A polyether ester-based thermoplastic elastomer and a method for preparing the same

Abstract

The application provides a polyether ester-based thermoplastic elastomer and a preparation method thereof, and belongs to the field of high polymer materials. Specifically, a random copolymer of an alkylene oxide and a lactone is used as a soft segment, and a levorotatory polylactic acid, a dextrorotatory polylactic acid, a racemic polylactic acid, a polyglycolide, a polycaprolactone or a polypentolactone is used as a hard segment; a homogeneous or heterogeneous bimetallic catalyst and a cheap and easily available cocatalyst are used to prepare a triblock elastomer through a one-pot two-step method; the performance of the elastomer can be directly controlled by adjusting the raw material addition ratio; and a series of polyether ester-based thermoplastic elastomers with controllable performance are prepared. The polyether ester-based thermoplastic elastomer has a use window temperature of -65-170 DEG C, a maximum tensile strength of 5-50 MPa and an elongation at break of 300-1500%.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials, specifically relating to a polyether ester-based thermoplastic elastomer and its preparation method. Background Technology

[0002] Thermoplastic elastomers (TPEs) are a new type of polymer material that combines the physical and mechanical properties of vulcanized rubber with the processing properties of plastics. Unlike traditional rubber, which requires heat vulcanization and other processes, TPEs can be manufactured into final products using only simple plastic processing machinery. This characteristic shortens the rubber industry production process by nearly a quarter, saves 25-40% of energy consumption, and increases efficiency by 10-20 times, representing a technological revolution in the rubber industry. Currently, TPEs are widely used in the automotive, construction, adhesive, and electronic communications industries, and show great promise in other sectors as well. Therefore, developing new TPE structures and their production and application technologies has become a global research focus. To this end, this invention provides a polyether ester-based thermoplastic elastomer and its preparation method. Specifically, triblock elastomers are prepared using random copolymers of epoxides and lactones as soft segments and polylactic acid (PLA), polylactic acid (PLA), racemic PLA, polyglycolic acid, polycaprolactone, or polyvalerol as hard segments. Homogeneous or heterogeneous bimetallic catalysts and inexpensive and readily available co-catalysts are used. The properties of the elastomers can be directly controlled by adjusting the ratio of raw materials added, thereby preparing a series of polyether ester-based thermoplastic elastomers with controllable properties. Summary of the Invention

[0003] The main content of this invention is to provide a polyether ester-based thermoplastic elastomer with controllable performance and its preparation method, based on the shortcomings of existing technologies.

[0004] Technical solution of the present invention

[0005] A polyether ester-based thermoplastic elastomer, characterized by using a random copolymer of polyether ester obtained by ring-opening copolymerization of epoxides and lactones as the soft segment, and a homopolymer of lactone as the hard segment, to obtain a polyether ester-based thermoplastic elastomer with an adjustable ratio of soft and hard segments through a one-pot, two-step process. The preparation route is as follows:

[0006]

[0007] The specific preparation process of the elastomer is as follows: Epoxy alkane and lactone 1 are added to a reactor, along with a homogeneous or heterogeneous bimetallic catalyst, a co-catalyst, an initiator, and an organic solvent. After heating, the first polymerization reaction is carried out to obtain a polyether ester random copolymer as the soft segment. Lactone 2 is added in situ according to the designed mass ratio of soft and hard segments of the polyether ester-based thermoplastic elastomer. Organic solvents are selectively added to ensure good system flowability, and the second polymerization reaction is carried out. This yields a polyester-polyether ester random copolymer-polyester triblock polymer, i.e., a hard-soft-hard triblock polymer. Finally, the crude product is dissolved in a small amount of dichloromethane, then a large amount of n-hexane is added, and the mixture is stirred vigorously to precipitate the polymer. Vacuum drying yields the polyether ester-based thermoplastic elastomer.

[0008] Furthermore, the synthesis equation for the homogeneous bimetallic catalyst used is as follows:

[0009]

[0010] In the formula:

[0011]

[0012] M is Cr 2+ Fe 2+ Mn 2+ Co 2+ Zn 2+ Mg 2+ Cu 2+ or Ni 2+ ;

[0013] R 1 and R 2 It is an H, C1-C6 alkyl, C1-C6 alkoxy, Cl, Br, F, or NO2 group; R 1 and R 2 Same or different;

[0014] Organic solvent 1 is dichloromethane;

[0015] Organic solvent 2 is one of toluene, dichloromethane, tetrahydrofuran, and 1,4-dioxane;

[0016] The metal chloride salt is one of chromium chloride, manganese chloride, ferrous chloride, cobalt chloride, zinc chloride, copper chloride, and nickel chloride; the alkyl metal is n-butylmagnesium.

[0017] The specific preparation steps of the homogeneous bimetallic catalyst are as follows: Raw material 1 and raw material 2 are mixed in a molar ratio of 1.0~1.5:1 and dissolved in organic solvent 1 in a mass ratio of 3~5:1 to raw material 1. The mixture is stirred at room temperature for 1~5 h. Then, raw material 3 or raw material 4 in a molar ratio of 1:2.0~2.3 to raw material 1 is added. The mixture is stirred at room temperature for 12~24 h. The reaction is stopped, the mixture is filtered, the filter cake is washed with organic solvent 1, and the solvent is removed by rotary evaporation to obtain the crude product. The crude product is separated and purified by column chromatography to obtain homogeneous binuclear metal ligand A or homogeneous binuclear metal ligand B. The obtained solid is dried under vacuum for 12~24 h and transferred to a glove box for later use. In the glove box, homogeneous binuclear metal ligand A or homogeneous binuclear metal ligand B is weighed and dissolved in organic solvent 2 in a mass ratio of 10~20:1 to the ligand. A metal chloride salt or alkyl metal in a molar ratio of 2.0~2.2:1 to the ligand is weighed. The reaction is carried out at room temperature for 1–12 h. The organic solvent is removed under vacuum to obtain homogeneous bimetallic catalyst A or homogeneous bimetallic catalyst B.

[0018] The structure of the heterogeneous bimetallic catalyst used is as follows:

[0019]

[0020] In the formula:

[0021] M1 is Cr 3+ Mn 3+ Co 3+ Fe 3+ Al 3+ One of them; M2 is Mg 2+ Co 2+ Zn 2+ Fe 2+ Mn 2+ Cu 2+ Ni 2+ One of them; X is OH − Cl − ,Br − CH3COO − NO3 − CF3COO − 2,4-dinitrophenoloxy, o-nitrophenoloxy, p-nitrophenoloxy, or m-nitrophenoloxy; CA is a complexing agent, which is one of n-butanol, isobutanol, tert-butanol, n-propanol, isopropanol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, glycerol, pentaerythritol, or water.

[0022] The solvent is deionized water;

[0023] The specific preparation steps of the heterogeneous bimetallic catalyst are as follows: Raw material 6 is dissolved in raw material 7 at a mass ratio of 10-20:1, and the mixture is stirred vigorously until dissolved. Then, raw material 5 at a mass ratio of 1.8-3.0:1 to raw material 6 is dissolved in a solvent and added dropwise at a uniform rate to the system composed of raw materials 6 and 7 over 10-60 minutes, wherein the mass ratio of solvent to raw material 5 is 20-50:1. The mixture is heated to 40-70 °C and stirred continuously for 3-5 hours. After the reaction is complete, the mixture is cooled, centrifuged, and vacuum dried to constant weight to obtain the heterogeneous bimetallic catalyst.

[0024] The co-catalyst used is one of the following: tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium acetate, tetrabutylammonium tribromide, tetrabutylammonium nitrate, tetrabutylammonium hydrogen sulfate, tetrabutylammonium fluoride, benzyltriethylammonium chloride, benzyltripropylammonium chloride, benzyltributylammonium chloride, benzyltributylammonium bromide, hexadecyltrimethylammonium chloride, dodecyltrimethylammonium chloride, bis(triphenyl)phosphine ammonium chloride, methyltriphenylphosphine bromide, and allyltriphenylphosphine bromide.

[0025] The molar ratio of homogeneous or heterogeneous bimetallic catalysts, co-catalysts and epoxides used is 1:1:1000~10000.

[0026] The initiators used are 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, o-phenylenediol, iso-phenylenediol, or terephthalic acid; the molar ratio of the initiator to the epoxide is 1~100:10000.

[0027] The epoxides used are one of the following: ethylene oxide, propylene oxide, 1,2-epoxidebutane, 1,2-epoxidehexane, 1,2-epoxideoctane, 1,2-epoxidedecane, 1,2-epoxidedodecane, epichlorohydrin, epichlorohydrin, 2,3-epoxidebutane, methyl glycidyl ether, ethyl glycidyl ether, isopropyl glycidyl ether, tert-butyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, and benzyl glycidyl ether; lactone 1 is one of the following: β-butyrolactone, β-propiolactone, δ-valerolactone, ε-caprolactone, and ε-decyllactone; lactone 2 is one of the following: δ-valerolactone, ε-caprolactone, L-lactide, D-lactide, racemic lactide, and glycolide.

[0028] The molar ratio of alkyl epoxide to lactone 1 used is 1:5 to 5:1. The structure of the polyether ester random copolymer (polyether:polyether ester:polyester) can be precisely controlled within the range of 10 to 70:15 to 18:12 to 75 by changing the feed ratio of alkyl epoxide to lactone 1.

[0029] The reaction temperature of the first polymerization reaction is 30–100°C, and the reaction time is 1–48 h.

[0030] The mass ratio of lactone 2 to the "soft" segment is 1:0.2~5.

[0031] The reaction temperature for the second polymerization step is 60~100 ℃, and the reaction time is 6~18 h.

[0032] The organic solvent used in the first and second polymerization reactions is one of 1,4-dioxane, tetrahydrofuran, toluene, diethanol dimethyl ether, and diethylene glycol dimethyl ether.

[0033] Beneficial effects of the present invention

[0034] (1) The “soft” segment of the polyether ester-based thermoplastic elastomer described in this invention is made from epoxy alkane and lactone. The crystallization properties of the soft segment can be controlled by adjusting the ratio of the two, thereby affecting the properties of the elastomer.

[0035] (2) The “hard” segment of the polyether ester-based thermoplastic elastomer of the present invention is one of L-polylactic acid, D-polylactic acid, racemic polylactic acid, and polyglycolic acid. The mass ratio of the “hard” segment to the “soft” segment is adjustable from 1:0.2 to 5. The maximum tensile strength of the elastomer is adjustable from 5 to 50 MPa. The elongation at break of the elastomer is 300 to 1500%.

[0036] (3) The polyether ester-based thermoplastic elastomer of the present invention is prepared by a “one-pot two-step method”, which is simple, low-cost and has the prospect and potential for large-scale production. Attached Figure Description

[0037] Figure 1 The nuclear magnetic resonance hydrogen spectrum of the elastomer prepared in Example 1. Detailed Implementation

[0038] The technical solution of the present invention will be further described below through embodiments.

[0039] Unless otherwise stated, the terms used in this invention generally have the meanings commonly understood by those skilled in the art.

[0040] In the following embodiments, various processes and methods not described in detail are conventional methods known in the art. Furthermore, due to the diverse proportions of polymer structures, not all preparation methods are described in detail; instead, typical examples are used to illustrate the specific process steps of the present invention.

[0041] In this invention, the catalysts used are numbered as shown in the following formula, and the specific process steps for preparing the catalysts will be described by way of examples.

[0042]

[0043]

[0044]

[0045] Example 1

[0046] A 150 mL pressure-resistant bottle equipped with a magnetic inlet was dried at 120 °C for more than 12 h, evacuated, and allowed to cool to room temperature before being placed in a glove box for use. Under argon protection, a certain amount of catalyst 1a (78.50 mg, 0.086 mmol), co-catalyst tetramethylammonium chloride (9.44 mg, 0.086 mmol), and initiator 1,4-butanediol (15.52 mg, 0.172 mmol) were weighed at room temperature and placed in the pressure-resistant bottle, with a molar ratio of catalyst to co-catalyst of 1:1. Then, propylene oxide (10.00 g, 172.18 mmol) was added, with a molar ratio of propylene oxide to catalyst of 2000:1 and a molar ratio of propylene oxide to initiator of 2000:1. Next, ε-caprolactone (19.65 g, 172.18 mmol) was added in a 1 / 1 molar ratio with propylene oxide. Finally, toluene (50.00 g) was added at five times the mass of propylene oxide. The mixture was then placed in an oil bath at 30 °C and magnetically stirred. After reacting for 48 h, stirring was stopped, yielding a "soft segment". A very small amount of the reaction solution was taken for analysis. 1 ¹H NMR analysis was used to calculate the conversion rate and characterize the structure of the "soft" segment, revealing that it contained polyether, polyether ester, and polyester segments in a ratio of approximately 23:18:59. L-lactide was added in situ at a mass ratio of 1:1 to the soft segment, and the mixture was heated to 60°C for 12 hours to obtain a triblock polymer. Finally, the crude product was dissolved in a small amount of dichloromethane, followed by the addition of a large amount of n-hexane and vigorous stirring to precipitate the polymer. After vacuum drying, the elastomer was obtained. Thermal performance testing showed that the elastomer had a service window temperature of -60 to 155 °C. Mechanical performance testing showed that the elastomer had a maximum tensile strength of 32 MPa and an elongation at break of 625%.

[0047] Example 2

[0048] A 150 mL pressure-resistant bottle equipped with a magnetic inlet was dried at 120 °C for more than 12 h, evacuated, and allowed to cool to room temperature before being placed in a glove box for use. Under argon protection, a certain amount of catalyst 1b (45.13 mg, 0.045 mmol), co-catalyst tetramethylammonium chloride (12.62 mg, 0.045 mmol), and initiator 1,4-butanediol (40.92 mg, 0.454 mmol) were weighed at room temperature and placed in the pressure-resistant bottle, with a molar ratio of catalyst to co-catalyst of 1:1. Then, ethylene oxide (10.00 g, 227.00 mmol) was added, with a molar ratio of ethylene oxide to catalyst of 5000:1 and a molar ratio of propylene oxide to initiator of 500:1. Next, δ-valerol (22.73 g, 227.00 mmol) was added in a 1 / 1 molar ratio with ethylene oxide. Finally, 1,4-dioxane (50.00 g) was added at five times the mass of ethylene oxide. The mixture was then placed in an oil bath at 60 °C and magnetically stirred. After reacting for 26 h, stirring was stopped, yielding a "soft segment". A very small amount of the reaction solution was taken for analysis. 1 ¹H NMR analysis was used to calculate the conversion rate and characterize the structure of the "soft" segment, revealing that it contained polyether, polyether ester, and polyester segments in a ratio of approximately 36:17:47. D-lactide was added in situ at a mass ratio of 1:5 to the soft segment, and the mixture was heated to 100°C for 16 h to obtain a triblock polymer. Finally, the crude product was dissolved in a small amount of dichloromethane, followed by the addition of a large amount of n-hexane and vigorous stirring to precipitate the polymer. After vacuum drying, the elastomer was obtained. Thermal performance testing showed that the elastomer had a service window temperature of -65 to 170°C. Mechanical performance testing showed that the elastomer had a maximum tensile strength of 50 MPa and an elongation at break of 300%.

[0049] Example 3

[0050] A 150 mL pressure-resistant bottle equipped with a magnetic inlet was dried at 120 °C for more than 12 h, evacuated, and allowed to cool to room temperature before being placed in a glove box for use. Under argon protection, a certain amount of catalyst 2a (25.33 mg, 0.026 mmol), co-catalyst tetrabutylammonium nitrate (7.86 mg, 0.026 mmol), and initiator phthalic acid (284.38 mg, 2.58 mmol) were weighed at room temperature and placed in the pressure-resistant bottle, with a molar ratio of catalyst to co-catalyst of 1:1. Then, add isopropyl glycidyl ether (30.00 g, 258.26 mmol), with a molar ratio of isopropyl glycidyl ether to catalyst of 10000:1 and a molar ratio of propylene oxide to initiator of 100:1. Next, add δ-valerolactone (5.17 g, 51.7 mmol), with a molar ratio of 1 / 0.2 to isopropyl glycidyl ether. Finally, add toluene (60.00 g), twice the mass of isopropyl glycidyl ether. Then, place the mixture in an oil bath at 100 °C and start magnetic stirring. After reacting for 1 h, stop stirring to obtain the "soft segment". Take a very small amount of the reaction solution for determination. 1 HNMR analysis was used to calculate the conversion rate and characterize the structure of the "soft" segment, revealing that it contained polyether, polyether ester, and polyester segments in a ratio of approximately 10:15:75. L-lactide was added in situ at a mass ratio of 1:0.2 to the soft segment, and the mixture was heated to 100°C for 18 hours to obtain a triblock polymer. Finally, the crude product was dissolved in a small amount of dichloromethane, followed by the addition of a large amount of n-hexane and vigorous stirring to precipitate the polymer. After vacuum drying, the elastomer was obtained. Thermal performance testing showed that the elastomer had a service window temperature of -58 to 140°C. Mechanical performance testing showed that the elastomer had a maximum tensile strength of 5 MPa and an elongation at break of 1500%.

[0051] Example 4

[0052] A 150 mL pressure-resistant bottle equipped with a magnetic inlet was dried at 120 °C for more than 12 h, evacuated, and allowed to cool to room temperature before being placed in a glove box for use. Under argon protection, a certain amount of catalyst 2b (9.49 mg, 0.010 mmol), co-catalyst bis(triphenyl)phosphine ammonium chloride (5.69 mg, 0.01 mmol), and initiator isophthalic acid (54.54 mg, 0.495 mmol) were weighed at room temperature and placed in the pressure-resistant bottle, with a molar ratio of catalyst to co-catalyst of 1:1. Then, 1,2-epoxybutane (5.00 g, 69.34 mmol) was added, with a molar ratio of 1,2-epoxybutane to catalyst of 7000:1 and a molar ratio of propylene oxide to initiator of 140:1. Next, β-butyrolactone (29.85 g, 346.71 mmol) was added in a molar ratio of 1 / 5 to 1,2-epoxybutane. Finally, toluene (15.00 g) with a mass three times that of 1,2-epoxybutane was added. The mixture was then placed in an oil bath at 80°C and magnetically stirred. After reacting for 10 h, stirring was stopped, yielding a "soft segment". A very small amount of the reaction solution was taken for analysis. 1 ¹H NMR analysis was used to calculate the conversion rate and characterize the structure of the "soft" segment, revealing that it contained polyether, polyether ester, and polyester segments in a ratio of approximately 70:18:12. δ-valerolactone was added in situ at a mass ratio of 1:2 to the soft segment, and the mixture was heated to 80°C for 12 hours to obtain a triblock polymer. Finally, the crude product was dissolved in a small amount of dichloromethane, followed by the addition of a large amount of n-hexane and vigorous stirring to precipitate the polymer. After vacuum drying, the elastomer was obtained. Thermal performance testing showed that the elastomer had a service window temperature of -53 to 60°C. Mechanical performance testing showed that the elastomer had a maximum tensile strength of 38 MPa and an elongation at break of 860%.

[0053] Example 5

[0054] A 150 mL pressure-resistant bottle equipped with a magnetic inlet was dried at 120 °C for more than 12 h, evacuated, and allowed to cool to room temperature before being placed in a glove box for use. Under argon protection, a certain amount of catalyst 3a (5 mg), co-catalyst tetrabutylammonium bromide (6.44 mg, 0.020 mmol), and initiator terephthalic acid (59.96 mg, 0.5 mmol) were weighed at room temperature and placed in the pressure-resistant bottle. The mass ratio of catalyst to 1,2-epoxyhexane was 1:2000. Then, 1,2-epoxyhexane (10.00 g, 99.84 mmol) was added, with a molar ratio of 1,2-epoxyhexane to co-catalyst of 5000:1 and a molar ratio of propylene oxide to initiator of 200:1. Next, ε-decanolide (17.00 g, 99.84 mmol) was added in a 1 / 1 molar ratio with 1,2-epoxyhexane. Finally, tetrahydrofuran (50 g) was added, five times the mass of 1,2-epoxyhexane. The mixture was then placed in an oil bath at 40 °C and magnetically stirred. After reacting for 26 h, stirring was stopped, yielding a "soft segment". A very small amount of the reaction solution was taken for analysis. 1 ¹H NMR analysis was used to calculate the conversion rate and characterize the structure of the "soft" segment, revealing that it contained polyether, polyether ester, and polyester segments in a ratio of approximately 25:20:55. Racemic lactide at a mass ratio of 1:1 to the soft segment was added in situ, and the mixture was heated to 60°C for 14 h to obtain a triblock polymer. Finally, the crude product was dissolved in a small amount of dichloromethane, followed by the addition of a large amount of n-hexane, and vigorous stirring was performed to precipitate the polymer. After vacuum drying, the elastomer was obtained. Thermal performance testing showed that the elastomer had a service window temperature of -60 to 60°C. Mechanical performance testing showed that the elastomer had a maximum tensile strength of 26 MPa and an elongation at break of 1020%.

[0055] Example 6

[0056] A 150 mL pressure-resistant bottle equipped with a magnetic inlet was dried at 120 °C for at least 12 h, evacuated, and allowed to cool to room temperature before being placed in a glove box for use. Under argon protection, a certain amount of catalyst 3b (10 mg), co-catalyst tetrabutylammonium chloride (47.9 mg, 0.170 mmol), and initiator phthalic acid (1.9 mg, 0.017 mmol) were weighed at room temperature and placed in the pressure-resistant bottle, with a catalyst-to-propylene oxide mass ratio of 1:1000. Propylene oxide (10.00 g, 172.18 mmol) was then added, with a propylene oxide-to-co-catalyst molar ratio of 1000:1 and a propylene oxide-to-initiator molar ratio of 10000:1. ε-caprolactone (9.83 g, 86.09 mmol) was added in a 2 / 1 molar ratio to propylene oxide. Finally, diethyl ether of diethanolamide (50 g) was added, which was five times the mass of propylene oxide. Then, it was placed in a 60 °C oil bath and magnetically stirred. The reaction was continued for 26 hours, after which stirring was stopped, yielding the "soft segment". A very small amount of the reaction solution was taken for analysis. 1 ¹H NMR analysis was used to calculate the conversion rate and characterize the structure of the "soft" segment, revealing that it contained polyether, polyether ester, and polyester segments in a ratio of approximately 60:18:22. L-lactide was added in situ at a mass ratio of 1:0.5 to the soft segment, and the mixture was heated to 60°C for 6 hours to obtain a triblock polymer. Finally, the crude product was dissolved in a small amount of dichloromethane, followed by the addition of a large amount of n-hexane and vigorous stirring to precipitate the polymer. After vacuum drying, the elastomer was obtained. Thermal performance testing showed that the elastomer had a service window temperature of -61 to 130°C. Mechanical performance testing showed that the elastomer had a maximum tensile strength of 32 MPa and an elongation at break of 920%.

[0057] Example 7

[0058] In a 250 mL three-necked flask equipped with a magnetic stir bar, cyclohexanediamine (2.5 g, 22 mmol) and 3,5-di-tert-butylsalicylaldehyde (5.13 g, 22 mmol) were mixed and dissolved in dichloromethane (15.39 g) at a mass ratio of 3:1 to 3,5-di-tert-butylsalicylaldehyde. The mixture was stirred at room temperature for 1 h. The reaction was monitored by thin-layer chromatography until the starting material spot disappeared or no longer changed. Then, 3,3'-diformyl-2,2'-dihydroxy-1,1'-biphenyl (2.65 g, 11 mmol) at a molar ratio of 1:2 to 3,5-di-tert-butylsalicylaldehyde was added. After stirring at room temperature for another 24 h, the reaction was stopped, the mixture was filtered, and the filter cake was washed several times with dichloromethane. The filtrate was then evaporated by rotary evaporation to remove the dichloromethane, yielding the crude product. The crude product was purified by column chromatography to obtain a yellow solid. The solid was dried under vacuum for 12 h and transferred to a glove box for later use. Weigh 0.5 g (576.55 mmol) of the yellow solid into a 50 mL single-necked flask equipped with a magnetic stirrup, and dissolve it in tetrahydrofuran (5 g) at a mass ratio of 10:1 to the yellow solid. Weigh 1.15 mL (1 M) of di-n-butylmagnesium at a molar ratio of 2:1 to the yellow solid and add it dropwise into the single-necked flask. React at room temperature for 12 h, and remove the tetrahydrofuran under vacuum to obtain the orange solid catalyst 1a. 1 H NMR (400 MHz, Chloroform-d) δ 8.69(s, 2H), 8.36 (s, 2H), 7.69 (d, J = 10.3 Hz, 4H), 7.06 (d, J = 7.7 Hz, 2H), 6.72 (s, 2H), 6.61 (t, J = 7.6 Hz, 2H), 3.62 (s, 2H), 3.42 (s, 2H), 2.06 (d,J = 23.4 Hz, 8H), 1.82 – 1.50 (m, 8H), 1.44 (s, 18H), 1.27 (s, 18H).

[0059] Example 8

[0060] In a 250 mL three-necked flask equipped with a magnetic stir bar, cyclohexanediamine (2.5 g, 22 mmol) and 5-tert-butylsalicylaldehyde (2.61 g, 14.7 mmol) were mixed and dissolved in dichloromethane (19.6 g) at a mass ratio of 5:1 to 5-tert-butylsalicylaldehyde. The mixture was stirred at room temperature for 5 h. The reaction was monitored by thin-layer chromatography until the starting material spot disappeared or no longer changed. Then, 3,3'-diformyl-2,2'-dihydroxy-1,1'-biphenyl (2.65 g, 11 mmol) at a molar ratio of 1:2 to 5-tert-butylsalicylaldehyde was added. After stirring at room temperature for another 12 h, the reaction was stopped, filtered, and the filter cake was washed several times with dichloromethane. The filtrate was then evaporated by rotary evaporation to remove the dichloromethane, yielding the crude product. The crude product was purified by column chromatography to obtain a yellow solid. The solid was dried under vacuum for 24 h and transferred to a glove box for later use. Weigh 0.5 g (0.663 mmol) of the yellow solid into a 50 ml single-necked flask equipped with a magnetic stirrup, and dissolve it in tetrahydrofuran (10 g) at a mass ratio of 20:1 to the yellow solid. Weigh 193 mg (1.458 mmol) of zinc chloride at a molar ratio of 2.2:1 to the yellow solid into the single-necked flask. React at room temperature for 1 h, and remove the tetrahydrofuran under vacuum to obtain the orange solid catalyst 1b. 1 H NMR (400 MHz, Chloroform-d) δ 8.96 (s, 2H), 8.32 (s, 2H), 7.51 (d, J = 7.6 Hz, 2H), 7.16 (s, 2H), 7.02 (dd, J = 13.0, 2.3 Hz, 2H), 6.93– 6.85 (m, 6H), 3.45 (d, J = 33.5 Hz, 4H), 2.09 – 1.81 (m, 8H), 1.81 – 1.64(m, 4H), 1.51 (d, J = 9.9 Hz, 4H), 1.36 (s, 18H).

[0061] Example 9

[0062] In a 250 mL three-necked flask equipped with a magnetic stir bar, 2,2-dimethylpropanediamine (2.25 g, 22 mmol) and 3-fluoro-5-tert-butylsalicylaldehyde (4.31 g, 22 mmol) were mixed and dissolved in dichloromethane (21.55 g) at a mass ratio of 5:1 to 3-fluoro-5-tert-butylsalicylaldehyde. The mixture was stirred at room temperature for 2 h, and the reaction was monitored by thin-layer chromatography until the starting material spot disappeared or no longer changed. Then, 3,3'-diformyl-2,2'-dihydroxy-1,1'-binaphthyl (3.77 g, 11 mmol) at a molar ratio of 1:2 to 3-fluoro-5-tert-butylsalicylaldehyde was added. The mixture was stirred at room temperature for another 20 h. The reaction was stopped, and the mixture was filtered. The filter cake was washed several times with dichloromethane, and the filtrate was evaporated by rotary evaporation to remove the dichloromethane, yielding the crude product. The crude product was purified by column chromatography to obtain a yellow solid. The obtained solid was dried under vacuum for 12 h and transferred to a glove box for later use. 0.5 g (0.652 mmol) of the yellow solid was weighed into a 50 mL single-necked flask equipped with a magnetic stirrup, and dissolved in tetrahydrofuran (5 g) at a mass ratio of 10:1 to the yellow solid. 168 mg (1.304 mmol) of cobalt chloride at a molar ratio of 2:1 to the yellow solid was weighed into the single-necked flask. The reaction was carried out at room temperature for 5 h, and the tetrahydrofuran was removed under vacuum to obtain the orange solid catalyst 2a. 1 H NMR (600 MHz, Chloroform-d) δ 8.78(s, 2H), 8.45 (s, 2H), 7.47 (td, J = 8.9, 8.5, 2.1 Hz, 4H), 7.24 (dd, J =7.7, 1.8 Hz, 4H), 7.15 (d, J = 2.5 Hz, 2H), 6.89 – 6.80 (m, 4H), 3.77 (dd, J =6.2, 1.2 Hz, 8H), 1.38 (s, 18H), 1.12 (s, 12H).

[0063] Example 10

[0064] In a 250 mL three-necked flask equipped with a magnetic stir bar, propylenediamine (1.63 g, 22 mmol) and 3-chloro-5-tert-butylsalicylaldehyde (4.67 g, 22 mmol) were mixed and dissolved in dichloromethane (14.01 g) at a mass ratio of 3:1 to 3-chloro-5-tert-butylsalicylaldehyde. The mixture was stirred at room temperature for 3 h, and the reaction was monitored by thin-layer chromatography until the starting material spot disappeared or no longer changed. Then, 3,3'-diformyl-2,2'-dihydroxy-1,1'-binaphthyl (3.77 g, 11 mmol) at a molar ratio of 1:2 to 3-chloro-5-tert-butylsalicylaldehyde was added. The mixture was stirred at room temperature for another 16 h. The reaction was stopped, and the mixture was filtered. The filter cake was washed several times with dichloromethane, and the filtrate was evaporated by rotary evaporation to remove the dichloromethane, yielding the crude product. The crude product was purified by column chromatography to obtain a yellow solid. The solid was dried under vacuum for 12 h and transferred to a glove box for later use. Weigh 0.5 g (0.674 mmol) of the yellow solid into a 50 mL single-necked flask equipped with a magnetic stirrup, and dissolve it in tetrahydrofuran (5 g) at a mass ratio of 10:1 to the yellow solid. Weigh 1.35 mL (1 M) of di-n-butylmagnesium at a molar ratio of 2:1 to the yellow solid and add it dropwise into the single-necked flask. React at room temperature for 4 h, and remove the tetrahydrofuran under vacuum to obtain the orange solid catalyst 2b. 1 H NMR (600 MHz, Chloroform-d) δ 8.78 (s, 2H), 8.45 (s, 2H), 7.47 (td, J = 8.9, 8.5, 2.1 Hz, 4H), 7.24 (dd, J = 7.7, 1.8 Hz, 4H), 7.15 (d, J = 2.5 Hz, 2H), 6.89 – 6.80 (m, 4H), 3.77 (dd, J = 6.2, 1.2 Hz, 8H), 2.12 – 2.01 (m, 4H), 1.38 (s, 18H).

[0065] Example 11

[0066] In a 250 mL single-necked flask equipped with a magnetic stir bar, magnesium hydroxide (2.00 g) was dissolved in tert-butanol (20.00 g) at a mass ratio of 10:1, and the mixture was stirred vigorously until dissolved. Then, potassium chromocyanate (3.60 g) at a mass ratio of 1.8:1 to magnesium chloride was dissolved in deionized water and added dropwise to the above system at a uniform rate over 10 min, wherein the mass ratio of deionized water (72.00 g) to potassium chromocyanate was 20:1. The mixture was heated to 70 °C and stirred continuously for 3 h. After the reaction was complete, the mixture was cooled, centrifuged, and vacuum dried to constant weight to obtain a dark brown solid catalyst 3a. Elemental analysis of the catalyst showed: C: 24.62; N: 17.33; H: 2.92.

[0067] Example 12

[0068] In a 250 mL single-necked flask equipped with a magnetic stir bar, zinc chloride (2.00 g) was dissolved in 1,3-propanediol (40.00 g) at a mass ratio of 20:1, and the solution was stirred vigorously until dissolved. Then, potassium aluminate (6.00 g) at a mass ratio of 3:1 to zinc chloride was dissolved in deionized water and added dropwise to the above system at a uniform rate over 60 min, wherein the mass ratio of deionized water (300.00 g) to potassium aluminate was 50:1. The mixture was heated to 40 °C and stirred continuously for 5 h. After the reaction was complete, the solution was cooled, centrifuged, and vacuum dried to constant weight to obtain a dark brown solid catalyst 3b. Elemental analysis of the catalyst showed: C: 26.73; N: 16.95; H: 2.13; Cl: 8.47.

Claims

1. A method for preparing a polyether ester-based thermoplastic elastomer, characterized in that, A polyether ester-based thermoplastic elastomer with adjustable soft and hard segment ratios was obtained by using a polyether ester random copolymer obtained by ring-opening copolymerization of epoxide alkane and lactone as the soft segment and lactone homopolymer as the hard segment through a one-pot two-step method. The preparation route of the polyether ester-based thermoplastic elastomer is as follows: ； Epoxy alkane and lactone 1 are added to the reactor, along with a homogeneous or heterogeneous bimetallic catalyst, a co-catalyst, an initiator, and an organic solvent. After heating, the first polymerization reaction is carried out to obtain a polyether ester random copolymer as the soft segment. Lactone 2 is added in situ according to the designed mass ratio of soft and hard segments of the polyether ester-based thermoplastic elastomer. Organic solvents are selectively added to ensure good system flowability, and the second polymerization reaction is carried out to obtain a polyester-polyether ester random copolymer-polyester triblock polymer, i.e., a hard-soft-hard triblock polymer. Finally, the crude product is first dissolved in a small amount of dichloromethane, then a large amount of n-hexane is added, and the mixture is stirred vigorously to precipitate the polymer. Vacuum drying yields the polyether ester-based thermoplastic elastomer. The synthesis equation for the homogeneous bimetallic catalyst used is as follows: ； In the formula: ； M is Cr 2+ Fe 2+ Mn 2+ Co 2+ Zn 2+ Mg 2+ Cu 2+ or Ni 2+ ; R 1 and R 2 It is an H, C1-C6 alkyl, C1-C6 alkoxy, Cl, Br, F, or NO2 group; R 1 and R 2 Same or different; Organic solvent 1 is dichloromethane; Organic solvent 2 is one of toluene, dichloromethane, tetrahydrofuran, and 1,4-dioxane; The metal chloride salt is one of chromium chloride, manganese chloride, ferrous chloride, cobalt chloride, zinc chloride, copper chloride, and nickel chloride; the alkyl metal is n-butylmagnesium; The specific preparation steps of the homogeneous bimetallic catalyst are as follows: Raw material 1 and raw material 2 are mixed in a molar ratio of 1.0~1.5:1 and dissolved in organic solvent 1 in a mass ratio of 3~5:1 to raw material 1. The mixture is stirred at room temperature for 1~5 h. The reaction is monitored by thin-layer chromatography until the raw material spots disappear or no longer change. Then, raw material 3 or raw material 4 in a molar ratio of 1:2.0~2.3 to raw material 1 is added. The mixture is stirred at room temperature for 12~24 h. The reaction is stopped, the mixture is filtered, and the filter cake is washed with organic solvent 1. The solvent is removed by rotary evaporation to obtain the crude product. The crude product is separated and purified by column chromatography to obtain homogeneous binuclear metal ligand A or homogeneous binuclear metal ligand B. The obtained solid is dried under vacuum for 12~24 h. h, transfer to a glove box for later use; weigh homogeneous binuclear metal ligand A or homogeneous binuclear metal ligand B in the glove box, and dissolve it in organic solvent 2 with a mass ratio of 10~20:1 to the ligand; weigh a metal chloride salt or alkyl metal with a molar ratio of 2.0~2.2:1 to the ligand; react at room temperature for 1~12 h; remove the organic solvent under vacuum to obtain homogeneous bimetallic catalyst A or homogeneous bimetallic catalyst B; The structure of the heterogeneous bimetallic catalyst used is as follows: ； In the formula: M1 is Cr 3+ Mn 3+ Co 3+ Fe 3+ Al 3+ One of them; M2 is Mg 2+ Co 2+ Zn 2+ Fe 2+ Mn 2+ Cu 2+ Ni 2+ One of them; X is OH − Cl − ,Br − CH3COO − NO3 − CF3COO − 2,4-Dinitrophenoloxy, o-nitrophenoloxy, p-nitrophenoloxy, or m-nitrophenoloxy; CA is a complexing agent, which is one of n-butanol, isobutanol, tert-butanol, n-propanol, isopropanol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, glycerol, pentaerythritol, or water; The solvent is deionized water; The specific preparation steps of the heterogeneous bimetallic catalyst are as follows: raw material 6 is dissolved in raw material 7 at a mass ratio of 10~20:1, and stirred vigorously until dissolved; then raw material 5 at a mass ratio of 1.8~3.0:1 to raw material 6 is dissolved in a solvent and added dropwise to the above system at a uniform rate over 10~60 min, wherein the mass ratio of solvent to raw material 5 is 20~50:1; the temperature is raised to 40~70°C and stirred continuously for 3~5 h. After the reaction is completed, the temperature is lowered, centrifuged, and vacuum dried to constant weight to obtain the heterogeneous bimetallic catalyst. The co-catalyst used is one of the following: tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium acetate, tetrabutylammonium tribromide, tetrabutylammonium nitrate, tetrabutylammonium hydrogen sulfate, tetrabutylammonium fluoride, benzyltriethylammonium chloride, benzyltripropylammonium chloride, benzyltributylammonium chloride, benzyltributylammonium bromide, hexadecyltrimethylammonium chloride, dodecyltrimethylammonium chloride, bis(triphenylphosphine)ammonium chloride, methyltriphenylphosphine bromide, and allyltriphenylphosphine bromide; The molar ratio of homogeneous or heterogeneous bimetallic catalysts, co-catalysts and epoxides is 1:1:1000~10000.

2. The preparation method according to claim 1, characterized in that, The initiators used are 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, o-phenylenediol, iso-phenylenediol, or terephthalic acid; the molar ratio of initiator to epoxide is 1~100:10000; the epoxides used are ethylene oxide, propylene oxide, 1,2-epoxybutane, 1,2-epoxyhexane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,2-epoxydodecane, epicyclohexane, epichlorohydrin, 2,3- The following are options: epoxide, methyl glycidyl ether, ethyl glycidyl ether, isopropyl glycidyl ether, tert-butyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, and benzyl glycidyl ether; the lactone 1 used is one of β-butyrolactone, β-propiolactone, δ-valerolactone, ε-caprolactone, and ε-decylactone; the lactone 2 used is one of δ-valerolactone, ε-caprolactone, L-lactide, D-lactide, racemic lactide, and glycolide.

3. The preparation method according to claim 1, characterized in that, The molar ratio of the alkyl epoxide to lactone 1 is 1:5 to 5:1; the structure of the obtained polyether ester random copolymer can be precisely controlled within the range of polyether:polyether ester:polyester = 10 to 70:15 to 18:12 to 75 by changing the feed ratio of alkyl epoxide to lactone 1.

4. The preparation method according to claim 1, characterized in that, The reaction temperature of the first polymerization reaction is 30–100°C, and the reaction time is 1–48 h.

5. The preparation method according to claim 1, characterized in that, The mass ratio of lactone 2 to soft segment is 1:0.2~5.

6. The preparation method according to claim 1 or claim 5, characterized in that, The reaction temperature for the second polymerization step is 60~100 ℃, and the reaction time is 6~18 h.

7. The preparation method according to claim 1, characterized in that, The organic solvent used in the first and second polymerization reactions is one of 1,4-dioxane, tetrahydrofuran, toluene, diethanol dimethyl ether, and diethylene glycol dimethyl ether.

8. A polyether ester-based thermoplastic elastomer prepared by the preparation method according to any one of claims 1 to 7, characterized in that, The polyether ester-based thermoplastic elastomer has a service temperature window of -65 to 170 °C, a maximum tensile strength of 5 to 50 MPa, and an elongation at break of 300 to 1500%.

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