Flame-retardant polyphenol-based coordination polymers, methods of making and using the same, and methods of recycling the polyphenol-based coordination polymers

Abstract

The application provides a kind of flame-retardant polyphenol-based coordination polymer and its preparation method and application and the recovery method of the polyphenol-based coordination polymer, the coordination bond structural unit formed by the coordination of central ion and polyphenol monomer is contained in the molecular chain of the polymer, and the polyphenol-based coordination polymer is formed by condensation of binary acid or its ester and / or ternary acid or its ester and C2-C10 binary alcohol, binary acid or its ester at least includes binary acid or its ester containing coordination bond structural unit, and ternary acid or its ester includes ternary acid or its ester containing coordination bond structural unit.The tensile strength of the polymer is flexibly adjustable in the range of 45.0-120.0MPa, and the highest can pass UL-94 vertical burning V-0 level, which can meet the application requirements in the fields of fiber, non-woven fabric, battery separator, film, medical and health care materials, etc., and can also be used as a modified processing aid.The polymer can be quickly and mildly chemically closed-loop recycled after use, solving the disposal problem of such waste materials.

Description

Technical Field

[0001] This invention belongs to the field of novel polymer preparation, application and waste recycling technology, specifically relating to a multifunctional, high-performance novel flame-retardant polyphenolic coordination polymer, its preparation method and application, and a recycling method for the polyphenolic coordination polymer. Background Technology

[0002] Polymer materials, due to their advantages such as good chemical stability, strong corrosion resistance, adjustable properties, ease of molding and processing, and low manufacturing cost, have become indispensable materials for economic and national defense construction and people's lives. Since the 1980s, with the near absence of new large-scale industrial polymers, the main development trend of polymer materials is to achieve multifunctionality and high performance through various modification methods to meet the higher performance requirements of various industries. Entering the 21st century, the widespread application of polymer materials has not only consumed large amounts of fossil resources, but also exacerbated the ecological and environmental damage caused by their disposal. Therefore, achieving rapid and effective recycling of polymer materials is of significant scientific and social importance.

[0003] Metal coordination bonds are a unique type of non-covalent interaction formed between metal ions and organic ligands. Their strength lies between that of covalent bonds and van der Waals forces, with bond energies ranging from 50 to 200 kJ / mol. Coordinate bonds possess the following characteristics: 1. Spontaneous bonding; 2. Highly tunable bond energy; 3. A combination of thermodynamic stability and kinetic variability; 4. Flexible tunability of the types of metal ions and ligands; 5. Multifunctionality. Currently, they are considered an effective research method in the design of novel supramolecular self-healing materials. Researchers have achieved a series of important results in the field of high-strength supramolecular self-healing materials by utilizing the combination of strong and weak coordination bonds. For example, by using a "building strength from weakness" design strategy, researchers have synthesized a carboxyl-Zn-based... 2+ A highly rigid supramolecular self-healing polymer network with weak coordination bonds (Nature Communications, 2019, 10: 1164); and a kinetically active yet thermodynamically stable metal-coordinated imine bond ~Zn 2+ By incorporating a polymer framework, a polydimethylsiloxane material with excellent toughness and room-temperature repair capabilities was obtained. The study also reported a hyperbranched polyurethane material in which the hydrophilic quaternary ammonium salt promotes chain segment movement when the polymer is damaged in a seawater environment, thereby facilitating the activation of catechol-Fe3+ under alkaline conditions. 3+ Reversible reconstruction of coordination crosslinking enables self-repair (ACS Applied Materials & Interfaces, 2020, 12(24): 27614-27624).

[0004] However, existing polymers containing coordination bonds are generally constructed using modular methods, mainly prepared through solution methods, diffusion methods, hydrothermal / solvothermal synthesis, and microwave-assisted hydrothermal / solvothermal synthesis. These methods are complex and the materials generally suffer from poor mechanical and thermal properties (Advanced Materials, 2020, 32(27):1903762). Furthermore, the molecular chains of existing thermoplastic polymers are typically composed of atoms or atomic groups (structural units) regularly connected by covalent bonds. The high strength of these covalent bonds makes it difficult to achieve rapid and effective recycling after the material's lifespan.

[0005] To meet the higher performance requirements of various industries for polymer materials, prepare multifunctional and high-performance polymer materials and their products, and achieve rapid and effective recycling of polymer materials, there is an urgent need to provide a new type of polymer material with excellent comprehensive properties such as mechanical properties, flame retardant properties, and self-healing properties. At the same time, there is a need to provide a simple, efficient, and green chemical closed-loop recycling method that facilitates the recycling of polymer materials after their use and disposal. This is of great practical significance for the research and development of new general-purpose polymer materials and the sustainable development of high-performance materials. Summary of the Invention

[0006] One of the objectives of this invention is to provide a flame-retardant polyphenolic coordination polymer.

[0007] The second objective of this invention is to provide a method for preparing flame-retardant polyphenolic coordination polymers.

[0008] A third objective of this invention is to provide a method for recycling flame-retardant polyphenolic coordination polymers.

[0009] The fourth objective of this invention is to provide an application of a flame-retardant polyphenolic coordination polymer.

[0010] The flame-retardant polyphenol-based coordination polymer provided in this application differs from traditional thermoplastic polymers linked by covalent bonds. The polyphenol-based coordination polymer molecular chain of this application contains a large number of coordination bond-containing structural units formed by the coordination of a central ion and polyphenol monomers. The strength of the coordination bonds in these structural units is close to that of covalent bonds, while also exhibiting both thermodynamic stability and kinetic variability. A novel polymer material with excellent thermal properties, mechanical properties, flame retardancy, and self-healing properties is prepared by stepwise polymerization of monomers / oligomers containing coordination bond structural units with diols, or with diols and diacids or their esters without coordination bond structural units. Furthermore, because the coordination bonds can be rapidly broken in acid / alkali environments, rapid and mild chemical closed-loop recycling can be achieved after its use and disposal. The degradation products can be easily separated and collected after degradation, and the degradation liquid can be recycled multiple times. This polyphenol-based coordination polymer has good recyclability.

[0011] To achieve the above objectives, the present invention provides the following technical solution:

[0012] In a first aspect, this application provides a flame-retardant polyphenol-based coordination polymer. The molecular chain of the polyphenol-based coordination polymer contains a structural unit with coordination bonds formed by the coordination of a central ion and a polyphenol monomer. The polyphenol-based coordination polymer is formed by the condensation polymerization of a diacid or its esterified form and / or a tricarboxylic acid or its esterified form and a C2-C10 diol. The diacid or its esterified form includes at least a diacid or its esterified form containing a coordination bond structural unit, and the tricarboxylic acid or its esterified form includes a tricarboxylic acid or its esterified form containing a coordination bond structural unit.

[0013] According to a preferred embodiment, the polyphenolic coordination polymer is composed of structural units represented by I, II, III, or I, II, IV, or I, II, V:

[0014] In the formula, R1 represents a C2 to C10 alkylene group.

[0015] In the formula, R2 represents aryl,

[0016] In the formula, R3 is any one of the following structural units:

[0017]

[0018]

[0019] as well as

[0020] Wherein, M1 is any one of the following ions with a valence of +2: Mg, Ca, V, Mn, Fe, Co, Ni, Cu, and Zn; M2 is any one of the following ions with a valence of +4: Si, Ge, Sn, Ti, Mn, and V; M3 is any one of the following ions with a valence of +3: B, Fe, Al, Ga, and In; N is any one of the following ions with a valence of +1: H, Li, Na, K, and NH4; and X1 is any one of the following: H atom, methyl, ethyl, methoxy, and phenyl.

[0021] In the formula, R4 can be any of the following structures:

[0022] as well as

[0023]

[0024] Wherein, M2 is any one of the following ions with a +4 valence: Si, Ge, Sn, Ti, Mn, and V; M3 is any one of the following ions with a +3 valence: B, Fe, Al, Ga, and In; and N is any one of the following ions with a +1 valence: H, Li, Na, K, and NH4+.

[0025] In the formula, R5 can be any of the following structures:

[0026]

[0027] as well as

[0028]

[0029] Wherein, M2 is any one of the following ions with a +4 valence: Si, Ge, Sn, Ti, Mn, and V; M3 is any one of the following ions with a +3 valence: B, Fe, Al, Ga, and In; N is any one of the following ions with a +1 valence: H, Li, Na, K, and NH4; X1 is any one of the following atoms: H, methyl, ethyl, methoxy, and phenyl; m is an integer from 2 to 50; R6 is any one of the following groups:

[0030] C1-C10 alkylene groups, as well as

[0031] According to a preferred embodiment, in the molecular chain of the polyphenolic coordination polymer, the number of structural units [Ⅲ] is 1 to 100% of the number of structural units [Ⅰ], and the ratio of structural units [Ⅰ] to structural units [Ⅱ+Ⅲ] is 1; the number of structural units [Ⅳ] is 1 to 66.7% of the number of structural units [Ⅰ], and the ratio of structural units [Ⅰ] to structural units [Ⅱ+Ⅳ] is 1 to 1.50, which is related to the number of structural units [Ⅳ]; the number of structural units [Ⅴ] is 1 to 100% of the number of structural units [Ⅰ], and the ratio of structural units [Ⅰ] to structural units [Ⅰ+Ⅴ] is 1; each structural unit or the chain segment it forms is arbitrarily connected and combined according to carboxyl and hydroxyl functional groups. The polymer has an intrinsic viscosity [η] of 0.35–1.80 dL / g; tensile strength of 45.0–120.0 MPa; elongation at break of 5.0–530.0%; initial decomposition temperature of 360–420 °C; limiting oxygen index of 22.0–35.0%; vertical flammability rating of V-2–V-0; and peak heat release rate (p-HRR) of 200–700 kW / m² in cone calorimetry. 2The total smoke release is 500–1500 m³. 2 / m 2 The self-healing temperature after the sample is cut is 100-150℃, the healing time is 5-60 min, and the healing efficiency is 75-100%.

[0032] According to a preferred embodiment, in the molecular chain of the polyphenolic coordination polymer, the number of structural units [Ⅲ] is 1 to 80% of the number of structural units [Ⅰ], and the ratio of structural units [Ⅰ] to structural units [Ⅱ+Ⅲ] is 1; the number of structural units [Ⅳ] is 1 to 40% of the number of structural units [Ⅰ], and the ratio of structural units [Ⅰ] to structural units [Ⅱ+Ⅳ] is 1 to 1.25, which is related to the number of structural units [Ⅳ]; the number of structural units [Ⅴ] is 1 to 80% of the number of structural units [Ⅰ], and the ratio of structural units [Ⅰ] to structural units [Ⅰ+Ⅴ] is 1; each structural unit or the chain segment it forms is arbitrarily connected and combined according to carboxyl and hydroxyl functional groups. The polymer has an intrinsic viscosity [η] of 0.40–1.70 dL / g; tensile strength of 50.0–110.0 MPa; elongation at break of 10.0–500.0%; initial decomposition temperature of 365–410 °C; limiting oxygen index of 23.0–33.0%; vertical flammability rating of V-2–V-0; and peak heat release rate (p-HRR) of 250–650 kW / m² in cone calorimetry. 2 The total smoke release is 550–1200 m³. 2 / m 2 The self-healing temperature after the sample is cut is 105-130℃, the healing time is 5-40 min, and the healing efficiency is 80-100%.

[0033] According to a preferred embodiment, in the molecular chain of the polyphenolic coordination polymer, the number of structural units [Ⅲ] is 1 to 60% of the number of structural units [Ⅰ], and the ratio of structural units [Ⅰ] to structural units [Ⅱ+Ⅲ] is 1; the number of structural units [Ⅳ] is 1 to 30% of the number of structural units [Ⅰ], and the ratio of structural units [Ⅰ] to structural units [Ⅱ+Ⅳ] is 1 to 1.18, which is related to the number of structural units [Ⅳ]; the number of structural units [Ⅴ] is 1 to 60% of the number of structural units [Ⅰ], and the ratio of structural units [Ⅰ] to structural units [Ⅰ+Ⅴ] is 1; each structural unit or the chain segment it forms is arbitrarily connected and combined according to carboxyl and hydroxyl functional groups. The polymer has an intrinsic viscosity [η] of 0.45–1.60 dL / g; tensile strength of 55.0–105.0 MPa; elongation at break of 20.0–450.0%; initial decomposition temperature of 370–405 °C; limiting oxygen index of 23.5–32.0%; vertical flammability rating of V-2–V-0; and peak heat release rate (p-HRR) of 300–620 kW / m² in cone calorimetry. 2The total smoke release is 600-1000m³. 2 / m 2 The self-healing temperature after the sample is cut is 105-120℃, the healing time is 5-30 min, and the healing efficiency is 85-100%.

[0034] Secondly, this application provides a method for preparing a flame-retardant polyphenolic coordination polymer. The method involves esterifying a C2-C10 diol monomer, a diacid or its esterified monomer without coordinate bonds, and a catalyst in a specific ratio using direct esterification or transesterification. The resulting polymer is then subjected to a polycondensation reaction with a monomer or oligomer containing coordinate bonds. The monomer or oligomer containing coordinate bonds is added to the reaction system at a molar percentage of 1-100% of the diol monomer before or after esterification and before polycondensation. The amount of the diacid or its esterified monomer without coordinate bonds is 0-99% of the molar percentage of the diol monomer.

[0035] Preferably, the process steps and specific conditions of the direct esterification and transesterification methods used in this invention are as follows:

[0036] Direct esterification method: Diol monomers, diacids or their esterified monomers without coordinate bonds, catalysts, and monomers / oligomers containing coordinate bonds are added to a reaction vessel according to the specified ratio. The vessel is pressurized and heated to 190–220°C for esterification reaction for 2–5 hours. After the esterification reaction is completed, polycondensation reaction is carried out at 220–240°C under low vacuum for 0.5–1.5 hours. Then, polycondensation is carried out at 230–260°C under high vacuum for 2–3 hours. After the polycondensation reaction is completed, nitrogen gas is introduced into the reaction vessel and the vessel is cooled with water to obtain the target polyphenolic coordination polymer.

[0037] Transesterification: Diol monomers, diacids or their esterified monomers without coordinate bonds, catalysts, and monomers / oligomers containing coordinate bonds are added to a reaction vessel according to the specified ratio. The transesterification reaction is carried out at 180–220°C under normal pressure for 2–6 hours. After the transesterification is completed, polycondensation is carried out at 220–240°C under low vacuum for 0.5–1.5 hours. Then, polycondensation is carried out at 230–260°C under high vacuum for 2–3 hours. After the polycondensation reaction is completed, nitrogen gas is introduced into the reaction vessel and the vessel is cooled with water to obtain the target polyphenolic coordination polymer.

[0038] Preferably, the catalyst used in the above method is at least one selected from zinc acetate, manganese acetate, cobalt acetate, potassium acetate, germanium oxide, antimony trioxide, antimony glycolate, and titanate.

[0039] Thirdly, this application provides a method for recovering flame-retardant polyphenolic coordination polymers, the method comprising the following steps:

[0040] The waste polyphenolic coordination polymer is crushed into blocks and then added to a mixed solution of reaction solvent and co-solvent or a mixed solution of recycled reaction solvent and recycled reaction co-solvent. A certain mass of acid or base is added to the mixed solution, and the reaction is carried out at 25-65°C for 30-240 min. The mass-volume ratio of the polyphenolic coordination polymer to the reaction solvent or recycled reaction solvent is 0.01-0.5 W / V, the mass-volume ratio of the polyphenolic coordination polymer to the co-solvent or recycled co-solvent is 0.05-1.0 W / V, and the mass-volume ratio of the added acid or base to the polyphenolic coordination polymer is 0.01-0.5 W / V.

[0041] After cooling the reaction solution obtained in the previous step to room temperature, the reaction solvent and co-solvent are removed by rotary evaporation at 30-100°C. Then, deionized water is added to the remaining solid product and the pH of the solution is adjusted to 1-5 to obtain the degradation product. The conversion rate of the polymer is 100%, and the yield of the degradation product is above 82%. The collected degradation product can be used again to synthesize the polyphenolic coordination polymer, and the collected reaction solvent and co-solvent are reused as recycled reaction solvent and recycled reaction co-solvent, respectively.

[0042] According to a preferred embodiment, the reaction solvent used in the recovery method is at least one selected from methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, pentanol, hexanol, 1,4-butanediol, and 1,4-cyclohexanediol; the co-solvent used is at least one selected from heptane, cyclohexane, acetone, acetonitrile, tetrahydrofuran, dichloromethane, trichloromethane, and chlorobenzene; the acid used is at least one selected from hydrochloric acid, sulfuric acid, phosphoric acid, perchloric acid, hydrobromic acid, and nitric acid; and the base used is at least one selected from potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonia, diethanolamine, and triethanolamine.

[0043] This application also provides another method for recovering flame-retardant polyphenolic coordination polymers, the recovery method being used to recover the prepared polyphenolic coordination polymers, the recovery method comprising the following steps:

[0044] The used polyphenolic coordination polymer is crushed into blocks and then added to a reaction solvent or a recycled reaction solvent. The mixture is reacted at 150–190°C for 60–240 min to obtain degradation products and a reaction solution. The mass-to-volume ratio of the polyphenolic coordination polymer to the reaction solvent or recycled reaction solvent is 0.05–0.2 W / V. The reaction solvent used is at least one of ethylene glycol, 1,3-propanediol, and 1,4-butanediol.

[0045] The reaction solution obtained in the previous step was poured into anhydrous ethanol while hot to precipitate the degradation product. The product was then filtered and dried to obtain the degradation product. The conversion rate of the polymer was 100%, and the yield of the degradation product was over 78%. The collected degradation product could be used again to synthesize the polyphenolic coordination polymer, and the collected reaction solvent was reused as a recycled reaction solvent.

[0046] Fourthly, this application provides applications of the aforementioned flame-retardant polyphenolic coordination polymer, including using the polyphenolic coordination polymer in plastics, fibers, nonwovens, battery separators, films, healthcare packaging materials, container materials, or 3D printing materials, or as a modified processing aid.

[0047] Based on the above technical solutions, the flame-retardant polyphenolic coordination polymer, its preparation method and application, and the recycling method of the polyphenolic coordination polymer of the present invention have at least the following technical effects compared with the prior art:

[0048] 1. The novel flame-retardant polyphenol-based coordination polymer of the present invention contains a large number of structural units with coordination bonds formed by the coordination of the central ion and the polyphenol monomer, which makes the structure of the polyphenol-based coordination polymer of the present application different from the traditional thermoplastic polymer materials connected by covalent bonds; the novel polyphenol-based coordination polymer can be mass-produced simply by stepwise condensation polymerization of the monomer / oligomer containing the coordination bond structural unit with a diol or with a diol and other diacids or their esters.

[0049] 2. The monomers / oligomers containing coordinate bond structural units used in the preparation of polyphenolic coordination polymers in this invention possess spontaneous bonding, highly tunable bond energies, a combination of thermodynamic stability and kinetic variability, and adjustable functionality. The coordinate bond structural units remain stable at the polymer synthesis and processing temperatures (190–280°C), with bond energies close to covalent bonds, making them difficult to decompose. Furthermore, the monomers / oligomers using coordinate bond structural units exhibit high polymerization activity, fast polymerization rates, and mild polymerization conditions, resulting in polyphenolic coordination polymers of this invention with sufficiently high molecular weights.

[0050] 3. The preparation method of the polyphenol-based coordination polymer provided by the present invention is basically the same as the conventional method for synthesizing polyester. Therefore, the process is mature, simple to operate, easy to control and industrialize.

[0051] 4. The novel polyphenol-based coordination polymer provided by this invention has high strength, high heat resistance, high flame retardancy, low smoke and low heat release, and excellent self-healing properties. Therefore, it can meet the application requirements in the fields of fibers, non-woven fabrics, battery separators, films, and medical and health care materials. It can also be used as a modified processing aid.

[0052] 5. The coordination bonds in the novel polyphenolic coordination polymer provided by this invention can be broken under acid / alkaline conditions, thus enabling pH response and controllable depolymerization and recycling of the material.

[0053] 6. The novel polyphenolic coordination polymer provided by this invention contains a large number of metal ions with transesterification catalytic activity, thus enabling the self-catalytic depolymerization and recovery of the material without the addition of an external catalyst.

[0054] 7. This invention enables rapid closed-loop chemical recycling of polyphenolic coordination polymers after their use is completed and they are discarded. It also facilitates the separation and collection of degradation products and reaction solutions. Therefore, the recycling process has the advantages of high economic efficiency, simple separation process, and low energy consumption.

[0055] 8. This invention not only synthesizes a novel, multifunctional, high-performance polyphenolic coordination polymer, but also realizes closed-loop chemical recycling of this type of waste material after use, solving the disposal problem of this type of waste material, and has important scientific and social significance. Attached Figure Description

[0056] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0057] Figure 1 The image shows the 1H NMR spectrum of the polyphenolic coordination polymer prepared in Example 3 of this invention. As can be seen from the spectrum, the peak at 8.27 ppm belongs to the hydrogen atom on the benzene ring of the DMT unit (peak a in the image); the peaks at 7.08 ppm and 7.75 ppm belong to the hydrogen atom on the benzene ring of the coordination bond structural unit Si(DHBM)2 (peaks d and c in the image, respectively); and the peak at 4.90 ppm belongs to the methylene hydrogen atom on the ethylene glycol unit (peak b in the image). It can be seen that each hydrogen atom has a corresponding assigned peak, proving the successful preparation of this polyphenolic coordination polymer.

[0058] Figure 2 Thermogravimetric curve (Tg) of the polyphenolic coordination polymer prepared in Example 13 of this invention is shown in the figure. The initial decomposition temperature (Tg) of the polyphenolic coordination polymer under nitrogen atmosphere is shown in the figure. 5％ The temperature reached 380℃, and the char residue at high temperature (700℃) reached 24.2wt%, proving that the polyphenol-based coordination polymer has excellent thermal properties and char-forming ability.

[0059] Figure 3Thermogravimetric curve (Tg) of the polyphenolic coordination polymer prepared in Example 18 of this invention is shown in the figure. The initial decomposition temperature (Tg) of the polyphenolic coordination polymer under nitrogen atmosphere is shown in the figure. 5％ The temperature reached 400℃, and the residual char content at high temperature (700℃) reached 48.9wt%, proving that the polyphenol-based coordination polymer has excellent thermal properties and char-forming ability.

[0060] Figure 4 The stress-strain curve of the polyphenolic coordination polymer prepared in Example 1 of this invention is shown. As can be seen from the stress-strain curve, the polyphenolic coordination polymer has a tensile strength of 49 MPa and an elongation at break of 315%, exhibiting excellent mechanical properties.

[0061] Figure 5 The stress-strain curve of the polyphenolic coordination polymer prepared in Example 23 of this invention is shown in the figure. As can be seen from the stress-strain curve, the polyphenolic coordination polymer has a tensile strength of 91 MPa and an elongation at break of 156%, exhibiting excellent mechanical properties.

[0062] Figure 6 This is a vertical combustion test diagram of the polyphenolic coordination polymer prepared in Example 12 of the present invention. As can be seen from the vertical combustion test diagram, this polyphenolic coordination polymer passes the UL-94 vertical combustion V-2 rating.

[0063] Figure 7 The image shows a sample of the polyphenolic coordination polymer prepared in Example 12 of this invention after oxygen index testing. The limiting oxygen index of this polyphenolic coordination polymer is 24.0%.

[0064] Figure 8 This is a vertical combustion test diagram of the polyphenolic coordination polymer prepared in Example 20 of the present invention. As can be seen from the vertical combustion test diagram, this polyphenolic coordination polymer passes the UL-94 vertical combustion V-0 rating.

[0065] Figure 9 The image shows a sample of the novel polyphenolic coordination polymer prepared in Example 20 of this invention after oxygen index testing. The limiting oxygen index of this polyphenolic coordination polymer is 31.5%.

[0066] Figure 10 This is a peak heat release rate curve of the polyphenolic coordination polymer prepared in Example 23 of the present invention. As can be seen from the peak heat release rate curve, the peak heat release rate p-HRR of this polyphenolic coordination polymer is 325 kW / m². 2 It has excellent low heat release performance.

[0067] Figure 11This is a peak heat release rate curve of the polyphenolic coordination polymer prepared in Example 26 of the present invention. As can be seen from the peak heat release rate curve, the peak heat release rate p-HRR of this polyphenolic coordination polymer is 281 kW / m². 2 It has excellent low heat release performance.

[0068] Figure 12 This is a graph showing the total smoke release of the polyphenolic coordination polymer prepared in Example 6 of the present invention. As can be seen from the total smoke release graph, the total smoke release of this polyphenolic coordination polymer is 1121 m³. 2 / m 2 It has excellent low smoke emission performance.

[0069] Figure 13 This is a graph showing the total smoke release of the polyphenolic coordination polymer prepared in Example 18 of the present invention. As can be seen from the total smoke release graph, the total smoke release of this polyphenolic coordination polymer is 859 m³ / s. 2 / m 2 It has excellent low smoke emission performance.

[0070] Figure 14 This is a digital photograph of the self-healing polyphenolic coordination polymer prepared in Example 31 of the present invention. As can be seen from the self-healing digital photograph, the scratches on the polymer film surface disappeared rapidly within 5 minutes, demonstrating the polymer's excellent self-healing properties. Detailed Implementation

[0071] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be described in detail below. Obviously, the described embodiments are merely some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other implementation methods obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0072] It is worth noting that the intrinsic viscosity [η] of the novel multifunctional, high-performance polyphenolic coordination polymers prepared in Examples 1-35 was measured using a solution of phenol / 1,1,2,2-tetrachloroethane (1:1, v:v) at a concentration of 0.5 g / dL, prepared with an Ubbelohde viscometer at 25°C. The mechanical properties of the polymers were measured at 25°C on an INSTRON 3366 universal testing machine at a tensile speed of 5 mm / min, with five samples tested repeatedly for each sample and the average value taken. The thermal properties of the polymers were measured using a NETZSCH TG 209F1 thermogravimetric analyzer, heating the samples from 40°C to 700°C at a heating rate of 10°C / min in a nitrogen atmosphere. The limiting oxygen index of the polymers was tested by preparing them into 120×6.5×3.2 mm samples. 3The standard oxygen index specimen was measured on an HC-2 oxygen indexer according to ASTM D2863-97 standard; the vertical combustion of the polymer was performed by preparing it into a sample measuring 125×12.7×3.2mm. 3 The standard sample was tested according to UL-94 standard using a CZF-2 vertical combustion apparatus (UL-94). The polymer cone calorimetry test involved preparing a 100×100×3mm cone. 3 The standard template, according to ISO 5660-1 standard, is tested on an FTT cone calorimeter at 50kW / m³. 2 The measurements were taken.

[0073] Example 1

[0074] In this embodiment, the coordinate bond-containing monomer Na2[Mn(DHBM)2] is prepared by reacting MnO, methyl 3,4-dihydroxybenzoate (H2DHBM) and NaOH in a molar ratio of 1:2:2 under reflux in acetonitrile solvent for 12 hours. 31.0 g of ethylene glycol, 87.4 g of dimethyl terephthalate, 21.7 g of coordinating monomer Na2[Mn(DHBM)2], and 0.02 wt% of zinc acetate and 0.02 wt% of antimony trioxide catalysts (based on the total mass of the reactants) were added to a reaction vessel. Nitrogen gas was purged to remove air from the vessel. The reaction was carried out at 180 °C under normal pressure for 2 hours, then at 200 °C for 2 hours, and then at 220 °C for 1 hour, at which point the transesterification reaction was completed. Subsequently, a polycondensation reaction was carried out at 220–240 °C under low vacuum (100 Pa < pressure < 1000 Pa) for 0.5–1.5 hours, followed by a polycondensation reaction at 230–260 °C under high vacuum (pressure < 100 Pa) for 2–3 hours. The product was discharged under a nitrogen atmosphere.

[0075] The polymer prepared in this example has the following properties: intrinsic viscosity [η] of 0.58 dL / g; tensile strength of 49 MPa; elongation at break of 315%; initial decomposition temperature of 390 °C; limiting oxygen index of 22.5%; vertical flammability rating of V-2; and peak heat release rate p-HRR of 683 kW / m² in cone calorimetry. 2 The total smoke release was 1360m³. 2 / m 2 The self-healing temperature after the strip is cut is 150℃, the healing time is 45min, and the healing efficiency is 82%.

[0076] Example 2

[0077] In this embodiment, the coordinating monomer Na2[Ca(THBM)2] was prepared by reacting CaO, methyl 3,4,5-trihydroxybenzoate (H2THBM), and NaOH in a molar ratio of 1:2:2 under reflux in acetonitrile for 12 hours. 31.0 g of ethylene glycol, 82.5 g of dimethyl terephthalate, 33.8 g of the coordinating monomer Na2[Ca(THBM)2], and 0.02 wt% of zinc acetate and 0.02 wt% of antimony trioxide catalysts (based on the total mass of the reactants) were added to a reaction vessel, and nitrogen was used to purge the air from the vessel. After transesterification and polycondensation according to the steps and conditions given in Example 1, the product was discharged under a nitrogen atmosphere.

[0078] The polymer prepared in this example has the following properties: intrinsic viscosity [η] of 0.46 dL / g; tensile strength of 45 MPa; elongation at break of 235%; initial decomposition temperature of 386 °C; limiting oxygen index of 22.0%; vertical flammability rating of V-2; and peak heat release rate p-HRR of 615 kW / m² in cone calorimetry. 2 The total smoke release was 1285m³. 2 / m 2 The self-healing temperature after the strip is cut is 135℃, the healing time is 50 minutes, and the healing efficiency is 85%.

[0079] Example 3

[0080] In this embodiment, the coordinating monomer Si(DHBM)2 was prepared by reacting SiO2 and methyl 3,4-dihydroxybenzoate (H2DHBM) in a molar ratio of 1:2 under reflux in acetonitrile for 12 hours. 31.0 g of ethylene glycol, 87.4 g of dimethyl terephthalate, 18.0 g of the coordinating monomer Si(DHBM)2, and 0.02 wt% of zinc acetate and 0.02 wt% of antimony trioxide catalysts (based on the total mass of the reactants) were added to a reaction vessel, which was then purged with nitrogen to remove air. After transesterification and polycondensation according to the steps and conditions given in Example 1, the product was discharged under a nitrogen atmosphere.

[0081] In this embodiment, the resulting polymer had an intrinsic viscosity [η] of 0.68 dL / g, a tensile strength of 52 MPa, an elongation at break of 360%, an initial decomposition temperature of 392 °C, a limiting oxygen index of 23.5%, a vertical flammability rating of V-2, and a peak heat release rate (p-HRR) of 685 kW / m² in cone calorimetry. 2 The total smoke release was 1500m³. 2 / m 2 The self-healing temperature after the strip is cut is 150℃, the healing time is 50min, and the healing efficiency is 75%.

[0082] Example 4

[0083] In this embodiment, the coordinating monomer Ge(DHBM)2 was prepared by reacting GeO2 and methyl 3,4-dihydroxybenzoate (H2DHBM) in a molar ratio of 1:2 under reflux in acetonitrile for 12 hours. 31.0 g of ethylene glycol, 92.2 g of dimethyl terephthalate, 10.1 g of the coordinating monomer Ge(DHBM)2, and 0.02 wt% of zinc acetate and antimony trioxide catalysts (based on the total mass of the reactants) were added to a reaction vessel, which was then purged with nitrogen to remove air. After transesterification and polycondensation according to the steps and conditions given in Example 1, the product was discharged under a nitrogen atmosphere.

[0084] The polymer prepared in this example has the following properties: intrinsic viscosity [η] of 0.58 dL / g; tensile strength of 52 MPa; elongation at break of 450%; initial decomposition temperature of 382 °C; limiting oxygen index of 23.0%; vertical flammability rating of V-2; and peak heat release rate p-HRR of 580 kW / m² in cone calorimetry. 2 The total smoke release was 1210m³. 2 / m 2 The self-healing temperature after the strip is cut is 130℃, the healing time is 50 minutes, and the healing efficiency is 85%.

[0085] Example 5

[0086] In this embodiment, the coordinating monomer Sn(THBM)2 was prepared by reacting SnO2 and methyl 3,4,5-trihydroxybenzoate (H2THBM) in a molar ratio of 1:2 under reflux in acetonitrile for 12 hours. 31.0 g of ethylene glycol, 82.5 g of dimethyl terephthalate, 36.2 g of the coordinating monomer Sn(THBM)2, and 0.02 wt% of zinc acetate and antimony trioxide catalysts (based on the total mass of the reactants) were added to a reaction vessel. Nitrogen gas was then used to purge air from the vessel. After transesterification and polycondensation according to the steps and conditions given in Example 1, the product was discharged under a nitrogen atmosphere.

[0087] The polymer prepared in this example has an intrinsic viscosity [η] of 0.39 dL / g, a tensile strength of 59 MPa, an elongation at break of 480%, an initial decomposition temperature of 378 °C, a limiting oxygen index of 24.5%, a vertical flammability rating of V-2, and a peak heat release rate (p-HRR) of 595 kW / m² in cone calorimetry. 2 The total smoke release was 1290m³. 2 / m 2 The self-healing temperature after the strip is cut is 120℃, the healing time is 40 minutes, and the healing efficiency is 80%.

[0088] Example 6

[0089] In this embodiment, the coordinate bond monomer Na[Fe(DHBM)2] is composed of Fe 3+ The product was prepared by reacting methyl 3,4-dihydroxybenzoate (H2DHBM) and NaOH in a molar ratio of 1:2:1 under reflux in acetonitrile for 12 hours. 31.0 g of ethylene glycol, 87.4 g of dimethyl terephthalate, 20.6 g of coordinating monomer Na[Fe(DHBM)2], and 0.02 wt% of zinc acetate and antimony trioxide catalysts (based on the total mass of the reactants) were added to a reaction vessel. Nitrogen gas was then used to purge air from the vessel. After transesterification and polycondensation according to the steps and conditions given in Example 1, the product was discharged under a nitrogen atmosphere.

[0090] The polymer prepared in this example has an intrinsic viscosity [η] of 0.53 dL / g, a tensile strength of 57 MPa, an elongation at break of 355%, an initial decomposition temperature of 400 °C, a limiting oxygen index of 24.5%, a vertical flammability rating of V-2, and a peak heat release rate (p-HRR) of 635 kW / m³ in cone calorimetry. 2 The total smoke release was 1121m³. 2 / m 2 The self-healing temperature after the strip is cut is 125℃, the healing time is 50 minutes, and the healing efficiency is 90%.

[0091] Example 7

[0092] In this embodiment, the coordinate bond-containing monomer Na[B(THBM)2] is composed of B 3+ The product was prepared by reacting methyl 3,4,5-trihydroxybenzoate (H2THBM) and NaOH in a molar ratio of 1:2:1 under reflux in acetonitrile for 12 h. 31.0 g of ethylene glycol, 87.4 g of dimethyl terephthalate, 19.9 g of coordinating monomer Na[B(THBM)2], and 0.02 wt% of zinc acetate and antimony trioxide catalysts (based on the total mass of the reactants) were added to a reaction vessel. Nitrogen gas was then used to purge the air from the vessel. After transesterification and polycondensation according to the steps and conditions given in Example 1, the product was discharged under a nitrogen atmosphere.

[0093] The polymer prepared in this example has an intrinsic viscosity [η] of 0.35 dL / g, a tensile strength of 53 MPa, an elongation at break of 530%, an initial decomposition temperature of 375 °C, a limiting oxygen index of 24.0%, a vertical flammability rating of V-2, and a peak heat release rate (p-HRR) of 682 kW / m³ in cone calorimetry. 2 The total smoke release was 1355m³. 2 / m 2The self-healing temperature after the strip is cut is 125℃, the healing time is 40 minutes, and the healing efficiency is 78%.

[0094] Example 8

[0095] In this embodiment, the coordinating monomer Na2[Ge(DHBM)2(CT)1] was prepared by reacting GeO2, methyl 3,4-dihydroxybenzoate (H2DHBM), catechol (H2CT), and NaOH in a molar ratio of 1:2:1:2 under reflux in acetonitrile for 12 hours. 31.0 g of ethylene glycol, 82.5 g of dimethyl terephthalate, 41.9 g of the coordinating monomer Na2[Ge(DHBM)2(CT)1], and 0.02 wt% of zinc acetate and 0.02 wt% of antimony trioxide catalysts (based on the total mass of the reactants) were added to a reaction vessel. Nitrogen gas was then used to purge air from the vessel. After transesterification and polycondensation according to the steps and conditions given in Example 1, the product was discharged under a nitrogen atmosphere.

[0096] The polymer prepared in this example has the following properties: intrinsic viscosity [η] of 0.56 dL / g; tensile strength of 62 MPa; elongation at break of 196%; initial decomposition temperature of 393 °C; limiting oxygen index of 25.5%; vertical flammability rating of V-2; and peak heat release rate p-HRR of 531 kW / m² in cone calorimetry. 2 The total smoke release was 985m³. 2 / m 2 The self-healing temperature after the strip is cut is 120℃, the healing time is 20 minutes, and the healing efficiency is 82%.

[0097] Example 9

[0098] In this embodiment, the coordinating monomer Na2[Si(DHBM)2(CT)1] was prepared by reacting SiO2, methyl 3,4-dihydroxybenzoate (H2DHBM), catechol (H2CT), and NaOH in a molar ratio of 1:2:1:2 under reflux in acetonitrile for 12 hours. 31.0 g of ethylene glycol, 87.4 g of dimethyl terephthalate, 25.7 g of the coordinating monomer Na2[Si(DHBM)2(CT)1], and 0.02 wt% of zinc acetate and 0.02 wt% of antimony trioxide catalysts (based on the total mass of the reactants) were added to a reaction vessel. Nitrogen gas was then used to purge the air from the vessel. After transesterification and polycondensation according to the steps and conditions given in Example 1, the product was discharged under a nitrogen atmosphere.

[0099] The polymer prepared in this example has an intrinsic viscosity [η] of 0.58 dL / g, a tensile strength of 68 MPa, an elongation at break of 236%, an initial decomposition temperature of 398 °C, a limiting oxygen index of 27.0%, a vertical flammability rating of V-1, and a peak heat release rate (p-HRR) of 569 kW / m³ in cone calorimetry. 2 The total smoke release was 1056m³. 2 / m 2 The self-healing temperature after the strip is cut is 120℃, the healing time is 30 minutes, and the healing efficiency is 85%.

[0100] Example 10

[0101] In this embodiment, the coordinate bond-containing monomer Na3[Fe(DHBM)2(CT)1] is composed of Fe 3+ The reaction mixture was prepared by adding methyl 3,4-dihydroxybenzoate (H2DHBM), catechol (H2CT), and NaOH in a molar ratio of 1:2:1:3 and refluxing in acetonitrile for 12 hours. 31.0 g of ethylene glycol, 87.4 g of dimethyl terephthalate, 28.3 g of coordinating monomer Na3[Fe(DHBM)2(CT)1], and 0.02 wt% of zinc acetate and 0.02 wt% of antimony trioxide catalysts (based on the total mass of the reactants) were added to a reaction vessel. Nitrogen gas was then used to purge air from the vessel. The transesterification and polycondensation reactions were carried out according to the steps and conditions given in Example 1, and the mixture was discharged under a nitrogen atmosphere.

[0102] The polymer prepared in this example has an intrinsic viscosity [η] of 0.68 dL / g, a tensile strength of 66 MPa, an elongation at break of 286%, an initial decomposition temperature of 379 °C, a limiting oxygen index of 28.0%, a vertical flammability rating of V-1, and a peak heat release rate (p-HRR) of 495 kW / m³ in cone calorimetry. 2 The total smoke release was 1255m³. 2 / m 2 The self-healing temperature after the strip is cut is 120℃, the healing time is 30 minutes, and the healing efficiency is 80%.

[0103] Example 11

[0104] In this embodiment, the coordinate bond-containing monomer Na3[Al(THBM)2(CT)1] is derived from Al 3+The reaction mixture was prepared by adding methyl 3,4,5-trihydroxybenzoate (H2THBM), catechol (H2CT), and NaOH in a molar ratio of 1:2:1:3 and refluxing in acetonitrile for 12 h. 31.0 g of ethylene glycol, 87.4 g of dimethyl terephthalate, 29.2 g of coordinating monomer Na3[Al(THBM)2(CT)1], and 0.02 wt% of zinc acetate and 0.02 wt% of antimony trioxide catalysts (based on the total mass of the reactants) were added to a reaction vessel. Nitrogen gas was used to purge the air from the vessel. After transesterification and polycondensation according to the steps and conditions given in Example 1, the mixture was discharged under a nitrogen atmosphere.

[0105] The polymer obtained in this example has an intrinsic viscosity [η] of 0.75 dL / g, a tensile strength of 71 MPa, an elongation at break of 152%, an initial decomposition temperature of 372 °C, a limiting oxygen index of 27.5%, a vertical flammability rating of V-1, and a peak heat release rate (p-HRR) of 506 kW / m³ in cone calorimetry. 2 The total smoke release was 1186m³. 2 / m 2 The self-healing temperature after the strip is cut is 120℃, the healing time is 30 minutes, and the healing efficiency is 75%.

[0106] Example 12

[0107] In this embodiment, the coordinating monomer Na2[Si(DHBM)3] was prepared by reacting SiO2, methyl 3,4-dihydroxybenzoate (H2DHBM), and NaOH in a molar ratio of 1:3:2 under reflux in acetonitrile for 12 hours. 31.0 g of ethylene glycol, 96.1 g of dimethyl terephthalate, 2.9 g of the coordinating monomer Na2[Si(DHBM)3], and 0.02 wt% of zinc acetate and 0.02 wt% of antimony trioxide catalysts (based on the total mass of the reactants) were added to a reaction vessel, which was then purged with nitrogen to remove air. After transesterification and polycondensation according to the steps and conditions given in Example 1, the product was discharged under a nitrogen atmosphere.

[0108] The polymer obtained in this example has an intrinsic viscosity [η] of 0.72 dL / g, a tensile strength of 82 MPa, an elongation at break of 185%, an initial decomposition temperature of 395 °C, a limiting oxygen index of 24.0%, a vertical flammability rating of V-2, and a peak heat release rate (p-HRR) of 700 kW / m² in cone calorimetry. 2 The total smoke release was 1476m³. 2 / m 2 The self-healing temperature after the strip is cut is 150℃, the healing time is 60 minutes, and the healing efficiency is 80%.

[0109] Example 13

[0110] In this embodiment, the coordinate bond-containing monomer Na3[Fe(DHBM)3] is derived from Fe 3+ The product was prepared by reacting methyl 3,4-dihydroxybenzoate (H2DHBM) and NaOH in a molar ratio of 1:3:3 under reflux in acetonitrile for 12 hours. 38.0 g of propylene glycol, 92.2 g of dimethyl terephthalate, 15.6 g of the complex monomer Na3[Fe(DHBM)3], and 0.02 wt% of zinc acetate and 0.02 wt% of antimony trioxide catalysts (based on the total mass of the reactants) were added to a reaction vessel. Nitrogen gas was then introduced to purge the air from the vessel. After transesterification and polycondensation according to the steps and conditions given in Example 1, the product was discharged under a nitrogen atmosphere.

[0111] The polymer obtained in this example has an intrinsic viscosity [η] of 0.69 dL / g, a tensile strength of 88 MPa, an elongation at break of 95%, an initial decomposition temperature of 385 °C, a limiting oxygen index of 25.0%, a vertical flammability rating of V-1, and a peak heat release rate (p-HRR) of 589 kW / m³ in cone calorimetry. 2 The total smoke release was 1235m³. 2 / m 2 The self-healing temperature after the strip is cut is 135℃, the healing time is 50 minutes, and the healing efficiency is 80%.

[0112] Example 14

[0113] In this embodiment, the coordinating monomer Na2[Ge(DHBM)3] was prepared by reacting GeO2, methyl 3,4-dihydroxybenzoate (H2DHBM), and NaOH in a molar ratio of 1:3:2 under reflux in acetonitrile for 12 hours. 31.0 g of ethylene glycol, 92.2 g of dimethyl terephthalate, 15.4 g of the coordinating monomer Na2[Ge(DHBM)3], and 0.02 wt% of zinc acetate and 0.02 wt% of antimony trioxide catalysts (based on the total mass of the reactants) were added to a reaction vessel, which was then purged with nitrogen to remove air. After transesterification and polycondensation according to the steps and conditions given in Example 1, the product was discharged under a nitrogen atmosphere.

[0114] The polymer obtained in this example has an intrinsic viscosity [η] of 0.52 dL / g, a tensile strength of 83 MPa, an elongation at break of 106%, an initial decomposition temperature of 385 °C, a limiting oxygen index of 25.5%, a vertical flammability rating of V-1, and a peak heat release rate (p-HRR) of 518 kW / m³ in cone calorimetry. 2 The total smoke release was 1062m³. 2 / m 2 The self-healing temperature after the strip is cut is 130℃, the healing time is 50 minutes, and the healing efficiency is 90%.

[0115] Example 15

[0116] In this embodiment, the monomer containing the coordination bond K3[Al(DHBM)3] is composed of Al 3+ The product was prepared by reacting methyl 3,4-dihydroxybenzoate (H2DHBM) and KOH in a molar ratio of 1:3:3 under reflux in acetonitrile for 12 h. 31.0 g of ethylene glycol, 92.2 g of dimethyl terephthalate, 16.1 g of K3[Al(DHBM)3] containing coordinating bonds, and 0.02 wt% of zinc acetate and antimony trioxide catalysts (based on the total mass of the reactants) were added to a reaction vessel. Nitrogen gas was then used to purge the air from the vessel. After transesterification and polycondensation according to the steps and conditions given in Example 1, the product was discharged under a nitrogen atmosphere.

[0117] The polymer obtained in this example has an intrinsic viscosity [η] of 0.51 dL / g, a tensile strength of 83 MPa, an elongation at break of 125%, an initial decomposition temperature of 385 °C, a limiting oxygen index of 26.0%, a vertical flammability rating of V-1, and a peak heat release rate (p-HRR) of 496 kW / m³ in cone calorimetry. 2 The total smoke release was 986m³. 2 / m 2 The self-healing temperature after the spline is cut is 130℃, the healing time is 50 minutes, and the healing efficiency is 89%.

[0118] Example 16

[0119] In this embodiment, the coordinating monomer Li2[Ge(DHBM)3] was prepared by reacting GeO2, methyl 3,4-dihydroxybenzoate (H2DHBM), and LiOH in a molar ratio of 1:3:2 under reflux in acetonitrile for 12 h. 31.0 g of ethylene glycol, 92.2 g of dimethyl terephthalate, 14.6 g of the coordinating monomer Li2[Ge(DHBM)3], and 0.02 wt% of zinc acetate and 0.02 wt% of antimony trioxide catalysts (based on the total mass of the reactants) were added to a reaction vessel, and nitrogen was used to purge the air from the vessel. After transesterification and polycondensation according to the steps and conditions given in Example 1, the product was discharged under a nitrogen atmosphere.

[0120] The polymer obtained in this example has an intrinsic viscosity [η] of 0.52 dL / g, a tensile strength of 85 MPa, an elongation at break of 118%, an initial decomposition temperature of 385 °C, a limiting oxygen index of 25.5%, a vertical flammability rating of V-1, and a peak heat release rate (p-HRR) of 515 kW / m³ in cone calorimetry. 2 The total smoke release was 1102m³. 2 / m 2The self-healing temperature after the strip is cut is 130℃, the healing time is 50 minutes, and the healing efficiency is 88%.

[0121] Example 17

[0122] In this embodiment, the coordinating monomer K2[Ge(THBM)3] was prepared by reacting GeO2, methyl 3,4,5-trihydroxybenzoate (H2THBM), and KOH in a molar ratio of 1:3:2 under reflux in acetonitrile for 12 h. 31.0 g of ethylene glycol, 87.4 g of dimethyl terephthalate, 34.9 g of the coordinating monomer K2[Ge(THBM)3], and 0.02 wt% of titanate ester of the total reactant mass were added to a reaction vessel, and nitrogen was purged to remove air from the vessel. After transesterification and polycondensation according to the steps and conditions given in Example 1, the product was discharged under a nitrogen atmosphere.

[0123] The polymer obtained in this example has an intrinsic viscosity [η] of 0.46 dL / g, a tensile strength of 88 MPa, an elongation at break of 135%, an initial decomposition temperature of 394 °C, a limiting oxygen index of 26.0%, a vertical burning rating of V-1, a peak heat release rate p-HRR of 481 kW / m² in cone calorimetry, a total smoke release of 883 m² / m², a self-healing temperature of 120 °C after sample cutting, a healing time of 40 min, and a healing efficiency of 90%.

[0124] Example 18

[0125] In this embodiment, the coordinate bond-containing monomer Na3[Fe(THBM)3] is derived from Fe 3+ The product was prepared by reacting methyl 3,4,5-trihydroxybenzoate (H2THBM) and NaOH in a molar ratio of 1:3:3 under reflux in acetonitrile for 12 h. 31.0 g of ethylene glycol, 77.7 g of dimethyl terephthalate, 67.1 g of coordinating monomer Na3[Fe(THBM)3], and 0.02 wt% of zinc acetate and 0.02 wt% of antimony trioxide catalysts (based on the total mass of the reactants) were added to a reaction vessel, which was then purged with nitrogen to remove air. After transesterification and polycondensation according to the steps and conditions given in Example 1, the product was discharged under a nitrogen atmosphere.

[0126] The polymer obtained in this example has an intrinsic viscosity [η] of 0.41 dL / g, a tensile strength of 89 MPa, an elongation at break of 156%, an initial decomposition temperature of 390 °C, a limiting oxygen index of 26.0%, a vertical flammability rating of V-1, and a peak heat release rate (p-HRR) of 416 kW / m³ in cone calorimetry. 2 The total smoke release was 859m³. 2 / m 2The self-healing temperature after the strip is cut is 110℃, the healing time is 40 minutes, and the healing efficiency is 90%.

[0127] Example 19

[0128] In this embodiment, the oligomer containing coordination bonds Ge 11 (DMBD) 10 (DHBM)2 is prepared by reacting GeO2, 4,4'-(2,3-dimethylbut-1,4-diyl)bis(phenyl-1,2-diol) (H2DMBD), and methyl 3,4-dihydroxybenzoate (H2DHBM) in a molar ratio of 11:10:2 under reflux in acetonitrile for 12 h. 31.0 g of ethylene glycol, 77.7 g of dimethyl terephthalate, and 411.5 g of the coordinate-bonded monomer GeO2 were also reacted. 11 (DMBD) 10 (DHBM)2 and 0.02 wt% of zinc acetate and 0.02 wt% of antimony trioxide catalysts were added to the reaction vessel, and nitrogen gas was used to purge the air from the vessel. After the transesterification reaction and polycondensation were carried out according to the steps and conditions given in Example 1, the product was discharged under a nitrogen atmosphere.

[0129] The polymer obtained in this example has an intrinsic viscosity [η] of 0.38 dL / g, a tensile strength of 68 MPa, an elongation at break of 326%, an initial decomposition temperature of 365 °C, a limiting oxygen index of 32.0%, a vertical flammability rating of V-0, and a peak heat release rate (p-HRR) of 386 kW / m³ in cone calorimetry. 2 The total smoke release was 952m³. 2 / m 2 The self-healing temperature after the spline is cut is 120℃, the healing time is 30 minutes, and the healing efficiency is 93%.

[0130] Example 20

[0131] In this embodiment, the oligomer containing coordination bonds Ge 11 (DOBD) 10 (DHBM)2 is prepared by reacting GeO2, 4,4'-(oxybis(methylene))bis(phenyl-1,2-diol) (H2DOBD), and methyl 3,4-dihydroxybenzoate (H2DHBM) in a molar ratio of 11:10:2 under reflux in acetonitrile for 12 h. 31.0 g of ethylene glycol, 77.7 g of dimethyl terephthalate, and 371.3 g of the coordinate-bonded monomer GeO2 were also reacted. 11 (DMBD) 10(DHBM)2 and 0.02 wt% of zinc acetate and 0.02 wt% of antimony trioxide catalysts were added to the reaction vessel, and nitrogen gas was used to purge the air from the vessel. After the transesterification reaction and polycondensation were carried out according to the steps and conditions given in Example 1, the product was discharged under a nitrogen atmosphere.

[0132] The polymer obtained in this example has an intrinsic viscosity [η] of 0.36 dL / g, a tensile strength of 63 MPa, an elongation at break of 283%, an initial decomposition temperature of 360 °C, a limiting oxygen index of 31.5%, a vertical flammability rating of V-0, and a peak heat release rate (p-HRR) of 365 kW / m³ in cone calorimetry. 2 The total smoke release was 869m³. 2 / m 2 The self-healing temperature after the strip is cut is 120℃, the healing time is 30 minutes, and the healing efficiency is 90%.

[0133] Example 21

[0134] In this embodiment, the oligomer containing coordination bonds Na 22 [Ge 11 (DMBD) 10 (CT) 11 [DHBM]2 was prepared by reacting GeO2, 4,4'-(2,3-dimethylbut-1,4-diyl)bis(phenyl-1,2-diol) (H2DMBD), catechol (H2CT), methyl 3,4-dihydroxybenzoate (H2DHBM), and NaOH in a molar ratio of 11:10:11:2:22 under reflux in acetonitrile for 12 h. 31.0 g of ethylene glycol, 77.7 g of dimethyl terephthalate, and 580.9 g of coordinating monomer Na... 22 [Ge 11 (DMBD) 10 (CT) 11 [(DHBM)2] and 0.02 wt% of the total mass of the reactants, zinc acetate catalyst and antimony trioxide catalyst, were added to the reaction vessel, and nitrogen gas was purged to remove air from the vessel. After the transesterification reaction and polycondensation were carried out according to the steps and conditions given in Example 1, the product was discharged under a nitrogen atmosphere.

[0135] The polymer obtained in this example has an intrinsic viscosity [η] of 0.49 dL / g, a tensile strength of 82 MPa, an elongation at break of 215%, an initial decomposition temperature of 372 °C, a limiting oxygen index of 32.0%, a vertical flammability rating of V-0, and a peak heat release rate (p-HRR) of 325 kW / m³ in cone calorimetry. 2 The total smoke release was 732m³. 2 / m 2The self-healing temperature after the spline is cut is 120℃, the healing time is 15 minutes, and the healing efficiency is 96%.

[0136] Example 22

[0137] In this embodiment, the oligomer containing coordination bonds Na 22 [Ge 11 (DMBD) 10 (CT) 11 [DHBM]2 was prepared by reacting GeO2, 4,4'-(2,3-dimethylbut-1,4-diyl)bis(phenyl-1,2-diol) (H2DMBD), catechol (H2CT), methyl 3,4-dihydroxybenzoate (H2DHBM), and NaOH in a molar ratio of 11:10:11:2:22 under reflux in acetonitrile for 12 h. 31.0 g of ethylene glycol, 58.3 g of dimethyl terephthalate, and 1161.8 g of coordinating monomer Na... 22 [Ge 11 (DMBD) 10 (CT) 11 [(DHBM)2] and 0.02 wt% of the total mass of the reactants, zinc acetate catalyst and antimony trioxide catalyst, were added to the reaction vessel, and nitrogen gas was purged to remove air from the vessel. After the transesterification reaction and polycondensation were carried out according to the steps and conditions given in Example 1, the product was discharged under a nitrogen atmosphere.

[0138] The polymer obtained in this example has an intrinsic viscosity [η] of 0.42 dL / g, a tensile strength of 114 MPa, an elongation at break of 80%, an initial decomposition temperature of 370 °C, a limiting oxygen index of 34.5%, a vertical flammability rating of V-0, and a peak heat release rate (p-HRR) of 308 kW / m³ in cone calorimetry. 2 The total smoke release was 658m³. 2 / m 2 The self-healing temperature after the strip is cut is 120℃, the repair time is 15min, and the repair efficiency is 100%.

[0139] Example 23

[0140] In this embodiment, the oligomer containing coordination bonds Na 22 [Ge 11 (DOBD) 10 (CT) 11[DHBM]2 was prepared by reacting GeO2, 4,4'-(oxybis(methylene))bis(phenyl-1,2-diol) (H2DOBD), catechol (H2CT), methyl 3,4-dihydroxybenzoate (H2DHBM), and NaOH in a molar ratio of 11:10:11:2:22 under reflux in acetonitrile for 12 h. 31.0 g of ethylene glycol, 77.7 g of dimethyl terephthalate, and 540.8 g of coordinating monomer Na... 22 [Ge 11 (DOBD) 10 (CT) 11 [(DHBM)2] and 0.02 wt% of the total mass of the reactants, zinc acetate catalyst and antimony trioxide catalyst, were added to the reaction vessel, and nitrogen gas was purged to remove air from the vessel. After the transesterification reaction and polycondensation were carried out according to the steps and conditions given in Example 1, the product was discharged under a nitrogen atmosphere.

[0141] The polymer obtained in this example has an intrinsic viscosity [η] of 0.38 dL / g, a tensile strength of 91 MPa, an elongation at break of 156%, an initial decomposition temperature of 368 °C, a limiting oxygen index of 31%, a vertical flammability rating of V-0, and a peak heat release rate (p-HRR) of 325 kW / m³ in cone calorimetry. 2 The total smoke release was 713m³. 2 / m 2 The self-healing temperature after the strip is cut is 120℃, the healing time is 15 minutes, and the healing efficiency is 95%.

[0142] Example 24

[0143] In this embodiment, the oligomer containing coordination bonds Na 22 [Ge 11 (DOBD) 10 (CT) 11 [DHBM]2 was prepared by reacting GeO2, 4,4'-(oxybis(methylene))bis(phenyl-1,2-diol) (H2DOBD), catechol (H2CT), methyl 3,4-dihydroxybenzoate (H2DHBM), and NaOH in a molar ratio of 11:10:11:2:22 under reflux in acetonitrile for 12 h. 31.0 g of ethylene glycol, 58.3 g of dimethyl terephthalate, and 1081.7 g of coordinating monomer Na... 22 [Ge 11 (DOBD) 10 (CT) 11[(DHBM)2] and 0.02 wt% of the total mass of the reactants, zinc acetate catalyst and antimony trioxide catalyst, were added to the reaction vessel, and nitrogen gas was purged to remove air from the vessel. After the transesterification reaction and polycondensation were carried out according to the steps and conditions given in Example 1, the product was discharged under a nitrogen atmosphere.

[0144] The polymer obtained in this example has an intrinsic viscosity [η] of 0.35 dL / g, a tensile strength of 118 MPa, an elongation at break of 68%, an initial decomposition temperature of 365 °C, a limiting oxygen index of 34.5%, a vertical flammability rating of V-0, and a peak heat release rate (p-HRR) of 287 kW / m³ in cone calorimetry. 2 The total smoke release was 596m³. 2 / m 2 The self-healing temperature after the spline is cut is 120℃, the healing time is 15 minutes, and the healing efficiency is 99%.

[0145] Example 25

[0146] In this embodiment, the coordinating monomer Si(DHBM)2 was prepared by reacting SiO2 and methyl 3,4-dihydroxybenzoate (H2DHBM) in a molar ratio of 1:2 under reflux in acetonitrile for 12 h. 59.1 g of 1,6-hexanediol, 180.2 g of the coordinating monomer Si(DHBM)2, and 0.02 wt% of zinc acetate and antimony trioxide catalysts (based on the total mass of the reactants) were added to a reaction vessel, which was then purged with nitrogen to remove air. After transesterification and polycondensation according to the steps and conditions given in Example 1, the product was discharged under a nitrogen atmosphere.

[0147] The polymer obtained in this example has an intrinsic viscosity [η] of 1.25 dL / g, a tensile strength of 88 MPa, an elongation at break of 108%, an initial decomposition temperature of 380 °C, a limiting oxygen index of 28%, a vertical flammability rating of V-0, and a peak heat release rate (p-HRR) of 364 kW / m³ in cone calorimetry. 2 The total smoke release was 728m³. 2 / m 2 The self-healing temperature after the strip is cut is 100℃, the healing time is 10 minutes, and the healing efficiency is 90%.

[0148] Example 26

[0149] In this embodiment, the coordinating monomer Ge(DHBM)2 was prepared by reacting GeO2 and methyl 3,4-dihydroxybenzoate (H2DHBM) in a molar ratio of 1:2 under reflux in acetonitrile for 12 h. 59.1 g of 1,6-hexanediol, 202.4 g of the coordinating monomer Ge(DHBM)2, and 0.02 wt% of zinc acetate and antimony trioxide catalysts (based on the total mass of the reactants) were added to a reaction vessel, which was then purged with nitrogen to remove air. After transesterification and polycondensation according to the steps and conditions given in Example 1, the product was discharged under a nitrogen atmosphere.

[0150] The polymer obtained in this example has an intrinsic viscosity [η] of 1.38 dL / g, a tensile strength of 92 MPa, an elongation at break of 26%, an initial decomposition temperature of 373 °C, a limiting oxygen index of 29%, a vertical flammability rating of V-0, and a peak heat release rate (p-HRR) of 281 kW / m³ in cone calorimetry. 2 The total smoke release was 610m³. 2 / m 2 The self-healing temperature after the strip is cut is 100℃, the healing time is 10 minutes, and the healing efficiency is 95%.

[0151] Example 27

[0152] In this embodiment, the coordinate bond-containing monomer Na[Fe(DHBM)2] is composed of Fe 3+ The product was prepared by reacting methyl 3,4-dihydroxybenzoate (H2DHBM) and NaOH in a molar ratio of 1:2:1 under reflux in acetonitrile for 12 h. 45.1 g of 1,4-butanediol, 205.6 g of coordinating monomer Na[Fe(DHBM)2], and 0.02 wt% of zinc acetate and antimony trioxide catalysts (based on the total mass of the reactants) were added to a reaction vessel. Nitrogen gas was then used to purge the air from the vessel. After transesterification and polycondensation according to the steps and conditions given in Example 1, the product was discharged under a nitrogen atmosphere.

[0153] The polymer obtained in this example has an intrinsic viscosity [η] of 1.42 dL / g, a tensile strength of 96 MPa, an elongation at break of 115%, an initial decomposition temperature of 382 °C, a limiting oxygen index of 28%, a vertical flammability rating of V-0, and a peak heat release rate (p-HRR) of 292 kW / m³ in cone calorimetry. 2 The total smoke release was 832m³. 2 / m 2 The self-healing temperature after the strip is cut is 100℃, the healing time is 10 minutes, and the healing efficiency is 90%.

[0154] Example 28

[0155] In this embodiment, the coordinating monomer Na2[Ge(DHBM)2(CT)1] was prepared by reacting GeO2, methyl 3,4-dihydroxybenzoate (H2DHBM), catechol (H2CT), and NaOH in a molar ratio of 1:2:1:2 under reflux in acetonitrile for 12 h. 73.1 g of 1,8-octanediol, 279.5 g of the coordinating monomer Na2[Ge(DHBM)2(CT)1], and 0.02 wt% of zinc acetate and 0.02 wt% of antimony trioxide catalysts (based on the total mass of the reactants) were added to a reaction vessel, and nitrogen was used to purge the air from the vessel. After transesterification and polycondensation according to the steps and conditions given in Example 1, the product was discharged under a nitrogen atmosphere.

[0156] The polymer obtained in this example has an intrinsic viscosity [η] of 1.56 dL / g, a tensile strength of 102 MPa, an elongation at break of 89%, an initial decomposition temperature of 372 °C, a limiting oxygen index of 28%, a vertical flammability rating of V-1, and a peak heat release rate (p-HRR) of 398 kW / m³ in cone calorimetry. 2 The total smoke release was 625m³. 2 / m 2 The self-healing temperature after the strip is cut is 100℃, the healing time is 10 minutes, and the healing efficiency is 95%.

[0157] Example 29

[0158] In this embodiment, the coordinating monomer Na2[Si(DHBM)2(CT)1] was prepared by reacting SiO2, methyl 3,4-dihydroxybenzoate (H2DHBM), catechol (H2CT), and NaOH in a molar ratio of 1:2:1:2 under reflux in acetonitrile for 12 h. 59.1 g of 1,6-hexanediol, 257.2 g of the coordinating monomer Na2[Si(DHBM)2(CT)1], and 0.02 wt% of zinc acetate and 0.02 wt% of antimony trioxide catalysts (based on the total mass of the reactants) were added to a reaction vessel, and nitrogen was used to purge the air from the vessel. After transesterification and polycondensation according to the steps and conditions given in Example 1, the product was discharged under a nitrogen atmosphere.

[0159] The polymer obtained in this example has an intrinsic viscosity [η] of 1.61 dL / g, a tensile strength of 104 MPa, an elongation at break of 58%, an initial decomposition temperature of 393 °C, a limiting oxygen index of 30%, a vertical flammability rating of V-0, and a peak heat release rate (p-HRR) of 325 kW / m³ in cone calorimetry. 2 The total smoke release was 756m³. 2 / m 2 The self-healing temperature after the strip is cut is 100℃, the healing time is 10 minutes, and the healing efficiency is 95%.

[0160] Example 30

[0161] In this embodiment, the coordinating monomer Na2[Ge(THBM)2(CT)1] was prepared by reacting GeO2, methyl 3,4,5-trihydroxybenzoate (H2THBM), catechol (H2CT), and NaOH in a molar ratio of 1:2:1:2 under reflux in acetonitrile for 12 h. 87.1 g of 1,10-decanediol, 295.5 g of the coordinating monomer Na2[Ge(THBM)2(CT)1], and 0.02 wt% of zinc acetate and 0.02 wt% of antimony trioxide catalysts (based on the total mass of the reactants) were added to a reaction vessel, and nitrogen was used to purge the air from the vessel. After transesterification and polycondensation according to the steps and conditions given in Example 1, the product was discharged under a nitrogen atmosphere.

[0162] The polymer obtained in this example has an intrinsic viscosity [η] of 1.72 dL / g, a tensile strength of 105 MPa, an elongation at break of 102%, an initial decomposition temperature of 368 °C, a limiting oxygen index of 27%, a vertical flammability rating of V-0, and a peak heat release rate (p-HRR) of 332 kW / m³ in cone calorimetry. 2 The total smoke release was 608m³. 2 / m 2 The self-healing temperature after the strip is cut is 100℃, the healing time is 10 minutes, and the healing efficiency is 95%.

[0163] Example 31

[0164] In this embodiment, the coordinate-bonded monomer Na2[Ge(DHBM)3] was prepared by reacting GeO2, methyl 3,4-dihydroxybenzoate (H2DHBM), and NaOH in a molar ratio of 1:3:2 under reflux in acetonitrile for 12 h. 59.1 g of 1,6-hexanediol, 308.5 g of the coordinate-bonded monomer Na2[Ge(DHBM)3], and 0.02 wt% of zinc acetate and 0.02 wt% of antimony trioxide catalysts (based on the total mass of the reactants) were added to a reaction vessel, and nitrogen was used to purge the air from the vessel. After transesterification and polycondensation according to the steps and conditions given in Example 1, the product was discharged under a nitrogen atmosphere.

[0165] The polymer obtained in this example has an intrinsic viscosity [η] of 1.78 dL / g, a tensile strength of 115 MPa, an elongation at break of 26%, an initial decomposition temperature of 418 °C, a limiting oxygen index of 33%, a vertical flammability rating of V-0, and a peak heat release rate (p-HRR) of 243 kW / m² in cone calorimetry. 2 The total smoke release was 521m³. 2 / m 2The self-healing temperature after the strip is cut is 100℃, the healing time is 5 minutes, and the healing efficiency is 92%.

[0166] Example 32

[0167] In this embodiment, the coordinating monomer K2[Ge(THBM)3] was prepared by reacting GeO2, methyl 3,4,5-trihydroxybenzoate (H2THBM), and KOH in a molar ratio of 1:3:2 under reflux in acetonitrile for 12 h. 59.1 g of 1,6-hexanediol, 348.6 g of the coordinating monomer K2[Ge(THBM)3], and 0.02 wt% of titanate ester of the total reactants were added to a reaction vessel, and nitrogen was used to purge the air from the vessel. After transesterification and polycondensation according to the steps and conditions given in Example 1, the product was discharged under a nitrogen atmosphere.

[0168] The polymer obtained in this example has an intrinsic viscosity [η] of 1.80 dL / g, a tensile strength of 120 MPa, an elongation at break of 12%, an initial decomposition temperature of 420 °C, a limiting oxygen index of 35%, a vertical flammability rating of V-0, and a peak heat release rate (p-HRR) of 200 kW / m² in cone calorimetry. 2 The total smoke release is 500m³. 2 / m 2 The self-healing temperature after the strip is cut is 100℃, the healing time is 5 minutes, and the healing efficiency is 90%.

[0169] Example 33

[0170] In this embodiment, the coordinate bond-containing monomer Na3[Fe(DHBM)3] is derived from Fe 3+ The product was prepared by reacting methyl 3,4-dihydroxybenzoate (H2DHBM) and NaOH in a molar ratio of 1:3:3 under reflux in acetonitrile for 12 h. 59.1 g of 1,6-hexanediol, 311.6 g of coordinating monomer Na3[Fe(DHBM)3], and 0.02 wt% of zinc acetate and antimony trioxide catalysts (based on the total mass of the reactants) were added to a reaction vessel. Nitrogen gas was then introduced to purge air from the vessel. After transesterification and polycondensation according to the steps and conditions given in Example 1, the product was discharged under a nitrogen atmosphere.

[0171] The polymer obtained in this example has an intrinsic viscosity [η] of 1.68 dL / g, a tensile strength of 112 MPa, an elongation at break of 5%, an initial decomposition temperature of 413 °C, a limiting oxygen index of 34.5%, a vertical flammability rating of V-0, and a peak heat release rate (p-HRR) of 231 kW / m³ in cone calorimetry. 2 The total smoke release was 536m³. 2 / m 2The self-healing temperature after the strip is cut is 100℃, the healing time is 5 minutes, and the healing efficiency is 95%.

[0172] Example 34

[0173] In this embodiment, the oligomer containing coordination bonds Na 22 [Ge 11 (DMBD) 10 (CT) 11 [DHBM]2 was prepared by reacting GeO2, 4,4'-(2,3-dimethylbut-1,4-diyl)bis(phenyl-1,2-diol) (H2DMBD), catechol (H2CT), methyl 3,4-dihydroxybenzoate (H2DHBM), and NaOH in a molar ratio of 11:10:11:2:22 under reflux in acetonitrile for 12 h. 87.1 g of 1,10-decanediol and 2904.7 g of the coordinate-bonded monomer Na... 22 [Ge 11 (DMBD) 10 (CT) 11 [(DHBM)2] and 0.02 wt% of the total mass of the reactants, zinc acetate catalyst and antimony trioxide catalyst, were added to the reaction vessel, and nitrogen gas was purged to remove air from the vessel. After the transesterification reaction and polycondensation were carried out according to the steps and conditions given in Example 1, the product was discharged under a nitrogen atmosphere.

[0174] The polymer obtained in this example has an intrinsic viscosity [η] of 1.53 dL / g, a tensile strength of 112 MPa, an elongation at break of 26%, an initial decomposition temperature of 386 °C, a limiting oxygen index of 32%, a vertical flammability rating of V-0, and a peak heat release rate (p-HRR) of 435 kW / m³ in cone calorimetry. 2 The total smoke release was 531m³. 2 / m 2 The self-healing temperature after the strip is cut is 110℃, the healing time is 10 minutes, and the healing efficiency is 90%.

[0175] Example 35

[0176] In this embodiment, the oligomer containing coordination bonds Na 22 [Ge 11 (DOBD) 10 (CT) 11[DHBM]2 was prepared by reacting GeO2, 4,4'-(oxybis(methylene))bis(phenyl-1,2-diol) (H2DOBD), catechol (H2CT), methyl 3,4-dihydroxybenzoate (H2DHBM), and NaOH in a molar ratio of 11:10:11:2:22 under reflux in acetonitrile for 12 h. 87.1 g of 1,10-decanediol and 2704.1 g of the coordinate-bonded monomer Na... 22 [Ge 11 (DOBD) 10 (CT) 11 [(DHBM)2] and 0.02 wt% of the total mass of the reactants, zinc acetate catalyst and antimony trioxide catalyst, were added to the reaction vessel, and nitrogen gas was purged to remove air from the vessel. After the transesterification reaction and polycondensation were carried out according to the steps and conditions given in Example 1, the product was discharged under a nitrogen atmosphere.

[0177] The polymer obtained in this example has an intrinsic viscosity [η] of 1.58 dL / g, a tensile strength of 105 MPa, an elongation at break of 34%, an initial decomposition temperature of 379 °C, a limiting oxygen index of 33%, a vertical flammability rating of V-0, and a peak heat release rate (p-HRR) of 418 kW / m³ in cone calorimetry. 2 The total smoke release was 509m³. 2 / m 2 The self-healing temperature after the strip is cut is 110℃, the healing time is 10 minutes, and the healing efficiency is 92%.

[0178] Example 36

[0179] Recycling Method 1: The waste polymer after use is crushed into blocks (approximately 1 cm in diameter). Then, 10.0 g of the crushed polymer is added to a mixed solution of 50 mL methanol and 100 mL dichloromethane, along with 3 g of concentrated hydrochloric acid. The reaction is carried out at 40°C for 120 min. After the reaction, methanol and dichloromethane are removed by rotary evaporation. Deionized water is then added to the remaining solid product, followed by filtration to obtain the degradation product, a diester ester. The pH of the filtrate is adjusted to 2 to obtain the degradation product, a polyphenol monomer. This monomer is then dried to obtain the dried degradation product. The polymer conversion rate is 100%, and the degradation product yield is 91%.

[0180] Example 37

[0181] Recycling Method 1: The waste polymer is crushed into blocks (approximately 1 cm in diameter). 10.0 g of the crushed polymer is then added to a mixed solution of 100 mL methanol and 100 mL dichloromethane, along with 5 g of concentrated hydrochloric acid. The reaction is carried out at 40°C for 60 min. After the reaction, methanol and dichloromethane are removed by rotary evaporation. Deionized water is then added to the remaining solid product, followed by filtration to obtain the degradation product, a diester ester. The pH of the filtrate is adjusted to 2 to obtain the degradation product, a polyphenol monomer. This monomer is then dried to obtain the dried degradation product. The polymer conversion rate is 100%, and the degradation product yield is 94%.

[0182] Example 38

[0183] Recycling Method 1: The waste polymer is crushed into blocks (approximately 1 cm in diameter). 10.0 g of the crushed polymer is then added to a mixed solution of 100 mL methanol and 200 mL dichloromethane, along with 5 g of concentrated hydrochloric acid. The reaction is carried out at 40°C for 60 min. After the reaction, methanol and dichloromethane are removed by rotary evaporation. Deionized water is then added to the remaining solid product, followed by filtration to obtain the degradation product, a diester ester. The pH of the filtrate is adjusted to 2 to obtain the degradation product, a polyphenol monomer. This monomer is then dried to obtain the dried degradation product. The polymer conversion rate is 100%, and the degradation product yield is 96%.

[0184] Example 39

[0185] Recycling Method 1: The waste polymer after use is crushed into blocks (approximately 1 cm in diameter). Then, 10.0 g of the crushed polymer is added to a mixed solution of 100 mL methanol and 100 mL dichloromethane, along with 5 g of concentrated hydrochloric acid. The reaction is carried out at 40°C for 60 min. After the reaction, methanol and dichloromethane are removed by rotary evaporation. Deionized water is then added to the remaining solid product, followed by filtration to obtain the degradation product, a diester ester. The pH of the filtrate is adjusted to 2 to obtain the degradation product, a polyphenol monomer. This monomer is then dried to obtain the dried degradation product. The polymer conversion rate is 100%, and the degradation product yield is 92%.

[0186] Example 40

[0187] Recycling Method 1: The waste polymer after use is crushed into blocks (approximately 1 cm in diameter). Then, 10.0 g of the crushed polymer is added to a mixed solution of 20 mL methanol and 100 mL dichloromethane, along with 3 g of concentrated hydrochloric acid. The reaction is carried out at 40°C for 120 min. After the reaction, methanol and dichloromethane are removed by rotary evaporation. Deionized water is then added to the remaining solid product, followed by filtration to obtain the degradation product, a diester ester. The pH of the filtrate is adjusted to 2 to obtain the degradation product, a polyphenol monomer. This monomer is then dried to obtain the dried degradation product. The polymer conversion rate is 100%, and the degradation product yield is 85%.

[0188] Example 41

[0189] Recycling Method 1: The waste polymer is crushed into blocks (approximately 1 cm in diameter). 10.0 g of the crushed polymer is then added to a mixed solution of 200 mL methanol and 200 mL dichloromethane, along with 5 g of concentrated hydrochloric acid. The reaction is carried out at 40°C for 60 min. After the reaction, methanol and dichloromethane are removed by rotary evaporation. Deionized water is then added to the remaining solid product, followed by filtration to obtain the degradation product, a diester ester. The pH of the filtrate is adjusted to 1 to obtain the degradation product, a polyphenol monomer. This monomer is then dried to obtain the dried degradation product. The polymer conversion rate is 100%, and the degradation product yield is 95%.

[0190] Example 42

[0191] Recycling Method 1: The waste polymer after use is crushed into blocks (approximately 1 cm in diameter). Then, 10.0 g of the crushed polymer is added to a mixed solution of 150 mL methanol and 200 mL dichloromethane, along with 5 g of concentrated hydrochloric acid. The reaction is carried out at 40°C for 60 min. After the reaction, methanol and dichloromethane are removed by rotary evaporation. Deionized water is then added to the remaining solid product, followed by filtration to obtain the degradation product, a diester ester. The pH of the filtrate is adjusted to 1 to obtain the degradation product, a polyphenol monomer. This monomer is then dried to obtain the dried degradation product. The polymer conversion rate is 100%, and the degradation product yield is 94%.

[0192] Example 43

[0193] Recycling Method 1: The waste polymer after use is crushed into blocks (approximately 1 cm in diameter). Then, 10.0 g of the crushed polymer is added to a mixed solution of 200 mL methanol and 10 mL dichloromethane, along with 5 g of concentrated hydrochloric acid. The reaction is carried out at 40°C for 60 min. After the reaction, methanol and dichloromethane are removed by rotary evaporation. Deionized water is then added to the remaining solid product, followed by filtration to obtain the degradation product, a diester ester. The pH of the filtrate is adjusted to 1 to obtain the degradation product, a polyphenol monomer. This monomer is then dried to obtain the dried degradation product. The polymer conversion rate is 100%, and the degradation product yield is 89%.

[0194] Example 44

[0195] Recycling Method 1: The waste polymer after use is crushed into blocks (approximately 1 cm in diameter). Then, 10.0 g of the crushed polymer is added to a mixed solution of 100 mL methanol and 10 mL chloroform, along with 1 g of concentrated hydrochloric acid. The reaction is carried out at 60°C for 30 min. After the reaction, methanol and chloroform are removed by rotary evaporation. Deionized water is then added to the remaining solid product, followed by filtration to obtain the degradation product, a diester ester. The pH of the filtrate is adjusted to 3 to obtain the degradation product, a polyphenol monomer. This monomer is then dried to obtain the dried degradation product. The polymer conversion rate is 100%, and the degradation product yield is 82%.

[0196] Example 45

[0197] Recycling Method 1: The waste polymer after use is crushed into blocks (approximately 1 cm in diameter). Then, 10.0 g of the crushed polymer is added to a mixed solution of 100 mL methanol and 100 mL chloroform, along with 1 g of concentrated hydrochloric acid. The reaction is carried out at 60 °C for 240 min. After the reaction, methanol and chloroform are removed by rotary evaporation. Deionized water is then added to the remaining solid product, followed by filtration to obtain the degradation product, a diester ester. The pH of the filtrate is adjusted to 3 to obtain the degradation product, a polyphenol monomer. This monomer is then dried to obtain the dried degradation product. The polymer conversion rate is 100%, and the degradation product yield is 94%.

[0198] Example 46

[0199] Recycling Method 1: The waste polymer after use is crushed into blocks (approximately 1 cm in diameter). Then, 10.0 g of the crushed polymer is added to a mixed solution of 100 mL ethanol and 100 mL dichloromethane, along with 5 g of sodium hydroxide. The reaction is carried out at 25°C for 120 min. After the reaction, ethanol and dichloromethane are removed by rotary evaporation. Deionized water is then added to the remaining solid product, followed by filtration to obtain the degradation product, a diester ester. The pH of the filtrate is adjusted to 2 to obtain the degradation product, a polyphenol monomer. This monomer is then dried to obtain the dried degradation product. The polymer conversion rate is 100%, and the degradation product yield is 91%.

[0200] Example 47

[0201] Recycling Method 1: The waste polymer after use is crushed into blocks (approximately 1 cm in diameter). Then, 10.0 g of the crushed polymer is added to a mixed solution of 100 mL ethanol and 100 mL dichloromethane, along with 1 g of sodium hydroxide. The reaction is carried out at 25°C for 120 min. After the reaction, the ethanol and dichloromethane are removed by rotary evaporation. Deionized water is then added to the remaining solid product, followed by filtration to obtain the degradation product, a diester ester. The pH of the filtrate is adjusted to 2 to obtain the degradation product, a polyphenol monomer. This monomer is then dried to obtain the dried degradation product. The polymer conversion rate is 100%, and the degradation product yield is 86%.

[0202] Example 48

[0203] Recycling Method 1: The waste polymer is crushed into blocks (approximately 1 cm in diameter). 10.0 g of the crushed polymer is then added to a mixed solution of 100 mL ethanol and 100 mL chloroform, along with 5 g of potassium carbonate. The reaction is carried out at 50°C for 60 min. After the reaction, the ethanol and chloroform are removed by rotary evaporation. Deionized water is then added to the remaining solid product, followed by filtration to obtain the degradation product, a diester ester. The pH of the filtrate is adjusted to 5 to obtain the degradation product, a polyphenol monomer. This monomer is then dried to obtain the dried degradation product. The polymer conversion rate is 100%, and the degradation product yield is 88%.

[0204] Example 49

[0205] Recycling Method 1: The waste polymer after use is crushed into blocks (approximately 1 cm in diameter). Then, 10.0 g of the crushed polymer is added to a mixed solution of 150 mL methanol and 50 mL dichloromethane, along with 5 g of potassium hydroxide. The reaction is carried out at 40°C for 120 min. After the reaction, methanol and dichloromethane are removed by rotary evaporation. Deionized water is then added to the remaining solid product, followed by filtration to obtain the degradation product, a diester ester. The pH of the filtrate is adjusted to 4 to obtain the degradation product, a polyphenol monomer. This monomer is then dried to obtain the dried degradation product. The polymer conversion rate is 100%, and the degradation product yield is 96%.

[0206] Example 50

[0207] Recycling Method 1: The waste polymer is crushed into blocks (approximately 1 cm in diameter). 10.0 g of the crushed polymer is then added to a mixed solution of 150 mL methanol and 50 mL dichloromethane, along with 1 g of potassium hydroxide. The mixture is reacted at 40°C for 60 min. After the reaction, methanol and dichloromethane are removed by rotary evaporation. Deionized water is then added to the remaining solid product, followed by filtration to obtain the degradation product, a diester ester. The pH of the filtrate is adjusted to 4 to obtain the degradation product, a polyphenol monomer. This monomer is then dried to obtain the dried degradation product. The polymer conversion rate is 100%, and the degradation product yield is 90%.

[0208] Example 51

[0209] Recycling Method 2: The used waste polymer is crushed into blocks (approximately 1 cm in diameter). 10.0 g of the crushed polymer is then added to 50 mL of ethylene glycol as a reaction solvent, and reacted at 190 °C for 60 min. After the reaction, the reaction solution is poured hot into anhydrous ethanol, and filtered to obtain the degradation products—monomers / oligomers with coordination bonds. The anhydrous ethanol is then removed by rotary evaporation, and deionized water is added to the remaining EG solution to obtain the degradation product—a diester ester. This diester ester is then dried to obtain the dried degradation product. The polymer conversion rate is 100%, and the degradation product yield is 78%.

[0210] Example 52

[0211] Recycling Method 2: The waste polymer is crushed into blocks (approximately 1 cm in diameter). 10.0 g of the crushed polymer is then added to 100 mL of ethylene glycol as a reaction solvent, and reacted at 150 °C for 120 min. After the reaction, the hot reaction solution is poured into anhydrous ethanol and filtered to obtain the degradation products, monomers / oligomers with coordination bonds. The anhydrous ethanol is then removed by rotary evaporation, and deionized water is added to the remaining EG solution to obtain the degradation product, a diester ester. This diester ester is then dried to obtain the dried degradation product. The polymer conversion rate is 100%, and the degradation product yield is 85%.

[0212] Example 53

[0213] Recycling Method 2: The used waste polymer is crushed into blocks (approximately 1 cm in diameter). Then, 10.0 g of the crushed polymer is added to 200 mL of ethylene glycol as a reaction solvent, and the reaction is carried out at 190 °C for 240 min. After the reaction, the reaction solution is poured into anhydrous ethanol while hot, and filtered to obtain the degradation products, monomers / oligomers with coordination bonds. The anhydrous ethanol is then removed by rotary evaporation, and deionized water is added to the remaining EG solution to obtain the degradation product, a diester ester. This diester ester is then dried to obtain the dried degradation product. The polymer conversion rate is 100%, and the degradation product yield is 99%.

[0214] Example 54

[0215] Recycling Method 2: The waste polymer is crushed into blocks (approximately 1 cm in diameter). 10.0 g of the crushed polymer is then added to 100 mL of 1,4-butanediol as a reaction solvent and reacted at 190 °C for 120 min. After the reaction, the hot reaction solution is poured into anhydrous ethanol and filtered to obtain the degradation product, a monomer / oligomer containing a coordination bond structure. The anhydrous ethanol is then removed by rotary evaporation. Deionized water is added to the remaining EG solution to obtain the degradation product, a diester ester, which is then dried to obtain the dried degradation product. The polymer conversion rate is 100%, and the degradation product yield is 95%.

[0216] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A flame-retardant polyphenolic coordination polymer, characterized in that, The molecular chain of the polyphenol-based coordination polymer contains coordination bond structural units formed by coordination between a central ion and a polyphenol monomer, and the polyphenol-based coordination polymer is formed by polycondensation of a diacid or its esterified form and / or a tricarboxylic acid or its esterified form and a C2-C10 diol, wherein the diacid or its esterified form includes at least a diacid or its esterified form containing coordination bond structural units, and the tricarboxylic acid or its esterified form includes a tricarboxylic acid or its esterified form containing coordination bond structural units. The polyphenolic coordination polymer is composed of structural units represented by the following I, II, III or I, II, IV or I, II, V or I, III or I, IV or I, V: [Ⅰ], where R1 represents a C2~C10 alkylene group. [Ⅱ], where R2 represents aryl, [Ⅲ], where R3 is any of the following structural units: 1A、 1B 1C , 1E, 1F 1G 1H, 1I and IJ, Wherein, M1 is any one of the following ions with a valence of +2: Mg, Ca, V, Mn, Fe, Co, Ni, Cu, and Zn; M2 is any one of the following ions with a valence of +4: Si, Ge, Sn, Ti, Mn, and V; M3 is any one of the following ions with a valence of +3: B, Fe, Al, Ga, and In; N is any one of the following ions with a valence of +1: H, Li, Na, K, and NH4; and X1 is any one of the following: H atom, methyl, ethyl, methoxy, and phenyl. [Ⅳ], where R4 is any of the following structures: 2A 2B 2C and 2D Wherein, M2 is any one of the following ions with a +4 valence: Si, Ge, Sn, Ti, Mn, and V; M3 is any one of the following ions with a +3 valence: B, Fe, Al, Ga, and In; and N is any one of the following ions with a +1 valence: H, Li, Na, K, and NH4+. [V], where R5 is any of the following structures: 3A、 3B、 3C and 3D， Wherein, M2 is any one of the following ions with a +4 valence: Si, Ge, Sn, Ti, Mn, and V; M3 is any one of the following ions with a +3 valence: B, Fe, Al, Ga, and In; N is any one of the following ions with a +1 valence: H, Li, Na, K, and NH4; X1 is any one of the following atoms: H, methyl, ethyl, methoxy, and phenyl; m is an integer from 2 to 50; R6 is any one of the following groups: C1~C10 alkylene groups, , , , , , , , , , as well as , In the molecular chain of the polyphenolic coordination polymer, the number of structural units [Ⅲ] is 1-80% of the number of structural units [Ⅰ], and the ratio of structural units [Ⅰ] to [Ⅱ+Ⅲ] is 1; the number of structural units [Ⅳ] is 1-40% of the number of structural units [Ⅰ], and the ratio of structural units [Ⅰ] to [Ⅱ+Ⅳ] is 1-1.25, which is related to the number of structural units [Ⅳ]; the number of structural units [Ⅴ] is 1-80% of the number of structural units [Ⅰ], and the ratio of structural units [Ⅰ] to [Ⅱ+Ⅴ] is 1; each structural unit or the chain segment it forms is arbitrarily connected and combined according to carboxyl and hydroxyl functional groups; the intrinsic viscosity [η] of the polymer is 0.40-1.70 dL / g; and the tensile strength is 50.0-110.

0. MPa; Limiting oxygen index: 23.0~33.0%; Vertical combustion rating: V-2~V-0; Peak heat release rate (p-HRR) in cone calorimetry: 250~650 kW / m³ 2 .

2. The polyphenolic coordination polymer according to claim 1, characterized in that, In the molecular chain of the polyphenolic coordination polymer, the number of structural units [Ⅲ] is 1-60% of the number of structural units [Ⅰ], and the ratio of structural units [Ⅰ] to structural units [Ⅱ+Ⅲ] is 1; the number of structural units [Ⅳ] is 1-30% of the number of structural units [Ⅰ], and the ratio of structural units [Ⅰ] to structural units [Ⅱ+Ⅳ] is 1-1.18, which is related to the number of structural units [Ⅳ]; the number of structural units [Ⅴ] is 1-60% of the number of structural units [Ⅰ], and the ratio of structural units [Ⅰ] to structural units [Ⅱ+Ⅴ] is 1; each structural unit or the chain segment it forms is arbitrarily connected and combined according to carboxyl and hydroxyl functional groups; the intrinsic viscosity [η] of the polymer is 0.45-1.60 dL / g; the tensile strength is 55.0-105.0 MPa; and the limiting oxygen index is 23.5-32.0%. Vertical combustion rating: V-2 to V-0; Peak heat release rate (p-HRR) in cone calorimetry testing: 300 to 620 kW / m³ 2 .

3. A method for preparing a flame-retardant polyphenolic coordination polymer, characterized in that, The preparation method is used to prepare the polyphenolic coordination polymer according to any one of claims 1 to 2. The preparation method is to esterify a C2-C10 diol monomer, a diacid or its esterified monomer without a coordinate bond structural unit, and a catalyst in a certain ratio using a direct esterification method or a transesterification method, and then prepare the polymer by polycondensation reaction with a monomer or oligomer containing a coordinate bond structural unit. The monomer or oligomer containing a coordinate bond structural unit is added to the reaction system at a molar percentage of 1-100% of the diol monomer before the esterification reaction or after the esterification reaction and before the polycondensation reaction. The amount of diacid or its esterified monomer without a coordinate bond structural unit added is 0-99% of the molar percentage of the diol monomer.

4. A method for recovering flame-retardant polyphenolic coordination polymers, characterized in that, The recovery method is used to recover the polyphenolic coordination polymer prepared according to claim 3, and the recovery method includes the following steps: The used polyphenolic coordination polymer is crushed into blocks and then added to a mixed solution of reaction solvent and co-solvent, or a mixed solution of recycled reaction solvent and recycled reaction co-solvent. A certain mass of acid or base is added to the mixed solution, and the reaction is carried out at 25~65 °C for 30~240 min. The mass-volume ratio of the polyphenolic coordination polymer to the reaction solvent or recycled reaction solvent is 0.01~0.5 W / V, the mass-volume ratio of the polyphenolic coordination polymer to the co-solvent or recycled co-solvent is 0.05~1.0 W / V, and the mass-volume ratio of the added acid or base to the polyphenolic coordination polymer is 0.01~0.5 W / V. The units of mass-volume ratio are g / ml. After cooling the reaction solution obtained in the previous step to room temperature, the reaction solvent and co-solvent are removed by rotary evaporation at 30~100 °C. Then, deionized water is added to the remaining solid product and the pH of the solution is adjusted to 1~5 to obtain the degradation product. The conversion rate of the polymer is 100%, and the yield of the degradation product is above 82%. The collected degradation product can be used again to synthesize the polyphenolic coordination polymer, and the collected reaction solvent and co-solvent are reused as recycled reaction solvent and recycled reaction co-solvent, respectively.

5. The recycling method according to claim 4, characterized in that, The reaction solvent used in the recovery method is at least one of methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, pentanol, hexanol, 1,4-butanediol, and 1,4-cyclohexanediol; the co-solvent used is at least one of heptane, cyclohexane, acetone, acetonitrile, tetrahydrofuran, dichloromethane, chloroform, and chlorobenzene; the acid used is at least one of hydrochloric acid, sulfuric acid, phosphoric acid, perchloric acid, hydrobromic acid, and nitric acid; and the base used is at least one of potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonia, diethanolamine, and triethanolamine.

6. A method for recovering flame-retardant polyphenolic coordination polymers, characterized in that, The recovery method is used to recover the polyphenolic coordination polymer prepared according to claim 3, and the recovery method includes the following steps: The used polyphenolic coordination polymer is crushed into blocks and then added to a reaction solvent or a recycled reaction solvent. The mixture is reacted at 150-190 °C for 60-240 min to obtain degradation products and a reaction solution. The mass-to-volume ratio of the polyphenolic coordination polymer to the reaction solvent or recycled reaction solvent is 0.05-0.2 W / V. The unit of mass-to-volume ratio is g / ml. The reaction solvent used is at least one of ethylene glycol, 1,3-propanediol, and 1,4-butanediol. The reaction solution obtained in the previous step was poured into anhydrous ethanol while hot to precipitate the degradation product. The product was then filtered and dried to obtain the degradation product. The conversion rate of the polymer was 100%, and the yield of the degradation product was over 78%. The collected degradation product could be used again to synthesize the polyphenolic coordination polymer, and the collected reaction solvent was reused as a recycled reaction solvent.

7. The application of the flame-retardant polyphenolic coordination polymer according to any one of claims 1 to 2, characterized in that, The applications include using the polyphenolic coordination polymer in plastics, fibers, nonwovens, battery separators, films, healthcare packaging materials, container materials, or 3D printing materials, or as a modified processing aid.

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