Synthesis method of carbon dioxide-based alkenyl / ether / ester group functionalized polyurethane high polymer material

Abstract

The invention discloses a synthesis method of a carbon dioxide-based alkene / ether / ester group functionalized polyurethane high polymer material, which is a novel method for synthesizing a novel alkene / ether / ester group functionalized polyurethane high polymer material with a clear structure and a specific spatial configuration by taking carbon dioxide platform molecule ethylene carbonate as a raw material and utilizing a hydroxyl-alkyne click reaction. Relates to the technical fields of organic synthesis, polymer synthesis, polymer chemistry, polymer materials and the like. The carbon dioxide-based bifunctional alcohol monomer is efficiently synthesized through aminolysis reaction of diamine and ethylene carbonate, a hydroxyl-alkyne polymerization system is developed, organic phosphine or organic amine which is low in price and easy to obtain is used as a catalyst, addition polymerization reaction of the bifunctional alcohol monomer and the bifunctional alkynoic acid ester monomer under mild conditions is achieved, and the carbon dioxide-based bifunctional alcohol monomer is synthesized. A series of novel alkene / ether / ester group functionalized polyurethane high polymer materials with clear structures and specific spatial configurations are constructed.

Description

Technical Field

[0001] The invention discloses a method for synthesizing a carbon dioxide-based olefin / ether / ester group functionalized polyurethane polymer material. The method uses carbon dioxide platform molecule ethylene carbonate as a raw material and utilizes a "hydroxyl-alkyne" click reaction to synthesize a novel olefin / ether / ester group functionalized polyurethane polymer material with a clear structure and specific stereo configuration. The method involves technical fields such as organic synthesis, polymer synthesis, polymer chemistry and polymer materials. Background Art

[0002] Polyurethane is a type of polymer material with a main chain containing carbamate groups, which is generated by the step-by-step polymerization of isocyanates and polyols. It is widely used in furniture, construction, automobiles, medical and electronics. In the furniture industry, polyurethane soft foam is used to make mattresses and upholstered furniture to provide comfortable support, while hard foam is used for thermal insulation materials. In the automotive field, it is used for seats, dashboards and interior parts. The medical industry uses its biocompatibility to make artificial organs and drug release systems. The electronics industry uses its electrical insulation to make sheaths and insulation materials for wires and cables. In addition, polyurethane materials have good weather resistance and UV resistance, and can be used outdoors for a long time without being easily degraded.

[0003] In recent years, in order to address the problems of isocyanate toxicity and dependence on petroleum resources in traditional processes, green synthesis technology has developed rapidly. Non-isocyanate polyurethanes have achieved environmentally friendly preparation through ring-opening polymerization of cyclic carbonates and amines. This synthesis method not only avoids the use of toxic phosgene, but also has the advantages of mild reaction conditions and low production of by-products. At the same time, the development of carbon dioxide-based polyol monomers further converts greenhouse gases into high-performance polyurethane materials, promoting their innovative applications in cutting-edge fields such as smart response materials and degradable medical devices.

[0004] At the same time, click polymerization has attracted widespread attention as an efficient, mild and easy-to-operate polymerization method. The "thiol-alkyne" Michael addition reaction is a type of green, efficient and atom-economical click chemistry reaction. In 2016, Andrew P. Dove's research group at the University of Birmingham in the UK used the "thiol-alkyne" click polymerization reaction to prepare polyene sulfide esters with adjustable cis-trans ratio of main chain double bonds between 32% and 80% (CA Bell, J. Yu, IA Barker, VXTruong, Z. Cao, AV Dobrinyin, ML Becker and AP Dove, Angew. Chem. Int. Ed, 2016, 55, 13076-13080.). The cis-rich and trans-rich polyene sulfide esters showed obvious differences in thermal and mechanical properties. Subsequently, Dove's team created a series of high-performance polymer materials with adjustable mechanical properties based on the stereochemically controllable "thiol-alkyne" addition strategy (JCWorch and APDove, Acc.Chem.Res, 2022, 55, 2355-2369.).

[0005] Compared with sulfur atoms, oxygen atoms have the characteristics of small atomic radius, low polarizability, and large electronegativity, which also causes the acidity and nucleophilicity of hydroxyl groups to be significantly lower than that of sulfhydryl groups, and therefore have lower reactivity. However, compared with sulfhydryl compounds, hydroxyl compounds are widely present in biomass and its derivatives in nature, and have the advantages of wide sources, low cost, rich structure, and green and non-toxic. In 1995, the Endo research team made a breakthrough and successfully realized the polycondensation reaction of aliphatic diols and dipropiolate using tri-n-butylphosphine as a catalyst. It is worth noting that the reaction has strict stereoselectivity and only generates trans-configuration polymers (H.Kuroda, I.Tomita, T.Endo, Macromolecules 1995, 28, 433-436.). In 2017, Tang's team made important progress in the synthesis of aromatic polymers. They innovatively developed an organic amine-catalyzed condensation system of aromatic diols and diaryl acetylates, and successfully prepared polyene ether ketone products with a single trans configuration (Y. Shi, T. Bai, W. Bai, Z. Wang, M. Chen, B. Yao, J. Z. Sun, A. Qin, J. Ling, B. Z. Tang, Chem. Eur. J. 2017, 23, 10725-10731.). In 2020, the research team of Tang and Qin introduced the strong nucleophilic catalyst bicyclo[2.2.2]-1,4-diazacyclooctane (DABCO), which significantly expanded the substrate applicability under mild reaction conditions. This catalytic system is not only suitable for aliphatic diol systems, but also can effectively catalyze the stereoselective polymerization of aromatic diols and dipropiolate (H.Si, K.Wang, B.Song, A.Qin, BZTang, Polym.Chem.2020,11,2568-2575). In addition, this method has also been successfully applied to the preparation of polymers with special properties, such as self-healing materials, drug carriers and fluorescent materials. Therefore, it is of great research value to construct a new carbon dioxide-based olefin / ether / ester group functionalized polyurethane polymer material using the "hydroxyl-alkyne" addition polymerization strategy. Summary of the invention

[0006] The present invention efficiently synthesizes six carbon dioxide-based difunctional alcohol monomers through the ring-opening reaction of difunctional amines on ethylene carbonate, and the difunctional alcohol monomers and difunctional acetylic acid ester monomers are subjected to a "hydroxyl-alkyne" click polymerization reaction to construct a series of novel olefin / ether / ester group functionalized polyurethane polymer materials with clear structures and specific stereo configurations, converting carbon dioxide into high-performance polyurethane materials, thereby achieving the regulation of the thermal stability and crystallinity of the polymer.

[0007] To achieve the above purpose, the present invention adopts the following technical solutions:

[0008] A method for synthesizing a carbon dioxide-based olefin / ether / ester group functionalized polyurethane polymer material, comprising the following steps:

[0009] Step (1) synthesizing a carbon dioxide-based difunctional alcohol monomer through a ring-opening reaction of ethylene carbonate and a difunctional amine:

[0010] The difunctional organic amine and ethylene carbonate are mixed, and then a solvent is added and stirred for reaction. After the reaction is completed, the reaction solution is concentrated in vacuo to obtain a crude product. The crude product is purified by column chromatography or recrystallized using an organic solvent to obtain a carbon dioxide-based difunctional alcohol monomer.

[0011] The molar ratio of the bifunctional organic amine to ethylene carbonate is 1:1 to 1:3.

[0012] The solvent is one or a mixture of two or more of dichloromethane, acetone, methanol, acetonitrile and tetrahydrofuran.

[0013] The reaction temperature is 0 to 60 degrees Celsius, and the reaction time is 3 to 8 hours.

[0014] In the above method, the crude product is purified by column chromatography or organic solvent recrystallization (n-hexane, n-pentane, acetonitrile, ether). In the column chromatography purification, the column chromatography eluent is a mixed solution of dichloromethane and anhydrous methanol, and the volume ratio of dichloromethane to anhydrous methanol is 10:1 to 2:1.

[0015] Step (2) The difunctional alcohol monomer and the difunctional alkyne ester monomer undergo a "hydroxyl-alkyne" click polymerization reaction to construct an olefin / ether / ester group functionalized polyurethane polymer material.

[0016] Add a difunctional alcohol monomer, an organic catalyst and a solvent to a reaction bottle, dissolve a difunctional acetylide ester monomer in a solvent to prepare a difunctional acetylide ester monomer solution, and then drop the difunctional acetylide ester monomer solution into the reaction bottle drop by drop, and polymerize after the addition is completed. After the reaction is completed, add a poor solvent used for recrystallization to the polymerization reaction solution to produce a white precipitate. Centrifuge and vacuum dry to constant weight to obtain a synthetic carbon dioxide-based olefin / ether / ester group functionalized polyurethane polymer material.

[0017] The molar ratio of the bifunctional alcohol monomer, the bifunctional acetylic acid ester monomer and the organic catalyst is 1:1:(0.03-0.10).

[0018] The organic catalyst is a commercial organic amine catalyst, including one or a mixture of two or more of triethylenediamine, quinuclidine and N-methylpyrrole.

[0019] The solvent is one of dimethyl sulfoxide, N,N-dimethylformamide and tetrahydrofuran or a mixture of two or more thereof.

[0020] The reaction temperature is 0 to 60 degrees Celsius, and the reaction time is 3 to 60 minutes.

[0021] The poor solvent is one or a mixture of two or more of ether, methanol, ethanol and toluene.

[0022] The difunctional alcohol monomer structural formula is one of the following:

[0023]

[0024] The difunctional acetylic acid ester monomer is one of the following:

[0025]

[0026] Beneficial effects of the present invention:

[0027] Using ethylene carbonate derived from carbon dioxide as raw material, a series of carbon dioxide-based bifunctional alcohol monomers were prepared by aminolysis reaction. The alcohol monomer and the alkyne ester monomer were polymerized by "hydroxy-alkyne" click polymerization to prepare a series of new olefin / ether / ester functionalized polyurethane polymer materials with clear structure and specific stereo configuration with a number average molecular weight of 10-15 kg / mol. The synthesized polyurethane material has good thermal stability. The introduction of oxygen atoms in the bifunctional alcohol or alkyne ester monomer can reduce the glass transition temperature and transform the polymer from a semi-crystalline material to an amorphous material. In addition, this type of polymer exhibits shape memory properties under thermal stimulation. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 and Figure 2 They are the DSC and TGA curves of carbon dioxide-based polyurethane materials respectively.

[0029] Figure 3 It is a dumbbell-shaped specimen of CO2-based polyurethane material in its initial state.

[0030] Figure 4 It is a dumbbell-shaped specimen of CO2-based polyurethane material in a fixed temporary shape.

[0031] Figure 5 It is a dumbbell-shaped specimen of the CO2-based polyurethane material after shape recovery. DETAILED DESCRIPTION

[0032] The specific implementation of the present invention is further described below in conjunction with the accompanying drawings and technical solutions.

[0033] 1. Monomer preparation (taking 1,4-butanediamine as an example)

[0034]

[0035] Six bifunctional alcohol monomers with different carbon chain lengths and containing carbamate bonds were synthesized by the reaction of ethylene carbonate with diamines of different carbon chain lengths. The specific experimental steps are as follows: 1,4-butanediamine (1 equiv.), ethylene carbonate (2-3 equiv.) and dichloromethane were added to a three-necked flask and stirred at room temperature for 3 hours. After the reaction, the dichloromethane in the reaction solution was removed by vacuum concentration to obtain a light yellow solid. In order to further purify the product, hot acetonitrile was used for recrystallization, and a white solid product (yield 95%) was finally obtained.

[0036] Example 1

[0037] 1,6-Hexanediamine (1 equiv.), ethylene carbonate (2.05 equiv.) and dichloromethane were added to a three-necked flask and stirred at room temperature for 3 hours. After the reaction was completed, dichloromethane was removed from the reaction solution by vacuum concentration to obtain a light yellow solid. In order to further purify the product, hot acetonitrile was used for recrystallization to finally obtain a white solid product 1b (yield 92%).

[0038] Example 2

[0039] 1,8-octanediamine (1 equiv.), ethylene carbonate (2.05 equiv.) and dichloromethane were added to a three-necked flask and stirred at room temperature for 3 hours. After the reaction was completed, dichloromethane was removed from the reaction solution by vacuum concentration to obtain a light yellow solid. In order to further purify the product, hot acetonitrile was used for recrystallization to finally obtain a white solid product 1c (yield 91%).

[0040] Example 3

[0041] 2,2'-oxybis(ethylamine) (1 equiv.), ethylene carbonate (2.05 equiv.) and dichloromethane were added to a three-necked flask and stirred at room temperature for 3 hours. After the reaction was completed, dichloromethane was removed from the reaction solution by vacuum concentration to obtain a light yellow solid. In order to further purify the product, hot acetonitrile was used for recrystallization to finally obtain a white solid product 1d (yield 86%).

[0042] Example 4

[0043] 1,8-diamino-3,6-dioxaoctane (1 equiv.), ethylene carbonate (2.05 equiv.) and dichloromethane were added to a three-necked flask and stirred at room temperature for 3 hours. After the reaction was completed, dichloromethane in the reaction solution was removed by vacuum concentration, and the reaction solution was concentrated in vacuum to form a light yellow oil. Subsequently, a solvent mixed with dichloromethane and methanol in a volume ratio of 5:1 was used as an eluent for column chromatography, and a transparent oily product monomer 1e was successfully separated and obtained (yield 76%).

[0044] Example 5

[0045] 1,8-diamino-3,6-dioxaoctane (1 equiv.), ethylene carbonate (2.05 equiv.) and dichloromethane were added to a three-necked flask and stirred at room temperature for 3 hours. After the reaction was completed, dichloromethane in the reaction solution was removed by vacuum concentration, and the reaction solution was concentrated in vacuum to form a light yellow oil. Subsequently, a solvent mixed with dichloromethane and methanol in a volume ratio of 5:1 was used as an eluent for column chromatography, and a transparent oily product monomer 1f was successfully separated and obtained (yield 72%).

[0046] The NMR characterization data are as follows:

[0047] Monomer 1a: 1 H NMR (500 MHz, DMSO-d 6 )δ7.02(s,2H),4.67(s,2H),3.93(s,4H),3.52(s,4H),2.94(s,4H),1.36(s,4H). 13 C NMR (101 MHz, DMSO-d 6 )δ156.64,65.70,59.76,40.16,27.02.HRMS(ESI):calcd for C 10 H 20 N 2 O 6 :264.1321[M+Na + ].Found:287.1213[M+Na + ].

[0048] Monomer 1b: 1 H NMR (500 MHz, DMSO-d 6 )δ7.02(s,2H),4.68(s,2H),3.93(s,4H),3.52(s,4H),3.05–2.82(m,4H),1.36(s,4H),1.22(s,4H). 13 C NMR (126 MHz, DMSO-d 6 )δ156.49,65.55,59.66,40.27,29.50,26.07.HRMS(ESI):calcd for C 12 H 24 N 2 O 6 :292.1634[M+Na + ].Found:315.1527[M+Na +.

[0049] Monomer 1c: 1 H NMR(500MHz,DMSO-d 6 )δ7.07(t,J = 5.7Hz,2H),4.71(s,2H),3.93(t,J = 5.3Hz,4H),3.51(t,J = 5.3Hz,4H),2.94(q,J = 6.7Hz,4H),1.37(t,J = 7.1Hz,4H),1.23(s,8H). 13 C NMR(101MHz,DMSO-d 6 )δ156.57,65.63,59.75,40.41,29.62,28.92,26.42.HRMS(ESI):calcd for C 14 H 28 N 2 O 6 :320.1947[M+Na + .Found:343.1840[M+Na + .

[0050] Monomer 1d: 1 H NMR(500MHz,DMSO-d 6 )δ7.15(d,J = 4.8Hz,2H),4.71(s,2H),3.95(t,J = 5.1Hz,4H),3.53(t,J = 4.9Hz,4H),3.37(t,J = 5.6Hz,5H),3.12(q,J = 5.6Hz,4H). 13 C NMR(101MHz,DMSO-d 6 )δ156.68,69.15,65.83,59.70,40.36.HRMS(ESI):calcd forC 10 H 20 N 2 O 7 :280.1271[M+Na + .Found:303.1163[M+Na + .

[0051] Monomer 1e: 1 H NMR(400MHz,DMSO-d 6 )δ7.09(t,J = 5.7Hz,2H),4.73(s,2H),3.94(t,J = 5.2Hz,4H),3.52(t,J = 5.2Hz,4H),3.48(s,4H),3.24–3.02(m,6H).13 C NMR (101 MHz, DMSO-d 6 )δ156.74,69.77,69.41,65.90,59.77,40.36.HRMS(ESI):calcd for C 12 H 24 N 2 O 8 :324.1533[M+Na + ].Found:347.1425[M+Na + ].

[0052] Monomer 1f: 1 H NMR (400 MHz, DMSO-d 6 )δ7.04(t,J=5.7Hz,2H),4.68(t,J=5.4Hz,2H),3.94(t,J=5.2Hz,4H),3.56–3.45(m,12H),3.41–3.36(m,4H),3.11(q,J=5.9Hz,4H). 13 CNMR (101MHz, DMSO-d 6 )δ156.86,70.19,69.99,69.59,66.03,59.92,40.54.HRMS(ESI):calcd for C 14 H 28 N 2 O 9 :368.1795[M+Na + ].Found:391.1687[M+Na + ].

[0053] 2. Monomer polymerization

[0054] At room temperature, a difunctional alcohol monomer, dimethyl sulfoxide (DMSO) and 5 mol% organic catalyst at a concentration of 1 mol / L are added to the reaction bottle, and a difunctional alkyne ester monomer of the same amount as the difunctional alcohol monomer is dissolved in DMSO to prepare a 1 mol / L solution, and then the difunctional alkyne ester monomer is added dropwise to the reaction bottle, and the reaction is carried out for 5 minutes after the addition is completed. After the reaction is completed, the reaction solution is poured into 0.01 mol / L to 0.05 mol / L methanol to obtain a polymer precipitate. Subsequently, the suspension is placed in a centrifuge and centrifuged at 8000 rpm for 5 minutes to ensure that the polymer particles are fully settled. After the centrifugation is completed, the supernatant is carefully poured. The precipitated polymer is redissolved in a dimethyl sulfoxide solution and washed three times to completely remove the unreacted monomer and impurities. Finally, the polymer is placed in a vacuum drying oven at 100°C and dried for 12 hours, and the solvent is removed until constant weight is obtained to obtain a pure polymer product.

[0055] It can be seen from Experiments 1-3 that the conversion rate of monomer 1a is greater than 99% under the catalysis of Quinuclidine and N-methylpyrrole (NMP), and the molecular weight of the polymer obtained under Quinuclidine catalysis is 3.4 kg mol -1 , molecular weight distribution is 2.4, and the molecular weight of the polymer under NMP catalysis is 4.7 kg mol -1 , with a molecular weight distribution of 1.6. Under the catalysis of triethylenediamine (DABCO), the conversion rate of monomer 1a was greater than 99% under nuclear magnetic resonance hydrogen spectrum monitoring, and the molecular weight of the obtained polymer increased to 12.3 kg mol -1 , and the molecular weight distribution is 2.4. Therefore, using DABCO as a polymerization catalyst can obtain a polymer with high conversion rate and high molecular weight.

[0056] The polymerization was carried out under the catalysis of DABCO, and the molecular weight of the obtained polymer P1b2a was 14.2 kg mol -1 , molecular weight distribution is 2.4 (as in Experiment 4); the molecular weight of polymer P1c2a is 10.2 kg mol -1 , molecular weight distribution is 1.8 (as in Experiment 5); the molecular weight of polymer P1d2a is 13.2 kg mol -1 , molecular weight distribution is 2.2 (as in Experiment 6); the molecular weight of polymer P1e2a is 10.5 kgmol -1 , molecular weight distribution is 2.1 (as in Experiment 7); the molecular weight of polymer P1f2a is 10.7 kg mol -1 , molecular weight distribution is 2.1 (as in Experiment 8); the molecular weight of polymer P1c2b is 11.1 kg mol -1, molecular weight distribution is 2.1 (as in Experiment 9); the molecular weight of polymer P1e2b is 11.9 kg mol -1 , the molecular weight distribution is 2.6 (as in Experiment 10).

[0057] Table 1 Polymerization reaction of difunctional alcohol monomers and difunctional acetylic acid ester monomers 1)

[0058]

[0059] 1) Polymerization conditions: room temperature, [M] = 0.50 mol / L, catalyst concentration of 10 mol%, reaction time of 5 min, solvent of DMSO. 2) Monomer conversion rate is 1 Calculated by the ratio of the relevant peak areas on the H NMR spectrum. 3) Dissolve the polymerization reaction solution in chromatographically pure THF and measure by gel permeation chromatography. Test temperature: 25°C, flow rate: 1.0 mL / min, standard sample: polystyrene. 4) Polydispersity index (D) = M w / M n .

[0060] Example 6

[0061] Taking the polymerization experiment No. 1 as an example, first mix monomer 1a (132 mg, 0.5 mmol) with 0.5 mL quinuclidine solution (concentration of 0.1 mmol / mL), take a 10 mL pressure tube, add a magnetic stirrer, add monomer 2a (125 mg, 0.5 mmol) and 0.5 mL dimethyl sulfoxide as solvent. Slowly add monomer 2a to the pressure tube, and continue to stir the reaction system at room temperature. After 5 minutes of reaction, transfer the reaction solution in the pressure tube to a test tube, and add anhydrous methanol solution to precipitate the polymer. Subsequently, place the suspension in a centrifuge and centrifuge at 8000 rpm for 5 minutes to ensure that the polymer particles are fully settled. After the centrifugation is completed, carefully pour off the supernatant. The precipitated polymer is redissolved in dimethyl sulfoxide solution and washed three times to completely remove unreacted monomers and impurities. Finally, the polymer is placed in a vacuum drying oven at 100 ° C and dried for 12 hours, and the solvent is removed until constant weight is obtained to obtain a pure polymer product.

[0062] Example 7

[0063] Taking the polymerization experiment No. 2 as an example, first mix monomer 1a (132 mg, 0.5 mmol) with 0.5 mL N-methylpyrrole solution (concentration of 0.1 mmol / mL), take a 10 mL pressure tube, add a magnetic stirrer, add monomer 2a (125 mg, 0.5 mmol) and 0.5 mL dimethyl sulfoxide as solvent. Slowly drop monomer 2a into the pressure tube, and continue to stir the reaction system at room temperature. After 5 minutes of reaction, transfer the reaction solution in the pressure tube to a test tube, and add anhydrous methanol solution to precipitate the polymer. Subsequently, place the suspension in a centrifuge and centrifuge at 8000 rpm for 5 minutes to ensure that the polymer particles are fully settled. After the centrifugation is completed, carefully pour the supernatant. The precipitated polymer is redissolved in dimethyl sulfoxide solution and washed three times to completely remove unreacted monomers and impurities. Finally, the polymer is placed in a vacuum drying oven at 100 ° C and dried for 12 hours, and the solvent is removed until constant weight to obtain a pure polymer product.

[0064] Example 8

[0065] Taking the polymerization experiment No. 3 as an example, first mix monomer 1a (132 mg, 0.5 mmol) with 0.5 mL triethylenediamine solution (concentration 0.1 mmol / mL), take a 10 mL pressure tube, add a magnetic stirrer, add monomer 2a (125 mg, 0.5 mmol) and 0.5 mL dimethyl sulfoxide as solvent. Slowly drop monomer 2a into the pressure tube, and stir the reaction system continuously at room temperature. After 5 minutes of reaction, transfer the reaction solution in the pressure tube to a test tube, and add anhydrous methanol solution to precipitate the polymer. Subsequently, place the suspension in a centrifuge and centrifuge at 8000 rpm for 5 minutes to ensure that the polymer particles are fully settled. After the centrifugation is completed, carefully pour the supernatant. The precipitated polymer is redissolved in dimethyl sulfoxide solution and washed three times to completely remove unreacted monomers and impurities. Finally, the polymer is placed in a vacuum drying oven at 100 ° C and dried for 12 hours, and the solvent is removed until constant weight to obtain a pure polymer product.

[0066] Example 9

[0067] Taking the polymerization experiment No. 4 as an example, first mix monomer 1b (146 mg, 0.5 mmol) with 0.5 mL triethylenediamine solution (concentration of 0.1 mmol / mL), take a 10 mL pressure tube, add a magnetic stirrer, add monomer 2a (125 mg, 0.5 mmol) and 0.5 mL dimethyl sulfoxide as solvent. Slowly drop monomer 2a into the pressure tube, and stir the reaction system continuously at room temperature. After 5 minutes of reaction, transfer the reaction solution in the pressure tube to a test tube, and add anhydrous methanol solution to precipitate the polymer. Subsequently, place the suspension in a centrifuge and centrifuge at 8000 rpm for 5 minutes to ensure that the polymer particles are fully settled. After the centrifugation is completed, carefully pour the supernatant. The precipitated polymer is redissolved in dimethyl sulfoxide solution and washed three times to completely remove unreacted monomers and impurities. Finally, the polymer is placed in a vacuum drying oven at 100 ° C and dried for 12 hours, and the solvent is removed until constant weight is obtained to obtain a pure polymer product.

[0068] Example 10

[0069] Taking the polymerization experiment No. 5 as an example, first mix monomer 1c (160 mg, 0.5 mmol) with 0.5 mL triethylenediamine solution (concentration 0.1 mmol / mL), take a 10 mL pressure tube, add a magnetic stirrer, add monomer 2a (125 mg, 0.5 mmol) and 0.5 mL dimethyl sulfoxide as solvent. Slowly drop monomer 2a into the pressure tube, and stir the reaction system continuously at room temperature. After 5 minutes of reaction, transfer the reaction solution in the pressure tube to a test tube, and add anhydrous methanol solution to precipitate the polymer. Subsequently, place the suspension in a centrifuge and centrifuge at 8000 rpm for 5 minutes to ensure that the polymer particles are fully settled. After the centrifugation is completed, carefully pour off the supernatant. The precipitated polymer is redissolved in dimethyl sulfoxide solution and washed three times to completely remove unreacted monomers and impurities. Finally, the polymer is placed in a vacuum drying oven at 100 ° C and dried for 12 hours, and the solvent is removed until constant weight is obtained to obtain a pure polymer product.

[0070] Embodiment 11

[0071] Taking the polymerization experiment No. 6 as an example, first mix monomer 1d (140 mg, 0.5 mmol) with 0.5 mL triethylenediamine solution (concentration 0.1 mmol / mL), take a 10 mL pressure tube, add a magnetic stirrer, add monomer 2a (125 mg, 0.5 mmol) and 0.5 mL dimethyl sulfoxide as solvent. Slowly drop monomer 2a into the pressure tube, and continue to stir the reaction system at room temperature. After 5 minutes of reaction, transfer the reaction solution in the pressure tube to a test tube, and add anhydrous methanol solution to precipitate the polymer. Subsequently, place the suspension in a centrifuge and centrifuge at 8000 rpm for 5 minutes to ensure that the polymer particles are fully settled. After the centrifugation is completed, carefully pour the supernatant. The precipitated polymer is redissolved in dimethyl sulfoxide solution and washed three times to completely remove unreacted monomers and impurities. Finally, the polymer is placed in a vacuum drying oven at 100 ° C and dried for 12 hours, and the solvent is removed until constant weight to obtain a pure polymer product.

[0072] Example 12

[0073] Taking the polymerization experiment No. 7 as an example, first mix monomer 1e (162 mg, 0.5 mmol) with 0.5 mL triethylenediamine solution (concentration 0.1 mmol / mL), take a 10 mL pressure tube, add a magnetic stirrer, add monomer 2a (125 mg, 0.5 mmol) and 0.5 mL dimethyl sulfoxide as solvent. Slowly drop monomer 2a into the pressure tube, and stir the reaction system continuously at room temperature. After 5 minutes of reaction, transfer the reaction solution in the pressure tube to a test tube, and add anhydrous methanol solution to precipitate the polymer. Subsequently, place the suspension in a centrifuge and centrifuge at 8000 rpm for 5 minutes to ensure that the polymer particles are fully settled. After the centrifugation is completed, carefully pour the supernatant. The precipitated polymer is redissolved in dimethyl sulfoxide solution and washed three times to completely remove unreacted monomers and impurities. Finally, the polymer is placed in a vacuum drying oven at 100 ° C and dried for 12 hours, and the solvent is removed until constant weight is obtained to obtain a pure polymer product.

[0074] Example 13

[0075] Taking the polymerization experiment No. 8 as an example, first mix the monomer 1f (184 mg, 0.5 mmol) with 0.5 mL triethylenediamine solution (concentration of 0.1 mmol / mL), take a 10 mL pressure tube, add a magnetic stirrer, add monomer 2a (125 mg, 0.5 mmol) and 0.5 mL dimethyl sulfoxide as solvent. Slowly drop monomer 2a into the pressure tube, and continue to stir the reaction system at room temperature. After 5 minutes of reaction, transfer the reaction solution in the pressure tube to a test tube, and add anhydrous methanol solution to precipitate the polymer. Subsequently, place the suspension in a centrifuge and centrifuge at 8000 rpm for 5 minutes to ensure that the polymer particles are fully settled. After the centrifugation is completed, carefully pour off the supernatant. The precipitated polymer is redissolved in dimethyl sulfoxide solution and washed three times to completely remove unreacted monomers and impurities. Finally, the polymer is placed in a vacuum drying oven at 100 ° C and dried for 12 hours, and the solvent is removed until constant weight is obtained to obtain a pure polymer product.

[0076] Embodiment 14

[0077] Taking the polymerization experiment No. 9 as an example, first mix monomer 1c (160 mg, 0.5 mmol) with 0.5 mL triethylenediamine solution (concentration of 0.1 mmol / mL), take a 10 mL pressure tube, add a magnetic stirrer, add monomer 2b (127 mg, 0.5 mmol) and 0.5 mL dimethyl sulfoxide as solvent. Slowly add 2b to the pressure tube, and continue to stir the reaction system at room temperature. After 5 minutes of reaction, transfer the reaction solution in the pressure tube to a test tube, and add anhydrous methanol solution to precipitate the polymer. Subsequently, place the suspension in a centrifuge and centrifuge at 8000 rpm for 5 minutes to ensure that the polymer particles are fully settled. After the centrifugation is completed, carefully pour the supernatant. The precipitated polymer is redissolved in dimethyl sulfoxide solution and washed three times to completely remove unreacted monomers and impurities. Finally, the polymer is placed in a vacuum drying oven at 100 ° C and dried for 12 hours, and the solvent is removed until constant weight is obtained to obtain a pure polymer product.

[0078] Embodiment 15

[0079] Taking the polymerization experiment No. 10 as an example, first mix monomer 1e (162 mg, 0.5 mmol) with 0.5 mL triethylenediamine solution (concentration 0.1 mmol / mL), take a 10 mL pressure tube, add a magnetic stirrer, add monomer 2b (127 mg, 0.5 mmol) and 0.5 mL dimethyl sulfoxide as solvent. Slowly drop monomer 2b into the pressure tube, and continue to stir the reaction system at room temperature. After 5 minutes of reaction, transfer the reaction solution in the pressure tube to a test tube, and add anhydrous methanol solution to precipitate the polymer. Subsequently, place the suspension in a centrifuge and centrifuge at 8000 rpm for 5 minutes to ensure that the polymer particles are fully settled. After the centrifugation is completed, carefully pour the supernatant. The precipitated polymer is redissolved in dimethyl sulfoxide solution and washed three times to completely remove unreacted monomers and impurities. Finally, the polymer is placed in a vacuum drying oven at 100 ° C and dried for 12 hours, and the solvent is removed until constant weight to obtain a pure polymer product.

[0080] The structural characterization data of the obtained polymer are shown below:

[0081] P1a2a: 1 H NMR (500 MHz, DMSO-d 6 )δ7.58(d,J=12.4Hz,2H),7.23(s,2H),5.27(d,J=12.5Hz,2H),4.23–3.85 (m,13H),2.95(s,5H),2.54(s,1H),1.55(s,4H),1.31(d,J=39.9Hz,14H). 13 C NMR (101 MHz, DMSO-d 6 )δ166.83,162.42,155.89,96.65,69.83,63.25,61.95,28.63,28.32,26.73,25.41.

[0082] P1b2a: 1 H NMR (400 MHz, DMSO-d 6 )δ7.58(d,J=12.5Hz,1H),7.21(s,1H),5.27(d,J=12.5Hz,1H),4.26–3.97(m, 6H), 2.94 (q, J = 6.8Hz, 2H), 2.50 (s, 1H), 1.67–1.48 (m, 2H), 1.48–1.10 (m, 9H). 13 C NMR (101 MHz, DMSO-d 6)δ166.78,162.40,155.82,96.61,69.83,63.20,61.87,29.29,28.58,28.27,25.91,25.35.

[0083] P1c2a: 1 H NMR(400MHz,DMSO-d 6 )δ7.66(d,J=12.5Hz,2H),7.26(s,2H),5.37(d,J=12.5Hz,2H),4.27–4.10(m,11H),3.69–3.55(m,8H),3.00(d,J=6.6Hz,4H),1.47–1.36(m,4H),1.28(s,9H). 13 C NMR(126MHz,DMSO-d 6 )δ166.80,162.73,155.88,96.44,69.93,69.77,68.51,62.67,61.90,29.37,28.72,26.23.

[0084] P1d2a: 1 H NMR(400MHz,DMSO-d 6 )δ7.54(d,J=12.5Hz,2H),7.37–6.99(m,2H),5.24(d,J=12.5Hz,2H),4.24–3.93(m,12H),3.34(t,J=5.9Hz,4H),3.08(q,J=5.8Hz,4H),1.61–1.43(m,4H),1.24(s,8H). 13 C NMR(101MHz,DMSO-d 6 )δ166.80,162.38,155.97,96.66,69.76,68.86,63.23,62.07,28.61,28.29,25.38.

[0085] P1e2a: 1 H NMR(400MHz,DMSO-d 6 )δ7.58(d,J=12.5Hz,2H),7.27(t,J=5.9Hz,2H),5.28(d,J=12.5Hz,2H),4.23–3.96(m,12H),3.37(d,J=6.1Hz,4H),3.12(d,J=6.4Hz,4H),1.61–1.49(m,4H),1.28(s,8H). 13 C NMR(126MHz,DMSO-d6 )δ166.80,162.40,155.93,96.63,69.75,69.49,69.04,63.22,62.04,28.58,28.27,25.36.

[0086] P1f2a: 1 H NMR(400MHz,DMSO-d 6 )δ7.54(d,J=12.5Hz,2H),7.20(s,2H),5.24(d,J=12.5Hz,2H),4.18–4.10(m,4H),4.10–4.02(m,4H),3.97(t,J=6.4Hz,4H),3.44(s,4H),3.35(t,J=5.9Hz,4H),3.11–3.03(m,4H),1.52(s,4H),1.23(s,10H). 13 C NMR(101MHz,DMSO-d 6 )δ166.80,162.40,155.94,96.63,69.76,69.50,69.05,63.22,62.05,40.43,28.60,28.28,25.37.

[0087] P1c2b: 1 H NMR(400MHz,DMSO-d 6 )δ7.66(d,J=12.5Hz,2H),7.26(s,2H),5.37(d,J=12.5Hz,2H),4.27–4.10(m,11H),3.69–3.55(m,8H),3.00(d,J=6.6Hz,4H),1.47–1.36(m,4H),1.28(s,9H). 13 C NMR(126MHz,DMSO-d 6 )δ166.80,162.73,155.88,96.44,69.93,69.77,68.51,62.67,61.90,29.37,28.72,26.23.

[0088] P1e2b: 1 H NMR(400MHz,DMSO-d 6)δ7.56(d,J=12.5Hz,2H),7.20(t,J=5.8Hz,2H),5.28(d,J=12.5Hz,2H),4.11(ddd,J=18.1,10. 5,4.0Hz,12H),3.57(t,J=4.8Hz,4H),3.49(s,4H),3.35(t,J=6.0Hz,4H),3.08(q,J=5.9Hz,4H). 13 C NMR (101 MHz, DMSO-d 6 )δ166.80,162.71,155.96,96.46,69.85,69.77,69.52,69.08,68.51,62.67,62.07.

[0089] 3. Thermal properties of polymers

[0090] Furthermore, the carbon dioxide-based polyurethane materials with polymer properties involved in this patent were systematically studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), such as Figure 1 and Figure 2 The test results show that the glass transition temperature of P1a2a is 5°C, a melting peak appears at 125°C, the melting enthalpy is -55 J / g, and the temperature of 5% weight loss is 278°C. The glass transition temperature of P1b2a is 6°C, a melting peak appears at 120°C, the melting enthalpy is -36 J / g, and the temperature of 5% weight loss is 292 o C. P1c2a has a melting peak at 118°C, a melting enthalpy of -67 J / g, and a temperature of 5% weight loss at 287°C. P1d2a has a glass transition temperature of 4°C, and a temperature of 5% weight loss at 295°C. P1e2a has a glass transition temperature of 2°C, and a temperature of 5% weight loss at 297°C. P1f2a has a glass transition temperature of -12°C, and a temperature of 5% weight loss at 303°C. P1c2b has a glass transition temperature of 8°C, a melting peak at 93°C, a melting enthalpy of -43 J / g, and a temperature of 5% weight loss at 277 o C. The glass transition temperature of P1e2b is -2°C and the temperature of 5% weight loss is 289°C.

[0091] 4. Shape memory properties of polymers

[0092] The shape memory property of a polymer refers to its ability to deform under external force and return to its original shape under certain conditions. Changing the temperature can trigger the shape memory effect of the polymer. Figure 3 The figure shows the initial shape of the dumbbell-shaped spline of this type of polymer. After heating to 40-60°C, the polymer is deformed to a temporary shape, and the dumbbell-shaped spline is fixed to a temporary shape when the temperature drops. Figure 4shape, the polymer is heated again and the deformation is restored, and the dumbbell-shaped specimen returns to Figure 5 Original condition shown.

Claims

1. A method for synthesizing a carbon dioxide-based olefin / ether / ester group functionalized polyurethane polymer material, characterized in that: Here are the steps: Step (1) synthesizes a carbon dioxide-based difunctional alcohol monomer through a ring-opening reaction of ethylene carbonate derived from carbon dioxide and a difunctional amine: Mixing a difunctional organic amine and ethylene carbonate, then adding a solvent, and stirring to react; after the reaction is completed, concentrating the reaction solution in vacuo to obtain a crude product; purifying the crude product by column chromatography or recrystallizing it using an organic solvent to obtain a carbon dioxide-based difunctional alcohol monomer; The molar ratio of the difunctional organic amine to ethylene carbonate is 1:1 to 1:3; Step (2) a bifunctional alcohol monomer and a bifunctional alkyne ester monomer are subjected to a "hydroxyl-alkyne" click polymerization reaction to construct an olefin / ether / ester group functionalized polyurethane polymer material; Add difunctional alcohol monomers, organic catalysts and solvents into a reaction bottle, dissolve difunctional acetylide ester monomers in the solvent to prepare difunctional acetylide ester monomer solutions, then drop the difunctional acetylide ester monomer solutions into the reaction bottle drop by drop, and initiate a polymerization reaction after the addition is completed; after the reaction is completed, add a poor solvent used for recrystallization into the polymerization reaction solution to generate a white precipitate; centrifuge, and vacuum dry to constant weight to obtain a synthetic carbon dioxide-based olefin / ether / ester group functionalized polyurethane polymer material.

2. The method for synthesizing a carbon dioxide-based olefin / ether / ester group functionalized polyurethane polymer material according to claim 1, characterized in that: The difunctional alcohol monomer structural formula is one of the following: The difunctional acetylic acid ester monomer is one of the following:

3. The method for synthesizing a carbon dioxide-based olefin / ether / ester group functionalized polyurethane polymer material according to claim 1, characterized in that: In step (1), the solvent is one or a mixture of two or more of dichloromethane, acetone, methanol, acetonitrile and tetrahydrofuran.

4. The method for synthesizing a carbon dioxide-based olefin / ether / ester group functionalized polyurethane polymer material according to claim 1, characterized in that: In step (1), the reaction temperature is 0 to 60 degrees Celsius and the reaction time is 3 to 8 hours.

5. The method for synthesizing a carbon dioxide-based olefin / ether / ester group functionalized polyurethane polymer material according to claim 1, characterized in that: In step (1), the crude product is purified by column chromatography or organic solvent recrystallization. In the column chromatography purification, the column chromatography eluent is a mixed solution of dichloromethane and anhydrous methanol, and the volume ratio of dichloromethane to anhydrous methanol is 10:1 to 2:

1.

6. The method for synthesizing a carbon dioxide-based olefin / ether / ester group functionalized polyurethane polymer material according to claim 1, characterized in that: In step (2), the organic catalyst is one or a mixture of two or more of triethylenediamine, quinuclidine and N-methylpyrrole.

7. The method for synthesizing a carbon dioxide-based olefin / ether / ester group functionalized polyurethane polymer material according to claim 1, characterized in that: In step (2), the solvent is one or a mixture of two or more of dimethyl sulfoxide, N,N-dimethylformamide, and tetrahydrofuran.

8. The method for synthesizing a carbon dioxide-based olefin / ether / ester group functionalized polyurethane polymer material according to claim 1, characterized in that: In step (2), the reaction temperature is 0 to 60 degrees Celsius and the reaction time is 3 to 60 minutes.

9. The method for synthesizing a carbon dioxide-based olefin / ether / ester group functionalized polyurethane polymer material according to claim 1, characterized in that: In step (2), the poor solvent is one or a mixture of two or more of ether, methanol, ethanol and toluene.

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