysis polymerization method of bis-methyl triethylene glycol tellurium

421.99mg of bis-methyltriglycol was dissolved in 1mL of a mixed solvent of methylene chloride and dimethylformamide to give component A, and 388.12mg of liquid bromine and 120.42mg of chlorine gas were added to component A to give component B. The solvent and unreacted liquid bromine and chlorine were removed by rotary evaporation to give component C. And fully mixing and stirring the component C and the deionized water. The reaction system produced a large amount of white solid. And drying the system in a vacuum oven to obtain the poly (dimethyl triethylene glycol tellurium-alkyl).

Example 31: preparation of Poly (dimethylhexaethyleneglycol telluroxane) (PTOEG 6 Me) based on Dimethylhexaethyleneglycol tellurium by hydrolytic polymerization

1372.62mg of tellurium bis-methylhexaglycol was dissolved in 1mL of a mixed solvent of toluene and dimethyl sulfoxide to obtain fraction A, and 664.05mg of elemental iodine and 412.20mg of liquid bromine were added to fraction A to obtain fraction B. And removing the solvent, unreacted elemental iodine and liquid bromine by rotary evaporation to obtain the component C. And fully mixing and stirring the component C and the deionized water. The reaction system produced a large amount of white solid. And (3) drying the system in a vacuum oven to obtain the dimethyl hexaethylene glycol telluroxane.

Example 32: preparation of Polytelluroxane diacetate (PTOC 1 COOH) by hydrolytic polymerization method based on tellurium diacetate

245.69mg of tellurium diacetate was dissolved in 1mL of a mixed solvent of dimethylformamide and acetonitrile to give component A, and 250.22mg of liquid bromine was added to component A to give component B. The solvent and unreacted liquid bromine were removed by rotary evaporation to give component C. And fully mixing and stirring the component C and the deionized water. The reaction system produced a large amount of white solid. And (3) freeze-drying the system to obtain the telluroxane diacetate.

Example 33: preparation of Polytelluroxane dibutyrate (PTOC 3 COOH) based on hydrolytic polymerization of tellurium dibutyrate

603.60mg of tellurium dibutyrate was dissolved in 1mL of a mixed solvent of toluene and acetonitrile to obtain a component A, and 120.96mg of chlorine gas, 184.59mg of liquid bromine, and 150.07mg of elemental iodine were added to the component A to obtain a component B. And removing the solvent, unreacted chlorine, liquid bromine and elementary iodine by rotary evaporation to obtain the component C. And fully mixing and stirring the component C and the deionized water. The reaction system produced a large amount of white solid. And (3) carrying out rotary evaporation on the system to obtain the poly-tellurium alkyl dibutyrate.

Example 34: preparation of Polytelluroctanoic acid siloxane (PTOC 7 COOH) based on hydrolytic polymerization of tellurium dioctoate

621.02mg of tellurium dioctoate was dissolved in 1mL of a mixed solvent of toluene, acetonitrile, and dimethylformamide to obtain component A, and 720.09mg of iodine simple substance was added to component A to obtain component B. And removing the solvent and the unreacted iodine simple substance through a vacuum oven to obtain the component C. And fully mixing and stirring the component C and the deionized water. The reaction system produced a large amount of white solid. And drying the system by nitrogen to obtain the poly (tellurium dioctoate siloxane).

Example 35: preparation of Polytelluroxane Diundecatenate (PTOC 11 COOH) based on hydrolytic polymerization of tellurium diundecate

996.34mg of tellurium diundecanoate was dissolved in 1mL of a mixed solvent of dichloromethane, ethyl acetate, toluene, chloroform, acetonitrile, dimethylformamide, dimethyl sulfoxide, and tetrahydrofuran to obtain component A, and 248.15mg of chlorine gas was added to component A to obtain component B. The solvent and unreacted chlorine were removed by blowing dry with nitrogen to give component C. And fully mixing and stirring the component C and the deionized water. The reaction system produced a large amount of white solid. And (3) carrying out rotary evaporation on the system to obtain the polydiundecylate telluroxane.

Example 36: preparation of Polydipropyldipentyltelluroxane (PTOC 3-C5) based on hydrolytic polymerization method of dipropyltellurium and dipentyltellurium

150.02mg of dipropyltellurium and 182.60mg of dipentyltellurium were dissolved in 1mL of toluene to obtain a fraction A, and 65.00mg of elemental iodine was added to the fraction A to obtain a fraction B. And drying the mixture in a vacuum oven to remove the solvent and unreacted elemental iodine to obtain the component C. And fully mixing and stirring the component C and the deionized water. The reaction system produced a large amount of white solid. And (3) freeze-drying the system to obtain the poly dipropyl diamyl telluroxane.

Example 37: preparation of Polybisdiethylene glycol Bihexaethylene glycol telluroxane (PTOEG 2OH-EG6 OH) based on hydrolytic polymerization of Bidiethylene glycol tellurium and Bihexaethylene glycol tellurium

212.56mg of tellurium bisdiglycol and 308.01mg of tellurium bishexaglycol were dissolved in 1mL of dimethyl sulfoxide to obtain component A, and 250.22mg of liquid bromine was added to component A to obtain component B. The solvent and unreacted liquid bromine were removed by rotary evaporation to give component C. And fully mixing and stirring the component C and the deionized water. The reaction system produced a large amount of white solid. And (3) freeze-drying the system to obtain the polybis-diethylene glycol bis-hexaethylene glycol telluroxane.

Example 38: poly (dimethyltriethylene glycol) dimethylpentaethylene glycol telluroxane (PTOEG 3Me-EG5 Me) prepared based on hydrolysis polymerization method of dimethyltriethylene glycol tellurium and dimethylpentaethylene glycol tellurium

210.44mg of dimethyltriethylene glycol and 294.86mg of dimethylpentaethylene glycol tellurium were dissolved in 1mL of a mixed solvent of methylene chloride and dimethylformamide to obtain component A, and 320.96mg of chlorine gas was added to component A to obtain component B. The solvent and unreacted chlorine were removed by rotary evaporation to give component C. And fully mixing and stirring the component C and the deionized water. The reaction system produced a large amount of white solid. And (3) carrying out rotary evaporation on the system to obtain the poly-bis-methyl triethylene glycol-bis-methyl pentaglycol telluroxane.

Example 39: preparation of Polytelluroctanoic acid didecanoate (PTOC 7COOH-C9 COOH) based on hydrolytic polymerization of tellurium dioctoate and tellurium didecanoate

315.02mg of tellurium dioctoate and 462.40mg of tellurium didecanoate are dissolved in 1mL of a mixed solvent of toluene, acetonitrile and dimethylformamide to obtain a component A, and 250.22mg of liquid bromine is added to the component A to obtain a component B. The solvent and unreacted liquid bromine were removed by rotary evaporation to give component C. And fully mixing and stirring the component C and the deionized water. The reaction system produced a large amount of white solid. And (3) freeze-drying the system to obtain the poly-dioctanoate-dicaprate-telluroxane.

Example 40: preparation of Polydibutylbis-hexaethylene glycol bis-methyl-tetraethylene glycol-tellurium-dihexanoate-based hydrolytic polymerization method of dibutyl-tellurium, bis-hexaethylene glycol tellurium, bis-methyl-tetraethylene glycol tellurium, and tellurium-dihexanoate (PTOC 4-EG6OH-EG4Me-C5 COOH)

232.10mg of dibutyltellurium, 148.30mg of bishexamethylenetellurium, 320.80mg of bishethyltetraethyleneglycol tellurium, and 279.31mg of tellurium dihexanoate were dissolved in 1mL of tetrahydrofuran to obtain component A, and 248.15mg of chlorine gas was added to component A to obtain component B. The solvent and unreacted chlorine were removed by blowing dry with nitrogen to give component C. And fully mixing and stirring the component C and the deionized water. The reaction system produced a large amount of white solid. And (3) carrying out rotary evaporation on the system to obtain the poly-dibutyl-bis-hexa-ethylene-glycol-bis-methyl-tetra-ethylene-glycol-bis-caproate telluroxane.

Example 41: preparation of Polydimethyltelluroxane (PTOC 1) by electrochemical polymerization based on dimethyl tellurium

Dissolving 15.77mg of dimethyl tellurium in 1mL of dichloromethane to obtain a component A, and adding 38.74mg of tetrabutylammonium hexafluorophosphate into the system to obtain a tetrabutylammonium hexafluorophosphate organic solution system with the concentration of 0.1 mol/L; a voltage of 0.5V was applied to the above system. And filtering the system, and drying in a vacuum oven to obtain the polydimethyl telluroxane.

Example 42: preparation of polydibutyltelluroxane (PTOC 4) by electrochemical polymerization method based on dibutyltellurium

Dissolving 120.92mg of dibutyl tellurium in 1mL of ethyl acetate to obtain a component A, and adding 77.48mg of tetrabutyl ammonium hexafluorophosphate into the system to obtain a tetrabutyl ammonium hexafluorophosphate organic solution system with the concentration of 0.2 mol/L; a voltage of 1.0V was applied to the above system. And (3) freeze-drying the system to obtain the polydibutyltelluroxane.

Example 43: preparation of Polydioctyltelluroxane (PTOC 8) by electrochemical polymerization based on dioctyltellurium

Dissolving 354.05mg of dioctyl tellurium in 1mL of toluene to obtain a component A, and adding 154.96mg of tetrabutyl ammonium hexafluorophosphate to the system to obtain a tetrabutyl ammonium hexafluorophosphate organic solution system with the concentration of 0.4 mol/L; a voltage of 1.5V was applied to the above system. And (3) carrying out rotary evaporation on the system to obtain the poly dioctyl tellurium siloxane.

Example 44: preparation of polydidodecyl tellurium oxole (PTOC 12) based on electrochemical polymerization of didodecyl tellurium

Dissolving 699.39mg of didodecyltellurium in 1mL of chloroform to obtain a component A, and adding 232.44mg of tetrabutylammonium hexafluorophosphate to the system to obtain a tetrabutylammonium hexafluorophosphate organic solution system with the concentration of 0.6 mol/L; a voltage of 2.0V was applied to the above system. And (3) carrying out rotary evaporation on the system to obtain the polydidodecyl tellurium oxoalkane.

Example 45: production of Polydicetyl telluroxanes (PTOC 16) by electrochemical polymerization based on dicetyl telluroxime

1156.96mg of dihexadecyl tellurium is dissolved in 1mL of tetrahydrofuran to obtain a component A, 309.92mg of tetrabutyl ammonium hexafluorophosphate is added into the system, and a tetrabutyl ammonium hexafluorophosphate organic solution system with the concentration of 0.8mol/L is obtained; a voltage of 1.5V was applied to the above system. And blowing the nitrogen of the system to dry the solvent to obtain the polyhexadecyl tellurium alkyl.

Example 46: electrochemical polymerization method for preparing polydiethylene glycol tellurium alkyl (PTOEGOH) based on diethene glycol tellurium

Dissolving 43.544mg of diethanoltellurium in 1mL of acetonitrile to obtain a component A, and adding 387.43mg of tetrabutylammonium hexafluorophosphate to the system to obtain a tetrabutylammonium hexafluorophosphate organic solution system with the concentration of 1.0 mol/L; a voltage of 1.0V was applied to the above system. And drying the system in a vacuum oven to obtain the polydiethylol telluroxane.

Example 47: preparation of Polybistetraglycol tellurium-Oxirane (PTOEG 3 OH) based on an electrochemical polymerization Process for bistetraglycol tellurium

196.97mg of ditrimethyleneglycol tellurium is dissolved in 1mL of dimethylformamide to obtain a component A, 774.86mg of tetrabutylammonium hexafluorophosphate is added into the system, and a tetrabutylammonium hexafluorophosphate organic solution system with the concentration of 2.0mol/L is obtained; a voltage of 0.5V was applied to the above system. And (3) freeze-drying the system to obtain the polybistetraglycol telluroxane.

Example 48: preparation of Polybishexaethylene glycol tellurium Oxoxane (PTOEG 6 OH) based on electrochemical polymerization of bishexaethylene glycol tellurium

658.25mg of bis-hexaethyleneglycol tellurium is dissolved in 1mL of dimethyl sulfoxide to obtain a component A, 1549.72mg of tetrabutylammonium hexafluorophosphate is added into the system, and a tetrabutylammonium hexafluorophosphate organic solution system with the concentration of 4.0mol/L is obtained; a voltage of 0.5V was applied to the above system. And (3) carrying out rotary evaporation on the system to obtain the poly-bis-hexaethyleneglycol telluroxane.

Example 49: preparation of poly (PTOEGMe) based on electrochemical polymerization of tellurium (DMT)

Dissolving 24.58mg of tellurium bismethylethoxide in 1mL of mixed solvent of dichloromethane and dimethylformamide to obtain a component A, and adding 1975.62mg of tetrabutylammonium tetrafluoroborate into the system to obtain a tetrabutylammonium tetrafluoroborate organic solution system with the concentration of 6.0 mol/L; a voltage of 1.0V was applied to the above system. And drying the system in a vacuum oven to obtain the poly (dimethyl ethyl alcohol tellurium-alkyl oxide).

Example 50: preparation of poly (dimethyltriglycol telluroxane) (PTOEG 3 Me) based on dimethyltriglycol tellurium electrochemical polymerization method

Dissolving 421.99mg of bis-methyl triethylene glycol in 1mL of mixed solvent of dichloromethane and dimethylformamide to obtain a component A, and adding 2634.52mg of tetrabutylammonium tetrafluoroborate into the system to obtain a tetrabutylammonium tetrafluoroborate organic solution system with the concentration of 8.0 mol/L; a voltage of 2.0V was applied to the above system. And drying the system in a vacuum oven to obtain the poly (dimethyl triethylene glycol tellurium-alkyl).

Example 51: preparation of Poly (dimethylhexaethyleneglycol) telluroxane (PTOEG 6 Me) based on electrochemical polymerization of Dimethylhexaethyleneglycol tellurium

1372.62mg of dimethylhexaethyleneglycol tellurium is dissolved in 1mL of a mixed solvent of toluene and dimethyl sulfoxide to obtain a component A, and 1937.15mg of tetrabutylammonium hexafluorophosphate and 1646.58mg of tetrabutylammonium tetrafluoroborate are added into the system to obtain a mixed organic solution system of tetrabutylammonium hexafluorophosphate and tetrabutylammonium tetrafluoroborate; a voltage of 2.0V was applied to the above system. And drying the system in a vacuum oven to obtain the dimethyl hexaethylene glycol telluroxane.

Example 52: preparation of Polytelluroxane diacetate (PTOC 1 COOH) by electrochemical polymerization based on tellurium diacetate

245.69mg of tellurium diacetate is dissolved in 1mL of mixed solvent of dimethylformamide and acetonitrile to obtain a component A, 232.44mg of tetrabutylammonium hexafluorophosphate is added into the system, and a tetrabutylammonium hexafluorophosphate organic solution system with the concentration of 0.6mol/L is obtained; a voltage of 2.0V was applied to the above system. And (3) freeze-drying the system to obtain the telluroxane diacetate.

Example 53: preparation of Polytellurous dibutyrate siloxane (PTOC 3 COOH) based on electrochemical polymerization of tellurium dibutyrate

603.60mg of tellurium dibutyrate is dissolved in 1mL of mixed solvent of toluene and acetonitrile to obtain a component A, 232.44mg of tetrabutylammonium hexafluorophosphate is added into the system, and a tetrabutylammonium hexafluorophosphate organic solution system with the concentration of 0.6mol/L is obtained; a voltage of 2.0V was applied to the above system. And (3) carrying out rotary evaporation on the system to obtain the poly-tellurium dibutyrate siloxane.

Example 54: preparation of Polytelluroctanoic acid siloxane (PTOC 7 COOH) based on electrochemical polymerization of tellurium dioctoate

621.02mg of tellurium dioctoate is dissolved in 1mL of a mixed solvent of toluene, acetonitrile and dimethylformamide to obtain a component A, 232.44mg of tetrabutylammonium hexafluorophosphate is added into the system, and a tetrabutylammonium hexafluorophosphate organic solution system with the concentration of 0.6mol/L is obtained; a voltage of 2.0V was applied to the above system. And drying the system by using nitrogen to obtain the tellurium dioctanoate siloxane.

Example 55: preparation of Polytellurodiumundecanoate (PTOC 11 COOH) by electrochemical polymerization based on tellurium diundecanoate

Dissolving 996.34mg of tellurium diundecanoate in 1mL of a mixed solvent of dichloromethane, ethyl acetate, toluene, chloroform, acetonitrile, dimethylformamide, dimethyl sulfoxide and tetrahydrofuran to obtain a component A, and adding 232.44mg of tetrabutylammonium hexafluorophosphate into the system to obtain a tetrabutylammonium hexafluorophosphate organic solution system with the concentration of 0.6 mol/L; a voltage of 2.0V was applied to the above system. And (3) carrying out rotary evaporation on the system to obtain the polydiundecylate telluroxane.

Example 56: preparation of poly dipropyl dipentyl tellurium alkyl (PTOC 3-C5) based on electrochemical polymerization method of dipropyl tellurium and dipentyl tellurium

150.02mg of dipropyl tellurium and 182.60mg of dipentyl tellurium are dissolved in 1mL of toluene to obtain a component A, 232.44mg of tetrabutyl ammonium hexafluorophosphate is added into the system to obtain a tetrabutyl ammonium hexafluorophosphate organic solution system with the concentration of 0.6 mol/L; a voltage of 2.0V was applied to the above system. And (3) carrying out rotary evaporation on the system to obtain the poly dipropyl dipentyl telluroxane.

Example 57: preparation of polybisdiglycol bis-hexaglycol telluroxane (PTOEG 2OH-EG6 OH) based on electrochemical polymerization of bis-diglycol tellurium and bis-hexaglycol tellurium

Dissolving 212.56mg of bis-diethylene glycol tellurium and 308.01mg of bis-hexaethylene glycol tellurium in 1mL of dimethyl sulfoxide to obtain a component A, and adding 1975.62mg of tetrabutylammonium tetrafluoroborate into the system to obtain a tetrabutylammonium tetrafluoroborate organic solution system with the concentration of 6.0 mol/L; a voltage of 1.0V was applied to the above system. And drying the system in a vacuum oven to obtain the poly-bis-diethylene glycol bis-hexaethylene glycol telluroxane.

Example 58: preparation of poly (dimethyltriethylene glycol) dimethylpentaethylene glycol tellurium-alkyl (PTOEG 3Me-EG5 Me) based on electrochemical polymerization of dimethyltriethylene glycol tellurium and dimethylpentaethylene glycol tellurium

Dissolving 210.44mg of dimethyltriethylene glycol and 294.86mg of dimethylpentaethylene glycol tellurium in 1mL of a mixed solvent of dichloromethane and dimethylformamide to obtain a component A, and adding 1937.15mg of tetrabutylammonium hexafluorophosphate and 1646.58mg of tetrabutylammonium tetrafluoroborate into the system to obtain a mixed organic solution system of tetrabutylammonium hexafluorophosphate and tetrabutylammonium tetrafluoroborate; a voltage of 2.0V was applied to the above system. And drying the system in a vacuum oven to obtain the poly-bis-methyl triethylene glycol-bis-methyl penta glycol tellurium alkane.

Example 59: preparation of Polytelluroctanoic acid didecanoate (PTOC 7COOH-C9 COOH) based on electrochemical polymerization of tellurium dioctoate and tellurium didecanoate

Dissolving 315.02mg of tellurium dioctoate and 462.40mg of tellurium didecanoate in 1mL of mixed solvent of toluene, acetonitrile and dimethylformamide to obtain a component A, and adding 774.86mg of tetrabutylammonium hexafluorophosphate into the system to obtain a tetrabutylammonium hexafluorophosphate organic solution system with the concentration of 2.0 mol/L; a voltage of 0.5V was applied to the above system. And (3) freeze-drying the system to obtain the poly-dioctanoate-dicaprate-telluroxane.

Example 60: preparation of Polydibutylbisinglycol bis-methyl-tetraglycol-tellurium-hexanoate (PTOC 4-EG6OH-EG4Me-C5 COOH) based on electrochemical polymerization of dibutyltellurium, bis-hexaglycol tellurium, bis-methyl-tetraglycol tellurium, and tellurium-hexanoate

232.10mg of dibutyl tellurium, 148.30mg of bis-hexaethylene glycol tellurium, 320.80mg of bis-methyl tetraethylene glycol tellurium and 279.31mg of tellurium dihexanoate are dissolved in 1mL of tetrahydrofuran to obtain a component A, 2634.52mg of tetrabutylammonium tetrafluoroborate is added into the system, and an organic solution system of tetrabutylammonium tetrafluoroborate with the concentration of 8.0mol/L is obtained; a voltage of 2.0V was applied to the above system. And drying the system in a vacuum oven to obtain the poly-dibutyl-bis-hexaethylene glycol-bis-methyl-tetraethylene glycol-bis-caproate telluroxane.

The validity of the disclosed embodiments is verified as follows:

1. structural characterization of Polytelluroxanes

The polytelluroxanes prepared in example 2 (polydibutyltelluroxane), example 23 (polydihexyltelluroxane) and example 43 (polydioctyltelluroxane) were dissolved in a deuterated nuclear magnetic reagent, structurally characterized by nuclear magnetic resonance hydrogen spectroscopy and compared based on their corresponding tellurium-containing monomers. The characterization results are shown in FIG. 4 (polydibutyltelluroxane), FIG. 5 (polydihexyltelluroxane), and FIG. 6 (polydioctyltelluroxane). In FIGS. 4-6, the light signal is from a tellurium-containing monomer and the dark signal is from a polytelluroxane, wherein the signals d and c are from the alpha-hydrogen and beta-hydrogen, respectively, of the tellurium-containing monomer. When the tellurium-containing monomer is converted into a polytelluroxane, the chemical shifts of the tellurium element and the tellurium-containing monomer from alpha-hydrogen to beta-hydrogen are both shifted from the high field region to the ground field region (to the left). At the same time, with the formation of the high molecular structure, the cleavage signal of the small molecular monomer disappears, and a broad peak having the characteristics of the polymer is generated. The above results demonstrate that the target polytelluroxane can be obtained by the relevant preparation method provided by the present disclosure. Meanwhile, characterization of the prepared solid is carried out by a Fourier transform infrared absorption spectrometer (FTIR), and the target poly-telluroxane can be obtained, and the related result is shown in figure 7. Wherein, the signal of 3000-2850cm < -1 > comes from the stretching vibration of a hydrocarbon chemical bond in a poly-telluroxane organic side chain; the signal of 1500-1300cm-1 comes from the bending vibration of the hydrocarbon chemical bond in the organic side chain of the poly-telluroxane; the signal of 800-500cm-1 comes from the stretching vibration of tellurium-oxygen chemical bonds in the main chain structure of the telluroxane. The above results also demonstrate that the target polytelluroxane can be obtained by the related preparation method provided by the present disclosure.

2. Characterization of the elemental composition of Polytelluroxanes

The polyteredothioxane prepared in example 5 (polydidodecyl telluroxane prepared by interfacial polymerization) was dispersed in chloroform, 20. Mu.L of the dispersion was placed on a copper mesh and dried, and the composition was characterized by energy dispersive X-ray spectroscopy (EDS), and the resulting polymer contained a tellurium element, as shown by the results in FIG. 8. Dispersing the reaction monomer and the prepared polytereloxane in chloroform, taking 20 mu L of the mixture, respectively placing the mixture in a smooth silicon wafer in a nitrogen atmosphere for drying, and carrying out further research on the valence states of tellurium elements in the reaction monomer and polytereloxane through X-ray photoelectron spectroscopy (XPS), wherein according to characteristic peaks, the tellurium element in the reaction monomer is +2 (shown as (a) in figure 9) and the tellurium element in the polytereloxane is +4 (shown as (b) in figure 9). The characteristic peak of the + 4-valent tellurium element proves the generation of the chemical structure of the tellurium-oxygen element repeated alternating main chain.

3. Microtopography characterization of Polytelluriloxanes

The polytereoxane prepared in example 5 (polydidodecyl telluroxane prepared by interfacial polymerization) was dispersed in chloroform, 20 μ L of the dispersion was placed in a copper mesh and dried, and the morphology was characterized by a Transmission Electron Microscope (TEM). As shown in FIG. 10, the prepared poly-telluroxane has a structure of nanofiber with a length of about 20 microns and a width of about 100 nanometers. Meanwhile, the prepared polytereoxirane is dispersed in chloroform, 20 μ L of the polytereoxirane is placed in a copper mesh for drying, the appearance of the polytereoxirane is characterized by a Scanning Transmission Electron Microscope (STEM), and the fibrous nanostructure of the polytereoxirane can be observed as well (fig. 11 (a)). By scanning transmission electron microscopy (STEM-Mapping), spatial distribution of tellurium elements can be observed (fig. 11 (b)), further illustrating that the microstructure of the polytelloxane is a nanofiber, which has the potential to prepare functional polymer materials.

4. Thermodynamic testing of polytelluloxanes

Taking the polyteretroxanes prepared in example 2 (polydibutyltelluroxane), example 3 (polydihexyltelluroxane) and example 4 (polydioctyltelluroxane) as examples, the polytereoxoxanes with different chemical structures were subjected to thermodynamic characterization by thermogravimetric analysis (TGA), and the related results are shown in fig. 12. Temperature at which 5% mass loss of polymer occurs during heating (T) _d,5％ ) And the point of maximum slope of the mass loss curve (T) _max ) Is a characteristic index for measuring the thermodynamic property of the polymer. As can be seen from FIG. 12, the three polytelluroxanes showed different thermal stability curves. Wherein, as shown in FIG. 12 (a), T of polydibutyltelluroxane _d,5％ At 145 ℃ and T _max Is 147 ℃; t of polyhexamethyltelluroxane, as shown in FIG. 12 (b) _d,5％ At 159 ℃ and T _max 179 deg.C; t of Polydioctyltelluroxane, as shown in FIG. 12 (c) _d,5％ At 155 ℃ and T _max The temperature was 184 ℃. T of three polytelluroxanes _d,5％ And T _max All changed with the change of alkyl side chain. The thermodynamic property of the polytelluroxane can be regulated and controlled by changing the organic side chain, so that the polytelluroxane can be applied to different practical scenes.

5. Molecular weight determination of Polytelluroxanes

The molecular weight and molecular weight distribution of a polymer are critical to its performance. Taking example 10 (poly-bis-methyl triethylene glycol telluroxane) as an example, the high molecular weight and the molecular weight distribution of the reaction in the preparation process of poly-telluroxane for 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22 and 24 hours were detected by gel permeation chromatography (fig. 13). The molecular weight of the polytelluloxane can be 500Da to 4502.5kDa according to the conversion of retention time, and the polytelluloxane has good adjustability. The result shows that the molecular weight of the polytelluroxane can be regulated and controlled by regulating and controlling the time of the polymerization reaction, and further the physical and chemical properties of the polytelluroxane material can be regulated and controlled.

6. Material preparation experiment of Polytelluroxane

Processing the prepared polytelluroxane into a macroscopic material through hot press molding and solvent molding. Based on different side chain structures, three telluroxane polymer materials with remarkable differences, namely glass (shown in figure 14), high-viscosity fluid (shown in figure 15) and plastic (shown in figure 16), can be obtained respectively. A polytelluroxane glass having good light transmittance can be obtained by example 5 (polydidodecyltelluroxane) (fig. 14); a polytelluroxane fluid with good hydrophilicity can be obtained by the method of example 11 (poly (dimethylhexaethyleneglycol telluroxane)); a polytelluroxane plastic with good mechanical properties can be obtained by example 33 (polytelluroxane dibutyrate). The result proves that the physical properties of the polyteretroxane material can be efficiently adjusted by changing the side chain structure of the polyteretroxane, so that the material is suitable for different application scenes.

Furthermore, in the description herein, reference to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Moreover, various embodiments or examples and features of various embodiments or examples described in this specification can be combined and combined by one skilled in the art without being mutually inconsistent.

Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims

1. A polytelluroxane, which is characterized by having a structural formula of- [ Te (R) ₂ )-O] _n -, wherein:

the repeating unit is-Te (R) ₂ ) -O-, n is the number of repeating units, n is an integer greater than or equal to 2;

r-is any one or more of the following organic side chains:

hydrophobic chain segment- (CH) ₂ ) X-, X is the number of repeating units, and X is an integer of 1 to 16;

hydrophilic chain segment- (CH) ₂ CH ₂ O) _Y -CH ₃ Or- (CH) ₂ CH ₂ O) _Y -H, Y is a repeating unit, Y is an integer from 1 to 6;

proton chain segment- (CH) ₂ ) _Z -COOH, Z is a repeating unit and Z is an integer from 1 to 10.

2. A method for preparing polytelluroxanes according to claim 1, comprising: dissolving a tellurium-containing monomer in an organic solvent to obtain a tellurium-containing organic solution system, mixing the tellurium-containing organic solution system with an aqueous hydrogen peroxide solution, carrying out interfacial polymerization reaction to obtain a reactant, and drying the reactant to obtain the polytereoxoalkane.

3. The method for producing polytereoxane in accordance with claim 2, wherein the molar concentration of the tellurium-containing organic solution system is 0.1mol/L to 2mol/L.

4. The method for producing polytelluroxane according to claim 2, wherein the molar concentration of the aqueous hydrogen peroxide solution is 0.1mol/L to 5mol/L.

5. The method for producing polyterefulones according to claim 2, wherein the volume ratio of the tellurium-containing organic solution system to the aqueous hydrogen peroxide solution is from 0.1 to 10.

6. A method for preparing polytelluroxanes according to claim 1, comprising: mixing a tellurium-containing dihalogen compound with deionized water, carrying out hydrolytic polymerization reaction to obtain a reactant, and drying the reactant to obtain the poly-tellurium oxoalkane.

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8. The method according to claim 6, wherein the tellurium-containing dihalogen compound is produced by the following steps:

dissolving a tellurium-containing monomer in an organic solvent to obtain a tellurium-containing organic solution system, and adding a halogen simple substance into the tellurium-containing organic solution system to obtain the tellurium-containing dihalogen compound.

9. The method according to claim 8, wherein the elementary halogen is a mixture of one or more of chlorine, liquid bromine and elementary iodine.

10. A method for preparing a polytelluroxane according to claim 1, comprising: dissolving a tellurium-containing monomer in an organic solvent to obtain a tellurium-containing organic solution system, adding an organic electrolyte into the tellurium-containing organic solution system, applying voltage, carrying out electrochemical polymerization reaction to obtain a reactant, and drying the reactant to obtain the polytereoxoalkane.

11. The production method according to claim 10, wherein the organic electrolyte employs a mixture of any one or more of tetrabutylammonium tetrafluoroborate and tetrabutylammonium hexafluorophosphate.

12. The method according to claim 10, wherein the molar concentration of the organic electrolyte in the organic solvent system is 0.1 to 10mol/L.

13. The method according to claim 10, wherein the voltage applied is 0.5V to 2.0V.

14. The production method according to claim 2, 8 or 10, wherein the tellurium-containing monomer is any one or a mixture of more of dimethyl tellurium, diethyl tellurium, dipropyl tellurium, dibutyl tellurium, diamyl tellurium, dihexyl tellurium, diheptyl tellurium, dioctyl tellurium, dinonyl tellurium, didecyl tellurium, diundecyl tellurium, didodecyl tellurium, ditridecyl tellurium, ditetradecyl tellurium, dipentadecyl tellurium, dihexadecyl tellurium, diethanol tellurium, bisdiglycol tellurium, ditrimethylene glycol tellurium, bistetraglycol tellurium, dipentaglycol tellurium, bistetraglycol tellurium, dihexaglycol tellurium, dimethyldiglycol tellurium, dimethyltetraethylene glycol tellurium, dimethylpentaglycol tellurium, bismethyl diglycol tellurium, diacetic acid tellurium, dipropionic acid tellurium, dibutyric acid tellurium, dipentanoic acid tellurium, dihexanoic acid tellurium, dioctoic acid tellurium, dinonylic acid tellurium, didecanoic acid tellurium and diundecyl tellurium.

15. The method according to claim 2, 8 or 10, wherein the organic solvent is any one or more of dichloromethane, ethyl acetate, toluene, chloroform, acetonitrile, dimethylformamide, dimethylsulfoxide and tetrahydrofuran.

16. The method according to claim 8 or 10, wherein the organic solution system has a molar concentration of 0.1 to 10mol/L.

17. The method of claim 2, 8 or 10, wherein the drying is performed by lyophilization, vacuum oven drying, solvent removal by rotary evaporation, or inert gas blow drying.