Synthetic method of polyene ether ester with controllable carbon-carbon double-bond cis-trans spatial configuration

Abstract

The invention belongs to the technical field of polyene ether ester synthesis, and relates to a synthesis method of polyene ether ester with a controllable carbon-carbon double bond cis-trans spatial configuration, which realizes the controllability of the carbon-carbon double bond cis-trans spatial configuration by regulating a reaction substrate, an organic catalyst and a reaction solvent. According to the method, bifunctional diphenol and bifunctional diacetylenic acid ester are taken as polymeric monomers, and selective preparation of different double-bond cis-trans spatial configuration polyene ether ester high polymer materials under mild conditions is realized by accurately regulating and controlling monomer types, organic catalyst types and reaction solvents. The method has the advantages of being high in atom economy, simple and convenient to operate, wide in monomer universality, green, environmentally friendly and the like. Besides, through accurate regulation and control of a main chain double-bond cis-trans stereo configuration, control of comprehensive performance of the polymer is successfully realized, and a convenient method is provided for constructing a high-performance polymer material with adjustable performance.

Description

Technical Field

[0001] The invention belongs to the technical field of polyolefin ether ester synthesis, and relates to a method for synthesizing polyolefin ether ester with controllable cis-trans stereo configuration of carbon-carbon double bonds. The method realizes the controllability of the cis-trans stereo configuration of carbon-carbon double bonds by regulating reaction substrates, organic catalysts and reaction solvents. Background Art

[0002] As of 2019, global polymer production has reached 368 million tons, of which China accounts for as much as 31%. However, China's polymer products are mainly concentrated in conventional low-end polymers, and there is a problem of overcapacity. At the same time, most high-end polymers, such as high-end polyolefins, functional membrane materials, and special rubbers, are still more than 50% dependent on foreign countries. Therefore, on the whole, China's polymer products have a structural contradiction of lack of high-end and surplus of low-end. The precise regulation of polymers is an important way to improve the performance of polymers, which mainly includes molecular weight, molecular weight distribution, sequence structure, stereoregularity and topological structure. Taking polyolefins as an example, ordinary polyethylene can only be used to produce low-end products such as ground films and industrial pipes, while ultra-high molecular weight polyethylene can be used to produce military bulletproof vests; random polypropylene can only be used for the production of low-end industrial products such as packaging films and strapping plastics, while isotactic polypropylene can be used for the manufacture of automobile shells.

[0003] The cis-trans stereo configuration of carbon-carbon double bonds has an important influence on the physical and chemical properties of small molecules. For example, indigo with Z-type double bonds is a blue dye molecule, while isoindigo with E-type double bonds is a red drug molecule (AV Bogdanov, LI Musin and VFMironov, ARKIVOC, 2015, 2015, 362-392.). Similarly, the cis-trans stereo configuration of carbon-carbon double bonds has an important influence on the stability, thermal properties, mechanical properties, barrier properties and optical properties of polymers. For example, natural rubber with a main chain double bond of cis stereo configuration exhibits a high elastic state at room temperature and is mainly used to produce elastic materials such as conveyor belts, rubber shoes and wires and cables, while gutta-percha with a main chain double bond of trans stereo configuration is used to make hard materials such as electrical insulation and golf ball covers because it is easy to crystallize at room temperature and has poor flexibility. Therefore, how to adjust the performance of polymers by controlling the stereo configuration of polymer double bonds and then realize the preparation of high-performance polymer materials has become an important research direction in the field of polymer materials. In 1974, Japanese scientist Hideki Momokawa used high-concentration Ziegler-Natta catalysts to selectively prepare two conductive plastics, cis-polyacetylene and trans-polyacetylene. Compared with cis-polyacetylene, trans-polyacetylene exhibits better conductivity because the σ-π bonds in trans-polyacetylene can promote the free movement of electrons on a large scale (CK Chiang, CR Fincher, YW Park, AJ Heeger, H. Shirakawa, EJ Louis, SC Gau and AG MacDiarmid, Phys. Rev. Lett, 1977, 39, 1098-1101.); In 2019, Antoine Buchard's research group at the University of Bath in the UK used erythritol and carbon dioxide as raw materials to synthesize seven-membered cyclic carbonates, and synthesized polycarbonates with trans- and cis-stereoconfigurations of the main chain double bonds respectively through the polymerization strategies of ring-opening polymerization and ring-opening heterogeneous polymerization (TMMcGuire, C. Perale, R. Castaing, G. Kociok- and A. Buchard, J. Am. Chem. Soc, 2019, 141, 13301-13305.). Among them, trans-polycarbonate is a soft amorphous material, while cis-polycarbonate is a hard semi-crystalline material; in the same year, Lu Xiaobing's research group at Dalian University of Technology used SalenCo(III)NO3 complex to catalyze the alternating copolymerization of ethylene oxide and maleic anhydride to prepare polyester with cis-stereoconfiguration of the main chain double bond, and used diethylamine catalytic reaction and photosensitive isomerization reaction to achieve reversible modulation of the main chain double bond stereoconfiguration from cis to trans, thus realizing the reversible modulation of polyester materials from amorphous to semi-crystalline for the first time (Z.-Q.Wan, W.-M.Ren, S.Yang, M.-R.Li, G.-G.Gu and X.-B.Lu, Angew.Chem.Int.Ed, 2019, 58, 17636-17640.). In 2023, the research group of Quenitin Michaudel at Texas A&M University in the United States used ruthenium carbene complexes with different reactivities to catalyze olefin exchange and metathesis reactions, achieving the selective synthesis of trans-rich and cis-rich stereo-configuration polyolefins (SJ Kempel, T.-W. Hsu, JL Nicholson and Q. Michaudel, J. Am. Chem. Soc, 2023, 145, 12459-12464.). The cis-rich polyolefin materials are mostly amorphous, while the trans-rich polyolefin materials show obvious crystallization behavior. Although some progress has been made in the construction of polymers with controllable double bond stereo configurations, in general, there are still problems such as few catalytic systems, cumbersome operation processes, harsh polymerization conditions and poor mechanical properties. Therefore, it is of great theoretical and practical significance to design and develop new and efficient polymerization methods for controlling the stereo configuration of main chain double bonds.

[0004] 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, UK, used the "thiol-alkyne" click polymerization reaction to prepare poly(ethylene sulfide ester) 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 poly(ethylene sulfide ester) showed obvious differences in thermal and mechanical properties. Subsequently, the Dove team created a series of high-performance polymer materials with adjustable mechanical properties based on the stereochemically controllable "thiol-alkyne" addition strategy (JC Worch and AP Dove, Acc. Chem. Res, 2022, 55, 2355-2369.). Compared with sulfur atoms, oxygen atoms have the characteristics of small atomic radius, low polarizability, and high electronegativity, which also causes the acidity and nucleophilicity of hydroxyl groups to be significantly lower than those of thiol groups, and therefore have lower reactivity. However, compared with thiol 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. So far, although a series of polymer materials have been constructed based on the "hydroxy-alkyne" addition strategy, the stereo configuration of the double bonds in the main chain of these polymer materials is still uncontrollable, and the relationship between performance and structure has not been studied (X. Fu, A. Qin and BZ Tang, Aggregate, 2023, 4, e350. JC Worch, H. Prydderch, S. Jimaja, P. Bexis, ML Becker and AP Dove, Nat. Rev. Chem, 2019, 3, 514-535.). Therefore, it is of great research value to use the "hydroxy-alkyne" addition polymerization strategy to construct high-performance polymer materials with controllable cis-trans stereo of carbon-carbon double bonds. Summary of the invention

[0005] In view of the problems existing in the prior art, the present invention is based on the Michael addition reaction of hydroxyl-alkyne, uses cheap and easily available organic phosphine or organic amine as a catalyst, realizes the addition polymerization reaction of difunctional phenol monomers and difunctional alkyne ester monomers under mild conditions, and prepares a new type of poly(alkenyl ether ester) with an adjustable cis-trans ratio of main chain double bonds between 40% and 100%. By adjusting the stereo configuration of the double bonds in the polymer main chain, the thermal stability, crystallinity, mechanical properties and barrier properties of the poly(alkenyl ether ester) are regulated.

[0006] To achieve the above purpose, the present invention adopts the following technical solutions:

[0007] A method for synthesizing a polyolefin ether ester with controllable cis-trans stereo configuration of a carbon-carbon double bond, comprising the following steps: mixing a difunctional phenol monomer, a difunctional acetylic acid ester monomer, an organic catalyst and a reaction solvent. After stirring and reacting until the monomers are completely converted, dichloromethane is added to dilute the reaction solution and stirred, and then the reaction solution is poured into methanol to obtain a polymer precipitate, filtered, and the filter cake is repeatedly washed with methanol, and the solid is collected to obtain a polyolefin ether ester with controllable cis-trans stereo configuration of a carbon-carbon double bond. The reaction is shown in the following formula:

[0008]

[0009] The organic catalyst has the following structure:

[0010]

[0011] The bifunctional phenol monomer has the following structure:

[0012]

[0013] The difunctional acetylic acid ester monomer has the following structure:

[0014]

[0015] The molar ratio of the difunctional phenol monomer to the difunctional acetylic acid ester monomer is 1:0.8-1:1.5.

[0016] The molar ratio of the sum of the difunctional phenol monomer and the difunctional acetylic acid ester monomer to the organic catalyst is 2:1 to 1000:1.

[0017] The molar concentration of the difunctional phenol monomer and the difunctional acetylic acid ester monomer in dichloromethane is 0.5 mol / L to 1 mol / L; the molar concentration of the difunctional phenol monomer and the difunctional acetylic acid ester monomer in methanol is 0.01 mol / L to 0.05 mol / L.

[0018] Add dichloromethane and stir for 5-10 minutes.

[0019] The reaction solvent is acetonitrile (CH3CN), chloroform (CHCl3), N,N-dimethylformamide (DMF), tetrahydrofuran (THF) or dimethyl sulfoxide (DMSO).

[0020] In the above method, the reaction temperature is 25-100°C.

[0021] In the above method, the reaction time is 1 to 24 hours.

[0022] Beneficial effects of the invention: The invention realizes the regulation of the stereo configuration of the main chain double bond in polyolefin ether ester for the first time, and creates a series of high-performance polymer materials with adjustable properties. The method has the characteristics of mild reaction conditions, safe and simple experimental operation, wide substrate universality and high atom economy. The invention has important application potential in the fields of organic synthesis, polymer synthesis, polymer chemistry and polymer materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of polyolefin ether esters P1a2d with different double bond stereo configurations.

[0024] Figure 2 The thermogravimetric analysis curves of polyolefin ether esters P1a2d with different double bond stereo configurations.

[0025] Figure 3 The differential scanning calorimetry curves of polyolefin ether esters P1a2d with different double bond stereo configurations.

[0026] Figure 4 Shown are the X-ray diffraction curves of polyolefin ether esters P1a2d with different double bond stereo configurations.

[0027] Figure 5 The stress-strain curves of polyolefin ether esters P1a2d with different double bond stereo configurations. DETAILED DESCRIPTION

[0028] The present invention is further described in detail below in conjunction with specific examples, but the implementation method and applicable substrates of the present invention are not limited thereto.

[0029] 1. Synthesis of polyolefin ether esters P1a2d (50%-100% trans) with different carbon-carbon double bond stereo configurations

[0030] The synthesis steps of polyolefin ether ester P1a2d with different carbon-carbon double bond stereo configurations are as follows: add difunctional phenol monomer 1a, difunctional alkyne ester monomer 2d, organic catalyst and reaction solvent into a reaction bottle respectively. Stir the reaction at 25°C for 1 to 24 hours, take samples from the reaction bottle at regular intervals, and monitor the conversion rate and the cis-trans ratio of carbon-carbon double bonds in the generated polymer backbone by nuclear magnetic hydrogen spectrum. When the conversion rate no longer increases or the monomer is completely converted, add 0.5 mol / L to 1 mol / L dichloromethane solution to dilute the reaction solution, and then pour the reaction solution into 0.01 mol / L to 0.05 mol / L methanol to form a polymer precipitate, filter and collect the polymer precipitate, and then vacuum dry it at 100°C to constant weight to obtain the final polymer.

[0031] Table 1: Synthesis examples of polyolefin ether esters P1a2d with different carbon-carbon double bond stereo configurations [a]

[0032]

[0033]

[0034]

[0035] Example 1

[0036] In a 100mL single-necked bottle, add a stirrer, 6mmol of difunctional phenol monomer 1a, 4.8mmol of difunctional alkyne ester monomer 2d, 0.06mmol of DABCO and 20mL of DMSO; after stirring at 100℃ for 1 hour, stop the reaction. Add 12mL of dichloromethane to the reaction bottle, stir for 3 minutes, and pour the reaction solution into 120mL of methanol to precipitate a white polymer. Then, filter and repeatedly wash the filter cake with methanol to collect the white solid. Finally, put the collected white polymer into a vacuum drying oven and vacuum dry it at 100℃ to constant weight to obtain a polyolefin ether ester P1a2d (100% trans) with a trans double bond content of 100%.

[0037]

[0038] The structural characterization data of the obtained polyolefin ether ester are as follows:

[0039] P1a2d (100% trans), white solid, yield: 95%. 1 H NMR(600MHz, CDCl3) δ7.69(d,J=12.0Hz,1H),7.18-6.99(m,3H),5.65(s,1H),5.39(d,J=12.0Hz,1 H),4.40(d,J=6.5Hz,1H),4.10(t,J=6.0Hz,2H),3.92(d,J=32.9Hz,5H),1.64(s,2H),1.38(s,2H); 13 C NMR (151MHz, CDCl3) δ167.4,160.5,150.5,145.0,135.4,120.3,119.1,110.8,101.5,101.3,73.9,68.9,64.2,56.2,28.8,25.8.

[0040] Example 2

[0041] In a 100mL single-mouth bottle, add a stirrer, 6mmol of difunctional phenol monomer 1a, 9mmol of difunctional alkyne ester monomer 2d, 0.06mmol of DMAP and 20mL of DMF; after stirring at 25°C for 3 hours, stop the reaction. Add 6mL of dichloromethane to the reaction bottle, stir for 3 minutes, and pour the reaction solution into 600mL of methanol to precipitate a white polymer. Then, filter and repeatedly wash the filter cake with methanol to collect the white solid. Finally, put the collected white polymer into a vacuum drying oven, dry it at 100°C for 12 hours, and then take it out to obtain a polyolefin ether ester P1a2d (93% trans) with a trans double bond content of 93%.

[0042] The structural characterization data of the obtained polyolefin ether ester are as follows:

[0043]

[0044] P1a2d (93% trans), dark yellow solid, yield: 80%. 1 H NMR (600MHz, CDCl3) δ7.69(d,J=12.0Hz,0.93H),7.15-7.04(m,3H),6.71(d,J=6.0Hz,0.07H),5.65(s,1H),5.39(d,J=12.0Hz ,0.93H),5.10(d,J=6.0Hz,0.07H),4.40(d,J=6.9Hz,1H),4.10(t,J=6.3Hz,2H),3.97-3.88(m,5H),1.64(s,2H),1.38(s,2H).

[0045] Example 3

[0046] In a 100mL single-necked bottle, add a stirrer, 6mmol of difunctional phenol monomer 1a, 9mmol of difunctional alkyne ester monomer 2d, 6mmol of DMAP and 20mL of DMSO; after stirring at 25°C for 4 hours, stop the reaction. Add 10mL of dichloromethane to the reaction bottle, stir for 3 minutes, and pour the reaction solution into 500mL of methanol to precipitate a white polymer. Then, filter and repeatedly wash the filter cake with methanol to collect the white solid. Finally, put the collected white polymer into a vacuum drying oven, dry it at 100°C for 12 hours, and then take it out to obtain a polyolefin ether ester P1a2d (80% trans) with a trans double bond content of 80%.

[0047] The structural characterization data of the obtained polyolefin ether ester are as follows:

[0048]

[0049] P1a2d (80% trans), dark yellow solid, yield: 85%. 1 H NMR (400MHz, CDCl3) δ7.69(d,J=12.0Hz,0.8H),7.16-7.03(m,3H),6.71(d,J=7.0Hz,0.2H),5.65(s,1H),5.42(d,J=12. 0Hz,0.8H),5.10(d,J=6.0Hz,0.2H),4.40(d,J=6.8Hz,1H),4.12(t,J=6.6Hz,2H),3.97-3.87(m,5H),1.65(m,2H),1.46 -1.36(m,2H).

[0050] Example 4

[0051] In a 100mL single-necked bottle, add a stirrer, 6mmol of difunctional phenol monomer 1a, 7mmol of difunctional alkyne ester monomer 2d, 0.06mmol of Et3N and 20mL of DMSO; after stirring at 45°C for 6 hours, stop the reaction. Add 7mL of dichloromethane to the reaction bottle, stir for 3 minutes, and pour the reaction solution into 420mL of methanol to precipitate a white polymer. Then, filter and repeatedly wash the filter cake with methanol to collect the white solid. Finally, put the collected white polymer into a vacuum drying oven and dry it at 100°C to constant weight to obtain a polyolefin ether ester P1a2d (69% trans) with a trans double bond content of 69%.

[0052]

[0053] The structural characterization data of the obtained polyolefin ether ester are as follows:

[0054] P1a2d (69% trans), white solid, yield: 80%. 1 H NMR (400MHz, CDCl3) δ7.69(d,J=12.0Hz,0.69H),7.09(m,3H),6.71(d,J=6.0Hz,0.31H),5.65(s,1H),5.42(d,J=12.0Hz,0.69 H),5.10(d,J=6.0Hz,0.31H),4.39(d,J=6.8Hz,1H),4.12(t,J=6.6Hz,2H),3.96-3.89(m,5H),1.71-1.60(m,2H),1.40(m,2H).

[0055] Example 5

[0056] In a 100mL single-necked bottle, add a stirrer, 6mmol of difunctional phenol monomer 1a, 6mmol of difunctional alkyne ester monomer 2d, 1.2mmol of TMG and 20mL of DMSO; after stirring at 25°C for 24 hours, stop the reaction. Add 10mL of dichloromethane to the reaction bottle, stir for 3 minutes, and pour the reaction solution into 300mL of methanol to precipitate a white polymer. Then, filter and repeatedly wash the filter cake with methanol to collect the white solid. Finally, put the collected white polymer into a vacuum drying oven and vacuum dry it at 100°C to constant weight to obtain a polyolefin ether ester P1a2d (50% trans) with a trans double bond content of 100%.

[0057]

[0058] P1a2d (50% trans), dark yellow solid, yield: 62%. 1 H NMR (400MHz, CDCl3) δ7.69(d,J=12.0Hz,0.5H),7.09(m,3H),6.71(d,J=6.0Hz,0.5H),5.64(s,1H),5.42(d,J=12.0Hz ,0.5H),5.10(d,J=6.0Hz,0.5H),4.38(s,1H),4.20-4.05(m,2H),3.99-3.85(m,5H),1.72-1.59(m,2H),1.41(m,2H).

[0059] 2. Synthesis of polyolefin ether esters P1e2d (46%-100% trans) with different carbon-carbon double bond stereo configurations

[0060] Example 6

[0061] In a 100mL single-mouth bottle, a stirring bar, 6mmol of difunctional phenol monomer 1e, 6mmol of difunctional alkyne ester monomer 2d, 0.012mmol of quinine and 20mL of THF were added respectively; after stirring at 76°C for 2 hours, the reaction was stopped. 7mL of dichloromethane was added to the reaction bottle, and after stirring for 3 minutes, the reaction solution was poured into 170mL of methanol to precipitate a white polymer. Then, the filter cake was filtered and repeatedly washed with methanol to collect the white solid. Finally, the collected white polymer was placed in a vacuum drying oven and vacuum dried at 100°C to constant weight to obtain a polyolefin ether ester P1e2d (100% trans) with a trans double bond content of 100%.

[0062]

[0063] P1e2d (100% trans), white solid, yield: 92%.1 H NMR (400MHz, CDCl3) δ7.69(d,J=12.2Hz,1H),7.14(s,1H),7.06(s,2H),5.45(s,1H),5.41(d,J=12.4Hz,1H), 4.85(d,J=11.0Hz,1H),4.10(t,J=5.8Hz,2H),3.88(s,5H),3.67(d,J=11.5Hz,1H),1.64(s,2H),1.38(s,2H); 13 C NMR (101MHz, CDCl3) δ167.4,160.5,150.4,144.8,136.2,120.2,118.9,110.6,101.6,101.2,71.1,70.6,64.1,56.1,32.6,28.7,25.7.

[0064] Example 7

[0065] In a 100mL single-necked bottle, a stirrer, 6mmol of difunctional phenol monomer 1e, 6mmol of difunctional alkyne ester monomer 2d, 3mmol of DMAP and 20mL of DMF were added respectively; after stirring at 25°C for 2 hours, the reaction was stopped. 8mL of dichloromethane was added to the reaction bottle, and after stirring for 3 minutes, the reaction solution was poured into 190mL of methanol to precipitate a white polymer. Then, the filter cake was filtered and repeatedly washed with methanol to collect the white solid. Finally, the collected white polymer was placed in a vacuum drying oven and vacuum dried at 100°C to constant weight to obtain a polyolefin ether ester P1e2d (91% trans) with a trans double bond content of 91%.

[0066]

[0067] P1e2d (91% trans), dark yellow solid, yield: 90%. 1 H NMR (400MHz, CDCl3) δ7.69(d,J=12.3Hz,0.91H),7.14(s,1H),7.06(s,2H),6.71(d,J=7.1Hz,0.09H),5.45(s,1H),5.41(d,J=12.3Hz,0.91 H),5.09(d,J=7.0Hz,0.09H),4.86(d,J=11.2Hz,1H),4.10(t,J=6.5Hz,2H),3.88(s,5H),3.67(d,J=11.6Hz,1H),1.64(s,2H),1.26(s,2H).

[0068] Example 8

[0069] In a 100mL single-mouth bottle, a stirrer, 6mmol of difunctional phenol monomer 1e, 8mmol of difunctional alkyne ester monomer 2d, 0.06mmol of DMAP and 20mL of THF were added respectively; after stirring at 25°C for 24 hours, the reaction was stopped. 10mL of dichloromethane was added to the reaction bottle, and after stirring for 3 minutes, the reaction solution was poured into 210mL of methanol to precipitate a white polymer. Then, the filter cake was filtered and repeatedly washed with methanol to collect the white solid. Finally, the collected white polymer was placed in a vacuum drying oven and vacuum dried at 100°C to constant weight to obtain a polyolefin ether ester P1e2d (82% trans) with a trans double bond content of 82%.

[0070]

[0071] P1e2d (82% trans), dark yellow solid, yield: 93%. 1 H NMR (400MHz, CDCl3) δ7.69(d,J=12.2Hz,0.82H),7.14(s,1H),7.06(s,2H),6.71(d,J=6.9Hz,0.18H),5.44(s ,1H),5.41(d,J=12.7Hz,0.82H),5.09(d,J=6.7Hz,0.18H),4.85(d,J=10.9Hz,1H),1.63(s,2H),1.38(s,2H).

[0072] Example 9

[0073] In a 100mL single-mouth bottle, add a stirrer, 6mmol of difunctional phenol monomer 1e, 6mmol of difunctional alkyne ester monomer 2d, 0.06mmol of Et3N and 20mL of DMF; after stirring at 25°C for 24 hours, stop the reaction. Add 10mL of dichloromethane to the reaction bottle, stir for 3 minutes, and pour the reaction solution into 220mL of methanol to precipitate a white polymer. Then, filter and repeatedly wash the filter cake with methanol to collect the white solid. Finally, put the collected white polymer into a vacuum drying oven, dry it at 100°C for 12 hours, and then take it out to obtain a polyolefin ether ester P1e2d (71% trans) with a trans double bond content of 71%.

[0074]

[0075] P1e2d (71% trans), dark yellow solid, yield: 93%. 1H NMR(400MHz, CDCl3) δ7.69(d,J=12.3Hz,0.71H),7.19-7.05(m,3H),6.71(d,J=6.9Hz,0.29H),5.44(s,1H),5.41(d,J=12.3Hz,0.71H) ,5.09(d,J=6.9Hz,0.29H),4.85(d,J=11.3Hz,1H),4.12(m,2H),3.93-3.75(m,5H),3.67(d,J=11.6Hz,1H),1.64(s,2H),1.40(s,2H).

[0076] Example 10

[0077] In a 100 mL single-necked bottle, a stirring bar, 6 mmol of a bifunctional phenol monomer 1e, 6 mmol of a bifunctional alkyne ester monomer 2d, and 0.06 mmol of i Pr3P and 20mL of THF; after stirring at 50°C for 24 hours, stop the reaction. Add 10mL of dichloromethane to the reaction bottle, stir for 3 minutes, and pour the reaction solution into 140mL of methanol to precipitate a white polymer. Then, filter and repeatedly wash the filter cake with methanol to collect the white solid. Finally, put the collected white polymer into a vacuum drying oven, dry it at 100°C for 12 hours, and take it out to obtain a polyolefin ether ester P1e2d (46% trans) with a trans double bond content of 46%.

[0078]

[0079] P1e2d (46% trans), dark yellow solid, yield: 63%. 1 H NMR (400MHz, CDCl3) δ7.69(d,J=12.3Hz,0.46H),7.09(m,3H),6.71(d,J=6.9Hz,0.54H),5.49-5.36(m,1.46H),5.09(d,J=6.9Hz,0.5 4H),4.87(d,J=11.3Hz,1H),4.12(dt,J=17.4,5.7Hz,2H),3.97-3.76(m,5H),3.66(d,J=11.4Hz,1H),1.73-1.59(m,2H),1.42(m,2H).

[0080] 3. Synthesis of polyolefin ether esters P1i2b (54%-100% trans) with different carbon-carbon double bond stereo configurations

[0081] Embodiment 11

[0082] In a 100mL single-mouth bottle, add a stirrer, 6mmol of difunctional phenol monomer 1i, 6mmol of difunctional alkyne ester monomer 2b, 0.9mmol of DABCO and 20mL of CH3CN; after stirring at 25°C for 2 hours, stop the reaction. Add 7mL of dichloromethane to the reaction bottle, stir for 3 minutes, and pour the reaction solution into 160mL of methanol to precipitate a white polymer. Then, filter and repeatedly wash the filter cake with methanol to collect the white solid. Finally, put the collected white polymer into a vacuum drying oven, dry it at 100°C for 12 hours, and then take it out to obtain a polyolefin ether ester P1i2b (100% trans) with a trans double bond content of 100%.

[0083]

[0084] P1i2b (100% trans), white solid, yield: 98%. 1 H NMR (400MHz, CDCl3) δ7.78(d,J=12.2Hz,1H),7.20(d,J=8.4Hz,2H),6.98(t,J =10.5Hz,2H),5.53(d,J=12.2Hz,1H),4.17(s,2H),1.74(s,2H),1.66(s,3H); 13 C NMR (101MHz, CDCl3) δ167.4,159.5,153.9,147.3,128.4,117.7,101.9,63.7,42.5,31.0,25.6.

[0085] Example 12

[0086] In a 100mL single-mouth bottle, add a stirrer, 6mmol of difunctional phenol monomer 1i, 6mmol of difunctional alkyne ester monomer 2b, 0.06mmol of DMAP and 20mL of THF; after stirring at 25°C for 3 hours, stop the reaction. Add 6mL of dichloromethane to the reaction bottle, stir for 3 minutes, and pour the reaction solution into 310mL of methanol to precipitate a white polymer. Then, filter and repeatedly wash the filter cake with methanol to collect the white solid. Finally, put the collected white polymer into a vacuum drying oven, dry it at 100°C for 12 hours, and then take it out to obtain a polyolefin ether ester P1i2b (82% trans) with a trans double bond content of 82%.

[0087]

[0088] P1i2b (82% trans), white solid, yield: 98%. 1H NMR (400MHz, CDCl3) δ7.78(d,J=12.2Hz,0.82H),7.20(d,J=8.4Hz,2H),6.98(t,J=10.5Hz,2H),6.86(d,J =7.0Hz,0.18H),5.53(d,J=12.2Hz,1H),5.13(d,J=6.9Hz,0.18H),4.17(s,2H),1.74(s,2H),1.66(s,3H).

[0089] Embodiment 13

[0090] In a 100mL single-necked bottle, a stirrer, 6mmol of difunctional phenol monomer 1i, 6mmol of difunctional alkyne ester monomer 2b, 0.3mmol of DMAP and 20mL of CH3CN were added respectively; after stirring at 30°C for 8 hours, the reaction was stopped. 6mL of dichloromethane was added to the reaction bottle, and after stirring for 3 minutes, the reaction solution was poured into 420mL of methanol to precipitate a white polymer. Then, the filter cake was filtered and repeatedly washed with methanol to collect the white solid. Finally, the collected white polymer was placed in a vacuum drying oven and dried at 100°C for 12 hours to obtain a polyolefin ether ester P1i2b (74% trans) with a trans double bond content of 74%.

[0091]

[0092] P1i2b (74% trans), white solid, yield: 95%. 1 H NMR (400MHz, CDCl3) δ7.78 (d, J=12.2Hz, 0.74H), 7.20 (dd, J=8.7, 4.5Hz, 2H), 6.98 (t, J=10.8Hz, 2H), 6.86 (d, J=7.0Hz,0.26H),5.53(d,J=12.2Hz,0.74H),5.13(d,J=6.9Hz,0.26H),4.16(s,2H),1.74(s,2H),1.66(s,3H).

[0093] Embodiment 14

[0094] In a 100mL single-mouth bottle, add a stirrer, 6mmol of difunctional phenol monomer 1i, 6mmol of difunctional alkyne ester monomer 2b, 5mmol of DBU and 20mL of CH3CN; after stirring at 65°C for 24 hours, stop the reaction. Add 6mL of dichloromethane to the reaction bottle, stir for 3 minutes, and pour the reaction solution into 150mL of methanol to precipitate a white polymer. Then, filter and repeatedly wash the filter cake with methanol to collect the white solid. Finally, put the collected white polymer into a vacuum drying oven, dry it at 100°C for 12 hours, and then take it out to obtain a polyolefin ether ester P1i2b (60% trans) with a trans double bond content of 60%.

[0095]

[0096] P1i2b (60% trans), white solid, yield: 90%. 1 H NMR(500MHz, CDCl3)δ7.81-7.73(m,0.6H),7.19(dt,J=8.4,5.7Hz,2H),6.98(m,2H),6.86(dd,J=7.0,2.7Hz,0.4H),5 .53(dd,J=12.2,1.5Hz,0.6H),5.13(d,J=6.9Hz,0.4H),4.20-4.14(m,2H),1.81-1.71(m,2H),1.66(d,J=3.2Hz,3H).

[0097] Embodiment 15

[0098] In a 100mL single-mouth bottle, add a stirrer, 6mmol of difunctional phenol monomer 1i, 6mmol of difunctional acetylene ester monomer 2b, 1.2mmol of Ph2CH3P and 20mL of THF; after stirring at 50°C for 24 hours, stop the reaction. Add 10mL of dichloromethane to the reaction bottle, stir for 3 minutes, and pour the reaction solution into 130mL of methanol to precipitate a white polymer. Then, filter and repeatedly wash the filter cake with methanol to collect the white solid. Finally, put the collected white polymer into a vacuum drying oven, dry it at 100°C for 12 hours, and then take it out to obtain a polyolefin ether ester P1i2b (54% trans) with a trans double bond content of 54%.

[0099]

[0100] P1i2b (54% trans), white solid, yield: 88%. 1H NMR(500MHz, CDCl3)δ7.81-7.73(m,0.54H),7.19(dt,J=8.4,5.7Hz,2H),6.98(m,2H),6.86(dd,J=7.0,2.7Hz,0.46H),5 .53(dd,J=12.2,1.5Hz,0.54H),5.13(d,J=6.9Hz,0.46H),4.20-4.14(m,2H),1.81-1.71(m,2H),1.66(d,J=3.2Hz,3H).

[0101] 4. Synthesis of polyolefin ether esters P1i2m (62%-100% trans) with different carbon-carbon double bond stereo configurations

[0102] Example 16

[0103] In a 100mL single-mouth bottle, add a stirrer, 6mmol of difunctional phenol monomer 1i, 6mmol of difunctional alkyne ester monomer 2m, 0.06mmol of NMP and 20mL of DMF; after stirring at 25°C for 3 hours, stop the reaction. Add 10mL of dichloromethane to the reaction bottle, stir for 3 minutes, and pour the reaction solution into 120mL of methanol to precipitate a white polymer. Then, filter and repeatedly wash the filter cake with methanol to collect the white solid. Finally, put the collected white polymer into a vacuum drying oven, dry it at 100°C for 12 hours, and then take it out to obtain a polyolefin ether ester P1i2m (100% trans) with a trans double bond content of 100%.

[0104]

[0105] P1i2m (100% trans), white solid, yield: 98%. 1 H NMR (500MHz, CDCl3) δ7.80 (t, J=8.4Hz, 1H), 7.20 (d, J=8.5Hz, 2H), 6.99 (dd, J=20.8, 8.4Hz,2H),5.84-5.74(m,1H),5.53(d,J=12.2Hz,1H),4.76(dd,J=11.6,4.5Hz,2H); 13 C NMR (101MHz, CDCl3) δ167.0,159.8,153.9,147.3,128.4,128.3,117.8,101.5,59.8,42.5,31.0.

[0106] Embodiment 17

[0107] In a 100mL single-mouth bottle, add a stirrer, 6mmol of difunctional phenol monomer 1i, 8.5mmol of difunctional alkyne ester monomer 2m, 0.3mmol of DBU and 20mL of DMF respectively; after stirring at 60°C for 12 hours, stop the reaction. Add 10mL of dichloromethane to the reaction bottle, stir for 3 minutes, and pour the reaction solution into 120mL of methanol to precipitate a white polymer. Then, filter and repeatedly wash the filter cake with methanol to collect the white solid. Finally, put the collected white polymer into a vacuum drying oven, dry it at 100°C for 12 hours, and then take it out to obtain a polyolefin ether ester P1i2m (92% trans) with a trans double bond content of 100%.

[0108]

[0109] P1i2m (92% trans), white solid, yield: 97%. 1 H NMR (500MHz, CDCl3) δ7.80(t,J=8.4Hz,0.92H),7.20(d,J=8.5Hz,2H),6.99(dd,J=20.8,8.4Hz,2H),6.88(d,J=7.1 Hz,0.08H),5.84–5.74(m,1H),5.53(d,J=12.2Hz,0.92H),5.15(d,J=6.9Hz,0.08H),4.76(dd,J=11.6,4.5Hz,2H).

[0110] Embodiment 18

[0111] In a 100mL single-mouth bottle, add a stirrer, 6mmol of difunctional phenol monomer 1i, 6mmol of difunctional alkyne ester monomer 2m, 0.3mmol of TBD and 20mL of DMF; after stirring at 60°C for 18 hours, stop the reaction. Add 10mL of dichloromethane to the reaction bottle, stir for 3 minutes, and pour the reaction solution into 175mL of methanol to precipitate a white polymer. Then, filter and repeatedly wash the filter cake with methanol to collect the white solid. Finally, put the collected white polymer into a vacuum drying oven, dry it at 100°C for 12 hours, and then take it out to obtain a polyolefin ether ester P1i2m (76% trans) with a trans double bond content of 100%.

[0112]

[0113] P1i2m (76% trans), white solid, yield: 85%. 1 H NMR (500MHz,CDCl3) 1H NMR (500MHz, CDCl3) δ7.80(t,J=8.4Hz,0.76H),7.20(d,J=8.5Hz,2H),6.99(dd,J=20.8,8.4Hz,2H),6.88(d,J=7.1 Hz,0.24H),5.84-5.74(m,1H),5.53(d,J=12.2Hz,0.76H),5.15(d,J=6.9Hz,0.24H),4.76(dd,J=11.6,4.5Hz,2H).

[0114] Embodiment 19

[0115] In a 100mL single-mouth bottle, add a stirrer, 6mmol of difunctional phenol monomer 1i, 6mmol of difunctional alkyne ester monomer 2m, 1.2mmol of Et3N and 20mL of DMF; after stirring at 30°C for 8 hours, stop the reaction. Add 10mL of dichloromethane to the reaction bottle, stir for 3 minutes, and pour the reaction solution into 270mL of methanol to precipitate a white polymer. Then, filter and repeatedly wash the filter cake with methanol to collect the white solid. Finally, put the collected white polymer into a vacuum drying oven, dry it at 100°C for 12 hours, and then take it out to obtain a polyolefin ether ester P1i2m (62% trans) with a trans double bond content of 100%.

[0116]

[0117] P1i2m (62% trans), white solid, yield: 89%. 1 H NMR (400MHz, CDCl3) δ7.84-7.76(m,0.62H),7.23-7.14(m,2H),6.98(m,2H),6.87(d,J=6.9Hz,0.38H),5. 79(dd,J=11.3,5.5Hz,1H),5.56-5.51(m,0.62H),5.14(d,J=6.9Hz,0.38H),4.77(dt,J=8.6,5.0Hz,2H).

[0118] Embodiment 20

[0119] In a 100 mL single-necked bottle, a stirring bar, 6 mmol of a bifunctional phenol monomer 1i, 6 mmol of a bifunctional acetylic acid ester monomer 2m, and 1.2 mmol of nBu3P and 20mL of THF; after stirring at 60°C for 24 hours, stop the reaction. Add 10mL of dichloromethane to the reaction bottle, stir for 3 minutes, and pour the reaction solution into 125mL of methanol to precipitate a white polymer. Then, filter and repeatedly wash the filter cake with methanol to collect the white solid. Finally, put the collected white polymer into a vacuum drying oven, dry it at 100°C for 12 hours, and then take it out to obtain a polyolefin ether ester P1i2m (51% trans) with a trans double bond content of 100%.

[0120]

[0121] P1i2m (51% trans), white solid, yield: 95%. 1 H NMR (400MHz, CDCl3) δ7.84-7.76(m,0.51H),7.23-7.14(m,2H),6.98(ddd,J=16.6,8.6,3.3Hz,2H),6.87(d,J=6.9Hz ,0.49H),5.79(dd,J=11.3,5.5Hz,1H),5.56-5.51(m,0.51H),5.14(d,J=6.9Hz,0.49H),4.77(dt,J=8.6,5.0Hz,2H).

[0122] 5. Synthesis of polyolefin ether esters P1m2m (50%-100% trans) with different carbon-carbon double bond stereo configurations

[0123] Embodiment 21

[0124] In a 100mL single-mouth bottle, add a stirrer, 6mmol of difunctional phenol monomer 1m, 7.5mmol of difunctional acetylic acid ester monomer 2m, 0.06mmol of DABCO and 20mL of THF; after stirring at 83°C for 2 hours, stop the reaction. Add 10mL of dichloromethane to the reaction bottle, stir for 3 minutes, and pour the reaction solution into 100mL of methanol to precipitate a white polymer. Then, filter and repeatedly wash the filter cake with methanol to collect the white solid. Finally, put the collected white polymer into a vacuum drying oven, dry it at 100°C for 12 hours, and then take it out to obtain a polyolefin ether ester P1m2m (100% trans) with a trans double bond content of 100%.

[0125]

[0126] P1m2m (100% trans), white solid, yield: 88%. 1H NMR (400MHz, CDCl3) δ7.75(d,J=12.2Hz,1H),7.14–7.01(m,2H),5.83-5.71(m,1H),5.54(d,J=12.2Hz,1H),4.81-4.70(m,2H); 13 C NMR (101MHz, CDCl3) δ166.8,159.5,152.8,128.3,119.8,102.1,59.9.

[0127] Embodiment 22

[0128] In a 100mL single-mouth bottle, add a stirrer, 6mmol of difunctional phenol monomer 1m, 6mmol of difunctional alkyne ester monomer 2m, 0.3mmol of Et3N and 20mL of THF; after stirring at 100°C for 8 hours, stop the reaction. Add 8mL of dichloromethane to the reaction bottle, stir for 3 minutes, and pour the reaction solution into 170mL of methanol to precipitate a white polymer. Then, filter and repeatedly wash the filter cake with methanol to collect the white solid. Finally, put the collected white polymer into a vacuum drying oven, dry it at 100°C for 12 hours, and then take it out to obtain a polyolefin ether ester P1m2m (88% trans) with a trans double bond content of 100%.

[0129]

[0130] P1m2m (88% trans), white solid, yield: 88%. 1 H NMR(500MHz, CDCl3) δ7.75(d,J=12.1Hz,0.88H),7.09(d,J=14.9Hz,2H),6.83(d,J=7.3Hz ,0.12H),5.78(s,1H),5.54(d,J=12.2Hz,0.88H),5.19(d,J=6.2Hz,0.12H),4.76(s,2H).

[0131] Embodiment 23

[0132] In a 100mL single-necked bottle, add a stirrer, 6mmol of difunctional phenol monomer 1m, 8.3mmol of difunctional alkyne ester monomer 2m, 0.06mmol of MTBD and 20mL of THF; after stirring at 50°C for 10 hours, stop the reaction. Add 10mL of dichloromethane to the reaction bottle, stir for 3 minutes, and pour the reaction solution into 125mL of methanol to precipitate a white polymer. Then, filter and repeatedly wash the filter cake with methanol to collect the white solid. Finally, put the collected white polymer into a vacuum drying oven, dry it at 100°C for 12 hours, and then take it out to obtain a polyolefin ether ester P1m2m (84% trans) with a trans double bond content of 100%.

[0133]

[0134] P1m2m (84% trans), white solid, yield: 92%. 1 H NMR(500MHz, CDCl3)δ7.75(d,J=12.2Hz,0.84H),7.14-7.03(m,2H),6.83(d,J=7.0Hz,0.16H),5 .85-5.73(m,1H),5.53(dd,J=12.2,5.8Hz,0.84H),5.19(d,J=6.9Hz,0.16H),4.82-4.71(m,2H).

[0135] Embodiment 24

[0136] In a 100mL single-necked bottle, add a stirrer, 6mmol of difunctional phenol monomer 1m, 6mmol of difunctional alkyne ester monomer 2m, 0.012mmol of Py and 20mL of DMSO; after stirring at 80°C for 16 hours, stop the reaction. Add 8mL of dichloromethane to the reaction bottle, stir for 3 minutes, and pour the reaction solution into 115mL of methanol to precipitate a white polymer. Then, filter and repeatedly wash the filter cake with methanol to collect the white solid. Finally, put the collected white polymer into a vacuum drying oven, dry it at 100°C for 12 hours, and then take it out to obtain a polyolefin ether ester P1m2m (70% trans) with a trans double bond content of 100%.

[0137]

[0138] P1m2m (70% trans), white solid, yield: 80%. 1H NMR (500MHz, CDCl3) δ7.75 (d, J=12.2Hz, 0.7H), 7.15-7.02 (m, 2H), 6.83 (d, J=6.9Hz, 0.3H), 5.85 -5.73(m,1H),5.53(dd,J=12.2,5.8Hz,0.7H),5.22-5.14(m,0.3H),4.77(dd,J=12.3,4.4Hz,2H).

[0139] Embodiment 25

[0140] In a 100mL single-necked bottle, add a stirrer, 6mmol of difunctional phenol monomer 1m, 6mmol of difunctional alkyne ester monomer 2m, 0.6mmol of Et3N and 20mL of DMSO; after stirring at 25°C for 8 hours, stop the reaction. Add 10mL of dichloromethane to the reaction bottle, stir for 3 minutes, and pour the reaction solution into 310mL of methanol to precipitate a white polymer. Then, filter and repeatedly wash the filter cake with methanol to collect the white solid. Finally, put the collected white polymer into a vacuum drying oven, dry it at 100°C for 12 hours, and then take it out to obtain a polyolefin ether ester P1m2m (60% trans) with a trans double bond content of 100%.

[0141]

[0142] P1m2m (60% trans), white solid, yield: 98%. 1 H NMR(500MHz, CDCl3)δ7.75(d,J=12.2Hz,0.6H),7.18-7.00(m,2H),6.83(d,J=7.0Hz,0.4H), 5.86-5.73(m,1H),5.53(dd,J=12.2,5.8Hz,0.6H),5.23-5.12(m,0.4H),4.86-4.68(m,2H).

[0143] Embodiment 26

[0144] In a 100mL single-mouth bottle, add a stirrer, 6mmol of difunctional phenol monomer 1m, 9.6mmol of difunctional alkyne ester monomer 2m, 4.2mmol of Ph3P and 20mL of THF; after stirring at 50°C for 24 hours, stop the reaction. Add 11mL of dichloromethane to the reaction bottle, stir for 3 minutes, and pour the reaction solution into 425mL of methanol to precipitate a white polymer. Then, filter and repeatedly wash the filter cake with methanol to collect the white solid. Finally, put the collected white polymer into a vacuum drying oven, dry it at 100°C for 12 hours, and then take it out to obtain a polyolefin ether ester P1m2m (50% trans) with a trans double bond content of 50%.

[0145]

[0146] P1m2m (50% trans), white solid, yield: 50%. 1 H NMR (400MHz, CDCl3) δ7.75 (d, J=12.2Hz, 0.5H), 7.17-7.01 (m, 2H), 6.82 (d, J=6.8Hz, 0.5H), 5.79 (d, J= 4.6Hz, 1H), 5.53 (dd, J=12.2, 4.6Hz, 0.5H), 5.18 (dd, J=6.7, 3.7Hz, 0.5H), 4.78 (dt, J=9.9, 4.8Hz, 2H).

[0147] Performance test of polyolefin ether esters with different carbon-carbon double bond stereo configurations

[0148] like Figure 1 As shown, the trans and cis configurations of vinyl hydrogen protons in polymer P1a2d can be clearly distinguished in the H NMR spectrum. The peaks of the vinyl protons of the trans configuration double bonds in the H NMR spectrum are 7.69 and 5.39 ppm, respectively, and the coupling constant J = 12.0 Hz. The peaks of the vinyl protons of the cis configuration double bonds in the H NMR spectrum are 6.71 and 5.10 ppm, and the coupling constant J = 6.0 Hz. The content of trans configuration double bonds in the polymer can be determined by the integrated area of ​​protons H1 and H2. Since the stereo configuration of the carbon-carbon double bond of the polymer main chain has a very important influence on the performance of the polymer material, the thermomechanical properties of polymer P1a2d with different carbon-carbon double bond stereo configurations were first evaluated using a thermogravimetric analyzer, a differential scanning calorimeter, an X-ray diffractometer, and a universal stretching machine (Examples 1-5). The evaluation results are shown in the following table. Figure 2-Figure 5 The results show that the temperature at which the polymer loses 5% of its thermal weight (T d5％ ) increases with the increase of trans double bond content in polymer P1a2d ( Figure 2In addition, DSC tests show that 50% trans P1a2d is an amorphous material with a glass transition temperature of 68.5°C. As the trans content increases, the crystallinity of the material gradually increases ( Figure 3 ), with a melting point of up to 136.3°C and a melting enthalpy of up to 30.3 J / g. Their crystallinity was further confirmed by X-ray diffractometer ( Figure 4 The test results of the universal tensile machine show that as the trans content in the main chain of the polymer P1a2d decreases, the mechanical properties of the polymer show a trend of first increasing and then decreasing, among which 80% trans P1a2d shows the best mechanical properties, with an ultimate tensile strength of 90MPa and an elongation at break of 200% ( Figure 5 ).

Claims

1. A method for synthesizing a polyolefin ether ester with controllable cis-trans stereo configuration of carbon-carbon double bonds, characterized in that: The steps are as follows: a difunctional phenol monomer, a difunctional acetylic acid ester monomer, an organic catalyst and a reaction solvent are mixed; after stirring the reaction until the monomer is completely converted, dichloromethane is added to dilute the reaction solution and stirred, and then the reaction solution is poured into methanol to obtain a polymer precipitate, filtered, and the filter cake is repeatedly washed with methanol, and the solid is collected to obtain a polyolefin ether ester with controllable cis-trans stereo configuration of the carbon-carbon double bond; the reaction is shown in the following formula: The organic catalyst has the following structure: The bifunctional phenol monomer has the following structure: The difunctional acetylic acid ester monomer has the following structure:

2. The method for synthesizing a polyolefin ether ester with controllable cis-trans stereo configuration of carbon-carbon double bonds according to claim 1, characterized in that: The molar ratio of the difunctional phenol monomer to the difunctional acetylic acid ester monomer is 1:0.8-1:1.

5.

3. A method for synthesizing a polyolefin ether ester with controllable cis-trans stereo configuration of a carbon-carbon double bond according to claim 1 or 2, characterized in that: The molar ratio of the sum of the difunctional phenol monomer and the difunctional acetylic acid ester monomer to the organic catalyst is 2:1 to 1000:

1.

4. The method for synthesizing a polyolefin ether ester with controllable cis-trans stereo configuration of a carbon-carbon double bond according to claim 1 or 2, characterized in that: The molar concentration of the difunctional phenol monomer and the difunctional acetylic acid ester monomer in dichloromethane is 0.5 mol / L to 1 mol / L; the molar concentration of the difunctional phenol monomer and the difunctional acetylic acid ester monomer in methanol is 0.01 mol / L to 0.05 mol / L.

5. The method for synthesizing a polyolefin ether ester with controllable cis-trans stereo configuration of carbon-carbon double bonds according to claim 3, characterized in that: The molar concentration of the difunctional phenol monomer and the difunctional acetylic acid ester monomer in dichloromethane is 0.5 mol / L to 1 mol / L; the molar concentration of the difunctional phenol monomer and the difunctional acetylic acid ester monomer in methanol is 0.01 mol / L to 0.05 mol / L.

6. A method for synthesizing a polyolefin ether ester with controllable cis-trans stereo configuration of a carbon-carbon double bond according to claim 1, 2 or 5, characterized in that: Add dichloromethane and stir for 5-10 minutes.

7. A method for synthesizing a polyolefin ether ester with controllable cis-trans stereo configuration of a carbon-carbon double bond according to claim 1, 2 or 5, characterized in that: The reaction solvent is acetonitrile, chloroform, N,N-dimethylformamide, tetrahydrofuran or dimethyl sulfoxide.

8. A method for synthesizing a polyolefin ether ester with controllable cis-trans stereo configuration of a carbon-carbon double bond according to claim 1, 2 or 5, characterized in that: The reaction temperature is 25-100°C.

9. A method for synthesizing a polyolefin ether ester with controllable cis-trans stereo configuration of carbon-carbon double bonds according to claim 1, 2 or 5, characterized in that: The reaction time is 1 to 24 hours.

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