High temperature resistant polymerizable material composition and use thereof

Abstract

This invention relates to the field of polymer materials technology, specifically to a high-temperature resistant polymerizable material composition and its application. The composition comprises monomers such as polyethylene glycol (200) dimethacrylate and isobornyl acrylate, Sardoma UV resin, photoinitiator TPO, and the core functional molecule ((2-(5,5,5-trifluoro-1-methylacrylamidopentan-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonic acid. This core functional molecule is prepared stepwise through condensation cyclization, Michael addition, Mannich reaction, catalytic hydrogenation acylation, and acid hydrolysis. After mixing the composition with the main matrix material, it is UV-cured to form a 20 μm thick polymer microcrystalline layer, thereby obtaining a 3MDT dimming film. This film possesses excellent high-temperature stability, strong interfacial adhesion, rapid dimming response, and good mechanical properties, maintaining stable dimming effects under high-temperature environments, making it suitable for high-end applications such as architecture and automobiles.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to a high-temperature resistant polymerizable material composition and its application. Background Technology

[0002] PDLC dimming films are increasingly used in fields such as building energy-saving glass, automotive window film, and privacy partitions because they have an electrically controllable "transparent-frosty" switching function. Their core advantage is that they can achieve flexible control of light and privacy without the need for additional shading structures, which is in line with the development trend of modern smart materials.

[0003] However, existing PDLC dimming films still have significant technical bottlenecks: most products rely on ordinary acrylate polymers as the matrix, lacking thermally stable reinforcing structures. In high-temperature environments (such as architectural glass and automotive interiors in summer), the thermal motion of molecular chains is easily intensified, leading to microdroplet aggregation of the matrix material, degradation of dimming performance, and even interlayer delamination. At the same time, the interfacial bonding between the polymer matrix and the PET-ITO conductive layer relies heavily on intermolecular forces, resulting in insufficient adhesion. Long-term use can easily lead to delamination failure due to environmental stress.

[0004] Furthermore, the structural design of functional molecules in existing compositions lacks synergy, making it difficult to simultaneously achieve high-temperature resistance, high adhesion, fast response speed, and excellent mechanical properties. Some products sacrifice response speed to improve high-temperature resistance, or reduce mechanical flexibility to optimize interfacial bonding, failing to meet the stringent requirements of high-end applications for comprehensive material performance. Therefore, developing a polymerizable material composition that combines excellent high-temperature stability, strong interfacial adhesion, fast dimming response, and good mechanical properties has become crucial for driving the expansion of PDLC dimming films into high-end fields. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and to propose a high-temperature resistant polymerizable material composition and its application.

[0006] To achieve the above objectives, the present invention provides a high-temperature resistant polymerizable material composition comprising the following raw materials in parts by weight: polyethylene glycol (200) dimethacrylate: 18-22 parts, isoborneol acrylate: 11-15 parts, isoborneol methacrylate: 11-15 parts, lauryl methacrylate: 12-16 parts, Sartoma UV resin SR9051NS: 0.8-1.2 parts, photoinitiator TPO: 2-4 parts, Sartoma UV resin CN9001NS: 26-30 parts, 4-hydroxybutyl acrylate: 1-3 parts, 4'-(6-(acryloyloxy)hexyloxy)biphenyl nitrile: 5-7 parts, ((2-(5,5,5-trifluoro-1-methylacrylamidopent-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonic acid: 5-20 parts;

[0007] The chemical structural formula of ((2-(5,5,5-trifluoro-1-methylacrylamidopentan-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonic acid is as follows:

[0008] .

[0009] Preferably, the preparation method of ((2-(5,5,5-trifluoro-1-methylacrylamidopent-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonic acid includes the following steps:

[0010] (1) Add o-phenylenediamine and cyanoacetic acid to a reaction vessel, then add polyphosphoric acid. Under nitrogen protection, heat to 110-120℃ and stir for 2-4 hours. After the reaction is complete, cool to room temperature, pour into ice water and stir. Adjust the pH to 7-8 with 10wt% NaOH. A solid is observed to precipitate. After filtration, the collected solid is recrystallized from ethanol to obtain 2-(1H-benzo[d]imidazol-2-yl)acetonitrile. The chemical reaction equation is as follows:

[0011] The product was characterized by ¹H NMR. This step is a condensation cyclization reaction of the benzimidazole ring, which relies on the dual catalytic and dehydration effects of polyphosphoric acid (PPA). Both amino groups in the o-phenylenediamine molecule are nucleophilic. The carboxyl group of cyanoacetic acid first undergoes a nucleophilic substitution reaction with one amino group of o-phenylenediamine to form an amide intermediate. Subsequently, under the acidic environment and high temperature provided by PPA, the amide intermediate undergoes intramolecular dehydration, and the other amino group of o-phenylenediamine attacks the carbon atom adjacent to the cyano group of cyanoacetic acid, completing the cyclization process and ultimately forming a stable benzimidazole heterocycle while retaining the cyano group, yielding 2-(1H-benzi[d]imidazole-2-yl)acetonitrile. In this process, PPA both activates the carboxyl group to promote condensation and promptly removes the water molecules generated in the reaction, driving the cyclization equilibrium forward.

[0012] (2) Add 2-(1H-benzo[d]imidazol-2-yl)acetonitrile, 3,3,3-trifluoropropene and 1,8-diazabicyclo[5.4.0]undec-7-ene to a reaction vessel, then add acetonitrile as a solvent. Under nitrogen protection, heat to 40-50℃ and react for 4-6 h. After the reaction, remove the solvent by vacuum distillation. The residue is purified by silica gel column chromatography with gradient elution to obtain 2-(1H-benzo[d]imidazol-2-yl)-5,5,5-trifluoropentadienonitrile; the chemical reaction equation is as follows:

[0013] The product was characterized by ¹H NMR. The reaction was a Michael addition reaction of cyano-activated methylene. 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) played a key role as an organic strong base. DBU abstracted the active hydrogen from the methylene group at the 2-position of benzimidazole in 2-(1H-benzimidazole-2-yl)acetonitrile, converting the methylene group into a nucleophilic carbanion. Due to the electron-withdrawing effect of the trifluoromethyl group, the carbon-carbon double bond of 3,3,3-trifluoropropene formed an electron-deficient unsaturated site. The nucleophilic carbanion launched a nucleophilic attack on the double bond, resulting in a Michael addition reaction, which introduced the trifluoropropyl chain into the molecular structure, ultimately generating 2-(1H-benzimidazole-2-yl)-5,5,5-trifluoropentadienonitrile.

[0014] (3) Add 2-(1H-benzo[d]imidazol-2-yl)-5,5,5-trifluoropentadienyl nitrile, diethyl phosphite, and 37wt% formaldehyde solution to the reaction vessel, then add ethanol as solvent, adjust the pH to 4-5 with 1mol / L hydrochloric acid solution, and reflux at 65-75℃ for 3-5 h. After the reaction, remove the solvent under reduced pressure, and purify the residue by gradient elution using silica gel column chromatography to obtain diethyl((2-(1-cyano-4,4,4-trifluorobutyl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonate; the chemical reaction equation is as follows:

[0015] The product was characterized by 1H NMR. This reaction belongs to the Mannich reaction and is a key step in the construction of the CP bond. A 37wt% formaldehyde solution under acidic conditions undergoes protonation to form an imine ion-active intermediate. The α-hydrogen atom in diethyl phosphite bonded to the phosphorus atom has a certain acidity and is activated in the reaction environment to form a nucleophilic phosphine anion. Simultaneously, the N atom on the benzimidazole ring participates in coordination through its lone pair electrons, further activating the molecular structure. The phosphine anion acts as a nucleophile, attacking the electron-deficient carbon center of the imine ion, undergoing a nucleophilic addition reaction. Subsequently, through proton transfer and structural rearrangement, diethyl((2-(1-cyano-4,4,4-trifluorobutyl)-1H-benzi[d]imidazol-1-yl)methyl)phosphonate is finally formed.

[0016] (4) Add diethyl((2-(1-cyano-4,4,4-trifluorobutyl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonate, 10% Pd / C and anhydrous tetrahydrofuran to the reaction vessel. Replace with hydrogen three times and maintain a hydrogen atmosphere. Heat to 40-60℃ and stir for 4-8 hours. Filter to remove Pd / C. Return the filtrate to the reaction vessel. Add triethylamine and hydroquinone. Cool to 0℃ in an ice bath. Slowly add acryloyl chloride over 1-2 hours. After the addition is complete, maintain the reaction at 0℃ for 2-4 hours. After the reaction is complete, wash the reaction solution with saturated brine, dry, concentrate, and then purify by gradient elution using silica gel column chromatography to obtain diethyl((2-(5,5,5-trifluoro-1-methylacrylamidopentan-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonate. The chemical reaction equation is as follows:

[0017] The product was characterized by H NMR; this step involves a series of catalytic hydrogenation reduction and acylation reactions. The first step is the catalytic hydrogenation reduction of the cyano group: Under a 10% Pd / C catalyst and hydrogen atmosphere, the cyano group undergoes selective hydrogenation, and the triple bond is gradually reduced, first forming an imine intermediate, and then further hydrogenating to generate a primary amino group. The Pd / C catalyst only activates the cyano group and has no effect on trifluoropropyl, diethyl phosphonate, and other groups in the molecule, thus achieving selective reduction. The second step is the Schotten-Baumann acylation reaction of the amino group: Triethylamine acts as an acid-binding agent, first combining with trace amounts of acidic substances in the reaction system to prevent the amino group from being protonated and deactivated. The carbonyl carbon of the acrylate chloride becomes an electrophilic center due to the electron-withdrawing effect of the chlorine atom. The amino group, as a nucleophile, attacks this center, undergoing a nucleophilic substitution reaction, removing HCl (neutralized by triethylamine), and forming an acrylamide group. Hydroquinone acts as a polymerization inhibitor, which can inhibit the self-polymerization side reaction of the carbon-carbon double bond in the acrylate chloride. The ice bath (0°C) condition further reduces the risk of self-polymerization and ensures the selectivity of the acylation reaction.

[0018] (5) Diethyl((2-(5,5,5-trifluoro-1-methylacrylamidopent-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonate was added to a reaction vessel, along with 10wt% citric acid solution. Using an ethanol / water mixture as the solvent, the mixture was heated to 60-70℃ and stirred for 2-4 hours. After the reaction, it was cooled to room temperature, and the ethanol was removed by vacuum distillation. The pH was adjusted to neutral with saturated sodium carbonate solution, and a solid precipitated. The solid obtained after filtration was washed three times with deionized water and dried under vacuum to obtain ((2-(5,5,5-trifluoro-1-methylacrylamidopent-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonic acid. The chemical reaction equation is as follows:

[0019] The product was characterized by ¹H NMR. This step is an acidic hydrolysis reaction of the diethyl phosphonate group, the core of which is the deprotection transformation of the ester group. A 10wt% citric acid solution provides a mild acidic environment, protonating the ester oxygen atom in the diethyl phosphonate group and enhancing the electrophilic activity of the carbonyl carbon. The ethanol / water mixed solution ensures the dissolution of the raw materials and provides sufficient water molecules as nucleophiles. The water molecules attack the protonated carbonyl carbon, undergoing a nucleophilic addition-elimination reaction, gradually removing the two ethyl ester groups to generate a hydroxyl group. After the reaction, the pH is adjusted to neutral with a saturated sodium carbonate solution to stabilize the phosphonate group and precipitate a solid, finally yielding the target product.

[0020] Preferably, in (1), the molar ratio of o-phenylenediamine and cyanoacetic acid is 1:1-1.2, and the weight ratio of o-phenylenediamine, polyphosphoric acid and ice water is 1:5-10:15-25.

[0021] Preferably, in (2), the molar ratio of 2-(1H-benzo[d]imidazol-2-yl)acetonitrile, 3,3,3-trifluoropropene and 1,8-diazabicyclo[5.4.0]undec-7-ene is 1:1-1.5:0.08-0.12.

[0022] Preferably, in (2), 2-(1H-benzo[d]imidazol-2-yl)acetonitrile and acetonitrile are in a weight ratio of 1:8-12.

[0023] Preferably, in step (2), gradient elution refers to the volume ratio of ethyl acetate to petroleum ether in each eluent step being 0:1, 1:20, 1:10 to 1:4.

[0024] Preferably, in (3), the molar ratio of 2-(1H-benzo[d]imidazol-2-yl)-5,5,5-trifluorovalerate and diethyl phosphite is 1:1.2-1.6.

[0025] Preferably, in (3), 2-(1H-benzo[d]imidazol-2-yl)-5,5,5-trifluoropentadienyl nitrile, 37wt% formaldehyde solution and ethanol are in a weight ratio of 1:0.45-0.55:8-12.

[0026] Preferably, in step (3), gradient elution refers to the volume ratio of dichloromethane to methanol in each step of the eluent changing from 1:0, 30:1, 20:1 to 10:1.

[0027] Preferably, in (4), the molar ratio of diethyl((2-(1-cyano-4,4,4-trifluorobutyl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonate, triethylamine, hydroquinone and acrylate chloride is 1:1.5-2:0.01-0.03:1-1.5.

[0028] Preferably, in (4), diethyl((2-(1-cyano-4,4,4-trifluorobutyl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonate, 10% Pd / C and anhydrous tetrahydrofuran are in a weight ratio of 1:0.02-0.06:10-20.

[0029] Preferably, in step (4), gradient elution refers to the volume ratio of dichloromethane to methanol in each eluent step being 1:0, 20:1, 10:1 to 5:1.

[0030] Preferably, in (5), the diethyl((2-(5,5,5-trifluoro-1-methylacrylamidopent-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonate, 10wt% citric acid solution and ethanol / water mixed solution are in a weight ratio of 1:0.5-1:8-12.

[0031] Preferably, the volume ratio of ethanol to water in the ethanol / water mixed solution in (5) is 1:1.

[0032] Furthermore, the present invention also provides an application of a high-temperature resistant polymerizable material composition for preparing a 3MDT dimming film; the method for preparing the 3MDT dimming film includes the following steps:

[0033] S1. Mix the high-temperature resistant polymerizable material composition and the main matrix material, and stir at room temperature for 30-60 min to obtain a homogeneous precursor;

[0034] S2. Take two layers of PET-ITO conductive film, apply the homogeneous precursor between the two layers of PET-ITO conductive film, and irradiate with ultraviolet light to completely cure the high-temperature resistant polymerizable material composition to form a polymer microcrystalline layer.

[0035] S3. After curing, the film is cut and cleaned to obtain the 3MDT dimming film;

[0036] The structure of the 3MDT dimming film is as follows: the upper and lower layers are PET-ITO conductive layers, and the middle layer is a cured polymer microcrystalline layer.

[0037] The thickness of the polymer microcrystalline layer is 5-30 μm.

[0038] Preferably, the high-temperature resistant polymerizable material composition and the main matrix material in S1 are in a weight ratio of 1:1.

[0039] Preferably, the ultraviolet light irradiation conditions in S2 are a wavelength of 365 nm and a power of 50-100 mW / cm². 2 The irradiation time is 30-60 seconds.

[0040] More preferably, the ultraviolet light irradiation conditions in S2 are a wavelength of 365 nm and a power of 80 mW / cm². 2 The irradiation time is 50 seconds.

[0041] More preferably, the thickness of the polymer microcrystalline layer is 20 μm.

[0042] Preferably, the high-temperature resistance mechanism of the high-temperature resistant polymerizable material composition described in this invention and its application in the preparation of 3MDT dimming films are as follows:

[0043] The high-temperature resistant polymerizable material composition of the present invention exhibits high-temperature resistance due to the fact that the benzimidazole ring in ((2-(5,5,5-trifluoro-1-methylacrylamidopentan-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonic acid is a typical rigid heterocyclic structure with a dense intracyclic conjugated system and high chemical bond energy, which can effectively inhibit the thermal motion and degradation of the molecular chain at high temperatures; the CF bond in the trifluoropropyl group has extremely strong bond energy and is not easily broken due to high temperatures, while the steric hindrance formed by the electronegativity of the fluorine atom further enhances the thermal stability of the molecular structure; the amide groups in the molecule can form intermolecular or intramolecular bonds. Hydrogen bonds form a stable supramolecular network, increasing the enthalpy of the system and delaying thermal decomposition. In addition, after the Sardoma UV resin (SR9051NS, CN9001NS) in the composition is cured with various acrylate monomers (such as isoborneol acrylate and polyethylene glycol (200) dimethacrylate), the crosslinked polymer network structure formed is dense and rigid, which can restrict the free migration of molecular chains and reduce thermal rheological phenomena at high temperatures. At the same time, phosphonic acid groups have certain flame retardant and thermal stabilizing auxiliary effects, which can reduce the burning or degradation rate of materials at high temperatures, thus giving the composition excellent high-temperature resistance.

[0044] In application, this composition ensures the structural stability and functional realization of the dimming film through the synergistic effect of polymerization-phase separation-interfacial bonding. First, after the composition and the host matrix material are mixed at a 1:1 weight ratio to form a homogeneous precursor, under 365nm ultraviolet light irradiation, the photoinitiator TPO rapidly decomposes to generate free radicals, initiating polymerization reactions of all polymerizable groups in the composition, rapidly forming a three-dimensional cross-linked polymer network. During this process, the polymer and the host matrix material undergo phase separation due to thermodynamic incompatibility, with the host matrix material uniformly dispersed in the polymer network, forming a composite structure of polymer matrix and host matrix material microdroplets. This is the core foundation of PDLC dimming technology. When power is off, the molecules within the host matrix material microdroplets are randomly arranged, strongly scattering light and making the film appear hazy. When power is applied, the molecules of the host matrix material are orderly arranged along the electric field direction, allowing light to pass through smoothly, resulting in a transparent state. Secondly, the functional molecule ((2-(5,5,5-trifluoro-1-methylacrylamide) The phosphonic acid group in (-1H-benzo[d]imidazol-1-yl)methyl)phosphonic acid can covalently bond with the hydroxyl groups on the surface of the PET-ITO conductive layer, significantly enhancing the interfacial adhesion between the polymer microcrystalline layer and the PET-ITO layer, preventing interlayer delamination during long-term use. Simultaneously, the three-dimensional network structure after curing imparts excellent mechanical strength and weather resistance to the film, extending its service life. Furthermore, the high-temperature resistance of the composition ensures that the dimming film, even in high-temperature environments during preparation and use, will not experience polymer matrix deformation or microdroplet aggregation of the main matrix material, maintaining a stable phase separation structure and dimming performance. The combination of multiple monomers and resins optimizes the curing rate and network uniformity, ensuring thorough phase separation of the main matrix material and improving the consistency and responsiveness of the dimming effect.

[0045] The beneficial effects of this invention are:

[0046] 1. This invention endows the composition with excellent high-temperature resistance through the structural design of the functional molecule ((2-(5,5,5-trifluoro-1-methylacrylamidopentan-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonic acid. The rigid conjugated system of the benzimidazole ring inhibits the high-temperature thermal motion of the molecular chain, the high bond energy (CF) of the trifluoropropyl group delays its fracture and degradation, and the hydrogen bond network formed by the amide group further enhances thermal stability. Combined with the dense cross-linked network formed by the curing of Sardoma UV resin and acrylate monomers, it can maintain the uniform distribution and structural integrity of the microdroplets in the main matrix material under high-temperature environments, avoiding the degradation of dimming performance and meeting the long-term use requirements in high-temperature scenarios.

[0047] 2. The composition of this invention can ensure excellent dimming effect of the dimming film through the synergistic effect of multiple components. The benzimidazole ring and acrylamide group in the functional molecule can regulate the polymer network, causing the main matrix material to form uniform micron-sized droplets during phase separation. This achieves efficient light scattering when the power is off, and the molecules are aligned when the power is on to ensure high light transmittance. At the same time, the good compatibility between each monomer and the functional molecule can avoid the aggregation of the main matrix material, ensuring the stability of the "transparent-hazy" switching, and maintaining continuous and reliable dimming function without frequent maintenance.

[0048] 3. This invention utilizes the phosphonic acid groups in the functional molecules to form stable covalent bonds with the hydroxyl groups on the surface of the PET-ITO conductive layer, which greatly improves the interfacial bonding strength between the polymer microcrystalline layer and the conductive layer. Compared with the traditional bonding method that relies on intermolecular forces, it can effectively resist the risk of interlayer delamination caused by environmental stress, reduce product scrap due to interface problems, and lower the cost of use.

[0049] 4. The three-dimensional network structure formed after curing of the composition of the present invention has both rigidity and flexibility: the benzimidazole ring in the functional molecule is a rigid heterocycle, which can improve the load-bearing capacity and tensile strength of the network and prevent the film from being damaged by external force during cutting, installation or use; at the same time, the crosslinking system of acrylamide group and various acrylate monomers can provide a certain degree of ductility, ensure the elongation at break, so that the film has sufficient mechanical strength to resist daily wear and tear, and can also adapt to slight deformation, thus improving the adaptability of processing and application. Attached Figure Description

[0050] Figure 1 The 1H NMR spectrum of 2-(1H-benzo[d]imidazol-2-yl)acetonitrile prepared in Example 3 of this invention;

[0051] Figure 2 The 1H NMR spectrum of 2-(1H-benzo[d]imidazol-2-yl)-5,5,5-trifluoropentadienyl nitrile prepared in Example 3 of this invention;

[0052] Figure 3 The 1H NMR spectrum of diethyl((2-(1-cyano-4,4,4-trifluorobutyl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonate prepared in Example 3 of this invention;

[0053] Figure 4 The 1H NMR spectrum of diethyl((2-(5,5,5-trifluoro-1-methylacrylamidopent-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonate prepared in Example 3 of this invention;

[0054] Figure 5The 1H NMR spectrum of ((2-(5,5,5-trifluoro-1-methylacrylamidopentan-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonic acid prepared in Example 3 of this invention;

[0055] Figure 6 This is a schematic diagram of the structure of the 3MDT dimming film prepared by using a high-temperature resistant polymerizable material composition in this invention. Detailed Implementation

[0056] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to specific embodiments.

[0057] Preparation Example 1: The specific preparation method of ((2-(5,5,5-trifluoro-1-methylacrylamidopentan-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonic acid includes the following steps:

[0058] (1) Add 10g of o-phenylenediamine and 7.87g of cyanoacetic acid to the reaction vessel, then add 50g of polyphosphoric acid. Under nitrogen protection, heat to 110℃ and stir for 2h. After the reaction is completed, cool to room temperature, pour into 150g of ice water and stir. Adjust the pH to 7-8 with 10wt% NaOH. A solid was observed to precipitate. After filtration, the collected solid was recrystallized with ethanol to obtain 2-(1H-benzo[d]imidazol-2-yl)acetonitrile;

[0059] (2) 10g of 2-(1H-benzo[d]imidazol-2-yl)acetonitrile, 6.11g of 3,3,3-trifluoropropene and 0.77g of 1,8-diazabicyclo[5.4.0]undec-7-ene were added to the reaction vessel, and then 80g of acetonitrile was added as solvent. Under nitrogen protection, the temperature was raised to 40℃ and the reaction was carried out for 4h. After the reaction was completed, the solvent was removed by vacuum distillation. The residue was purified by silica gel column chromatography with gradient elution. The volume ratio of ethyl acetate to petroleum ether in each step of the eluent was 0:1, 1:20, 1:10 to 1:4, respectively, to obtain 2-(1H-benzo[d]imidazol-2-yl)-5,5,5-trifluoropentonitrile;

[0060] (3) 10g of 2-(1H-benzo[d]imidazol-2-yl)-5,5,5-trifluoropentadienonitrile, 6.54g of diethyl phosphite, and 4.5g of 37wt% formaldehyde solution were added to the reaction vessel, and 80g of ethanol was added as solvent. The pH was adjusted to 4-5 with 1mol / L hydrochloric acid solution, and the mixture was heated to 65℃ and refluxed for 3h. After the reaction was completed, the solvent was removed by vacuum distillation. The residue was purified by silica gel column chromatography with gradient elution. The volume ratio of dichloromethane to methanol in each eluent was 1:0, 30:1, 20:1 to 10:1, respectively, to obtain diethyl((2-(1-cyano-4,4,4-trifluorobutyl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonate;

[0061] (4) Add 10g of diethyl((2-(1-cyano-4,4,4-trifluorobutyl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonate and 0.2g of 10% phosphate to the reaction vessel. Pd / C and 100g of anhydrous tetrahydrofuran were purged with hydrogen three times and kept in a hydrogen atmosphere. The mixture was heated to 40℃ and stirred for 4h. Pd / C was removed by filtration, and the filtrate was returned to the reactor. 3.76g of triethylamine and 0.03g of hydroquinone were added, and the mixture was cooled to 0℃ in an ice bath. 2.59g of acrylate chloride was slowly added dropwise over 1h. After the addition was complete, the mixture was kept at 0℃ for 2h. After the reaction was completed, the reaction solution was washed with saturated brine, dried, concentrated, and purified by gradient elution using silica gel column chromatography. The volume ratio of dichloromethane to methanol in the eluent was 1:0, 20:1, 10:1 to 5:1, respectively, to obtain diethyl((2-(5,5,5-trifluoro-1-methylacrylamidopentan-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonate.

[0062] (5) 10g of diethyl((2-(5,5,5-trifluoro-1-methylacrylamidopent-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonate was added to the reaction vessel, along with 5g of 10wt% citric acid solution. 80g of ethanol / water mixture (ethanol and water volume ratio of 1:1) was used as the solvent. The mixture was heated to 60℃ and stirred for 2h. After the reaction was completed, it was cooled to room temperature. Ethanol was removed by vacuum distillation. The pH was adjusted to neutral with saturated sodium carbonate solution, and a solid was precipitated. The solid obtained after filtration was washed three times with deionized water and dried under vacuum to obtain ((2-(5,5,5-trifluoro-1-methylacrylamidopent-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonic acid.

[0063] Preparation Example 2: The specific preparation method of ((2-(5,5,5-trifluoro-1-methylacrylamidopent-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonic acid includes the following steps:

[0064] (1) Add 10g of o-phenylenediamine and 8.65g of cyanoacetic acid to the reaction vessel, then add 80g of polyphosphoric acid. Under nitrogen protection, heat to 115℃ and stir for 3h. After the reaction is completed, cool to room temperature, pour into 200g of ice water and stir. Adjust the pH to 7-8 with 10wt% NaOH. A solid was observed to precipitate. After filtration, the collected solid was recrystallized with ethanol to obtain 2-(1H-benzo[d]imidazol-2-yl)acetonitrile;

[0065] (2) 10g of 2-(1H-benzo[d]imidazol-2-yl)acetonitrile, 7.33g of 3,3,3-trifluoropropene and 0.97g of 1,8-diazabicyclo[5.4.0]undec-7-ene were added to the reaction vessel, and then 100g of acetonitrile was added as solvent. Under nitrogen protection, the temperature was raised to 45℃ and the reaction was carried out for 5h. After the reaction was completed, the solvent was removed by vacuum distillation. The residue was purified by silica gel column chromatography with gradient elution. The volume ratio of ethyl acetate to petroleum ether in each step of the eluent was 0:1, 1:20, 1:10 to 1:4, respectively, to obtain 2-(1H-benzo[d]imidazol-2-yl)-5,5,5-trifluoropentonitrile;

[0066] (3) 10g of 2-(1H-benzo[d]imidazol-2-yl)-5,5,5-trifluoropentadienonitrile, 7.63g of diethyl phosphite, and 5g of 37wt% formaldehyde solution were added to the reaction vessel, and 100g of ethanol was added as solvent. The pH was adjusted to 4-5 with 1mol / L hydrochloric acid solution, and the mixture was heated to 70℃ and refluxed for 4h. After the reaction was completed, the solvent was removed by vacuum distillation. The residue was purified by silica gel column chromatography with gradient elution. The volume ratio of dichloromethane to methanol in each eluent was 1:0, 30:1, 20:1 to 10:1, respectively, to obtain diethyl((2-(1-cyano-4,4,4-trifluorobutyl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonate;

[0067] (4) Add 10g of diethyl((2-(1-cyano-4,4,4-trifluorobutyl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonate and 0.5g of 10% phosphate to the reaction vessel. Pd / C and 150g of anhydrous tetrahydrofuran were purged with hydrogen three times and kept in a hydrogen atmosphere. The mixture was heated to 50℃ and stirred for 6h. Pd / C was removed by filtration, and the filtrate was returned to the reactor. 4.52g of triethylamine and 0.05g of hydroquinone were added, and the mixture was cooled to 0℃ in an ice bath. 3.11g of acryloyl chloride was slowly added dropwise over 1.5h. After the addition was complete, the mixture was kept at 0℃ for 3h. After the reaction was completed, the reaction solution was washed with saturated brine, dried, concentrated, and purified by gradient elution using silica gel column chromatography. The volume ratio of dichloromethane to methanol in the eluent was 1:0, 20:1, 10:1 to 5:1, respectively, to obtain diethyl((2-(5,5,5-trifluoro-1-methylacrylamidopentan-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonate.

[0068] (5) 10g of diethyl((2-(5,5,5-trifluoro-1-methylacrylamidopent-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonate was added to the reaction vessel, along with 8g of 10wt% citric acid solution. 100g of ethanol / water mixture (ethanol and water volume ratio of 1:1) was used as the solvent. The mixture was heated to 65℃ and stirred for 3h. After the reaction was completed, it was cooled to room temperature. Ethanol was removed by vacuum distillation. The pH was adjusted to neutral with saturated sodium carbonate solution, and a solid was precipitated. The solid obtained after filtration was washed three times with deionized water and dried under vacuum to obtain ((2-(5,5,5-trifluoro-1-methylacrylamidopent-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonic acid.

[0069] Preparation Example 3: The specific preparation method of ((2-(5,5,5-trifluoro-1-methylacrylamidopent-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonic acid includes the following steps:

[0070] (1) 10 g of o-phenylenediamine and 9.44 g of cyanoacetic acid were added to a reaction vessel, followed by 100 g of polyphosphoric acid. The mixture was heated to 120 °C under nitrogen protection and stirred for 4 h. After the reaction was completed, the mixture was cooled to room temperature and poured into 250 g of ice water and stirred. The pH was adjusted to 7-8 with 10 wt% NaOH. Solid precipitation was observed. The collected solid was collected by filtration and recrystallized from ethanol to obtain 2-(1H-benzo[d]imidazol-2-yl)acetonitrile. The product was characterized by H NMR, and the spectrum is attached. Figure 1 As shown;

[0071] (2) 10 g of 2-(1H-benzo[d]imidazol-2-yl)acetonitrile, 9.17 g of 3,3,3-trifluoropropene and 1.16 g of 1,8-diazabicyclo[5.4.0]undec-7-ene were added to a reaction vessel, and then 120 g of acetonitrile was added as a solvent. Under nitrogen protection, the temperature was raised to 50 °C and the reaction was carried out for 6 h. After the reaction was completed, the solvent was removed by vacuum distillation. The residue was purified by silica gel column chromatography with gradient elution. The volume ratio of ethyl acetate to petroleum ether in each eluent was 0:1, 1:20, 1:10 to 1:4, respectively, to obtain 2-(1H-benzo[d]imidazol-2-yl)-5,5,5-trifluoropentadienonitrile. The product was characterized by H NMR, and the spectrum is attached. Figure 2 As shown;

[0072] (3) 10 g of 2-(1H-benzo[d]imidazol-2-yl)-5,5,5-trifluoropentadienonitrile, 8.73 g of diethyl phosphite, and 5.5 g of 37 wt% formaldehyde solution were added to the reaction vessel, followed by 120 g of ethanol as solvent. The pH was adjusted to 4-5 with 1 mol / L hydrochloric acid solution, and the mixture was heated to 75 °C and refluxed for 5 h. After the reaction, the solvent was removed by vacuum distillation, and the residue was purified by silica gel column chromatography using gradient elution. The volume ratio of dichloromethane to methanol in the eluent was 1:0, 30:1, 20:1 to 10:1, respectively, to obtain diethyl((2-(1-cyano-4,4,4-trifluorobutyl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonate. The product was characterized by 1H NMR, and the spectrum is attached. Figure 3 As shown;

[0073] (4) Add 10g of diethyl((2-(1-cyano-4,4,4-trifluorobutyl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonate and 0.6g of 10% phosphate to the reaction vessel. Pd / C and 200g of anhydrous tetrahydrofuran were reacted under hydrogen atmosphere for three purgings, and the mixture was heated to 60℃ and stirred for 8h. Pd / C was removed by filtration, and the filtrate was returned to the reactor. 5.02g of triethylamine and 0.08g of hydroquinone were added, and the mixture was cooled to 0℃ in an ice bath. 3.88g of acryloyl chloride was slowly added dropwise over 2h. After the addition was complete, the mixture was kept at 0℃ for 4h. After the reaction, the reaction solution was washed with saturated brine, dried, and concentrated. Then, it was purified by gradient elution using silica gel column chromatography. The volume ratio of dichloromethane to methanol in the eluent was successively 1:0, 20:1, 10:1 to 5:1 to obtain diethyl((2-(5,5,5-trifluoro-1-methylacrylamidopentan-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonate. The product was characterized by 1H NMR, and the spectrum is attached. Figure 4 As shown;

[0074] (5) 10 g of diethyl((2-(5,5,5-trifluoro-1-methylacrylamidopent-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonate was added to a reaction vessel, along with 10 g of 10 wt% citric acid solution. 120 g of a mixed ethanol / water solution (ethanol to water volume ratio 1:1) was used as the solvent. The mixture was heated to 70 °C and stirred for 4 h. After the reaction was completed, the mixture was cooled to room temperature, and the ethanol was removed by vacuum distillation. The pH was adjusted to neutral with saturated sodium carbonate solution, and a solid precipitated. The solid obtained after filtration was washed three times with deionized water and dried under vacuum to obtain ((2-(5,5,5-trifluoro-1-methylacrylamidopent-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonic acid. The product was characterized by ¹H NMR, and the spectrum is attached. Figure 5 As shown.

[0075] Comparative Preparation Example 1: The difference between Comparative Preparation Example 1 and Preparation Example 3 is that step (2) is omitted, and the resulting product structure is: .

[0076] Comparative Preparation Example 2: The difference between Comparative Preparation Example 2 and Preparation Example 3 is that steps (3) and (5) are omitted, and the resulting product structure is: .

[0077] Comparative Preparation Example 3: The difference between Comparative Preparation Example 3 and Preparation Example 3 is that step (5) is omitted, and the resulting product structure is: .

[0078] Comparative Preparation Example 4: The difference between Comparative Preparation Example 4 and Preparation Example 3 is that step (4) is omitted, and the resulting product structure is: .

[0079] Application Example 1: The composition of the high-temperature resistant polymerizable material composition is as follows:

[0080]

[0081] Application Example 2: The composition of the high-temperature resistant polymerizable material composition is as follows:

[0082]

[0083] Application Example 3: The composition of the high-temperature resistant polymerizable material composition is as follows:

[0084]

[0085] Comparative Application Example 1: The difference between Comparative Application Example 1 and Application Example 3 is that the ((2-(5,5,5-trifluoro-1-methylacrylamidopent-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonic acid prepared according to Preparation Example 3 is replaced with the product prepared according to Comparative Preparation Example 1.

[0086] Comparative Application Example 2: The difference between Comparative Application Example 2 and Application Example 3 is that the ((2-(5,5,5-trifluoro-1-methylacrylamidopent-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonic acid prepared according to Preparation Example 3 is replaced with the product prepared according to Comparative Preparation Example 2.

[0087] Comparative Application Example 3: The difference between Comparative Application Example 3 and Application Example 3 is that the ((2-(5,5,5-trifluoro-1-methylacrylamidopent-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonic acid prepared according to Preparation Example 3 is replaced with the product prepared according to Comparative Preparation Example 3.

[0088] Comparative Application Example 4: The difference between Comparative Application Example 4 and Application Example 3 is that the ((2-(5,5,5-trifluoro-1-methylacrylamidopent-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonic acid prepared according to Preparation Example 3 is replaced with the product prepared according to Comparative Preparation Example 4.

[0089] Comparative Application Example 5: The difference between Comparative Application Example 5 and Application Example 3 is that the ((2-(5,5,5-trifluoro-1-methylacrylamidopent-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonic acid prepared according to Preparation Example 3 is replaced with benzimidazole.

[0090] Comparative Application Example 6: The difference between Comparative Application Example 6 and Application Example 3 is that ((2-(5,5,5-trifluoro-1-methylacrylamidopent-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonic acid prepared according to Preparation Example 3 is not added.

[0091] The application of the high-temperature resistant polymerizable material compositions corresponding to Examples 1-3 and Comparative Application Examples 1-6 is carried out according to the following steps:

[0092] S1. Mix the high-temperature resistant polymerizable material composition and the main matrix material at a weight ratio of 1:1, and stir at room temperature for 30-60 min to obtain a homogeneous precursor;

[0093] S2. Take two layers of PET-ITO conductive film, coat the homogeneous precursor between the two layers of PET-ITO conductive film, and irradiate with ultraviolet light at a wavelength of 365nm and a power of 80mW / cm². 2The irradiation time is 50 seconds, which allows the high-temperature resistant polymerizable material composition to be completely cured and form a polymer microcrystalline layer.

[0094] S3. After curing, the film is cut and cleaned to obtain the 3MDT dimming film.

[0095] Performance testing:

[0096] 1. Core performance test of normal dimming: Under the standard environment of room temperature and 50% relative humidity, 50mm×50mm 3MDT dimming film samples of application examples 1-3 and comparative application examples 1-6 were cut. The haze when the power was off and the haze when the power was on were tested using a haze meter (20V DC voltage was applied). The transmittance (T%) under the power-on state was recorded simultaneously. The experimental results are shown in Table 1.

[0097] 2. Normal interface adhesion test: The 3MDT dimming film samples of Application Examples 1-3 and Comparative Application Examples 1-6 were cut into strips of 150mm×25mm. A 100mm peel seam was pre-cut along the interface between the PET-ITO layer and the polymer microcrystalline layer. A 180° peel test was performed using a tensile testing machine at a speed of 50mm / min. The average peel force was recorded. The experimental results are shown in Table 1.

[0098] 3. Normal mechanical performance test: The 3MDT dimming film samples of Application Examples 1-3 and Comparative Application Examples 1-6 were made into dumbbell-shaped standard strips. Tensile tests were performed using a miniature tensile testing machine at a speed of 10 mm / min. The tensile strength and elongation at break were recorded simultaneously. The experimental results are shown in Table 1.

[0099] 4. Dimming response time test: 50mm×50mm 3MDT dimming film samples from Application Examples 1-3 and Comparative Application Examples 1-6 were taken and tested using an oscilloscope with a photodetector. The rise time (time required for haze to drop to 90% stable value) of "power off → power on" and the fall time (time required for haze to rise to 90% stable value) of "power on → power off" were tested. The experimental results are shown in Table 1.

[0100] 5. Thermal decomposition temperature test: 50mm×50mm 3MDT dimming film samples from Application Examples 1-3 and Comparative Application Examples 1-6 were cut and tested using a thermogravimetric analyzer under a nitrogen atmosphere. The heating rate was 10℃ / min, and the temperature range was room temperature to 500℃. The thermal decomposition temperature (Td) when the sample mass loss was 5% was recorded. The experimental results are shown in Table 1.

[0101] 6. High-temperature aging comprehensive performance test: 50mm×50mm 3MDT dimming film samples from Application Examples 1-3 and Comparative Application Examples 1-6 were cut and placed in a constant temperature oven at 150℃ for 3 hours. After cooling to room temperature, the procedures of "normal dimming core performance test" and "normal interface adhesion test" were repeated. The changes in haze when the power was off and when the power was on were calculated, as well as the light transmittance retention rate and peel strength retention rate. The appearance integrity was also observed. The experimental results are shown in Table 1.

[0102] Table 1 Performance Test Results:

[0103]

[0104] Performance Analysis:

[0105] As can be seen from the experimental data in Table 1, the 3MDT dimming films prepared in Application Examples 1-3 are significantly better than the comparative application examples in terms of key indicators such as dimming core performance, interface adhesion, mechanical strength, dimming response speed and high temperature stability. Among them, Application Example 3 has the best overall performance.

[0106] The excellent dimming performance of Application Example 3 is due to the synergistic effect of the multifunctional groups of ((2-(5,5,5-trifluoro-1-methylacrylamidopent-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonic acid in its composition: the rigid structure of the benzimidazole ring and the crosslinking activity of the acrylamide group jointly regulate the polymer network, so that the main matrix material forms uniform micron-sized droplets when phase separation, with high scattering efficiency when power is off and orderly molecular orientation when power is on; the hydrophobicity of trifluoropropyl group has good compatibility with other monomers (such as isobornyl acrylate and polyethylene glycol 200 dimethacrylate), avoiding the aggregation of the main matrix material and further improving the light transmittance. Comparative Application Example 1, due to the use of a molecule lacking trifluoropropyl groups, resulted in an imbalance of hydrophobicity, leading to uneven distribution of microdroplets in the host matrix material and a decrease in dimming performance. Comparative Application Example 2, lacking phosphonate-related structures, resulted in insufficient polymer network regularity and poor phase separation. Comparative Application Example 3, failing to hydrolyze diethyl phosphonate into phosphonate groups, resulted in insufficient interfacial control over microdroplet distribution, leading to poor transmittance and haze performance. Comparative Application Example 4, lacking acrylamide groups, resulted in insufficient crosslinking sites, causing irregular network pores and hindering the orientation of the host matrix material. Comparative Application Example 5, using benzimidazole to replace the target molecule, lacked key functional groups such as trifluoropropyl and phosphonate groups, making structural synergy impossible. Comparative Application Example 6, without adding the target molecule and relying solely on ordinary monomer crosslinking, had the worst polymer-host matrix material compatibility and the weakest dimming performance.

[0107] The strong interfacial adhesion and high-temperature stability of Application Example 3 are mainly due to the phosphonic acid group in ((2-(5,5,5-trifluoro-1-methylacrylamidopentan-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonic acid, which can form a stable covalent bond with the hydroxyl group on the surface of the PET-ITO conductive layer. This chemical bonding is much stronger than the intermolecular force, and it is not easy to break even under high-temperature aging. Compared to Example 1, which lacks a trifluoropropyl group, the interfacial compatibility between the molecule and the PET-ITO layer is weakened, resulting in reduced adhesion. Example 2, lacking phosphonate ester-related structures, cannot form covalent bonds and relies solely on intermolecular forces, leading to weak adhesion. Example 3, lacking phosphonate groups, relies only on the weak interaction between diethyl phosphonate and hydroxyl groups, resulting in significantly insufficient interfacial bonding strength. Example 4, lacking acrylamide groups, weakens the dispersion of interfacial stress by the crosslinking network, indirectly affecting adhesion. Example 5, with its benzimidazole lacking phosphonate groups, cannot achieve covalent bonding, resulting in poor interfacial adhesion. Example 6, lacking the target molecule, completely lacks the interfacial strengthening effect of phosphonate groups, resulting in the weakest interfacial bonding and the most significant decrease in peel strength after high-temperature aging.

[0108] Application Example 3 exhibits excellent mechanical properties because the benzimidazole ring in ((2-(5,5,5-trifluoro-1-methylacrylamidopent-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonic acid is a rigid heterocycle with a dense conjugated system and high chemical bond energy, which can enhance the rigidity and load-bearing capacity of the polymer network. At the same time, the acrylamide group forms a three-dimensional network with moderate crosslinking density with other acrylate monomers, which combines rigidity and flexibility, enabling the film to withstand high stress while maintaining a certain degree of ductility when stretched. Compared to Example 1, the absence of trifluoropropyl groups weakens the steric hindrance effect between molecular chains, resulting in insufficient network density and decreased mechanical properties. Compared to Example 2, the absence of phosphonate ester-related structures impairs the integrity of the crosslinked network and reduces its load-bearing capacity. Compared to Example 3, the lack of phosphonic acid groups weakens intermolecular interactions and reduces network stability. Compared to Example 4, the absence of acrylamide groups reduces crosslinking density and deteriorates network continuity. Compared to Example 5, the lack of synergistic effect between benzimidazole in rigidity enhancement and crosslinking optimization results in weak mechanical properties. Compared to Example 6, the absence of target molecules and reliance on ordinary monomer crosslinking leads to a poor balance between network rigidity and flexibility, resulting in the lowest tensile strength and elongation at break.

[0109] The fast response speed of Application Example 3 is mainly due to the regulation of the polymer network by ((2-(5,5,5-trifluoro-1-methylacrylamidopent-2-yl)-1H-benzimidazole-1-yl)methyl)phosphonic acid: the synergistic effect of the benzimidazole ring and the trifluoropropyl group makes the network formation more uniform, the main matrix material is confined in the microdroplets formed by polymer crosslinking, the molecular orientation resistance is small, and it can respond quickly when the power is applied or de-energized. Compared to Example 1, which lacks trifluoropropyl groups, the main matrix material exhibits a wide droplet size distribution, with some droplets being too large, leading to increased orientation resistance and prolonged response time. In Example 2, the absence of phosphonate groups results in irregular network pores, hindering molecular orientation in the main matrix material. In Example 3, the lack of phosphonate groups leads to insufficient interfacial control over pore size, resulting in uneven droplet distribution. In Example 4, the absence of acrylamide groups leads to inconsistent crosslinking network pore sizes and reduced orientation efficiency. In Example 5, the benzimidazole cannot effectively control droplet size, resulting in a slow response speed. In Example 6, the absence of the target molecule leads to significant droplet aggregation in the main matrix material, resulting in the greatest orientation resistance and the longest response time.

[0110] The outstanding high-temperature resistance of Application Example 3 stems from the multiple thermally stable structure of ((2-(5,5,5-trifluoro-1-methylacrylamidopentan-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonic acid: the conjugated system of the benzimidazole ring inhibits the thermal motion of the molecular chain; the high bond energy of the CF bond in the trifluoropropyl group makes it difficult to break at high temperatures; and the electronegativity of the fluorine atom forms steric hindrance, further delaying degradation; the hydrogen bonds formed by the amide group construct a supramolecular stable network; and the phosphonic acid group can also help improve thermal stability. Compared to Example 1, the absence of the trifluoropropyl group results in the loss of the thermal stabilizing effect of the CF bond, a decrease in thermal decomposition temperature, and significant performance degradation after aging. In Example 2, the absence of the phosphonate group-related structure leads to insufficient supramolecular network stability and reduced high-temperature resistance. In Example 3, the lack of a phosphonate group results in the absence of thermal stabilizing assistance, making the network easily degraded at high temperatures. In Example 4, the absence of the acrylamide group weakens hydrogen bonding, making the supramolecular network easily destroyed. In Example 5, the benzimidazole lacks the aforementioned synergistic thermal stabilizing effect, resulting in a low thermal decomposition temperature and poor performance retention after aging. In Example 6, the absence of the target molecule completely lacks a thermally stable structure, resulting in the worst high-temperature resistance and the most significant performance degradation after aging.

[0111] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A high-temperature resistant polymerizable material composition, characterized in that, The raw materials include the following parts by weight: polyethylene glycol (200) dimethacrylate: 18-22 parts, isoborneol acrylate: 11-15 parts, isoborneol methacrylate: 11-15 parts, lauryl methacrylate: 12-16 parts, Sartoma UV resin SR9051NS: 0.8-1.2 parts, photoinitiator TPO: 2-4 parts, Sartoma UV resin CN9001NS: 26-30 parts, 4-hydroxybutyl acrylate: 1-3 parts, 4'-(6-(acryloyloxy)hexyloxy)biphenyl nitrile: 5-7 parts, ((2-(5,5,5-trifluoro-1-methacrylamidopent-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonic acid: 5-20 parts; The chemical structural formula of ((2-(5,5,5-trifluoro-1-methylacrylamidopentan-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonic acid is as follows: 。 2. The high-temperature resistant polymerizable material composition according to claim 1, characterized in that, The preparation method of ((2-(5,5,5-trifluoro-1-methylacrylamidopentan-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonic acid includes the following steps: (1) Add o-phenylenediamine and cyanoacetic acid to the reaction vessel, then add polyphosphoric acid, heat to 110-120℃ under nitrogen protection and stir for 2-4 hours. After the reaction is completed, cool to room temperature, pour into ice water and stir. Adjust the pH to 7-8 with 10wt% NaOH. Observe that solid precipitates out. After filtration, collect the solid and recrystallize it with ethanol to obtain 2-(1H-benzo[d]imidazol-2-yl)acetonitrile; (2) 2-(1H-benzo[d]imidazol-2-yl)acetonitrile, 3,3,3-trifluoropropene and 1,8-diazabicyclo[5.4.0]undec-7-ene were added to the reaction vessel, and acetonitrile was added as a solvent. Under nitrogen protection, the temperature was raised to 40-50℃ and the reaction was carried out for 4-6 h. After the reaction was completed, the solvent was removed by vacuum distillation. The residue was purified by silica gel column chromatography with gradient elution to obtain 2-(1H-benzo[d]imidazol-2-yl)-5,5,5-trifluoropentonitrile; (3) 2-(1H-benzo[d]imidazol-2-yl)-5,5,5-trifluoropentadienyl nitrile, diethyl phosphite, and 37wt% formaldehyde solution were added to the reaction vessel, and ethanol was added as solvent. The pH was adjusted to 4-5 with 1mol / L hydrochloric acid solution, and the temperature was raised to 65-75℃ and refluxed for 3-5h. After the reaction was completed, the solvent was removed by vacuum distillation, and the residue was purified by silica gel column chromatography with gradient elution to obtain diethyl((2-(1-cyano-4,4,4-trifluorobutyl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonate; (4) Add diethyl((2-(1-cyano-4,4,4-trifluorobutyl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonate, 10% Pd / C and anhydrous tetrahydrofuran to the reaction vessel, replace with hydrogen three times and maintain hydrogen atmosphere, heat to 40-60℃ and stir for 4-8h, filter to remove Pd / C, return the filtrate to the reaction vessel, add triethylamine and hydroquinone, cool to 0℃ in an ice bath, slowly add acryloyl chloride, the addition time is 1-2h, after the addition is completed, maintain 0℃ for 2-4h, after the reaction is completed, wash the reaction solution with saturated brine, dry and concentrate, and then purify by gradient elution by silica gel column chromatography to obtain diethyl((2-(5,5,5-trifluoro-1-methylacrylamidopent-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonate; (5) Diethyl((2-(5,5,5-trifluoro-1-methylacrylamidopent-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonate was added to a reaction vessel, 10wt% citric acid solution was added, and an ethanol / water mixture was used as a solvent. The mixture was heated to 60-70℃ and stirred for 2-4 hours. After the reaction was completed, it was cooled to room temperature, and the ethanol was removed by vacuum distillation. The pH was adjusted to neutral with saturated sodium carbonate solution, and a solid was precipitated. The solid obtained by filtration was washed three times with deionized water and dried under vacuum to obtain ((2-(5,5,5-trifluoro-1-methylacrylamidopent-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonic acid.

3. The high-temperature resistant polymerizable material composition according to claim 2, characterized in that, In (1), the molar ratio of o-phenylenediamine and cyanoacetic acid is 1:1-1.2, and the weight ratio of o-phenylenediamine, polyphosphoric acid and ice water is 1:5-10:15-25.

4. The high-temperature resistant polymerizable material composition according to claim 2, characterized in that, In step (2), the molar ratio of 2-(1H-benzo[d]imidazol-2-yl)acetonitrile, 3,3,3-trifluoropropene and 1,8-diazabicyclo[5.4.0]undec-7-ene is 1:1-1.5:0.08-0.12, and the weight ratio of 2-(1H-benzo[d]imidazol-2-yl)acetonitrile and acetonitrile is 1:8-12. Gradient elution refers to the volume ratio of ethyl acetate and petroleum ether in each eluent step from 0:1, 1:20, 1:10 to 1:

4.

5. The high-temperature resistant polymerizable material composition according to claim 2, characterized in that, In step (3), the molar ratio of 2-(1H-benzo[d]imidazol-2-yl)-5,5,5-trifluorovalerate and diethyl phosphite is 1:1.2-1.6, and the weight ratio of 2-(1H-benzo[d]imidazol-2-yl)-5,5,5-trifluorovalerate, 37wt% formaldehyde solution and ethanol is 1:0.45-0.55:8-12. Gradient elution refers to the volume ratio of dichloromethane and methanol in each eluent step from 1:0, 30:1, 20:1 to 10:

1.

6. The high-temperature resistant polymerizable material composition according to claim 2, characterized in that, In step (4), the molar ratio of diethyl((2-(1-cyano-4,4,4-trifluorobutyl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonate, triethylamine, hydroquinone, and acrylate chloride is 1:1.5-2:0.01-0.03:1-1.5, and the weight ratio of diethyl((2-(1-cyano-4,4,4-trifluorobutyl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonate, 10% Pd / C, and anhydrous tetrahydrofuran is 1:0.02-0.06:10-20. Gradient elution refers to the volume ratio of dichloromethane and methanol in the eluent of each step, which is successively from 1:0, 20:1, 10:1 to 5:

1.

7. The high-temperature resistant polymerizable material composition according to claim 2, characterized in that, In (5), the diethyl((2-(5,5,5-trifluoro-1-methylacrylamidopent-2-yl)-1H-benzo[d]imidazol-1-yl)methyl)phosphonate, 10wt% citric acid solution and ethanol / water mixed solution are in a weight ratio of 1:0.5-1:8-12, and the volume ratio of ethanol to water in the ethanol / water mixed solution is 1:

1.

8. The application of the high-temperature resistant polymerizable material composition according to any one of claims 1-7, characterized in that, Used for preparing a 3MDT dimming film; the method for preparing the 3MDT dimming film includes the following steps: S1. Mix the high-temperature resistant polymerizable material composition and the main matrix material, and stir at room temperature for 30-60 min to obtain a homogeneous precursor; S2. Take two layers of PET-ITO conductive film, apply the homogeneous precursor between the two layers of PET-ITO conductive film, and irradiate with ultraviolet light to completely cure the high-temperature resistant polymerizable material composition to form a polymer microcrystalline layer. S3. After curing, the film is cut and cleaned to obtain the 3MDT dimming film; The structure of the 3MDT dimming film is as follows: the upper and lower layers are PET-ITO conductive layers, and the middle layer is a cured polymer microcrystalline layer; The thickness of the polymer microcrystalline layer is 5-30 μm.

9. The application of the high-temperature resistant polymerizable material composition according to claim 8, characterized in that, The high-temperature resistant polymerizable material composition and the main matrix material in S1 are in a weight ratio of 1:

1.

10. The application of the high-temperature resistant polymerizable material composition according to claim 8, characterized in that, The ultraviolet light irradiation conditions in S2 are a wavelength of 365nm and a power of 50-100mW / cm². 2 The irradiation time is 30-60 seconds.

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