Performance-adjustable polyester-based multi-block thermotropic shape memory material and preparation method thereof

Abstract

The invention discloses a performance-adjustable polyester-based multi-block thermotropic shape memory material and a preparation method thereof, and belongs to the field of high polymer materials. Adding a synthesized catalyst, a catalyst promoter and a chain transfer agent into a reaction kettle, then adding an organic solvent, selectively and uniformly mixing cyclosiloxane and a third monomer according to a certain proportion, then adding the mixture into the reaction kettle at a constant speed to prepare a biopolymer, then adding cyclic ester according to a certain proportion, and carrying out a first polymerization reaction at a certain temperature for a certain time to obtain a second polymer; a triblock polymer is prepared; and adding a chain extender into the reaction system, and carrying out a second polymerization reaction at a certain temperature for a certain time to prepare the multi-block polymer. The shape recovery of the multi-block polymer can be triggered by adjusting the temperature. By changing the monomer type and the feeding proportion, the polymer structure can be directly regulated and controlled so as to regulate and control the material performance. In addition, the polymerization reaction adopted by the invention is an atom economical route, the post-treatment is simple, no waste is discharged, and the method has a good industrial application prospect.

Description

Technical Field

[0001] The invention relates to a polyester-based multi-block thermal shape memory material with adjustable performance and a preparation method thereof, belonging to the field of polymer materials, in particular to the technical field of thermal shape memory intelligent materials. Background Art

[0002] Thermal shape memory materials are intelligent materials that can reversibly change their shape and restore their original shape under external temperature stimulation. Their performance mainly depends on the synergistic effect of the "stationary phase" and the "reversible phase" in the molecular chain. They are widely used in biomedicine, aerospace, electronic devices, flexible robots and other fields. Among them, polymer shape memory materials have become a research hotspot due to their advantages such as light weight, easy processing and strong designability. At present, the mainstream shape memory polymer materials include polyurethane, polyimide, polysiloxane, etc. Polyester materials (such as polylactic acid and polycaprolactone) are often used to construct the stationary phase of thermal shape memory materials due to their high crystallinity and excellent mechanical properties; while polysiloxane is known for its flexibility, temperature resistance and chemical stability, and is often used as a reversible phase component. However, a single material system often finds it difficult to take into account both high strength and high recovery rate, and the thermal response temperature range (such as glass transition temperature or melting temperature) is fixed, which limits its application in complex environments. For example: Although polyester materials have excellent mechanical properties, their thermal response temperature range is narrow and it is difficult to regulate through simple blending; polysiloxane materials have good flexibility, but insufficient mechanical strength, making it difficult to meet the needs of high-load scenarios.

[0003] In recent years, researchers have tried to optimize material properties through copolymerization or composite methods. In addition, blending systems of materials such as fluorinated polymers and cross-linked polyethylene have also been used to broaden the thermal response temperature range. However, existing copolymer materials still have the following problems: (1) Poor compatibility. Polyester and polysiloxane are prone to phase separation due to their polarity differences, resulting in weak interfacial bonding; (2) Uncontrollable performance. Traditional blending or grafting methods make it difficult to accurately control the ratio and distribution of the two phases, affecting shape memory efficiency and cycle stability.

[0004] With the growing demand for smart materials in the high-end manufacturing sector, the development of thermo-induced shape memory materials with high mechanical strength, wide temperature range response and performance adjustability has become an urgent need. According to market analysis, the global polymer shape memory material market is expected to grow at a compound annual growth rate of 5%-10%, with the fastest growth in the Asia-Pacific region, but high-end products still rely on imports. In the prior art, although chemical cross-linking or physical blending can partially improve performance, the preparation process is complicated and it is difficult to achieve large-scale production. In response to the above problems, this patent proposes to construct a polyester-polysiloxane block copolymer system through molecular structure design and controllable polymerization process, and utilize the synergistic effect of the two phases to achieve performance adjustability. Summary of the invention

[0005] The main content of the present invention is to develop a polyester-based multi-block thermally induced shape memory material with adjustable properties in view of the deficiencies of the prior art.

[0006] The technical solution of the present invention:

[0007] A preparation method of a polyester-based multi-block thermally induced shape memory material with adjustable properties, comprising the following steps: adding a catalyst, a cocatalyst and a chain transfer agent into a reaction kettle, then adding an organic solvent, mixing a cyclic siloxane and a third monomer evenly and adding them into the reaction kettle at a constant speed to obtain a binary copolymer, then adding a cyclic ester for the first polymerization reaction to obtain a triblock polymer; adding a chain extender into the reaction system for the second polymerization reaction to obtain a multi-block polymer; the obtained multi-block polymer has a shape memory effect under heat treatment; the reaction general formula of the copolymer is as follows:

[0008]

[0009] Furthermore, the catalyst is a metal complex, specifically catalyst 1, catalyst 2-1 or catalyst 2-2, and the structures are as follows:

[0010]

[0011] In the formula: M 1 is selected from Zr 4+ , Ti 4+ ; M 2 is selected from one or two of Al 3+ , In 3+ , Cr 3+ , Ga 3+ or Fe 3+ ; p is a non-zero natural number;

[0012] R is

[0013]

[0014] R' is

[0015]

[0016] R 5 , R 6 , R 7 are H, C1-C4 alkyl, C1-C4 alkoxy; R 5 , R 6 and R 7 are the same or different;

[0017] X is F -1 , Cl -1 , Br -1 , I -1 , NO 3-1 , CH 3 COO -1 or a C1-C4 alkoxy group.

[0018] Furthermore, the cyclic ester is one of ε-caprolactone (ε-CL), δ-valerolactone (δ-VL), L-lactide (L-LA), D-lactide (D-LA), DL-lactide (DL-LA), glycolide (GA-1);

[0019] Furthermore, the cyclic siloxane is hexamethylcyclotrisiloxane (D 3 ), octamethylcyclotetrasiloxane (D 4 ), hexaethylcyclotrisiloxane (D 3 6Et ), 2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane (D 3 3Vi ), 2,4,6-trimethyl-2,4,6-triphenylcyclotrisiloxane (D 3 -Ph), hexaphenylcyclotrisiloxane (D 3 6Ph ), tetramethyltetravinylcyclotetrasiloxane (D 4 4Vi ), 1,3,5-trimethyl-1,3,5-tris(3,3,3-trifluoropropyl)cyclotrisiloxane (D 3 -CF 3 ) of one kind;

[0020] Furthermore, the third monomer is one of carbon dioxide (CO 2 ), carbon disulfide (CS 2 ), cyclic anhydride, cyclic siloxane; wherein the cyclic anhydride is one of succinic anhydride (SA), methylsuccinic anhydride (MSA), maleic anhydride (MA), glutaric anhydride (GA-2), diglycolic anhydride (DGA), 3-methylglutaric anhydride (MGA), 3,3-dimethylglutaric anhydride (3,3-DMGA), hexahydrophthalic anhydride (HHPA), phthalic anhydride (PA), 4-methylphthalic anhydride (MPA); Monomer refers to monomer;

[0021] Furthermore, the structural formulas of the cyclic ester, cyclic siloxane and cyclic anhydride used are as follows:

[0022]

[0023] x, y, z, g, m are non-zero natural numbers, n = 3, 4, 5.

[0024] Further, the cocatalyst used is one of: tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium fluoride, tetramethylammonium iodide, tetramethylammonium acetate, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetraethylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium acetate, tetrabutylammonium tribromide, tetrabutylammonium nitrate, tetrabutylammonium hydrogensulfate, tetrabutylammonium fluoride, benzyltriethylammonium chloride, benzyltripropylammonium chloride, benzyltributylammonium chloride, benzyltributylammonium bromide, cetyltrimethylammonium chloride, dodecyltrimethylammonium chloride, bis(triphenylphosphonium) chloride, methyltriphenylphosphonium bromide, allyltriphenylphosphonium bromide;

[0025] Further, the chain transfer agent is one of: ethylene glycol, 1,3 - propanediol, glycerol, 1,4 - butanediol, pentaerythritol, p - xylyl alcohol, m - xylyl alcohol, o - xylyl alcohol, polyethylene glycol 400, polyethylene glycol 600, polypropylene glycol 400, polypropylene glycol 600;

[0026] Further, the organic solvent is one of: toluene, xylene, acetonitrile, tetrahydrofuran, dichloromethane, 1,2 - dichloroethane, 1,4 - dioxane, n - hexane, cyclohexane;

[0027] Further, the chain extender is one of: 4,4'-methylenebis(phenyl isocyanate) (MDI), hexamethylene diisocyanate (HDI), toluene - 2,4 - diisocyanate (TDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (HMDI), L - lysine diisocyanate (LDI).

[0028] Further, the molar ratio of the cyclic ester, cyclic siloxane and the third monomer added is 1:0.1 - 0.7:0.1 - 0.7;

[0029] Further, in the first polymerization reaction, the molar ratio of the catalyst to the cyclic ester is 1:500 - 20000, the molar ratio of the cocatalyst to the catalyst is 0.5 - 3:1, the molar ratio of the chain transfer agent to the cyclic ester is 1 - 500:20000, the reaction temperature is 30 - 150 °C, and the reaction time is 1 - 6 h.

[0030] Further, in the second polymerization reaction, the molar ratio of the chain extender to the triblock polymer is 1 - 1.5:1, the reaction temperature is 40 - 100 °C, and the reaction time is 1 - 6 h.

[0031] Further, the reaction temperature for preparing the binary copolymer is 30 - 150 °C, and the reaction time is 1 - 10 h.

[0032] Further, the synthesis equation of the catalyst 1 is as follows:

[0033]

[0034] The preparation steps of the described catalyst 1 are as follows:

[0035] Under the protection of inert gas, dialdehyde and monoamine with a molar ratio of 1:2 - 2.5 are mixed and dissolved in ethanol with a mass ratio of ethanol to dialdehyde of 2 - 5:1, and stirred at room temperature for 2 - 10 h; after the reaction stops, filtration is carried out, the filter cake is rinsed with ethanol 2 - 3 times, the filtrate is distilled under reduced pressure and dried in vacuum to obtain intermediate product 1, which is transferred to a glove box for standby; in the glove box, weigh intermediate product 1 into a container equipped with a magnetic stirrer and dissolve it in an organic solvent with a mass ratio of organic solvent to intermediate product 1 of 3 - 10:1; weigh a metal salt or an alkyl metal with a molar ratio of 1 - 1.2:1 to intermediate product 1; react at 25 - 80 °C for 12 - 36 h; after removing the organic solvent under reduced pressure, catalyst 1 is obtained; the metal salt or alkyl metal is one of metal halides, metal nitrates, metal acetates, C1 - C4 alkoxymetal salts, and alkyl metals;

[0036] Furthermore, the synthesis equation of the described catalyst 2 - 1 is as follows:

[0037]

[0038] The preparation steps of the described catalyst 2 - 1 are as follows:

[0039] Under the protection of inert gas, diamine - 1 and monoaldehyde with a molar ratio of 1 - 1.5:2 are mixed and dissolved in ethanol with a mass ratio of ethanol to monoaldehyde of 2 - 5:1, stirred at 25 - 80 °C for 1 - 6 h to stop the reaction, filtration is carried out, the filter cake is rinsed with ethanol 2 - 3 times, the filtrate is distilled under reduced pressure and dried in vacuum to obtain mononuclear ligand 1; under the protection of inert gas, mononuclear ligand 1 and diacyl chloride with a molar ratio of 2:1 - 1.5 are mixed, then 4 - dimethylaminopyridine with a molar ratio of 1 - 1.5:2 to mononuclear ligand 1 and triethylamine with a molar ratio of 3 - 5:1 are added, and stirred at 25 - 80 °C for 3 - 10 h; stop the reaction, carry out filtration, distill under reduced pressure and dry in vacuum to obtain L2 - 1, which is transferred to a glove box for standby; in the glove box, weigh L2 - 1 and dissolve it in an organic solvent with a mass ratio of organic solvent to L2 - 1 of 5 - 10:1; weigh a metal salt or an alkyl metal with a molar ratio of 2 - 2.2:1 to L2 - 1; react at 25 - 100 °C for 12 - 36 h; after removing the organic solvent under reduced pressure, catalyst 2 - 1 is obtained; the metal salt or alkyl metal is one of metal halides, metal nitrates, metal acetates, C1 - C4 alkoxymetal salts, and alkyl metals;

[0040] Furthermore, the synthesis equation of the described catalyst 2 - 2 is as follows:

[0041]

[0042] The preparation steps of the catalyst 2-2 are as follows:

[0043] Under the protection of inert gas, diamine-2 and monoaldehyde with a molar ratio of 1-1.5:2 are mixed, paraformaldehyde with a molar ratio of 2-4:1 to diamine-2 is added, and it is dissolved in ethanol with a mass ratio of 2-5:1 to monoaldehyde. The mixture is stirred and reacted at 25-80 °C for 2-14 h, and the solvent is removed by rotary evaporation to obtain a white solid. The white solid is dissolved in water, neutralized with sodium bicarbonate, and extracted with methyl tert-butyl ether for 3-5 times. The organic layers are combined, dried with anhydrous sodium sulfate, the solid is filtered off, and methyl tert-butyl ether is removed by rotary evaporation to obtain a mononuclear ligand 2. The subsequent reaction steps are the same as those of the preparation method of catalyst 2-1.

[0044] A polyester-based multi-block thermally induced shape memory material with adjustable properties prepared by the above method.

[0045] The triblock copolymer includes a polyester segment and a binary copolymer segment. Among them, the binary copolymer segment can be subdivided into four categories according to different comonomers: polyester-co-polysilicate carbonate-co-polysiloxane, polyester-co-polysilithiocarbonate-co-polysiloxane, polyester-co-polysilicate ester-co-polysiloxane, and polysiloxane. The structural general formulas of the triblock copolymer and the binary copolymer are as follows:

[0046]

[0047] In the triblock copolymer, the molar content of the polyester segment is 30-80%, and the molar content of the binary copolymer segment is 20-70%. The number-average molecular weight of the triblock copolymer is 20.0-90.0 kg / mol, and the molecular weight distribution is 1.1-1.6. The number-average molecular weight of the multi-block polymer is 60.0-300.0 kg / mol, and the molecular weight distribution is 1.1-2.7.

[0048] Furthermore, the use window temperature of the obtained multi-block polymer is -40-230 °C, the maximum tensile strength is 3-26 MPa, the elongation at break is 200-1500%, the shape recovery rate > 90%, and the thermal response temperature range is 50-220 °C.

[0049] The beneficial effects of the present invention:

[0050] (1) For the polyester-based multi-block thermally induced shape memory material described in the present invention, by introducing functionalized segments, the use window temperature of the obtained multi-block polymer is -40-230 °C, the shape recovery rate > 90%, and the thermal response temperature range is 50-220 °C;

[0051] (2) The polyester-based multi-block thermotropic shape memory material of the present invention has both flexibility and rigidity, and has good compatibility between blocks, improving the mechanical properties of the material. The maximum tensile strength of the multi-block polymer is 3-26 MPa, and the elongation at break is 300-1500%.

[0052] (3) The preparation method of the polyester-based multi-block thermotropic shape memory material of the present invention is efficient, low-energy-consuming and waste-free, which is an atom-economic route, in line with the concept of green sustainable development. At the same time, the raw materials used are cheap and easily available, suitable for industrial production. Detailed implementation mode

[0053] The technical solutions of the present invention are further described below through examples.

[0054] The terms used in the present invention generally have the meanings commonly understood by those of ordinary skill in the art unless otherwise specified.

[0055] In the following examples, various processes and methods not described in detail are conventional methods well known in the art. At the same time, due to the large variety of catalysts and diverse polymer structure ratios, not all preparation methods are described in detail. Typical examples are taken to illustrate the specific process steps of the present invention.

[0056] Examples 1-6 are examples of the catalyst preparation method.

[0057] Examples 7-14 are examples of the polyester-based multi-block thermotropic shape memory material with adjustable properties using the catalyst of the present invention. The numbers of the catalysts, cyclic esters, cyclic siloxanes and cyclic anhydrides used in the examples are shown in the following formula.

[0058] Catalyst:

[0059]

[0060] 1a: M1 = Zr 4+ , R = benzyl, X = isopropoxy

[0061] 1b: M1 = Ti 4+ , R = 2-picolyl, X = Cl

[0062] 2a: M2 = Al 3+ , R' = cyclohexyl, R5 = R6 = R7 = tert-butyl, X = isopropoxy, p = 6

[0063] 2b: M2 = In 3+ , R' = n-propyl, R5 = R6 = R7 = tert-butyl, X = Cl, p = 3

[0064] 2c: M2 = Cr3+ , R' = cyclohexyl, R5 = tert-butyl, R6 = R7 = hydrogen atom, X = Cl, p = 6

[0065] 2d: M2 = Al 3+ , R' = phenyl, R5 = R6 = R7 = tert-butyl, X = Cl, p = 3

[0066]

[0067] Example 1

[0068] Under nitrogen protection, in a reaction flask, benzylamine (2.36 g, 22 mmol), 2,2'-dihydroxybiphenyl-3,3'-dicarboxaldehyde (2.66 g, 11 mmol) and ethanol (9.44 g) were weighed at room temperature and stirred vigorously to mix evenly. The mixture was stirred at 25 °C for 2 h. Filtration was carried out, and the filter cake was washed 3 times with ethanol. The solid was dried to obtain a yellow solid. Under nitrogen protection, in a reaction flask, the yellow solid (2.79 g, 6.63 mmol) and tetrahydrofuran (8.37 g) were stirred evenly, and then zirconium isopropoxide isopropanol complex (2.56 g, 6.63 mmol) with a molar ratio of 1:1 to the yellow solid was added to the reaction flask. The reaction was carried out at 25 °C for 12 h. Filtration was carried out and the solid was washed with tetrahydrofuran. The solid was dried to obtain catalyst 1a. 1 H NMR (400 MHz, DMSO-d 6 ) δ 8.11 (s, 2H), 7.75 (s, 2H), 7.69 (d, J = 13.3 Hz, 2H), 7.36 (d, J = 8.7 Hz, 8H), 7.29 (s, 2H), 7.25 (s, 2H), 4.81 (t, J = 7.6 Hz, 4H), 3.80 (s, 2H), 1.11 (s, 12H). 13 C NMR (151 MHz, CDCl 3 ): δ 163.71, 156.74, 138.93, 133.56, 131.02, 128.61, 127.98, 127.37, 125.74, 125.13, 118.92, 39.14, 31.14, 28.25. Elemental analysis (mass percentage of catalyst 1a structure C34H36N2O4Zr), theoretical values: C 65.04, H 5.78, N 4.46, O 10.19; measured values: C 65.41, H 5.61, N 4.08, O 10.26.

[0069] Example 2

[0070] Under nitrogen protection, 2-aminomethylpyridine (2.48 g, 23 mmol), 2,2'-dihydroxybiphenyl-3,3'-dicarboxaldehyde (2.66 g, 11 mmol) and ethanol (11.85 g) were weighed at room temperature in a reaction flask, stirred vigorously and mixed evenly. The mixture was stirred at 25 °C for 6 h. Filtration was carried out by suction, and the filter cake was rinsed with ethanol three times. The solid was dried to obtain a yellow solid. Under nitrogen protection, the yellow solid (2.80 g, 6.63 mmol) and dichloromethane (10.40 g) were weighed at room temperature in a reaction flask and stirred evenly. Subsequently, titanium chloride (1.38 g, 7.29 mmol) with a molar ratio of 1.1:1 to the yellow solid was added to the reaction flask, and the reaction was carried out at room temperature for 16 h. Filtration was carried out by suction and the solid was washed with dichloromethane. The solid was dried to obtain catalyst 1b. 1 H NMR (400 MHz, DMSO-d 6 ) δ 8.51 (s, 2H), 8.23 (s, 2H), 7.75 (d, J = 10.3 Hz, 2H), 7.68 (d, J = 7.7 Hz, 4H), 7.25 (s, 2H), 7.15 (t, J = 5.8 Hz, 4H), 5.14 (s, 4H). 13 C NMR (151 MHz, CDCl 3 ): δ 163.72, 159.03, 156.75, 148.63, 136.26, 133.57, 131.07, 127.38, 125.41, 122.24, 120.93, 118.97, 32.16. Elemental analysis (mass percentage of the structure C26H20Cl2N4O2Ti of catalyst 1b), theoretical values: C 57.91, H 3.74, N 10.39, O 5.93; measured values: C 57.41, H 3.91, N 10.08, O 5.26.

[0071] Example 3

[0072] Under nitrogen protection, 1,2-diaminocyclohexane (2.51 g, 22 mmol), 3,5-di-tert-butylsalicylaldehyde (10.31 g, 44 mmol) and ethanol (20.62 g) were weighed at room temperature in a reaction flask, stirred vigorously and mixed evenly, and then stirred at 40 °C for 2 h. Filtration was carried out by suction, and the filter cake was rinsed with ethanol three times. The solid was dried to obtain yellow solid 1. Under nitrogen protection, yellow solid 1 (8.20 g, 15 mmol) and 1,8-dioctanoyl chloride (1.58 g, 7.5 mmol) were weighed at room temperature in a reaction flask and stirred evenly. Subsequently, 4-dimethylaminopyridine (0.92 g, 7.5 mmol) and triethylamine (4.55 g, 45 mmol) were added, and the mixture was stirred at 50 °C for 5 h; filtration was carried out by suction, and the solid was dried to obtain yellow solid 2. Under nitrogen protection, yellow solid 2 (5.75 g, 5 mmol) and toluene (28.75 g) were weighed at room temperature in a reaction flask, stirred vigorously and mixed evenly. 2.0 M diethylaluminum chloride (5 mL, 10 mmol) was added dropwise to the reaction flask through a constant pressure dropping funnel, and the reaction was carried out at 80 °C for 16 h. After removing the solvent under reduced pressure, catalyst 2a was obtained. 1 H NMR(400MHz,CDCl 3 ):δ8.30(s,2H),8.22(s,2H),7.31(d,J=2.5Hz,2H),6.97(d,J=2.5Hz,2H),6.91(d,J=2.8Hz,2H),6.75(d,J=2.8Hz,2H),3.32(d,J=9.7Hz,4H),2.51(t,J=7.5Hz,4H),1.98–1.84(m,8H),1.76(s,8H),1.50–1.43(m,8H),1.41(s,18H),1.38(s,18H),1.24(s,18H). 13 C NMR(151MHz,CDCl 3 ):δ172.52,165.91,164.70,158.12,157.97,141.58,140.00,138.58,136.40,126.92,125.98,122.77,121.37,118.23,117.80,72.48,72.22,34.95,34.89,34.20,34.03,33.19,33.12,31.42,29.46,29.16,28.74,26.93,24.71,24.28. Elemental analysis (mass percentage of the structure C72H98Al2Cl2N4O8 of catalyst 2a), theoretical values: C 67.96, H 7.76, N 4.40, O 10.06; measured values: C 67.41, H 7.91, N 4.08, O 10.26.

[0073] Example 4

[0074] Under nitrogen protection, 1,3-propanediamine (1.63 g, 22 mmol), 3,5-di-tert-butylsalicylaldehyde (10.31 g, 44 mmol) and ethanol (20.62 g) were weighed at room temperature in a reaction flask and stirred vigorously to mix evenly. The mixture was stirred at 40 °C for 4 h. Filtration was carried out by suction, and the filter cake was rinsed with ethanol three times. The solid was dried to obtain yellow solid 1. Under nitrogen protection, yellow solid 1 (8.20 g, 15 mmol) and glutaroyl dichloride (1.27 g, 7.5 mmol) were weighed into the reaction flask and mixed evenly. Subsequently, 4-dimethylaminopyridine (0.92 g, 7.5 mmol) and triethylamine (4.55 g, 45 mmol) were added, and the mixture was stirred at 60 °C for 5 h; filtration was carried out by suction, and the solid was dried to obtain yellow solid 2. Under nitrogen protection, yellow solid 2 (5.14 g, 5 mmol) and toluene (25.70 g) were weighed into the reaction flask and stirred vigorously to mix evenly. Indium chloride (1.54 g, 10 mmol) with a molar ratio of 2:1 to yellow solid 2 was weighed into the reaction flask, and the reaction was carried out at 80 °C for 18 h. After removing the solvent under reduced pressure, catalyst 2b was obtained. 1 H NMR (400 MHz, CDCl 3 ): δ8.28 (s, 2H), 8.20 (s, 2H), 7.21 (d, J = 2.5 Hz, 2H), 6.90 (d, J = 2.5 Hz, 2H), 6.85 (d, J = 2.8 Hz, 2H), 6.71 (d, J = 2.8 Hz, 2H), 3.30 (d, J = 9.7 Hz, 4H), 2.50 (t, J = 7.5 Hz, 8H), 2.01–1.89 (m, 2H), 1.55–1.46 (m, 4H), 1.41 (s, 18H), 1.37 (s, 18H), 1.21 (s, 18H). 13 C NMR (151 MHz, CDCl 3 ): δ172.13, 163.75, 151.42, 143.61, 138.45, 137.77, 128.33, 124.68, 123.81, 122.82, 120.17, 118.94, 34.53, 34.42, 34.14, 34.08, 32.93, 32.08, 31.67, 31.35, 20.4. Elemental analysis (mass percentage of catalyst 2b structure C63H84N4O8In2Cl2), theoretical values: C 57.07, H 6.39, N 4.23, O 9.65; measured values: C 57.92, H 6.10, N 4.04, O 9.33.

[0075] Example 5

[0076] Under nitrogen protection, weigh N,N'-dimethyl-1,2-cyclohexanediamine (3.13 g, 22 mmol), 5-tert-butylsalicylaldehyde (7.84 g, 44 mmol), paraformaldehyde (1.71 g, 57.2 mmol) and ethanol (15.68 g) in a reaction flask at room temperature, stir vigorously to mix evenly, and stir and react at 30 °C for 4 h. Rotavapor to remove the solvent to obtain a white solid; dissolve the white solid in water, add sodium bicarbonate for neutralization, and extract with methyl tert-butyl ether 3 times. Combine the organic layers, dry with anhydrous sodium sulfate, filter to remove the solid, and rotavapor to remove methyl tert-butyl ether to obtain yellow solid 1. Under nitrogen protection, weigh yellow solid 1 (6.39 g, 15 mmol) and 1,8-dioctanoyl chloride (1.58 g, 7.5 mmol) into a reaction flask and mix evenly, then add 4-dimethylaminopyridine (0.92 g, 7.5 mmol) and triethylamine (4.55 g, 45 mmol), and stir and react at 60 °C for 8 h; filter by suction, and dry the solid to obtain yellow solid 2. Under nitrogen protection, weigh yellow solid 2 (4.95 g, 5 mmol) and tetrahydrofuran (24.75 g) in a reaction flask, stir vigorously to mix evenly, weigh chromium dichloride (1.23 g, 10 mmol) with a molar ratio of 2.2:1 to yellow solid 2 into the reaction flask, react at 80 °C for 16 h, then take it out of the glove box and continue to react for 8 h, and remove the solvent under reduced pressure to obtain catalyst 2c. 1 H NMR(400MHz,CDCl 3 ):δ8.30(s,2H),8.22(s,2H),7.31(d,J=2.5Hz,2H),6.97(d,J=2.5Hz,2H),6.91(d,J=2.8Hz,2H),6.75(d,J=2.8Hz,2H),3.32(d,J=9.7Hz,4H),2.51(t,J=7.5Hz,8H),2.32(s,12H),1.98–1.84(m,8H),1.76(s,8H),1.50–1.43(m,8H),1.41(s,18H),1.38(s,18H),1.24(s,18H). 13 C NMR(151MHz,CDCl 3): δ 172.31, 151.35, 143.23, 141.96, 138.17, 137.34, 125.05, 124.57, 122.03, 118.53, 52.36, 41.16, 34.85, 34.42, 31.37, 28.79, 27.34, 25.43, 25.35, 16.70. Elemental analysis (catalyst 2c structure C60H82N4O8Cr2Cl2, mass percentage), theoretical values: C 62.01, H 7.11, N 4.82, O 11.01; measured values: C 63.01, H 6.89, N 4.02, O 13.01.

[0077] Example 6

[0078] Under nitrogen protection, weigh N,N'-dimethyl-1,2-phenylenediamine (2.99 g, 22 mmol), 3,5-di-tert-butylsalicylaldehyde (10.31 g, 44 mmol), paraformaldehyde (1.71 g, 57.2 mmol) and ethanol (30.93 g) into a reaction flask at room temperature, stir vigorously to mix evenly, and stir the reaction at room temperature for 5 h. Rotavapor to remove the solvent to obtain a white solid; dissolve the white solid in water, add sodium bicarbonate for neutralization, and extract with methyl tert-butyl ether 3 times. Combine the organic layers, dry with anhydrous sodium sulfate, filter to remove the solid, and rotavapor to remove methyl tert-butyl ether to obtain yellow solid 1. Under nitrogen protection, weigh yellow solid 1 (7.99 g, 15 mmol) and glutaroyl dichloride (1.27 g, 7.5 mmol) into a reaction flask and mix evenly, then add 4-dimethylaminopyridine (0.92 g, 7.5 mmol) and triethylamine (4.55 g, 45 mmol), and stir the reaction at room temperature for 5 h; filter by suction, and dry the solid to obtain yellow solid 2. Under nitrogen protection, weigh yellow solid 2 (5.80 g, 5 mmol) and toluene (29.00 g) into a reaction flask, stir vigorously to mix evenly, and add 2.0 M diethylaluminum chloride (5 mL, 10 mmol) dropwise to the reaction flask through a constant pressure dropping funnel, and react at 75 °C for 24 h to obtain a yellow suspension. After distilling off toluene under reduced pressure, the obtained yellow solid is dissolved in 0.5 mL of dichloromethane, and an excess of cold n-hexane is added. Filter to retain the solid phase, wash with 5 mL of cold n-hexane, collect the yellow solid and dry to obtain catalyst 2d. 1 H NMR (400 MHz, CDCl 3): δ 6.97 (s, 2H), 6.79 (s, 2H), 6.55 (s, 4H), 6.49 (s, 4H), 4.61 (8H), 2.85 (d, J = 2.5 Hz, 12H), 6.90 (d, J = 2.5 Hz, 2H), 6.85 (d, J = 2.8 Hz, 2H), 6.71 (d, J = 2.8 Hz, 2H), 3.30 (d, J = 9.7 Hz, 4H), 2.50 (t, J = 7.5 Hz, 8H), 2.01–1.89 (m, 2H), 1.55–1.46 (m, 4H), 1.41 (s, 18H), 1.37 (s, 18H), 1.21 (s, 18H). 13 C NMR (151 MHz, CDCl 3 ): δ 172.65, 150.44, 143.23, 142.20, 138.72, 129.41, 124.93, 124.61, 123.37, 122.29, 119.41, 116.12, 115.22, 45.36, 34.81, 34.42, 32.94, 31.67, 31.34, 20.01. Elemental analysis (for the 2d structure of catalyst C73H96N4O8Al2Cl2, mass percentage), theoretical values: C 64.41, H 8.11, N 3.58, O 12.26; measured values: C 63.41, H 8.91, N 3.08, O 13.26.

[0079] Example 7

[0080] 1a (54.86 mg, 0.09 mmol), tetramethylammonium bromide (13.86 mg, 0.09 mmol) and ethylene glycol (11.18 mg, 0.18 mmol) were added to the reaction kettle, and then D 3 6Et (12.08 g, 43.81 mmol), CS 2A mixture of 1a (1.67 g, 21.91 mmol) and 1,2-dichloroethane (30 g) was reacted at 60 °C for 2 h; ε-CL (10.27 g, 90.01 mmol) was added to the reaction kettle. The molar ratio of ε-CL to 1a was 1000:1, and the molar ratio of ε-CL to ethylene glycol was 500:1. The reaction was continued for 2 h to obtain a triblock polymer. An appropriate amount of the reaction solution was taken for molecular weight testing. The molecular weight of the triblock polymer was 69.8 kg / mol, and the molecular weight distribution was 1.35. TDI with a molar ratio of 1.1:1 to the triblock polymer was added in situ, and the temperature was raised to 80 °C and reacted for 2 h to obtain a multi-block polymer. The crude multi-block polymer was diluted with dichloromethane and precipitated in methanol, and then filtered and dried to obtain a pure multi-block polymer. A small amount of the pure product was taken for nuclear magnetic resonance spectroscopy testing. The results showed that the molar content of the polyester segment was 47%, the molar content of the polysilthionocarbonate segment was 18%, and the molar content of the polysiloxane segment was 35%. 1 H NMR (400 MHz, CDCl 3 ): δ 4.08 (t, J = 6.7 Hz, 2H), 2.32 (t, J = 7.5 Hz, 2H), 1.71–1.60 (m, 4H), 1.40 (p, J = 7.8 Hz, 2H), 0.94 (m, 2.3H), 0.81 (m, 4.5H), 0.67 (m, 1.5H), 0.56 (m, 3H). A small amount of the pure product was taken for molecular weight testing. The results showed that the molecular weight of the multi-block polymer was 201.3 kg / mol, and the molecular weight distribution was 2.43. A circular membrane with a uniform thickness was prepared by solution casting for performance testing. The test results showed that the temperature range of use was -20 to 58 °C, the maximum tensile strength was 19 MPa, the elongation at break was 510%, the deformation recovery rate was 94.4%, and the thermal response temperature was 58 °C. The structure of the obtained multi-block polymer is as follows:

[0081]

[0082] Example 8

[0083] 1b (27.23 mg, 0.022 mmol), bis(triphenylphosphonium) ammonium chloride (25.83 mg, 0.045 mmol) and 1,4-butanediol (16.22 mg, 0.09 mmol) were added to the reaction kettle, and then D 4 (8.67 g, 29.21 mmol) and 1,4-dioxane (20 g) were added to the reaction kettle at a constant speed, and CO 2(2 MPa), react for 3 h at 70 °C; add δ-VL (4.39 g, 43.81 mmol) to the reaction kettle, the molar ratio of δ-VL to 1b is 2000:1, and the molar ratio of δ-VL to 1,4-butanediol is 500:1, and continue to react for 2 h to obtain a triblock polymer. Take an appropriate amount of the reaction solution for molecular weight testing. The molecular weight of the triblock polymer is 68.0 kg / mol, and the molecular weight distribution is 1.24. In-situ add MDI with a molar ratio of 1.2:1 to the triblock polymer, and continue to react at 70 °C for 2 h to obtain a multiblock polymer. Dilute the crude multiblock polymer with dichloromethane, precipitate it in methanol, filter and dry to obtain the pure multiblock polymer. Take a small amount of the pure product for nuclear magnetic resonance spectroscopy testing. The results show that the molar content of the polyester segment is 61%, the molar content of the polysilicate carbonate segment is 10%, and the molar content of the polysiloxane segment is 29%. 1 H NMR(400 MHz, CDCl 3 ): δ 4.06 (t, J = 6.7 Hz, 2H), 2.32 (t, J = 7.5 Hz, 2H), 1.30–1.60 (m, 4H), 0.14 (m, 1H), 0.06 (s, 3H). Take a small amount of the pure product for molecular weight testing. The results show that the molecular weight of the multiblock polymer is 193.5 kg / mol, and the molecular weight distribution is 2.11. Make a circular membrane with a uniform thickness by the solution casting method for performance testing. The test results show that the temperature range of use is -20 to 50 °C, the maximum tensile strength is 10 MPa, the elongation at break is 300%, the deformation recovery rate is 95.3%, and the thermoresponsive temperature is 50 °C. The structure of the obtained multiblock polymer is as follows:

[0084]

[0085] Example 9

[0086] Add 2a (67.17 mg, 0.045 mmol), tetramethylammonium chloride (4.93 mg, 0.045 mmol) and ethylene glycol (5.59 mg, 0.09 mmol) to the reaction kettle, and then add D to the reaction kettle at a constant speed 3 3Vi(22.65 g, 87.61 mmol), SA (4.38 g, 43.81 mmol) and 1,4-dioxane (45 g) were reacted at 100 °C for 3 h; L-LA (18.94 g, 131.42 mmol) was added to the reaction kettle, and the molar ratio of L-LA to 2a was 3000:1, and the molar ratio of L-LA to ethylene glycol was 1500:1. The reaction was continued for 2 h to obtain a triblock polymer. An appropriate amount of the reaction solution was taken for molecular weight measurement. The molecular weight of the triblock polymer was 89.8 kg / mol, and the molecular weight distribution was 2.25. IPDI with a molar ratio of 1.1:1 to the triblock polymer was added in situ, and the reaction was continued at 100 °C for 2 h to obtain a multiblock polymer. The crude multiblock polymer was diluted with dichloromethane and precipitated in methanol, and then filtered and dried to obtain a pure multiblock polymer. A small amount of the pure product was taken for nuclear magnetic resonance spectroscopy measurement. The results showed that the molar content of the polyester segment was 57%, the molar content of the polysilicate segment was 15%, and the molar content of the polysiloxane segment was 28%. 1 H NMR (400 MHz, CDCl 3 ): δ 5.45–5.50 (m, 1.5H), 5.20 (m, 0.8H), 5.12–5.18 (q, J = 6.7 Hz, 1H), 2.59 (s, 1H), 1.50–1.59 (m, 3H), 0.19 (m, 2.3H). A small amount of the pure product was taken for molecular weight measurement. The results showed that the molecular weight of the multiblock polymer was 261.3 kg / mol, and the molecular weight distribution was 2.33. A circular membrane with a uniform thickness was prepared by solution casting for performance testing. The test results showed that the temperature range of use was -20 to 173 °C, the maximum tensile strength was 26 MPa, the elongation at break was 500%, the deformation recovery rate was 96.4%, and the thermoresponsive temperature was 173 °C. The structure of the obtained multiblock polymer was as follows:

[0087]

[0088] Example 10

[0089] 2b (37.81 mg, 0.03 mmol), tetrabutylammonium fluoride (7.84 mg, 0.03 mmol) and o-phthalic alcohol (40.07 mg, 0.29 mmol) were added to the reaction kettle, and then D was added to the reaction kettle at a constant speed. 3A mixture of -Ph (39.78 g, 97.34 mmol), PA (7.21 g, 48.67 mmol) and toluene (45 g) was reacted at 110 °C for 3 h; D-LA (21.04 g, 146.02 mmol) was added to the reaction kettle. The molar ratio of D-LA to 2b was 5000:1, and the molar ratio of D-LA to 1,3-propanediol was 500:1. The reaction was continued for 2 h to obtain a triblock polymer. An appropriate amount of the reaction solution was taken for molecular weight testing. The molecular weight of the triblock polymer was 21.9 kg / mol, and the molecular weight distribution was 1.40. HMDI with a molar ratio of 1.1:1 to the triblock polymer was added in-situ, and the temperature was lowered to 60 °C and reacted for 3 h to obtain a multiblock polymer. The crude multiblock polymer was diluted with dichloromethane and precipitated in methanol, and then filtered and dried to obtain the pure multiblock polymer. A small amount of the pure product was taken for nuclear magnetic resonance spectroscopy testing. The results showed that the molar content of the polyester segment was 58%, the molar content of the polysiloxane segment was 29%, and the molar content of the polysilicate segment was 13%. 1 H NMR(400MHz,CDCl 3 ):δ7.55–7.67(m,0.4H),7.34–7.48(m,0.4H),6.96-7.43(m,3.5H),5.12–5.18(q,J=6.7Hz,1H),1.50–1.59(m,3H),0.19(m,2.2H). An appropriate amount of the pure product was taken for molecular weight testing. The results showed that the molecular weight of the multiblock polymer was 67.0 kg / mol, and the molecular weight distribution was 1.98. A circular membrane with a uniform thickness was prepared by the solution casting method for performance testing. The test results showed that the temperature range of use was -20 to 172 °C, the maximum tensile strength was 26 MPa, the elongation at break was 500%, the deformation recovery rate was 94.4%, and the thermoresponsive temperature was 172 °C. The structure of the prepared multiblock polymer is as follows:

[0090]

[0091] Example 11

[0092] 2c (34.81 mg, 0.03 mmol), dodecyltrimethylammonium chloride (2.64 mg, 0.03 mmol) and p-xylene glycol (20.72 mg, 0.15 mmol) were added to the reaction kettle, and then D was added to the reaction kettle at a constant speed 3A mixture of (21.66 g, 97.34 mmol), MA (4.77 g, 48.67 mmol) and xylene (45 g) was reacted at 70 °C for 3 h; DL-LA (21.04 g, 146.02 mmol) was added to the reaction kettle, and the molar ratio of DL-LA to 2b was 5000:1, and the molar ratio of DL-LA to 1,3-propanediol was 1000:1. The reaction was continued for 2 h to obtain a triblock polymer. An appropriate amount of the reaction solution was taken for molecular weight testing. The molecular weight of the triblock polymer was 32.9 kg / mol, and the molecular weight distribution was 1.40. LDI with a molar ratio of 1.1:1 to the triblock polymer was added in situ, and the temperature was raised to 90 °C and reacted for 4 h to obtain a multiblock polymer. The crude multiblock polymer was diluted with dichloromethane and precipitated in methanol, and then filtered and dried to obtain a pure multiblock polymer. A small amount of the pure product was taken for nuclear magnetic resonance spectroscopy testing. The results showed that the molar content of the polyester segment was 58%, the molar content of the polysiloxane segment was 29%, and the molar content of the polysilicate segment was 13%. 1 H NMR (400 MHz, CDCl 3 ): δ6.31 (s, 0.4H), 5.12–5.18 (q, J=6.7 Hz, 1H), 1.50–1.59 (m, 3H), 0.19 (m, 1.3H), 0.06 (s, 3H). A small amount of the pure product was taken for molecular weight testing. The results showed that the molecular weight of the multiblock polymer was 77.0 kg / mol, and the molecular weight distribution was 2.28. A circular membrane with a uniform thickness was prepared by the solution casting method for performance testing. The test results showed that the temperature range of use was -20~150 °C, the maximum tensile strength was 3.5 MPa, the elongation at break was 200%, the deformation recovery rate was 91.4%, and the thermal response temperature was 150 °C. The structure of the obtained multiblock polymer is as follows:

[0093]

[0094] Example 12

[0095] 2d (115.26 mg, 0.09 mmol), tetrabutylammonium chloride (23.90 mg, 0.09 mmol) and 1,3-propanediol (13.31 mg, 0.18 mmol) were added to the reaction kettle, and then D was added to the reaction kettle at a constant speed 3A mixture of (10.00 g, 44.95 mmol), GA-2 (5.22 g, 44.95 mmol) and tetrahydrofuran (20.00 g) was reacted at 60 °C for 2 h; GA-1 (10.16 g, 87.61 mmol) was added to the reaction kettle, the molar ratio of GA-1 to 1a was 1000:1, and the molar ratio of GA-1 to 1,3-propanediol was 500:1, and the reaction was continued for 2 h to obtain a triblock polymer. An appropriate amount of the reaction solution was taken for molecular weight testing. The molecular weight of the triblock polymer was 43.0 kg / mol, and the molecular weight distribution was 1.26. HDI with a molar ratio of 1.1:1 to the triblock polymer was added in situ, and the temperature was raised to 80 °C and reacted for 5 h to obtain a multi-block polymer. The crude multi-block polymer was diluted with dichloromethane and precipitated in methanol, and the pure multi-block polymer was obtained by filtration and drying. A small amount of the pure product was taken for nuclear magnetic resonance spectroscopy testing. The results showed that the molar content of the polyester segment was 47%, the molar content of the polysilicate segment was 18%, and the molar content of the polysiloxane segment was 35%. 1 H NMR (400 MHz, CDCl 3 ): δ 5.04 (s, 2H), 2.22–2.35 (m, 1.5H), 1.77–1.90 (m, 0.8H), 0.19 (m, 2.3H), 0.06 (s, 4.5H). A small amount of the pure product was taken for molecular weight testing. The results showed that the molecular weight of the multi-block polymer was 83.3 kg / mol, and the molecular weight distribution was 2.02. A circular membrane with a uniform thickness was prepared by the solution casting method for performance testing. The test results showed that the temperature range of use was -20 to 230 °C, the maximum tensile strength was 26 MPa, the elongation at break was 500%, the deformation recovery rate was 94.4%, and the thermal response temperature was 200 °C. The structure of the prepared multi-block polymer is as follows:

[0096]

[0097] Comparative Example 12-1

[0098] 2d (115.26 mg, 0.09 mmol), tetrabutylammonium chloride (23.90 mg, 0.09 mmol) and 1,3-propanediol (13.31 mg, 0.18 mmol) were added to the reaction kettle, and then D was added to the reaction kettle at a constant speed 3A mixture of 1a (10.00 g, 44.95 mmol), GA-2 (5.22 g, 44.95 mmol) and tetrahydrofuran (20.00 g) was reacted at 60 °C for 2 h; GA-1 (10.16 g, 87.61 mmol) was added to the reaction kettle, the molar ratio of GA-1 to 1a was 1000:1, and the molar ratio of GA-1 to 1,3-propanediol was 500:1, and the reaction was continued for 2 h to obtain a triblock polymer. An appropriate amount of the reaction solution was taken for molecular weight measurement. The molecular weight of the triblock polymer was 44.0 kg / mol, and the molecular weight distribution was 1.23. The crude triblock polymer was diluted with dichloromethane and precipitated in methanol, and then filtered and dried to obtain a pure triblock polymer. A small amount of the pure product was taken for nuclear magnetic resonance spectroscopy measurement. The results showed that the molar content of the polyester segment was 47%, the molar content of the polysilicate segment was 18%, and the molar content of the polysiloxane segment was 35%. 1 H NMR (400 MHz, CDCl 3 ): δ 5.04 (s, 2H), 2.22–2.35 (m, 1.5H), 1.77–1.90 (m, 0.8H), 0.19 (m, 2.3H), 0.06 (s, 4.5H). A circular film with a uniform thickness was prepared by solution casting for performance testing. The test results showed that the temperature range of use was -20 to 230 °C, the maximum tensile strength was 21 MPa, the elongation at break was 300%, the deformation recovery rate was 50.1%, and the thermal response temperature was 201 °C. The structure of the prepared triblock polymer is as follows:

[0099]

[0100] Example 13

[0101] 1a (54.86 mg, 0.09 mmol), tetrabutylammonium chloride (23.90 mg, 0.09 mmol) and 1,3-propanediol (13.31 mg, 0.18 mmol) were added to the reaction kettle, and then D was added to the reaction kettle at a constant speed 3A mixture of 1a (10.00 g, 44.95 mmol), GA-2 (5.22 g, 44.95 mmol) and tetrahydrofuran (20.00 g) was reacted at 70 °C for 2 h; ε-CL (10.00 g, 87.61 mmol) was added to the reaction kettle. The molar ratio of ε-CL to 1a was 1000:1, and the molar ratio of ε-CL to 1,3-propanediol was 500:1. The reaction was continued for 2 h to obtain a triblock polymer. An appropriate amount of the reaction solution was taken for molecular weight testing. The molecular weight of the triblock polymer was 25.0 kg / mol, and the molecular weight distribution was 1.26. HDI with a molar ratio of 1.1:1 to the triblock polymer was added in-situ, and the temperature was raised to 80 °C and reacted for 4 h to obtain a multiblock polymer. The crude multiblock polymer was diluted with dichloromethane and precipitated in methanol, and then filtered and dried to obtain a pure multiblock polymer. A small amount of the pure product was taken for nuclear magnetic resonance spectroscopy testing. The results showed that the molar content of the polyester segment was 47%, the molar content of the polysilicate segment was 18%, and the molar content of the polysiloxane segment was 35%. 1 H NMR (400 MHz, CDCl 3 ): δ 4.08 (t, J = 6.7 Hz, 2H), 2.32 (t, J = 7.5 Hz, 2H), 1.71–1.60 (m, 4H), 1.40 (p, J = 7.8 Hz, 2H), 2.22–2.35 (m, 1.5H), 1.77–1.90 (m, 0.8H), 0.19 (m, 2.2H), 0.06 (s, 4.5H). A small amount of the pure product was taken for molecular weight testing. The results showed that the molecular weight of the multiblock polymer was 91.3 kg / mol, and the molecular weight distribution was 1.98. A circular membrane with a uniform thickness was prepared by the solution casting method for performance testing. The test results showed that the temperature range of use was -20 to 55 °C, the maximum tensile strength was 19 MPa, the elongation at break was 600%, the deformation recovery rate was 95.4%, and the thermal response temperature was 55 °C. The structure of the prepared multiblock polymer is as follows:

[0102]

[0103] Comparative Example 13-1

[0104] 1a (54.86 mg, 0.09 mmol), tetrabutylammonium chloride (23.90 mg, 0.09 mmol) and 1,3-propanediol (13.31 mg, 0.18 mmol) were added to the reaction kettle, and then D was added to the reaction kettle at a constant speed. 3A mixture of (10.00 g, 44.95 mmol) and tetrahydrofuran (20.00 g) was reacted at 70 °C for 2 h; ε-CL (10.00 g, 87.61 mmol) was added to the reaction kettle. The molar ratio of ε-CL to 1a was 1000:1, and the molar ratio of ε-CL to 1,3-propanediol was 500:1. The reaction was continued for 2 h to obtain a triblock polymer. An appropriate amount of the reaction solution was taken for molecular weight testing. The molecular weight of the triblock polymer was 24.3 kg / mol, and the molecular weight distribution was 1.21. HDI with a molar ratio of 1.1:1 to the triblock polymer was added in situ, and the temperature was raised to 80 °C and reacted for 4 h to obtain a multiblock polymer. The crude multiblock polymer was diluted with dichloromethane and precipitated in methanol, and then filtered and dried to obtain a pure multiblock polymer. A small amount of the pure product was taken for nuclear magnetic resonance spectroscopy testing. The results showed that the molar content of the polyester segment was 47% and the molar content of the polysiloxane segment was 53%. 1 H NMR (400 MHz, CDCl 3 ): δ 4.08 (t, J = 6.7 Hz, 2H), 2.32 (t, J = 7.5 Hz, 2H), 1.71–1.60 (m, 4H), 1.40 (p, J = 7.8 Hz, 2H), 0.06 (s, 6.7H). A small amount of the pure product was taken for molecular weight testing. The results showed that the molecular weight of the multiblock polymer was 89.3 kg / mol, and the molecular weight distribution was 2.02. A circular membrane with a uniform thickness was prepared by the solution casting method for performance testing. The test results showed that the temperature range of use was -20 to 54 °C, the maximum tensile strength was 15 MPa, the elongation at break was 500%, the deformation recovery rate was 81.4%, and the thermoresponsive temperature was 50 °C. The structure of the prepared multiblock polymer is as follows:

[0105]

[0106] Comparative Example 13-2

[0107] 1a (54.86 mg, 0.09 mmol), tetrabutylammonium chloride (23.90 mg, 0.09 mmol) and 1,3-propanediol (13.31 mg, 0.18 mmol) were added to the reaction kettle, and then D was added to the reaction kettle at a constant speed 3A mixture of (10.00 g, 44.95 mmol) and tetrahydrofuran (20.00 g) was reacted at 70 °C for 2 h; ε-CL (10.00 g, 87.61 mmol) was added to the reaction kettle. The molar ratio of ε-CL to 1a was 1000:1, and the molar ratio of ε-CL to 1,3-propanediol was 500:1. The reaction was continued for 2 h to obtain a triblock polymer. An appropriate amount of the reaction solution was taken for molecular weight testing. The molecular weight of the triblock polymer was 24.1 kg / mol, and the molecular weight distribution was 1.20. The crude triblock polymer was diluted with dichloromethane and precipitated in methanol, and then filtered and dried to obtain the pure triblock polymer. A small amount of the pure product was taken for nuclear magnetic resonance spectroscopy testing. The results showed that the molar content of the polyester segment was 47% and the molar content of the polysiloxane segment was 53%. 1 H NMR(400MHz,CDCl 3 ):δ4.08(t,J=6.7Hz,2H),2.32(t,J=7.5Hz,2H),1.71–1.60(m,4H),1.40(p,J=7.8Hz,2H),0.06(s,6.7H). A circular film with a uniform thickness was prepared by solution casting for performance testing. The test results showed that the temperature range of use was -20 to 52 °C, the maximum tensile strength was 10 MPa, the elongation at break was 400%, the deformation recovery rate was 55.4%, and the thermoresponsive temperature was 52 °C. The structure of the prepared triblock polymer was as follows:

[0108]

[0109] Example 14

[0110] 1a (54.86 mg, 0.09 mmol), tetrabutylammonium chloride (23.90 mg, 0.09 mmol) and 1,3-propanediol (13.31 mg, 0.18 mmol) were added to the reaction kettle, and then D was added to the reaction kettle at a constant speed 3A mixture of 1a (10.00 g, 44.95 mmol), GA-2 (5.22 g, 44.95 mmol) and tetrahydrofuran (20.00 g) was reacted at 65 °C for 2 h; L-LA (16.62 g, 87.61 mmol) was added to the reaction kettle, and the molar ratio of L-LA to 1a was 1000:1, and the molar ratio of L-LA to 1,3-propanediol was 500:1, and the reaction was continued for 2 h to obtain a triblock polymer. An appropriate amount of the reaction solution was taken for molecular weight testing. The molecular weight of the triblock polymer was 35.0 kg / mol, and the molecular weight distribution was 1.16. HDI with a molar ratio of 1.1:1 to the triblock polymer was added in situ, and the temperature was raised to 80 °C and reacted for 2 h to obtain a multiblock polymer. The crude multiblock polymer was diluted with dichloromethane and precipitated in methanol, and the pure multiblock polymer was obtained by filtration and drying. A small amount of the pure product was taken for nuclear magnetic resonance spectroscopy testing. The results showed that the molar content of the polyester segment was 49%, the molar content of the polysilicate segment was 17%, and the molar content of the polysiloxane segment was 34%. 1 H NMR (400 MHz, CDCl 3 ): δ 5.12–5.18 (q, J = 6.7 Hz, 1H), 2.22–2.35 (m, 1.4H), 1.77–1.90 (m, 0.7H), 1.50–1.59 (m, 3H), 0.19 (m, 2H), 0.06 (s, 4H). A small amount of the pure product was taken for molecular weight testing. The results showed that the molecular weight of the multiblock polymer was 103.3 kg / mol, and the molecular weight distribution was 2.12. A circular film with a uniform thickness was prepared by the solution casting method for performance testing. The test results showed that the temperature range of use was -20 to 175 °C, the maximum tensile strength was 21 MPa, the elongation at break was 450%, the deformation recovery rate was 95.4%, and the thermal response temperature was 175 °C. The structure of the obtained multiblock polymer is as follows:

[0111]

[0112] Comparative Example 14-1

[0113] 1a (54.86 mg, 0.09 mmol), tetrabutylammonium chloride (23.90 mg, 0.09 mmol) and 1,3-propanediol (13.31 mg, 0.18 mmol) were added to the reaction kettle, and then D was added to the reaction kettle at a constant speed 3A mixture of (10.00 g, 44.95 mmol) and tetrahydrofuran (20.00 g) was reacted at 65 °C for 2 h; L-LA (16.62 g, 87.61 mmol) was added to the reaction kettle. The molar ratio of L-LA to 1a was 1000:1, and the molar ratio of L-LA to 1,3-propanediol was 500:1. The reaction was continued for 2 h to obtain a triblock polymer. An appropriate amount of the reaction solution was taken for molecular weight testing. The molecular weight of the triblock polymer was 34.3 kg / mol, and the molecular weight distribution was 1.22. HDI with a molar ratio of 1.1:1 to the triblock polymer was added in situ, and the temperature was raised to 80 °C and reacted for 2 h to obtain a multi-block polymer. The crude multi-block polymer was diluted with dichloromethane and precipitated in methanol, and then filtered and dried to obtain a pure multi-block polymer. A small amount of the pure product was taken for nuclear magnetic resonance spectroscopy testing. The results showed that the molar content of the polyester segment was 50%, and the molar content of the polysiloxane segment was 50%. 1 H NMR (400 MHz, CDCl 3 ): δ 5.12–5.18 (q, J = 6.7 Hz, 1H), 1.50–1.59 (m, 3H), 0.06 (s, 6H). A small amount of the pure product was taken for molecular weight testing. The results showed that the molecular weight of the multi-block polymer was 101.3 kg / mol, and the molecular weight distribution was 2.03. A circular membrane with a uniform thickness was prepared by the solution casting method for performance testing. The test results showed that the temperature range of use was -20 to 172 °C, the maximum tensile strength was 15 MPa, the elongation at break was 400%, the deformation recovery rate was 85.4%, and the thermal response temperature was 172 °C. The structure of the prepared multi-block polymer is as follows:

[0114]

[0115] Comparative Example 14-2

[0116] 1a (54.86 mg, 0.09 mmol), tetrabutylammonium chloride (23.90 mg, 0.09 mmol) and 1,3-propanediol (13.31 mg, 0.18 mmol) were added to the reaction kettle, and then D was added to the reaction kettle at a constant speed 3A mixture of (10.00 g, 44.95 mmol) and tetrahydrofuran (20.00 g) was reacted at 65 °C for 2 h; L-LA (16.62 g, 87.61 mmol) was added to the reaction kettle. The molar ratio of L-LA to 1a was 1000:1, and the molar ratio of L-LA to 1,3-propanediol was 500:1. The reaction was continued for 2 h to obtain a triblock polymer. An appropriate amount of the reaction solution was taken for molecular weight testing. The molecular weight of the triblock polymer was 35.9 kg / mol, and the molecular weight distribution was 1.26. The crude triblock polymer was diluted with dichloromethane and precipitated in methanol, and then filtered and dried to obtain a pure triblock polymer. A small amount of the pure product was taken for nuclear magnetic resonance spectroscopy testing. The results showed that the molar content of the polyester segment was 51% and the molar content of the polysiloxane segment was 49%. 1 H NMR (400 MHz, CDCl 3 ): δ 5.12–5.18 (q, J = 6.7 Hz, 1H), 1.50–1.59 (m, 3H), 0.06 (s, 6H). A circular membrane with a uniform thickness was prepared by solution casting for performance testing. The test results showed that the temperature range of use was -20 to 170 °C, the maximum tensile strength was 11 MPa, the elongation at break was 370%, the deformation recovery rate was 65.4%, and the thermoresponsive temperature was 170 °C. The structure of the prepared triblock polymer is as follows:

[0117]

Claims

1. A method for preparing a polyester-based multi-block thermo-induced shape memory material with adjustable performance, characterized in that: The method comprises the following steps: adding a catalyst, a co-catalyst and a chain transfer agent into a reaction kettle, then adding an organic solvent, uniformly mixing cyclosiloxane and a third monomer and then uniformly adding the mixture into the reaction kettle to obtain a binary copolymer, then adding a cyclic ester to carry out a first polymerization reaction to obtain a triblock polymer; adding a chain extender into the reaction system to carry out a second polymerization reaction to obtain a multiblock polymer; the obtained multiblock polymer has a shape memory effect under heat treatment; the general reaction formula of the copolymer is as follows:

2. The preparation method according to claim 1, characterized in that: The catalyst is a metal complex, specifically catalyst 1, catalyst 2-1 or catalyst 2-2, and has the following structure: Where: M 1 Selected from Zr 4+ 、Ti 4+ ;M 2 Selected from Al 3+ 、In 3+ Cr 3+ , Ga 3+ or Fe 3+ One or two of them; p is a non-zero natural number; R is R' is R 5 , R 6 , R 7 is H, C1-C4 alkyl, C1-C4 alkoxy; R 5 , R 6 and R 7 Same or different; X is F -1 , Cl -1 Br -1 ,I -1 、NO3 -1 、CH3COO -1 Or C1~C4 alkoxy.

3. The preparation method according to claim 1, characterized in that: The cyclic ester is one of ε-caprolactone (ε-CL), δ-valerolactone (δ-VL), levorotatory lactide (L-LA), dextrorotatory lactide (D-LA), racemic lactide (DL-LA), and glycolide (GA-1); Cyclosiloxanes are hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), hexaethylcyclotrisiloxane (D3 6Et )、2,4,6-trivinyl-2,4,6-trimethylcyclotrisiloxane (D3 3Vi ), 2,4,6-trimethyl-2,4,6-triphenylcyclotrisiloxane (D3-Ph), hexaphenylcyclotrisiloxane (D3 6Ph ), tetramethyltetravinylcyclotetrasiloxane (D4 4Vi ), one of 1,3,5-trimethyl-1,3,5-tris(3,3,3-trifluoropropyl)cyclotrisiloxane (D3-CF3); The third monomer is one of carbon dioxide (CO2), carbon disulfide (CS2), cyclic anhydride, and cyclosiloxane; wherein the cyclic anhydride is one of succinic anhydride (SA), methylsuccinic anhydride (MSA), maleic anhydride (MA), glutaric anhydride (GA-2), diglycolic anhydride (DGA), 3-methylglutaric anhydride (MGA), 3,3-dimethylglutaric anhydride (3,3-DMGA), hexahydrophthalic anhydride (HHPA), phthalic anhydride (PA), and 4-methylphthalic anhydride (MPA); Monomer refers to monomer; The structural formulas of the cyclic esters, cyclosiloxanes and cyclic anhydrides used are shown below: x, y, z, g, m are non-zero natural numbers, and n=3, 4, 5.

4. The preparation method according to claim 1, characterized in that: The co-catalyst used is one of tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium fluoride, tetramethylammonium iodide, tetramethylammonium acetate, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetraethylammonium fluoride, 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(triphenylphosphorane)ammonium chloride, methyltriphenylphosphonium bromide and allyltriphenylphosphonium bromide; The chain transfer agent is one of ethylene glycol, 1,3-propylene glycol, glycerol, 1,4-butanediol, pentaerythritol, terephthalic acid alcohol, isophthalic acid alcohol, o-phthalic acid alcohol, polyethylene glycol 400, polyethylene glycol 600, polypropylene glycol 400, and polypropylene glycol 600; The organic solvent is one of toluene, xylene, acetonitrile, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dioxane, n-hexane and cyclohexane; The chain extender is one of 4,4'-methylenebis(phenyl isocyanate) (MDI), hexamethylene diisocyanate (HDI), toluene-2,4-diisocyanate (TDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (HMDI), and L-lysine diisocyanate (LDI).

5. The preparation method according to claim 1, characterized in that: The molar ratio of the cyclic ester, cyclosiloxane and the third monomer added is 1:0.1-0.7:0.1-0.7; in the first polymerization reaction, the molar ratio of the catalyst to the cyclic ester is 1:500-20000, the molar ratio of the co-catalyst to the catalyst is 0.5-3:1, the molar ratio of the chain transfer agent to the cyclic ester is 1-500:20000, the reaction temperature is 30-150°C, and the reaction time is 1-6h.

6. The preparation method according to claim 1, characterized in that: In the second polymerization reaction, the molar ratio of the chain extender to the triblock polymer is 1 to 1.5:1, the reaction temperature is 40 to 100° C., and the reaction time is 1 to 6 hours.

7. The preparation method according to claim 1, characterized in that: The reaction temperature for obtaining the binary copolymer is 30-150°C, and the reaction time is 1-10 hours.

8. The preparation method according to claim 1, characterized in that: The synthesis equation of the catalyst 1 is as follows: The preparation steps of the catalyst 1 are as follows: Under the protection of inert gas, dialdehyde and monoamine are mixed in a molar ratio of 1:2 to 2.5, dissolved in ethanol in a mass ratio of 2 to 5:1 to dialdehyde, and stirred at room temperature for reaction for 2 to 10 hours; after the reaction stops, suction filtration is performed, and the filter cake is rinsed with ethanol for 2 to 3 times, the filtrate is decompressed and distilled and vacuum dried to obtain an intermediate product 1, which is transferred into a glove box for standby use; in the glove box, the intermediate product 1 is weighed into a container equipped with a magnet, and dissolved in an organic solvent in a mass ratio of 3 to 10:1 to the intermediate product 1; a metal salt or an alkyl metal in a molar ratio of 1 to 1.2:1 to the intermediate product 1 is weighed; the reaction is carried out at 25 to 80° C. for 12 to 36 hours; the catalyst 1 is obtained after the organic solvent is removed under reduced pressure; the metal salt or the alkyl metal is one of a metal halide, a metal nitrate, a metal acetate, a C1-C4 alkoxy metal salt, and an alkyl metal; The synthesis equation of the catalyst 2-1 is as follows: The preparation steps of the catalyst 2-1 are as follows: Under the protection of inert gas, diamine-1 and monoaldehyde in a molar ratio of 1 to 1.5:2 are mixed, and ethanol in a mass ratio of 2 to 5:1 to the monoaldehyde is dissolved, and the reaction is stirred at 25 to 80°C for 1 to 6 hours to stop the reaction, and the filter is filtered, and the filter cake is rinsed with ethanol 2 to 3 times, and the filtrate is decompressed and distilled and vacuum dried to obtain mononuclear ligand 1; under the protection of inert gas, mononuclear ligand 1 and diacyl chloride in a molar ratio of 2:1 to 1.5 are mixed, and then 4-dimethylaminopyridine and triethylamine in a molar ratio of 1 to 1.5:2 to the mononuclear ligand 1 are added, and the mixture is stirred at 25 to 80°C for 1 to 6 hours. Stir and react for 3 to 10 hours; stop the reaction, filter, distill under reduced pressure and dry under vacuum to obtain L2-1, and move it into a glove box for use; weigh L2-1 in the glove box, and dissolve it in an organic solvent with a mass ratio of 5 to 10:1 to L2-1; weigh a metal salt or alkyl metal with a molar ratio of 2 to 2.2:1 to L2-1; react at 25 to 100° C. for 12 to 36 hours; remove the organic solvent under reduced pressure to obtain catalyst 2-1; the metal salt or alkyl metal is one of metal halide, metal nitrate, metal acetate, C1-C4 alkoxy metal salt, and alkyl metal; The synthesis equation of the catalyst 2-2 is as follows: The preparation steps of the catalyst 2-2 are: Under the protection of inert gas, diamine-2 and monoaldehyde in a molar ratio of 1 to 1.5:2 are mixed, polyformaldehyde in a molar ratio of 2 to 4:1 to diamine-2 is added, and it is dissolved in ethanol in a mass ratio of 2 to 5:1 to the monoaldehyde, and the reaction is stirred at 25 to 80°C for 2 to 14 hours, and the solvent is removed by rotary evaporation to obtain a white solid; the white solid is dissolved in water, sodium bicarbonate is added to neutralize it, and it is extracted with methyl tert-butyl ether for 3 to 5 times; the organic layers are combined, dried with anhydrous sodium sulfate, the solid is filtered out, and the methyl tert-butyl ether is removed by rotary evaporation to obtain mononuclear ligand 2; the subsequent reaction steps are the same as the preparation method of catalyst 2-1.

9. A polyester-based multi-block thermo-induced shape memory material with adjustable properties obtained by the preparation method according to any one of claims 1 to 8.

10. The polyester-based multi-block thermo-induced shape memory material with adjustable properties according to claim 9, characterized in that: The triblock copolymer comprises a polyester segment and a binary copolymer segment, wherein the binary copolymer segment can be subdivided into four categories according to different comonomers: polyester-co-polysilocarbonate-co-polysiloxane, polyester-co-polysilothiocarbonate-co-polysiloxane, polyester-co-polysilicone-co-polysiloxane, and polysiloxane. The general structural formulas of the triblock copolymer and the binary copolymer are as follows: The molar content of the polyester segment in the triblock copolymer is 30-80%, and the molar content of the binary copolymer segment is 20-70%; the number average molecular weight of the triblock copolymer is 20.0-90.0 kg / mol, and the molecular weight distribution is 1.1-1.6; the number average molecular weight of the multiblock polymer is 60.0-300.0 kg / mol, and the molecular weight distribution is 1.1-2.7; the use window temperature of the obtained multiblock polymer is -40-230°C, the maximum tensile strength is 3-26 MPa, the elongation at break is 200-1500%, the shape recovery rate is>90%, and the thermal response temperature range is 50-220°C.

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