A method for synthesizing olefin-functionalized polyester-polyether copolymer

Abstract

The invention discloses a method for synthesizing an olefin-functionalized polyester-polyether copolymer. The method comprises the following steps: mixing an organic chromium complex, bis(triphenylphosphorane)ammonium chloride, 3-ethylene-6-vinyltetrahydro-2H-pyran-2-one, and an epoxy compound monomer for reaction to prepare the olefin-functionalized polyester-polyether copolymer; the structural formula of the organic chromium complex is shown in the following formula I: #imgabs0# The 3-ethylene-6-vinyltetrahydro-2H-pyran-2-one used in the invention is prepared by carbon dioxide and butadiene, and the olefin-functionalized polyester-polyether copolymer is prepared by using 3-ethylene-6-vinyltetrahydro-2H-pyran-2-one and the epoxy compound monomer. The prepared olefin-functionalized polyester-polyether copolymer has a specific number average molecular weight and its distribution, and carbon dioxide is distributed in the polymer. The invention effectively fixes carbon dioxide, thereby achieving green and sustainable development.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer synthesis, and specifically relates to a method for synthesizing an olefin-functionalized polyester-polyether copolymer, and in particular, to a method for synthesizing an olefin-functionalized polyester-polyether copolymer by a ring-opening copolymerization reaction regulated by an organic chromium complex. Background Art

[0002] Carbon dioxide is an inexpensive, low-toxic C1 resource. Using it to synthesize other high-value-added industrial raw materials not only helps mitigate the global greenhouse effect but also achieves resource utilization. Carbon dioxide and butadiene react over a palladium catalyst to produce 3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one (EVP), a δ-valerolactone containing two unsaturated double bonds. Polymers with diverse structures can be obtained through methods such as ring-opening polymerization, free radical polymerization, and coordination polymerization. At present, EVP polymerization research mainly focuses on free radical polymerization, and its polymerization process conditions are harsh and the reaction efficiency is low (Nat.Chem2014,6,325-331), and the structure of the resulting polymer product is difficult to accurately control; the main chain structure of the product obtained by coordination polymerization is a carbon-carbon bond, which is difficult to carry out subsequent polymerization modification, and is difficult to degrade in the natural environment, and has low use value (J.Am.Chem.Soc.2021,143,17953-17957). Since the main structure of EVP is a six-membered ring lactone, and the unsaturated double bond structure at the α-position of the carbonyl group causes the lactone to have low activity, it is not easy to directly ring-opening polymerize, so using its ring-opening polymerization to obtain olefin functionalized polymers is still a challenge in the field of polymer synthesis. Summary of the Invention

[0003] The purpose of the present invention is to address the problems existing in the prior art and provide a method for synthesizing an olefin-functionalized polyester-polyether copolymer, so that the prepared olefin-functionalized polyester-polyether copolymer has a specific number average molecular weight (2 to 200 kDa) and its distribution (1.05 to 2.50), and the unsaturated olefin structure of the side chain can be functionalized and modified through a click reaction, the polyester structure of the main chain can be effectively degraded through a hydrolysis reaction, and the polyether structure has a strong lithium ion transmission ability. Therefore, the polymer has broad application prospects in the field of materials.

[0004] To achieve the above object, the technical solution adopted by the present invention is:

[0005] A method for synthesizing an olefin-functionalized polyester-polyether copolymer, comprising:

[0006] The organic chromium complex, bis(triphenylphosphorane)ammonium chloride, 3-ethylene-6-vinyltetrahydro-2H-pyran-2-one, and epoxy compound monomer are mixed and reacted to prepare the olefin functionalized polyester-polyether copolymer;

[0007] The structural formula of the organic chromium complex is shown in the following formula I:

[0008]

[0009] Wherein, R1, R2 and R3 are the same or different and are independently selected from H, C 1-20 Alkyl, C 1-20 Alkoxy and fluorine-substituted C 1-20 or R2 and R3 can form a ring; preferably, R2 and R3 can form a substituted or unsubstituted C 6-20 Aryl, substituted by halogen or C 1-20 alkyl;

[0010] R4 is substituted or unsubstituted C 1-20 Alkylene, substituted or unsubstituted C 1-20 Alkyleneoxy, substituted or unsubstituted C 6-20 Arylene, substituted or unsubstituted C 3-20 Cycloalkylene, substituent A is halogen, nitro, amino or cyano;

[0011] The X is one of halogen, -NO3, CH3COO-, CF3COO-, ClO4-, BF4-, BPh4-, -CN, -N3, p-toluate, p-toluenesulfonate, o-nitrophenoloxy, p-nitrophenoloxy, m-nitrophenoloxy, 2,4-dinitrophenoloxy, 3,5-dinitrophenoloxy, 2,4,6-trinitrophenoloxy, 3,5-dichlorophenoloxy, 3,5-difluorophenoloxy, 3,5-di-trifluoromethylphenoloxy or pentafluorophenoloxy anion.

[0012] According to an embodiment of the present invention, said R1, R2 and R3 are the same or different and are independently selected from H, C 1-10 Alkyl, C 1-10 Alkoxy and fluorine-substituted C 1-10 One of the alkyl groups, or R2 and R3 can form a substituted or unsubstituted C 6-12 Aryl, substituted by halogen or C 1-6 Said R1, R2 and R3 are the same or different and are independently of each other and more preferably H, C 1-6 Alkyl, C 1-6 Alkoxy and fluorine-substituted C 1-6One of the alkyl groups, or R2 and R3 can form a phenylene group, a tert-butyl-substituted phenylene group, a fluorine group, and a tert-butyl-substituted phenylene group.

[0013] According to an embodiment of the present invention, the R4 substituted or unsubstituted C 1-10 Alkylene, substituted or unsubstituted C 1-10 Alkoxy, substituted or unsubstituted C 6-12 Arylene, substituted or unsubstituted C 3-10 Cycloalkylene.

[0014] According to an embodiment of the present invention, the molar ratio of 3-ethylene-6-vinyltetrahydro-2H-pyran-2-one:epoxide compound:organic chromium complex:bis(triphenylphosphorane)ammonium chloride is (10-10000):(10-30000):1:(0.1-5); preferably (100-1000):(100-3000):1:(0.5-2); more preferably (100-800):(100-1000):1:(1-1.5).

[0015] According to an embodiment of the present invention, the structural formula of the 3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one is as follows:

[0016]

[0017] According to an embodiment of the present invention, the epoxy compound monomer has a structure shown in the following formula III or formula IV:

[0018]

[0019] Wherein, in formula III, R5 and R6 are the same or different and are independently selected from H, C containing a substituent group B 1-20 Alkyl or C containing substituent group B 6-20 One of the aryl groups, the substituent group B is one of halogen, nitro or cyano;

[0020] In formula IV, R7 is selected from C 1-20 Alkyl, C 6-20 One of the bases.

[0021] According to an embodiment of the present invention, R5 and R6 are the same or different and are independently selected from H, C containing a substituent group B, 1-10 Alkyl or C containing substituent group B 6-12 Aryl, more preferably H, C containing a substituent group B 1-6 Alkyl or C containing substituent group B 6-12 Aryl.

[0022] According to an embodiment of the present invention, R7 is selected from C 1-10 Alkyl, C 6-12 One of the aromatic groups.

[0023] According to an embodiment of the present invention, the reaction is carried out under protective gas, which is nitrogen, argon or other inert gases.

[0024] According to an embodiment of the present invention, the reaction temperature is 40-180°C, exemplarily 40°C, 50°C, 60°C, 80°C, 100°C, 120°C, 140°C, 150°C, 160°C, and 180°C.

[0025] According to an embodiment of the present invention, the reaction time is not less than 1 hour, preferably, the reaction time is 1 hour to 10 days.

[0026] According to an embodiment of the present invention, the reaction further comprises a post-treatment step: removing the organic chromium complex and unreacted monomers from the prepared crude product, purifying and drying it to obtain the olefin functionalized polyester-polyether copolymer.

[0027] According to an embodiment of the present invention, the specific number average molecular mass of the olefin functionalized polyester-polyether copolymer is 2 to 200 kDa.

[0028] As an exemplary embodiment of the present invention, the synthesis method of preparing olefin functionalized polyester-polyether copolymer by ring-opening copolymerization regulated by the organic chromium complex is:

[0029] S1: Under a protective gas atmosphere, 3-ethylene-6-vinyltetrahydro-2H-pyran-2-one, an epoxy compound monomer, an organic chromium complex, and bis(triphenylphosphorane)ammonium chloride are uniformly mixed in a reaction vessel to form a pre-reaction mixture;

[0030] S2: subjecting the pre-reaction mixture in step S1 to a ring-opening copolymerization reaction at 40-180° C. to prepare the olefin-functionalized polyester-polyether copolymer.

[0031] According to an embodiment of the present invention, the mixing time of the pre-reaction mixture in step S1 is 5 to 30 minutes.

[0032] Beneficial effects of the present invention:

[0033] (1) The present invention uses an organic chromium complex as a catalyst to achieve the ring-opening copolymerization reaction of the 3-ethylene-6-vinyltetrahydro-2H-pyran-2-one and the epoxy compound monomer.

[0034] (2) The organic chromium complex of the present invention has a clear structure, stable catalytic performance when used as a catalyst, a simple synthesis process, excellent solubility in the 3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one and the epoxy compound monomer, and the catalytic process is bulk polymerization without the need to add other organic solvents.

[0035] (3) The 3-ethylene-6-vinyltetrahydro-2H-pyran-2-one used in the present invention is prepared by carbon dioxide and butadiene, and the olefin-functionalized polyester-polyether copolymer is prepared by using 3-ethylene-6-vinyltetrahydro-2H-pyran-2-one and an epoxy compound monomer, so that the prepared olefin-functionalized polyester-polyether copolymer has a specific number average molecular weight and its distribution, and carbon dioxide can be distributed in the polymer, effectively fixing carbon dioxide, and realizing green and sustainable development.

[0036] (4) The polymer side chains prepared by the present invention contain unsaturated olefin structures, which can be modified after polymerization through reactions such as thiol-olefin and Michael addition to obtain dendritic structures and cross-linked structures, thereby effectively regulating the physical / chemical properties of the polymer products.

[0037] (5) The main chain structure of the polymer prepared by the present invention is an ester group, which can break the ester bond through reactions such as hydrolysis and aminolysis, thereby achieving effective degradation of the polymer.

[0038] (6) The method of the present invention is conducive to the establishment of a model for the relationship between the microstructure and properties of polymer materials, and provides the possibility for targeted improvement of material properties.

[0039] Definitions and Explanations of Terms

[0040] The term "halogen" refers to fluorine, chlorine, bromine and iodine.

[0041] The term "C 1-20 "Alkyl" is understood to mean a straight-chain or branched saturated monovalent hydrocarbon group having 1 to 20 carbon atoms. For example, "C 1-10 "Alkyl" means straight-chain and branched alkyl groups having 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms, "C 1-6The term "alkyl" refers to straight-chain and branched alkyl groups having 1, 2, 3, 4, 5 or 6 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl or 1,2-dimethylbutyl, or the like or isomers thereof.

[0042] The term "C 1-20 "Alkoxy" is understood to mean an oxygen atom that is directly bonded to a C 1-20 A group formed by connecting alkyl groups, and oxygen is directly connected to the main chain group.

[0043] The term "C 1-20 "Alkyleneoxy" is understood to mean C 1-20 An alkoxy group is formed when it loses a hydrogen atom.

[0044] The term "C 1-20 "Alkylene" is understood to mean C 1-20 A group formed when an alkyl group loses a hydrogen.

[0045] The term "C 3-20 "Cycloalkyl" is understood to mean a saturated monovalent monocyclic, bicyclic hydrocarbon ring or bridged cycloalkane having 3 to 20 carbon atoms, preferably "C 3-10 Cycloalkyl". The term "C 3-10 "Cycloalkyl" is understood to mean a saturated monovalent monocyclic, bicyclic hydrocarbon ring or bridged cycloalkane having 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. 3-10 The cycloalkyl group may be a monocyclic hydrocarbon group, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl, or a bicyclic hydrocarbon group such as decalin. The cycloalkyl group may be a spiro ring, such as spiro[3,3] ring, spiro[3,4] ring, spiro[3,5] ring, spiro[4,4] ring, spiro[4,5] ring, spiro[5,5] ring.

[0046] The term "C 3-20 "Cycloalkylene" is understood to mean C 3-20 A cycloalkyl group formed when it loses a hydrogen atom.

[0047] The term "C 6-20 "Aryl" is understood to mean preferably a monovalent aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring having 6 to 20 carbon atoms, preferably "C 6-12 Aryl". The term "C 6-12"Aryl" is understood to mean preferably a monovalent aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring ("C 6-12 or a ring having 9 carbon atoms ("C9 aryl"), for example indanyl or indenyl, or a ring having 10 carbon atoms ("C 10 aryl”), such as tetrahydronaphthyl, dihydronaphthyl or naphthyl. When the C 6-20 When the aryl group is substituted, it may be monosubstituted or polysubstituted. Furthermore, there is no limitation on the position of substitution, and for example, substitution may be at the ortho, para or meta position.

[0048] The term "C 6-20 "Arylene" should be understood as C 6-20 A radical formed when an aryl group loses a hydrogen. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Figure 1 The H NMR spectrum of the copolymerization product in Example 1 is ( 1 H NMR,CDCl3) spectra;

[0050] Figure 2 The carbon NMR spectrum of the copolymerization product in Example 2 ( 13 C NMR,CDCl3) spectra;

[0051] Figure 3 This is the gel permeation chromatography (GPC) chart of the copolymerization product in Example 4. DETAILED DESCRIPTION

[0052] The technical solutions of the present invention will be described in further detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanations of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are encompassed within the scope of protection that the present invention is intended to protect.

[0053] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0054] Example 1

[0055] S1: Under an argon atmosphere, 21 μL of 3-ethylene-6-vinyltetrahydro-2H-pyran-2-one, 16 μL of cyclohexene oxide, 9.2 mg of an organic chromium complex catalyst (whose structure is shown in Formula A below), and 0.9 mg of bis(triphenylphosphorane)ammonium chloride were mixed uniformly in a reaction vessel to form a pre-reaction mixture, wherein the molar ratio of 3-ethylene-6-vinyltetrahydro-2H-pyran-2-one:epoxide:organic chromium complex:bis(triphenylphosphorane)ammonium chloride was 10:10:1:0.1. The reaction process is shown in the figure below;

[0056]

[0057] S2: The reaction vessel described in step S1 is sealed and placed at 40° C. for reaction; the 3-ethylene-6-vinyltetrahydro-2H-pyran-2-one described in step S1 is subjected to a ring-opening copolymerization reaction with the epoxy compound monomer to generate a side-group-containing unsaturated olefin polyester-polyether copolymer having a specific number average molecular weight (22.7 kDa) and its distribution (1.88).

[0058] The H NMR spectrum of the prepared copolymer ( 1 H NMR,CDCl3) Figure 1 As shown in the figure, it can be clearly seen that the functional groups in the copolymer are closely related to the hydrogen spectrum. Figure 1 Correspondingly, it is shown that the polyester-polyether copolymer containing an unsaturated olefin structure in the side chain is successfully prepared by the preparation method of Example 1.

[0059] Example 2

[0060] S1: Under an argon atmosphere, 212 μL of 3-ethylene-6-vinyltetrahydro-2H-pyran-2-one, 162 μL of cyclohexene oxide, 10.1 mg of an organic chromium complex catalyst (shown in Formula B below), and 9.4 mg of bis(triphenylphosphorane)ammonium chloride were mixed in a reaction vessel to form a pre-reaction mixture, wherein the molar ratio of 3-ethylene-6-vinyltetrahydro-2H-pyran-2-one:epoxide:organic chromium complex:bis(triphenylphosphorane)ammonium chloride was 100:100:1:1. The reaction process is shown in the figure below;

[0061]

[0062] S2: The reaction vessel described in step S1 is sealed and placed at 120° C. for reaction; the 3-ethylene-6-vinyltetrahydro-2H-pyran-2-one described in step S1 is subjected to a ring-opening copolymerization reaction with the epoxy compound monomer to generate a side-group-containing unsaturated olefin polyester-polyether copolymer having a specific number average molecular weight (10.8 kDa) and its distribution (1.21).

[0063] The C NMR spectrum of the copolymerized product ( 13 C NMR,CDCl3) Figure 2 As shown in the figure, it can be clearly seen that the functional groups in the copolymer are closely related to the carbon spectrum. Figure 1 Correspondingly, it is shown that the preparation method of Example 2 is used to successfully prepare an official polyester-polyether copolymer containing an unsaturated olefin structure in the side chain.

[0064] Example 3

[0065] S1: Under an argon atmosphere, 1.70 ml of 3-ethylene-6-vinyltetrahydro-2H-pyran-2-one, 1.64 ml of ethylene oxide, 10.2 mg of an organochromium complex catalyst (shown in Formula C below), and 18.8 mg of bis(triphenylphosphorane)ammonium chloride were mixed uniformly in a reaction vessel to form a pre-reaction mixture, wherein the molar ratio of 3-ethylene-6-vinyltetrahydro-2H-pyran-2-one:epoxide:organochromium complex:bis(triphenylphosphorane)ammonium chloride was 800:1000:1:2. The reaction process is shown in the figure below;

[0066]

[0067] S2: The reaction vessel described in step S1 is sealed and placed at 150° C. for reaction; the 3-ethylene-6-vinyltetrahydro-2H-pyran-2-one described in step S1 is subjected to a ring-opening copolymerization reaction with the epoxy compound monomer to generate a side-group-containing unsaturated olefin polyester-polyether copolymer having a specific number average molecular weight (200.4 kDa) and its distribution (2.48).

[0068] Example 4

[0069] S1: Under an argon atmosphere, 423 ml of 3-ethylene-6-vinyltetrahydro-2H-pyran-2-one, 224 μl of propylene oxide, 10 mg of an organochromium complex catalyst (shown in Formula D below), and 9.4 mg of bis(triphenylphosphorane)ammonium chloride were mixed in a reaction vessel to form a pre-reaction mixture. The molar ratio of 3-ethylene-6-vinyltetrahydro-2H-pyran-2-one:epoxide:organochromium complex:bis(triphenylphosphorane)ammonium chloride was 200:200:1:1. The reaction process is shown in the figure below.

[0070]

[0071] S2: The reaction vessel described in step S1 is sealed and placed at 80° C. for reaction; the 3-ethylene-6-vinyltetrahydro-2H-pyran-2-one described in step S1 is subjected to a ring-opening copolymerization reaction with the epoxy compound monomer.

[0072] The gel permeation chromatography (GPC) diagram of the prepared copolymer is shown in FIG. Figure 3 As shown in the figure, it can be clearly seen that the spectrum curve of the copolymerization product has a single peak distribution, indicating that the preparation method of Example 3 is successfully used to prepare a functionalized polyester-polyether copolymer with a specific number average molecular weight (10.1 kDa) and its distribution (1.98).

[0073] Example 5

[0074] S1: Under an argon atmosphere, 21.2 ml of 3-ethylene-6-vinyltetrahydro-2H-pyran-2-one, 5.5 ml of styrene oxide, 10 mg of an organochromium complex catalyst (shown in Formula E below), and 47 mg of bis(triphenylphosphorane)ammonium chloride were mixed in a reaction vessel to form a pre-reaction mixture. The molar ratio of 3-ethylene-6-vinyltetrahydro-2H-pyran-2-one:epoxide:organochromium complex:bis(triphenylphosphorane)ammonium chloride was 10,000:30,000:1:5. The reaction process is shown in the figure below.

[0075]

[0076] S2: The reaction vessel described in step S1 is sealed and placed at 180° C. for reaction; the 3-ethylene-6-vinyltetrahydro-2H-pyran-2-one described in step S1 is subjected to a ring-opening copolymerization reaction with the epoxy compound monomer to generate a side-group-containing unsaturated olefin polyester-polyether copolymer having a number average relative molecular mass (4.5 kDa) and a distribution (1.32).

[0077] The above is an exemplary description of the embodiments of the present invention. However, the scope of protection of the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc. made by those skilled in the art within the spirit and principles of the present invention shall be included in the scope of protection of the present invention.

Claims

1. A method for synthesizing an olefin-functionalized polyester-polyether copolymer, characterized in that: The method is: The organic chromium complex, bis(triphenylphosphorane)ammonium chloride, 3-ethylene-6-vinyltetrahydro-2H-pyran-2-one, and epoxy compound monomer are mixed and reacted to prepare the olefin functionalized polyester-polyether copolymer; The structural formula of the organic chromium complex is shown in Formula A, Formula B, Formula C or Formula E below: The epoxy compound monomer has a structure shown in the following formula III or formula IV: Wherein, in formula III, R5 and R6 are the same or different and are independently selected from H, C containing a substituent group B 1-20 Alkyl or C containing substituent group B 6-20 One of the aryl groups, the substituent group B is one of halogen, nitro or cyano; In formula IV, R7 is selected from C 1-20 Alkyl, C 6-20 One of the aromatic groups.

2. The method according to claim 1, characterized in that The molar ratio of the 3-ethylene-6-vinyltetrahydro-2H-pyran-2-one: the epoxy compound: the organic chromium complex: the bis(triphenylphosphorane)ammonium chloride is (10-10000):(10-30000):1:(0.1-5).

3. The method according to claim 1, characterized in that The reaction is carried out under protective gas, which is nitrogen, argon or other inert gases.

4. The method according to claim 1, wherein The reaction temperature of the reaction is 40-180°C.

5. The method according to claim 1, wherein The reaction time of the reaction is not less than 1 hour.

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