A hyperbranched polyarylate resin and a method for preparing the same

Abstract

The application belongs to the technical field of special engineering plastics, and particularly relates to a hyperbranched polyarylate (HBPAR) resin and a preparation method thereof. The resin is composed of an aromatic diacyl structure, a bisphenol structure and a triphenol structure, and is prepared by using a triphenol compound, a bisphenol compound and an aromatic diacyl compound as an electrophilic monomer, performing phase transfer catalytic interfacial co-condensation in a specific solvent, and then performing processes such as static stratification, water washing of an organic phase and alcohol precipitation. The hyperbranched polyarylate resin prepared by the method has the characteristics of heat resistance, light transmittance, mechanical mechanical properties, dimensional stability, weather resistance, high transparency, low dielectric loss and low dielectric constant, and has advantages in specific application scenarios.

Description

Technical Field

[0001] This invention belongs to the field of special engineering plastics technology, specifically relating to a hyperbranched polyarylate (HBPAR) resin, its preparation method, and a method for preparing a transparent film. Background Technology

[0002] As microelectronics and display technologies continue to develop towards higher integration, higher intelligence, higher density, higher sensitivity, and ultrathinness, increasingly stringent requirements are being placed on the heat resistance, light transmittance, mechanical properties, dimensional stability, and weather resistance of polymer-based optical thin film materials. Traditionally used polyester resins such as PET, PEN, triacetate cellulose, polyvinyl alcohol, and PC films, due to insufficient heat resistance, can no longer meet the growing demands of the microelectronics industry. With the increasing demand for high-transparency, low-dielectric-loss, and low-dielectric-constant high-temperature thin film materials, the development of low-cost, high-performance electronic-grade thin film materials has become a hot topic. Summary of the Invention

[0003] Based on the above technical issues

[0004] This invention provides a hyperbranched polyarylate resin, its preparation method, and a method for preparing a transparent film.

[0005] In a first aspect, the present invention provides a hyperbranched polyarylate resin.

[0006] A hyperbranched polyarylate resin containing aryl diacyl, bisphenol, and triphenol structures.

[0007] In some embodiments, the hyperbranched polyarylate resin has monomers with the structure shown in formula (I).

[0008]

[0009] in,

[0010] A2 has an aryl diacyl structure.

[0011] B2 has a bisphenol structure.

[0012] B3 has a triphenol structure;

[0013] Where m, n, p, and q are positive integers.

[0014] In some embodiments, the hyperbranched polyarylate resin contains repeating units of -A2-B2-, and the repeating units are connected to each other via A2 and B3.

[0015] In some embodiments, each B3 is associated with at least one repeating unit. In some embodiments, the aramid structure is selected from... and One or more of them.

[0016] In some embodiments, the triphenol structure includes one or more of the following: pyrogallol, naphthalenepyrine, and biphenylpyrogallol.

[0017] In some embodiments, the pyrogallol structure is selected from... and One or more of them.

[0018] In some embodiments, the pyrogallol structure is selected from... One or more of them.

[0019] In some embodiments, the structure of the biphenyl pyrogallol is as follows:

[0020] In some embodiments, the bisphenol structure is selected from

[0021] One or more of them.

[0022] In some embodiments, the logarithmic viscosity of the hyperbranched polyarylate resin is 0.74 g / dl to 1.51 g / dl.

[0023] In some embodiments, the bisphenol structure in the hyperbranched polyarylate resin is selected from... (Bisphenol fluorene), the aromatic diacyl structure is selected from (TPC), the triphenol structure is selected from (pyrogallol).

[0024] In some embodiments, the logarithmic viscosity of the hyperbranched polyarylate resin is 0.74 g / dl to 1.25 g / dl.

[0025] In some embodiments, the bisphenol structure in the hyperbranched polyarylate resin is selected from... (Bisphenol fluorene), the aromatic diacyl structure is selected from (TPC) At least one of (IPC), wherein the triphenol structure is selected from (Phoroglucinol); the aforementioned (TPC) and The molar ratio of (IPC) is 9:1 to 0:1, preferably 9:1 to 1:9, and particularly preferably 8:2, 7:3, 6:4, 5:5, 4:6, 3:7, 2:8, or 1:9. The logarithmic viscosity of the hyperbranched polyarylate resin is 0.95 g / dl to 1.40 g / dl.

[0026] In some embodiments, the bisphenol structure in the hyperbranched polyarylate resin is selected from... (bisphenol fluorene) or At least one of (bisphenol AF), wherein the triphenol structure is selected from (Phosphoryl pyrophenone), the aromatic diacyl structure is selected from (TPC); the (bisphenol fluorene) and The molar ratio of (bisphenol AF) is 9:1 to 0:10, preferably 9:1, 8:2, 7:3, 6:4, 5:5, 4:6, 3:7, 2:8, 1:9, or 0:10; the logarithmic viscosity of the hyperbranched polyarylate resin is 0.75 g / dl to 1.51 g / dl.

[0027] In some embodiments, the trichol structure in the hyperbranched polyarylate resin is selected from... (Phosphoryl pyrogallol), the bisphenol structure is selected from (Bisphenol fluorene), the aromatic diacyl structure is selected from (IPC) (2,6-Naphthaloyl chloride); the logarithmic viscosity of the hyperbranched polyarylate resin is 1.25 g / dl-1.50 g / dl.

[0028] In some embodiments, the aramid structure in the hyperbranched polyarylate resin is selected from... (4,4'-dicarboxylic acid chloride), At least one of (TPC), wherein the bisphenol structure is selected from (Bisphenol fluorene), the triphenol structure is selected from (Phoroglucinol); the aforementioned (4,4'-biphenyldicarboxylic acid chloride) and The molar ratio of (TPC) is 1:0 to 0:1, 1:0.5 to 1:2, or 1:1.

[0029] In some embodiments, the logarithmic viscosity of the hyperbranched polyarylate resin is 1.05 g / dl to 1.15 g / dl. In a second aspect, the present invention provides a method for preparing the hyperbranched polyarylate resin described in the first aspect.

[0030] In a second aspect, a method for preparing the hyperbranched polyarylate resin described in the first aspect is characterized by comprising the following steps:

[0031] P1: Mix bisphenol compounds with alkali and water, and optionally add a catalyst to obtain solution 2;

[0032] P2: The solution 2 obtained in step P1 above is mixed with an organic solution of an aramid compound and reacted to obtain solution 3;

[0033] P3: The solution 3 obtained in step P2 above is mixed with triphenol compounds, reacted, and then post-treated to obtain the hyperbranched polyarylate resin.

[0034] In some embodiments, the aryl diacyl compounds are selected from: and One or more of them.

[0035] In some embodiments, the triphenolic compound includes one or more of pyrogallol, naphthol, and biphenyl pyrogallol.

[0036] In some embodiments, the phloroglucinol compounds are selected from... and One or more of them.

[0037] In some embodiments, the pyrogallol is selected from... One or more of them.

[0038] In some embodiments, the biphenyl pyrogallol is

[0039] In some embodiments, the bisphenol compounds are selected from... One or more of them.

[0040] In some embodiments, the molar ratio of the triphenolic compound to the bisphenolic compound is 0.01:100.00–10.00:100.00, 0.01:100.00–8.00:100.00, or 0.01:100.00–5.00:100.00.

[0041] 0.05:100.00~2.00:100.00, 1.00:100.00~5.00:100.00, 1.00:100.00~2.00:100.00, 0.01:100.00, 0.10:100.00, 0.50:100.00, 1.00:100.00, 1.50:100.00, 2.00:100.00, 3.00:100.00, 4.00:100.00, 5.00:100.00, 6.00:100.00, 7.00:100.00, or 8.00:100.00. In some embodiments, the molar ratio of the bisphenol compound to the aramid compound is 1.00:1.00 to 1.05:1.00 or 1.00:1.00 to 1.04:1.00.

[0042] In some embodiments, the logarithmic viscosity of the hyperbranched polyarylate resin is 0.74 g / dl to 1.51 g / dl.

[0043] In some embodiments, the bisphenol compound in the preparation method is selected from... The aramid compounds are selected from... The triphenol compounds are selected from Optionally, the triphenol compounds Molar amount and the aromatic diacyl compounds The ratio of molar amounts of the feed is

[0044] 1.00:100.00~10.00:100.00, preferably 1.00:100.00~3.00:100.00 or 1.00:100.00, 2.00:100.00,

[0045] 3.00:100.00, 4.00:100.00, 5.00:100.00, 6.00:100.00, 7.00:100.00, 8.00:100.00, 9.00:100.00, or 10.00:100.00; and / or the molar ratio of the bisphenol compound to the aromatic diacyl compound is 1.00:1.00 to 1.04:1.00.

[0046] 1.00:1.00, 1.015:1.00, 1.02:1.00, 1.03:1.00 or 1.04:1.00; optionally, the logarithmic viscosity of the hyperbranched polyarylate resin is 0.74 g / dl-1.25 g / dl.

[0047] In some embodiments, the bisphenol compound in the preparation method is selected from... The aramid compounds are selected from... At least one of the following, the triphenol compound is selected from Optionally, the and The molar ratio of the feed compounds is 9:1 to 0:1, preferably 9:1 to 1:9, and particularly preferably 8:2, 7:3, 6:4, 5:5, 4:6, 3:7, 2:8, or 1:9; and / or the molar ratio of the triphenolic compound to the bisphenolic compound is 0.01:100.00 to 8.00:100.00, 0.01:100.00 to 5.00:100.00, or 0.05:100.00 to 2.00:100.00.

[0048] 1.00:100.00~5.00:100.00, 1.00:100.00~2.00:100.00, 0.01:100.00, 0.10:100.00, 0.50:100.00, 1.00:100.00, 1.50:100.00, 2.00:100.00, 3.00:100.00, 4.00:100.00, 5.00:1 00.00, 6.00:100.00, 7.00:100.00 or 8.00:100.00; and / or the molar ratio of the bisphenol compound to the aramid compound is 1.00:1.00 to 1.05:1.00, or 1.01:1.00 to 1.04:1.00; optionally, the logarithmic viscosity of the hyperbranched polyarylate resin is 0.95 g / dl to 1.40 g / dl.

[0049] In some embodiments, the bisphenol compound in the preparation method is selected from...

[0050] At least one of the following, the triphenol compound is selected from The aramid compounds are selected from... Optionally, the and The molar ratio of the feed compounds is 9:1 to 0:10, preferably 9:1, 8:2, 7:3, 6:4, 5:5, 4:6, 3:7, 2:8, 1:9, or 0:10. The molar ratio of the bisphenol compound to the aramid compound is 1.00:1.00 to 1.05:1.00. The molar ratio of the triphenol compound to the bisphenol compound is 0.01:100.00 to 8. 00:100.00, 0.01:100.00~5.00:100.00, 0.05:100.00~2.00:100.00, 1.00:100.00~5.00:100.00, 1.00:100.00~2.00:100.00, 0.01:100.00, 0.10:100.00, 0.50:100.00

[0051] 1.00:100.00, 1.50:100.00, 2.00:100.00, 3.00:100.00, 4.00:100.00, 5.00:100.00, 6.00:100.00, 7.00:100.00 or 8.00:100.00; optionally, the logarithmic viscosity of the hyperbranched polyarylate resin is 0.75 g / dl-1.51 g / dl.

[0052] In some embodiments, the triphenolic compound in the preparation method is selected from... The bisphenol compounds are selected from The aramid compounds are selected from... At least one of the following; optionally, the molar ratio of the triphenolic compound to the bisphenolic compound is 0.01:100.00 to 8.00:100.00.

[0053] 0.01:100.00~5.00:100.00, 0.05:100.00~2.00:100.00, 1.00:100.00~5.00:100.00, 1.00:100.00~2.00:100.00, 0.01:100.00, 0.10:100.00, 0.50:100.00, 1.00:100.00, 1.50:100.00, 2.00:100. 00, 3.00:100.00, 4.00:100.00, 5.00:100.00, 6.00:100.00, 7.00:100.00 or 8.00:100.00; and / or the molar ratio of the bisphenol compound to the aramid compound is 1.0:0.5 to 1.0:2.0 or 1.0:1.0; optionally, the logarithmic viscosity of the hyperbranched polyarylate resin is 1.25 g / dl to 1.50 g / dl.

[0054] In some embodiments, the preparation method uses aryl compounds selected from... At least one of the bisphenol compounds, wherein the bisphenol compound is selected from The triphenol compounds are selected from

[0055] Optionally, the and The molar ratio of feed is

[0056] The feed molar ratio of the triphenolic compound to the bisphenolic compound is 0.01:100.00–0:1.0, 1.0:0.5–1.0:2.0, or 1.0:1.0, wherein the ratio is 1.0:0–0:1.0, 1.0:0.5–1.0:2.0, or 1.0:1.0, and the molar ratio of the triphenolic compound to the bisphenolic compound is 0.01:100.00–8.00:100.00, 0.01:100.00–5.00:100.00, 0.05:100.00–2.00:100.00, 1.00:100.00–5.00:100.00, 1.00:100.00–2.00:100.00, 0.01:100.00, 0.10:100.00, 0.5 0:100.00, 1.00:100.00, 1.50:100.00, 2.00:100.00, 3.00:100.00, 4.00:100.00, 5.00:100.00, 6.00:100.00, 7.00:100.00 or 8.00:100.00; and / or the molar ratio of the bisphenol compound to the aramid compound is 1.0:0.5 to 1.0:2.0 or 1.0:1.0; optionally, the logarithmic viscosity of the hyperbranched polyarylate resin is 1.05 g / dl to 1.15 g / dl.

[0057] In some embodiments, the aramid compound in the hyperbranched polyarylate resin is The bisphenol compounds are selected from The triphenol compounds are selected from Optionally, the and The molar ratio of the feed ingredients is 1:1; the molar ratio of the triphenolic compound to the bisphenolic compound is 0.01:100.00~8.00:100.00, 0.01:100.00~5.00:100.00, 0.05:100.00~2.00:100.00, 1.00:100.00~5.00:100.00, 1.00:100.00~2.00:100.00, 0.01:100.00, 0.10:100.00, 0.50:100.00, 1.00 The molar ratios of the bisphenol compound to the aramid compound are 1.0:0.5 to 1.0:2.0 or 1.0:1.0; and / or the molar ratio of the bisphenol compound to the aramid compound is 1.0:0.5 to 1.0:2.0 or 1.0:1.0; optionally, the logarithmic viscosity of the hyperbranched polyarylate resin is 1.05 g / dl to 1.15 g / dl.

[0058] In some embodiments, the aramid structure in the hyperbranched polyarylate resin is as follows: The bisphenol structure is selected from The triphenol structure is selected from The molar ratio of the triphenolic compound to the bisphenolic compound is 0.01:100.00–8.00:100.00, 0.01:100.00–5.00:100.00, 0.05:100.00–2.00:100.00, 1.00:100.00–5.00:100.00, 1.00:100.00–2.00:100.00, 0.01:100.00, 0.10:100.00, 0.50:100.00.

[0059] 1.00:100.00, 1.50:100.00, 2.00:100.00, 3.00:100.00, 4.00:100.00, 5.00:100.00, 6.00:100.00, 7.00:100.00 or 8.00:100.00; and / or the molar ratio of the bisphenol compound to the aramid compound is 1.0:0.5 to 1.0:2.0 or 1.0:1.0; optionally, the logarithmic viscosity of the hyperbranched polyarylate resin is 1.05 g / dl to 1.15 g / dl.

[0060] In some embodiments, the preparation method is carried out in an inert gas atmosphere, wherein the inert gas atmosphere is nitrogen or argon.

[0061] In some embodiments, the reaction temperature of step P1 is 30–80°C, 50–70°C, or 30–60°C, preferably 40°C. In some embodiments, the reaction temperature of step P1 is 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, or 80°C.

[0062] In some embodiments, the reaction temperature of step P2 is 0–35°C, preferably 15–30°C. In some embodiments, the reaction temperature of step P2 is 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, or 35°C.

[0063] In some embodiments, the reaction time of step P2 is 30–60 min, preferably 45 min. In some embodiments, the reaction time of step P2 is 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, or 60 min.

[0064] In some embodiments, the reaction temperature of step P3 is 15°C to 30°C, preferably 20°C to 25°C.

[0065] In some embodiments, the reaction time of step P3 is 2 hours to 5 hours. In some embodiments, the reaction time of step P3 is 2 hours, 3 hours, 4 hours, or 5 hours.

[0066] In some embodiments, the catalyst for step P1 is a surfactant.

[0067] In some embodiments, the surfactant includes at least one of benzyltriethylamine chloride, benzyltriethylamine bromide, tert-butylammonium chloride, tert-butylammonium bromide, and tert-butylammonium iodide, preferably benzyltriethylamine bromide.

[0068] In some embodiments, the molar ratio of the catalyst to the bisphenol compound is 0.01:100 to 10:100. In some embodiments, the molar ratio of the catalyst to the bisphenol compound is 0.1:100 to 5:100. In some embodiments, the molar ratio of the catalyst to the bisphenol compound is 0.5:100 to 2:100. In some embodiments, the molar ratio of the catalyst to the bisphenol compound is 0.5:100 to 1.5:100. In some embodiments, the molar ratio of the catalyst to the bisphenol compound is 0.01:100, 0.1:100, ...

[0069] 0.5:100, 1:100, 1.5:100, 2:100, 3:100, 4:100, 5:100 or 10:100.

[0070] In some embodiments, the alkali in step P1 is one or more of potassium hydroxide and sodium hydroxide.

[0071] In some embodiments, the mass ratio of the alkaline solution to water is 3.0:100.0 to 10.0:100.0, preferably 3.0:100.0 to 9.0:100.0, and more preferably 4.5:100.0 to 5.0:100.0.

[0072] In some embodiments, the organic solvent of the organic solution in step P2 includes one or more of chlorinated hydrocarbons, bromine hydrocarbons, fluorinated hydrocarbons, chlorofluorocarbons, and bromofluorocarbons. In some embodiments, the organic solvent of the organic solution in step P2 is chloroform.

[0073] In some embodiments, the concentration of the aryl diacyl compound in the organic solution of the aryl diacyl compound in step P2 is greater than 0 mol / L to ≤1.0 mol / L. In some embodiments, the concentration of the aryl diacyl compound in the organic solution of the aryl diacyl compound in step P2 is 0.3 mol / L to 0.7 mol / L. In some embodiments, the concentration of the aryl diacyl compound in the organic solution of the aryl diacyl compound in step P2 is 0.3 mol / L to 0.5 mol / L. In some preferred embodiments, the concentration of the aryl diacyl compound in the organic solution of the aryl diacyl compound in step P2 is 0.4 mol / L.

[0074] In some embodiments, the method further includes refining the hyperbranched polyarylate resin:

[0075] Step 1: Let the solution from step S3 stand to separate into layers, wash the resin layer, and evaporate the organic solvent from the resin layer to obtain a resin layer with the organic solvent removed.

[0076] Step 2: Mix the resin layer obtained in Step 1 (after removing the organic solvent) with alcohol, precipitate, crush, filter, wash with water and dry.

[0077] In some embodiments, the drying is performed at 140℃±10℃ for 8h to 12h.

[0078] Thirdly, the present invention provides a hyperbranched polyarylate resin film.

[0079] A hyperbranched polyarylate resin film is formed by crosslinking the hyperbranched polyarylate resin described in the first aspect or the hyperbranched polyarylate resin prepared by the method described in the second aspect.

[0080] Fourthly, the present invention provides a method for preparing the hyperbranched polyarylate resin film described in the third aspect.

[0081] A method for preparing a hyperbranched polyarylate resin film as described in the third aspect, comprising,

[0082] S1: Dissolve the hyperbranched polyarylate resin according to any one of claims 1-9 or the hyperbranched polyarylate resin prepared by the method according to any one of claims 4-9 in an organic solvent to obtain solution 1;

[0083] S2: Prepare a thin film from solution 1 obtained in step S1;

[0084] In some embodiments, the content of hyperbranched polyarylate resin in solution 1 obtained in step S1 is 5 wt% to 20 wt%, preferably 5 wt% to 10 wt% or 8 wt%. In some embodiments, the content of hyperbranched polyarylate resin in solution 1 obtained in step S1 is 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt%, or 20 wt%.

[0085] In some embodiments, the organic solvent in step S1 is chloroform.

[0086] In some embodiments, step S2 employs a solvent casting method.

[0087] In some embodiments, step S2 further includes a solvent evaporation step.

[0088] In some embodiments, step S2 includes drying under vacuum.

[0089] In some embodiments, step S2 includes drying at 170°C to 180°C.

[0090] In some embodiments, step S2 includes operation under a vacuum of 3 mmHg to 5 mmHg.

[0091] In some embodiments, step S2 includes: filtering the solution 1 obtained in step S1, evaporating part of the organic solvent to obtain a slurry with a hyperbranched polyaryl ester resin concentration of 30wt%-40wt%, preparing a crude film by solvent casting, evaporating the organic solvent, and vacuum drying to obtain the hyperbranched polyaryl ester resin film.

[0092] Beneficial effects

[0093] Compared with the prior art, a certain embodiment of the present invention includes at least one of the following beneficial effects:

[0094] 1. High temperature resistance; 2. Extremely low water absorption; 3. Good mechanical properties in the temperature range of 4K-300℃; 4. Excellent light transmittance; 5. Good electrical properties over a wide range; 6. Flame retardancy, extremely low gas release under vacuum conditions, and radiation resistance; 7. Low water absorption and excellent gas barrier properties; 8. Recyclable and environmentally friendly.

[0095] Terminology definition:

[0096] In the foregoing description of this invention, all figures disclosed herein, whether or not the words “approximately” or “about” are used, are approximate values. Based on the disclosed figures, the value of each figure may vary by less than ±10% or by a difference that is considered reasonable by those skilled in the art, such as ±1%, ±2%, ±3%, ±4%, or ±5%.

[0097] The terms "above", "below", and "within" are understood to include the number itself. For example, "two or more" means ≥ two.

[0098] The term “and / or” should be understood to mean any one of the options or any combination of two or more of the options.

[0099] The term "%vol" indicates a volume percentage.

[0100] The term "wt%" represents a percentage by mass.

[0101] The term "more" indicates a quantity of 2 or more, such as 2, 3, 4 or 5, etc.

[0102] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0103] Definition of testing performance terminology:

[0104] Detailed Implementation

[0105] The following embodiments are further illustrations of the present invention, but are not intended to limit the scope of the invention.

[0106] All technical terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The use of "and" or "or" in this invention includes any and all combinations of one or more of the associated listed items.

[0107] (1) Logarithmic viscosity of resin (η) inh Measurement:

[0108] The resin was prepared into a 0.5 g / dL tetrachloroethane solution and measured in a constant temperature water bath at 30℃±0.5℃, according to formula η. inh =C -1 ln(t1 / t0) calculation: where C is the concentration of resin in tetrachloroethane (g / dL), and t0 and t1 are the time that the tetrachloroethane solvent and the tetrachloroethane resin solution flow through the capillary of the Ubbelohde viscometer, respectively, in seconds;

[0109] (2) Differential scanning calorimetry (DSC) was used to determine the glass transition temperature (T) of the polymer. g ) or melting temperature (T) m ):

[0110] A NETZSCHDSC214 differential scanning calorimeter was used, with a heating and cooling rate of 10K / min, a test temperature range of 50–400℃, and a nitrogen atmosphere.

[0111] (3) Thermogravimetric analysis (TGA) was performed using a NETZSCH TG 209F thermogravimetric analyzer:

[0112] The thermal decomposition temperature (Td) of the polymer was determined, with a test temperature range of 20–800 °C and a heating rate of 20 K / min.

[0113] (4) Solubility test method:

[0114] Weigh 2g of dried resin and place it in a 25mL white volumetric flask. Add about 10mL of solvent and place it in a 30℃ constant temperature water bath for 3-6 hours, shaking the flask. Then add the same solvent to the mark, shake well, and let it stand. Observe the changes in the physical state of the resin.

[0115] a. Dissolved (+): The solute and solvent are homogeneous and transparent.

[0116] b. Swelling (+-): The solute and solvent are turbid and opaque, and swollen resin particles can be observed.

[0117] c. Insoluble (-): The solute and solvent are clearly separated into layers.

[0118] Main raw materials and their structure:

[0119] Bisphenol Fluoride: Bisphenol AF: Bisphenol S

[0120] Phenolphthalein: 4,4'-Dihydroxybenzophenone:

[0121] terephthaloyl chloride: isophthaloyl chloride:

[0122] 2,6-Naphthalenedicarboxylate: 4,4'-Biphenyldimethylacetyl chloride:

[0123] 1.3.5 Phloroglucinol: 1,2,4-Phoroglossol: pyrogallol:

[0124] 1,3,7-Naphthylpyrogallol: 1,3,8-Naphthylpyrogallol:

[0125] 3,5,4-Biphenylpyrogallol:

[0126] A hyperbranched polyarylate resin (HBPAR) containing a monomer of formula (I),

[0127]

[0128] This invention employs a phase-transfer interfacial polycondensation method to prepare high molecular weight HBPAR resin. Hyperbranched polyarylate resins with the following structures are prepared by copolymerization with different monomers:

[0129]

[0130] The asterisk (*) can represent a connection point.

[0131] In the formula: A2 is connected to B2 and B3 by a bond.

[0132] Wherein A2 is one or more of the following structures: terephthaloyl structure, isophthaloyl structure, 2,6-naphthalenediyl structure or 4,4'-biphenylacetyl structure, preferably terephthaloyl structure or isophthaloyl structure.

[0133] Wherein B2 is one or more of the following structures: bisphenol fluorene structure, bisphenol AF structure, bisphenol S structure or phenolphthalein structure, with bisphenol fluorene structure and bisphenol AF structure being preferred.

[0134] Wherein B3 is one or more of the following structures: pyrogallol, pyrogallol, 1,2,4-phenylpyrogallol, 2,6,8-naphthylpyrrolidone, 1,3,8-naphthylpyrrolidone, or 3,5,9-biphenylpyrrolidone, with the pyrogallol structure being preferred.

[0135] This invention allows for the preparation of various polymers with different logarithmic ratios, viscosities (ηinh), glass transition temperatures (Tg) (°C), and thermal decomposition temperatures (T) by adjusting the feed ratios of A2, B2, and B3. d Hyperbranched polyarylate resins (HBPAR) have different solubilities in various organic solvents.

[0136] This invention provides a method for preparing hyperbranched polyarylate resin (HBPAR):

[0137] Hyperbranched polyarylate resin was prepared by using triphenol (B3), bisphenol (B2), and aramid chloride as electrophilic monomers (A2) in a specific solvent for phase transfer catalytic interfacial copolymerization, followed by static separation, water washing of the organic phase, and alcohol precipitation.

[0138] The specific implementation steps of the method are as follows:

[0139] Step 1: Preparation of the aqueous phase

[0140] In a dry and clean four-necked reaction flask equipped with a nitrogen inlet / outlet tube and nitrogen gas introduced into it, add alkali and B2 monomer bisphenol. The molar ratio of alkali to bisphenol compound (hereinafter also referred to as B2 monomer bisphenol) is 2.1 to 2.5: 1.0. Stir and heat to 30°C to 50°C. The bisphenol compound reacts with the alkali to form disodium salt or disodium salt. Dissolve the disodium salt or disodium salt in water, add a surfactant as a phase transfer catalyst, and prepare an aqueous phase to obtain solution 2.

[0141] Step 2: Preparation of the organic phase

[0142] Aryl dichloroisocyanurate (hereinafter also referred to as A2 monomer) is dissolved in a certain volume of haloalkanes solvent (such as one or more of chlorinated hydrocarbons, bromine hydrocarbons, fluorinated hydrocarbons, chlorofluorocarbons, and bromofluorocarbons) to obtain solution 3. The molar concentration of aryl dichloroisocyanurate in solution 3 is controlled to be greater than 0.1 mol / L and less than or equal to 1.00 mol / L, preferably 0.3 mol / L to 0.7 mol / L.

[0143] Step 3: Interfacial condensation reaction

[0144] Solution 2 and solution 3 were mixed under stirring. The reaction proceeded immediately at the two-phase interface. The reaction temperature was controlled at 15℃~25℃. After 30min~1h of reaction, a triphenol compound (hereinafter also referred to as B3 monomer) was added. The reaction was continued to be stirred at 20℃~30℃ for 3~5h. Dilute hydrochloric acid was added to neutralize to pH 6~7. After standing and separating, hyperbranched polyarylate resin layer (crude hyperbranched polyarylate resin) was obtained.

[0145] In the above methods, depending on the different properties of the hyperbranched polyarylate resin to be prepared, the ratio of monomers A2, B2, and B3 of the present invention can be adjusted.

[0146] After steps 1 to 3, the crude hyperbranched polyarylate resin undergoes solvent recovery, purification, and resin crushing.

[0147] The crude hyperbranched polyarylate resin obtained in steps 1-3 above is heated in a water bath with stirring to distill off chloroform. The fraction at 61℃-63℃ (i.e., chloroform) is collected, with a chloroform recovery rate of ≥95%. The chloroform is then recycled after azeotropic dehydration. The resin is filtered and crushed 3-5 times with 95% vol ethanol or 95% vol methanol. The separated resin is then washed with deionized water and dried to obtain refined HBPAR resin with a yield of ≥98%.

[0148] The following are specific product examples of the method:

[0149] Examples 1-1 to 1-6:

[0150] Preparation of hyperbranched polyarylate resin with code name HBPAR-355

[0151] The constituent monomers are pyrogallol (TFA) (B3 monomer), bisphenol fluorene (B2 monomer), and terephthaloyl chloride (TPC) (A2 monomer). The amount of each constituent monomer in the hyperbranched polyarylate resin of different embodiments is shown in Table 1.

[0152] In a dry, clean four-necked flask equipped with an electric stirrer, a thermometer, and an inert gas inlet / outlet tube (such as nitrogen or argon), 35.04 g (0.1 mol) of bisphenol fluorene was mixed with 8.5 g of sodium hydroxide and 200 ml of deionized water. The mixture was stirred and heated to 50 °C to dissolve the bisphenol fluorene, resulting in solution 2.

[0153] After cooling solution 2 to 10℃±10℃, add 0.27g of surfactant benzyl triethylamine bromide, 20.3g (0.10mol) of terephthaloyl chloride (TPC), and 250ml of chloroform. Stir the reaction for 30min, then mix with 0.126g of pyrogallol. Slowly raise the reaction temperature to 20℃±5℃ and continue stirring for 5h. Neutralize the reaction solution with 5wt% hydrochloric acid aqueous solution to a pH of 6.0~7.0.

[0154] After standing and separating, a resin layer was obtained. The resin layer was washed with deionized water, and then the resin layer was distilled to recover chloroform. The distilled resin layer was pulverized 3-5 times in 95% vol ethanol aqueous solution, filtered, washed with water, and white fine granular resin was obtained. The resin was dried in an oven at 140℃±10℃ for 8-12 hours to obtain the hyperbranched polyarylate resin of Example 1-1 (referred to as HBPAR-355). Keeping the molar amount of TPC constant, the molar amounts of other constituent monomers were adjusted according to the molar amounts of the constituent monomers in Table 1, and the same operation was performed to obtain the hyperbranched polyarylate resins of Examples 1-2 to 1-5 (referred to as HBPAR-355) and the hyperbranched polyarylate resin of the control example. The ηinh, Tg, Td and solubility in chloroform and tetrachloroethane of the obtained hyperbranched polyarylate resins were tested, and the results are shown in Table 1.

[0155] Table 1: Preparation of hyperbranched polyarylate resins with different feed ratios in Example 1

[0156]

[0157]

[0158] *The values ​​of the second heating curve in DSC are the same below.

[0159] **Thermal decomposition temperature

[0160] ***: "-" indicates no dissolution; "+-" indicates swelling; "++" indicates dissolution, and so on.

[0161] Conclusion: High molecular weight hyperbranched polyarylate resins can be prepared using the preparation method and formulation ratio provided by this invention. The results show that the glass transition temperature (Tg) and thermal decomposition temperature (Td) of HBPAR prepared by this invention are significantly improved. In Example 1, the molar amount of branching agent TFA added during copolymerization is preferably 1-2% of bisphenol fluorene (i.e., the ratio shown in Examples 1-1 and 1-2).

[0162] Examples 2-1 to 2-10:

[0163] Preparation of hyperbranched polyarylate resin with code name HBPAR-325

[0164] The constituent monomers are: pyrogallol (TFA) (B3 monomer), bisphenol fluorene (B2 monomer), terephthaloyl chloride (TPC) (A2 monomer), and isophthaloyl chloride (IPC) (A2 monomer). The molar amounts of the constituent monomers of the hyperbranched polyarylate resins in different embodiments are shown in Table 2.

[0165] In a dry, clean four-necked flask equipped with an electric stirrer, a thermometer, and an inert gas inlet / outlet tube for nitrogen or argon, 35.04 g (0.1 mol) of bisphenol fluorene (molar amounts of the added materials are shown in Table 2), 8.5 g of sodium hydroxide, and 200 ml of deionized water were added. The mixture was stirred and heated to 50 °C to dissolve the bisphenol fluorene, resulting in solution 2.

[0166] After cooling solution 2 to 10℃±10℃, add 0.22g of surfactant benzyl triethylamine chloride, 20.3g of terephthaloyl chloride (TPC) and isophthaloyl chloride (the feeding ratio is shown in Table 2), and 250ml of chloroform. Stir the reaction for 30min, then mix with 0.12g of pyrogallol. Slowly raise the reaction temperature to 20℃±5℃ and continue stirring for 5h. Neutralize the reaction solution with 5wt% hydrochloric acid aqueous solution until the pH value is 6.0~7.0.

[0167] After standing and separating, a resin layer was obtained. The resin layer was washed with deionized water, and then the resin layer was distilled to recover chloroform. The distilled resin layer was pulverized 3-5 times in a 95% vol ethanol aqueous solution, filtered, washed with water, and a white fine granular resin was obtained. The resin was dried in an oven at 140℃±10℃ for 8-12 hours to obtain HBPAR resin (referred to as HBPAR-325). The logarithmic viscosity (ηinh), melt thermal stability Tg (℃), Td (℃), and solubility in chloroform and tetrachloroethane of the obtained HBPAR resin were tested. The results are shown in Table 2.

[0168] Table 2: Preparation of hyperbranched polyarylate resins with different feed amounts in Example 2

[0169]

[0170] *The Tg value determined by DSC is the value of the second temperature rise curve.

[0171] **++Easily soluble; -+dissolved; +-swelling; -insoluble.

[0172] Table 2 shows that by adjusting the addition ratio of terephthaloyl chloride (TPC) and isophthaloyl chloride (IPC), HBPAR resins with different thermal properties and varying solubility in chloroform, DCM, and tetrachloroethane were obtained. High molecular weight copolymers could also be prepared by adding pyrogallol as a branching agent after reacting with bisphenol fluorene, IPC, and / or TPC as comonomers for 30 min to 1 h. As the proportion of TPC decreased, the resin's Tg decreased, while Td remained relatively stable. When the molar ratio of TPC to IPC was 0.8:0.2–0.3:0.7, especially 0.7:0.3–0.3:0.7, the solubility of the resin improved with increasing TPC content; it became soluble not only in tetrachloroethane but also in DMF, chloroform, dichloromethane, and other solvents.

[0173] The monomer molar ratios in Examples 2-1 to 2-10 can effectively control the end-group structure and molecular weight of the HBPAR polymer. The molar amount of B3 monomer pyrogallol (TFA) can be 0.1–8% mol of the molar amount of B2 monomer bisphenol fluorene, preferably 0.5–1.5% mol. The ratio of the molar amount of bisphenol fluorene to the sum of the molar amounts of TPC and IPC can be 1.00:1.00–1.05:1.00, preferably 1.01–1.04:1.00. A suitable excess of bisphenol fluorene is selected to control the molecular weight of the polymer. By changing the molar ratio of TPC to IPC, a balance can be achieved between the thermal properties of HBPAR and its solubility in common low-toxicity organic solvents (DCM, chloroform, DMF), facilitating the fabrication of colorless, transparent, high-performance films of varying thicknesses using solvent casting, suitable for the field of flexible optoelectronic displays.

[0174] Examples 3-1 to 3-10:

[0175] Preparation of hyperbranched polyarylate resin with code name HBPAR-F

[0176] The constituent monomers are: pyrogallol (TFA) (B3 monomer), bisphenol fluorene (B2 monomer), bisphenol AF (B2 monomer), and terephthaloyl chloride (TPC) (A2 monomer). The molar amounts of the constituent monomers of the hyperbranched polyarylate resins in different embodiments are shown in Table 3.

[0177] In a dry, clean four-necked flask equipped with an electric stirrer, a thermometer, and an inert gas inlet / outlet tube for nitrogen or argon, bisphenol fluorene (molar amounts shown in Table 3) and bisphenol AF (molar amounts shown in Table 3) are mixed with 8.5 g of sodium hydroxide and 200 ml of deionized water. The mixture is stirred and heated to 35 °C to dissolve bisphenol fluorene and bisphenol AF, resulting in solution 2.

[0178] Cool solution 2 to 10℃±10℃, then add 0.27g of surfactant benzyl triethylamine bromide and 20.3g (0.10mol) of terephthaloyl chloride (TPC) (molar amounts of the feed are shown in Table 3) and 250ml of chloroform. Stir the reaction for 30min, then add pyrogallol (molar amounts of the feed are shown in Table 3). Slowly raise the reaction temperature to 20℃±5℃ and continue stirring for 5h. Neutralize the reaction solution with 5wt% hydrochloric acid aqueous solution or benzoyl chloride until the pH value is 6.0~7.0.

[0179] After standing and separating, a resin layer was obtained. The resin layer was washed with deionized water, and then the resin layer was distilled. The resin layer after chloroform distillation was crushed 3-5 times in 95% vol ethanol aqueous solution, filtered, washed with water, and white fine granular resin was obtained. The resin was dried in an oven at 140℃±10℃ for 8-12 hours to obtain HBPAR resin. The logarithmic viscosity (ηinh), melt thermal stability Tg, Td and solubility of the obtained HBPAR resin were tested. The results are shown in Tables 3 and 6.

[0180] Table 3: Properties of hyperbranched polyarylate resins with different feed amounts in Example 3

[0181]

[0182]

[0183] Conclusion: Introducing the strongly electron-withdrawing -CF3- into the HBPAR molecular chain is beneficial to improving the transparency of the film after formation. At the same time, as the molar ratio of bisphenol AF increases, the Tg decreases.

[0184] Example 4-1, Example 4-2

[0185] Preparation of hyperbranched polyarylate resin with code name HBPAR-N

[0186] Monomers: Pyrogallol (TFA) (B3 monomer), Bisphenol fluorene (B2 monomer), Terephthaloyl chloride (TPC) (A2 monomer)

[0187] 2,6-Naphthalenedicarboxylate (A2 monomer); the molar amounts of the constituent monomers in each different embodiment are shown in Table 4.

[0188] In a dry, clean four-necked flask equipped with an electric stirrer, a thermometer, and an inert gas inlet / outlet tube for nitrogen or argon, 35.04 g (0.1 mol) of bisphenol fluorene (feed amounts are shown in Table 4), 8.5 g of sodium hydroxide, and 200 ml of deionized water are mixed, stirred, and heated to 50 °C to dissolve the bisphenol fluorene, resulting in solution 2.

[0189] Solution 2 was cooled to 10℃±10℃, and then 0.22g of surfactant benzyl triethylamine chloride was added, along with terephthaloyl chloride (TPC) (feed amounts are shown in Table 4), 2,6-naphthalenedilicate chloride (feed amounts are shown in Table 4), and 250ml of chloroform. After stirring for 30min, it was mixed with pyrogallol (feed amounts are shown in Table 4). The reaction temperature was slowly raised to 20℃±5℃, and the reaction was continued to be stirred for 5h. The pH of the reaction solution was neutralized to 6.0~7.0 with 5wt% hydrochloric acid aqueous solution or benzoyl chloride.

[0190] After standing and separating, a resin layer was obtained. The resin layer was washed with deionized water, and then the resin layer was distilled to recover chloroform. The distilled resin layer was crushed 3-5 times in a 95% vol ethanol aqueous solution, filtered, washed with water, and a white fine granular resin was obtained. The resin was dried in an oven at 140℃±10℃ for 8-12 hours to obtain HBPAR resin. The logarithmic viscosity (ηinh), melt thermal stability (Tg), Td, solubility, etc. of the obtained HBPAR resin were tested. The results are shown in Tables 4 and 6.

[0191] Table 4. Properties of hyperbranched polyarylate resins with different feed amounts in Example 4

[0192]

[0193] Conclusion: The HBPA resin synthesized from bisphenol fluorene and 2,6-naphthalenedicarboxylate chloride showed a significant improvement in temperature resistance, with a Tg reaching 368.5℃. Examples 5-1 and 5-2:

[0194] Preparation of hyperbranched polyarylate resin with the code name HBPAR-L.

[0195] The constituent monomers are: pyrogallol (TFA) (B3 monomer), bisphenol fluorene (B2 monomer), terephthaloyl chloride (TPC) (A2 monomer), and 4,4'-biphenyl dicarboxylate chloride (A2 monomer). The molar amounts of the constituent monomers of the hyperbranched polyarylate resins in different embodiments are shown in Table 5.

[0196] In a dry, clean four-necked flask equipped with an electric stirrer, a thermometer, and inert gas inlet / outlet tubes for nitrogen, argon, etc., and with the inert gas introduced, add 35.04 g (0.1 mol) of bisphenol fluorene, 8.5 g of sodium hydroxide, and 200 ml of deionized water. Stir and heat to 50°C to dissolve the bisphenol fluorene.

[0197] Cool the aqueous phase to 10℃±10℃ and add 0.22g of surfactant benzyl triethylamine chloride, 18.27g of terephthaloyl chloride (TPC), and 2.79g of 4,4'-biphenyldicarboxylic acid chloride. Simultaneously add 250ml of chloroform to ensure complete transfer of terephthaloyl chloride (TPC) and 4,4'-biphenyldicarboxylic acid chloride. Stir the reaction for 30 minutes and add 0.126g of pyrogallol. Slowly raise the reaction temperature to 20℃±5℃ and continue stirring for 5 hours. Neutralize the reaction solution with 5% dilute hydrochloric acid to a pH of approximately 6.0–7.0.

[0198] After standing and separating, a resin layer was obtained. The resin layer was washed with deionized water, and then the resin layer was distilled to recover chloroform. The distilled resin layer was crushed 3 to 5 times in a 95% vol ethanol aqueous solution, filtered, washed with water, and white fine granular HBPAR resin was obtained. The resin was dried in an oven at 140℃±10℃ for 8 to 12 hours. The logarithmic viscosity (ηinh) and melt thermal stability of the resin were tested.

[0199] Table 5: Properties of HBPAR-L hyperbranched polyarylate resins prepared with different feed amounts in Example 5

[0200]

[0201] Conclusion: HBPAR resin prepared from 4,4'-biphenyl dicarboxylate chloride maintains a high level of temperature resistance and has improved physical properties;

[0202] Example 6

[0203] The hyperbranched polyarylate resins obtained in Examples 2-5 were used to test the solubility of each resin. The results are shown in Table 6.

[0204] Table 6: Solubility of each resin in Examples 1-5

[0205]

[0206]

[0207] **++Easily soluble; -+dissolved; +-swelling; -insoluble.

[0208] Conclusion: HBPARs with different properties obtained by controlling different molecular structures all have good solvent solubility and meet the processing requirements of solvent coating film formation.

[0209] Example 7

[0210] (5) Preparation and properties of HBPAR thin films

[0211] The HBPAR resins prepared in Examples 1-6, 2-3, 3-7, and 4-1 of this invention, as well as commercially available CPI resins from different countries, were dissolved in chloroform organic solvent to prepare resin solutions with a concentration of 8%. After filtration and ultrafiltration to remove insoluble impurities, a purified resin solution was obtained. After purification, part of the solvent was evaporated to prepare a 30%-40% concentration solution. A colorless and transparent HBPAR film of a certain thickness was prepared by solvent casting. After the solvent was slowly evaporated and basically completely, the film was vacuum dried at 170℃-180℃ to constant weight (vacuum degree 3-5 mmHg) to obtain a colorless, transparent, high-temperature resistant HBPAR electronic-grade optical film.

[0212] Table 6 Performance Comparison Table

[0213]

[0214]

[0215] As shown in the table, the HBPAR film prepared by this invention has a high glass transition temperature, excellent folding resistance, transparency and dielectric properties; it has broad application prospects in the fields of microelectronics and flexible displays.

[0216] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A hyperbranched polyarylate resin, characterized by, monomers having a structure as shown in formula (I), ， wherein, A2 is an aromatic diacyl structure, B2 is a bisphenol structure, B3 is a triphenol structure; wherein, m, n, p, q are positive integers respectively; the hyperbranched polyarylate resin contains repeating units of -A2-B2-, each repeating unit is connected by A2 and B3; the aryl diacyl structure is selected from , , and ; the triol structure comprises one or more of a benzene triol structure, a naphthalene triol structure, a biphenyl triol structure; the benzotriol structure is selected from , and one or more of the naphthol structure is selected from one or more of , . The biphenyl triol structure is ; The bisphenol structure is selected from one or more of , , , , . the logarithmic reduced viscosity of the hyperbranched polyarylate resin is 0.74g / dl -1.51g / dl.

2. The hyperbranched polyarylate resin according to claim 1, wherein, in the hyperbranched polyarylate resin, the bisphenol structure is selected from bisphenol fluorene, the aromatic diacyl structure is selected from TPC, and the triphenol structure is selected from pyrogallol; the logarithmic reduced viscosity of the hyperbranched polyarylate resin is 0.74g / dl -1.25g / dl.

3. The hyperbranched polyarylate resin according to claim 1, wherein, in the hyperbranched polyarylate resin, the bisphenol structure is selected from bisphenol fluorene, the aromatic diacyl structure is selected from at least one of TPC and IPC, and the triphenol structure is selected from pyrogallol; optionally, the molar ratio of TPC to IPC is 9:1~0:1; optionally, the logarithmic reduced viscosity of the hyperbranched polyarylate resin is 0.95g / dl -1.40g / dl.

4. The hyperbranched polyarylate resin according to claim 3, wherein the molar ratio of TPC to IPC is 9:1~1:

9.

5. The hyperbranched polyarylate resin according to claim 4, wherein the molar ratio of TPC to IPC is 8:2, 7:3, 6:4, 5:5, 4:6, 3:7, 2:8 or 1:

9.

6. The hyperbranched polyarylate resin according to claim 1, wherein in the hyperbranched polyarylate resin, the bisphenol structure is selected from at least one of bisphenol fluorene and bisphenol AF, the triphenol structure is selected from pyrogallol, and the aromatic diacyl structure is selected from TPC; optionally, the molar ratio of bisphenol fluorene to bisphenol AF is 9:1~0:10; optionally, the logarithmic reduced viscosity of the hyperbranched polyarylate resin is 0.75g / dl -1.51g / dl.

7. The hyperbranched polyarylate resin according to claim 6, wherein the molar ratio of bisphenol fluorene to bisphenol AF is 9:1, 8:2, 7:3, 6:4, 5:5, 4:6, 3:7, 2:8, 1:9 or 0:

10.

8. The hyperbranched polyarylate resin according to claim 1, wherein in the hyperbranched polyarylate resin, the triphenol structure is selected from pyrogallol, the bisphenol structure is selected from bisphenol fluorene, and the aromatic diacyl structure is selected from IPC and 2,6-naphthalene diacyl chloride; optionally, the logarithmic reduced viscosity of the hyperbranched polyarylate resin is 1.25g / dl -1.50g / dl.

9. The hyperbranched polyarylate resin according to claim 1, wherein, The hyperbranched polyarylate resin, the aromatic diacyl structure is selected from 4,4 ， The hyperbranched polyarylate resin, the aromatic diacyl structure is selected from 4,4 at least one of oxalyl chloride, TPC, the bisphenol structure is selected from bisphenol fluorene, the triphenol structure is selected from pyrogallol; optionally, the 4,4 ， - the molar ratio of diphenyl dicarboxylic acid chloride to TPC is 1 :0 to 0:1 ; optionally, the hyperbranched polyarylate resin has a log- reduced viscosity of 1.05 g / dl to 1.15 g / dl.

10. A method for preparing the hyperbranched polyarylate resin according to any one of claims 1 to 9, characterized in that, comprising the steps of: P1: mixing a bisphenol compound with a base and water, and optionally adding a catalyst to obtain solution 2; P2: mixing the solution 2 obtained in the step P1 with an organic solution of an aromatic diacyl compound to react and obtain solution 3; P3: mixing the solution 3 obtained in the step P2 with a triphenol compound to react, standing to separate layers, washing the resin layer, evaporating the organic solvent in the resin layer to obtain a resin layer with evaporated organic solvent; mixing the resin layer with evaporated organic solvent with an alcohol, precipitating, crushing, filtering, washing with water and drying at 140℃±10℃ for 8~12h to obtain the hyperbranched polyarylate resin. The aryl dicarboxylic compound is selected from one or more of: , , and . The triphenolic compound includes one or more of pyrogallol, naphthalene triphenol, and diphenyl triphenol; The benzotriol compound is selected from , with one or more of the following: the naphthotriol is selected from one or more of , . The biphenyl triol is ; The bisphenol compound is selected from one or more of , , , , . The molar ratio of the triphenolic compound to the bisphenol compound is 0.01:100.00-10.00:100.00, and / or the molar ratio of the bisphenol compound to the aromatic diacyl compound is 1.00:1.00-1.05:1.00; The logarithmic specific viscosity of the hyperbranched polyarylate resin is 0.74 g / dl-1.51 g / dl.

11. The method according to claim 10, wherein the bisphenol compound is selected from , the aromatic diacyl compound is selected from , and the triphenol compound is selected from ; optionally, the triphenol compound has a molar ratio of 1.00:100.00 to 10.00:100.00 to the molar amount of the aromatic diacyl compound , and / or the molar ratio of the bisphenol compound to the aromatic diacyl compound is 1.00:1.00 to 1.04:1.00; optionally, the hyperbranched polyarylate resin has a log reduced specific viscosity of 0.74 g / dl to 1.25 g / dl.

12. The method according to claim 11, wherein the triphenolic compound the molar ratio of the aromatic diacid compound the molar ratio of the bisphenolic compound to the aromatic diacid compound is 1.00:1.00, 1.015:1.00, 1.02:1.00, 1.03:1.00, or 1.04:1.

00.

13. The method of claim 12, said triphenolic compound molar amount of said aromatic diacid compound a ratio of the molar amount of the feedstock of 1.00:100.00, 2.00:100.00, or 3.00:100.

00.

14. The method of claim 10, the bisphenol compound is selected from , the aromatic diacyl compound is selected from , , the triphenol compound is selected from ; optionally, the to molar ratio is 9:1 to 0:1; and / or the molar ratio of the triphenol compound to the bisphenol compound is 0.01:100.00 to 8.00:100.00; and / or the molar ratio of the bisphenol compound to the aromatic diacyl compound is 1.00:1.00 to 1.05:1.00; optionally, the log reduced specific viscosity of the hyperbranched polyarylate resin is 0.95 g / dl to 1.40 g / dl.

15. The method of claim 14, wherein the molar ratio of the and is from 9:1 to 1:

9.

16. The method of claim 15, wherein the with a feed molar ratio of 8:2, 7:3, 6:4, 5:5, 4:6, 3:7, 2:8, or 1:

9.

17. The method of claim 14, wherein the molar ratio of the bisphenol compound to the aromatic diacyl compound is 1.01:1.00-1.04:1.

00.

18. The method of claim 10, the bisphenol compound is selected from at least one of or the triphenol compound is selected from the aromatic diacyl compound is selected from ; optionally, the feed molar ratio of the to is 9:1 to 0:10, the feed molar ratio of the bisphenol compound to the aromatic diacyl compound is 1.00:1.00 to 1.05:1.00; the ratio of the feed molar amount of the triphenol compound to the bisphenol compound is 0.01:100.00 to 8.00:100.00; optionally, the log reduced specific viscosity of the hyperbranched polyarylate resin is 0.75 g / dl to 1.51 g / dl.

19. The method of claim 18, wherein the molar ratio of the to is 9:1, 8:2, 7:3, 6:4, 5:5, 4:6, 3:7, 2:8, 1:9, or 0:

10.

20. The method of claim 10, the triphenolic compound is selected from the biphenolic compound is selected from the aromatic diacyl compound is selected from 、 at least one; optionally, a feed molar ratio of the triphenolic compound to the biphenolic compound is 0.01:100.00 to 8.00:100.00; and / or a feed molar ratio of the biphenolic compound to the aromatic diacyl compound is 1.0:0.5 to 1.0:2.0; optionally, a log reduced specific viscosity of the hyperbranched polyarylate resin is 1.25 g / dl to 1.50 g / dl.

21. The method of claim 20, wherein the molar ratio of the bisphenol compound to the aromatic diacyl compound is 1.0:1.

0.

22. The method of claim 10, the aromatic diacid compound is selected from at least one of , the bisphenol compound is selected from the triphenol compound is selected from ; the molar feed ratio of the triphenol compound to the bisphenol compound is 0.01:100.00-8.00:100.00; and / or the molar feed ratio of the bisphenol compound to the aromatic diacid compound is 1.0:0.5-1.0:2.0; optionally, the log reduced specific viscosity of the hyperbranched polyarylate resin is 1.05 g / dl-1.15 g / dl.

23. The method of claim 22, wherein the with a feed molar ratio of 1.0:0 to 0:1.0; and / or a feed molar ratio of 1.0:1.

0.

24. The method of claim 22, wherein the with feed molar ratio of 1.0:0.5 to 1.0:2.

0.

25. The method of claim 24, wherein the with a feed molar ratio of 1.0:1.

0.

26. The method of claim 10, wherein, The preparation method is reacted under an inert gas atmosphere, and the inert gas atmosphere is nitrogen or argon, and / or The reaction temperature of the P1 step is 30-80°C, and / or The reaction temperature of the P2 step is 0-35°C, and / or The reaction time of the P2 step is 30-60 min, and / or The reaction temperature of the P3 step is 15-30°C, and / or The reaction time of the P3 step is 2-5 h, and / or The catalyst of the P1 step is a surfactant, and / or The surfactant includes at least one of benzyl triethylammonium chloride, benzyl triethylammonium bromide, tert-butyl ammonium chloride, tert-butyl ammonium bromide, and tert-butyl ammonium iodide, and / or The molar ratio of the catalyst to the bisphenol compound is 0.01:100-10:

100.

27. The method of claim 26, wherein the reaction temperature of the P1 step is 40°C, and / or The reaction temperature of the P2 step is 15-30°C, and / or The reaction time of the P2 step is 45 min, and / or The reaction temperature of the P3 step is 20-25°C, and / or The surfactant is benzyl triethylammonium bromide.

28. The method of claim 10, wherein The base in the P1 step is one or more of potassium hydroxide and sodium hydroxide, and / or The mass ratio of the base to water is 3.0:100.0-10.0:100.0, and / or The organic solvent of the organic solution in the P2 step includes one or more of chlorinated hydrocarbon, brominated hydrocarbon, fluorinated hydrocarbon, fluorochlorinated hydrocarbon, and fluorobrominated hydrocarbon, and / or The concentration of the aromatic diacyl compound in the aromatic diacyl compound organic solution of the P2 step is greater than 0 mol / L to ≤1.0 mol / L.

29. The method of claim 28, wherein The mass ratio of the base to water is 4.5:100.0-5.0:100.0, and / or The organic solvent of the organic solution in the P2 step is chloroform, and / or The concentration of the aromatic diacid compound in the organic solution of the aromatic diacid compound in the P2 step is 0.4 mol / L.

30. An ultrahydrophobic polyarylate resin film, characterized in that, The hyperbranched polyarylate resin prepared by the method of any one of claims 10-29 is crosslinked to form.

31. A method for preparing the hyperbranched polyarylate resin film of claim 30, comprising, S1: dissolving the hyperbranched polyarylate resin of any one of claims 1-9 or the hyperbranched polyarylate resin prepared by the method of any one of claims 10-29 in an organic solvent to obtain a solution 1; S2: preparing the solution 1 obtained in step S1 into a film; Optionally, the content of the hyperbranched polyarylate resin in the solution 1 obtained in step S1 is 5 wt%-20 wt%, and / or The organic solvent in step S1 is chloroform; and / or The solvent casting method is used in step S2, and / or Step S2 further comprises a solvent evaporation step, and / or Step S2 comprises drying under vacuum, and / or Step S2 comprises drying at 170°C-180°C, and / or Step S2 comprises operating under vacuum, and the vacuum degree is 3 mmHg-5 mmHg; and / or The S2 step comprises: The solution 1 obtained in step S1 is filtered, and part of the organic solvent is evaporated to obtain a hyperbranched polyarylate resin solution with a hyperbranched polyarylate resin concentration of 30 wt%-40 wt%, and then a solvent casting method is used to prepare a film crude product, and then the organic solvent is volatilized, and vacuum drying is performed to obtain the hyperbranched polyarylate resin film.

32. The method of claim 31, optionally, the content of the hyperbranched polyarylate resin in the solution 1 obtained in step S1 is 5 wt%-10 wt%.

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