TEMPO polymer as well as preparation method and application thereof

Abstract

The invention provides a TEMPO polymer and a preparation method and application thereof.The polymer comprises a structure shown in the formula I. The polymer is wide in application, can be used for preparing a positive electrode material of a flow battery and can also serve as a flame retardant, a light stabilizer, an antistatic agent and the like to be used for high polymer materials, coatings, pigments, paint, printing ink and adhesives to delay or prevent aging of the high polymer materials, the coatings, the pigments, the paint, the printing ink and the adhesives. And the polymer can also be used in the fields of automobile interior or exterior decoration materials, floating devices, road traffic devices, agricultural products, electric appliances, furniture, shoes, sanitary products, health-care products and the like. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to the field of polymer technology, and particularly relates to a TEMPO polymer, a preparation method thereof, and an application thereof. Background Art

[0002] With the development of society and the rapid increase in population, people have a huge demand for energy. Fossil energy is a typical non-renewable energy source, and a large amount of greenhouse gases will be generated during its consumption. Therefore, the energy crisis problem is becoming increasingly prominent. In order to actively address these problems, energy storage technologies have emerged.

[0003] Energy storage technology is a technology that stores energy through a medium or device and then releases the energy according to actual conditions to achieve the function of energy regulation. A flow battery is a technology that can achieve controllable energy storage and release through a reversible redox reaction of a liquid electrolyte. Its unique structure gives the flow battery inherent advantages of being independent, flexible, and adjustable, and is very suitable for large-scale energy storage.

[0004] Among them, aqueous flow batteries use widely available organic molecules as electrochemically active substances and water as a solvent. Especially for battery systems operating under neutral conditions, the requirements for equipment investment and maintenance are low, and the cost requirements are relatively low. As a representative of them, the TEMPO flow battery stands out among the battery materials of flow batteries due to its low raw material cost.

[0005] It should be noted that most of the active substances with a TEMPO structure have low solubility in aqueous solutions. At the same time, during the long-term charge-discharge cycle process, due to the occurrence of side reactions, the structure of the electrolyte is damaged, resulting in a decrease in the battery capacity and low long-term cycle stability. Therefore, it is necessary to further develop new TEMPO flow batteries.

[0006] In addition, various different groups can be grafted onto TEMPO and added to chemical materials to delay their aging, extend their lifespan, or increase their antistatic performance. Therefore, it is necessary to further develop new additives containing TEMPO groups. Summary of the Invention

[0007] To overcome the deficiencies of the prior art, the present invention provides a TEMPO polymer, a preparation method thereof, and an application thereof.

[0008] In the first aspect of the present invention, a polymer is provided, which comprises the structure shown in Formula I:

[0009]

[0010] Wherein,

[0011] Y1 is selected from: O, NH;

[0012] X is selected from: Cl, Br, I;

[0013] R1 and R2 are independently selected from: a single bond,

[0014] R3, R4, R5, R7, R8, R9 are independently selected from: C1-C 10 alkyl;

[0015] R6 is selected from: H, C1-C 10 alkyl;

[0016] Y2 is selected from: O, NH;

[0017] m is an integer from 1 to 20 (such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20);

[0018] n and p are independently integers from 1 to 20 (such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20);

[0019] f is an integer from 2 to 6 (such as 2, 3, 4, 5, 6).

[0020] Furthermore, the molecular weight of the polymer is 1000 - 50000 (such as 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, 10000, 11000, 11500, 12000, 12500, 13000, 13500, 14000, 14500, 15000, 15500, 16000, 16500, 17000, 17500, 18000, 18500, 19000, 19500, 20000, 21000, 21500, 22000, 22500, 23000, 23500, 24000, 24500, 25000, 25500, 26000, 26500, 27000, 27500, 28000, 28500, 29000, 29500, 30000, 31000, 31500, 32000, 32500, 33000, 33500, 34000, 34500, 35000, 35500, 36000, 36500, 37000, 37500, 38000, 38500, 39000, 39500, 40000, 41000, 41500, 42000, 42500, 43000, 43500, 44000, 44500, 45000, 45500, 46000, 46500, 47000, 47500, 48000, 48500, 49000, 49500, 50000), preferably 2000 - 20000.

[0021] Furthermore, R3 is a C1 - C6 alkyl group, such as preferably -CH3.

[0023] Furthermore, R4 is a C1 - C6 alkyl group, preferably -CH3.

[0024] Furthermore, R5 is a C1 - C6 alkyl group, preferably -CH3.

[0025] Furthermore, R7 is a C1 - C6 alkyl group, preferably -CH3.

[0026] Furthermore, R8 is a C1 - C6 alkyl group, preferably -CH3.

[0027] Furthermore, R9 is a C1 - C6 alkyl group, preferably -CH3.

[0028] Furthermore, R6 is H or a C1 - C6 alkyl group, preferably H or -CH3.

[0029] Furthermore, f is an integer from 2 to 4, preferably 2.

[0030] Furthermore, the polymer has the following structure:

[0031]

[0032] Wherein, R T1 , R T2 are capping groups, for example,

[0033] In a second aspect of the present invention, there is provided a method for preparing the polymer according to the first aspect, and the preparation method includes the following steps:

[0034] S1: Add the compound of the structure shown in Formula II and the compound of the structure shown in Formula III into an organic solvent, and react to obtain the compound of the structure shown in Formula IV;

[0035] S2: Carry out a polymerization reaction on the compound of the structure shown in Formula IV under the action of an initiator to obtain a polymer containing the structure shown in Formula I; or,

[0036] Carry out a polymerization reaction on the compound of the structure shown in Formula IV with the compound of the structure shown in Formula V and / or the compound of the structure shown in Formula VI under the action of an initiator to obtain a polymer containing the structure shown in Formula I;

[0037]

[0038] Wherein, Y1, Y2, X, R3, R4, R5, R6, R7, R8, R9, f have the definitions described in the first aspect of the present invention.

[0039] Furthermore, in the step S1, the organic solvent is a polar solvent, and it is selected from one or more of: N,N-dimethylformamide, acetonitrile, dimethyl sulfoxide, methanol, ethanol, and water.

[0040] Further, in the step S1, the molar ratio of the compound of the structure shown in Formula II to the compound of the structure shown in Formula III is 1:0.1 - 10 (such as 1:0.1, 1:0.2, 1:0.3, 1:0.4, 1:0.5, 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1:1.1, 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, 1:2.2, 1:2.4, 1:2.6, 1:2.8, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:9.5, 1:10), preferably 1:1 - 1.5, and more preferably 1:1.

[0041] Further, in the step S1, the reaction temperature is 30 - 150 °C (such as 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58, 60, 62, 64, 66, 68, 70, 72, 74, 76, 78, 80, 82, 84, 86, 88, 90, 92, 94, 96, 98, 100, 102, 104, 106, 108, 110, 112, 114, 116, 118, 120, 122, 124, 126, 128, 130, 132, 134, 136, 138, 140, 142, 144, 146, 148, 150 °C).

[0042] Further, in the step S1, the reaction time is 4 - 48 hours (such as 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48 hours).

[0043] Further, in the step S2, the initiator is selected from one or more of: N,N-dimethylformamide, 4,4'-azobis(4-cyanovaleric acid), azobisisobutyronitrile, azodiisooctanenitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 1,1'-azobis(cyclohexanenitrile), azodiisopentanenitrile, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-imidazoline) dihydrochloride, 1-((cyano-1-methylethyl)azo)formamide, azobis(2-methylimidazoline) hydrochloride, tert-butyl hydroperoxide, hydrogen peroxide.

[0044] Further, in the step S2, the reaction temperature is 30 - 150 °C (such as 30, 32, 34, 36, 38, 40, 42, 44, 46, 48, 50, 52, 54, 56, 58, 60, 62, 64, 66, 68, 70, 72, 74, 76, 78, 80, 82, 84, 86, 88, 90, 92, 94, 96, 98, 100, 102, 104, 106, 108, 110, 112, 114, 116, 118, 120, 122, 124, 126, 128, 130, 132, 134, 136, 138, 140, 142, 144, 146, 148, 150 °C).

[0045] Further, in the step S2, the reaction time is 2 - 12 hours (such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 hours).

[0046] Further, in the step S2, the polymerization reaction is carried out in an acidic system.

[0047] Further, the acidic system is obtained by adding an acidic reagent, and the acidic reagent is selected from: one or more of hydrogen halide, sulfuric acid, phosphoric acid, nitric acid, perchloric acid, acetic acid, trifluoromethanesulfonic acid, water, preferably an aqueous solution of hydrogen halide, such as an aqueous solution of HF, an aqueous solution of HCl, an aqueous solution of HBr, an aqueous solution of HI, and more preferably an aqueous solution of HCl or an aqueous solution of HBr.

[0048] Further, in the step S2, the polymerization reaction also needs to react under the action of 2 - mercaptoethanol.

[0049] Further, the preparation method further includes: filtering and concentrating the polymer shown in formula I.

[0050] In the third aspect of the present invention, there is provided an application of the polymer described in the first aspect as a positive electrolyte of a flow battery system.

[0051] In the fourth aspect of the present invention, there is provided a flow battery system comprising the polymer described in the first aspect, including a positive electrode storage tank, a negative electrode storage tank, and a flow battery stack; both ends of the flow battery stack are respectively connected to the positive electrode storage tank and the negative electrode storage tank.

[0052] Further, the positive electrode storage tank and the negative electrode storage tank are respectively storage tanks storing electrolytes. The positive electrode storage tank contains a positive electrode active material and a supporting electrolyte, and the negative electrode storage tank contains a negative electrode active material and a supporting electrolyte. The positive electrode active material and the negative electrode active material are directly dissolved or dispersed in a water-based solvent system in a bulk form, and the positive electrode active material is the polymer described in the first aspect.

[0053] Furthermore, the flow battery stack includes a battery separator which divides the flow battery stack into a positive electrode region and a negative electrode region. The positive electrode region is communicated with a positive electrode liquid storage tank, and the negative electrode region is communicated with a negative electrode liquid storage tank.

[0054] Furthermore, the negative electrode active material is methyl viologen and / or a derivative of methyl viologen.

[0055] Furthermore, the concentration of the positive electrode active material is 0.05 - 3 mol / L (such as 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.22, 0.24, 0.26, 0.28, 0.30, 0.32, 0.34, 0.36, 0.38, 0.40, 0.42, 0.44, 0.46, 0.48, 0.50, 0.55, 1.0, 1.5, 2.0, 2.5, 3.0 mol / L), preferably 0.1 mol / L.

[0056] Furthermore, the concentration of the negative electrode active material is 0.05 - 3 mol / L (such as 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.22, 0.24, 0.26, 0.28, 0.30, 0.32, 0.34, 0.36, 0.38, 0.40, 0.42, 0.44, 0.46, 0.48, 0.50, 0.55, 1.0, 1.5, 2.0, 2.5, 3.0 mol / L), preferably 0.1 mol / L.

[0057] Furthermore, the supporting electrolyte is selected from one or more of an aqueous solution of NaCl, an aqueous solution of KCl, an aqueous solution of Na2SO4, an aqueous solution of K2SO4, an aqueous solution of MgCl2, an aqueous solution of MgSO4, an aqueous solution of CaCl2, and an aqueous solution of NH4Cl, preferably an aqueous solution of NaCl or an aqueous solution of KCl.

[0058] Further, the concentration of the supporting electrolyte is 0.1 - 8 mol / L (such as 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0 mol / L), preferably 1.0 mol / L.

[0059] Further, the positive electrode liquid storage tank and the negative electrode liquid storage tank are pressurized sealed containers with a pressure of 0.1 - 0.5 MPa.

[0060] Further, an inert gas (such as argon) is introduced into the positive electrode liquid storage tank and the negative electrode liquid storage tank for purging and maintaining pressure.

[0061] Further, the battery separator is selected from: cation exchange membrane, anion exchange membrane, selective permeation membrane, polymer porous membrane.

[0062] Further, the battery separator can penetrate the supporting electrolyte and prevent the penetration of the positive electrode active material and the negative electrode active material.

[0063] Further, electrodes are respectively arranged in the positive electrode area and the negative electrode area, the electrodes are carbon material electrodes, and the carbon material electrodes are selected from one or more of: carbon felt, carbon paper, carbon cloth, carbon black, activated carbon fiber, activated carbon particles, graphene, graphite felt, glass carbon material.

[0064] Further, the electrodes are formed into electrode plates.

[0065] Further, a positive electrode current collector is installed in the positive electrode area, and a negative electrode current collector is installed in the negative electrode area; the current collector can collect and conduct the current generated by the active material of the flow battery stack to an external wire.

[0066] Further, the current collector is selected from: conductive metal plate, graphite plate, carbon-plastic composite plate.

[0067] Further, the conductive metal plate contains at least one metal of copper, nickel, and aluminum.

[0068] Further, the positive electrode area is communicated with the positive electrode liquid storage tank through a positive electrode circulation pipeline, and the negative electrode area is communicated with the negative electrode liquid storage tank through a negative electrode circulation pipeline.

[0069] Further, the flow battery system further includes a pump group system for transporting the electrolyte.

[0070] Further, the pump group is selected from: peristaltic pumps, mechanical pumps, and magnetic pumps.

[0071] In a fifth aspect of the present invention, there is provided a liquid composition comprising the polymer according to the first aspect and a dispersion of fine particulate solid materials selected from pigments and fillers and a liquid diluent.

[0072] Further, the liquid diluent is selected from one or more of: water, alcohols (such as ethanol, isopropanol, tert-butanol), ketones (such as acetone, dibutyl ketone), ethers (such as diethyl ether, petroleum ether), esters (such as ethyl acetate, ethyl formate), and is preferably ethanol and / or water.

[0073] Further, the liquid composition can be used as an additive in high molecular materials, coatings, pigments, paints, inks or adhesives.

[0074] In a sixth aspect of the present invention, there is provided a composition comprising the polymer according to the first aspect and an organic substance sensitive to light, heat or oxidation.

[0075] Further, the organic substance is selected from one or more of: polyolefins, acrylonitrile, butadiene, styrene, polyvinyl chloride, polymethyl methacrylate, polyacetal, polyamide, polyimide, epoxy resin, polyurethane, polycarbonate, polyurethane, polyester, polysulfone, polyurea, polystyrene, thermoplastic elastomers.

[0076] Further, the composition can be used as an additive in high molecular materials, coatings, pigments, paints, inks or adhesives, such as light stabilizers, flame retardants, antistatic agents.

[0077] Further, the amount of the polymer is determined by the nature of the organic substance, the end use and the additive, and the polymer can be used in various proportions.

[0078] Further, the amount of the polymer is 0.01-50 wt% (such as 0.01, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50%) of the weight of the product, preferably 0.01-10 wt%, more preferably 0.01-5 wt%.

[0079] Further, the product is selected from: high molecular materials, coatings, pigments, paints, inks, adhesives.

[0080] Furthermore, the composition further comprises an auxiliary agent.

[0081] Furthermore, the auxiliary agent is selected from one or more of the following: antioxidant, UV absorber, hindered amine light stabilizer, reinforcing agent, filler, flame retardant, plasticizer, lubricant, emulsifier, pigment, rheological additive, catalyst, flow control agent, optical brightener, fireproofing agent, antistatic agent, foaming agent.

[0082] Furthermore, the antioxidant is selected from one or more of the following: phenolic antioxidant, amine antioxidant, phosphite, thioester, such as antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 168, etc.

[0083] Furthermore, the UV absorber is selected from one or more of the following: salicylate, benzoate, benzophenone, benzotriazole, triazine.

[0084] Furthermore, the hindered amine light stabilizer is selected from one or more of the following: bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, polymer of succinic acid and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidylethanol, Chimassorb 944, Chimassorb2020, UV-3346, UV-3529, Tinuvin 770, Tinuvin 622LD, Tinuvin292, HS-625, HS-950.

[0085] Furthermore, the filler or reinforcing agent is selected from one or more of the following: calcium carbonate, silicate, glass fiber, glass bead, asbestos, talc, kaolin, mica, barium sulfate, metal oxide, hydroxide, carbon black, graphite, wood powder, flour, natural product fiber, synthetic fiber.

[0086] In the seventh aspect of the present invention, there is provided an application of the polymer according to the first aspect, the liquid composition according to the fifth aspect or the composition according to the sixth aspect as an additive in high molecular materials, coatings, pigments, paints, inks or adhesives.

[0087] Furthermore, the additive is a surface product additive.

[0088] Furthermore, the additive is an additive for solid materials.

[0089] Furthermore, the additive is a resin component, light stabilizer, thickener, dispersant, flame retardant, antistatic agent.

[0090] Further, the resin component, light stabilizer, thickener, dispersant, flame retardant, and antistatic agent can delay or prevent the aging of polymer materials, coatings, pigments, paints, inks, and adhesives, and improve their service performance, service life, and antistatic performance.

[0091] Further, the polymer material can be selected from: polyolefins, polyesters, polyethers, polyketones, polyamides, natural and synthetic rubbers, polyurethanes, high-impact polystyrene, polyacrylates, polymethacrylates, polyacetals, polyacrylonitriles, polybutadienes, polystyrenes, acrylonitrile-butadiene-styrene, styrene acrylonitrile, acrylate styrene acrylonitrile, cellulose acetate butyrate, cellulose polymers, polyimides, polyamideimides, polyetherimides, polyphenylene sulfides, polyphenylene ether polysulfones, polyethersulfones, polyvinyl chlorides, polycarbonates, amino resin-crosslinked polyacrylates and polyesters, polyisocyanate-crosslinked polyesters and polyacrylates, phenol / formaldehyde, urea / formaldehyde, and melamine / formaldehyde resins, alkyd resins, acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, urethanes, and epoxy resins, crosslinked epoxy resins derived from aliphatic, alicyclic, heterocyclic, and aromatic glycidyl compounds, which are crosslinked with acid anhydrides or amines, polysiloxanes, Michael addition polymers, amines, amines blocked with activated unsaturated and methylene compounds, ketimines having activated unsaturated and methylene compounds, polyketimines combined with unsaturated acrylic polyacetoacetate resins, polyketimines combined with unsaturated acrylic resins, radiation-curable compositions, epoxy melamine resins, organic dyes, cosmetic products, cellulose-based paper formulations, photographic film paper, fibers, waxes, inks, and their blends, especially polyurethanes, polycarbonates, and polyesters.

[0092] In an eighth aspect of the present invention, there is provided an application of the polymer according to the first aspect, the liquid composition according to the fifth aspect, or the composition according to the sixth aspect in the preparation of an additive.

[0093] Further, the additive is a resin component, light stabilizer, thickener, dispersant, flame retardant, and antistatic agent.

[0094] Further, the resin component, light stabilizer, thickener, dispersant, flame retardant, and antistatic agent can be independently used for polymer materials, coatings, pigments, paints, inks, and adhesives to delay or prevent their aging and improve their service performance, service life, and antistatic performance.

[0095] In a ninth aspect of the present invention, there is provided an application of the polymer according to the first aspect, the liquid composition according to the fifth aspect, or the composition according to the sixth aspect as an additive in the surface coating of articles.

[0096] Further, the article is selected from: plastics, rubbers, fibers, coatings, pigments, paints, inks, adhesives, binders, composite materials, etc., and can be used in fields such as automotive interior or exterior decoration materials, floating devices, road traffic devices, agricultural products, electrical appliances, furniture, footwear, sanitary products, health care products, etc.

[0097] Further, plastic products can be manufactured by any method known to those skilled in the art, including but not limited to, extrusion, extrusion blow molding, film casting, calendering, injection molding, blow molding, compression molding, thermoforming, spin forming, coextrusion, and rotational casting.

[0098] Compared with the prior art, the present invention has the following advantages:

[0099] (1) The raw materials used in the present invention have a wide source and low cost;

[0100] (2) The overall operation steps of the present invention are simple, the reaction is safe and reliable, and it is suitable for industrial production;

[0101] (3) The polymer prepared by the present invention can not only be applied to the positive electrode material of the flow battery, but also be used as a flame retardant, a light stabilizer, and an antistatic agent;

[0102] (4) The molecular structure of the high molecular weight modified TEMPO has an increased steric hindrance, which inhibits the degradation of TEMPO, is not easily penetrated in the selective permeable membrane, and enhances the cycle stability of the flow battery. Detailed Embodiments

[0103] Unless otherwise defined, all scientific and technical terms used in the present invention have the same meaning as commonly understood by those skilled in the technical field to which the present invention pertains.

[0104] The term "alkyl" refers to a straight-chain or branched-chain hydrocarbon chain radical that does not contain unsaturated bonds, and the hydrocarbon chain radical is connected to other parts of the molecule by a single bond. Typical alkyl groups contain 1 to 10 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10) carbon atoms, preferably 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, isohexyl, etc. In the present invention, C0 alkyl refers to H, i.e., C 0-10 alkyl (or C0-C 10 alkyl) includes H and C 1-10 alkyl (or C1-C 10 alkyl).

[0105] The term "alkylene" refers to a hydrocarbon group (divalent alkyl group) formed by removing two hydrogen atoms from an alkane molecule. It can be straight-chain or branched-chain and is connected to other parts of the molecule by a single bond. In this text, typical alkylene groups have 1 to 10 (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10) carbon atoms, preferably 1 to 6 carbon atoms, such as methylene (-CH2-), ethylene, propylene, butylene, etc. In the present invention, C0 alkylene refers to a single bond, that is, C 0-10 alkylene (or C0-C 10 alkylene) includes a single bond and C 1-10 alkylene (or C1-C 10 alkylene).

[0106] The term "cycloalkyl" refers to an alicyclic hydrocarbon, such as a monocyclic and / or fused-ring hydrocarbon containing 1 to 4 rings and 3 - 18 carbon atoms, preferably 3 - 10 (e.g., 3, 4, 5, 6, 7, 8, 9, 10) carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, or adamantyl, etc.

[0107] The term "alkoxy" refers to a substituent formed by replacing the hydrogen in a hydroxyl group with an alkyl group, such as an alkoxy group containing 1 - 10 carbon atoms, for example, methoxy, ethoxy, propoxy, butoxy, etc.

[0108] The term "halogen" refers to fluorine, chlorine, bromine, or iodine.

[0109] The term "haloalkyl" refers to a group formed by replacing one or more hydrogens in an alkyl group with halogen atoms (e.g., fluorine, chlorine, bromine, or iodine), such as -CHF2, -CH2F, -CF3, -CH2-CF3, -CH2CH2-CF3, -CH2CH2CH2-CF3.

[0110] The term "aryl" refers to a monocyclic or polycyclic radical, including polycyclic radicals containing monoaryl groups and / or fused aryl groups, such as those containing 1 - 3 monocyclic or fused rings and 6 - 18 (e.g., 6, 8, 10, 12, 14, 16, 18) carbon ring atoms. In the present invention, the C6-C 12 aryl refers to an aryl group containing 6 - 12 carbon ring atoms, such as phenyl, naphthyl, biphenyl, indenyl, etc.

[0111] The term "heterocyclic group" refers to a 3- to 18-membered non-aromatic ring group containing 2 to 17 carbon atoms and 1 to 10 heteroatoms. The heterocyclic group can be a monocyclic, bicyclic, tricyclic, or tetracyclic ring system, which can include fused, spiro, or bridged ring systems. The heterocyclic group can be partially saturated (heteroaryl) or fully saturated (heterocycloalkyl). Suitable heteroaryls in the compounds of the present invention contain 1, 2, or 3 heteroatoms selected from N, O, S, and P atoms, and the heteroaryls include, for example, coumarin, including 8-coumarin, quinolinyl, including 8-quinolinyl, isoquinolinyl, pyridyl, pyrazinyl, pyrazolyl, pyrimidinyl, furyl, pyrrolyl, thienyl, thiazolyl, isothiazolyl, triazolyl, tetrazolyl, isoxazolyl, oxazolyl, imidazolyl, indolyl, isoindolyl, indazolyl, indazinyl, phthalazinyl, pteridinyl, purinyl, oxadiazolyl, thiadiazolyl, furazanyl, pyridazinyl, triazinyl, cinnolinyl, benzimidazolyl, benzofuranyl, benzofurazanyl, benzothienyl, benzothiazolyl, benzoxazolyl, quinazolinyl, quinoxalinyl, naphthyridinyl, and furanopyridyl. Suitable heterocycloalkyls in the compounds of the present invention contain 1, 2, or 3 heteroatoms selected from N, O, or S atoms, and the heterocycloalkyls include, for example, pyrrolidinyl, tetrahydrofuryl, dihydrofuran, tetrahydrothienyl, tetrahydrothiopyranyl, piperidinyl, morpholinyl, thiomorpholinyl, oxathianyl, piperazinyl, azetidinyl, oxetanyl, thietanyl, homopiperidinyl, oxiranyl, thiiranyl, azepinyl, oxazepinyl, diazepinyl, triazepinyl, 1,2,3,6-tetrahydropyridyl, 2-pyrrolinyl, 3-pyrrolinyl, dihydroindolyl, 2H-pyranyl, 4H-pyranyl, dioxanyl, 1,3-dioxolanyl, pyrazolinyl, dithianyl, dithiolanyl, dihydropyranyl, dihydrothienyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, 3-azabicyclo[3.1.0]hexyl, 3-azabicyclo[4.1.0]heptyl, 3H-indolyl, and quinuclidinyl. In the present invention, for an optionally substituted heterocyclic group, the substitution position can be any suitable carbon atom or heteroatom. For example, for where the substitution position of R can be any suitable carbon atom or nitrogen atom, and it can be, for example

[0112] The disclosures of various publications, patents, and published patent specifications cited herein are incorporated herein by reference in their entirety.

[0113] The polymer monomers used in the present invention are known in the art, some are commercially available, or can be synthesized according to methods known in the art.

[0114] Next, in combination with the embodiments of the present invention, the technical solutions of the present invention will be clearly and completely described. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without making creative efforts belong to the scope of protection of the present invention.

[0115] The molecular weight of the product prepared in each embodiment is the number average molecular weight Mn, which is measured according to the gel permeation chromatography (GPC) method of GB / T 21863-2008.

[0116] The viscosity of the product prepared in each embodiment is measured according to the viscosity measurement method of GB / T 10247-2008.

[0117] Example 1:

[0118] Raw material 1-1:

[0119] Raw material 1-2:

[0120] Raw material 1-3:

[0121] Intermediate M1:

[0122] In a 2000 mL round-bottom flask, 0.5 mol of raw material 1-1 and 0.5 mol of raw material 1-2 were dissolved in 500 mL of deionized water, heated to 90 °C, and reacted for 16 hours under stirring to obtain intermediate M1. 0.5 mol of raw material 1-3 was added, and 1% by weight of dimethyl 2,2'-azobis(2-methylpropionate) based on the raw material 1-3 was added. The reaction was continued at 100 °C for 6 hours. After complete reaction, filtration and concentration were carried out to obtain the target product P1-EX1 (yield: 89.1%, molecular weight: 10266, viscosity (100 °C): 1968 cps).

[0123] Example 2:

[0124] Raw material 2-1:

[0125] Raw material 2-2:

[0126] In a 2000 mL round-bottom flask, 0.5 mol of raw material 2-1 and 0.55 mol of raw material 2-2 were dissolved in 500 mL of deionized water. The mixture was heated to 90 °C and reacted under stirring for 16 hours to obtain an intermediate. 1% by weight of 2,2'-azobis(isobutyramidine) dihydrochloride based on the raw material 2-1 was added, and the reaction was continued at 80 °C for 2 hours. After complete reaction, filtration and concentration were carried out to obtain the target product P1-EX2 (yield: 91.4%, molecular weight: 4320, viscosity (100 °C): 1031 cps).

[0127] Example 3:

[0128] Raw material 3-1:

[0129] Raw material 3-2:

[0130] Raw material 3-3:

[0131] In a 2000 mL round-bottom flask, 0.5 mol of raw material 3-1 and 0.5 mol of raw material 3-2 were dissolved in 500 mL of deionized water. The mixture was heated to 80 °C and reacted under stirring for 15 hours to obtain an intermediate. 0.5 mol of raw material 3-3 was added, and 1% by weight of tert-butyl hydroperoxide based on the raw material 3-3 was added. The reaction was continued at 80 °C for 2 hours. After complete reaction, filtration and concentration were carried out to obtain the target product P1-EX3 (yield: 87.1%, molecular weight: 7024, viscosity (100 °C): 1380 cps).

[0132] Example 4:

[0133] Raw material 4-1:

[0134] Raw material 4-2:

[0135] Raw material 4-3:

[0136] Raw material 4-4:

[0137] In a 2000 mL round-bottom flask, 0.5 mol of raw material 4-1 and 0.5 mol of raw material 4-2 were dissolved in 600 mL of deionized water. The mixture was heated to 100 °C and reacted under stirring for 16 hours to obtain an intermediate. 0.55 mol of raw material 4-3 and 0.5 mol of raw material 4-4 were added, and 2% by weight of azobisisobutyronitrile based on the raw material 4-4 was added. The reaction was continued at 60 °C for 3 hours. After complete reaction, filtration and concentration were carried out to obtain the target product P1-EX4 (yield: 92.3%, molecular weight: 8120, viscosity (100 °C): 1423 cps).

[0138] Example 5: Electrochemical Performance Test

[0139] In this experiment, the electrochemical performance was tested by assembling a single cell. The measured geometric area of the cell used was 2×2 cm 2 , and the cell diaphragm was a HoAM G-1204 anion exchange membrane, which was directly immersed in 1 mol / L NaCl aqueous solution for 1 h before use; the mold for cell testing was provided by Wuhan Chuxin Technology Co., Ltd.; the positive electrolyte was 0.1 mol / L positive active material + 1 mol / L NaCl aqueous solution; the negative electrolyte was methyl viologen + 1 mol / L NaCl aqueous solution;

[0140] The assembled flow battery was tested for cycle stability at room temperature (25°C). The test equipment was a Shenzhen Neware battery tester. The test voltage was set at 0.1 - 1.7 V, and the flow rate was 25 mL / min.

[0141] Among them,

[0142] No. 1 is the nitroxide radical of 2,2,6,6-tetramethylpiperidinol;

[0143] No. 2 is a polymer Ⅰ P1-EX1 (Example 1) containing TEMPO radicals;

[0144] No. 3 is a polymer Ⅰ P1-EX2 (Example 2) containing TEMPO radicals;

[0145] No. 4 is a polymer Ⅰ P1-EX3 (Example 3) containing TEMPO radicals;

[0146] No. 5 is a polymer Ⅰ P1-EX4 (Example 4) containing TEMPO radicals;

[0147] The electrochemical performance test was a result comparison at the same piperidine radical concentration in the solution. The results are as follows:

[0148] Table 1 Electrochemical Performance Comparison Table

[0149]

[0150]

[0151] Example 6: Light Stability Experiment of Stable Coating

[0152] The waterborne dispersed polyurethane was purchased from Yoshida Waterborne Polyurethane 1926, the dispersant was purchased from Yoshida Anti-Settling Agent 2521, the leveling agent was purchased from Yoshida Waterborne Leveling Agent J2102, the defoamer was purchased from Guangzhou Zhonglianbang Polyether Defoamer B-299, and the auxiliary agent was purchased from Bluekerun HA-SOFT80.

[0153] Table 2 Standard Formulation of the Stable Coating Test

[0154]

[0155] No. 1 is the 100 wt% standard formulation;

[0156] No. 2 is the 99.7 wt% standard formulation and 0.3 wt% coating auxiliary agent P1-EX1 (Example 1);

[0157] No. 3 is the 99.7 wt% standard formulation and 0.3 wt% coating auxiliary agent P1-EX2 (Example 2);

[0158] No. 4 is the 99.7 wt% standard formulation and 0.3 wt% coating auxiliary agent P1-EX3 (Example 3);

[0159] No. 5 is the 99.7 wt% standard formulation and 0.3 wt% coating auxiliary agent P1-EX4 (Example 4);

[0160] Preparation of the test samples:

[0161] Prepare the raw materials according to the formulation in Table 2. Add the dispersant, coating auxiliary agent, water and half of the proportion of the defoamer into a container with high-speed stirring. While stirring, add the thickener. After the thickener is completely dissipated, add nano silicon carbide and disperse it at high speed. Quickly transfer the dispersed liquid in Step 1 to a defoaming device. After the bubbles are basically eliminated, transfer it to a low-speed stirring tank. After dispersing evenly, adjust the pH to 8 with a pH regulator to obtain the coating slurry.

[0162] Among them, the high-speed stirring rate is 1500 r / min; the low-speed stirring rate is 450 r / min;

[0163] Based on the above coating smear samples, the samples were subjected to xenon lamp aging test according to the standard GB / T 16422.2-2014, and the test results are shown in Table 3:

[0164] Table 3 △E* of the samples after xenon lamp aging (low value is required)

[0165]

[0166] Example 7: Performance Test as a Flame Retardant in the Coating

[0167] Based on the paint smear sample of Example 6, finally, the sample was tested for flame retardancy according to the DIN 4102-B2 standard, and the test results are shown in Table 4:

[0168] Table 4 Flame Retardant Performance of the Sample

[0169] Sample Weight loss / % Burning length / mm Burning droplets Qualified / unqualified 1# 100 190 Yes Unqualified 2# 6.3 74.3 Yes Qualified 3# 5.8 63.6 Yes Qualified 4# 7.8 93.5 Yes Qualified 5# 7.1 68.4 Yes Qualified

[0170] Example 8: Performance Test of Antistatic Agent

[0171] Table 5 Standard Formulation

[0172] Component Ratio PP 100 Antioxidant 1010 0.1 Antioxidant 168 0.2

[0173] No. 1 is 100% standard formulation;

[0174] No. 2 is 98.5 wt% standard formulation and 1.5 wt% Clariant SAS93 antistatic agent;

[0175] No. 3 is 98 wt% standard formulation and 2 wt% P1-EX1 (Example 1);

[0176] No. 4 is 98 wt% standard formulation and 2 wt% P1-EX2 (Example 2);

[0177] No. 5 is 98 wt% standard formulation and 2 wt% P1-EX3 (Example 3);

[0178] No. 6 is 98 wt% standard formulation and 2 wt% P1-EX4 (Example 4);

[0179] Mix the above materials, and then obtain standard test specimens through melt extrusion, granulation, and injection molding.

[0180] Test its antistatic performance using the resistivity test method for conductive and antistatic fiber-reinforced plastics in GB / T 15738-2008, and the test results are shown in Table 6.

[0181] Table 6 Antistatic Performance

[0182] Number Surface resistivity (Ω) 1# <![CDATA[7.63*10 13 > 2# <![CDATA[1.3*10 9 > 3# <![CDATA[1.15*10 9 > 4# <![CDATA[1.41*10 9 > 5# <![CDATA[1.33*10 9 > 6# <![CDATA[1.08*10 9 >

[0183] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

[0184] The foregoing embodiments and methods described in the present invention may vary based on the capabilities, experience, and preferences of those skilled in the art.

[0185] The listing of the steps of the method in a certain order in the present invention does not constitute any limitation on the order of the method steps.

Claims

1. A polymer comprising the structure shown in Formula I: Wherein, Y1 is selected from: O, NH; X is selected from: Cl, Br, I; R1 and R2 are independently selected from: a single bond, R3, R4, R5, R7, R8, R9 are independently selected from: C1-C 10 alkyl; R6 is selected from: H, C1-C 10 alkyl; Y2 is selected from: O, NH; m is an integer from 1 to 20; n and p are each an integer from 1 to 20; f is an integer from 2 to 6; Preferably, the molecular weight of the polymer is 1000 - 50000, preferably 2000 - 20000.

2. The polymer according to claim 1, wherein R3 is a C1 - C6 alkyl group, preferably -CH3; Preferably, R4 is a C1 - C6 alkyl group, preferably -CH3; Preferably, R5 is a C1 - C6 alkyl group, preferably -CH3; Preferably, R7 is a C1 - C6 alkyl group, preferably -CH3; Preferably, R8 is a C1 - C6 alkyl group, preferably -CH3; Preferably, R9 is a C1 - C6 alkyl group, preferably -CH3; Preferably, R6 is H or a C1 - C6 alkyl group, preferably H or -CH3; Preferably, f is an integer from 2 to 4, preferably 2.

3. A method for preparing the polymer according to any one of claims 1 - 2, the preparation method comprising the following steps: S1: Add the compound of the structure shown in Formula II and the compound of the structure shown in Formula III to an organic solvent, and react to obtain the compound of the structure shown in Formula IV; S2: Subject the compound of the structure shown in Formula IV to a polymerization reaction under the action of an initiator to obtain a polymer comprising the structure shown in Formula I; or, Subject the compound of the structure shown in Formula IV and the compound of the structure shown in Formula V and / or the compound of the structure shown in Formula VI to a polymerization reaction under the action of an initiator to obtain a polymer comprising the structure shown in Formula I; 4. The preparation method according to claim 3, characterized in that, In the S1 step, the organic solvent is a polar solvent, which is selected from one or more of: N,N - dimethylformamide, acetonitrile, dimethyl sulfoxide, methanol, ethanol, water; Preferably, in the S1 step, the molar ratio of the compound of the structure shown in Formula II to the compound of the structure shown in Formula III is 1:0.1 - 10, preferably 1:1 - 1.5, more preferably 1:1; Preferably, in the S1 step, the reaction temperature is 30 - 150 °C.

5. The preparation method according to claim 3, characterized in that, In the S2 step, the initiator is selected from: N,N - dimethylformamide, 4,4'-azobis(4 - cyanovaleric acid), azobisisobutyronitrile, azobisisoheptonitrile, 2,2'-azobis(2,4 - dimethylvaleronitrile), dimethyl 2,2'-azobis(2 - methylpropionate), 2,2'-azobis(2 - methylpropionamidine) dihydrochloride, 1,1'-azobis(cyclohexanecarbonitrile), azobisisovaleronitrile, 4,4'-azobis(4 - cyanovaleric acid), 2,2'-azobis(2 - imidazoline) dihydrochloride, 1 - ((cyano - 1 - methylethyl)azo)formamide, azobis(2 - methylpropionimidazole) hydrochloride, tert - butyl hydroperoxide, hydrogen peroxide, etc.; Preferably, in the S2 step, the reaction temperature is 30 - 150 °C.

6. An application of the polymer according to any one of claims 1 - 2 as a positive electrolyte of a flow battery system.

7. A flow battery system comprising the polymer according to any one of claims 1-2, including a positive electrode reservoir, a negative electrode reservoir and a flow battery stack; both ends of the flow battery stack are respectively connected to the positive electrode reservoir and the negative electrode reservoir.

8. A liquid composition comprising the polymer according to any one of claims 1-2 and a dispersion of fine particulate solid materials selected from pigments and fillers and a liquid diluent.

9. A composition comprising the polymer according to any one of claims 1-2 and an organic substance sensitive to light, heat or oxidation; Preferably, the organic substance is selected from one or more of: polyolefin, acrylonitrile, butadiene, styrene, polyvinyl chloride, polymethyl methacrylate, polyacetal, polyamide, polyimide, epoxy resin, polyurethane, polycarbonate, polyurethane, polyester, polysulfone, polyurea, polystyrene, thermoplastic elastomer.

10. Use of the polymer according to any one of claims 1-2, the liquid composition according to claim 10 or the composition according to claim 9 as an additive in high molecular materials, coatings, pigments, paints, inks or adhesives; Preferably, the additive is a surface product additive; Preferably, the additive is an additive for solid materials; Preferably, the additive is a resin component, a light stabilizer, a thickener, a dispersant, a flame retardant, an antistatic agent.

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