Phosphorus-containing polymers, methods of making and using the same

Abstract

The application discloses a phosphorus-containing polymer, a preparation method and application thereof, the phosphorus-containing polymer comprises repeating units derived from alpha, omega-non-conjugated diene monomers and repeating units derived from phosphorus source monomers, the alpha, omega-non-conjugated diene monomers are selected from the group consisting of diallyl oligomeric ethylene glycol, diallyl piperazine, diallyl ether and octadiene, and the phosphorus source monomers are selected from the group consisting of hypophosphorous acid and hypophosphite. The lithium salt complex polyelectrolyte based on the phosphorus-containing polymer has relatively high conductivity and can be used in lithium ion batteries; the polyphosphonate surfactant has chemical stability, biocompatibility and hydrophilicity and the like, the phosphonate alkyl ester surfactant has diversified functions; the flame retardant based on the phosphorus-containing polymer has excellent flame retardant performance.

Description

Technical Field

[0001] This invention belongs to the field of functional polymer materials, specifically relating to a novel phosphorus-containing polymer, a method for preparing it by mild and easily achievable free radical addition polymerization, and its applications, particularly the various functional polymer materials derived from it. Background Technology

[0002] Since the 1940s, researchers have recognized the complexity and high value of phosphorus chemistry. Phosphorus chemistry research has yielded numerous outstanding results in various aspects, including structure, bonding, and reactivity, resulting in many products with significant industrial applications. In fact, phosphorus and carbon are located diagonally opposite each other in the periodic table, and phosphorus is also known as a carbon template because many phosphorus-containing compounds exhibit similar structures and behaviors to their corresponding carbon-based compounds (see K. Dillon, F. Mathey, JF Nixon, In Phosphorus: The Carbon Copy, 1998). However, most of the research and development of phosphorus chemistry has been limited to the small molecule level. It is not until recent years that significant progress has been made in the research of phosphorus-containing polymers (see F. Mathey, Angew. Chem. Int. Ed. 2003, 42, 1578-1604; T. Baumgartner, R. Re'au, Chem. Rev. 2006, 106, 4681-4727; JIBates, J. Dugal-Tessier, DPGates, Dalton Trans. 2010, 39, 3151-3159). Phosphorus-containing polymer materials possess many excellent properties, including flame retardancy, good metal adhesion, biodegradability, and blood compatibility. Therefore, they are widely used in various fields such as textile finishing agents, flame retardants, adhesives, and biomedical materials (see D.A. Spiro, W.C. Carrell, R.Q. Donna, Ind. Eng. Chem. Res., 1991, 30, 772-778; J. Canadell, B.J. Ghunt Cook, Polym. Degrad. and...). Stabil., 2007, 92, 1482-1490; S. Monge, B. Canniccioni, A. Graillot, Biomacromolecules, 2011, 12, 1973-1982; KNBauer, HTTee, MMVe lencoso, FR Wurm, Prog. Polym. Sci., 2017, 73, 61-122; S. Hiranphinyophat, Y. Iwasaki, Sci. Technol. Adv. Mater., 2021, 22, 301-316).

[0003] The introduction of the inorganic element phosphorus into organic polymers can result in either main-chain phosphorus-containing polymers or side-chain phosphorus-containing polymers. Main-chain phosphorus-containing polymers possess unique chemical functions, such as applications in catalysts, sensors, and biomaterials (see B. Thomas, R. Regis, Chem. Rev., 2006, 106, 4681-4727; K. Huynh, A.J. Lough, I. Manners, J. Am. Chem. Soc., 2006, 128, 14002-14003). One major category of main-chain phosphorus-containing polymers is polyphosphate esters (salts) based on the main-chain PO bonds, while another category is organic polyphosphine and its oxides or polyphosphonic acids (esters / salts) based on the main-chain PC bonds. Polyphosphate polymers have good biocompatibility, biodegradability and flame retardancy, but their poor long-term hydrolysis resistance is also their biggest drawback for certain applications. Therefore, their use is greatly limited in application scenarios where uncontrolled or excessively rapid hydrolysis is undesirable. Compared to polyphosphates, organic polyphosphonic acid (ester / salt) polymers overcome this significant shortcoming. The PC bonds in these polymers are highly resistant to oxidation and hydrolysis, even more stable than C-C bonds in this respect. Therefore, the preparation and application of organic polyphosphonic acid (ester / salt) polymers have attracted much attention (see S. Maiti, S. Banerjee, SK Palit, Prog. Polym. Sci., 1993, 18, 227-261; Y. Liu, N. Yan, F. Li, P. Chen, Polym. Int., 2013, 62, 390-396; KNBauer, HTTee, I. Lieberwirth, FRWurm, Macromolecules, 2016, 49, 3761-3768).

[0004] Research on polyphosphate ester polymers with PO bonds as the main chain is quite advanced. In recent years, there has been much new progress in the preparation of biomimetic phosphorus-containing polymers by functionalizing and modifying polyphosphate esters based on PO bonds. For example, by using the random copolymerization of two cyclic phosphate anions and then introducing side chain carboxylic acid modification through a thiol-ene click reaction, the prepolymer is transformed into a non-cytotoxic and degradable thermoresponsive polymer that exhibits UCST behavior in water within the temperature range of 43 to 71 °C, thereby controlling the self-assembly and decomposition of block copolymers in water. Polyphosphate surfactants with different binding group sequences were synthesized via anionic ring-opening polymerization of cyclic phosphates. After encapsulating nanocarriers, these surfactants reduced the adsorption of blood proteins and prevented recognition by immune cells (macrophages). This strategy successfully transformed nanocarriers into biocompatible, disguised nanocarriers by utilizing the chemical multifunctionality of polyphosphates, which can be applied to advanced drug delivery systems (see J. Simon, T. Wolf, K. Klein, K. Landfester, FR. Wurm, Angew. Chem. Int. Ed., 2018, 57, 5548-5553; K. N. Lauer, J. Simon, V.). K. Landfester, FR Wurm, Acta Biomater., 2020, 116, 318-328).

[0005] Synthetic methods for organophosphine or polyphosphonate (salt) based on PC bonds have been reported to date, mainly including phosphine polymerization, phosphorus-containing heterocyclic ring-opening polymerization, and polymerization (usually step-growth polymerization reactions such as condensation polymerization) of pre-synthesized reactive polyfunctional monomers with PC bonds. Polyphosphine is obtained by chain addition polymerization of phosphine monomers (RP=CR'2). These polymers have certain stability to air and water in the solid state, but after being dissolved in solutions such as dichloromethane and exposed to air for four days, they are partially oxidized to polyphosphine oxide. Ring-opening polymerization of phosphorus-containing heterocycles can also produce trivalent or pentavalent phosphorus backbone polymers through anionic, cationic, or free radical reaction mechanisms. For example, Michelle, through theoretical calculations, explored the chain growth mechanism and kinetics of free radical-initiated ring-opening polymerization of a series of phosphorus-containing heterocycles, indicating that the most likely pathway is the attack of carbon free radicals on phosphorus atoms in the ring to initiate chain growth. However, regardless of the active species mechanism used in ring-opening polymerization, phosphorus-containing cyclic monomers are not common, requiring specialized synthesis, and the reaction conditions for polymerization are also demanding, making it difficult to achieve. In recent years, an indirect synthetic strategy has emerged, utilizing polyfunctional reactive monomers with introduced PC bonds and employing relatively efficient reaction pathways such as click reactions to prepare polymers containing PC bonds. Liu Chengmei et al. synthesized a more stable and safer diurethane monomer with introduced PC bonds using tetramethylolphosphonium sulfate (THPS) as a phosphorus source, and further prepared polyureas with introduced PC bonds through transesterification. A recent report describes a multifunctional monomer of styrene derivatives with two epoxy groups introduced at the para position via PC bonds. The styrene and epoxy functional groups can be independently polymerized into chains via free radical controlled polymerization or condensation polymerization without interference, resulting in a phosphorus-containing reactive polymer with a high density of functional groups (see CWTsang, M.Yam, DPGates, J.Am.Chem.Soc., 2003, 125, 1480-1481; LHJennifer, LCMichelle, Macromolecules, 2005, 38, 8902-8910; ZWTan, M.Zhang, HZGuo, JJQiu, CMLiu, Des.Monomers Polym., 2014, 17, 762-774; J.Sun, YLHong, C.Wang, ZWTan, CMLiu, Polym.Chem., 2022, 13, 1520-1536).

[0006] Several patents have been published regarding phosphorus-containing functional polymers, mostly based on polyphosphate esters or polyphosphoramides. For example, Chinese patent CN 100445320 C synthesized a polyphosphate ester suitable for drug sustained release using a melt method with lactic acid, glycol compounds, and phosphorus-containing monomers; Chinese patent CN 101914208 B prepared a polyphosphoramide-based intumescent flame-retardant polymer by solution polycondensation or melt polycondensation of diphosphoryl chloride or diphosphoryl bromide and diamine compounds, which is used as an additive flame retardant in flame-retardant formulations of various polymers such as polyesters; Chinese patent application CN 114984236 A prepared a nucleic acid system with a surface-coated crosslinked polymer by polymerizing imidazole cationic monomers, phosphorocholine-containing monomers, and disulfide bonds, exhibiting high stability and realizing a responsive nucleic acid delivery system.

[0007] As can be seen from the above patents and journal articles, there are very limited reports on phosphorus-containing polymers that introduce PC bonds, and the existing systems are either cumbersome and time-consuming in monomer preparation, or have harsh polymerization reaction conditions or obvious safety hazards. Summary of the Invention

[0008] In view of this, the purpose of this invention is to address the technical problems existing in the prior art by providing phosphorus-containing polymers containing PC bonds, their preparation methods, and applications.

[0009] The objective of this invention is achieved through the following technical solutions.

[0010] The inventors of this application have discovered that phosphorus-containing polymers are obtained by stepwise free radical addition polymerization using α,ω-non-conjugated diene functional monomers selected from diallyl oligopolyethylene glycol, diallyl piperazine, diallyl ether, and octadiene, as well as inexpensive and readily available commercial raw materials such as hypophosphite (HPA) or hypophosphite compounds, under relatively mild reaction conditions. Such phosphorus-containing polymers can be used to further prepare phosphorus-containing functional polymer materials such as lithium salt complex polyelectrolytes, polyphosphonate surfactants, and flame retardants, and have improved properties, thus constituting the present invention.

[0011] In a first aspect, the present invention provides a phosphorus-containing polymer comprising a PC bond, the phosphorus-containing polymer comprising repeating units derived from α,ω-non-conjugated diene monomers and repeating units derived from phosphorus source monomers, wherein the α,ω-non-conjugated diene monomers are selected from diallyl oligoethylene glycol, diallyl piperazine, diallyl ether, and octadiene, etc., and the phosphorus source monomers are selected from hypophosphorous acid and hypophosphite.

[0012] According to the phosphorus-containing polymer provided by the present invention, the number average molecular weight of the phosphorus-containing polymer is 1000-20000 g / mol, preferably 2000-15000 g / mol.

[0013] According to the phosphorus-containing polymer provided by the present invention, the molecular weight distribution index Mw / Mn of the phosphorus-containing polymer is 1.1-3.0, preferably 1.2-2.6.

[0014] According to the phosphorus-containing polymer provided by the present invention, the degree of polymerization of the ethylene glycol unit in the diallyl oligopolyethylene glycol is 1-10 (in the present invention, the diallyl oligopolyethylene glycol reactive monomer can also be represented as M(EG)). n (where n = 1 to 10). For example, the degree of polymerization of the ethylene glycol unit in the diallyl oligopolyethylene glycol can be 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. The inventors have found that when the degree of polymerization of the diallyl oligopolyethylene glycol is above 8, the synthesis efficiency decreases, and a small number of crystallization peaks appear, reducing the conductivity of the polyelectrolyte prepared from it. In some embodiments, the degree of polymerization of the ethylene glycol unit in the diallyl oligopolyethylene glycol is 2-7.

[0015] According to the phosphorus-containing polymer provided by the present invention, the phosphorus-containing polymer is a polymer obtained by stepwise free radical addition polymerization of the α,ω-nonconjugated diene monomer and the phosphorus source monomer.

[0016] Secondly, the present invention provides a method for preparing a phosphorus-containing polymer comprising PC bonds, the method comprising the following steps:

[0017] In the presence of a free radical initiator, an α,ω-nonconjugated diene monomer and a phosphorus source monomer undergo a stepwise free radical addition polymerization reaction, wherein the α,ω-nonconjugated diene monomer is selected from diallyl oligoethylene glycol, diallyl piperazine, diallyl ether, and octadiene, and the phosphorus source monomer is selected from hypophosphorous acid and hypophosphite.

[0018] In this invention, the α,ω-nonconjugated diene monomers used, such as diallyl oligoethylene glycol, are easy to synthesize or can be directly purchased, while the phosphorus source monomers are inexpensive and readily available. Therefore, this easy-to-implement synthetic route (method) and its polymer products have broad application prospects.

[0019] According to the preparation method provided by the present invention, the free radical addition step-growth polymerization reaction is carried out in the presence of a free radical initiator.

[0020] In this invention, the free radical initiator can be an organic phase initiator and / or an aqueous phase initiator. The organic phase initiator can be an azo initiator or an organic peroxide initiator, such as azobisisobutyronitrile (AIBN) or benzoyl peroxide (BPO), preferably azobisisobutyronitrile. The aqueous phase initiator can be a persulfate initiator or a water-soluble azo initiator, preferably a persulfate initiator, such as sodium persulfate, potassium persulfate, or ammonium persulfate.

[0021] In some implementations, the free radical initiator is added in batches, for example, in 2-4 separate additions.

[0022] According to the preparation method provided by the present invention, the molar ratio of the α,ω-nonconjugated diene monomer, the phosphorus source monomer and the free radical initiator is 1:1:(0.05-0.75), preferably 1:1:(0.2-0.3), for example, 1:1:0.25; and / or, the free radical initiator is selected from azobisisobutyronitrile, benzoyl peroxide and persulfate.

[0023] According to the preparation method provided by the present invention, the free radical addition step-growth polymerization reaction is carried out in the presence of a solvent. Examples of solvents suitable for use in the present invention include, but are not limited to: toluene, chlorobenzene, acetonitrile, tetrahydrofuran, 1,4-dioxane, n-propanol, isopropanol, n-butanol, methyl ethyl ketone, ethanol, and dimethyl sulfoxide.

[0024] In some embodiments, the solvent is selected from chlorobenzene, n-propanol, and ethanol, preferably ethanol. It is believed that using these solvents results in phosphorus-containing polymers with high degrees of polymerization and relatively low polydispersity indices.

[0025] The present invention does not have any special requirements on the amount of solvent used. However, when the volume-to-mass ratio of the solvent to the α,ω-nonconjugated diene monomer is 1.5-5.0 mL:1.0 g, preferably 2-3 mL:1.0 g, the reaction is more likely to proceed better.

[0026] According to the preparation method provided by the present invention, the conditions for the free radical addition stepwise polymerization reaction include: a temperature of 50-100°C, preferably 75±5°C, a reaction time of 1-80 h, preferably 36-72 h; and / or, carried out under an inert atmosphere, preferably a nitrogen atmosphere; and / or, a stirring speed of 500-1500 rpm, preferably 1000-1200 rpm.

[0027] According to the preparation method provided by the present invention, the preparation method includes the following steps:

[0028] S101. Add α,ω-nonconjugated diene monomer, phosphorus source monomer and the first part of free radical initiator to the solvent, mix, and introduce nitrogen gas to remove oxygen to obtain a nitrogen atmosphere reaction system.

[0029] S102. Under stirring conditions, at a temperature of 50–100°C, preferably 75±5°C, the polymerization reaction is carried out for 1–80 h, preferably 36–72 h, to obtain the reaction product.

[0030] S103. Add ethanol to the reaction product to dilute it, and then add the diluted reaction product to petroleum ether for phase separation precipitation. Remove the upper solvent and dry to obtain the phosphorus-containing polymer.

[0031] Preferably, in step S102, a first portion of free radical initiator is added to initiate the polymerization reaction. During the polymerization reaction, particularly at intervals of 24-72 hours, a second portion of free radical initiator and a third portion of free radical initiator are added. More preferably, the first portion of free radical initiator, the second portion of free radical initiator, and the third portion of free radical initiator each independently account for 30-40% of the total amount of free radical initiator.

[0032] Preferably, in step S102, the stirring speed is 500-1500 rpm, more preferably 1000-1200 rpm.

[0033] Preferably, in step S103, the drying temperature is 60–80°C.

[0034] In this invention, in step S103, the polymer is separated by adding petroleum ether, which can remove unreacted raw materials and low molecular weight polymers.

[0035] Thirdly, the present invention provides a lithium salt complex polyelectrolyte, the lithium salt complex polyelectrolyte comprising the phosphorus-containing polymer described in the first aspect or the phosphorus-containing polymer prepared by the preparation method described in the second aspect, and a doped lithium trifluoromethanesulfonate salt.

[0036] In this invention, compared with lithium salt composite polyelectrolytes based on long-chain polyethylene glycol (PEG), the lithium salt composite polyelectrolyte of this invention exhibits reduced AC impedance and increased ionic conductivity. It is believed that in the lithium salt composite polyelectrolyte of this invention, the phosphorus-containing polymer of short-chain oligoethylene glycol suppresses the crystallinity of conventional long-chain PEG, thereby improving the ionic conductivity of the resulting phosphorus-containing polymer polyelectrolyte.

[0037] According to the lithium salt complex polyelectrolyte provided by the present invention, the doping amount of the lithium trifluoromethanesulfonate is 0-50 wt%, preferably 1-50 wt%, and more preferably 5-30 wt%, based on the mass of the lithium salt complex polyelectrolyte.

[0038] The lithium salt complex polyelectrolyte provided by the present invention, wherein the α,ω-non-conjugated diene monomer in the phosphorus-containing polymer is diallyl oligoethylene glycol. In the present invention, the diallyl oligoethylene glycol is as described in the first aspect. In some embodiments, the degree of polymerization of the ethylene glycol unit in the diallyl oligoethylene glycol is 2-7, for example 2, 3, 4, 5, 6, or 7.

[0039] Fourthly, the present invention provides a method for preparing the lithium salt complex polyelectrolyte of the third aspect, wherein the preparation method includes:

[0040] S201. Add the phosphorus-containing polymer and LiCF3SO3 to the first reaction solvent, mix, and obtain the reaction system;

[0041] S202. The reaction system in step S201 is reacted at a temperature of 60±5℃ and a rotation speed of 500~1200rpm for 5-7h, and then dried to obtain lithium salt composite polyelectrolyte.

[0042] According to the preparation method provided by the present invention, the first reaction solvent in step S201 is water, preferably ultrapure water.

[0043] According to the preparation method provided by the present invention, in step S201, the mass ratio of the phosphorus-containing polymer to LiCF3SO3 is 1:(0-1), preferably 1:(0.01-1), more preferably 1:(0.05-0.43), for example 17:3.

[0044] According to the preparation method provided by the present invention, the drying in step S201 includes: rotary evaporating the first reaction solvent to dryness; vacuum drying at a temperature of 60±5°C for 24 to 72 hours, preferably 36 to 48 hours; and holding at a temperature of 100±5°C for 8 to 24 hours, preferably 12 to 18 hours.

[0045] Fifthly, the present invention provides a polyphosphonate surfactant comprising the reaction product of the phosphorus-containing polymer described in the first aspect or the phosphorus-containing polymer prepared by the preparation method described in the second aspect, a catalyst, and 1-bromododecane.

[0046] The polyphosphonate surfactant provided according to the present invention, wherein the catalyst is cesium carbonate.

[0047] According to the polyphosphonate surfactant provided by the present invention, the α,ω-non-conjugated diene monomer in the phosphorus-containing polymer is diallyl oligoethylene glycol. In some embodiments, the degree of polymerization of the ethylene glycol unit in the diallyl oligoethylene glycol is preferably 2-7, for example 2, 5, or 7.

[0048] According to the polyphosphonate surfactant provided by the present invention, the molar ratio of the phosphorus-containing polymer, the catalyst and 1-bromododecane is 1:(0.25-2):2, preferably 1:2:2, based on the total number of repeating units derived from α,ω-nonconjugated diene monomers and phosphorus-derived monomers in the phosphorus-containing polymer.

[0049] In this invention, the term "based on the total number of repeating units derived from α,ω-nonconjugated diene monomers and phosphorus source monomers in the phosphorus-containing polymer" means that the amount of phosphorus-containing polymer is calculated based on the molecular weight of the repeating units formed by the reaction of α,ω-nonconjugated diene monomers and phosphorus source monomers in the phosphorus-containing polymer, rather than based on the molecular weight of the phosphorus-containing polymer.

[0050] The polyphosphonate surfactant provided according to the present invention may be in the form of an aqueous solution.

[0051] In some embodiments, the concentration of the aqueous solution is 0.01–1 mg / mL, for example 0.1 mg / mL. At such concentrations, the polyphosphonate surfactant can assemble into a micelle structure exhibiting surfactant characteristics.

[0052] Sixthly, the present invention provides a method for preparing the polyphosphonate surfactant described in the fifth aspect, wherein the preparation method includes the following steps:

[0053] S301. Add the phosphorus-containing polymer, catalyst, and 1-bromododecane to the second reaction solvent, and introduce an inert gas to remove oxygen to obtain the reaction system.

[0054] S302. Under a temperature of 75±5℃ and stirring conditions, the reaction system obtained in step S301 is subjected to an esterification reaction to obtain the reaction product.

[0055] S303. The reaction product obtained in step S302 is filtered to remove the catalyst, ethanol is added to dilute the reaction product, petroleum ether is added to perform phase separation precipitation, the upper layer is removed, and the product is dried to obtain polyphosphonate surfactant.

[0056] According to the preparation method provided by the present invention, the second reaction solvent in step S301 is acetonitrile. After purging with an inert gas to remove oxygen, the mixture is sealed. Examples of suitable inert gases for use in the present invention include, but are not limited to, argon and nitrogen.

[0057] According to the preparation method provided by the present invention, the esterification reaction time in step S302 is 12-36 h.

[0058] According to the preparation method provided by the present invention, the stirring speed in step S302 is 500-1500 rpm, preferably 1000-1200 rpm.

[0059] According to the preparation method provided by the present invention, the drying in step S303 includes: rotary evaporating the precipitate obtained after removing the supernatant to dryness; and vacuum drying at a temperature of 60±5°C.

[0060] In a seventh aspect, the present invention provides a flame retardant based on a phosphorus-containing polymer, the flame retardant comprising the neutralization reaction product of the phosphorus-containing polymer described in the first aspect or the phosphorus-containing polymer prepared by the preparation method described in the second aspect and an alkaline substance.

[0061] According to the flame retardant provided by the present invention, the α,ω-non-conjugated diene monomer in the phosphorus-containing polymer is diallyl piperazine.

[0062] According to the flame retardant provided by the present invention, the alkaline substance is selected from aluminum chloride and ammonia.

[0063] According to the flame retardant provided by the present invention, the molar ratio of the phosphorus-containing polymer to the alkaline substance is 1.8-2.2:1, based on the total repeating units derived from α,ω-non-conjugated diene monomers and phosphorus-derived monomers in the phosphorus-containing polymer.

[0064] Eighthly, the present invention provides a method for preparing a phosphorus-containing polymer-based flame retardant, as described in the seventh aspect, wherein the preparation method includes:

[0065] A phosphorus-containing polymer, an alkaline substance, and a third reaction solvent are mixed and stirred to obtain a flame retardant based on the phosphorus-containing polymer.

[0066] According to the preparation method provided by the present invention, the third reaction solvent is selected from water and ethanol.

[0067] According to the preparation method provided by the present invention, the alkaline substance is aluminum chloride, and the preparation method includes:

[0068] S401. The reaction system containing phosphorus-containing polymer, alkaline substance and ethanol is reacted at a temperature of 70-85℃ and a speed of 500-1200rpm, preferably 1000-1200rpm, for 12-18h. After washing and vacuum drying, a flame retardant based on phosphorus-containing polymer is obtained.

[0069] Preferably, in step S401, the molar ratio of the phosphorus-containing polymer to the alkaline substance is 1.8-2.2:1, for example, 2:1.

[0070] Preferably, in step S401, a reaction system is formed by adding an ethanol solution of an alkaline substance dropwise to an ethanol solution of a phosphorus-containing polymer.

[0071] Preferably, in step S401, ethanol is used for washing.

[0072] Preferably, in step S401, the vacuum drying temperature is 60±5℃.

[0073] According to the preparation method provided by the present invention, the alkaline substance is ammonia water, and the preparation method includes:

[0074] S402. The reaction system containing phosphorus-containing polymer, alkaline substance and water is reacted at a temperature of 20-30°C and a speed of 500-1200 rpm, preferably 1000-1200 rpm, for 12-24 hours, and then vacuum dried to obtain a flame retardant based on phosphorus-containing polymer.

[0075] Preferably, in step S402, the reaction system is prepared by adding ammonia dropwise to an aqueous solution of the phosphorus-containing polymer until the pH reaches 10, thereby obtaining the reaction system.

[0076] Preferably, in step S402, the vacuum drying temperature is 60±5℃.

[0077] According to the preparation method and application provided by the present invention, the stirring speed in steps S401 and S402 is 500-1200 rpm, preferably 1000-1200 rpm.

[0078] In a ninth aspect, the present invention provides a flame-retardant epoxy resin, said flame-retardant epoxy resin comprising a cured epoxy resin and a flame retardant dispersed therein by the flame retardant of the seventh aspect or the flame retardant prepared by the preparation method of the eighth aspect.

[0079] According to the flame-retardant epoxy resin provided by the present invention, the flame-retardant epoxy resin comprises a reaction product of epoxy resin, flame retardant and curing agent.

[0080] Examples of epoxy resins suitable for use in this invention include, but are not limited to, E-51 and E-44. Examples of curing agents suitable for use in this invention include, but are not limited to, 4,4′-diaminodiphenylmethane (DDM).

[0081] In some embodiments, the mass ratio of the epoxy resin, the flame retardant, and the curing agent is 4:(0.05-0.55):(0.8-1.2), preferably 4:(0.05-0.55):1, and more preferably 4:0.26:1.

[0082] In a tenth aspect, the present invention provides a method for preparing the flame-retardant epoxy resin of the ninth aspect, wherein the preparation method includes:

[0083] S403. Under stirring conditions, epoxy resin, flame retardant and curing agent are mixed, and then vacuum degassed and cured.

[0084] According to the preparation method provided by the present invention, step S403 specifically includes: mixing and dispersing epoxy resin and flame retardant for 20-40 min at a temperature of 115-125℃ and a stirring speed of 800-1200 rpm, cooling to 100-110℃, adding DDM and stirring and dispersing for 5-15 min, and vacuum degassing at 115-125℃ to obtain a prepolymer; transferring the prepolymer into a mold (preparing test strips), curing at 115-125℃ for 1.5-2.5 h, and then heating to 170±5℃ for 3-5 h.

[0085] Compared with the prior art, the present invention has the following advantages:

[0086] (1) This invention is the first to use the free radical stepwise addition polymerization method to realize the free radical addition polymerization of readily available hypophosphoric acid or hypophosphite with α,ω-nonconjugated dienes compatible with a wide range of functional groups under mild reaction conditions. New organophosphonic acid polymers (phosphorus-containing polymers) based on PC bonds and their derived functional polymer materials were prepared, which provides a foundation and new path for the preparation of phosphorus-containing polymer materials based on PC bonds and has broad application prospects.

[0087] (2) In existing reports on battery electrolytes and related research, conventional battery electrolytes suffer from problems such as easy crystallization and low conductivity at low temperatures, leading to dendrite puncture and leakage damage. Taking the most commonly used polyethylene glycol (PEG)-based polyelectrolytes as an example, they easily crystallize at room temperature, inhibiting chain segment movement and significantly reducing the conductivity of PEG / lithium salt polymer electrolytes. The lithium salt composite polyelectrolyte based on a phosphorus-containing polymer of polyethylene glycol prepared in this invention is amorphous at room temperature, completely avoiding the crystallization inhibition effect of conventional PEG and significantly improving the conductivity of Li. + Its high mobility and conductivity make it suitable for use in lithium-ion batteries.

[0088] (3) Polymer surfactants have good emulsifying, coagulating, dispersing, and detergency properties, and low toxicity. Currently, various polyphosphate surfactants have been reported, but to meet the special application requirements of these phosphate surfactants, polyphosphates with high purity requirements need to be prepared by other methods, such as using phosphorus oxychloride to prepare monoesters and phosphorus trichloride to prepare diesters, which greatly increases the toxicity and danger of the raw materials used. Based on the obtained phosphorus-containing polymer, this invention modifies it by partial esterification to obtain polyphosphonic acid long-chain alkyl ester surfactants. At the same time, it combines the excellent chemical stability and biocompatibility of the PC bond polymer with the good hydrophilicity of the remaining polyphosphonic acid anions, which can assemble into micelles in solution and have the diverse functional uses of organic polyphosphonic acid alkyl ester surfactants.

[0089] (4) Another major advantage of phosphorus-containing polymers lies in their excellent flame-retardant properties. Due to environmental protection requirements, the use of halogenated flame retardants is strictly limited, while halogen-free flame retardants such as phosphorus-based and phosphorus-nitrogen synergistic flame retardants are receiving increasing attention. However, small-molecule flame retardants in polymer materials suffer from poor compatibility and are prone to phase separation and exudation, while polymer macromolecular flame retardants have a greater advantage in compatibility. The phosphorus-containing polymer polyP(Pz) of this invention is further used to prepare aluminum or ammonium salt flame retardants for the polymer, which synergistically enhance the flame retardancy of the flame-retardant polymer material.

[0090] (5) In the preparation method of the phosphorus-containing polymer of the present invention, the polymerization reaction is carried out under conventional and mild conditions without special operation or facilities (such as glove box). The solvents and other chemical reagents used are all used directly and are not highly toxic or corrosive raw materials that are difficult to handle. Hypophosphoric acid or sodium hypophosphite is economical and readily available. The synthesis of α,ω-non-conjugated diene monomers is simple and efficient, and the polymerization reaction yield is high. This type of addition step-growth polymerization does not involve the removal of small molecules, which is more in line with atom economy and is conducive to the large-scale expansion and application of this type of novel free radical addition step-growth polymerization. Attached Figure Description

[0091] The accompanying drawings, which form part of this application, are used to enhance the understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention.

[0092] Figure 1 These are the hydrogen NMR and phosphorus NMR spectra of the phosphorus-containing polymer polyP(EG5) of the present invention.

[0093] Figure 2 The present invention relates to the phosphorus-containing polymer polyP(EG). n (n=2~7) and the curves showing the ionic conductivity of PEG doped with 15wt% LiCF3SO3 as a function of temperature.

[0094] Figure 3 The present invention relates to the phosphorus-containing polymer polyP(EG). n XRD patterns of (n=2~7) and the comparative PEG doped with 15wt% LiCF3SO3.

[0095] Figure 4 The images show TEM images and dynamic light scattering (DLS) characterization results of micelles assembled in 0.1 mg / mL aqueous solution of poly(EG2)-C12 surfactants of different lengths: (a) polyP(EG2)-C12; (b) polyP(EG5)-C12; (c) polyP(EG7)-C12; (d) DLS image.

[0096] Figure 5 These are photographs of blank control and composite flame-retardant epoxy resin samples: (a) blank sample; (b) composite flame-retardant epoxy resin sample with 1% polyP(Pz)Al added; (c) composite flame-retardant epoxy resin sample with 1% polyP(Pz)NH4 added; (d) composite flame-retardant epoxy resin sample with 5% polyP(Pz)Al added; (e) composite flame-retardant epoxy resin sample with 5% polyP(Pz)NH4 added.

[0097] Figure 6 The images show the TGA graphs of four groups of composite flame-retardant epoxy resins and blank control samples in (a) nitrogen atmosphere and (b) air atmosphere. Detailed Implementation

[0098] The present invention will be further described below with reference to the accompanying drawings and embodiments. The description below is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention can have various modifications and variations. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

[0099] Chemical reagents: hypophosphorous acid (50wt% aqueous solution, Maclean); 2,2-azobisisobutyronitrile (98%, Aladdin); anhydrous potassium carbonate (AR, Sinopharm-Shanghai Testing); bromopropylene (98%, Merrill); ammonia (AR 25.0-28.0%, Sinopharm-Shanghai Testing); diethylene glycol (CR, Sinopharm-Shanghai Testing); triethylene glycol (AR, Sinopharm-Shanghai Testing); tetraethylene glycol (99%, Aladdin); pentaethylene glycol (97%, Merrill); hexaethylene glycol (97%, Aladdin); heptaethylene glycol (95%, Acce). (la); (di- to heptaethylene glycols are all oligomeric polyethylene glycols); lithium trifluoromethanesulfonate (98%, Maclean); polyethylene glycol (number average molecular weight 6000 g / mol, Maclean); piperazine (99%, Sinopharm-Shanghai Testing); allyl chloride (CP, Sinopharm-Shanghai Testing); aluminum chloride hexahydrate (AR, Nanjing Testing); epoxy resin (E-51, Maclean); 4,4′-diaminodiphenylmethane (AR, Sinopharm-Shanghai Testing); high vacuum silicone grease (7051, ReLAB); anhydrous sodium sulfate (AR, Sinopharm-Shanghai Testing); hydroxide Sodium (AR, Sinopharm-Shanghai Testing); High-purity nitrogen (≥99.5%, Nanjing Shangyuan Gas Plant); 1-bromododecane (98%, Bailingwei); Pyrene (97%, Bid Pharmaceutical); Butane (≥95%, Iwatani); Dimethyl sulfoxide (AR, Sinopharm-Shanghai Testing); N,N-dimethylformamide (AR, Sinopharm-Shanghai Testing); Methanol (AR, Asia-Pacific); Ethanol (AR, Asia-Pacific); n-Propanol (AR, Sinopharm-Shanghai Testing); Isopropanol (AR, Sinopharm-Shanghai Testing); n-Butanol (AR, Nanjing Testing); Methyl ethyl ketone (AR, Nanjing); Chlorobenzene (AR, Shanghai Lingfeng); Toluene (AR, Nanjing); Acetonitrile (AR, Shanghai Lingfeng); Tetrahydrofuran (AR, Maclean); 1,4-Dioxane (AR, Sinopharm-Shanghai); Chloroform (AR, Nanjing); Ethyl acetate (AR, Yashi); Dichloromethane (AR, Yashi); Petroleum ether (AR, Yashi); Acetone (AR, Shanghai Lingfeng); 1,4-Dioxane (AR, Sinopharm-Shanghai); Deuterated chloroform (0.03% TMS, 99.8% D, Bailingwei).

[0100] In addition, reagents not listed are all conventional reagents in the field and can be obtained by self-preparation or purchase.

[0101] 200-300 mesh silica gel was used in the chromatography column, and the chromatography was observed by color development in an iodine bath.

[0102] Nuclear magnetic resonance spectroscopy analysis ( 1 H NMR and 31 P NMR)

[0103] A Bruker Avance III 400MHz liquid nuclear magnetic resonance spectrometer was used, with CDCl3 as the deuterated reagent. 1 ¹H NMR used tetramethylsilane TMS as an internal standard and the corresponding residual solvent hydrogen proton peak CDCl₃ (δ = 7.26) in the deuterated solvent as an auxiliary reference. 13 C NMR reference CDCl3 (δ = 77.16).

[0104] Fourier transform infrared spectroscopy (FT-IR)

[0105] A Thermo Scientific Nicolet iS10 FTIR spectrometer was used, employing either the attenuated total reflectance mode direct method or the potassium bromide pellet transmission mode method. The test scanning range was 4000-400 cm⁻¹. -1 .

[0106] Aqueous gel permeation chromatography (GPC)

[0107] An Agilent Technologies PL-GPC50 aqueous gel permeation chromatograph equipped with a differential refractive index detector was used. The mobile phase was a 0.1 M sodium nitrate aqueous solution, the temperature was kept constant at 35 °C, and the flow rate was set to 1.0 mL / min. The test sample was prepared as a 2 mg / mL sodium nitrate aqueous solution and filtered through a 0.45 μm polyethersulfone membrane. The test results were calculated by calibrating the relative molecular mass using polyethylene glycol (PEG) standards.

[0108] High-resolution mass spectrometry (HRMS)

[0109] The Thermo Fisher Q Exactive electrospray quadrupole-orbit trap tandem high-resolution mass spectrometer was used for testing in either electrospray ionization (ESI) or atmospheric pressure chemical ionization (APCI) mode, with a test range of 100.0000–1500.0000 g / mol. The test samples were prepared as 1 μg / mL methanol or dichloromethane solutions for testing.

[0110] Fluorescence emission spectroscopy analysis

[0111] The Shimadzu RF-5301PC fluorescence spectrophotometer from Japan was used, with a 150W xenon lamp as the light source, and the wavelength measurement range was 220-900nm.

[0112] Thermogravimetric analysis (TGA)

[0113] A Swiss Mettler Toledo TGA 1 / 1100LF simultaneous thermogravimetric analyzer was used. During the test, the sample was purged with nitrogen or air at a rate of 20 mL / min. The accurately weighed sample of 5-20 mg was placed in a 70 μL alumina crucible. A crucible of the same standard was used as a reference. The temperature was gradually increased from room temperature to 800 °C at a rate of 20 °C / min.

[0114] X-ray powder diffraction (XRD) analysis

[0115] The tests were conducted using a German Panalytical XPERT Powder X-ray powder diffractometer. The specific method was as follows: approximately 0.1 g of powder sample was placed on a glass slide, compacted, and then tested. Cu-Kα was used as the radiation source, and the wavelength was... The scanning range is 2θ = 5° - 90°.

[0116] Dynamic Ionic Conductivity (DIC) Measurement

[0117] An American Princeton VersaSTAT 3F electrochemical workstation, equipped with a Leitz-350 temperature-controlled hot stage and VersaStudio processing software, was used for testing in AC impedance mode. The amplitude voltage was 0.3V, and the start and stop frequencies were 100Hz and 1MHz, respectively. The impedance spectrum was tested once every 10°C increase from room temperature.

[0118] Dynamic laser light scattering analysis (DLS)

[0119] A Brookhaven BI-200SM dynamic laser light scattering instrument (USA) was used, with a 532nm green light source, a test angle of 90°, and a test temperature of 25℃. The correlation function of the data was analyzed using the CONTIN mode to determine the hydrodynamic average diameter D of the assembled particles. h And particle size polydispersity index (PSD).

[0120] Transmission electron microscopy (TEM) analysis

[0121] Using a JEOL JEM-2100 transmission electron microscope (TEM) from Japan, 7 μL of the sample solution was dropped onto a 200-mesh carbon support film TEM copper grid of the instrument. After the solution had completely evaporated, the morphology was observed and photographed.

[0122] Limiting Oxygen Index (LOI) Test

[0123] An HC-2C oxygen index analyzer from Nanjing Leijiong Instruments Co., Ltd., China, was used. It was equipped with a heat-resistant glass tube with an inner diameter of 80 mm, a height of 450 mm, and a top outlet inner diameter of 40 mm, as well as a butane igniter. The top ignition method was used for testing, and the testing method followed GB / T2406-93. The oxygen index, expressed as a volume percentage, was calculated according to formula (1):

[0124]

[0125] In equation (1), LOI is the limiting oxygen index, in percent.

[0126] —The last oxygen concentration measured in the NT series, rounded to one decimal place, %;

[0127] d—The difference between the two oxygen concentrations during the test, i.e., the step size, rounded to one decimal place;

[0128] K – The corresponding coefficient provided by GB / T 2406-93.

[0129] Preparation Example 1: Synthesis of Diallyl Diethylene Glycol Ether M (EG2)

[0130] In a 100 mL flask, weigh out diethylene glycol (3.18 g, 30 mmol), bromopropylene (12.70 g, 105 mmol), and flake-shaped solid sodium hydroxide catalyst (3.00 g, 75.0 mmol), and measure out 40 mL of toluene solvent. Heat to 45 °C and stir for 24 h.

[0131] After the reaction was complete, the catalyst sodium hydroxide was removed by filtration, and the solvent was removed by rotary evaporation to dryness. 150 mL of dichloromethane was added, and the mixture was washed with 3 × 100 mL of water. The organic phases were combined, and anhydrous sodium sulfate was added to remove water. The solvent was then removed by rotary evaporation to dryness, and the mixture was separated by column chromatography (eluting with ethyl acetate). After vacuum drying, 3.92 g of a pale yellow liquid was obtained, which was the monomer M (EG2) of diallyl diethylene glycol ether, with a yield of 70.2%.

[0132] The monomer M(EG2) of dielyl diethylene glycol ether 1 H NMR (400MHz, CDCl3, 298K, δin ppm): 5.97-5.87(m,2H), 5.30-5.16(m,4H), 4.04-4.02(m,4H), 3.69-3.60(m,8H). 13 C NMR (100MHz, CDCl3, 298K, δin ppm): 134.86, 117.12, 72.30, 70.75, 69.52. HRMS (ESI) (m / z): [M+Na] + calc.for C10 H 18 NaO3 + ,209.1154;found,209.1143.

[0133] Preparation Examples 2-6: Synthesis of Diallyl Tri, Tetra, Penta, Hexa, and Heptaglycol Monomers

[0134] Diallyl triethylene glycol ether monomers M(EG3), M(EG4), M(EG5), M(EG6), and M(EG7) were synthesized using essentially the same method as in Preparation Example 1, with the only difference being that equal amounts of triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, and heptaethylene glycol were used instead of diethylene glycol in Preparation Example 1. The properties, yields, and other characteristics of the synthesized monomers were observed. 1 H NMR, 13 The C NMR and HRMS are as follows.

[0135] Diallyl triethylene glycol ether monomer M(EG3): pale yellow liquid, yield 75.4%; 1 H NMR (400MHz, CDCl3, 298K, δin ppm): 5.96-5.87(m,2H),5.30-5.16(m,4H),4.04-4.01(m,4H),3.67-3.65(m,8H),3.65-3.59(m,4H). 13 C NMR (100MHz, CDCl3, 298K, δin ppm): 134.85, 117.16, 72.31, 70.72, 69.51. HRMS (ESI) (m / z): [M+Na] + calc.for C 12 H 22 NaO4 + ,253.1416;found,253.1403.

[0136] Diallyl tetraethylene glycol ether monomer M(EG4): pale yellow liquid; yield 79.5%; 1 H NMR (400MHz, CDCl3, 298K, δin ppm): 5.96-5.87(m,2H),5.29-5.16(m,4H),4.03-4.02(d,4H),3.66(d,12H),3.61-3.59(m,4H). 13C NMR (100MHz, CDCl3, 298K, δin ppm): 134.84, 117.16, 72.30, 70.70, 69.50. HRMS (ESI) (m / z): [M+Na] + calc.for C 14 H 26 NaO5 + ,297.1678;found,297.1662.

[0137] Diallyl pentaethylene glycol ether monomer M(EG5): pale yellow liquid; yield 75.9%; 1 H NMR (400MHz, CDCl3, 298K, δin ppm): 5.96-5.87(m,2H),5.29-5.17(m,4H),4.03-4.02(d,4H),3.66(m,16H),3.66-3.59(m,4H). 13 C NMR (100MHz, CDCl3, 298K, δin ppm): 134.85, 117.13, 72.30, 70.67, 69.50. HRMS (ESI) (m / z): [M+Na] + calc.for C 16 H 30 NaO6 + ,341.1940; found,341.1925.

[0138] Diallyl hexaethylene glycol ether monomer M(EG6): pale yellow liquid; yield 73.2%; 1 H NMR (400MHz, CDCl3, 298K, δin ppm): 5.96-5.87(m,2H),5.30-5.17(m,4H),4.04-4.02(d,4H),3.67(m,20H),3.65-3.59(m,4H). 13 C NMR (100MHz, CDCl3, 298K, δin ppm): 134.83, 117.12, 72.28, 70.65, 69.49. HRMS (ESI) (m / z): [M+Na] + calc.for C 18 H 34 NaO7 + ,385.2202;found,385.2186.

[0139] Diallyl heptaethylene glycol ether monomer M(EG7): pale yellow liquid; yield 70.9%; 1H NMR (400MHz, CDCl3, 298K, δin ppm): 5.96-5.85(m,2H),5.29-5.15(m,4H),4.03-4.00(d,4H),3.66(m,24H),3.64-3.58(m,4H). 13 C NMR (100MHz, CDCl3, 298K, δin ppm): 134.82, 117.17, 72.29, 70.63, 69.49. HRMS (ESI) (m / z): [M+Na] + calc.for C 20 H 38 NaO8 + ,429.2464;found,429.2439.

[0140] Preparation Example 7: Synthesis of Diallylpiperazine Monomer M(Pz)

[0141] In a 100 mL flask, weigh 14 mL of a saturated aqueous solution of anhydrous piperazine (4.30 g, 0.050 mol) and anhydrous potassium carbonate (15.00 g, 0.108 mol), place it in an ice-water bath, and slowly add allyl chloride (8.42 g, 0.110 mol) dropwise through a constant pressure dropping funnel over 1 hour. After the addition is complete, stir the mixture at room temperature for 24 hours.

[0142] After the reaction was completed, the mixture was extracted with 3×50 mL of dichloromethane, the organic phases were combined, anhydrous sodium sulfate was added and dried, the solution was rotary evaporated to dryness and then separated by column chromatography (dichloromethane:methanol v / v = 10:1), and after vacuum drying, 6.70 g of yellow liquid was obtained, which was the diallylpiperazine monomer M(Pz), with a yield of 80.6%.

[0143] Diallyl piperazine monomer M(Pz) 1 H NMR (400MHz, CDCl3, 298K, δin ppm): 5.88-5.78(m,2H),5.18-5.09(m,4H),2.98-2.96(m,4H),2.47(s,8H). 13 C NMR (100MHz, CDCl3, 298K, δinppm): 134.97, 118.07, 61.39, 53.01. HRMS (ESI) (m / z): [M+H] + calc.for C 10 H 19 N2 + ,167.1548;found,167.1539.

[0144] Example 1

[0145] This example illustrates the effect of solvent on the stepwise addition polymerization of hypophosphite and diallyl pentaethylene glycol ether.

[0146] According to the initial molar ratio of [M(EG5)]0:[HPA]0:[AIBN]0 = 1:1:0.25, diallyl pentaethylene glycol ether M(EG5) (318 mg, 1 mmol), hypophosphite HPA (66 mg, 1 mmol), and initiator AIBN (14 mg, 0.083 mmol) were added to different solvents (0.75 mL) as shown in Table 1. After adding a stir bar and performing three deoxygenation and inert gas (nitrogen) purging operations, the U-shaped tube was sealed with silicone oil. The Shrek flask was then transferred to a magnetic stirrer set to 1000 rpm and heated in an oil bath (75°C) for polymerization (14 mg of AIBN was added every 24 hours, for a total of three additions). After a total reaction time of 72 hours, the sealed container was removed and the polymerization system was opened. The system was diluted with ethanol (1 mL) and poured into about 40 mL of petroleum ether. The mixture was then separated by phase separation in a round-bottom flask. The upper solvent was removed by decantation, and the remaining solvent was removed by rotary evaporation. The mixture was then dried under vacuum at 60°C to obtain the polymer product.

[0147] Table 1. Effect of solvent on the polymerization of hypophosphoric acid with dielyl pentaethylene glycol ether

[0148]

[0149] Remark: a Obtained by gravimetric analysis; b The results were obtained by aqueous phase GPC testing calibrated with polyethylene glycol standard samples. c Obtained through GPC testing; d Unable to obtain.

[0150] As shown in Experiment 1-1, under solvent-free bulk melt reaction conditions, hypophosphite and diallyl pentaethylene glycol ether underwent rapid polymerization, resulting in cross-linking. The resulting blocky product exhibited only a certain degree of swelling but was insoluble. As shown in Experiments 1-2 to 1-12, polymerization reactions were conducted in various solvents (toluene, acetonitrile, tetrahydrofuran, dimethyl sulfoxide, 1,4-dioxane, n-propanol, isopropanol, n-butanol, methyl ethyl ketone, chlorobenzene, and ethanol). The number-average molecular weights of the resulting polymers ranged from 5000 to 10000 g / mol, and the polydispersity index (PDI) ranged from 1.65 to 2.57, which is a reasonable range for stepwise polymerization. When chlorobenzene, n-propanol, and ethanol were used as polymerization solvents, the degree of polymerization, based on GPC testing, exceeded 20. When ethanol was used as the polymerization solvent, the number-average molecular weight of the polymer reached 9500 g / mol, the degree of polymerization was 24, and the PDI was 1.82. Therefore, ethanol is a relatively ideal solvent. In the following experiments, ethanol was primarily used as the polymerization solvent.

[0151] Example 2

[0152] This example illustrates the effect of polymerization time on the stepwise addition polymerization of hypophosphite and diallyl pentaethylene glycol ether.

[0153] Following an initial molar ratio of [M(EG5)]0:[HPA]0:[AIBN]0 = 1:1:0.25, diallyl pentaethylene glycol ether M(EG5) (636 mg, 2 mmol), hypophosphite HPA (132 mg, 2 mmol), and initiator AIBN (27 mg, 0.17 mmol) were added to an ethanol solvent system (1.5 mL). A stir bar was placed in the system, and after three deoxygenation and inert gas (argon or nitrogen) purging operations, the U-shaped tube was sealed with silicone oil. The Shrek flask was then transferred to a magnetic stirrer set to 1000 rpm and heated in an oil bath (75°C) for polymerization. After the specified polymerization time was reached (if it exceeded 24 hours, 27 mg of AIBN was added every 24 hours for a total of three additions),... After the reaction is complete, the mixture is cooled to room temperature. The sealed container is removed and opened. The polymerization system is diluted with ethanol (1 mL) and poured into about 35 mL of petroleum ether. The mixture is then separated by phase separation and precipitation in a round-bottom flask. The upper solvent layer is removed by decantation, and any remaining solvent is removed by rotary evaporation. The mixture is then thoroughly dried under vacuum at 60 °C to obtain the polymer product.

[0154] Table 2. Effect of polymerization time on the polymerization of hypophosphite and dielyl pentaglycol ether

[0155]

[0156] Remark: a Obtained by gravimetric analysis; b The results were obtained by aqueous phase GPC testing calibrated with polyethylene glycol standard samples. c Obtained through GPC testing; d Unable to obtain.

[0157] Time analysis of the stepwise polymerization reaction can determine the degree of polymerization. Table 2 shows that the entire polymerization process can be divided into three stages, corresponding to the three batches of initiator AIBN added. In the first stage, HPA and M(EG)5 rapidly convert to lower molecular weight oligomers with a number-average molecular weight of 2000–3000 g / mol, at which point the yield is less than 50%. In the latter two stages of polymerization, the conversion rate continues to increase, but quite slowly, reaching 63.4% and 80.1% in the second and third stages, respectively. The significant decrease in polymerization rate in the latter two stages is mainly due to the significant reduction in the concentration of HPA and M(EG)5 monomers in the system. With the continuous addition of AIBN, free radicals are further replenished, and the oligomers gradually convert to higher molecular weight polymers until the highest yield is approximately 80%. GPC characterization results further confirm that after batch addition of AIBN, the molecular weight of the polymer product from the stepwise polymerization continuously increases throughout the three stages of the polymerization process, with a PDI of approximately 1.5–1.8.

[0158] The phosphorus-containing polymer polyP(EG5) was prepared according to Experiment 2-12. Its NMR characterization results (H NMR and phosphorus NMR spectra) are as follows: Figure 1 As shown. Figure 1 middle 1 H proton peak and 31 The clear attribution of the phosphorus peak confirms the correctness of the polyP(EG5) structure, demonstrating the highly efficient and successful preparation of a novel phosphorus-containing polymer, polyP(EG5), with the desired composition under optimized polymerization conditions. This lays the foundation for the systematic development of work on the preparation of lithium salt polyelectrolytes and further functionalization of phosphorus-containing surfactants through polymer esterification modification, as well as the expansion of functional polymers.

[0159] Example 3

[0160] This embodiment is used to illustrate the phosphorus-containing polymer polyP(EG) n Preparation and characterization of (n = 2 to 7).

[0161] Following the method in Experiment 2-12, phosphorus-containing polymers were prepared, with the only difference being that the α,ω-nonconjugated diene monomer was changed to M(EG). n (n = 2 to 7) can be used to prepare a series of phosphorus-containing polymers polyP(EG) n (n = 2 to 7). Table 3 shows the characterization results of the stepwise addition polymerization of dielyl n-glycol ether (oligoethylene glycol) monomer with hypophosphite.

[0162] Table 3. List of addition polymerization and characterization results of dielyl n-glycol ether monomers with hypophosphite

[0163]

[0164] Remark: a Obtained by gravimetric analysis; b The results were obtained from aqueous phase GPC tests calibrated with PEG standard samples. c Obtained through GPC testing.

[0165] As shown in Table 3, under the above optimized reaction conditions, the polyoxyethylene glycol polyphosphonic acid polymer prepared by the polymerization of functional non-conjugated diene monomers and hypophosphite has a high yield (>70%), a degree of polymerization of around 20 (19-24), which is relatively consistent, and the molecular weight distribution also conforms to the step-growth polymerization characteristic range (1.24-2.32), providing a basis for the preparation of functional polyelectrolyte composite materials.

[0166] Example 4

[0167] This embodiment illustrates the preparation and characterization of phosphorus-containing polymer lithium salt composite polyelectrolyte materials.

[0168] 1. Preparation of phosphorus-containing polymer-lithium salt composite polyelectrolyte materials

[0169] PolyP(EG2) was prepared according to the scale-up experiment in Experiment 3-1. 0.1 g of polyP(EG2) sample and 0.015 g of lithium trifluoromethanesulfonate (accounting for 15 wt% of the polymer sample) were weighed and dissolved in 10 mL of ultrapure water. Then, the flask was transferred to a magnetic stirrer with a set speed of 1000 rpm and heated in an oil bath (60 °C) for doping reaction preparation. After 6 h, the water was evaporated to dryness, vacuum dried at 60 °C for 48 h, and then kept at 100 °C for 12 h.

[0170] Based on experiments 3-2 to 3-6, several other polymers in the same series, polyP(EG3), polyP(EG4), polyP(EG5), polyP(EG6), and polyP(EG7), and the comparative polyethylene glycol PEG(M) were prepared using the same method. n A polyelectrolyte composed of a complex of lithium trifluoromethanesulfonate (6000 g / mol) and 15 wt% lithium trifluoromethanesulfonate.

[0171] 2. Ionic conductivity and powder diffraction XRD characterization analysis of the composite polyelectrolyte

[0172] The composite polyelectrolyte was characterized by electrochemical impedance spectroscopy (EIS) and powder X-ray diffraction (XRD). The ionic conductivity of the composite polyelectrolyte was measured using EIS at a frequency of 10⁻⁶ ppm. 6 The frequency was ~10Hz, the amplitude was 800mV, and the testing instrument was a Princeton multichannel electrochemical workstation. The interdigitated electrode method was used for testing, and the test temperature range was 30~140℃. Figure 2 The phosphorus-containing polymer polyP(EG) was prepared. nThe ionic conductivity of the polyelectrolytes of the composites (n=2-7) and the control example PEG doped with 15 wt% LiCF3SO3 as a function of temperature is shown in Table 4. n The range of AC impedance and ionic conductivity of composite polyelectrolytes doped with 15 wt% LiCF3SO3 at different temperatures (n=2-7) and control examples were studied. Figure 2 As shown in Table 4, with the increase of the polyoxyethylene glycol chain length in the polymer, the ionic conductivity at 30℃ increases from 1.13 × 10⁻⁶ to 1.13 × 10⁻⁶. -6 Significantly improved to 1.58×10 -4 S / cm, and compared to the control example based on PEG polyelectrolyte, the polymer contains oligoethylene glycol P (EG) n In polyelectrolytes with n greater than 4, the ionic conductivity is significantly improved. The ionic conductivity increases with increasing temperature, reaching up to 10. -3 On the order of magnitude of S / cm.

[0173] Table 4. Variation range of AC impedance and ionic conductivity of composite polyelectrolytes at different temperatures

[0174]

[0175] Figure 3 The prepared phosphorus-containing polymer polyP(EG) n XRD patterns of composite polyelectrolytes of PEG (n=2-7) and PEG-doped with 15 wt% LiCF3SO3, respectively. (The XRD patterns are also shown for the PEG-15 wt% LiCF3SO3 composite polyelectrolytes.) + It can be seen that there are obvious PEG crystallization characteristic diffraction peaks at 2θ = 19° and 25°, while the composite polyelectrolyte sample prepared in this invention does not show obvious crystallization peaks, but only broad peaks between 2θ = 10° and 30°, indicating its amorphous polymer characteristics. The phosphorus-containing polymer lithium salt composite polyelectrolyte based on poly(ethylene glycol) completely suppresses PEG crystallization within the investigated oligomer range. It is believed that ion conduction in PEG-based lithium salt polyelectrolytes occurs in the amorphous region, so the ionic conductivity of such materials is significantly enhanced by suppressing PEG crystallization, which is more conducive to ion conduction. Combining diffraction analysis and ionic conductivity testing, it can be seen that the phosphorus-containing ionic polymer based on PC bonding provides a new approach for the design and preparation of high-performance battery polyelectrolyte materials.

[0176] Example 5

[0177] This example illustrates the preparation and characterization of dodecyl ester surfactants containing phosphorus polymers.

[0178] 1. Preparation of dodecyl ester surfactants from poly(ethylene glycol) phosphorus-containing polymers of different lengths

[0179] PolyP(EG2) was prepared according to the scale-up experiment in Experiment 3-1. PolyP(EG2) (0.480 g, 2 mmol, based on the molecular weight of repeating units), 1-bromododecane (0.997 g, 4 mmol), cesium carbonate catalyst (1.303 g, 4 mmol), and 3 mL of acetonitrile solvent were weighed into an ampoule. A stir bar was placed inside, and the ampoule was sealed after three oxygen removal and inert gas (argon or nitrogen) purging operations. The ampoule was then transferred to a magnetic stirrer at a set speed of 1000 rpm and heated in an oil bath (75 °C) for 24 hours. After filtration to remove cesium carbonate, 5 mL of ethanol was added to dilute the reaction solution, and approximately 80 mL of petroleum ether was added dropwise. The mixture was then separated by phase separation in a round-bottom flask. The upper solvent layer was removed by decantation, and the remaining solvent was removed by rotary evaporation. The mixture was then thoroughly dried under vacuum at 60 °C to obtain 0.694 g of a pale yellow viscous liquid, namely polyP(EG2)-C12.

[0180] Based on experiments 3-4 and 3-6, dodecyl ester surfactants polyP(EG5)-C12 and polyP(EG7)-C12 of two other polymers in the same series, polyP(EG5) and polyP(EG7), were prepared using the same method. The degree of esterification of dodecyl esters of different lengths of oligomeric polyethylene glycol phosphorus-containing polymers is shown in Table 5.

[0181] Table 5. Degree of esterification of dodecyl esters of oligomeric polyethylene glycol phosphorus-containing polymers of different lengths

[0182]

[0183] Remark: a The degree of esterification is calculated from the area ratio of the characteristic peaks in the 1H NMR spectrum.

[0184] 2. Solution assembly behavior of dodecyl ester surfactants containing phosphorus and their polymeric nanomicelles preparation

[0185] Weigh 10 mg of the dodecyl ester surfactant sample containing phosphorus polymer and dissolve it in 2 mL of THF. Add a stir bar and stir at room temperature for 1 h to ensure complete dissolution. Add 10 mL of ultrapure water dropwise to the above solution, stir at room temperature for 0.5 h, and then rotary evaporate at 20 °C for 2 h to remove THF. Finally, add 90 mL of ultrapure water to obtain a polymer assembly solution with a concentration of 0.1 mg / mL. Then, use a pipette to drop 7 μL of the sample solution onto a carbon-plated copper grid, dry at room temperature for 24 h, and perform TEM characterization. The remaining solution was subjected to DLS analysis. The results are shown in the figure. Figure 4 See Table 6.

[0186] Table 6. Particle size of micelles assembled from dodecyl esters of phosphorus-containing polymers in 0.1 mg / mL aqueous solution.

[0187]

[0188]

[0189] Figure 4 Images a-4c show TEM images of polyP(EG2)-C12, polyP(EG5)-C12, and polyP(EG7)-C12, respectively. The images show that when the assembly solution concentration is 0.1 mg / mL, all three groups of phosphorus-containing polymer dodecyl ester surfactant samples successfully assembled to form nano-sized polymer micelles. The nanoparticles were spherical. With changes in the length of the oligomeric polyethylene glycol in the polymer chain, the diameter of the polymer surfactant nanoparticles observed in the TEM field of view gradually increased from 30 nm to 270 nm, exhibiting good particle size uniformity. The corresponding DLS test results (…) Figure 4 The results (d and Table 6) show good agreement with the TEM characterization results. This type of phosphorus-containing polymer long-chain alkyl ester surfactant is a novel phosphorus-containing polymer surfactant and nano-assembly material, which is expected to be applied in the field of biomedical research.

[0190] 3. Determination of the critical micelle concentration of dodecyl ester surfactants in phosphorus-containing polymers by fluorescence spectroscopy. (CMC)

[0191] The critical micelle concentration of dodecyl ester surfactants containing phosphorus polymers in aqueous solution was determined using the pyrene fluorescent probe method. The specific experimental steps are as follows: First, a 0.012 mg / mL pyrene-acetone solution was prepared; then, 0.1 mL of the pyrene-acetone solution was added to each of ten 10 mL volumetric flasks. The acetone in the volumetric flasks was evaporated by heating to ensure that the concentration of the volumetric flasks was 6 × 10⁻⁶ during calibration. -7 mol / L (saturated solubility of pyrene in aqueous solution at room temperature). A series of polymer solutions of different concentrations were prepared and added to the aforementioned volumetric flasks to achieve a concentration ranging from 0.05 μg / mL to 1 mg / mL. The volumetric flasks were placed in a 60°C water bath and stirred for 2 hours to ensure uniform dispersion of pyrene in the aqueous solution. After cooling to room temperature, water was added to make up the volume before testing.

[0192] Pyrene is a fluorescent probe with strong hydrophobicity and a solubility of 10 in water. -7 M. If micelles or other macromolecular systems are present in the system, pyrene will enter the hydrophobic region of the micelles. As the content of pyrene in the polar solvent changes, the forbidden transition of the first singlet state fluorescence of pyrene changes, and the emission spectrum shows a significant change. When the lasing wavelength is 394 nm, its emission spectrum is typically measured to be in the range of I. 337nm with I334nm The intensity ratio and its dependence on polymer concentration were determined from the transition point. Table 7 lists the critical micelle concentrations (CMCs) of the dodecyl ester surfactants polyP(EG2)-C12, polyP(EG5)-C12, and polyP(EG7)-C12 of phosphorus-containing polymers in aqueous solution. These surfactants have CMC values ​​similar to those of protein-related polysaccharides, including polylactose, polyliposuction, and polymannose (see CGAnaukwu, Br. Microbiol. Res. J., 2015, 10, 1-9; DKF Fantos, Front. Microbiol., 2017, 8, 1-11), making them promising candidates for applications in biomedicine and everyday personal care and cosmetic products.

[0193] Table 7. Critical micelle concentrations of dodecyl ester surfactant solutions containing phosphorus polymers

[0194]

[0195] Example 6

[0196] This invention illustrates the preparation and characterization of a phosphorus-containing polymer polyP(Pz) that simultaneously incorporates nitrogen.

[0197] According to the initial molar ratio of [M(Pz)]0:[HPA]0:[AIBN]0 = 1:1:0.25, diallyl piperazine M(Pz) (831 mg, 5 mmol), hypophosphite HPA (330 mg, 5 mmol), and AIBN (68 mg, 0.42 mmol) were added to a Shrek flask containing ethanol solvent (5 mL), a stir bar was placed in, and the flask was sealed after three oxygen removal and inert gas (argon or nitrogen) purging operations. The Shrek flask was then transferred to a magnetic stirrer set to 1000 rpm and heated in an oil bath (75°C) for polymerization (68 mg of AIBN was added every 24 hours, for a total of three additions). After 72 hours of reaction, the mixture was removed and cooled to room temperature. The sealed container was opened, and the polymerization system was diluted with ethanol (5 mL). The solution was then poured into approximately 80 mL of petroleum ether and allowed to separate by phase separation in a round-bottom flask. The upper solvent layer was removed by decantation, and any remaining solvent was removed by rotary evaporation. The mixture was then thoroughly dried under vacuum at 60°C to obtain a pale yellow solid phosphorus-containing polymer, polyP(Pz), weighing 856 mg, with a yield of 73.7%. GPC analysis of the aqueous phase showed that the polymer had a number-average molecular weight of 10600 g / mol and a polydispersity index of 2.41.

[0198] Example 7

[0199] This embodiment illustrates the polymer flame retardant polyP(Pz)Al and its preparation method.

[0200] The phosphorus-containing polymer polyP(Pz) was prepared according to the scale-up experiment in Example 6. 4.645 g (0.02 mol, calculated as a repeating unit) of polyP(Pz) was dissolved in 100 mL of ethanol. 2.414 g (0.01 mol) of aluminum chloride hexahydrate was dissolved in 20 mL of ethanol. The solutions were slowly added dropwise over 10 min using a constant-pressure dropping funnel to the polyP(Pz) ethanol solution. The reaction was carried out at 80 °C and 1000 rpm for 16 h. After the reaction, the solution was washed with a large amount of ethanol (500 mL) and dried under vacuum at 60 °C to obtain 4.351 g of white powder.

[0201] Example 8

[0202] This embodiment illustrates the polymer flame retardant polyP(Pz)NH4 and its preparation method.

[0203] The phosphorus-containing polymer polyP(Pz) was prepared according to the scale-up experiment in Example 6. 5g of the phosphorus-containing polymer polyP(Pz) was weighed and dissolved in 100mL of deionized water. At room temperature and a rotation speed of 1000rpm, concentrated ammonia solution was slowly added dropwise to the aqueous solution of the phosphorus-containing polymer polyP(Pz) through a constant pressure dropping funnel over 10min. The pH of the solution was adjusted to pH=10, and the reaction was stirred for 18h. After the reaction was completed, the solution was rotary evaporated to dryness and vacuum dried at 60℃ to obtain 5.31g of yellow powder.

[0204] Example 9

[0205] This embodiment illustrates flame-retardant polymer composite materials containing polymer flame retardants and their characterization.

[0206] 1. Preparation of flame-retardant polymer composites using phosphorus-containing polymer flame retardants

[0207] Epoxy resin E-51 (15g) and different masses of polymer flame retardants, such as the polymer flame retardant polyP(Pz)Al (0.989g, 5wt%) prepared in Example 7, were weighed into a 250mL beaker. The mixture was mechanically stirred at 120℃ and 500rpm for 30min. Then, curing agent DDM (3.75g) was added, and the mixture was mechanically stirred at 110℃ and 500rpm for 10min. Afterward, the mixture was vacuum degassed at 120℃ for 3min to obtain a prepolymer. The prepolymer was poured into a polytetrafluoroethylene mold (110mm × 12mm × 4mm, pre-coated with high-vacuum silicone grease, and preheated at 120℃). The mold was cured at 120℃ for 2h, then heated to 170℃ for 4h. The resulting sample is shown in the figure. Figure 5.

[0208] 2. Preparation of blank control specimens of cured epoxy resin without added polymer flame retardants

[0209] 15g of epoxy resin E-51 and 3.75g of curing agent DDM were weighed into a 250mL beaker. The mixture was mechanically stirred at 110℃ and 500rpm for 30min, followed by vacuum degassing at 120℃ for 3min to obtain a prepolymer. The prepolymer was poured into a polytetrafluoroethylene mold (110mm×12mm×4mm, pre-coated with high-vacuum silicone grease and preheated to 120℃), cured at 120℃ for 2h, and then heated to 170℃ for 4h. After demolding, a blank control sample of cured epoxy resin without phosphorus-containing polymer flame retardant was obtained. The prepared sample is shown in [reference needed]. Figure 5 .

[0210] The formulation of the cured epoxy resin flame-retardant composite material is shown in Table 8.

[0211] Table 8. Formulation of Cured Epoxy Resin Flame Retardant Composite Materials

[0212]

[0213] 3. Thermogravimetric analysis characterization of flame-retardant epoxy resin composites with added phosphorus and nitrogen synergistic polymer flame retardants

[0214] The thermal stability of the blank control sample and four groups of epoxy resin flame-retardant polymer composite samples was characterized by thermogravimetric analysis (TGA) in nitrogen and air atmospheres. The TGA curves of the blank control and the flame-retardant polymer composites are shown below. Figure 6 As shown, some typical data are listed in Table 9.

[0215] Table 9. TGA thermogravimetric analysis results of blank control and flame-retardant epoxy resin composites

[0216]

[0217] Remark: a The temperature at which 5% decomposition occurs; b The temperature at which the decomposition rate is fastest; c Residual amount after decomposition at 700℃.

[0218] Depend on Figure 6 As shown in Table 9, in flame-retardant epoxy resin composites with added polymer flame retardants polyP(Pz)Al or polyP(Pz)NH4, under nitrogen or air atmosphere, the initial decomposition temperature (T) of the flame-retardant epoxy resin composite with 1% flame retardant is... d,5％ ) and the temperature of maximum decomposition rate (T) maxThe values ​​were comparable to the blank sample; however, the addition of 5% more flame retardant resulted in a decrease in both temperatures, especially a significant decrease in the initial decomposition temperature, exceeding 20K. At 700℃, the char residue (R) of the four composite samples... 700 The residual char content was improved compared to the blank sample, increasing by about 8% under nitrogen atmosphere and by 2-3% under air atmosphere. Therefore, this flame-retardant polymer composite system retains the high thermal stability of the cured epoxy resin itself and improves its char retention rate in nitrogen atmosphere and air.

[0219] 4. Determination of Limiting Oxygen Index and Fire Resistance Rating of Flame-Retardant Epoxy Resin Composites

[0220] The limiting oxygen index of the blank control and four groups of flame-retardant epoxy resin composite samples in nitrogen atmosphere and air atmosphere were determined, and the fire resistance rating was evaluated. The oxygen index of the flame-retardant epoxy resin composite was determined according to the national standard GB / T 2406-93 Test Method for Burning Performance of Plastics, and the fire resistance rating was measured by UL94 vertical burning test. The results are shown in Table 10.

[0221] Table 10. Limiting Oxygen Index (LOI) Determination and Fire Resistance Rating Evaluation of Flame-Retardant Epoxy Resin Composites

[0222]

[0223] Table 10 shows that the LOI of the blank sample was 24.4%, classifying it as a combustible sample (20%–26%). The prepared flame-retardant epoxy resin composites, with the addition of more than 1% polyP(Pz)Al or 1% polyP(Pz)NH4, had an LOI greater than 26.8%, classifying them as flame-retardant samples (26%–34%). The UL94 vertical burning test results showed that the blank thermosetting sample did not reach the lowest flame retardant rating in the UL94 standard during the first burn, while the thermosetting epoxy resin sample with only 1% polymer flame retardant reached the UL94 V-1 rating, with a shorter burning time and no dripping. During the second ignition, only the blank pure epoxy resin thermosetting sample burned; the four groups of flame-retardant epoxy resin composite samples failed to ignite. This indicates that during the first ignition and extinguishing process, the flame-retardant substances released by the two composite samples coated the sample surface, preventing secondary combustion and improving flame retardant performance.

Claims

1. A phosphorus-containing polymer, characterized in that, The phosphorus-containing polymer comprises repeating units derived from α,ω-nonconjugated diene monomers and repeating units derived from phosphorus source monomers. The α,ω-nonconjugated diene monomers are selected from diallyl n-glycol ethers and diallyl piperazine. The phosphorus source monomers are selected from hypophosphorous acid and hypophosphite. The phosphorus-containing polymer is a polymer obtained by stepwise free radical addition polymerization of the α,ω-nonconjugated diene monomers and the phosphorus source monomers, wherein n = 2 to 7 in the diallyl n-glycol ethers.

2. The phosphorus-containing polymer according to claim 1, characterized in that, The number-average molecular weight of the phosphorus-containing polymer is 1000-20000 g / mol; And / or, the molecular weight distribution index of the phosphorus-containing polymer. M w / M n is 1.1-3.

0.

3. The phosphorus-containing polymer according to claim 2, characterized in that, The number-average molecular weight of the phosphorus-containing polymer is 2000-15000 g / mol; And / or, the molecular weight distribution index of the phosphorus-containing polymer. M w / M n is 1.2-2.

6.

4. A method for preparing phosphorus-containing polymers, characterized in that, The preparation method includes the following steps: In the presence of a free radical initiator, an α,ω-nonconjugated diene monomer is subjected to a stepwise free radical addition polymerization reaction with a phosphorus source monomer, wherein the α,ω-nonconjugated diene monomer is selected from diallyl n-glycol ether and diallyl piperazine, and the phosphorus source monomer is selected from hypophosphorous acid and hypophosphite, wherein n = 2 to 7 in the diallyl n-glycol ether.

5. The preparation method according to claim 4, characterized in that, The molar ratio of the α,ω-nonconjugated diene monomer, the phosphorus source monomer, and the free radical initiator is 1:1:(0.05~0.75); and / or, the free radical initiator is selected from azobisisobutyronitrile, benzoyl peroxide, or persulfate; And / or, the radical addition step-growth polymerization reaction is carried out in the presence of a solvent; And / or, the conditions for the free radical addition stepwise polymerization reaction include: a temperature of 50~100℃ and a reaction time of 1~80h; and / or, carried out under an inert atmosphere; and / or, a stirring speed of 500~1500 rpm.

6. The preparation method according to claim 5, characterized in that, The molar ratio of the α,ω-nonconjugated diene monomer, the phosphorus source monomer, and the free radical initiator is 1:1:(0.2~0.3); And / or, the solvent is selected from toluene, chlorobenzene, acetonitrile, tetrahydrofuran, 1,4-dioxane, n-propanol, isopropanol, n-butanol, methyl ethyl ketone, ethanol, and dimethyl sulfoxide; and / or, the volume-to-mass ratio of the solvent to the α,ω-nonconjugated diene monomer is 1.5-5 mL: 1 g; And / or, the conditions for the free radical addition stepwise polymerization reaction include: a temperature of 75 ± 5 ℃, and / or, a reaction time of 36-72 h; and / or, the inert atmosphere is a nitrogen atmosphere; and / or, the stirring speed is 1000~1200 rpm.

7. The preparation method according to claim 5, characterized in that, The molar ratio of the α,ω-nonconjugated diene monomer, the phosphorus source monomer, and the free radical initiator is 1:1:0.25; And / or, the solvent is ethanol; and / or, the volume-to-mass ratio of the solvent to the α,ω-nonconjugated diene monomer is 2-3 mL: 1 g.

8. A lithium salt complex polyelectrolyte, characterized in that, The lithium salt complex polyelectrolyte comprises the phosphorus-containing polymer of any one of claims 1-3 or the phosphorus-containing polymer prepared by any one of claims 4-7, and the doped lithium trifluoromethanesulfonate.

9. The lithium salt complex polyelectrolyte according to claim 8, characterized in that, The α,ω-nonconjugated diene monomer in the phosphorus-containing polymer is diallyl n-glycol ether.

10. The lithium salt complex polyelectrolyte according to claim 9, characterized in that, Based on the mass of the lithium salt complex polyelectrolyte, the doping amount of the lithium trifluoromethanesulfonate is 1-50 wt.

11. The lithium salt complex polyelectrolyte according to claim 9, characterized in that, Based on the mass of the lithium salt complex polyelectrolyte, the doping amount of the lithium trifluoromethanesulfonate is 5-30 wt.

12. A polyphosphonate surfactant, characterized in that, The polyphosphonate surfactant comprises the reaction product of the phosphorus-containing polymer of any one of claims 1-3 or the phosphorus-containing polymer prepared by any one of claims 4-7, the catalyst, and 1-bromododecane.

13. The polyphosphonate surfactant according to claim 12, characterized in that, The catalyst is cesium carbonate; And / or, the α,ω-nonconjugated diene monomer in the phosphorus-containing polymer is diallyl n-glycol ether; And / or, based on the total number of repeating units derived from α,ω-nonconjugated diene monomers and phosphorus-derived monomers in the phosphorus-containing polymer, the molar ratio of the phosphorus-containing polymer, the catalyst, and 1-bromododecane is 1 : (0.25~2) :

2.

14. The polyphosphonate surfactant according to claim 12, characterized in that, The molar ratio of the phosphorus-containing polymer, the catalyst, and 1-bromododecane is 1:2:2, based on the total repeating units derived from α,ω-nonconjugated diene monomers and phosphorus-derived monomers in the phosphorus-containing polymer.

15. A flame retardant based on a phosphorus-containing polymer, characterized in that, The flame retardant comprises the reaction product of a phosphorus-containing polymer according to any one of claims 1-3 or a phosphorus-containing polymer prepared by any one of claims 4-7 with an alkaline substance.

16. The flame retardant according to claim 15, characterized in that, The α,ω-nonconjugated diene monomer in the phosphorus-containing polymer is diallyl piperazine; And / or, the alkaline substance is selected from aluminum chloride and ammonia; And / or, based on the total number of repeating units derived from α,ω-nonconjugated diene monomers and phosphorus-derived monomers in the phosphorus-containing polymer, the molar ratio of the phosphorus-containing polymer to the alkaline substance is 1.8-2.2:

1.

17. A flame-retardant epoxy resin, characterized in that, The flame-retardant epoxy resin comprises a cured epoxy resin and a flame retardant as described in claim 15 or 16 dispersed therein.

18. The flame-retardant epoxy resin according to claim 17, characterized in that, The flame-retardant epoxy resin comprises the reaction product of epoxy resin, the flame retardant, and the curing agent.

19. The flame-retardant epoxy resin according to claim 18, characterized in that, The epoxy resin is E-51; And / or, the mass ratio of the epoxy resin, the flame retardant and the curing agent is 4 : (0.05-0.55) : (0.8-1.2).

20. The flame-retardant epoxy resin according to claim 19, characterized in that, The mass ratio of the epoxy resin, the flame retardant, and the curing agent is 4:(0.05-0.55):

1.

21. The flame-retardant epoxy resin according to claim 19, characterized in that, The mass ratio of the epoxy resin, the flame retardant, and the curing agent is 4:0.26:1.

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