CN112480418A - Modified polyrotaxane block copolymer, preparation method thereof and solid polymer electrolyte - Google Patents
Modified polyrotaxane block copolymer, preparation method thereof and solid polymer electrolyte Download PDFInfo
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- CN112480418A CN112480418A CN202011284405.4A CN202011284405A CN112480418A CN 112480418 A CN112480418 A CN 112480418A CN 202011284405 A CN202011284405 A CN 202011284405A CN 112480418 A CN112480418 A CN 112480418A
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- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
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Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a modified polyrotaxane block copolymer, a preparation method thereof and a solid polymer electrolyte. The modified polyrotaxane block copolymer provided by the invention comprises at least one modified polyrotaxane block and at least one polymer block, wherein the modified polyrotaxane block is obtained by modifying polyrotaxane through a polymer with ion transmission capacity, and has higher chain segment motion capacity and ion conductivity; the Young modulus of the polymer block is more than or equal to 0.01GPa, and the modified polyrotaxane block copolymer obtained by polymerizing the Young modulus and the Young modulus has excellent ionic conductivity and mechanical property and good application prospect.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a modified polyrotaxane block copolymer, a preparation method thereof and a solid polymer electrolyte.
Background
Electrochemical batteries, particularly lithium ion batteries, have many advantages and have entered energy fields such as intelligent electronic products, electric vehicles, and large-scale energy storage power grids on a large scale. The further development of secondary electrochemical batteries with higher specific energy and higher safety has important significance and value for the secondary great development of new energy industries. However, the frequent explosion of electrochemical cell safety accidents in recent years indicates that the safety problem has become a technical bottleneck restricting the wider and deeper application of the electrochemical cell. The solid-state battery based on the polymer electrolyte has a larger space for improving the energy density, the high-temperature working temperature range, the cycle life and the like of the battery, and the solid-state electrochemical battery using the solid-state polymer electrolyte to replace organic micromolecular electrolyte is expected to thoroughly solve the safety worry of the battery while improving the energy density.
However, the solid polymer electrolyte generally has the problems of low room temperature ionic conductivity, need of heating to a certain temperature to improve the ionic conductivity, poor mechanical properties and the like, so that the application field of the current solid polymer electrolyte is very narrow. Therefore, a solid polymer electrolyte having both good ionic conductivity and mechanical properties is needed.
Disclosure of Invention
The invention aims to provide a modified polyrotaxane block copolymer, a preparation method thereof and a solid polymer electrolyte, and aims to solve the technical problems of low ionic conductivity and poor mechanical property of the conventional solid polymer electrolyte.
In order to achieve the above object, according to one aspect of the present invention, there is provided a modified polyrotaxane block copolymer comprising at least one modified polyrotaxane block and at least one polymer block, the modified polyrotaxane block being alternately linked to the polymer block by a covalent bond; wherein the modified polyrotaxane block is obtained by modifying polyrotaxane by a polymer with ion transmission capability, and the Young modulus of the polymer block is more than or equal to 0.01 GPa.
The modified polyrotaxane block copolymer provided by the invention comprises at least one modified polyrotaxane block and at least one polymer block, wherein the modified polyrotaxane block is obtained by modifying polyrotaxane through a polymer with ion transmission capability, the molecular weight is lower, little or no entanglement exists in the copolymer, and the purpose of greatly improving the segment motion capability and the lithium ion transmission efficiency is achieved by utilizing the characteristic that a polyrotaxane host molecule can freely rotate and slide on a guest molecule, so that the modified polyrotaxane block copolymer provided by the invention has higher ion conductivity. Meanwhile, the Young modulus of the polymer block is more than or equal to 0.01GPa, so that higher mechanical toughness and strength can be provided for the modified polyrotaxane copolymer. The two types of block bonds are combined together, and the nano-scale micro-phase separation can occur, so that the lithium ion transmission and mechanical support functions of the two phases are not interfered with each other, and the lithium ion battery has excellent ionic conductivity and mechanical properties and good application prospect.
In another aspect of the present invention, there is provided a method for preparing a modified polyrotaxane block copolymer, comprising the steps of:
providing a polyrotaxane guest and a polyrotaxane host, and reacting the polyrotaxane guest with the polyrotaxane host to obtain a polyrotaxane block;
providing a polymer with ion transmission capacity, and reacting the polymer with the polyrotaxane block to obtain a modified polyrotaxane block;
providing a polymer block with Young modulus of more than or equal to 0.01GPa, and reacting the polymer block with the modified polyrotaxane block to obtain a modified polyrotaxane block copolymer;
or
Providing a polyrotaxane guest and a polyrotaxane host, and reacting the polyrotaxane guest with the polyrotaxane host to obtain a polyrotaxane block;
providing a polymer block with Young modulus of more than or equal to 0.01GPa, and reacting the polymer block with the polyrotaxane block to obtain a polyrotaxane block copolymer;
providing a polymer with ion transmission capability, and reacting the polymer with the polyrotaxane block copolymer to obtain the modified polyrotaxane block copolymer.
According to the preparation method of the modified polyrotaxane block copolymer, the polyrotaxane block is modified by the polymer with ion transmission capacity, so that the modified polyrotaxane block has higher ion transmission capacity, and the ion conductivity of the modified polyrotaxane block copolymer is improved; meanwhile, the polymer block with the Young modulus of more than or equal to 0.01GPa is reacted with the modified polyrotaxane block, so that the two blocks are covalently bonded together, and the nano-scale micro-phase separation can be realized, so that the lithium ion transmission function and the mechanical support function of the two phases are not interfered with each other, and the obtained modified polyrotaxane block copolymer has high ionic conductivity and high mechanical strength. In addition, in the preparation method provided by the invention, the polyrotaxane block can be reacted with the polymer block with the Young modulus of more than or equal to 0.01GPa to obtain a polyrotaxane block copolymer, and then the modified polyrotaxane block copolymer is prepared in a manner of modifying the obtained polyrotaxane block copolymer by the polymer with ion transmission capability.
In a final aspect of the present invention, a solid polymer electrolyte is provided, which includes the modified polyrotaxane block copolymer provided by the present invention or the modified polyrotaxane block copolymer prepared by the preparation method of the modified polyrotaxane block copolymer provided by the present invention, and an electrolyte salt.
The solid polymer electrolyte provided by the invention has sufficiently high conductivity, excellent film-forming performance and high mechanical strength, and can form a self-supporting electrolyte film. The room-temperature conductivity of the solid polymer electrolyte provided by the invention can reach 4.5 multiplied by 10-4S/cm, electrochemical window up to 5.3V, transference number of lithium ion up to 0.45, and breaking strength up to 16 MPa. MakingWhen the electrolyte is an electrolyte of an all-solid-state battery, the flammable safety problem possibly existing in liquid electrolyte is avoided, and the safety performance of the battery can be greatly improved.
Drawings
FIG. 1 is a schematic structural diagram of a modified polyrotaxane diblock copolymer (BA) provided by an embodiment of the present invention;
FIG. 2 is a schematic structural view of a modified polyrotaxane triblock copolymer (BAB) provided by an embodiment of the present invention;
FIG. 3 is a schematic structural diagram of a modified polyrotaxane triblock copolymer (ABA) provided by an embodiment of the present invention;
FIG. 4 shows a modified polyrotaxane multiblock copolymer (BA) according to an embodiment of the present invention2Schematic structural diagram of (a);
FIG. 5 is a schematic molecular structure diagram of a modified polyrotaxane block provided in an embodiment of the present invention;
FIG. 6 is a schematic structural view of a polyrotaxane host in a modified polyrotaxane block provided by an embodiment of the present invention;
FIG. 7 is a schematic view showing a microphase-separated structure of a modified polyrotaxane block copolymer obtained in example 2 of the present invention;
FIG. 8 is a nuclear magnetic spectrum of a modified polyrotaxane block copolymer obtained in example 2 of the present invention;
FIG. 9 is a graph showing the results of mechanical property tests of a solid electrolyte membrane obtained in example 2 of the present invention;
FIG. 10 is a graph showing the results of an ion conductivity test of a solid polymer electrolyte membrane obtained in example 2 according to an experimental example of the present invention;
FIG. 11 is a graph showing the results of an electrochemical stability window test of an experimental example of the present invention on a solid polymer electrolyte membrane obtained in example 2;
FIG. 12 is a graph showing the results of tests on the transference number of lithium ions of the solid polymer electrolyte membrane obtained in example 2 according to the experimental example of the present invention.
Detailed Description
In order to make the objects, technical solutions and technical effects of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are clearly and completely described, and the embodiments described below are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention. Those whose specific conditions are not specified in the examples are carried out according to conventional conditions or conditions recommended by the manufacturer; the reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In the description of the present invention, the term "and/or" describing an association relationship of associated objects means that there may be three relationships, for example, a and/or B, may mean: a is present alone, A and B are present simultaneously, and B is present alone. Wherein A and B can be singular or plural. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
In the description of the present invention, "at least one" means one or more, "a plurality" means two or more. "at least one of the following" or similar expressions refer to any combination of these items, including any combination of the singular or plural items. For example, "at least one (a), b, or c", or "at least one (a), b, and c", may each represent: a. b, c, a-b (i.e. a and b), a-c, b-c, or a-b-c, wherein a, b, and c can be single or multiple respectively.
It should be understood that the weight of the related components mentioned in the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, it is within the scope of the disclosure that the content of the related components is scaled up or down according to the embodiments of the present invention. Specifically, the weight described in the embodiments of the present invention may be a unit of mass known in the chemical field such as μ g, mg, g, kg, etc.
In addition, unless the context clearly uses otherwise, an expression of a word in the singular is to be understood as including the plural of the word. The terms "comprises" or "comprising" are intended to specify the presence of stated features, quantities, steps, operations, elements, portions, or combinations thereof, but are not intended to preclude the presence or addition of one or more other features, quantities, steps, operations, elements, portions, or combinations thereof.
The embodiment of the invention provides a modified polyrotaxane block copolymer, which comprises at least one modified polyrotaxane block and at least one polymer block, wherein the modified polyrotaxane block and the polymer block are alternately connected through a covalent bond; wherein the modified polyrotaxane block is obtained by modifying polyrotaxane by a polymer with ion transmission capability, and the Young modulus of the polymer block is more than or equal to 0.01 GPa.
The modified polyrotaxane block copolymer provided by the embodiment of the invention comprises at least one modified polyrotaxane block and at least one polymer block, wherein the modified polyrotaxane block is obtained by modifying polyrotaxane through a polymer with ion transmission capability, the molecular weight is lower, little or no entanglement exists in the copolymer, and the purpose of greatly improving the segment motion capability and the lithium ion transmission efficiency is achieved by utilizing the characteristic that a polyrotaxane host molecule can freely rotate and slide on a guest molecule, so that the modified polyrotaxane block copolymer provided by the embodiment of the invention has higher ion conductivity. Meanwhile, the Young modulus of the polymer block is more than or equal to 0.01GPa, so that higher mechanical toughness and strength can be provided for the modified polyrotaxane copolymer. The two types of block bonds are combined together, and the nano-scale micro-phase separation can occur, so that the lithium ion transmission and mechanical support functions of the two phases are not interfered with each other, and the lithium ion battery has excellent ionic conductivity and mechanical properties and good application prospect.
The number of the modified polyrotaxane blocks and the number of the polymer blocks in the modified polyrotaxane block copolymer provided by the embodiment of the invention can be infinite theoretically, and the larger the total number of the blocks is, the higher the mechanical strength of the obtained modified polyrotaxane block copolymer is. In some embodiments, the number of modified polyrotaxane blocks and the number of polymer blocks are both 1 or more and 100 or less, and the number of modified polyrotaxane blocks and the number of polymer blocks may be equal to or different from each other.
The following description will discuss the modified polyrotaxane diblock copolymers provided by the embodiments of the present invention with reference to FIGS. 1 to 4The polymer, the modified polyrotaxane triblock copolymer, and the modified polyrotaxane multiblock copolymer will be described in detail, respectively, wherein the modified polyrotaxane block is represented by B, and the polymer block is represented by a. FIG. 1 shows the structure of a modified polyrotaxane diblock copolymer (BA). As can be seen from FIG. 1, the modified polyrotaxane diblock copolymer comprises 1 modified polyrotaxane block B and 1 polymer block A, and the modified polyrotaxane block B is covalently bonded to the polymer block A. FIG. 2 shows the structure of a modified polyrotaxane triblock copolymer (BAB). As can be seen from fig. 2, the modified polyrotaxane triblock copolymer comprises 2 modified polyrotaxane blocks B and 1 polymer block a, and the modified polyrotaxane blocks B and the polymer blocks a are alternately linked by covalent bonds. FIG. 3 shows the structure of another modified polyrotaxane triblock copolymer (ABA). As can be seen from fig. 3, the modified polyrotaxane triblock copolymer comprises 1 modified polyrotaxane block B and 2 polymer blocks a, and the modified polyrotaxane blocks B and the polymer blocks a are alternately linked by covalent bonds. FIG. 4 shows a modified polyrotaxane multiblock copolymer (BA)2The structure of (1). As can be seen from fig. 4, the modified polyrotaxane multi-block copolymer comprises 2 modified polyrotaxane blocks B, and 2 polymer blocks a, and the modified polyrotaxane blocks B are alternately linked to the polymer blocks a through covalent bonds. FIG. 4 is a view showing only modified polyrotaxane multiblock copolymer (BA)nThe simple structure is not limited to the value of n. If necessary, 1 modified polyrotaxane block B and 1 polymer block a may be used as 1 unit, and the modified polyrotaxane multiblock copolymer may be n units (n is an integer of 1 or more), or 1 modified polyrotaxane block B may be added to the side of the polymer block a at the end of n units, or 1 polymer block a may be added to the side of the modified polyrotaxane block B at the end of n units.
In some embodiments, the modification of the polyrotaxane block by the polymer with ion transmission capability is to modify the hydroxyl group of the main cyclodextrin on the polyrotaxane, and the modification can be partial modification of the hydroxyl group of the cyclodextrin or complete modification of the hydroxyl group of the cyclodextrin. Through the modification mode, the ionic conductivity of the modified polyrotaxane block can be remarkably improved, and the ion conductivity of the modified polyrotaxane block copolymer can be further improved. In addition, through the modification mode, the hydrogen bond interaction between cyclodextrin molecules can be effectively destroyed, and the solubility and the solution processability of the polyrotaxane block copolymer are remarkably improved. The modified polyrotaxane block will be specifically described below with reference to FIGS. 5 and 6. The polyrotaxane structure comprises a ring-shaped host and a linear object, wherein the linear object is used as an axis to penetrate through the hollow area of the ring-shaped host, and the ring-shaped host is strung together to form the polyrotaxane. Among them, cyclodextrin, which is a cyclic host, has a part OR all of its hydroxyl groups modified with a polymer (R in fig. 5) having ion transport ability, and changes from original-OH to-OR. The cyclodextrin as the main body can be selected from any one of alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin and delta-cyclodextrin, and the structural formula of the alpha-cyclodextrin, the beta-cyclodextrin and the gamma-cyclodextrin is shown in figure 6.
Further, the polymer having ion transport ability may be selected from at least one of polyether, polyester, polycarbonate, polyurethane, polyamide, polyimide, polysiloxane, polynitrile, and polyphosphazene, and may be selected from comb polymers having a main chain and a side chain group. In some embodiments, the repeating unit of at least one of the polyether, polyester, polycarbonate, polyurethane, polyamide, polyimide, polysiloxane, polynitrile, polyphosphazene may be 1 to 100, preferably 1 to 50, to achieve higher segmental mobility and higher ionic conductivity; the main chain in the comb polymer with the main chain and the side chain groups is selected from at least one of polysiloxane, polyphosphazene, polynitrile, polyether, polyolefin, polyacrylate and polymethacrylate; the side chain is selected from at least one of oligoether, nitrile group, sulfone group, thiol, polyether, polyester, polycarbonate, polyurethane, polyamide, polyimide, polynitrile, and the repeating unit thereof may be 1 to 100, preferably 1 to 50, to achieve higher segmental motion capability and higher ionic conductivity.
Further, in the modified polyrotaxane block, the polyrotaxane guest is selected from at least one of polyether, polyester, polycarbonate, polyurethane, polyamide, polyimide, polysiloxane, polynitrile, polyphosphazene and polyolefin.
Further, in the modified polyrotaxane block, the chain ends of the polyrotaxane are subjected to end-capping treatment by a capping agent having a large volume to prevent the cyclic host from falling off from the chain guest. When the structure of the polymer block has a branched structure and/or a comb-like structure, the cyclic host can be prevented from falling off from the chain guest, and the end-capping treatment may not be performed.
In some embodiments, the young's modulus of the polymer block is 5GPa or less.
In some embodiments, the polymer block is selected from at least one of polystyrene, hydrogenated polystyrene, polyvinylcyclohexane, polyvinylpyridine, polyalkylacrylate, polyalkylmethacrylate, polyphenylene ether, polyimide, polyamide, polyester, polyolefin, polyalkylvinyl ether, polycyclohexylvinyl ether, polyvinylidene fluoride-hexafluoropropylene copolymer, styrene-alkyl methacrylate copolymer, styrene-vinylpyridine copolymer, alkyl methacrylate-vinylpyridine copolymer, styrene-alkyl methacrylate-vinylpyridine copolymer. The polymer blocks have high molecular weight and rigidity on the molecular structure, and a large number of intramolecular and intermolecular chain entanglements exist in the structure, and the chain entanglements endow the modified polyrotaxane block copolymer with better mechanical toughness and strength.
It is understood that the polymer block has a generally linear structure, and in the embodiment of the present invention, the polymer block may further have a branched structure and/or a comb-shaped structure, so that the cyclic host may be prevented from falling off from the chain guest, and the step of performing the end-capping treatment on the modified polyrotaxane block may be omitted.
The modified polyrotaxane block copolymer provided by the embodiment of the invention can be prepared by the following preparation method.
Accordingly, embodiments of the present invention provide a method for preparing a modified polyrotaxane block copolymer, which includes the following steps:
s11, providing a polyrotaxane guest and a polyrotaxane host, and reacting the polyrotaxane guest with the polyrotaxane host to obtain a polyrotaxane block;
s12, providing a polymer with ion transmission capacity, and reacting the polymer with a polyrotaxane block to obtain a modified polyrotaxane block;
s13, providing a polymer block with Young modulus more than or equal to 0.01GPa, and reacting the polymer block with the modified polyrotaxane block to obtain the modified polyrotaxane block copolymer.
Or
S21, providing a polyrotaxane guest and a polyrotaxane host, and reacting the polyrotaxane guest with the polyrotaxane host to obtain a polyrotaxane block;
s22, providing a polymer block with Young modulus more than or equal to 0.01GPa, and reacting the polymer block with a polyrotaxane block to obtain a polyrotaxane block copolymer;
s23, providing a polymer with ion transmission capability, and reacting the polymer with the polyrotaxane block copolymer to obtain the modified polyrotaxane block copolymer.
In the preparation method of the modified polyrotaxane block copolymer provided by the embodiment of the invention, the polyrotaxane block obtained by preparation is modified by the polymer with ion transmission capability, so that the obtained modified polyrotaxane block has higher ion transmission capability, and the ion conductivity of the obtained modified polyrotaxane block copolymer is further improved; meanwhile, the polymer block with the Young modulus of more than or equal to 0.01GPa is reacted with the modified polyrotaxane block, so that the two blocks are covalently bonded together, and the nano-scale micro-phase separation can be realized, so that the lithium ion transmission function and the mechanical support function of the two phases are not interfered with each other, and the obtained modified polyrotaxane block copolymer has high ionic conductivity and high mechanical strength. In addition, in the preparation method provided by the embodiment of the invention, the polyrotaxane block can be reacted with the polymer block with the Young modulus of more than or equal to 0.01GPa to obtain a polyrotaxane block copolymer, and then the modified polyrotaxane block copolymer is prepared in a manner that the obtained polyrotaxane block copolymer is modified by the polymer with ion transmission capacity.
The preparation method provided by S11-S13 is that the polyrotaxane block is modified, and then the polyrotaxane block is copolymerized with the polymer block to obtain a modified polyrotaxane block copolymer; the preparation method provided by S21-S23 is that polyrotaxane block and polymer block are copolymerized to obtain polyrotaxane block copolymer, and then the polyrotaxane block copolymer is modified to obtain modified polyrotaxane block copolymer. In some embodiments, when the chain ends of the polyrotaxane are not subjected to the end-capping treatment and the polymer block has a comb-like or branched structure, it is preferably prepared by the preparation method provided in S21 to S23; when the chain ends of the polyrotaxane are subjected to the capping treatment, the preparation may be carried out by the preparation method provided in S11-S13, or by the preparation method provided in S21-S23.
Specifically, in S11, depending on the particular choice of polyrotaxane guest and polymer block in the actual preparation process, it may be desirable to functionalize at least one of the end groups of the polyrotaxane guest. Functionalization herein refers to modification of the functional groups at the guest end of the polyrotaxane to other functional groups that are readily covalently attached to the polymer block or that can initiate the monomer polymer of the polymer block. The polyrotaxane guest can be made capable of covalent attachment to the polymer block by functionalizing at least one of its end groups. Wherein different terminal functionalization modes can be selected for the polyrotaxane guest according to the number of blocks in the obtained modified polyrotaxane copolymer. When the obtained modified polyrotaxane copolymer is a diblock copolymer, one of the end groups of the polyrotaxane guest is functionalized. When the resulting modified polyrotaxane copolymer is a triblock copolymer, there are two cases: firstly, the modified polyrotaxane triblock copolymer has a BAB structure, and one end group of a polyrotaxane guest is functionalized; second, the modified polyrotaxane triblock copolymer is an ABA structure, where both end groups of the polyrotaxane guest should be functionalized so that both ends can be covalently linked to the polymer block. When the resulting modified polyrotaxane copolymer is a multiblock copolymer (BA)nIn the structureBoth end groups of the polyrotaxane guest are functionalized. The polyrotaxane guest can be either directly purchased as a commercial polymer or prepared by itself. The preparation method of the polyrotaxane guest in the embodiment of the present invention is not particularly limited, and the polyrotaxane guest can be prepared according to the actual selection and the conventional method in the art. In some embodiments, the polyrotaxane guest is selected from at least one of a polyether, a polyester, a polycarbonate, a polyurethane, a polyamide, a polyimide, a polysiloxane, a polynitrile, a polyphosphazene, a polyolefin; the functional group after the end group functionalization treatment is at least one selected from hydroxyl, amino, carboxyl, sulfydryl, aldehyde group, alkenyl, alkynyl, azido, cyanate group, isocyanate group and halogen group.
The polyrotaxane guest (polyrotaxane guest with at least one end group functionalized) reacts with the polyrotaxane host to obtain a polyrotaxane block. In some embodiments, the polyrotaxane host is cyclodextrin, and specifically any one of alpha-cyclodextrin, beta-cyclodextrin, gamma-cyclodextrin, and delta-cyclodextrin can be selected.
In some embodiments, the chain ends of the polyrotaxane block obtained in S11 are capped with a capping agent having a large volume to prevent the cyclic host from falling off the chain guest.
S12, a polymer having ion transport ability is provided, and the polyrotaxane block is modified with the polymer to obtain a modified polyrotaxane block. In some embodiments, the ion transport polymers are either available as such or can be obtained by polymerizing the monomers forming the polymers while the polyrotaxane block is being modified. In some embodiments, the ion transport capable polymer is selected from at least one of a polyether, a polyester, a polycarbonate, a polyurethane, a polyamide, a polyimide, a polysiloxane, a polynitrile, a polyphosphazene, or a comb polymer having a backbone and pendant groups; wherein the main chain is selected from at least one of polysiloxane, polyphosphazene, polynitrile, polyether, polyolefin, polyacrylate and polymethacrylate; the side chain is selected from at least one of oligoether, nitrile group, sulfone group, thiol, polyether, polyester, polycarbonate, polyurethane, polyamide, polyimide and polynitrile.
In some embodiments, it is desirable to functionalize at least one end group of the ion transport capable polymer. The functionalization here means that the terminal functional group located on the polymer having ion transport ability is modified to another functional group that readily reacts with the functional group on the cyclodextrin host molecule to form a covalent bond. By functionalizing at least one end group of the ion transport capable polymer, it can be made capable of covalent attachment to a cyclodextrin host molecule. In some embodiments, according to the type of the terminal functional group of the modified polymer with ion transport capability, the hydroxyl group of the cyclodextrin can be modified into a functional group that can be easily and efficiently bonded with the terminal functional group of the modified polymer with ion transport capability, so as to improve the effect of modifying the polyrotaxane block. In some embodiments, the modified functional group is selected from at least one of a hydroxyl group, an amine group, a carboxyl group, a thiol group, an aldehyde group, an alkenyl group, an alkynyl group, an azide group, a cyanate group, an isocyanate group, and a halogen group.
In some embodiments, the modification of the polyrotaxane block is specifically a modification of some or all of the hydroxyl groups on the host cyclodextrin in the polyrotaxane.
S13 provides a polymer block having a Young' S modulus of 0.01GPa or more, and a modified polyrotaxane block copolymer is obtained by reacting the polymer block with a modified polyrotaxane block. The Young modulus of the polymer block is more than or equal to 0.01GPa, and the polymer block has higher mechanical toughness and strength, so that the obtained modified polyrotaxane block copolymer has higher mechanical toughness and strength and good conductivity. In some embodiments, the polymer blocks are either directly available commercially or can be obtained by polymerizing the monomers forming these polymer blocks simultaneously with the reaction with the modified polyrotaxane block.
Depending on the particular choice of polyrotaxane guest and polymer block in the actual preparation process, it may be desirable to functionalize at least one of the end groups of the polymer block. By functionalized is meant herein the modification of functional groups located at the end of the polymer blockTo form other functional groups which can be easily covalently linked to the modified polyrotaxane block. Wherein, depending on the number of blocks in the resulting modified polyrotaxane copolymer, different terminal functionalization modes can be selected for the polymer blocks. When the resulting modified polyrotaxane copolymer is a diblock copolymer, one of the end groups of the polymer block may be functionalized. When the resulting modified polyrotaxane copolymer is a triblock copolymer, there are two cases: firstly, the modified polyrotaxane triblock copolymer is of a BAB structure, two end groups of a polymer block are functionalized, and two ends of the polymer block can be respectively connected with the modified polyrotaxane block in a covalent way; second, the modified polyrotaxane triblock copolymer is of an ABA structure, where one of the end groups of the polymer block should be functionalized. When the resulting modified polyrotaxane copolymer is a multiblock copolymer (BA)nIn the structure, both end groups of the polymer block are functionalized. In some embodiments, the functional group after the end-group functionalization treatment is selected from at least one of hydroxyl group, amine group, carboxyl group, mercapto group, aldehyde group, alkenyl group, alkynyl group, azide group, cyanate group, isocyanate group, and halogen group.
The preparation method provided by S21-S23 is that polyrotaxane block and polymer block are copolymerized to obtain polyrotaxane block copolymer, and then the polyrotaxane block copolymer is modified to obtain modified polyrotaxane block copolymer. Wherein S21 is the same as S11, and is not described herein for brevity. In some embodiments, the chain ends of the polyrotaxane block obtained in S21 are capped with a capping agent having a large volume to prevent the cyclic host from falling off the chain guest.
In S22, the polymer block is reacted with a polyrotaxane block to obtain a polyrotaxane block copolymer. Wherein, the Young modulus of the polymer block is more than or equal to 0.01GPa, and the polymer block has higher mechanical toughness and strength, so that the obtained polyrotaxane block copolymer has higher mechanical toughness and strength. The specific choice of the polymer block, whether the end group is functionalized, and the specific choice of the functional group after the end group functionalization treatment are the same as those of the polymer block, whether the end group is functionalized, and the specific choice of the functional group after the end group functionalization treatment in S13, and are not repeated herein for brevity.
In S23, a polymer with ion transmission capacity is adopted to react with the polyrotaxane block copolymer to improve the ion conductivity of the polyrotaxane block copolymer, so that the obtained modified polyrotaxane block copolymer has good mechanical toughness and strength and good ion conductivity. The specific selection of the polymer with ion transport capability, whether to perform end group functionalization, and the specific selection of the functional group after end group functionalization are the same as the specific selection of the polymer with ion transport capability, whether to perform end group functionalization, and the specific selection of the functional group after end group functionalization in S12, and are not repeated herein for brevity.
The embodiment of the invention also provides a solid polymer electrolyte, which comprises the modified polyrotaxane block copolymer provided by the embodiment of the invention or the modified polyrotaxane block copolymer prepared by the preparation method of the modified polyrotaxane block copolymer provided by the embodiment of the invention, and electrolyte salt.
The solid polymer electrolyte provided by the embodiment of the invention has high enough conductivity, excellent film-forming property and can form a self-supporting electrolyte film with high mechanical strength. The room-temperature conductivity of the solid polymer electrolyte provided by the embodiment of the invention can reach 4.5 multiplied by 10-4S/cm, electrochemical window up to 5.3V, transference number of lithium ion up to 0.45, and breaking strength up to 16 MPa. When the electrolyte is used as the electrolyte of an all-solid battery, the flammable safety problem possibly existing in liquid electrolyte is avoided, and the safety performance of the battery can be greatly improved.
In the solid polymer electrolyte provided in the embodiment of the present invention, there is no particular limitation on the selection of the electrolyte salt, and any electrolyte salt that is usable in the art is applicable to the embodiment of the present invention. In some embodiments, electrolyte salts with good ionic loading properties and large dissociation constants in polymer electrolytes in the art are preferred, including but not limited to chlorides, bromides, sulfates, nitrates, sulfides, hydrides, nitrides, phosphides, lithium, sodium, potassium, silver, barium, lead, calcium, ruthenium, tantalum, rhodium, iridium, cobalt, nickel, molybdenum, tungsten, or vanadium, and the like,Sulfonamides, triflates, thiocyanates, perchlorates, borates or selenides. In some embodiments, LiCF is selected3SO3、LiB(C2O4)2、LiN(CF3SO2)2、LiC(CF3SO2)3、LiC(CH3)(CF3SO2)2、LiCH(CF3SO2)2、LiCH2(CF3SO2)、LiC2F5SO3、LiN(C2F5SO2)2、LiN(CF3SO2)2、LiB(CF3SO2)2、LiPF6、LiSbF6、LiClO4、LiSCN、LiAsF6、NaCF3SO3、NaPF6、NaClO4、NaI、NaBF4、NaAsF6、KCF3SO3、KPF6、KI、LiCF3CO3、NaClO3、NaSCN、KBF4、KPF6、Mg(ClO4)2And Mg (BF)4)2As an electrolyte salt.
In order to clearly understand the details and operation of the above-mentioned embodiments of the present invention by those skilled in the art and to obviously show the advanced performance of the modified polyrotaxane block copolymer, the preparation method thereof and the solid polymer electrolyte in the embodiments of the present invention, the above-mentioned technical solutions are illustrated by a plurality of examples.
Example 1
This example provides a process for the preparation of a modified polyrotaxane diblock copolymer (BA) in which the Young's modulus of the polyethylene terephthalate as the other polymer block is 2 GPa. The method comprises the following steps:
(31) preparation of PCL (polycaprolactone) guest
Adding 100g of caprolactone monomer, 2g of 9-anthracene methanol and 10g of stannous octoate into a 500mL three-neck round-bottom flask, vacuumizing and back flushing nitrogen, placing reactants at 80 ℃ for reaction for 24h, pouring the mixture into methanol for precipitation after the reaction is finished, washing for 3 times by using methanol to obtain a white solid, and drying to obtain PCL;
(32) PCL (polycaprolactone) guest end group functionalization
Adding 20g of PCL obtained in the step (31) into 180mL of dry chloroform, sequentially adding 2.5g of bromoisobutyryl bromide, 1.1g of triethylamine and 0.5g of 4-dimethylaminopyridine, stirring the mixture at room temperature for 24h in a nitrogen atmosphere, filtering after the reaction is finished, concentrating the filtrate, precipitating in 500mL of methanol, washing for 3 times by using the methanol, and drying in vacuum to obtain a PCL guest with a modified end group as a bromo group;
(33) preparation of pseudorotaxane pPR
Firstly, preparing a mixed solution of 40g of alpha-cyclodextrin and 300mL of deionized water, heating the mixed solution to 60 ℃, then dropwise adding a mixed solution of 5g of a product obtained in the step (32) and 50mL of acetone, then carrying out ultrasound treatment on the mixture at room temperature for 2h, continuously stirring at room temperature for 24h to obtain turbid paste, adding 200mL of water for dilution, then centrifuging to obtain a milky white solid, and drying to obtain the pseudorotaxane pPR;
(34) preparation of Polyrotaxane diblock copolymers
Adding 10g of pseudorotaxane pPR, 50g of methacrylate-terminated ethylene terephthalate with the molecular weight of 500g/mol and 2g of Pentamethyldiethylenetriamine (PMDETA) obtained in the step (33) into 50mL of DMF, carrying out freezing-air extraction-unfreezing and oxygen removal circulation treatment for three times, quickly adding Cu (I) Cl, placing the mixture in a nitrogen atmosphere at 60 ℃ for reaction for 24 hours, precipitating the solution into cold methanol, centrifuging to remove a supernatant, redissolving the remained solid in dichloromethane, passing through a silica gel column to remove copper salt, precipitating the filtrate into methanol again, and washing the methanol for three times to obtain a white solid which is the polyrotaxane diblock copolymer;
(35) polycaprolactone grafted modified polyrotaxane (PCL-g-PR)
And (3) dissolving 10g of the polyrotaxane diblock copolymer obtained in the step (34) in 40mL of DMF (dimethyl formamide), adding 40g of epsilon-caprolactone monomer, adding 12.2g of 4-dimethylaminopyridine, introducing nitrogen for protection, stirring and reacting at 160 ℃ for 24h, precipitating a product by using cold methanol, washing for three times, drying to obtain a white solid, wherein the number average molecular weight of the white solid is 26000g/mol according to a molecular weight test, and the obtained white solid is the modified polyrotaxane diblock copolymer.
Example 2
This example provides a process for the preparation of a modified polyrotaxane triblock copolymer (ABA) in which the Young's modulus of the polystyrene as the other polymer block is 3 GPa. The method comprises the following steps:
(41) preparation of pseudorotaxane pPR
A 1000mL three-necked round bottom flask was charged with 10g of α, ω -thiolated PEO (Mn ═ 20000g/mol), dissolved in 20mL of deionized water, and then a solution containing 70g of α -cyclodextrin and 500mL of deionized water was added, and stirred at room temperature for 48h to give a cloudy paste. Adding 200mL of water for dilution, centrifuging to obtain a milky white solid, and drying to obtain pseudorotaxane pPR;
(42) polyrotaxane PR endcapping
Adding 20g of pseudorotaxane pPR obtained in the step (41) into 150mL of DMF, sequentially adding 2.50g of 3- (2-bromoisobutyryloxy) adamantyl methacrylate and 2.5g of triethylamine, stirring the mixture at room temperature for 24 hours in a nitrogen atmosphere, washing the solid obtained after centrifugation twice by using a DMF and methanol mixed solution with the volume ratio of 1:1, washing twice by using anhydrous methanol, dissolving the solid in 50mL of DMSO, precipitating in deionized water, washing twice by using deionized water after centrifugation, and freeze-drying to obtain polyrotaxane PR;
(43) preparation of polycaprolactone grafted and modified polyrotaxane (PCL-g-PR)
Adding 10g of polyrotaxane PR obtained in the step (42) into 150g of epsilon-caprolactone monomer, adding 50mL of DMF and 2.5g of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene, placing the mixture at 60 ℃ for stirring reaction for 48 hours, washing a product with anhydrous methanol for three times, centrifuging, and drying to obtain white solid of the polyrotaxane grafted and modified by PCL;
(44) preparation of modified polyrotaxane triblock copolymer
And (3) adding 10g of PCL grafted modified polyrotaxane obtained in the step (43), 20g of styrene monomer and 2g of Pentamethyldiethylenetriamine (PMDETA) into 150mL of THF, bubbling nitrogen for 1h, quickly adding Cu (I) Cl, reacting for 24h in a nitrogen atmosphere at 60 ℃, precipitating the solution into methanol, centrifuging to remove supernatant, redissolving the remained solid into dichloromethane, passing through a silica gel column to remove copper salt, precipitating the filtrate into methanol again, and washing with methanol for three times to obtain a white solid which is the modified polyrotaxane triblock copolymer, wherein a nuclear magnetic spectrum of the white solid is shown in figure 8. As can be seen from FIG. 8, in which peaks of 6.2 to 7.2ppm were assigned to hydrogen on the benzene ring in polystyrene, peaks of 1.4, 2.3 and 4.1ppm were assigned to hydrogen on polycaprolactone, and small peaks at 3.9, 4.4 and 5.0ppm and the like were assigned to hydrogen on cyclodextrin, the assignment of these nuclear magnetic resonance peaks confirmed that the molecular structure of the resulting polymer was consistent with the designed molecular structure. The number average molecular weight is 51000g/mol according to the molecular weight test.
Example 3
This example provides a process for the preparation of a modified polyrotaxane triblock copolymer (BAB) in which the Young's modulus of polystyrene as the other polymer block is 3 GPa. The method comprises the following steps:
(51) preparation of PCL Guest
Adding 100g of caprolactone monomer, 2g of 9-anthracene methanol, 200mL of toluene and 4g of 1,5, 7-triazabicyclo [4.4.0] dec-5-ene into a 500mL three-neck round-bottom flask, vacuumizing, back flushing nitrogen, placing reactants at 60 ℃ for reacting for 24 hours, pouring the mixture into methanol for precipitation after the reaction is finished, washing for 3 times by using methanol to obtain a white solid, and drying to obtain a PCL guest;
(52) PCL guest end group functionalization
Adding 20g of the PCL guest obtained in the step (51) into 180mL of dry tetrahydrofuran, sequentially adding 4g of bromopropyne and 0.8g of sodium hydride, stirring the mixture at room temperature for 24h in a nitrogen atmosphere, filtering after the reaction is finished, concentrating the filtrate, precipitating in 500mL of methanol, washing for 3 times by using the methanol, and performing vacuum drying to obtain a terminal group functionalized PCL guest;
(53) preparation of pseudorotaxane pPR
Firstly, preparing a mixed solution of 40g of alpha-cyclodextrin and 300mL of deionized water, heating the solution to 60 ℃, then dropwise adding 5g of the mixed solution of the end group functionalized PCL guest obtained in the step (52) and 50mL of acetone, continuously stirring the mixture at room temperature for 24h after carrying out ultrasound treatment for 2h to obtain turbid paste, adding 200mL of water for dilution, then centrifuging to obtain a milky white solid, and drying to obtain the pseudorotaxane pPR;
(54) preparation of Polyrotaxane triblock copolymer
And (3) adding 10g of the pseudorotaxane pPR obtained in the step (53), 20g of monoazide-terminated polystyrene (Mn is 10000g/mol) and 2.5g of Pentamethyldiethylenetriamine (PMDETA) into 150mL of THF, removing oxygen by freezing-air extraction-thawing, quickly adding 3.1g of Cu (I) Cl, reacting for 24 hours in an argon atmosphere at 60 ℃, precipitating the solution into methanol, centrifuging to remove a supernatant, re-dissolving the residual solid into dichloromethane, passing through a silica gel column to remove copper salt, precipitating the filtrate into the methanol again, and washing with the methanol for three times to obtain a white solid, namely the polyrotaxane triblock copolymer.
(55) Preparation of modified polyrotaxane triblock copolymer BAB
Taking 10g of the polyrotaxane triblock copolymer obtained in the step (54), 12g of monocarboxylic end-capped polyethylene glycol monomethyl ether (Mn ═ 200g/mol), 3.5g of BOP reagent and 2.5mL of N, N-diisopropylethylamine, adding the mixture into 150mL of THF, reacting the mixture at 4 ℃ for 24h in a nitrogen atmosphere, then precipitating the mixture in a DMF/methanol (1: 1) mixed solution and centrifuging twice, then centrifuging twice with methanol, and washing the white solid, wherein the number-average molecular weight of the white solid is 47000g/mol according to a molecular weight test, and the obtained white solid is the modified polyrotaxane triblock copolymer.
Example 4
This example provides a modified polyrotaxane multiblock copolymer (BA)nThe production method of (1), wherein the Young's modulus of polystyrene as the other polymer block is 3 GPa. The method comprises the following steps:
(61) preparation of pseudorotaxane pPR
A 1000mL three necked round bottom flask was charged with 10g of α, ω -alkynyl functionalized PEO (Mn ═ 20000g/mol), dissolved in 20mL deionized water, and then a solution containing 70g of α -cyclodextrin and 500mL deionized water was added and stirred at room temperature for 48h to give a cloudy paste. Adding 200mL of water for dilution, centrifuging to obtain a milky white solid, and drying to obtain pseudorotaxane pPR;
(62) preparation of modified polyrotaxane multiblock copolymer
And (3) taking 20g of the pseudorotaxane pPR10g obtained in the step 61, alpha, omega-azido functionalized polystyrene (Mn is 2000g/mol) and 2.2g of Pentamethyldiethylenetriamine (PMDETA) to be added into 150mL of THF, bubbling nitrogen for 1h, then quickly adding 3.1g of Cu (I) Cl, placing the mixture in a nitrogen atmosphere at 60 ℃ for reaction for 24h, precipitating the solution into methanol, centrifuging to remove a supernatant, redissolving the remained solid in dichloromethane, passing through a silica gel column to remove copper salt, precipitating the filtrate into methanol again, and washing the methanol for three times to obtain a white solid, namely the polyrotaxane/polystyrene multiblock copolymer.
(63) Modified polyrotaxane multiblock copolymer (BA)nPreparation of
Taking 10g of polyrotaxane obtained in the step (62), adding the polyrotaxane into 150g of epsilon-caprolactone monomer, adding 50mL of DMF and 2.5g of 1,5, 7-triazabicyclo [4.4.0]Deca-5-ene (TBD), stirring at 60 deg.C for 48h, washing with methanol for three times, centrifuging, and drying to obtain white solid. The molecular weight test shows that the number average molecular weight is 92000g/mol, and the finally obtained modified polyrotaxane multi-block copolymer is (BA)2。
Example 5
This example provides a method for preparing a copolymer film, comprising the following steps:
the modified polyrotaxane block copolymers prepared in examples 1 to 4 were dissolved in toluene to obtain a 10 w/v% solution, filtered through a 5 μm filter, poured into a flat glass petri dish to slowly volatilize the solvent, and heated to 150 ℃ for vacuum drying to ensure complete volatilization of the solvent, thereby obtaining a flat polymer film.
The microphase separation structure of the copolymer film obtained in example 2 was observed by TEM after taking the frozen section of the film and staining, and the microphase separation structure of the copolymer film obtained in example 1 and examples 3 to 4 was similar to that of fig. 7, as shown in fig. 7;
as can be seen from fig. 7, the white region (modified polyrotaxane phase) and the gray region (polystyrene phase) are respectively in phase, the size is about 20-50nm, and the microphase separation structural characteristics endow the two phases with the property of non-interfering lithium ion transmission and mechanical support function, so that the obtained modified polyrotaxane block copolymer not only has higher ionic conductivity, but also has higher mechanical strength.
The copolymer film obtained in example 2 was cut into a long strip, and the mechanical strength thereof was measured by using a universal tester at a tensile rate of 0.01/s.
The detailed test results of example 2 are shown in fig. 9. As can be seen from FIG. 9, the modified polyrotaxane block copolymer obtained in example 2 of the present invention was excellent in mechanical properties when it was formed into a copolymer film, and it had a breaking strength of 13MPa, an elongation at break of 19%, and a Young's modulus of 0.29 GPa. The mechanical property data for examples 1-4 are summarized in Table 1.
TABLE 1 summary of mechanical Properties of modified polyrotaxane Block copolymers obtained in examples 1 to 4
Example 6
This example provides a method for preparing a solid polymer electrolyte membrane, comprising the following steps:
(71) 1g of the modified polyrotaxane block copolymer obtained in example 1 to 4 was dissolved in 10mL of THF to obtain a uniform polymer solution, 0.5g of lithium salt LiFSI was added to the uniform polymer solution, and after the addition, stirring was continued until complete dissolution;
(72) and pouring the completely dissolved solution in a tetrafluoroethylene mold to prepare a membrane, and drying in vacuum to obtain the solid polymer electrolyte membrane.
Comparative example
This comparative example is substantially the same as example 3 except that the monoazide-terminated polystyrene in step (54) of example 3 was replaced with a monoazide-terminated polyethylene glycol monomethyl ether having a molecular weight of 10000g/mol (Young's modulus of less than 0.01 GPa). The polymer solid electrolyte prepared in the comparative example was found to be waxy and not strong enough to be self-supporting and to be used independently as a polymer solid electrolyte.
Examples of the experiments
The electrochemical properties (ionic conductivity, lithium ion transport number, electrochemical window) of the solid polymer electrolyte membrane obtained in example 6 were tested as follows:
ionic conductivity: the solid polymer electrolyte membrane was sandwiched between two pieces of stainless steel and placed in a 2025 type cell can, and the lithium ion conductivity was measured using electrochemical ac impedance spectroscopy using the formula: sigma-L/ARbWherein L is the thickness of the solid polymer electrolyte membrane, A is the area of the stainless steel sheet, and RbThe impedance measured by the impedance meter.
Ion transport number: two lithium sheets are used for clamping a solid polymer electrolyte membrane, the solid polymer electrolyte membrane is placed in a 2025 type battery shell, and the transference number of lithium ions is usually tested by a steady state current method and is calculated by the following formula:
wherein R is0And RssRespectively measuring the impedance before and after polarization by an alternating current impedance method; i is0And IssRespectively an initial current and a steady-state current before polarization; Δ V means the polarization voltage, which is 10mV in this experiment.
Electrochemical window: a solid polymer electrolyte membrane is clamped by a stainless steel sheet and a lithium sheet and placed in a 2025 type battery case, an electrochemical working window is used for carrying out linear volt-ampere scanning measurement by an electrochemical working station, the initial potential is-2.5V, the highest potential is 6V, and the scanning speed is 1 mV/s.
The detailed test results of example 2 are shown in FIGS. 7-12. As can be seen from FIGS. 7 to 12, the room-temperature conductivity of the solid polymer electrolyte provided by the embodiment of the present invention can reach 3.2X 10-4S/cm, the conductivity steadily increases with the temperature, the electrochemical window can reach 5.2V, and the transference number of lithium ions reaches 0.45. The electrochemical data for examples 1-4 are summarized in Table 2.
TABLE 2 summary of electrochemical data for polymer solid electrolytes obtained in examples 1-4
The results show that the modified polyrotaxane block copolymer obtained in the embodiment of the invention has good mechanical properties and higher room-temperature ionic conductivity after being used as a solid polymer electrolyte to prepare an electrolyte membrane, and has good application prospects when being used as an electrolyte of a solid battery.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. A modified polyrotaxane block copolymer, wherein the modified polyrotaxane block copolymer comprises at least one modified polyrotaxane block and at least one polymer block, and the modified polyrotaxane block and the polymer block are alternately linked by a covalent bond; wherein the modified polyrotaxane block is obtained by modifying polyrotaxane by a polymer with ion transmission capability, and the Young modulus of the polymer block is more than or equal to 0.01 GPa.
2. The modified polyrotaxane block copolymer according to claim 1, wherein the young's modulus of the polymer block is 5GPa or less.
3. The modified polyrotaxane block copolymer according to claim 1, wherein the modified polyrotaxane block comprises a polyrotaxane host and a polyrotaxane guest, the polyrotaxane host is cyclodextrin, and a part or all of hydroxyl groups on the cyclodextrin are modified with a polymer having an ion transport ability.
4. The modified polyrotaxane block copolymer according to claim 3, wherein the polymer having ion transport ability is at least one selected from the group consisting of polyether, polyester, polycarbonate, polyurethane, polyamide, polyimide, polysiloxane, polynitrile and polyphosphazene; or
The polymer with ion transmission capability is a comb-shaped polymer with a main chain and side chain groups, wherein the main chain is selected from at least one of polysiloxane, polyphosphazene, polynitrile, polyether, polyolefin, polyacrylate and polymethacrylate; the side chain is selected from at least one of oligoether, nitrile group, sulfone group, thiol, polyether, polyester, polycarbonate, polyurethane, polyamide, polyimide and polynitrile.
5. The modified polyrotaxane block copolymer according to claim 3, wherein the polyrotaxane guest is at least one selected from the group consisting of polyether, polyester, polycarbonate, polyurethane, polyamide, polyimide, polysiloxane, polynitrile, polyphosphazene and polyolefin.
6. The modified polyrotaxane block copolymer according to any one of claims 1 to 5, wherein the polymer block is at least one selected from polystyrene, hydrogenated polystyrene, polyvinylcyclohexane, polyvinylpyridine, polyalkylacrylate, polyalkylmethacrylate, polyphenylene ether, polyimide, polyamide, polyester, polyolefin, polyalkyl vinyl ether, polycyclohexyl vinyl ether, polyvinylidene fluoride-hexafluoropropylene copolymer, styrene-alkyl methacrylate copolymer, styrene-vinylpyridine copolymer, alkyl methacrylate-vinylpyridine copolymer, styrene-alkyl methacrylate-vinylpyridine copolymer.
7. The modified polyrotaxane block copolymer according to claim 6, wherein the polymer block has a branched structure and/or a comb structure.
8. A preparation method of a modified polyrotaxane block copolymer is characterized by comprising the following steps:
providing a polyrotaxane guest and a polyrotaxane host, and reacting the polyrotaxane guest with the polyrotaxane host to obtain a polyrotaxane block;
providing a polymer with ion transmission capacity, and reacting the polymer with the polyrotaxane block to obtain a modified polyrotaxane block;
providing a polymer block with Young modulus of more than or equal to 0.01GPa, and reacting the polymer block with the modified polyrotaxane block to obtain a modified polyrotaxane block copolymer;
or
Providing a polyrotaxane guest and a polyrotaxane host, and reacting the polyrotaxane guest with the polyrotaxane host to obtain a polyrotaxane block;
providing a polymer block with Young modulus of more than or equal to 0.01GPa, and reacting the polymer block with the polyrotaxane block to obtain a polyrotaxane block copolymer;
providing a polymer with ion transmission capability, and reacting the polymer with the polyrotaxane block copolymer to obtain the modified polyrotaxane block copolymer.
9. The method for producing a modified polyrotaxane block copolymer according to claim 8, wherein the polyrotaxane block is subjected to end-capping treatment.
10. A solid polymer electrolyte comprising the modified polyrotaxane block copolymer according to any one of claims 1 to 7 or the modified polyrotaxane block copolymer produced by the production method of the modified polyrotaxane block copolymer according to any one of claims 8 to 9, and an electrolyte salt.
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| CN113773539A (en) * | 2021-09-18 | 2021-12-10 | 华东理工大学 | Preparation method of pseudopolyrotaxane film and pseudopolyrotaxane film prepared by preparation method |
| WO2022105189A1 (en) * | 2020-11-17 | 2022-05-27 | 南方科技大学 | Modified polyrotaxane block copolymer and preparation method therefor, and solid polymer electrolyte |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022105189A1 (en) * | 2020-11-17 | 2022-05-27 | 南方科技大学 | Modified polyrotaxane block copolymer and preparation method therefor, and solid polymer electrolyte |
| CN113773539A (en) * | 2021-09-18 | 2021-12-10 | 华东理工大学 | Preparation method of pseudopolyrotaxane film and pseudopolyrotaxane film prepared by preparation method |
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