A block polytelluroxane and a method for preparing the same

Abstract

The application belongs to the technical field of functional polymers, and relates to a block-type polytelluroxane and a preparation method thereof. The structure of the polytelluroxane is shown in formula (1). In formula (1), R1 and R2 are different and each is independently selected from at least one of C2-C20 unsubstituted or end group substituted alkyl and C2-C20 unsubstituted or end group substituted oligomeric oxyethylene; m and n are each independently any one integer from 3 to 24, and m:n is 1:4 to 4:1. The block-type non-carbon main chain polytelluroxane is prepared by a two-step method of interfacial (hydrolysis) polymerization and condensation reaction, the polymer molecular chain structure is adjusted, the glass transition temperature of the polymer is changed, the monomer types are rich, the polymerization method is simple and various, the structure and application of the non-carbon main chain polymer are expanded, and the obtained block-type non-carbon main chain polytelluroxane has good application value in the fields of nano drugs and electronic devices.

Description

Technical Field

[0001] This invention belongs to the field of functional polymer technology, specifically relating to a block polytelluric alkane and its preparation method. Background Technology

[0002] The synthesis and performance exploration of novel polymer materials play a crucial role in promoting basic scientific research and the development of engineering technology. Traditional polymers typically have a carbon-based backbone, with common carbon-chain polymers including polyethylene, polypropylene, and polystyrene. Heterochain polymers introduce nitrogen, oxygen, and sulfur atoms into the carbon backbone, such as nylon, polyester, polyoxymethylene, and polyethersulfone. Organic polymers with non-carbon backbone elements have a backbone structure entirely composed of atoms other than carbon. Currently, the variety of such polymers is far less than that of carbon-based backbone polymers. Synthesizing organic polymers with novel non-carbon backbone structures helps enrich the research objects in polymer science. These non-carbon element-constructed polymers often demonstrate application value in fields such as biomedicine and organic optoelectronic materials.

[0003] However, the development of non-carbon backbone organic polymers still faces many challenges. Research often encounters problems such as poor backbone structure stability, complex synthesis methods, difficulty in material molding, and unclear properties. Currently, the most widely used non-carbon backbone polymers are polysiloxanes and polyphosphononitriles. The industrial synthesis method for polysiloxanes is the hydrolytic ring-opening polymerization of organohalosilanes, also known as the Müller-Rochow process (Org.Chem.Front.2020,7(24):4108-4120). Polyphosphononitriles are usually synthesized using a two-step method of ring-opening of six-membered rings of halogenated nitrogen and phosphorus followed by organic substitution modification (J.Am.Chem.Soc.1965,87:4216-4217). Their synthesis methods are all ring-opening polymerizations, and the synthesis means are relatively simple, making it difficult to meet the diverse practical application needs. CN202210768087.1, CN202210769521.8, and CN202210769490.6 disclose a novel class of non-carbon backbone organic polymers, polytelluroxanes, and their potential applications in biodegradable materials and organic polymer optoelectronic materials. However, research shows that the glass transition temperatures of most polytelluroxane polymers fall within the operating temperature range (20-60℃), which is unfavorable for the use of polytelluroxane materials. Summary of the Invention

[0004] To address the aforementioned problems in existing technologies, this invention provides a block-type polytelluroxane and its preparation method. By adjusting the polymer molecular chain structure and changing the polymer's glass transition temperature to outside its operating temperature range, it is applicable to a wide variety of monomers and employs simple and diverse polymerization methods. This expands the structure and applications of non-carbon backbone polymers. The resulting block-type non-carbon backbone polytelluroxane has significant application value in fields such as nanomedicine and electronic devices.

[0005] To achieve the above objectives, a first aspect of the present invention provides a block polytelluride, the structure of which is shown in formula (1):

[0006]

[0007] In formula (1), R1 and R2 are different and are each independently selected from at least one of unsubstituted or terminally substituted alkyl groups from C2 to C20 and unsubstituted or terminally substituted oligooxyethylene groups from C2 to C20; m and n are each independently any integer from 3 to 24, preferably any integer from 4 to 20, and m:n is 1:4 to 4:1.

[0008] A second aspect of the present invention provides a method for preparing the block polytelluric alkane, comprising the following steps:

[0009] (1) Obtain prepolymers with telluryl end groups as shown in formula (4) and formula (5), respectively;

[0010] (2) In the presence of a first organic solvent and a catalyst, the prepolymers with tellurol end groups shown in formulas (4) and (5) are subjected to a condensation reaction. After the reaction is completed, the block polytelluric alkane is separated and purified.

[0011]

[0012] In equations (4) and (5), R1, R2, m and n are defined as in equation (1).

[0013] Compared with the prior art, the present invention has the following advantages:

[0014] This invention utilizes a two-step method involving interfacial (hydrolysis) polymerization and condensation reaction to prepare block-type non-carbon backbone polytellurethanes. By adjusting the polymer molecular chain structure and altering the polymer's glass transition temperature to a range outside its operating temperature range, this invention is applicable to a wide variety of monomers and employs simple and diverse polymerization methods. This further expands the structure and applications of non-carbon backbone polymers, demonstrating significant application value in fields such as nanomedicine and electronic devices.

[0015] Other features and advantages of the present invention will be described in detail in the following detailed description section. Attached Figure Description

[0016] Exemplary embodiments of the present invention will be described in more detail with reference to the accompanying drawings.

[0017] Figure 1 The following are DSC diagrams of the three polytelluric alkanes in Example 1, Comparative Example 1, and Comparative Example 2. Detailed Implementation

[0018] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0019] A first aspect of the present invention provides a block polytelluride, the structure of which is shown in formula (1):

[0020]

[0021] In formula (1), R1 and R2 are different and are each independently selected from at least one of unsubstituted or terminally substituted alkyl groups from C2 to C20 and unsubstituted or terminally substituted oligooxyethylene groups from C2 to C20; m and n are each independently any integer from 3 to 24, preferably any integer from 4 to 20, and m:n is 1:4 to 4:1.

[0022] According to the present invention, preferably, the substituents of the terminal group are selected from C1-C4 alkoxy groups.

[0023] According to the present invention, preferably, R1 and R2 are each independently selected from at least one of unsubstituted or terminally substituted alkyl groups having the structure of formula (2) and unsubstituted or terminally substituted oligooxyethylene having the structure of formula (3);

[0024]

[0025] In formula (2), x is any integer from 2 to 18, and R3 is selected from at least one of methyl and C1-C4 alkoxy groups, preferably methyl or methoxy.

[0026] In formula (3), y is any integer from 1 to 10, and R4 is a hydrogen atom or a methyl group, preferably a methyl group.

[0027] According to the present invention, preferably, the polytellurethane has a number-average molecular weight of 0.5 × 10⁻⁶. 4 ~20.0×10 4 g·mol -1 Preferably 1.0×10 4 ~15.0×10 4 g·mol -1 The molecular weight distribution is 1.8–5.0, preferably 2.0–4.0.

[0028] A second aspect of the present invention provides a method for preparing the block polytelluric alkane, comprising the following steps:

[0029] (1) Obtain prepolymers with telluryl end groups as shown in formula (4) and formula (5), respectively;

[0030] (2) In the presence of a first organic solvent and a catalyst, the prepolymers with tellurol end groups shown in formulas (4) and (5) are subjected to a condensation reaction. After the reaction is completed, the block polytelluric alkane is separated and purified.

[0031]

[0032] In equations (4) and (5), R1, R2, m and n are defined as in equation (1).

[0033] According to the present invention, preferably, in step (2), the first organic solvent is selected from at least one of dichloromethane, chloroform, tetrahydrofuran, acetonitrile, toluene, ethyl acetate, dimethylformamide, dimethyl sulfoxide, 1,4-dioxane and N-methylpyrrolidone;

[0034] The catalyst is selected from at least one of organic bases, organotin compounds and organotitanium compounds, preferably from at least one of triethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, dibutyltin dilaurate, dibutyltin oxide, tetraisopropyl titanate and tetrabutyl titanate;

[0035] The mass ratio of the prepolymers with telluryl end groups shown in formulas (4) and (5) is 0.1 to 10:1;

[0036] The amount of the catalyst used is 0.01 to 20 wt% of the total amount of the prepolymers with telluryl end groups as shown in formulas (4) and (5);

[0037] The conditions for the condensation reaction include: a reaction temperature of -20℃ to 150℃, preferably 0 to 100℃, and a reaction time of 1 to 100 h, preferably 3 to 50 h.

[0038] According to the present invention, preferably, in step (1), the prepolymers with tellurol end groups shown in formula (4) and formula (5) are obtained independently by interfacial polymerization or hydrolytic polymerization.

[0039] According to the present invention, preferably, the interface aggregation method includes the following steps:

[0040] In the presence of a second organic solvent, the first tellurium-containing monomer and an oxidant are subjected to an interfacial polymerization reaction. After the reaction is completed, a first undesirable solvent is added dropwise to precipitate and separate the prepolymer with tellurol end groups.

[0041] According to the present invention, preferably, the oxidant is provided in the form of an aqueous solution, and the oxidant is selected from at least one of hydrogen peroxide, tert-butyl hydroperoxide and cumene hydroperoxide;

[0042] The second organic solvent is selected from at least one of dichloromethane, chloroform, tetrahydrofuran, acetonitrile, toluene, ethyl acetate, dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, and N-methylpyrrolidone;

[0043] The first undesirable solvent is selected from at least one of methanol, ethanol, petroleum ether, n-hexane, and diethyl ether;

[0044] The amount of the first tellurium-containing monomer and the oxidant added is such that the molar concentration of the first tellurium-containing monomer in the polymerization system is 0.05–2 mol·L⁻¹. -1 The molar concentration of the oxidant is 0.1–6 mol·L⁻¹. -1 ;

[0045] The conditions for the interfacial polymerization reaction include: a reaction temperature of -20℃ to 100℃, preferably 0 to 50℃, and a reaction time of 1 to 100 h, preferably 4 to 70 h.

[0046] According to the present invention, preferably, the hydrolysis-polymerization method includes the following steps:

[0047] Under the presence of a third organic solvent, a tellurium dihalogen monomer and deionized water are subjected to a hydrolysis polymerization reaction. After the reaction is completed, a second undesirable solvent is added dropwise to precipitate and separate the prepolymer with tellurol end groups.

[0048] According to the present invention, preferably, the tellurium dihalogen monomer is selected from at least one of the monomers having the structures shown in formula (8) and formula (9);

[0049]

[0050] In equations (8) and (9), R3, R4, x, and y are as defined in equations (2) and (3); R5 and R6 are each independently selected from at least one of chlorine, bromine, and iodine.

[0051] In some embodiments, the tellurium-containing dihalogen monomer is one or more selected from dichlorodialkyl tellurium, dibromodialkyl tellurium, diiododialkyl tellurium, dichlorodimethoxyalkyl tellurium, dibromodimethoxyalkyl tellurium, diiododimethoxyalkyl tellurium, dichlorodiolipoethyleneoxymonomethyl ether tellurium, dibromodiolipoethyleneoxymonomethyl ether tellurium, and diiododiolipoethyleneoxymonomethyl ether tellurium. Possible structures are shown below, where x is any integer from 1 to 20, and y is any integer from 1 to 10.

[0052]

[0053] According to the present invention, preferably, the third organic solvent is selected from at least one of dichloromethane, chloroform, tetrahydrofuran, acetonitrile, toluene, ethyl acetate, dimethylformamide, dimethyl sulfoxide, 1,4-dioxane and N-methylpyrrolidone;

[0054] The second undesirable solvent is selected from at least one of methanol, ethanol, petroleum ether, n-hexane, and diethyl ether;

[0055] The amount of tellurium dihalogen monomer added resulted in a molar concentration of 0.05–2 mol·L⁻¹ in the polymerization system. -1 ;

[0056] The conditions for the hydrolysis-polymerization reaction include: a reaction temperature of -20℃ to 150℃, preferably 0 to 100℃, and a reaction time of 1 to 100 h, preferably 2 to 40 h.

[0057] According to the present invention, preferably, the tellurium-containing dihalogen compound is prepared by the following steps: dissolving a second tellurium-containing monomer in a fourth organic solvent, then adding a halogen element to react, and after the reaction is completed, removing the solvent, purifying, and drying to obtain the tellurium-containing dihalogen compound.

[0058] According to the present invention, preferably, the halogen is selected from at least one of chlorine, bromine and iodine;

[0059] The fourth organic solvent is selected from at least one of dichloromethane, chloroform, tetrahydrofuran, acetonitrile, toluene, ethyl acetate, dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, and N-methylpyrrolidone;

[0060] The molar ratio of the halogen element to the second tellurium-containing monomer is 1 to 10:1.

[0061] According to the present invention, preferably, the first tellurium-containing monomer and the second tellurium-containing monomer are each independently selected from at least one of the monomers having the structures shown in formula (6) and formula (7);

[0062]

[0063] In equations (6) and (7), R3, R4, x and y are defined as in equations (2) and (3).

[0064] In some embodiments, the first or second tellurium-containing monomer is one or more of dialkyl tellurium, dimethoxyalkyl tellurium, and diolipoethoxymonomethyl ether tellurium. Possible structures are shown below, where x is any integer from 1 to 20, and y is any integer from 1 to 10.

[0065]

[0066] The present invention will be further described below with reference to the embodiments, but the scope of the present invention is not limited to these embodiments.

[0067] In this embodiment of the invention, the number-average molecular weight (Mn) and molecular weight distribution index (PDI) of the block polytelluroxane were determined using gel permeation chromatography (GPC). Specifically, a GPC1260 Infinity II (Agilent Technologies) gel permeation chromatograph was used for analysis, with a 2×PLgel 5um MIXED-C column (300mm×7.5mm, Agilent Technologies). The solvent and mobile phase were both tetrahydrofuran (containing 0.025% antioxidant 2,6-dibutyl-p-cresol), the column temperature was 40℃, the flow rate was 1.0 mL / min, and a narrow-distribution polystyrene standard was used for universal standardization. The sample concentration was 2 mg / mL.

[0068] Glass transition temperature: Determined using differential scanning calorimetry (DSC), specifically a TA Q100 series thermal analyzer, with an experimental temperature range of -60 to 120℃. The temperature was first increased to 120℃ at a rate of 10℃ / min and held for 5 min, then cooled at a rate of 10℃ / min, followed by a second temperature scan at a rate of 10℃ / min.

[0069] The substances and process parameters not limited in this invention can be selected according to existing technology, which is a conventional technical means in this field.

[0070] Example 1

[0071] Dilute a 30% hydrogen peroxide aqueous solution with water to prepare a 5 mol·L⁻¹ solution. -1 The aqueous solution is prepared for use.

[0072] Dissolve 3.540 g (10 mmol) of dioctyltelluride in 10 mL of dichloromethane, and add 5 mol·L⁻¹ -1 10 mL of an aqueous hydrogen peroxide solution was thoroughly mixed and reacted at 30 °C for 6 hours. The organic phase in the reaction system was then added to methanol, a poor solvent, and the mixture was filtered, washed, and dried to obtain dioctyl tellurium prepolymer. GPC analysis showed that the number average molecular weight of this prepolymer was 2.05 × 10⁻⁶. 3 g / mol, molecular weight distribution is 2.02, degree of polymerization m = 5.

[0073] Dissolve 2.979 g (10 mmol) of dihexyltelluride in 10 mL of dichloromethane, and add 5 mol·L⁻¹ -110 mL of an aqueous hydrogen peroxide solution was thoroughly mixed and reacted at 25 °C for 10 hours. The organic phase in the reaction system was then added to methanol, a poor solvent, and the mixture was filtered, washed, and dried to obtain dihexyltellurium prepolymer. GPC analysis showed that the number average molecular weight of this prepolymer was 1.85 × 10⁻⁶. 3 g / mol, molecular weight distribution is 2.01, degree of polymerization n = 6.

[0074] 2.00 g of dioctyl telluride prepolymer and 2.00 g of dihexyl telluride prepolymer were dissolved in 20 mL of toluene and thoroughly mixed. 0.004 g of dibutyltin dilaurate was added, and the mixture was reacted at 60 °C for 8 hours, with small molecules removed under reduced pressure. After the reaction, the organic phase was added to methanol, a poor solvent, filtered, washed, and dried to obtain block copolymer P1. GPC analysis showed that the number-average molecular weight of P1 was 3.70 × 10⁻⁶. 4 It has a molecular weight distribution of 2.64 g / mol and no glass transition temperature in the range of -50 to 80 °C as determined by DSC.

[0075] Example 2

[0076] The prepolymer was prepared in the same manner as in Example 1, except that the condensation catalyst was replaced with 0.2 g of triethylamine, and the reaction was carried out at 40 °C for 12 hours, followed by decompression to remove small molecules. After the reaction, the organic phase was added to methanol, a poor solvent, and then filtered, washed, and dried to obtain the block copolymer P2. GPC analysis showed that the number average molecular weight of P2 was 3.03 × 10⁻⁶. 4 It has a molecular weight distribution of 2.61 g / mol and no glass transition temperature in the range of -50 to 80 °C as determined by DSC.

[0077] Example 3

[0078] Dilute a 30% hydrogen peroxide aqueous solution with water to prepare a 3 mol·L⁻¹ solution. -1 The aqueous solution is prepared for use.

[0079] Dissolve 4.662 g (10 mmol) of dodecyl tellurium in 10 mL of dichloromethane, and add 3 mol·L⁻¹ -1 10 mL of an aqueous hydrogen peroxide solution was thoroughly mixed and reacted at 35 °C for 10 hours. The organic phase in the reaction system was then added to petroleum ether, a poor solvent, and the mixture was filtered, washed, and dried to obtain a dodecyl telluride prepolymer. GPC analysis showed that the number average molecular weight of this prepolymer was 3.86 × 10⁻⁶. 3 g / mol, molecular weight distribution is 2.42, degree of polymerization m = 8.

[0080] Dissolve 2.738 g (10 mmol) of dimethoxypropyl tellurium in 10 mL of tetrahydrofuran, and add 3 mol·L⁻¹ -110 mL of an aqueous hydrogen peroxide solution was thoroughly mixed and reacted at 15 °C for 8 hours. The organic phase in the reaction system was then added to petroleum ether, a poor solvent, and the mixture was filtered, washed, and dried to obtain dimethoxypropyl tellurium prepolymer. GPC analysis showed that the number average molecular weight of this prepolymer was 1.62 × 10⁻⁶. 3 g / mol, molecular weight distribution is 1.98, degree of polymerization n = 5.

[0081] 3.00 g of dodecyl telluride prepolymer and 1.00 g of dimethoxypropyl telluride prepolymer were dissolved in 20 mL of toluene and thoroughly mixed. 0.008 g of stannous octoate was added, and the mixture was reacted at 45 °C for 10 hours, followed by decompression to remove small molecules. After the reaction was complete, the organic phase was added to methanol, a poor solvent, filtered, washed, and dried to obtain block copolymer P3. GPC analysis showed that the number-average molecular weight of P3 was 4.24 × 10⁻⁶. 4 It has a molecular weight distribution of 3.68 g / mol and no glass transition temperature in the range of -50 to 80 °C as determined by DSC.

[0082] Example 4

[0083] The prepolymer was prepared in the same manner as in Example 3, except that the condensation catalyst was replaced with 0.01 g of tetrabutyl titanate, and the reaction was carried out at 100°C for 6 hours, followed by decompression to remove small molecules. After the reaction, the organic phase was added to methanol, a poor solvent, filtered, washed, and dried to obtain the block copolymer P4. GPC analysis showed that the number average molecular weight of P4 was 3.91 × 10⁻⁶. 4 It has a molecular weight distribution of 2.83 g / mol and no glass transition temperature in the range of -50 to 80 °C as determined by DSC.

[0084] Example 5

[0085] 70 wt% tert-butyl hydroperoxide was diluted with water to prepare a 6 mol·L⁻¹ solution. -1 The aqueous solution is prepared for use.

[0086] Dissolve 2.418 g (10 mmol) of dibutyltellurium in 10 mL of ethyl acetate, and add 6 mol·L⁻¹ -1 10 mL of an aqueous solution of tert-butyl hydrogen peroxide was thoroughly stirred and reacted at 0 °C for 10 hours. The organic phase in the reaction system was then added to petroleum ether, a poor solvent, and the mixture was filtered, washed, and dried to obtain the dibutyltellurium prepolymer. GPC analysis showed that the number average molecular weight of this prepolymer was 1.58 × 10⁻⁶. 3 g / mol, molecular weight distribution is 1.89, degree of polymerization m=16.

[0087] Dissolve 4.220 g (10 mmol) of bis(monomethyl) ether triethylene glycol tellurium in 10 mL of tetrahydrofuran, and add 6 mol·L⁻¹ -110 mL of an aqueous solution of tert-butyl hydrogen peroxide was thoroughly stirred and reacted at 20 °C for 8 hours. The organic phase in the reaction system was then added to petroleum ether, a poor solvent, and the mixture was filtered, washed, and dried to obtain a dimonomethyl ether triethylene glycol tellurium prepolymer. GPC analysis showed that the number average molecular weight of this prepolymer was 2.23 × 10⁻⁶. 3 g / mol, molecular weight distribution is 2.36, degree of polymerization n = 4.

[0088] 2.00 g of dibutyl tellurium prepolymer and 2.00 g of dimethyl ether triethylene glycol tellurium prepolymer were dissolved in 20 mL of toluene and thoroughly mixed. 0.4 g of pyridine was added, and the mixture was reacted at 50 °C for 9 hours, followed by decompression to remove small molecules. After the reaction, the organic phase was added to petroleum ether, a poor solvent, filtered, washed, and dried to obtain block copolymer P5. GPC analysis showed that the number average molecular weight of P5 was 2.50 × 10⁻⁶. 4 It has a molecular weight distribution of 2.60 g / mol and no glass transition temperature in the range of -50 to 80 °C as determined by DSC.

[0089] Example 6

[0090] The prepolymer was prepared in the same manner as in Example 5, except that the condensation catalyst was replaced with 0.01 g of tetraisopropyl titanate, and the reaction was carried out at 90°C for 7 hours, followed by decompression to remove small molecules. After the reaction, the organic phase was added to the unsuitable solvent petroleum ether, filtered, washed, and dried to obtain the block copolymer P6. GPC analysis showed that the number average molecular weight of P6 was 2.79 × 10⁻⁶. 4 It has a molecular weight distribution of 2.55 g / mol and no glass transition temperature in the range of -50 to 80 °C as determined by DSC.

[0091] Example 7

[0092] 4.662 g (10 mmol) of didodecyl tellurium was dissolved in 10 mL of dichloromethane, and 5.076 g (20 mmol) of elemental iodine was added. After removing the solvent and unreacted elemental iodine, diiododecyl tellurium diiodocyanine was obtained. 7.200 g (10 mmol) of diiododecyl tellurium diiodocyanine was dissolved in 10 mL of acetonitrile and thoroughly mixed with deionized water. After the reaction was complete, ethanol, a poor solvent, was added to the reaction system. The mixture was filtered, washed, and dried to obtain the didodecyl tellurium prepolymer. GPC analysis showed that the number average molecular weight of this prepolymer was 2.98 × 10⁻⁶. 3 g / mol, molecular weight distribution is 2.53, degree of polymerization m = 7.

[0093] 4.220 g (10 mmol) of diisomethyl ether triethylene glycol tellurium was dissolved in 10 mL of ethyl acetate, and 3.807 g (15 mmol) of elemental iodine was added. After removing the solvent and unreacted elemental iodine, diiodoisomethyl ether triethylene glycol tellurium was obtained. 6.758 g (10 mmol) of diiodododecyl tellurium was dissolved in 10 mL of N,N-dimethylformamide and thoroughly mixed with deionized water. After the reaction was complete, hexane, a poor solvent, was added to the reaction system. The mixture was filtered, washed, and dried to obtain the diisomethyl ether triethylene glycol tellurium prepolymer. GPC analysis showed that the number average molecular weight of this prepolymer was 2.12 × 10⁻⁶. 3 g / mol, molecular weight distribution is 2.31, degree of polymerization n = 4.

[0094] 1.50 g of didodecyl telluride prepolymer and 2.50 g of dimonomethyl ether triethylene glycol telluride prepolymer were dissolved in 20 mL of toluene and thoroughly mixed. 0.002 g of dibutyltin oxide was added, and the mixture was reacted at 45 °C for 15 hours, followed by decompression to remove small molecules. After the reaction, the organic phase was added to petroleum ether, a poor solvent, filtered, washed, and dried to obtain block copolymer P7. GPC analysis showed that the number-average molecular weight of P7 was 2.85 × 10⁻⁶. 4 It has a molecular weight distribution of 3.55 g / mol and no glass transition temperature in the range of -50 to 80 °C as determined by DSC.

[0095] Example 8

[0096] The prepolymer was prepared in the same manner as in Example 7, except that the condensation catalyst was replaced with 0.03 g of dibutyltin oxide, and the reaction was carried out at 40°C for 10 hours, followed by depressurization to remove small molecules. After the reaction, the organic phase was added to the unsuitable solvent petroleum ether, filtered, washed, and dried to obtain the block copolymer P8. GPC analysis showed that the number average molecular weight of P8 was 3.23 × 10⁻⁶. 4 It has a molecular weight distribution of 3.60 g / mol and no glass transition temperature in the range of -50 to 80 °C as determined by DSC.

[0097] Example 9

[0098] 2.738 g (10 mmol) of dimethoxypropyl tellurium was dissolved in 10 mL of dimethyl sulfoxide, and 4.794 g (30 mmol) of liquid bromine was added. After removing the solvent and unreacted liquid bromine, dibromodimethoxypropyl tellurium was obtained. 4.336 g (10 mmol) of dibromodimethoxypropyl tellurium was dissolved in 10 mL of 1,4-dioxane and thoroughly mixed with deionized water. After the reaction was complete, diethyl ether, a poor solvent, was added to the reaction system. The mixture was filtered, washed, and dried to obtain the dimethoxypropyl tellurium prepolymer. GPC analysis showed that the number average molecular weight of this prepolymer was 1.59 × 10⁻⁶. 3 g / mol, molecular weight distribution is 2.03, degree of polymerization m = 5.

[0099] 3.339 g (10 mmol) of dibromodimethyl ether diethylene glycol tellurium was dissolved in 10 mL of N-methylpyrrolidone, and 6.392 g (40 mmol) of liquid bromine was added. After removing the solvent and unreacted liquid bromine, dibromodimethyl ether diethylene glycol tellurium was obtained. 4.937 g (10 mmol) of dibromodimethyl ether diethylene glycol tellurium was dissolved in 10 mL of acetonitrile and thoroughly mixed with deionized water. After the reaction was complete, hexane, a poor solvent, was added to the reaction system. The mixture was filtered, washed, and dried to obtain the dibromodimethyl ether diethylene glycol tellurium prepolymer. GPC analysis showed that the number average molecular weight of this prepolymer was 1.95 × 10⁻⁶. 3 g / mol, molecular weight distribution is 2.18, degree of polymerization n = 5.

[0100] 2.80 g of dimethoxypropyl tellurium prepolymer and 1.20 g of di(monomethyl ether) diethylene glycol tellurium prepolymer were dissolved in 20 mL of toluene and thoroughly mixed. 0.002 g of dibutyltin dilaurate was added, and the mixture was reacted at 50 °C for 11 hours, followed by decompression to remove small molecules. After the reaction, the organic phase was added to petroleum ether, a poor solvent, filtered, washed, and dried to obtain block copolymer P9. GPC analysis showed that the number-average molecular weight of P9 was 3.75 × 10⁻⁶. 4 It has a molecular weight distribution of 2.74 g / mol and no glass transition temperature in the range of -50 to 80 °C as determined by DSC.

[0101] Example 10

[0102] The prepolymer was prepared in the same manner as in Example 9, except that the condensation catalyst was replaced with 0.6 g DBU, and the reaction was carried out at 60 °C for 8 hours, followed by depressurization to remove small molecules. After the reaction, the organic phase was added to the unsuitable solvent petroleum ether, filtered, washed, and dried to obtain the block copolymer P10. GPC analysis showed that the number average molecular weight of P10 was 3.26 × 10⁻⁶. 4 It has a molecular weight distribution of 2.68 g / mol and no glass transition temperature in the range of -50 to 80 °C as determined by DSC.

[0103] Example 11

[0104] Dilute a 30% hydrogen peroxide aqueous solution with water to prepare a 3 mol·L⁻¹ solution. -1 The aqueous solution is prepared for use.

[0105] Dissolve 4.662 g (10 mmol) of dodecyl tellurium in 10 mL of dichloromethane, and add 3 mol·L⁻¹ -110 mL of an aqueous hydrogen peroxide solution was thoroughly mixed and reacted at 35 °C for 10 hours. The organic phase in the reaction system was then added to petroleum ether, a poor solvent, and the mixture was filtered, washed, and dried to obtain a dodecyl telluride prepolymer. GPC analysis showed that the number average molecular weight of this prepolymer was 3.86 × 10⁻⁶. 3 g / mol, molecular weight distribution is 2.42, degree of polymerization m = 8.

[0106] Dissolve 2.979 g (10 mmol) of dihexyltelluride in 10 mL of dichloromethane, and add 5 mol·L⁻¹ -1 10 mL of an aqueous hydrogen peroxide solution was thoroughly mixed and reacted at 40 °C for 60 hours. The organic phase in the reaction system was then added to methanol, a poor solvent, and the mixture was filtered, washed, and dried to obtain dihexyltellurium prepolymer. GPC analysis showed that the number average molecular weight of this prepolymer was 7.60 × 10⁻⁶. 3 g / mol, molecular weight distribution is 2.38, degree of polymerization n = 24.

[0107] 2.00 g of dodecyl telluride prepolymer and 2.00 g of dihexyl telluride prepolymer were dissolved in 20 mL of toluene and thoroughly mixed. 0.004 g of dibutyltin dilaurate was added, and the mixture was reacted at 60 °C for 8 hours, followed by decompression to remove small molecules. After the reaction, the organic phase was added to methanol, a poor solvent, filtered, washed, and dried to obtain the block copolymer P11. GPC analysis showed that the number-average molecular weight of P11 was 3.54 × 10⁻⁶. 4 It has a molecular weight distribution of 3.26 g / mol and a glass transition temperature of 70℃ as determined by DSC.

[0108] Comparative Example 1

[0109] 3.540 g (10 mmol) of dioctyl tellurium and 2.979 g (10 mmol) of dihexyl tellurium were dissolved in 20 mL of dichloromethane to obtain component 1. A 30% aqueous solution of hydrogen peroxide was diluted with water to prepare a 5 mol·L⁻¹ solution. -1 Component 2 was obtained by reacting an aqueous solution of the solution. 20 mL of component 2 was added to 20 mL of component 1, and the mixture was stirred thoroughly and allowed to react for 48 hours. The organic phase in the reaction system was then added to methanol, a poor solvent, and the mixture was filtered, washed, and dried to obtain a random copolymer of poly(dioctyl tellurium) and dihexyl tellurium, Pc1. GPC analysis showed that the number-average molecular weight of this random copolymer was 3.04 × 10⁻⁶. 4 The sample has a molecular weight distribution of 2.79 and a glass transition temperature of 50°C, as determined by DSC. A comparison of the DSC results with Example 1 is shown below. Figure 1 .

[0110] Comparative Example 2

[0111] Dilute a 30% hydrogen peroxide aqueous solution with water to prepare a 5 mol·L⁻¹ solution.-1 The aqueous solution is prepared for use.

[0112] Dissolve 3.540 g (10 mmol) of dioctyltelluride in 10 mL of dichloromethane, and add 5 mol·L⁻¹ -1 10 mL of an aqueous hydrogen peroxide solution was thoroughly mixed and reacted at 25 °C for 1 hour. The organic phase in the reaction system was then added to methanol, a poor solvent, and the mixture was filtered, washed, and dried to obtain the dioctyl tellurium prepolymer. GPC analysis showed that the number average molecular weight of this prepolymer was 1.51 × 10⁻⁶. 3 g / mol, molecular weight distribution is 2.04, degree of polymerization m = 4.

[0113] Dissolve 2.979 g (10 mmol) of dihexyltelluride in 10 mL of dichloromethane, and add 5 mol·L⁻¹ -1 10 mL of an aqueous hydrogen peroxide solution was thoroughly mixed and reacted at 40 °C for 60 hours. The organic phase in the reaction system was then added to methanol, a poor solvent, and the mixture was filtered, washed, and dried to obtain dihexyltellurium prepolymer. GPC analysis showed that the number average molecular weight of this prepolymer was 7.60 × 10⁻⁶. 3 The molecular weight distribution is 2.38 g / mol, and the degree of polymerization is n = 24. The m:n = 1:6, which is outside the range of 1:4 to 4:1.

[0114] 2.00 g of dioctyl telluride prepolymer and 2.00 g of dihexyl telluride prepolymer were dissolved in 20 mL of toluene and thoroughly mixed. 0.004 g of dibutyltin dilaurate was added, and the mixture was reacted at 60 °C for 8 hours, followed by decompression to remove small molecules. After the reaction, the organic phase was added to methanol, a poor solvent, filtered, washed, and dried to obtain the block copolymer Pc2. GPC analysis showed that the number-average molecular weight of Pc2 was 3.37 × 10⁻⁶. 4 The sample has a molecular weight distribution of 2.80 and a glass transition temperature of 47°C as determined by DSC. A DSC comparison with Example 1 is shown below. Figure 1 .

[0115] The various embodiments of the present invention have been described above. These descriptions are exemplary and not exhaustive, nor are they limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments.

[0116] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

Claims

1. A block polytellurethane, characterized in that, The structure of the polytellurethane is shown in formula (1): In formula (1), R1 and R2 are different and are each independently selected from at least one of unsubstituted or terminally substituted alkyl groups from C2 to C20 and unsubstituted or terminally substituted oligooxyethylene groups from C2 to C20; m and n are each independently any integer from 3 to 24, preferably any integer from 4 to 20, and m:n is 1:4 to 4:

1.

2. The block polytellurethane according to claim 1, wherein, The substituents of the terminal group are selected from C1-C4 alkoxy groups.

3. The block polytellurethane according to claim 2, wherein, R1 and R2 are each independently selected from at least one of an unsubstituted or terminally substituted alkyl group having the structure of formula (2) and an unsubstituted or terminally substituted oligooxyethylene having the structure of formula (3); In formula (2), x is any integer from 2 to 18, and R3 is selected from at least one of methyl and C1-C4 alkoxy groups, preferably methyl or methoxy. In formula (3), y is any integer from 1 to 10, and R4 is a hydrogen atom or a methyl group, preferably a methyl group.

4. The block polytellurethane according to claim 1, wherein, The polytelluric acid has a number average molecular weight of 0.5 × 10⁻⁶. 4 ~20.0×10 4 g·mol -1 Preferably 1.0×10 4 ~15.0×10 4 g·mol -1 The molecular weight distribution is 1.8–5.0, preferably 2.0–4.

0.

5. The method for preparing the block polytellurethane according to any one of claims 1-4, characterized in that, Includes the following steps: (1) Obtain prepolymers with telluryl end groups as shown in formula (4) and formula (5), respectively; (2) In the presence of a first organic solvent and a catalyst, the prepolymers with tellurol end groups shown in formulas (4) and (5) are subjected to a condensation reaction. After the reaction is completed, the block polytelluric alkane is separated and purified. In equations (4) and (5), R1, R2, m and n are defined as in equation (1).

6. The preparation method according to claim 5, wherein, In step (2), the first organic solvent is selected from at least one of dichloromethane, chloroform, tetrahydrofuran, acetonitrile, toluene, ethyl acetate, dimethylformamide, dimethyl sulfoxide, 1,4-dioxane and N-methylpyrrolidone; The catalyst is selected from at least one of organic bases, organotin compounds and organotitanium compounds, preferably from at least one of triethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, dibutyltin dilaurate, dibutyltin oxide, tetraisopropyl titanate and tetrabutyl titanate; The mass ratio of the prepolymers with telluryl end groups shown in formulas (4) and (5) is 0.1 to 10:1; The amount of the catalyst used is 0.01 to 20 wt% of the total amount of the prepolymers with telluryl end groups as shown in formulas (4) and (5); The conditions for the condensation reaction include: a reaction temperature of -20℃ to 150℃, preferably 0 to 100℃, and a reaction time of 1 to 100 h, preferably 3 to 50 h.

7. The preparation method according to claim 5, wherein, In step (1), the prepolymers with tellurol end groups shown in formulas (4) and (5) are obtained independently by interfacial polymerization or hydrolytic polymerization.

8. The preparation method according to claim 7, wherein, The interface aggregation method includes the following steps: In the presence of a second organic solvent, the first tellurium-containing monomer and an oxidant are subjected to an interfacial polymerization reaction. After the reaction is completed, a first undesirable solvent is added dropwise to precipitate and separate the prepolymer with tellurol end groups.

9. The preparation method according to claim 8, wherein, The oxidant is provided in the form of an aqueous solution, and the oxidant is selected from at least one of hydrogen peroxide, tert-butyl hydroperoxide and cumene hydroperoxide. The second organic solvent is selected from at least one of dichloromethane, chloroform, tetrahydrofuran, acetonitrile, toluene, ethyl acetate, dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, and N-methylpyrrolidone; The first undesirable solvent is selected from at least one of methanol, ethanol, petroleum ether, n-hexane, and diethyl ether; The amount of the first tellurium-containing monomer and the oxidant added is such that the molar concentration of the first tellurium-containing monomer in the polymerization system is 0.05–2 mol·L⁻¹. -1 The molar concentration of the oxidant is 0.1–6 mol·L⁻¹. -1 ; The conditions for the interfacial polymerization reaction include: a reaction temperature of -20℃ to 100℃, preferably 0 to 50℃, and a reaction time of 1 to 100 h, preferably 4 to 70 h.

10. The preparation method according to claim 7, wherein, The hydrolysis-polymerization method includes the following steps: Under the presence of a third organic solvent, a tellurium dihalogen monomer and deionized water are subjected to a hydrolysis polymerization reaction. After the reaction is completed, a second undesirable solvent is added dropwise to precipitate and separate the prepolymer with tellurol end groups.

11. The preparation method according to claim 10, wherein, The third organic solvent is selected from at least one of dichloromethane, chloroform, tetrahydrofuran, acetonitrile, toluene, ethyl acetate, dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, and N-methylpyrrolidone; The second undesirable solvent is selected from at least one of methanol, ethanol, petroleum ether, n-hexane, and diethyl ether; The amount of tellurium dihalogen monomer added resulted in a molar concentration of 0.05–2 mol·L⁻¹ in the polymerization system. -1 ; The conditions for the hydrolysis-polymerization reaction include: a reaction temperature of -20℃ to 150℃, preferably 0 to 100℃, and a reaction time of 1 to 100 h, preferably 2 to 40 h.

12. The preparation method according to claim 10, wherein, The tellurium dihalogen monomer is selected from at least one of the monomers having the structures shown in formula (8) and formula (9); In equations (8) and (9), R3, R4, x and y are as defined in equations (2) and (3); R5 and R6 are each independently selected from at least one of chlorine, bromine and iodine.

13. The preparation method according to claim 12, wherein, The tellurium dihalogen compound is prepared according to the following steps: a second tellurium monomer is dissolved in a fourth organic solvent, and then a halogen is added to react. After the reaction is completed, the solvent is removed, the compound is purified, and dried to obtain the tellurium dihalogen compound.

14. The preparation method according to claim 13, wherein, The halogen is selected from at least one of chlorine, bromine and iodine; The fourth organic solvent is selected from at least one of dichloromethane, chloroform, tetrahydrofuran, acetonitrile, toluene, ethyl acetate, dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, and N-methylpyrrolidone; The molar ratio of the halogen element to the second tellurium-containing monomer is 1 to 10:

1.

15. The preparation method according to claim 8 or 13, wherein, The first tellurium-containing monomer and the second tellurium-containing monomer are each independently selected from at least one of the monomers having the structures shown in formula (6) and formula (7); In equations (6) and (7), R3, R4, x and y are defined as in equations (2) and (3).

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