polymer

Abstract

The present invention relates to polymer materials exhibiting a superparamagnetic / spin glass state. In one embodiment, the present invention relates to a polymer material exhibiting both high-charge electrical properties and a superparamagnetic / spin glass state. A polymer is described that is paramagnetic, comprising a polymer backbone and pendant groups which are organic electron acceptors capable of forming a stable zwitterion. In one embodiment, the present invention describes a substituted conjugated polymer comprising a conjugated polymer containing two or more nitrogen atoms in close proximity to each other, wherein the conjugated polymer is substituted with organic electron acceptors capable of forming a stable zwitterion.

Description

Technical Field

[0001] The present invention relates to a polymer material that exhibits a superparamagnetic / spin glass state. In one embodiment, the present invention relates to a polymer material that exhibits both highly charged electrical properties and a superparamagnetic / spin glass state.

Background Art

[0002] Medical devices, specialized applications such as biomimetic robotics, and consumer products such as touch screen devices, as well as generally all charged products, all face existing challenges in terms of performance, long-term stability, and reliable mass production. This is typically due to the inorganic materials used in their manufacturing processes, which are expensive, heavy, and difficult to manufacture.

[0003] In recent years, there has been great interest in the formation of new highly charged electrical materials derived from non-metallic molecules. Heretofore, polymers have failed to make an impact in this area, primarily due to the difficulties presented in the production of highly ordered or homogeneous crystalline polymers. Such structural order is required to observe these effects.

[0004] In particular, little progress has been made in the formation of non-metallic highly charged / superparamagnetic materials. Such materials have many uses, for example, in the fields of actuators and sensors, robotics, as well as in the development of artificial muscles, electromagnets and transistors.

[0005] WO 03 / 062305 describes substituted conjugated polymers comprising conjugated polymers substituted with organic electron acceptors. An example of such a polymer is provided as polyaniline. The polymers of WO 03 / 062305 are ferromagnetic. However, they do not exhibit highly charged electrical properties and a superparamagnetic / spin glass state.

Summary of Invention

[0006] The objective is to provide polymer nonmetallic materials that exhibit superparamagnetic / spin glass states. In one embodiment, the objective is to provide polymer nonmetallic materials that exhibit both high-charge electrical properties and superparamagnetic / spin glass states.

[0007] The present invention provides a polymer comprising a polymer skeleton and pendant groups that are organic electron acceptors capable of forming stable zwitterions, and which is paramagnetic.

[0008] Preferably, the polymer is superparamagnetic. The polymer has a mass magnetization of 0.003 JT at room temperature. -1 Kg -1 It is even more preferable that it be less than [a certain value].

[0009] In one embodiment, the polymer backbone comprises repeating units containing one or more aromatic groups.

[0010] Preferably, at least one of the aromatic groups includes a fused ring, and the nitrogen atom is located within one or more of the aromatic groups.

[0011] The polymer backbone is more preferably derived from a polymer selected from polybenzimidazole and polyetherimide.

[0012] In another embodiment, the repeating unit includes a benzophenone moiety.

[0013] Preferably, the polymer backbone is derived from a polyether ether ketone.

[0014] In another embodiment, the polymer backbone comprises repeating units, each containing one or more aliphatic chains. Preferably, the aliphatic chains are linear.

[0015] The polymer backbone is more preferably derived from a polymer selected from polyacrylonitrile, polyethylene glycol, and polyethylene.

[0016] In another embodiment, the polymer backbone is selected from the group consisting of polysiloxanes, polyisoprenes, polysaccharides, polyols, polypeptides, DNA fragments, or RNA fragments.

[0017] Preferably, the number-average molecular weight of the polymer is in the range of 4,000 to 200,000 daltons.

[0018] Preferably, the pendant groups, which are organic electron acceptors, are present in an amount of 0.2 to 10 per monomer unit.

[0019] Preferably, the electron acceptor is selected from quinone, fumarate, trimethylamine N-oxide, and dimethyl sulfoxide derivatives.

[0020] Electron receptors are, Tetracyanoquinodimethane (TCNQ) Tetafluorotetracyanoquinodimethan (TCNQF4) 2,5-Dibromotetracyanoquinodimethane (TCNQBr2) Tetracyanoethylene (TCNE) Dichlorodicyanobenzoquinone (DDQ), or TCNQ derivative It is even more preferable that it originates from [something].

[0021] In one embodiment, the electron acceptor is given by formula I:

[0022] [ka] [In the formula, Is R1=R2=R3=R4=H, F, Me, or Et? R1=R2=H, Br, I, Me or Et, OMe, CN, PhCH2, C1~C8 alkyl group (preferably hexyl, Me, Et or iPr), and R3 and R4 are selected from H, F, Me or Et. R2=R4=H, R1=OMe, and R3=OEt, O i Pr, O i Bu, or R2=R4=H and R1=OEt and R3=SMe, or R2=R4=H and R3=Me and R1=I, Br or Cl, or R1=R2=OCH2CH2O and R3=OMe and R4=H, or R2=R4=H and R3=Br and R1=OCH2CH2OH, or R2=R3=R4=H and R1=Me, Et, OMe, CO2Me. It is derived from a TCNQ derivative having [a specific characteristic].

[0023] In another embodiment, the electron acceptor is formula II, III, IV, or V:

[0024] [ka] It is derived from a TCNQ derivative having [a specific characteristic].

[0025] Preferably, the electron acceptor is derived from tetracyanoquinone dimethane (TCNQ).

[0026] Preferably, the polymer is selected from the group consisting of polybenzimidazole tricyanoquinone dimethane (PBICNQ), sulfonated polyether ether ketone tricyanoquinone dimethane (SPEEKCNQ), polyetherimide tricyanoquinone dimethane (PEICNQ), polyacrylonitrile tricyanoquinone dimethane (PANCNQ), polyethylene glycol tricyanoquinone dimethane (PEGCNQ), and polyethylene tricyanoquinone dimethane (PECNQ).

[0027] The polymer is particularly preferably polybenzimidazole tricyanoquinone dimethane (PBICNQ).

[0028] Furthermore, an electroactive material containing a paramagnetic polymer according to the present invention is also provided. Preferably, this material is highly charged at room temperature.

[0029] Furthermore, a method for producing a paramagnetic polymer, comprising reacting a precursor polymer with an organic electron acceptor, comprising the following steps: a) A step of dissolving the precursor polymer in a suitable solvent, b) Adding an organic electron acceptor to the solution and heating the resulting mixture, c) The solid obtained in step b is cooled and filtered, d) Optionally, a step to evaporate the filtrate obtained from step c) to recover more product, e) A step of drying the product and Methods including the following are also provided.

[0030] Preferably, the precursor polymer is completely dissolved in the solvent used in step a) under the reaction conditions.

[0031] Preferably, the solvent is selected from the group consisting of dimethylformamide (DMF), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), and toluene.

[0032] The molar ratio of the precursor polymer to the organic electron acceptor in the mixture of step b is preferably approximately 1:3. Optionally, the molar ratio of the precursor polymer to the organic electron acceptor in the mixture of step b may be approximately 1:5, 1:10, 1:15, or 1:20.

[0033] It is also preferable that the electron acceptor be tetracyanoquinone dimethane (TCNQ).

[0034] Preferably, the precursor polymer is selected from the group consisting of polybenzimidazole (PBI), sulfonated polyether ether ketone (SPEEK), polyetherimide (PEI), polyacrylonitrile (PAN), polyethylene glycol (PEG), and polyethylene (PE).

[0035] The precursor polymer is more preferably polybenzimidazole or a polymer obtained from substituted diaminobenzidine and terephthalic acid monomers.

[0036] Furthermore, polymers that can be obtained by the method according to the present invention are also provided.

[0037] The present invention also provides graphite, graphene, or fullerene, which comprises a pendant group that is an organic electron acceptor capable of forming a stable zwitterion, and which is paramagnetic.

[0038] Preferably, graphite, graphene, or fullerene is superparamagnetic. Graphite, graphene, or fullerene has a mass magnetization of 0.003 JT at room temperature. -1 Kg -1 It is even more preferable that it be less than [a certain value].

[0039] Preferably, the electron acceptor is selected from quinone, fumarate, trimethylamine N-oxide, and dimethyl sulfoxide derivatives.

[0040] Electron receptors are, Tetracyanoquinodimethane (TCNQ) Tetafluorotetracyanoquinodimethane (TCNQF4) 2,5-Dibromotetracyanoquinodimethane (TCNQBr2) Tetracyanoethylene (TCNE) Dichlorodicyanobenzoquinone (DDQ), or TCNQ derivative It is even more preferable that it originates from [something].

[0041] In one embodiment, the electron acceptor is given by formula I:

[0042] [ka] [In the formula, Is R1=R2=R3=R4=H, F, Me, or Et? R1=R2=H, Br, I, Me or Et, OMe, CN, PhCH2, C1~C8 alkyl group (preferably hexyl, Me, Et or iPr), and R3 and R4 are selected from H, F, Me or Et. R2=R4=H, R1=OMe, and R3=OEt, O i Pr, O i Bu, or R2=R4=H and R1=OEt and R3=SMe, or R2=R4=H and R3=Me and R1=I, Br or Cl, or R1=R2=OCH2CH2O and R3=OMe and R4=H, or R2=R4=H and R3=Br and R1=OCH2CH2OH, or R2=R3=R4=H and R1=Me, Et, OMe, CO2Me. It is derived from a TCNQ derivative having [a specific characteristic].

[0043] In another embodiment, the electron acceptor is formula II, III, IV, or V:

[0044] [ka] It is derived from a TCNQ derivative having [a specific characteristic].

[0045] Preferably, the electron acceptor is derived from tetracyanoquinone dimethane (TCNQ). It is also preferable that the electron acceptor is tetracyanoquinone dimethane (TCNQ).

[0046] Furthermore, electroactive materials comprising graphite, graphene, or fullerene according to the present invention are also provided. Preferably, this material is highly charged at room temperature.

[0047] The present invention also provides a polymer comprising a polymer backbone and pendant groups that are organic electron acceptors capable of forming stable zwitterions, wherein the organic electron acceptor pendant groups are present in amounts of 0.05 to 10 per monomer unit.

[0048] Optionally, the organic electron acceptor pendant groups are present in amounts of 0.05 to 8, 0.1 to 8, 0.1 to 6, 0.2 to 6, 0.2 to 4, 0.5 to 4, 1 to 4, or 1 to 2 per monomer unit. Optionally, the organic electron acceptor pendant groups are present in amounts of approximately 1 per monomer unit.

[0049] Preferably, the electron acceptor is selected from quinone, fumarate, trimethylamine N-oxide, and dimethyl sulfoxide derivatives.

[0050] Electron receptors are, Tetracyanoquinodimethane (TCNQ) Tetafluorotetracyanoquinodimethane (TCNQF4) 2,5-Dibromotetracyanoquinodimethane (TCNQBr2) Tetracyanoethylene (TCNE) Dichlorodicyanobenzoquinone (DDQ), or TCNQ derivative It is even more preferable that it originates from [something].

[0051] More preferably, the electron acceptor is derived from tetracyanoquinone dimethane (TCNQ). It is also preferable that the electron acceptor is tetracyanoquinone dimethane (TCNQ).

[0052] In one embodiment, the distance between pendant groups that are organic electron acceptors is about 15 angstroms or less, 10 angstroms or less, 8 angstroms or less, 6 angstroms or less, or 4 angstroms or less.

[0053] The present invention also provides octasulfur comprising pendant groups that are organic electron acceptors capable of forming stable zwitterions, wherein the octasulfur is paramagnetic.

[0054] Preferably, octasulfur is superparamagnetic. More preferably, octasulfur has a mass magnetization at room temperature of less than 0.003 J / T -1 Kg -1

[0055] The organic electron acceptor can be any of the organic electron acceptors discussed in the present disclosure. The electron acceptor is preferably tetracyanoquinodimethane (TCNQ).

[0056] Also provided is an electroactive material comprising octasulfur according to the present invention. Preferably, this material is highly charged at room temperature.

[0057] A particular advantage of the present invention is that it enables the conversion of commodity polymers, graphite, graphene, fullerenes, and / or octasulfur into electroactive materials using a simple, inexpensive, scalable method. [Brief Description of the Drawings]

[0058] [Figure 1] FIG. 2 is a diagram showing a scheme illustrating the reaction between polybenzimidazole and TCNQ to form a highly charged polymer (PBICNQ), as described in Example 1. [Figure 2] FIG. 3 is a diagram showing the UV absorption spectrum of PBICNQ synthesized in Example 1. [Figure 3] FIG. 4 is a diagram showing the Fourier-transform infrared (FTIR) spectrum of PBICNQ synthesized in Example 1. [Figure 4] ​This graph shows the PXRD data of PBICNQ synthesized in Example 1. [Figure 5] This graph shows the magnetic relaxation data of the PBICNQ synthesized in Example 1. [Figure 6] This graph shows the magnetization pair temperature of the PBICNQ synthesized in Example 1. [Figure 7] This photograph shows the charge behavior of electrons / zwitterions in PBICNQ when a charged rod is inserted into a polymer-containing vial. [Figure 8] This figure shows the ESR data of the PBICNQ synthesized in Example 1. [Figure 9] This figure shows a scheme illustrating the reaction between SPEEK and TCNQ to form the polymer (SPEEKCNQ) described in Example 8. [Figure 10] This figure shows a scheme illustrating the reaction between polyetherimide and TCNQ to form a polymer (PEICNQ), as described in Example 11. [Figure 11] This figure shows a scheme illustrating the reaction between polyacrylonitrile and TCNQ to form a polymer (PANCNQ), as described in Example 14. [Figure 12] This figure shows a scheme illustrating the reaction between polyethylene glycol and TCNQ to form a polymer (PEGCNQ), as described in Example 17. [Figure 13] This figure shows a scheme illustrating the reaction between polyethylene and TCNQ to form a polymer (PECNQ), as described in Example 19. [Figure 14] This figure shows the PXRD data of SPEEKCNQ synthesized in Example 8. [Figure 15] This figure shows the ESR data of SPEEKCNQ synthesized in Example 8. [Figure 16] This graph shows the film formation and conductivity behavior of SPEEKCNQ synthesized in Example 8. [Figure 17]This figure shows the PXRD data of PEICNQ synthesized in Example 11. [Figure 18] This figure shows the ESR data of PEICNQ synthesized in Example 11. [Figure 19] This graph shows the ESR line intensity versus temperature of PEICNQ synthesized in Example 11. [Figure 20] This figure shows the PXRD data of PANCNQ synthesized in Example 14. [Figure 21] This figure shows the ESR data of PANCNQ synthesized in Example 14. [Figure 22] This figure shows the ESR data of PEGCNQ synthesized in Example 17. [Figure 23] This figure shows the ESR data of the PECNQ synthesized in Example 19. [Modes for carrying out the invention]

[0059] definition The following are definitions of terms used herein. The first definition provided for any base or term herein applies throughout this specification, either individually or as part of another base, unless otherwise indicated.

[0060] As used herein, the term “polymer” refers to a molecule composed of repeating structural units linked by covalent chemical bonds. Polymers are typically polymerization products of one or more monomer precursors. Polymers generally include a backbone, side chains, and ends. The backbone is a linear chain from which all side chains hang. Side chains are groups that hang from or branch off from the backbone. Ends are the ends of the backbone. The term polymer includes homopolymers, or polymers that essentially consist of a single repeating monomer subunit. The term polymer also includes copolymers, which are formed when two or more different types of monomers are linked into the same polymer. Copolymers may contain two or more monomer subunits and include random copolymers, block copolymers, alternating copolymers, segmented copolymers, grafted copolymers, tapered copolymers, and other copolymers.

[0061] With respect to polymers, the term "linear," as used herein, refers to a long, continuous chain of carbon-carbon bonds along the polymer backbone.

[0062] With respect to polymers, the term "branched chain," as used herein, refers to the attachment of side chains that are regular or irregular to the polymer backbone.

[0063] As used herein, the term “monomer unit” refers to the smallest repeating unit within a polymer backbone, corresponding to the raw material compound from which the polymer is derived.

[0064] As used herein, the term “conjugated polymer” refers to a polymer containing alternating single and double bonds between carbon atoms such that a π-electron system is formed along the polymer chain. The structure of a conjugated polymer is not limited, however, the alternating single and double bonds are located along the polymer backbone. The present invention is not limited to polymers conjugated along their entire length, but polymers conjugated along at least a portion of their backbone are also included in the teachings provided herein. Preferably, the conjugated polymer is conjugated along its entire backbone.

[0065] The present invention also relates to non-conjugated polymers. As used herein, the term "non-conjugated polymer" refers to a polymer that does not have conjugation along its polymer chain. The structure of a conjugated polymer is not limited, and double and single bonds may coexist along the polymer backbone. In one embodiment, the polymer backbone of a non-conjugated polymer consists only of single bonds.

[0066] When used herein, the term "M" applies to polymers. n " refers to the number-average molecular weight of the polymer. n This is usually measured by gel permeation chromatography (GPC). n In some cases, this can also be measured by nuclear magnetic resonance (NMR) if the visible characteristic peaks of polymer end groups (i.e., chain transfer agents) can be identified in the NMR spectrum and compared to the intensities of other individual peaks in the spectrum resulting from the polymer repeating units.

[0067] As used herein, the term "substitution" means that, provided that the hydrogen atoms of the specified atom have their normal valence, one or more hydrogen atoms of the specified atom are replaced with those selected from the indicated groups.

[0068] As used herein, the term "alkyl" refers to a linear or branched saturated monovalent hydrocarbon radical having the number of carbon atoms indicated by the prefix. 1~4 "Alkyl" refers to a linear saturated monovalent hydrocarbon radical with 1 to 4 carbon atoms, or a branched saturated monovalent hydrocarbon radical with 3 or 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl. To avoid misunderstanding, if two or more alkyl groups are present, the alkyl groups may be the same or different. Preferably, the alkyl group is C 1~12 Alkyl alkyl groups, more C 1~8 Alkyl alkyl groups, and more preferably C 1~6 Alkyl alkyl group, most preferably C 1~4 It is an alkyl group.

[0069] As used herein, the term “alkenyl” refers to a linear or branched saturated monovalent hydrocarbon radical having the number of carbon atoms indicated by the prefix and containing at least one double bond. 2~6 "Alkenyl" refers to a linear saturated monovalent hydrocarbon radical of 2 to 6 carbon atoms having at least one double bond, or a branched saturated monovalent hydrocarbon radical of 3 to 6 carbon atoms having at least one double bond, such as ethenyl, propenyl, 1,3-butadienyl, (CH2)2CH=C(CH3)2, CH2CH=CHCH(CH3)2, etc. Preferably, the alkenyl group is C 2~12 Alkenyl group, more preferably C 2~8 Alkenyl group, more preferably C 2~6 Alkenyl group, most preferably C 2~4 It is an alkenyl group.

[0070] As used herein, the term "alkynyl" refers to a linear or branched saturated monovalent hydrocarbon radical having the number of carbon atoms indicated by the prefix and containing at least one triple bond. 2~6 "Alkynyl" refers to a linear saturated monovalent hydrocarbon radical of 2 to 6 carbon atoms having at least one triple bond, or a branched saturated monovalent hydrocarbon radical of 4 to 6 carbon atoms having at least one double bond, such as ethynyl and propynyl. Preferably, the alkynyl group is C 2~12 Alkynyl group, more preferably C 2~8 Alkynyl group, more preferably C 2~6 Alkynyl group, most preferably C 2~4 It is an alkynyl group.

[0071] As used herein, the term “cycloalkyl” refers to a cyclic saturated monovalent hydrocarbon radical having 3 to 10 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl.

[0072] As used herein, the term “heterocycloalkyl” means a compound in which one or more carbon atoms are replaced by O, S, or NR, and R is H or C 1~6 This refers to alkyl groups, specifically cycloalkyl groups with 3 to 10 members.

[0073] As used herein, the term “alkoxy” refers to an -OR radical where R is an alkyl group as defined above, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, etc. Preferably, the alkoxy group is C 1~12 Alkoxy group, more preferably C 1~8 Alkoxy group, more preferably C 1~6 Alkyl group, most preferably C 1~4 It is an alkoxy group.

[0074] As used herein, the term “alkylthio” refers to an -SR radical in which R is an alkyl group as defined above. Preferably, the alkylthio group is C 1~12 Alkylthio group, more preferably C 1~8 Alkylthio group, more preferably C 1~6 Alkylthio group, most preferably C 1~4 It is an alkylthio group.

[0075] As used herein, the term "halo" means fluoro, chloro, bromo, or iodine, preferably fluoro, chloro, or bromo, more preferably fluoro or chloro.

[0076] As used herein, the term “alkylamino” refers to a radical of -NHR or -NR2 where R is the alkyl group described above. Preferably, the alkylamino group is C 1~12 Alkylamino group, more preferably C 1~8 Alkylamino group, more preferably C 1~6 Alkylamino group, most preferably C 1~4It is an alkylamino group. To avoid misunderstanding, if an alkylamino group contains two alkyl groups, these alkyl groups may be the same or different.

[0077] As used herein, the term "amino" refers to the group of the formula -NH2.

[0078] As used herein, the term "hydroxyl" refers to the group of the formula -OH.

[0079] As used herein, the term "thiol" refers to the group of formula -SH.

[0080] The term "aromatic" refers to a conjugated ring system. Examples of such systems include aryl and heteroaryl groups.

[0081] The term "aliphatic" refers to the part of a molecule that contains carbon and hydrogen atoms covalently bonded together in a straight or branched chain.

[0082] As used herein, the term “aryl” is intended to mean an aromatic moiety in which the ring system contains a specified number of carbon atoms. Preferred aryl groups are C 6~14 An aryl group, more preferably a C such as phenyl or naphthyl. 6~10 It is an aryl group. Unless otherwise specified, the preferred aryl group is phenyl.

[0083] As used herein, the term “heteroaryl” refers to an aromatic moiety in which the ring system contains 5 to 20 ring atoms, one or more of the ring atoms, preferably 1, 2, or 3, are heteroatoms selected from N, O, or S, and the remaining ring atoms are carbon. Preferred heteroaryl groups are 5 to 14-membered heteroaryl groups (i.e., containing 5 to 14 ring atoms), and more preferably 5 to 10-membered heteroaryl groups (i.e., containing 5 to 10 ring atoms). Heteroaryl groups can be monocyclic, and heteroaryl groups in which two or more rings are fused together can be polycyclic. Both fused rings can be heteroaryl groups, or they can be a combination of one or more heteroaryl groups and one or more aryl groups, for example, one heteroaryl group and one aryl group. An example of a monocyclic group is imidazyl, and an example of a polycyclic group is a bicyclic group such as benzimidazyl.

[0084] As used herein, the term “highly charged” refers to the strong reaction of the polymer of the present invention to an externally applied charge. In one embodiment, the polymer has a strong reaction when in contact with a charged rod. In this regard, the strong reaction includes the polymer adhering to the charged rod and remaining attached for a period of one hour or more, preferably two hours or more, more preferably four hours or more, and particularly preferably twelve hours or more.

[0085] polymer The present invention relates to a polymer comprising a polymer skeleton and a pendant group that are organic electron acceptors capable of forming stable zwitterions, and which is paramagnetic.

[0086] In one embodiment, the present invention relates to a substituted conjugated polymer having a conjugated polymer comprising repeating units having two or more nitrogen atoms in close proximity to each other, wherein the repeating units are substituted with at least one organic electron acceptor capable of forming a stable zwitterion.

[0087] As used herein, the term “proximity” refers to two atoms separated by four or fewer bonds. The number of bonds between two atoms is determined based on the minimum number of bonds that must traverse from one nitrogen atom to reach the other nitrogen atom, including the bonds connecting the two nitrogen atoms. Thus, the part -NC=CN- has three bonds between its nitrogen atoms. Similarly, the imidazil part has two bonds between its two nitrogen atoms, pyrimidine has two bonds between its nitrogen atoms, and pyrazine has three bonds between its nitrogen atoms.

[0088] In one embodiment, the polymer is a conjugated polymer, which contains two or more nitrogen atoms that are in close proximity to each other. If there are two nitrogen atoms, they are separated by four or fewer bonds. If there are three or more nitrogen atoms, they are in close proximity, but there are four or fewer bonds between them and any other nitrogen atoms present. Not all nitrogen atoms need to be separated by four or fewer bonds from all other nitrogen atoms within the repeating unit of the conjugated polymer.

[0089] Preferably, two or more nitrogen atoms are separated by three or fewer bonds. More preferably, nitrogen atoms are separated by two or three bonds. Most preferably, nitrogen atoms are separated by two bonds.

[0090] As used herein, a repeating unit refers to a structural portion that appears multiple times in the polymer backbone. Such repeating units may be separated from each other by other structural portions. Preferably, the repeating units appear at regular intervals along a portion of the polymer backbone. More preferably, the repeating units appear at regular intervals along the entire polymer backbone. In a particularly preferred embodiment, the polymer backbone consists solely of repeating units.

[0091] In this embodiment, the nitrogen atom may be part of the polymer backbone or present in a side chain. Preferably, the nitrogen atom is present in the polymer backbone.

[0092] In one embodiment, the polymer backbone comprises repeating units comprising one or more aromatic groups. The term “aromatic” refers to a part that is a conjugated ring system. Examples of such parts include aryl groups such as phenyl, tolyl, and xyl groups, and heteroaryl groups such as pyridyl, thiophenyl, and furanyl groups. In one embodiment, the polymer is a conjugated polymer comprising two or more nitrogen atoms in close proximity to each other, and the repeating units having two or more nitrogen atoms in close proximity to each other preferably comprise one or more aromatic groups. In one embodiment, the aromatic groups comprise heteroaryl groups and optionally comprise aryl groups. A repeating unit may comprise one aromatic group, in which case the repeating unit may comprise a heteroaryl group or two or more aromatic groups. In one embodiment, the repeating unit comprises two or more aromatic groups linked together to ensure that the repeating unit is conjugated. Thus, in one embodiment, the repeating unit comprises one or more heteroaryl groups together with optionally one or more aryl groups, and the heteroaryl and optionally aryl groups are linked by single bonds, -NH- moieties, or vinyl groups.

[0093] Preferably, the repeating unit comprises one or more heteroaryl groups containing one or more nitrogen atoms. The heteroaryl group may contain two or more nitrogen atoms. When two or more nitrogen atoms are present in the heteroaryl group, the nitrogen atoms may be located within the same ring structure or in adjacent ring systems.

[0094] In one embodiment, the polymer is a conjugated polymer comprising repeating units having two or more nitrogen atoms in close proximity to each other. Preferably, the nitrogen atoms of the polymer according to this embodiment are located on aromatic groups. More preferably, the nitrogen atoms of the conjugated polymer are located on the ring system of aromatic groups.

[0095] In one embodiment, the repeating unit includes a fused ring system in which two, three, four or more rings are fused together. For example, the repeating unit may include a fused bicyclic system in which a heteroaryl ring is fused to one aryl group or another heteroaryl group. As used herein, a fused bicyclic group is a group that includes two cyclic parts that share a common bond between two atoms. Typical examples include benzimidazyl, prinyl, imidazopyridinyl, pyrazolopyridinyl, oxazolopyridinyl, isoxazolopyridinyl, thiazolopyrazinyl, and isothiazolopyridinyl.

[0096] In one embodiment, the repeating unit is a heteroaryl group. Preferably, such a heteroaryl group is selected from imidazyl, pyrazyl, pyridadinyl, pyrazinyl, pyrimidinyl, triazinyl, tetradinyl, pentadinyl, benzimidazyl, purinyl, imidazopyridinyl, pyrazolopyridinyl, oxazolopyridinyl, isoxazolopyridinyl, thiazolopyrazinyl, and isothiazolopyridinyl. More preferably, the repeating unit is a condensed bicyclic heteroaryl selected from benzimidazyl, purinyl, imidazopyridinyl, pyrazolopyridinyl, oxazolopyridinyl, isoxazolopyridinyl, thiazolopyrazinyl, and isothiazolopyridinyl. Most preferably, the repeating unit is a benzimidazyl moiety.

[0097] In another embodiment, the repeating unit comprises two or more aromatic groups. Preferably, such repeating groups comprise two or more heteroaryl groups. Preferably, the two or more heteroaryl groups are joined by a single bond. More preferably, the repeating unit comprises two or more fused bicyclic heteroaryls selected from benzimidazyl, prinyl, imidazopyridinyl, pyrazolopyridinyl, oxazolopyridinyl, isoxazolopyridinyl, thiazolopyrazinyl, and isothiazolopyridinyl. Most preferably, the repeating unit comprises two or more benzimidazyl moieties. In a particularly preferred embodiment, the repeating unit comprises two benzimidazyl moieties linked by a single bond between their phenyl rings.

[0098] In another embodiment, the repeating unit comprises at least one heteroaryl group and at least one aryl group. Preferably, at least one heteroaryl group and at least one aryl group are joined by a single bond. More preferably, the repeating unit comprises at least one condensed bicyclic heteroaryl selected from benzimidazyl, prinyl, imidazopyridinyl, pyrazolopyridinyl, oxazolopyridinyl, isoxazolopyridinyl, thiazolopyrazinyl, and isothiazolopyridinyl, and at least one aryl group which is a phenyl group. Most preferably, the repeating unit comprises two benzimidazyl groups and a phenyl group. In a particularly preferred embodiment, the repeating unit comprises two benzimidazyl moieties and a phenyl moiety in which the two benzimidazyl moieties are linked by a single bond between their phenyl rings, with a single bond between one carbon of the imidazyl group and the phenyl moiety. In one embodiment, the polymer is a conjugated polymer, which is polybenzimidazole, and its structure is shown below.

[0099] [ka]

[0100] In one embodiment, the repeating unit includes a fused ring system. Typical examples of fused ring systems include phthalimide, indole, isoindole, indridine, quinoline, isoquinoline, carbazole, benzimidazyl, purinyl, imidazopyridinyl, pyrazolopyridinyl, oxazolopyridinyl, isoxazolopyridinyl, thiazolopyrazinyl, and isothiazolopyrazinyl. In this embodiment, each fused ring in the repeating unit preferably contains one nitrogen atom. Typical examples of fused ring systems containing one nitrogen atom include phthalimide, indole, isoindole, indridine, quinoline, isoquinoline, and carbazole. Preferably, the polymer backbone is derived from a polymer selected from the polyimide class of polymers. More preferably, the repeating unit includes a phthalimide moiety. In one embodiment, the repeating unit includes at least one fused ring together with other moieties such as one or more aromatic groups. In one embodiment, the repeating unit includes at least two fused rings and two or more aromatic groups. In one embodiment, the fused ring and other parts can be directly bonded or joined by a linker. Typically, the fused ring and other parts are joined by a linker. Typical examples of linkers are O, S, or alkyl groups. Preferably, the linker is O. In one embodiment, the repeating unit comprises at least two phthalimide moieties and at least one diphenylpropane moiety. In a particularly preferred embodiment, the polymer that makes up the polymer backbone is polyetherimide, whose structure is shown below.

[0101] [ka]

[0102] As described above, when a repeating unit contains two or more aromatic moieties, the aromatic moieties can be linked by single bonds, -NH- moieties, or vinyl groups. As used herein, a vinyl group refers to a moiety -CR1=CR2-, where R1 and R2 may be the same or different, and can be a hydrogen group, halo group, amino group, hydroxyl group, thiol group, or C1-C 12 Alkyl alkyl groups, C1-C 12 Alkenyl group, C1-C12 Alkynyl group, C3~C 12 Cycloalkyl groups, C3-C 12 Heterocyclic group, C6~C 12 Aryl group or C6~C 12 A heteroaryl group can be selected. Preferably, a hydrogen group, a fluoro group, a chloro group, a bromo group, an amino group, a hydroxyl group, a thiol group, a C1-C6 alkyl group, a C1-C6 alkenyl group, a C1-C6 alkynyl group, or a C5-C 16 Cycloalkyl groups, C5-C6 heterocyclic groups, C6-C 10 Aryl group or C6~C 10 R1 and R2, selected from heteroaryl groups, are either the same or different. More preferably, R1 and R2, selected from hydrogen, fluoro, chloro, bromo, amino, hydroxyl, thiol, or C1-C4 alkyl groups, are either the same or different. Most preferably, both R1 and R2 are hydrogen. Typically, the substituents on the R1 and R2 groups themselves are not substituted. Typically, the aromatic moieties are linked by a single vinyl group. However, a large number of vinyl groups, e.g., 2-100 or 2-10, may be present between the aromatic groups.

[0103] In one embodiment, the polymer skeleton comprises one or more aromatic groups. Preferably, the polymer skeleton is derived from a polymer selected from the polyether ketone class. In one embodiment, the polymer skeleton comprises a benzophenone moiety. In one embodiment, the polymer skeleton comprises one or more benzophenone moieties together with one or more other moieties, such as aromatic groups. The aromatic groups may be substituted or unsubstituted. Preferably, the aromatic groups are substituted. Typical substituents include COOH, CHO, halo, alkyl, or SO3H. Preferably, the aromatic groups are substituted with at least one SO3H moiety. In one embodiment, the benzophenone moiety and the other moieties may be directly bonded or joined by a linker. Typically, the benzophenone moiety and the other moieties are joined by a linker. Typical examples of linkers are O, S, or alkyl groups. Preferably, the linker is O. More preferably, the polymer skeleton is derived from a polymer selected from polyether ketones, polyether ether ketones, and sulfonated polyether ether ketones. In a particularly preferred embodiment, the polymer backbone is derived from a sulfonated polyether ether ketone, and its structure is shown below.

[0104] [ka]

[0105] In the repeating unit, the aromatic group may or may not be substituted. Typical substituents are C1-C 12 Alkyl alkyl groups, C2-C 12 Alkenyl group, C2~C 12 Alkynyl group, C3~C 10 Cycloalkyl groups, 3-10 membered heterocyclic groups, C1-C 12 Alkoxy group, C1~C 12 Alkylthio group, C1~C 12 It includes alkylamino groups, halo groups, hydroxyl groups, thiol groups, and amino groups. If possible, these substituents are, for example, C1-C 12The substituents can be further substituted with alkyl groups, halogen groups, or hydroxyl groups. Preferably, the substituents are selected from C1-C6 alkyl groups, C1-C6 alkoxy groups, C1-C6 alkenyl groups, C3-C6 cycloalkyl groups, 3-6 membered heterocyclic groups, fluoro groups, chloro groups, bromo groups, hydroxyl groups, thiol groups, and amino groups. More preferably, the substituents are selected from C1-C6 alkyl and amino groups. In one embodiment, the aromatic group is substituted at each available position of the ring. In a further embodiment, the aromatic group is substituted with a C1-C6 alkyl group at each available position of the ring.

[0106] In one embodiment, the polymer backbone comprises repeating units containing one or more aliphatic chains. Preferably, the polymer backbone comprises linear aliphatic chains. In one embodiment, the polymer backbone is derived from a polymer selected from the polyalkyl class of polymers. In this embodiment, the polyalkyl chains of the polymer backbone can be directly bonded or joined with linkers. Typical linkers in this embodiment are O and S. Preferably, the linker is O. In this embodiment, the alkyl chains of the polymer backbone may be substituted or unsubstituted. Typical substituents are C1-C 12 Alkyl alkyl groups, C2-C 12 Alkenyl group, C2~C 12 Alkynyl group, C3~C 10 Cycloalkyl groups, 3-10 membered heterocyclic groups, C1-C 12 Alkoxy group, C1~C 12 Alkylthio group, C1~C 12 The substituents include alkylamino groups, halo groups, hydroxyl groups, thiol groups, amino groups, and cyano groups. Preferably, the substituents are selected from C1-C6 alkyl groups, halo groups, and cyano groups. More preferably, the substituents are cyano groups.

[0107] In a particularly preferred embodiment, the polymer backbone is polyacrylonitrile, and its structure is shown below.

[0108] [ka]

[0109] In a particularly preferred embodiment, the polymer backbone is polyethylene glycol, and its structure is shown below.

[0110] [ka]

[0111] In a particularly preferred embodiment, the polymer backbone is polyethylene, and its structure is shown below.

[0112] [ka]

[0113] In a particularly preferred embodiment, the polymer backbone is a polysiloxane, and its structure is shown below.

[0114] [ka]

[0115] In the formula, R is an organic group such as alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, alkoxy, alkylthio, alkylamino, aryl, or heteroaryl.

[0116] In a particularly preferred embodiment, the polymer backbone is polyisoprene. Polyisoprene may be one of the isomers shown below, or a mixture of any of the isomers in any ratio.

[0117] [ka]

[0118] In a particularly preferred embodiment, the polymer backbone is a polysaccharide.

[0119] In a particularly preferred embodiment, the polymer backbone is a polyol.

[0120] In a particularly preferred embodiment, the polymer backbone is a polypeptide.

[0121] In a particularly preferred embodiment, the polymer backbone is a DNA fragment.

[0122] In a particularly preferred embodiment, the polymer backbone is an RNA fragment.

[0123] The polymer used to derive the polymer backbone of the polymer of the present invention can be obtained by polymerizing optimal monomers using approaches and techniques well known to those skilled in the art. In one embodiment, the monomer relates to a repeating unit of the polymer. In another embodiment, the repeating unit is formed by a reaction between two or more monomers so as not to correspond to a specific monomer. In one embodiment, the polymer is a conjugated polymer. Preferably, the conjugated polymer is prepared from substituted monomers of diaminobenzidine tetrahydrochloride and terephthalic acid, aniline, pyridine, pyrrole, phenylene-vinylene, phenylene, thiophene, or fluorene. Preferably, the conjugated polymer is a polymer obtained from polybenzimidazole, a polybenzimidazole derivative, or a polymer obtained from substituted diaminobenzidine and terephthalic acid, a benzenedibasic acid, or a maleic anhydride monomer. More preferably, the conjugated polymer may be a polymer obtained by polymerizing substituted monomers of diaminobenzidine tetrahydrochloride and terephthalic acid.

[0124] The polymer preferably has a number-average molecular weight in the range of 4,000 to 200,000 daltons. Preferably, the number-average molecular weight is in the range of 20,000 to 150,000 daltons, more preferably 50,000 to 100,000 daltons, and most preferably in the range of 75,000 to 80,000 daltons. In one embodiment, the polymer is a conjugated polymer.

[0125] In the polymer of the present invention, the repeating units contain organic electron acceptors capable of forming stable zwitterions. "Capable of forming stable zwitterions" refers to a reaction between the polymer chain and the electron acceptor molecules, where charge transfer from a portion of the polymer chain to the electron acceptor results in the formation of a stable zwitterion, which is a pendant chain with the electron acceptor molecules bonded to the polymer backbone, and the charge is stable along the chain.

[0126] In one embodiment, the polymer is a conjugated polymer, in which the repeating units contain organic electron acceptors capable of forming stable zwitterions. In this embodiment, "capable of forming stable zwitterions" refers to a reaction between the polymer chain and the electron acceptor molecules, where charge transfer from two or more nitrogen atoms to the electron acceptors results in the formation of a stable zwitterion, which is a pendant chain with the electron acceptor molecules bonded to the polymer backbone, and the charge is stable along the chain.

[0127] In the polymer of the present invention, the repeating units include organic electron acceptors as pendant chains bonded to the polymer backbone. The organic electron acceptors form charge transfer complexes with the polymer. Preferably, the organic electron acceptors readily form radicals. In one embodiment, the polymer is a conjugated polymer.

[0128] Preferably, the organic electron acceptor can be selected from quinone, fumarate, trimethylamine N-oxide, and dimethyl sulfoxide derivatives. More preferably, the organic electron acceptor can be selected from quinone derivatives.

[0129] More preferably, the organic electron acceptor can be selected from tetracyanoquinodimethane (TCNQ), tetrafluorotetracyanoquinodimethane (TCNQF4), 2,5-dibromotetracyanoquinodimethane (TCNQBr2), tetracyanoethylene (TCNE), dichlorodicyanobenzoquinone (DDQ), TCNQ derivatives, or other such electron acceptors.

[0130] These receptor molecules are known to form stable zwitterions on polymer chains when they can react and stack, enabling them to generate excellent properties on the polymer backbone. This is because exchange interactions occur between adjacent chains, resulting in a highly charged three-dimensional exchange mechanism in organic systems.

[0131] The family of TCNQ derivatives includes:

[0132] [ka] [In the formula, Is R1=R2=R3=R4=H, F, Me, or Et? R1=R2=H, Br, I, Me or Et, OMe, CN, PhCH2, C1~C8 alkyl group (preferably hexyl, Me, Et or iPr), and R3 and R4 are selected from H, F, Me or Et. R2=R4=H, R1=OMe, and R3=OEt, O i Pr, O i Bu, or R2=R4=H and R1=OEt and R3=SMe, or R2=R4=H and R3=Me and R1=I, Br or Cl, or R1=R2=OCH2CH2O and R3=OMe and R4=H, or R2=R4=H and R3=Br and R1=OCH2CH2OH, or R2=R3=R4=H and R1=Me, Et, OMe, CO2Me. This includes, but is not limited to, the following:

[0133] The following structure:

[0134] [ka] It is also included in TNCQ derivatives.

[0135] In preferred embodiments of the present invention, the organic electron acceptor is preferably tetracyanoquinone dimethane (TCNQ). This is a stable radical-forming molecule that readily forms charge-transfer complexes with electron donors such as the nitrogen atom of a heterocyclic conjugated polymer having nitrogen in its ring structure.

[0136] Since organic electron acceptors bind to polymers, a covalent bond exists between the polymer and the electron acceptor molecule. The electron acceptor molecules provided herein are identified by their structure before they bind to the polymer. In this regard, electron acceptors are said to be derivatives of certain compounds or to originate from certain compounds.

[0137] Therefore, when it is said that the electron acceptor is selected from tetracyanoquinodimethane (TCNQ), tetrafluorotetracyanoquinodimethane (TCNQF4), 2,5-dibromotetracyanoquinodimethane (TCNQBr2), tetracyanoethylene (TCNE), dichlorodicyanobenzoquinone (DDQ), and TCNQ derivatives, the part that bonds to the polymer backbone is based on such compounds, but one of the cyano groups is absent, and a single bond exists between the polymer backbone and the carbon to which the cyano group is bonded.

[0138] The family of TCNQ derivatives found in polymers is,

[0139] [ka] [In the formula, Is R1=R2=R3=R4=H, F, Me, or Et? R1=R2=H, Br, I, Me or Et, OMe, CN, PhCH2, C1~C8 alkyl group (preferably hexyl, Me, Et or iPr), and R3 and R4 are selected from H, F, Me or Et. R2=R4=H, R1=OMe, and R3=OEt, O i Pr, O i Bu, or R2=R4=H and R1=OEt and R3=SMe, or R2=R4=H and R3=Me and R1=I, Br or Cl, or R1=R2=OCH2CH2O and R3=OMe and R4=H, or R2=R4=H and R3=Br and R1=OCH2CH2OH, or R2=R3=R4=H and R1=Me, Et, OMe, CO2Me. The wavy bonds indicate bonding sites to the polymer backbone, and these bonding sites are preferably aromatic groups.

[0140] The following structure:

[0141] [ka] It is also included in TCNQ derivatives, and the wave-shaped bond indicates a bond site to the polymer backbone, and the bond site is preferably an aromatic group.

[0142] Preferably, the polymer of the present invention contains two or more electron acceptor molecules in each repeating unit. Preferably, the polymer of the present invention contains one electron acceptor molecule for each aromatic group in each repeating unit. In one particular embodiment, the repeating unit contains three aromatic groups and three electron acceptor molecules. In one embodiment, the polymer is a substituted conjugated polymer.

[0143] Preferably, the polymer of the present invention contains 0.2 to 10 organic electron acceptor molecules per monomer unit along the polymer chain. More preferably, the polymer contains 0.5 to 5 organic electron acceptor molecules per monomer unit. Even more preferably, the polymer contains 0.5 to 3 organic electron acceptor molecules per monomer unit. Most preferably, the polymer contains 1 to 3 organic electron acceptor molecules per monomer unit.

[0144] In particularly preferred embodiments, the polymer of the present invention is selected from the group consisting of polybenzimidazole tricyanoquinone dimethane (PBICNQ), sulfonated polyetheretherketone tricyanoquinone dimethane (SPEEKCNQ), polyetherimide tricyanoquinone dimethane (PEICNQ), polyacrylonitrile tricyanoquinone dimethane (PANCNQ), polyethylene glycol tricyanoquinone dimethane (PEGCNQ), and polyethylene tricyanoquinone dimethane (PECNQ).

[0145] In a particularly preferred embodiment, the polymer of the present invention is polybenzimidazole tricyanoquinone dimethane (PBICNQ).

[0146] The polymer of the present invention is paramagnetic.

[0147] In one embodiment, the polymer of the present invention is superparamagnetic.

[0148] The mass magnetization of the polymer of the present invention is thought to depend on the degree of substitution of the polymer backbone with organic electron acceptors. Preferably, the degree of substitution is such that the mass magnetization of the polymer at room temperature is 0.003 JT. -1 Kg -1 It is less than the specified value.

[0149] In one embodiment, the polymer of the present invention is not ferromagnetic. In one embodiment, the polymer is a substituted conjugated polymer, and substituted conjugated polymers are not ferromagnetic.

[0150] In one embodiment, the polymer of the present invention exhibits high electrical properties.

[0151] In preferred embodiments, the polymer of the present invention exhibits solubility in water. Preferably, the polymer of the present invention has a water solubility of 20 mg / mL or more at 25°C. In particularly preferred embodiments, PEGCNQ exhibits solubility in water. It is even more preferable that PEGCNQ has a water solubility of 20 mg / mL or more at 25°C.

[0152] Furthermore, electroactive materials containing the polymer of the present invention are also provided herein. Preferably, such materials are highly charged at room temperature. In one embodiment, the electroactive material includes the polymer of the present invention, which is a substituted conjugated polymer.

[0153] Method for producing paramagnetic polymers Furthermore, a method for producing a paramagnetic polymer, comprising reacting a precursor polymer with an organic electron acceptor, comprising the following steps: (a) A step of dissolving the precursor polymer in a suitable solvent, (b) Adding an organic electron acceptor to the solution and heating the resulting mixture, (c) A step of cooling and filtering the solid obtained in step (b), (d) Optionally, a step to evaporate the filtrate obtained from step (c) to recover more product, (e) A step of drying the product and Methods including the following are also provided.

[0154] One embodiment of the present invention provides a method for producing a polymer of the present invention, as described herein, comprising reacting a conjugated polymer with an organic electron acceptor, wherein the conjugated polymer contains two or more nitrogen atoms in close proximity to each other.

[0155] Preferably, the method according to this embodiment involves the following steps: (a) The step of dissolving the conjugated polymer in a suitable solvent, (b) Adding an organic electron acceptor to the solution and heating the resulting mixture, (c) A step of cooling and filtering the solid obtained in step (b), (d) Optionally, a step to evaporate the filtrate obtained from step (c) to recover more product, (e) A step of drying the product and Includes.

[0156] In step (a), the precursor polymer is dissolved in a suitable solvent. In one embodiment, the polymer is conjugated, and the conjugated polymer is dissolved in a suitable solvent. Typical examples of solvents include dimethylformamide (DMF), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), and toluene. Preferably, the solvent is DMF. The polymer and solvent are selected so that the polymer is completely soluble in the solvent used in step a) under the reaction conditions. In one embodiment, the polymer has a solubility of 20 mg / mL or more in the solvent used in step a) at 25°C.

[0157] In one embodiment, the heating step (b) includes refluxing the resulting mixture.

[0158] In another embodiment, step (b) heating includes heating the mixture for at least 2 hours, preferably at least 4 hours, more preferably at least 8 hours, and particularly preferably at least 24 hours.

[0159] Typically, the molar ratio of the precursor polymer to the organic electron acceptor in the mixture is at least 1:2, preferably at least 1:3, and more preferably at least 1:4. The molar ratio of the precursor polymer to the organic electron acceptor in the mixture may be 1:5, 1:10, 1:15, or 1:20. In certain embodiments, the molar ratio of the precursor polymer to the organic electron acceptor in the mixture is approximately 1:3.

[0160] In one embodiment, the precursor polymer is selected from the group consisting of polybenzimidazole (PBI), sulfonated polyetheretherketone (SPEEK), polyetherimide (PEI), polyacrylonitrile (PAN), polyethylene glycol (PEG), and polyethylene (PE), and the organic electron acceptor is TCNQ. The resulting paramagnetic polymers are polybenzimidazole tricyanoquinone dimethane (PBICNQ), sulfonated polyetheretherketone tricyanoquinone dimethane (SPEEKCNQ), polyetherimide tricyanoquinone dimethane (PEICNQ), polyacrylonitrile tricyanoquinone dimethane (PANCNQ), polyethylene glycol tricyanoquinone dimethane (PEGCNQ), and polyethylene tricyanoquinone dimethane (PECNQ).

[0161] In one embodiment, the precursor polymer is a conjugated polymer. In a particularly preferred embodiment, the conjugated polymer is polybenzimidazole (PBI) and the organic electron acceptor is TCNQ. The resulting substituted conjugated polymer is polybenzimidazole tricyanoquinone dimethane (PBICNQ).

[0162] The present invention also relates to polymers that can be obtained by the methods described above.

[0163] Graphite, graphene, or fullerene The present invention also relates to graphite, graphene, or fullerene, which contains a pendant group that is an organic electron acceptor capable of forming a stable zwitterion, and which is paramagnetic. Preferably, the graphite, graphene, or fullerene containing a pendant group that is an organic electron acceptor capable of forming a stable zwitterion is superparamagnetic.

[0164] Graphite is understood to consist of multiple layers of planar carbon atoms. In each layer, each carbon atom is bonded to three other carbon atoms that form a continuous layer of bonded carbons. A single layer of bonded carbons is understood to be graphene. Fullerenes are understood to be allotropes of carbon, consisting of carbon atoms linked by single and double bonds so that their molecules form a closed or partially closed structure, including a fused ring of 5 to 7 atoms. The molecules may have hollow spherical and elliptical forms, tubes, or other shapes. Preferably, fullerenes are conjugated.

[0165] In one embodiment of the present invention, graphite, graphene, or fullerene is functionalized by adding a pendant group. Adding a pendant group to graphite, graphene, or fullerene can be achieved using approaches and techniques well known to those skilled in the art. The pendant group is an organic electron acceptor capable of forming a stable zwitterion such as TCNQ. Since the organic electron acceptor can bind to graphite, graphene, or fullerene, a covalent bond exists between the graphite, graphene, or fullerene and the electron acceptor molecule. Optionally, the organic electron acceptor can bind to graphite, graphene, or fullerene via non-covalent interactions.

[0166] eight sulfur Octasulfur is understood to be an inorganic substance consisting of sulfur atoms with the chemical formula S8. It may also be known as cyclooctasulfur or cyclooctasulfan. In one embodiment of the present invention, octasulfur is functionalized by adding a pendant group. Adding a pendant group to octasulfur can be achieved using approaches and techniques well known to those skilled in the art. The pendant group is an organic electron acceptor capable of forming a stable zwitterion such as TCNQ. Since the organic electron acceptor can bind to octasulfur, a covalent bond exists between octasulfur and the electron acceptor molecule.

[0167] Use of polymers, graphite, graphene, fullerene, or octagonal sulfur according to the present invention Without wishing to be bound by any theory, and using the substituted conjugated polymer PBICNQ merely as an example, and without limiting the scope of teaching or the invention, it is believed that PBICNQ contains stable radicals and charges resulting from charge transfer from TCNQ to the amine moiety of PBI and protonation of the imine moiety of the conjugated polymer. This results in π-stacking of adjacent chains, which can lead to interchain spacings of approximately 15 angstroms or less, 10 angstroms or less, 8 angstroms or less, 6 angstroms or less, or 4 angstroms or less. This results in exchange interactions between adjacent chains, thus creating a highly charged mechanism of three-dimensional exchange in organic systems. Furthermore, if the charge is evenly distributed along the polymer chain, the charge can be synchronized along the polymer backbone to enhance the polarization effect, which acts like a wave or ripple in the new polymer structure. The substituted conjugated polymers according to embodiments of the invention are electroactive polymers (EAPs). Experiments involving these polymers demonstrate that it is possible to enable movement, generate forces, and electrically control surface properties. Furthermore, its electrical activation mechanism allows for the conversion of electrical energy into mechanical energy. This means the polymer has potential for use in professional applications and consumer products, particularly in relation to its use in actuators.

[0168] The following are illustrative examples of the present invention. However, these examples are not intended to limit the scope of the present invention. [Examples]

[0169] In the following example, polybenzimidazole was obtained from High Performance Products (molecular weight 60,000 D). The organic electron acceptor was obtained from Fluorochem and used without further purification with DMF.

[0170] [Example 1] Polymer preparation Polybenzimidazole was purchased from High Performance Products (molecular weight 60,000 D). 5 g of the polymer was dissolved in 100 ml of DMF. 0.5 g of TCNQ (Fluorochem) was added to the resulting solution, and the mixture was heated overnight at 80°C. The solution was cooled, and the DMF was evaporated to obtain a dark gray / black polymer (PBICNQ). The dark gray / black polymer (PBICNQ) was dried under vacuum. The reaction scheme for the formation of the substituted polymer is shown in Figure 1.

[0171] The method described in the above examples can also be carried out using 0.5 to 1 g of polybenzimidazole in 100 to 250 mL of DMF.

[0172] [Example 2] Characterization of polymers using UV spectroscopy A sample of the polymer (PBICNQ) produced in Example 1 was analyzed using UV spectroscopy. The UV absorption spectrum showed strong absorbance bands at λmax=495 and at λmax=625 and 665 (see Figure 2). When dissolved in DMF, the polymer became a strong dark blue / green solution. The UV absorption spectrum of this blue / green solution indicates that charge transfer occurred between TCNQ and polybenzimidazole, thereby forming a stable zwitterion.

[0173] [Example 3] Characterization of polymers using Fourier transform infrared spectroscopy (FTIR) A sample of the polymer (PBICNQ) produced in Example 1 was analyzed using FTIR spectroscopy. As shown in Figure 3, the FTIR spectrum was obtained from 2980 to 3200 cm⁻¹. -1 Wide-range absorption with (NH), and 2159cm -1 and 2157cm -1 A sharp and strong absorption was observed at (CN), which was attributed to TCNQ covalently bonded to the polymer. 2980~3200 cm -1 The broad absorption observed indicated the presence of amines.

[0174] [Example 4] Characterization of polymers using X-ray spectroscopy A sample of the polymer (PBICNQ) produced in Example 1 was analyzed using X-ray spectroscopy (see Figure 4). X-ray analysis of the polymer revealed that it was semi-crystalline. This may be in contrast to pure polybenzimidazole, which was completely amorphous.

[0175] [Example 5] Magnetic relaxation analysis of polymers Samples of the polymer (PBICNQ) produced in Example 1 were analyzed using low-temperature magnetic relaxation analysis (see Figure 5). The obtained low-temperature data indicated that the polymer exhibited magnetic relaxation. The results also showed a rapid change in magnetic moment at a stable heating rate. This suggests a superparamagnetic or spin / cluster glass-like response. Investigation of magnetization-to-temperature (see Figure 6) showed that the material was paramagnetic with a large diamagnetic offset. There was no evidence of a ferromagnetic component.

[0176] [Example 6] Visual observation of polymer behavior A charged rod was placed in a vial containing a sample of the polymer (PBICNQ) produced in Example 1. The powder was observed to be attracted to the rod in a configuration resembling sharp, needle-like structures (see Figure 7). This indicated that the charges within the polymer backbone were perfectly balanced. This effect was instantaneous, and no change in appearance was observed when left overnight. The material was observed to still exhibit this zwitterionic behavior after almost one year. This clearly demonstrated that the effect was not due to any static effect, but rather an intrinsic effect originating from within the molecule.

[0177] [Example 7] Characterization of polymer PBICNQ using electron spin resonance (ESR) spectroscopy Samples of the polymer (PBICNQ) produced in Example 1 were analyzed using ESR spectroscopy (see Figure 8). The ESR data showed the presence of many free electrons or spins in the polymer backbone, affected by the addition of the TCNQ moiety, with 1 × 10⁶ per gram of polymer. 17 The spin values ​​for each individual were calculated.

[0178] [Example 8] Preparation of SPEEKCNQ 5 g of sulfonated polyether ether ketone was dissolved in 100 ml of DMF. 1 g of TCNQ (Fluorochem) was added to the resulting solution, and the mixture was heated overnight at 80°C. The DMF was removed under vacuum, and the solid polymer was washed twice with cold DMF (25 ml per wash). The polymer (SPEEKCNQ) was dried under vacuum. The reaction scheme for polymer formation is shown in Figure 9.

[0179] The method described in the above examples can also be carried out using 0.5 to 1 g of sulfonated polyether ether ketone in 100 to 250 mL of DMF.

[0180] The polymer (SPEEKCNQ) was found to form films, yielding orange / golden films. These films were found to respond to an externally charged rod, suggesting that the material could be used as a response layer material. This phenomenon is similar to that observed in artificial muscles, in that the film responds to a charge in response to an externally applied stimulus. The polymer (SPEEKCNQ) also exhibits electrical conductivity (see Figure 16). The FTIR spectrum is approximately 2200–2159 cm⁻¹. -1 The spectrum showed a peak, indicating the presence of a CN group. The UV spectrum presented an absorption band indicating the presence of both quinoid and zwitterionic forms of the polymer.

[0181] [Example 9] Characterization of polymers using X-ray spectroscopy (SPEEKCNQ) Samples of the polymer (SPEEKCNQ) produced in Example 8 were analyzed using X-ray spectroscopy (see Figure 14). X-ray analysis of the polymer revealed the presence of crystalline polymer backbone. This may be in contrast to the completely amorphous starting polymer SPEEK. Figure 14 clearly shows a shift of 2.5° from 18.5° to 21.5°, and approximately 45° from the starting material.

[0182] [Example 10] Characterization of the polymer SPEEKCNQ using electron spin resonance (ESR) spectroscopy. Samples of the polymer (SPEEKCNQ) produced in Example 8 were analyzed using ESR spectroscopy (see Figure 15). The ESR data showed that SPEEKCNQ exhibited high spin or paramagnetic properties, with 1 × 10⁶ per gram of polymer. 18 The spin values ​​for each individual were calculated.

[0183] [Example 11] Preparation of PEICNQ 5 g of polyetherimide was dissolved in 100 ml of DMF. 1 g of TCNQ (Fluorochem) was added to the resulting solution, and the mixture was heated overnight at 80°C. The DMF was removed under vacuum, and the solid polymer was washed twice with cold DMF (25 ml per wash). The polymer (PEICNQ) was dried under vacuum. The reaction scheme for polymer formation is shown in Figure 10.

[0184] The method described in the above examples can also be carried out using 0.5 to 1 g of polyetherimide in 100 to 250 mL of DMF.

[0185] PEICNQ turned dark. When dissolved in DMF, it became a yellow solution, and when the solution was heated with a hot air gun, it changed to purple. Upon cooling, the solution returned to yellow. This indicates that the polymer converts from its quinoid form to its zwitterionic form and then back to its quinoid form. This interconversion during temperature changes suggests that the material can be used in sensor applications. FTIR analysis showed a temperature of 2159 cm⁻¹.-1 and 2157cm -1 Two absorption peaks were observed, confirming the presence of the TCNQ moiety bound to the PEI chain. UV analysis also confirmed the presence of both quinoid and zwitterionic forms.

[0186] [Example 12] Characterization of polymers (PEICNQ) using X-ray spectroscopy A sample of the polymer (PEICNQ) produced in Example 11 was analyzed using X-ray spectroscopy (see Figure 17). X-ray analysis of the polymer showed a prominent peak at 45° relative to the starting polymer before reaction with TCNQ. However, after the reaction, a significant change appeared at approximately 25°. This suggests that the presence of the TCNQ portion imparts a certain degree of crystallinity to the polymer backbone compared to the starting material PEI.

[0187] [Example 13] Characterization of polymer PEICNQ using electron spin resonance (ESR) spectroscopy Samples of the polymer (PEICNQ) produced in Example 11 were analyzed using ESR spectroscopy (see Figure 18). The ESR data showed the presence of many free electrons or spins in the polymer backbone, affected by the addition of the TCNQ moiety, with 1 × 10⁶ per gram of polymer. 18 The spin values ​​were calculated. Figure 19 shows the ESR intensity versus temperature. The decrease in intensity at 185K may indicate a phase transition with a possible structural change. A small temperature increase may indicate paramagnetic spin.

[0188] [Example 14] Preparation of PANCNQ 5 g of polyacrylonitrile was dissolved in 100 ml of DMF. 1 g of TCNQ (Fluorochem) was added to the resulting solution, and the mixture was heated overnight at 80°C. The DMF was removed under vacuum, and the solid polymer was washed twice with cold DMF (25 ml per wash). The polymer (PANCNQ) was dried under vacuum. The reaction scheme for polymer formation is shown in Figure 11.

[0189] The method of the above examples can also be carried out using 0.5 to 1 g of polyacrylonitrile with 100 to 250 mL of DMF.

[0190] The polymer PANCNQ has high responsiveness to applied charges and responded to an external magnetic field, which indicates that it has potential for use in conductive fabrics. FTIR analysis showed 2159cm -1 and 2157cm -1 two absorption peaks, confirming the presence of TCNQ moieties bound to the PAN chains. UV analysis also confirmed the presence of both quinoid and zwitterionic forms.

[0191] [Example 15] Characterization of Polymer (PANCNQ) Using X-ray Spectroscopy A sample of the polymer (PANCNQ) produced in Example 14 was analyzed using X-ray spectroscopy (see Figure 20). X-ray analysis of the polymer showed a shift at 17° to 18° and a broad peak at 29°. This suggests that the presence of the TCNQ moiety imparts a certain degree of crystallinity to the polymer backbone compared to the starting material PAN.

[0192] [Example 16] Characterization of Polymer PANCNQ Using Electron Spin Resonance (ESR) Spectroscopy A sample of the polymer (PANCNQ) produced in Example 14 was analyzed using ESR spectroscopy (see Figure 21). The ESR data showed the presence of many free electrons or spins within the polymer backbone affected by the addition of the TCNQ moiety, and a value of 1×10 18 spins per gram of polymer was calculated.

[0193] [Example 17] Preparation of PEGCNQ 5 g of polyethylene glycol was dissolved in 100 ml of DMF. 1 g of TCNQ (Fluorochem) was added to the resulting solution, and the mixture was heated overnight at 80°C. The DMF was removed under vacuum, and the solid polymer was washed twice with cold DMF (25 ml per wash). The polymer (PEGCNQ) was dried under vacuum. The reaction scheme for polymer formation is shown in Figure 12.

[0194] The method described in the above examples can also be carried out using 0.5 to 1 g of polyethylene glycol in 100 to 250 mL of DMF.

[0195] The resulting polymer PEGCNQ was a dark-colored, water-soluble material. Polymer PEGCNQ showed high responsiveness to applied charge and external magnetic fields, suggesting potential applications in drug delivery and medicine. FTIR analysis at 2200 cm² showed... -1 Two absorption peaks were observed, confirming the presence of the TCNQ moiety bound to the PEG chain. UV analysis also confirmed the presence of both quinoid and zwitterionic forms. X-ray analysis showed that the presence of the TCNQ moiety imparts a certain degree of crystallinity to the polymer backbone compared to the starting material PEG.

[0196] [Example 18] Characterization of polymer PEGCNQ using electron spin resonance (ESR) spectroscopy Samples of the polymer (PEGCNQ) produced in Example 17 were analyzed using ESR spectroscopy (see Figure 22). The ESR data showed the presence of many free electrons or spins in the polymer backbone, affected by the addition of the TCNQ moiety, with 1 × 10⁶ per gram of polymer. 18 The spin values ​​for each individual were calculated.

[0197] [Example 19] Preparation of PECNQ 5 g of polyethylene was dissolved in 100 ml of DMF. 1 g of TCNQ (Fluorochem) was added to the resulting solution, and the mixture was heated to 80°C overnight. DMF was removed under vacuum, and the solid polymer was washed twice with cold DMF (25 ml per wash). The polymer (PECNQ) was dried under vacuum. The reaction scheme for polymer formation is shown in Figure 13.

[0198] The method of the above example can also be carried out using 0.5 to 1 g of polyethylene with 100 to 250 mL of DMF.

[0199] The resulting polymer PECNQ was a dark-colored material. The polymer PECNQ was highly responsive to applied charges, responded to external magnetic fields, and had potential to be used in industrial applications. In FTIR analysis, 2220 cm -1 showed two absorption peaks, confirming the presence of TCNQ moieties bound to the PE chains. UV analysis also confirmed the presence of both quinoid and zwitterionic forms. X-ray analysis showed that the presence of the TCNQ moieties imparted a certain degree of crystallinity to the polymer backbone compared to the starting material PE.

[0200] [Example 20] Characterization of polymer PECNQ using electron spin resonance (ESR) spectroscopy A sample of the polymer (PECNQ) produced in Example 19 was analyzed using ESR spectroscopy (see Figure 23). The ESR data indicated the presence of many free electrons or spins within the polymer backbone affected by the addition of the TCNQ moieties, and a value of 1×10 18 spins per gram of polymer was calculated.

[0201] References

[0202] [Table 1]

[0203] Embodiments of the Invention Embodiments of the present invention are described below. These embodiments define preferred combinations of features. The applicant reserves the right to pursue protection for any combination of these features and / or any other subject matter contained in the present application at the time of filing the present application or any divisional application thereof. The following numbered embodiments are not the claims of the present application contained in a separate section entitled "Claims".

[0204] [1] A substituted conjugated polymer comprising a conjugated polymer containing a repeating unit having two or more nitrogen atoms adjacent to each other, wherein the repeating unit is substituted with at least one organic electron acceptor capable of forming a stable zwitterion.

[0205] [2] The substituted conjugated polymer according to embodiment [1], wherein the nitrogen atoms are separated by no more than 4 bonds.

[0206] [3] The substituted conjugated polymer according to embodiment [1] or [2], wherein the nitrogen atoms are separated by no more than 3 bonds.

[0207] [4] The substituted conjugated polymer according to any one of embodiments [1] to [3], wherein the repeating units are present in the conjugated polymer at regular intervals.

[0208] [5] The substituted conjugated polymer according to any one of embodiments [1] to [4], wherein the repeating unit comprises one or more aromatic groups.

[0209] [6] The substituted conjugated polymer according to any one of embodiments [1] to [5], wherein the repeating unit comprises one or more aromatic groups, and at least one of the aromatic groups comprises a fused ring.

[0210] [7] The substituted conjugated polymer according to embodiment [5] or [6], wherein the nitrogen atoms are present in one or more of the aromatic groups.

[0211] [8] The substituted conjugated polymer according to embodiment [6] or [7], wherein the nitrogen atoms are present in the same ring of the fused aromatic moiety.

[0212] [9] A substituted conjugated polymer according to any one embodiment of [1] to [8], wherein the repeating unit comprises an imidazyl moiety.

[0213]

[10] A substituted conjugated polymer according to any one embodiment of Embodiments [1] to [9], wherein the repeating unit comprises a benzimidadyl moiety.

[0214]

[11] A substituted conjugated polymer according to any one embodiment of [1] to

[10] , wherein the conjugated polymer is polybenzimidazole.

[0215]

[12] The substituted conjugated polymer according to any one embodiment of [1] to

[11] , wherein the conjugated polymer can be obtained from diaminobenzidine and terephthalic acid monomers.

[0216]

[13] A substituted conjugated polymer according to any one embodiment of Embodiments [1] to

[12] , wherein the number average molecular weight of the conjugated polymer is in the range of 4,000 to 200,000 daltons.

[0217]

[14] A substituted conjugated polymer according to any one embodiment of [1] to

[13] , wherein the electron acceptor is selected from quinone, fumarate, trimethylamine N-oxide and dimethyl sulfoxide derivatives.

[0218]

[15] The electron acceptor Tetracyanoquinodimethane (TCNQ) Tetafluorotetracyanoquinodimethane (TCNQF4) 2,5-Dibromotetracyanoquinodimethane (TCNQBr2) Tetracyanoethylene (TCNE) Dichlorodicyanobenzoquinone (DDQ), or TCNQ derivative A substituted conjugated polymer according to any one embodiment [1] to

[14] derived from [1].

[0219]

[16] The electron acceptor is given by formula I:

[0220] [ka] [In the formula, Is R1=R2=R3=R4=H, F, Me, or Et? R1=R2=H, Br, I, Me or Et, OMe, CN, PhCH2, C1~C8 alkyl group (preferably hexyl, Me, Et or iPr), and R3 and R4 are selected from H, F, Me or Et. R2=R4=H, R1=OMe, and R3=OEt, O i Pr, O i Bu, or R2=R4=H and R1=OEt and R3=SMe, or R2=R4=H and R3=Me and R1=I, Br or Cl, or R1=R2=OCH2CH2O and R3=OMe and R4=H, or R2=R4=H and R3=Br and R1=OCH2CH2OH, or R2=R3=R4=H and R1=Me, Et, OMe, CO2Me. A substituted conjugated polymer according to embodiment

[15] , derived from a TCNQ derivative having the above.

[0221]

[17] The electron acceptor is formula II, III, IV, or V:

[0222] [ka] A substituted conjugated polymer according to embodiment

[15] , derived from a TCNQ derivative having the above.

[0223]

[18] The substituted conjugated polymer according to Embodiment

[21] , wherein the electron acceptor is derived from tetracyanoquinone dimethane (TCNQ).

[0224]

[19] A substituted conjugated polymer according to any one embodiment of [1] to

[18] , wherein each repeating unit having two or more nitrogen atoms in close proximity to each other is substituted with two or more organic electron acceptors capable of forming a stable zwitterion.

[0225]

[20] A substituted conjugated polymer according to any one embodiment of [1] to

[19] , wherein each repeating unit having two or more nitrogen atoms in close proximity to each other is substituted with three organic electron acceptors capable of forming a stable zwitterion.

[0226]

[21] A substituted conjugated polymer according to any one embodiment of [1] to

[20] , which is polybenzimidazole tricyanoquinone dimethane (PBICNQ).

[0227]

[22] An electroactive material comprising a substituted conjugated polymer according to any one embodiment of [1] to

[21] .

[0228]

[23] An electroactive material according to embodiment

[22] , which is highly charged at room temperature.

[0229]

[24] A method for producing a substituted conjugated polymer according to any one embodiment of [1] to

[21] , comprising reacting the conjugated polymer with an organic electron acceptor.

[0230]

[25] The following steps: a) A step of dissolving the conjugated polymer in a suitable solvent, b) Adding an organic electron acceptor to the solution and heating the resulting mixture, c) The solid obtained in step b is cooled and filtered, d) Optionally, a step to evaporate the filtrate obtained from step c) to recover more product, e) A step of drying the product and The method according to embodiment

[24] , including the method described in embodiment

[24] .

[0231]

[26] The method according to embodiment

[25] , wherein the molar ratio of the conjugated polymer to the organic electron acceptor in the mixture of step b is approximately 1:3.

[0232]

[27] The method according to any one embodiment of

[24] to

[26] , wherein the electron acceptor is tetracyanoquinone dimethane (TCNQ).

[0233]

[28] The method according to any one embodiment of Embodiments

[24] to

[27] , wherein the conjugated polymer is a polybenzimidazole or a polymer obtained from substituted diaminobenzidine and terephthalic acid monomers.

Claims

1. A polymer comprising a polymer skeleton and pendant groups that are organic electron acceptors capable of forming stable zwitterions, and which is paramagnetic.

2. The polymer according to claim 1, which is superparamagnetic.

3. Mass magnetization at room temperature is 0.003 JT －１ kg －１ The polymer according to claim 1 or 2, wherein the polymer is less than [amount missing].

4. The polymer according to any one of claims 1 to 3, wherein the polymer skeleton comprises a repeating unit having one or more aromatic groups.

5. The polymer according to claim 4, wherein at least one of the aromatic groups includes a fused ring, and a nitrogen atom is present within one or more of the aromatic groups.

6. The polymer according to claim 4 or 5, wherein the polymer skeleton is derived from a polymer selected from polybenzimidazole and polyetherimide.

7. The polymer according to claim 4, wherein the repeating unit includes a benzophenone moiety.

8. The paramagnetic polymer according to claim 7, wherein the polymer skeleton is derived from a polyether ether ketone.

9. The polymer according to any one of claims 1 to 3, wherein the polymer backbone comprises repeating units comprising one or more aliphatic chains.

10. The polymer according to claim 9, wherein the aliphatic chain is linear.

11. The polymer according to claim 9 or 10, wherein the polymer backbone is derived from a polymer selected from polyacrylonitrile, polyethylene glycol, and polyethylene.

12. The polymer according to any one of claims 1 to 3, wherein the polymer skeleton is selected from the group consisting of polysiloxane, polyisoprene, polysaccharide, polyol, polypeptide, DNA fragment, or RNA fragment.

13. The polymer according to any one of claims 1 to 12, wherein the number-average molecular weight of the polymer is in the range of 4,000 to 200,000 Daltons.

14. The polymer according to any one of claims 1 to 13, wherein the pendant group, which is an organic electron acceptor, is present in an amount of 0.2 to 10 per monomer unit.

15. The polymer according to any one of claims 1 to 14, wherein the electron acceptor is selected from quinone, fumarate, trimethylamine N-oxide, and dimethyl sulfoxide derivatives.

16. The aforementioned electron acceptor, Tetracyanoquinodimethane (TCNQ) Tetafluorotetracyanoquinodimethane (TCNQF4) 2,5-Dibromotetracyanoquinodimethane (TCNQBr2) Tetracyanoethylene (TCNE) Dichlorodicyanobenzoquinone (DDQ), or TCNQ derivatives A polymer according to any one of claims 1 to 15, derived from [the specified source].

17. The electron acceptor is given by formula I: 【Chemistry 1】 [In the formula, R １ = R ２ = R ３ = R ４ = H, F, Me, or Et, R １ =R ２ =H, Br, I, Me or Et, OMe, CN, PhCH ２ , C １ to C ８ alkyl group (preferably hexyl, Me, Et or iPr), and R ３ and R ４ are selected from H, F, Me or Et, or R ２ = R ４ = H and R １ = OMe and R ３ = OEt, O ｉ Pr, O ｉ Is it Bu, or R ２ = R ４ = H and R １ = OEt and R ３ = SMe, or R ２ = R ４ = H and R ３ = Me and R １ = I, Br, or Cl, or R １ = R ２ = OCH ２ CH ２ O and R ３ = OMe and R ４ = H, or R ２ = R ４ = H and R ３ = Br and R １ = OCH ２ CH ２ It is OH, or R ２ = R ３ = R ４ = H and R １ =Me, Et, OMe, CO ２ [I am Me] The polymer according to claim 16, derived from a TCNQ derivative having the above properties.

18. The electron acceptor is formula II, formula III, formula IV, or formula V: 【Chemistry 2】 A paramagnetic polymer according to claim 16, derived from a TCNQ derivative having the above.

19. The paramagnetic polymer according to claim 16, wherein the electron acceptor is derived from tetracyanoquinone dimethane (TCNQ).

20. A polymer according to any one of claims 1 to 19, selected from the group consisting of polybenzimidazole tricyanoquinone dimethane (PBICNQ), sulfonated polyetheretherketone tricyanoquinone dimethane (SPEEKCNQ), polyetherimide tricyanoquinone dimethane (PEICNQ), polyacrylonitrile tricyanoquinone dimethane (PANCNQ), polyethylene glycol tricyanoquinone dimethane (PEGCNQ), and polyethylene tricyanoquinone dimethane (PECNQ).

21. The polymer according to any one of claims 1 to 20, wherein the polymer is polybenzimidazole tricyanoquinone dimethane (PBICNQ).

22. An electroactive material comprising a paramagnetic polymer according to any one of claims 1 to 21.

23. The electroactive material according to claim 22, which is highly charged at room temperature.

24. A method for producing a paramagnetic polymer, comprising reacting a precursor polymer with an organic electron acceptor, The following steps: a) The step of dissolving the precursor polymer in a suitable solvent, b) Adding the organic electron acceptor to the solution and heating the resulting mixture, c) The solid obtained in step b is cooled and filtered, d) Optionally, a step to evaporate the filtrate obtained from step c) to recover more product, e) A step of drying the product Methods that include...

25. The method according to claim 24, wherein the precursor polymer is completely dissolved in the solvent used in step a) under the reaction conditions.

26. The method according to claim 24 or 25, wherein the solvent is selected from the group consisting of dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and tetrahydrofuran (THF).

27. The method according to any one of claims 24 to 26, wherein the molar ratio of the precursor polymer to the organic electron acceptor in the mixture of step b is approximately 1:

3.

28. The method according to any one of claims 24 to 27, wherein the electron acceptor is tetracyanoquinone dimethane (TCNQ).

29. The method according to any one of claims 24 to 28, wherein the precursor polymer is selected from the group consisting of polybenzimidazole (PBI), sulfonated polyetheretherketone (SPEEK), polyetherimide (PEI), polyacrylonitrile (PAN), polyethylene glycol (PEG), and polyethylene (PE).

30. The method according to any one of claims 24 to 29, wherein the precursor polymer is polybenzimidazole or a polymer obtained from substituted diaminobenzidine and terephthalic acid monomers.

31. A polymer that can be obtained by the method described in any one of claims 24 to 30.

32. A graphite, graphene, or fullerene containing a pendant group which is an organic electron acceptor capable of forming a stable zwitterion, and which is paramagnetic.

33. The graphite, graphene, or fullerene according to claim 32, which is superparamagnetic.

34. Mass magnetization at room temperature is 0.003 JT －１ kg －１ A graphite, graphene, or fullerene according to claim 32 or 33, which is less than [amount missing].

35. The graphite, graphene, or fullerene according to any one of claims 32 to 34, wherein the electron acceptor is selected from quinone, fumarate, trimethylamine N-oxide, and dimethyl sulfoxide derivatives.

36. The aforementioned electron acceptor, Tetracyanoquinodimethane (TCNQ) Tetafluorotetracyanoquinodimethane (TCNQF4) 2,5-Dibromotetracyanoquinodimethane (TCNQBr2) Tetracyanoethylene (TCNE) Dichlorodicyanobenzoquinone (DDQ), or TCNQ derivatives A graphite, graphene, or fullerene according to any one of claims 32 to 35, derived from the above.

37. The electron acceptor is given by formula I: 【Transformation 3】 [In the formula, R １ = R ２ = R ３ = R ４ = H, F, Me, or Et, R １ = R ２ = H, Br, I, Me or Et, OMe, CN, PhCH ２ , C １ ~C ８ The alkyl group is preferably hexyl, Me, Et, or iPr, and R ３ and R ４ The following can be selected from H, F, Me, or Et, R ２ = R ４ = H and R １ = OMe and R ３ = OEt, O ｉ Pr, O ｉ Is it Bu, or R ２ = R ４ = H and R １ = OEt and R ３ = SMe, or R ２ = R ４ = H and R ３ = Me and R １ = I, Br, or Cl, or R １ = R ２ = OCH ２ CH ２ O and R ３ = OMe and R ４ = H, or R ２ = R ４ = H and R ３ = Br and R １ = OCH ２ CH ２ It is OH, or R ２ = R ３ = R ４ = H and R １ =Me, Et, OMe, CO ２ [I am Me] The graphite, graphene, or fullerene according to claim 36, derived from a TCNQ derivative having the above.

38. The electron acceptor is formula II, formula III, formula IV, or formula V: 【Chemistry 4】 The graphite, graphene, or fullerene according to claim 36, derived from a TCNQ derivative having the above.

39. The graphite, graphene, or fullerene according to claim 36, wherein the electron acceptor is derived from tetracyanoquinone dimethane (TCNQ).

40. An electroactive material comprising graphite, graphene, or fullerene according to any one of claims 32 to 39.

41. The electroactive material according to claim 40, which is highly charged at room temperature.

42. Octasulfur containing a pendant group, which is an organic electron acceptor capable of forming a stable zwitterion, and which is paramagnetic.

43. The octagonal sulfur according to claim 42, which is superparamagnetic.

44. The mass magnetization at room temperature is 0.003 JT －１ kg －１ less than that, the octasulfur according to claim 42 or 43.

45. The octasulfur according to any one of claims 42 to 44, wherein the electron acceptor is selected from quinone, fumarate, trimethylamine N-oxide, and dimethyl sulfoxide derivatives.

46. The electron acceptor Tetracyanoquinodimethane (TCNQ) Tetafluorotetracyanoquinodimethane (TCNQF4) 2,5-Dibromotetracyanoquinodimethane (TCNQBr2) Tetracyanoethylene (TCNE) Dichlorodicyanobenzoquinone (DDQ), or TCNQ derivatives Octasulfur according to any one of claims 42 to 45, derived from.

47. The electron acceptor is given by formula I: 【Transformation 5】 [In the formula, R １ = R ２ = R ３ = R ４ = H, F, Me, or Et, R １ =R ２ =H, Br, I, Me or Et, OMe, CN, PhCH ２ , C １ to C ８ alkyl group (preferably hexyl, Me, Et or iPr), R ３ and R ４ are selected from H, F, Me or Et, or R ２ = R ４ = H and R １ = OMe and R ３ = OEt, O ｉ Pr, O ｉ Is it Bu, or R ２ = R ４ = H and R １ = OEt and R ３ = SMe, or R ２ = R ４ = H and R ３ = Me and R １ = I, Br, or Cl, or R １ = R ２ = OCH ２ CH ２ O and R ３ = OMe and R ４ = H, or R ２ = R ４ = H and R ３ = Br and R １ = OCH ２ CH ２ It is OH, or R ２ = R ３ = R ４ = H and R １ =Me, Et, OMe, CO ２ [I am Me] The octulfur according to claim 46, derived from a TCNQ derivative having the above properties.

48. The electron acceptor is formula II, formula III, formula IV, or formula V: 【Transformation 6】 The octulfur according to claim 46, derived from a TCNQ derivative having the above properties.

49. The octasulfur according to claim 46, wherein the electron acceptor is derived from tetracyanoquinone dimethane (TCNQ).

50. An electroactive material containing octasulfur according to any one of claims 42 to 49.

51. The electroactive material according to claim 50, which is highly charged at room temperature.

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