TW572922B - Novel poly(arylene ether) with high function - Google Patents

Abstract

This invention relates to novel poly (arylene ether), which is represented by formula I: wherein Y is shown below and where R1, R2, R3, R4, R5, and R6 each represent a fluoro atom, alkyl or perfluoroalkyl aliphatic group of from 0 to 2 carbon atoms, and where R7, R8 each represent a hydrogen atom, fluorine atom, methyl or trifluoromethyl substituted phenyl group. Due to their rigid polymer backbone, these novel poly (arylene ether) present high glass transition temperature and excellent thermal stability. Furthermore, the perfluoroalkyl side groups bring up several extraordinary advantages to these poly (arylene ether), such as low dielectric constant, high hydrophobicity, high solubility and good insularity. Therefore, these novel polymers are particularly suitable for multi-functional engineering plastics.

Description

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 572922 A7 ------- _______B7 V. Description of the invention (1 ') --- Scope of the invention The present invention relates to a new type of high-function polyaromatic ether polymer material, more specifically, It is a highly functional engineering plastic that can be used in display electrode plates or in substrate circuit board insulation materials, organic photosensitive drum materials, jet heads for inkjet printers, and gas-permeable membranes. BACKGROUND OF THE INVENTION Polyaromatic ethers are generally considered to be high-performance engineering plastics, which have good physical properties such as plasticity, castability, high glass transition temperature, good thermal stability and chemical resistance. Polyscales are generally polymerized by dihalo or dinitro monomers and bisphenoxides to form polymers, and sulfone or ketone groups have good nucleophilic substitution activity for aromatic halides, so poly (aryl ether sulfone) s and poly (aryl ether ketone) s, and heterocyclic compounds and amide groups can also be used as a reactive group to polymerize into a high molecular weight polyaromatic ether. And its general characteristics are: when performing nucleophilic halogen transfer, it becomes

Meisenheimer complex 'These reactive groups all have stable negative charge formation at the 2-, 4- position of these aryi moieti, and Labadie et al (see Labadie, J.W .; Hedrick, JL Polymer Preprint) · reported The perfluoro-alkyl group suspends on the main chain or activates fluoro or nitro on the main chain. This is because the perHuoro-alkylgroup electron attraction group does not participate in resonance stabilization. This group uses super-conjugation or negatively induces the paper wave. Dimensions are applicable to China Standard S (CNS) A4 specifications (210X 297 public holidays) (Please read the precautions on the back before filling this page)

5 572922 A7 B7 V. Explanation of the invention (2) (negative inductive) The effect will be that a stable negative charge will be formed and activated at the 2-, 4- position, and the space is crowded due to the huge trifluoro-methyl group, which also helps the Meisenheimer complex The formation of three-dimensional distortion is released (see: ParK, S.K .; Kim, SY Macromolecules 1998, 31, 3385). Polyaromatic ethers are mostly used in display electrode plates or substrate circuit board insulation materials, organic photosensitive drum materials, inkjet printer heads and separation from gas films. Fluoropolymers, especially in Good help in providing low dielectric and low water absorption (see: Tullos, G.L .; Cassidy, P.E. Macromolecules 1991, 24, 6059), while the 6 fluoro group is on the side chain of the polymer It also increases the solubility of the polymer (commonly known as the fluorine effect) without losing its original thermal stability, and increases the glass transition temperature to reduce crystallinity, and the huge CF3 group also increases polymerization The free volume of the polymer improves the various properties of the polymer, such as gas permeability and electronic insulation. Because of the many characteristics of the fluorine-containing polymer, Susauta Banerjee and Gerhard Maier have synthesized several oxazole and thiazole monomers. Fluoropoly (arylene ether) polymer. (Please read the notes on the back before filling out this page)

The size of the paper is applicable to the Chinese National Standard (CNS) A4 (210X 297 mm) 6 572922 A7 B7 V. Description of the invention (3) The monomer] has considerable activity, because the fluorine atom is not only activated by the% group, but also Due to insufficient electrons on the oxazole ring, it can be activated under mild conditions to form a polymer with a high molar mass, but the monomer ^ cannot form a polymer with a high molar amount under mild conditions T. This is because thiazole The electron deficiency on the ring is less than that on oxazole Hng. The polymer polymerized by monomer 1 (b1Soxazole) has a more limited thermal stability, while the polymer polymerized by monomer 2 (bisthiazole) Polymers have high thermal stability, while polyethers produced by St. Polymer have good thermal stability because of the lack of any substituents at the 4-position of oxazole (see Hedrick, JL; Twieg, R. Macromolecules 1992, 25, 2021) ° In order to expect the polymer to have low dielectric constant and high thermal stability, in molecular design, as long as the oxazole group can be replaced by a low-polar or polyaromatic phenyl unit, four more ( Chemistry (A) through (D)) different from the polymerization of monomers in the polymer. (Please read the notes on the back before filling out this page.

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The paper size of the table applies the Chinese National Standard (CNS) A4 specification (210X29 * 7mm) 7 572922 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (4) High conversion rate and high polymer quality, its glass transition temperature is about 150t-240t. The polymer containing pyridine and thiophene rings is 70 80 C lower than the glass transition plate of the polymer formed by ordinary monomers. This is due to the difference in catenatiang angies, and another reason that affects the glass transition temperature It is a type of bisphenol. Generally, a polymer containing a large fluorine atom group has a higher glass transition temperature, while a polymer containing a softer bisphen0A has a lower glass transition temperature. In Thermogravimetric Analysis (TGA) test 4, when the weight of s is reduced by 5% (generally determined as the thermal decomposition temperature of the material), its temperature is approximately between 444_536t, and under the air, Poiy (aryiene ether) containing thiophene ring is 20-30c lower than others. This is because at high temperature, thiophene is oxidized to thiophene dioxide, which causes the aromatic cyclization to be destroyed. The polymer is almost the same. One application of the polyaromatic ether polymer material of the present invention is as an electrode plate for a display. Such as liquid crystal (LC) displays and organic electroluminescence (oEL) displays. The main requirements for display electrode plates are: (1) light, (2) thin, (3) large size, (4) flexible, (5) freely shapeable, and (6) cheap. To meet these needs, the use of plastic electrode plates should be an inevitable choice. At the same time, as the electrode plate of the display, the plastic substrate must also meet the following requirements: (1) in the visible light region, it must be light transparent; that is, it must be light that does not absorb visible light. National Standard (CNS) M Specification (WO7mm) (Please read the precautions on the back before filling this page)

8 572922 A7

Optically isotropic; that is, no color interference (3) must be able to withstand high temperature (20 (TC)); that is, it can tolerate high temperature processing in the process (4) must be hydrophobic and phobic; In other words, it can block water and oxygen from entering the device. Similar patents can be referred to the issued US patents No. 6,117,967, 4,802,742, 4,387,133, 4,409,268, No. 4,419,399, etc. Another application field of the polyaromatic ether polymer material of the present invention is as a low-dielectric insulation material. The electronic manufacturing industry often uses dielectric materials as manufacturing integrated circuits or related electronics. Components are 'insulating materials between different circuits or layers and layers of circuits. Due to the advancement of the times, the manufacturing of electronic components tends to be light, thin, short, and small. Under such developments, the lines of integrated circuits The width also has to move toward miniaturization. In order to meet the requirements of the era of miniaturization, the demand for insulating materials with low dielectrics is becoming more and more urgent. Therefore, the electronics manufacturing industry is really It is necessary to find new insulating materials with low dielectrics to replace the traditional insulating materials mainly based on dioxide dioxide. Generally, the dielectric value of stone dioxide and its modified derivatives often ranges from 3.0 to 5.0 The dielectric value of polymers used to replace silicon dioxide as integrated circuits is mostly between 1.9 and 3.5. However, the dielectric value of polymers depends entirely on the molecular Structure. Among many polymers that have been used as integrated circuit insulation materials, polyimide is the most widely used. Because polyimide has (1) good mechanical properties and (2) excellent heat Safety (3) Easy to apply (4) Good film-forming properties, etc. Therefore, polyurethane, amine is often used as integrated circuit. The paper size is applicable to Chinese National Standard (CNS) A4 specification (210X 297) (Please read the notes on the back before filling out this page}. Packing-Ordered by the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the Consumer Consumption Cooperative 9 572922 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the Employee Consumption Cooperative Α7 Β7 V. Description of the Invention (6) Insulation material. However, by Polyimide has a relatively high dielectric value; especially when it is exposed to a humid environment (like the environment in Taiwan), it is aggravated by polyimide due to its severe water absorption properties (up to 3 ~ 4%). Changes and enhancements in the dielectric value of amines have reduced their functionality. In order to overcome this problem, although 'there have been (see U.S. Patent Nos. 4,835,197, 5,658,994, 5,108,840, 5,114,780 No. 5,145,936, No. 5,155,175, No. 5,173,542, No. 5,204,416, No. 5,235,044, No. 5,270,453) try to improve the water absorption of polyimide by fluorination or cross-linking method; however, none of the effects Ideal. For example, the general polyimide material has a dielectric value of 3.2 when the relative humidity is 0% (0% RH); however, when the relative humidity increases to 60%, the dielectric value also rises to 3.8. To make matters worse, when polyimide absorbs water, many disadvantages also appear at the same time; for example, (1) the conductivity becomes better; that is, the insulation effect is reduced. (2) The adhesiveness is deteriorated; that is, the peeling phenomenon easily occurs. In view of the above problems, it is necessary to develop a high-functional polymer having good thermal stability, low dielectric value, low water absorption, and good solvent resistance. ‘The polyaromatic ether polymer of the present invention is a good choice of materials that meets the above needs. Due to the rigid structure design of the polymer main chain, the polyaromatic polymer of the present invention not only has good mechanical strength and thermal stability (both thermal decomposition temperatures are greater than 400 ° C), but also has an extremely high glass transition temperature. (Between 200 and 335 ° C). In addition, due to the introduction of a fluorine atom-containing group, the polyaromatic ether polymer of the present invention has the special properties of a fluorine-containing polymer. For example, (1) a lower dielectric value (between 2.5 and 3.0), but still has the original " sheet paper size applicable to China National Standard (CNS) A4 specification (2) 0 × 297 mm ( (Please read the notes on the back before filling out this page)

10 572922 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (7) Mechanical properties and thermal stability of polymers. (2) Low water absorption characteristics; however, it still has the gas permeability of the original polymer. (3) Good solubility; however, it still has the insulation properties of the original polymer. (4) Higher fire resistance. In addition to the above two main uses of the polyaromatic ether polymer of the present invention: (1) as an electrode plate for a display, (2) as a low-dielectric insulating material, the polymer has (1) good mechanical properties Strength (2) Good film-forming properties; therefore, it meets the applications described below: (1) As the head of an inkjet printer (see US Patent Nos. 4,601,777, 4,251,824, 4.532.530 No. 4,774,530, 4,678,529, 4,829,324, 4.774.530, 5,057,853, 4,410,899) (2) as a film forming binder for organic photosensitive drums (see US Patent Nos. 2,297,691, 3, 121,006, 4,265,990, 4,251,612, 5,328,789, 5,725,982., 5,665,503, 5,536,61 1, 5,328,788). Summary of the Invention A new type of highly functional polyaromatic ether polymer material, such as a substance represented by Chemical Formula I:

This paper size applies to China National Standard (CNS) A4 specification (210X297). · · · · · (Please read the precautions on the back before filling this page)

11 572922 A7 V. Description of the invention (8 where Y can be represented by any of the following chemical structures

(Please read the notes on the back before filling out this page) • Equipment · Aliphatic or fluoroalkyl groups with 1 to 2 carbon atoms. R7 and r8 represent hydrogen atom, phenyl, fluorinated phenyl, tolyl or difluorotolyl. This polyaromatic ether compound has good physical properties such as high glass transition temperature and good thermal stability due to its hard main chain structure. Furthermore, it provides many additional advantages due to its fluorine-containing side chain groups; such as low dielectric, low water absorption, high solubility, and electronic insulation. Therefore, it can be used as high-functional engineering plastics, such as plastic substrates with high glass transition temperature, gas-permeable films, and electronic insulation materials. 11、11. The Intellectual Property Bureau of the Ministry of Economic Affairs (a brief description of the diagrams printed by the Industrial and Consumer Cooperatives): Figure 1 Figure 2 Figure 3 Figure 4 Flow chart of synthetic route of polyaromatic ether monomer II. Flow chart of high-segment synthesis route of polyaromatic ether of the present invention Thermogravimetric analysis chart (TGA) of polyaromatic ether polymer P4-4,4F 12 572922

V. Description of the invention (9 丨 > _ Figure 5: Differential scanning analysis chart (DSC) of polyaromatic fluorene polymer P4-4,4F Figure 6. UV chart of polyaromatic ether polymer P4_4,4F Exemplified by this example, Mingming provides a kind of highly functional polyaromatic ether polymer with low dielectric, low water absorption, and high glass transition overflow, which can be applied to display electrode plates, microelectronic insulation, and inkjet printing. The jet head of the machine, the film-forming substrate of the organic photosensitive drum, and the gas film separation, etc., and the polymer can be represented by the following materials:

: The molecular structural formulas listed below are part of the names that conform to the examples in the present invention (please read the precautions on the back before filling this page).

13 572922 A7 B7 V. Description of the invention (10)

〇-Y-0 η Ρ3-Υ CF3v -0 — Y—ο- cf3

P4-Y Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs cf3

0—Y—0_ cf3

P4-2F-Y This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) n (Please read the precautions on the back before filling this page)

14 572922 A7 B7 V. Description of the invention (11)

F F

F F

P4-4F-Y Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

F F

P4-2F2CF3-Y (Please read the precautions on the back before filling this page)

This paper size applies to Chinese National Standard (CNS) A4 specification (2IOX297 mm) 15 572922 A7 B7 V. Description of the invention (12)

P4-4CF3-Y where Y can be represented by any of the following chemical structures:

Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs The following specific examples are given in conjunction with the drawings to explain the method of the present invention and its advantages in more detail. For the synthesis steps of the following Examples 1-3, please refer to the flowchart in FIG. -One U (Please read the notes on the back before filling this page)

This paper size applies the Chinese National Standard (CNS) A4 specification (210X29 * 7 mm) 16 572922 A7 B7 i 'Explanation of the invention (13) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics Example 1: No benzene ring on the center Synthesis of fluoromonomer M2 Synthesis of compound 1 In a 500-liter three-necked flask, add 200 ml of 33% NaOH aqueous solution, 160 ml of benzene, 20 g of 4-bromobenzyl bromide, 3.09 g of tetrabutylamonium bromide, and 15.68 g of ir On Pentacarbonyl, stirred at room temperature for 6 hours. Then add ether and water to extract, dry with an appropriate amount of anhydrous magnesium sulfate, concentrate, and purify by column chromatography (diluent, ethyl acetate: positively burned == 1: 8) to obtain white solid L, yield 51% 〇 Synthesis of compound 2 In a 250¾-liter three-necked flask, i6g of compound 1, 70 liters of triethylene glycob 9.14g of benzil and 6.59 ml of a 40% benzyltrimethyl ammonium hydroxide methanol solution were added under reflux. Stir for 1 hour. After cooling, the solution was poured into methanol, filtered, and dried to give the product 2 as a black solid with a yield of 89%. Synthesis of compound 3 In a 100-ml three-necked flask, 7 g of compound 2, 45 mL of toluene and 2.37 g of bicyclo (2, 2, 1) hepta-2, 5-diene were added, and stirred under reflux for 24 hours. After cooling down, the solution was poured into methanol, filtered, and dried to obtain an off-white solid product with a yield of 85%. Synthesis of compound 4 In a 100 ml three-necked flask, 7 g of compound 2, 20 ml of diphenyl ether and 1.32 g of phenylacetylene were added, and the mixture was refluxed for 72 hours. After cooling, the solution was poured into methanol, filtered, and dried to obtain the off-white solid product 4, yield 88%. This paper size applies to China National Standard (CNS) A4 (210X297 cm) (Please read the precautions on the back before filling out this page}. Packing. 17 17572922 5. Description of the invention (14) Synthesis of compound 5 in ; 'A 100 ml three-necked flask, add 7 g of compound 2, 20 ml of diphenyl ether'! 72 g of 4, 4, and coffee, and simmer for 72 hours under reflux. After cooling, then pour the solution into methanol , Filtered and dried to obtain off-white solid product 5, yield 86% ^ Synthesis of compound 6 In a 250 mL two-necked flask, 150 mL of anhydrous TfjF, 1.94 g of town metal #, 〇〇 was added. 5 g of moth. Heated to 45 ° C to activate the metal sheet. Then 15 g of 5-bromo-2-fluorobenzotrifluoride was mixed with 50 ml of THF. The reaction solution under reflux was slowly added to the reaction solution under reflux. The preparation of the Grenadine reagent was carried out in a 500-ml three-necked flask. Anhydrous diethyl ether 2000W and β 7 g of ^ Zi Caicai borate were added at -7fC to agitate the freshly prepared Grenadine reagent. Add to the reaction solution slowly, return to room temperature, and stir overnight. After adding ether and water for extraction, it was dried with an appropriate amount of anhydrous magnesium sulfate, concentrated, and then purified by column chromatography (diluent, ethyl acetate, n-hazanol = 1: 8) to obtain white solid 6. Yield 71%. _ Synthesis of monomer M2 'Printed by a Consumer Consumption Agency of the Intellectual Property Bureau of the Ministry of Economic Affairs in a 100 mL two-necked flask, added 30 mi of iM sodium carbonate solution, 30 ml of toluene, 0.28 g of tetrakis (triphenyl phosphine) palladium (0), 5 g of compound 3 and 3.88 g of compound 6, and stirred under reflux for 5 days. Return to room temperature ', then extract with ether and water, dry with an appropriate amount of anhydrous magnesium sulfate, and concentrate Then, column chromatography (the paper size of the dike solution is applicable to China National Standard (CNS) A4 (210X297 mm) 18 572922

V. Description of the invention (15) Ethyl acetate: n-hexane yield 82%. 2) Purified to obtain white solid M2. Example 2: Synthesis of non-fluorine-containing monomer 3 on the central benzene ring In a 100 mL two-necked flask, 30 ml of a 1 M sodium carbonate solution, 30 W of toluene, 0.88 g of tetrakis (tHphenyi phospMne) palladium (0), 5. 8 g of compound 4 and 3 88 g of compound 6 were reacted under reflux for 5 days. Return to room temperature, then extract with ether and water, dry with an appropriate amount of anhydrous magnesium sulfate, concentrate, and purify by column chromatography (diluent, ethyl acetate: n-hexane = 1: 20) to obtain a white solid. Clumsy, yield 85%. (Read the precautions on the back before you fill out this page.) • 燊 · Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Example 2: The synthesis of non-fluorine-containing monomers on the central benzene ring 3 in a 100 mL Add 30 mi of it to the neck; [μ sodium carbonate solution, 30 ml of toluene, 0.28 g of tetrakis (triphenyl phosphine) palladium (0), 5.8 g of compound 4 and 3.88 g of compound 6 and stir The reaction was carried out under reflux for 5 days. Return to room temperature, then add ether and water, extract, dry with an appropriate amount of anhydrous magnesium sulfate, concentrate, and purify by column chromatography (diluent, ethyl acetate: n-hexane = 1: 20) to obtain a white solid. City stand, yield 85%. Example 3: Synthesis of fluorine-free monomer M4 on the central benzene ring In a 100 mL three-necked flask, 30 ml of a 1 M sodium carbonate solution, 30 ml of toluene, and 0.28 g of tetrakis (triphenyl phosphine) were added. The scale applies to the Chinese National Standard (CNS) A4 specification (210X 297 mm) 19 palladiUm (0), 6.9 g of compound 5 and 3 88 g of compound, and it is reacted under reflux for 5 days. Return to room temperature, then extract with ether and water, dry with an appropriate amount of anhydrous magnesium sulfate, concentrate, and purify by column chromatography (diluent, ethyl acetate: n-hexane = 1: 20) to obtain a white solid. Cong ^, yield 88%. For the synthesis steps of the following embodiments 4 and 5, please refer to the flowchart in FIG. Example 4: Synthesis of synthetic compound 7 (4,4'-Fluorophenyl benzoin) with fluorinated monomer M4_2F on the central benzene ring Weigh 11.6 g (0.178 mol) of KCN into a 500 ml reactor and add 90 ml of water to make After dissolving, add 100g (0.806mol) of 4-fluorobenzaldehyde and 108ml of alcohol, heat to reflux, react for 7-8 hours, cool, pour into a separatory funnel and extract with CH2C12, take the organic layer to concentrate, and then vacuum The raw materials were distilled off, and the product was purified by column chromatography. The extraction solvent was n-hexane, and the collection range was determined by TLC film, and then recrystallized with alcohol to obtain a yellow-green solid product, 26.9 g (62%) ° Rf ( EAC: Hexane = 1: 20): 0.48. '' The synthetic scale of compound 8 (4,4'-Fluorophenyl benzil) printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs took 16.6 g (0.0663 mol) of CuS04-5H20 and 13 ml of water and 26.7 ml of pyridine in a 250 ml reactor. After heating under reflux, 18 g (0_0322 mol) of compound was added, and after reacting for 6 to 7 hours, it was cooled, filtered, and the filter cake was washed with water several times, dried, and recrystallized with alcohol to obtain a yellow solid product 8. 6.73 g (85%). Rf (EAC: Hexane = 1: 20): This paper size applies the Chinese National Standard (CMS) A4 specification (210X297 mm) 20 572922 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (17) 0.6 〇Synthesis of compound 9 (2,5-Bis (4-bromophenyI) -3,4-bis (4-fIuorophenyl) cyclope-nta-2,4-dienone) Compound 2.21g and 1,3-bis ( 4-bromo phenyl) prop an-2-one 2.46g In a 50ml reactor, add 5ml of triethylene glycol, heat to 120 ° C, and after it is completely dissolved, add Ci〇Hi7NO (Benzyltrimethyl ammonium hydeoxide 40wt% solution in methanol) 1 ml, after reacting for 10 minutes, cool, add methanol and stir, filter and dry to obtain a black solid product £, 3.1g (75%). Rf (EAC: Hexane = 1: 20): 0.47 〇 The compound of compound 10 (2,5-Bis (4_bromophenyl) -3,4_bis (4-fluorophenyl) cyclopenta_2,4-dienone) is 4.0 g and 4 -4'-diphenylacetylene 2.2 g was put into a 50ml reactor, nitrogen gas was added, 5ml diphenyl ether was added, heated to 220 ° C, reacted for 3 days, cooled, methanol was added, stirred, filtered and dried, and an off-white solid product was obtained. 5 〇g (86〇 / 〇). Rf (EAC: Hexane = 1: 20): 0.67 〇 Compound 11 (4,4 ,,-Dibromo_2,, 3,5,6, -tetra (4-fluorophenyl) [l, l '; 4', 1 ”] Terphenyl) Synthesis Weigh out 4.0 g of compound and 2.2 g of 4-4'-di- (4-fluorophenyl) acetylene in a 50 ml reactor, add nitrogen, and add (please read the precautions on the back before filling in this Page)-Loading ·

1. The paper size of the 1T line is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) 21 572922 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (18) diphenyl ether 5ml, heated to 220 ° C, react for 3 days, cool, add methanol, stir, filter and dry to obtain an off-white solid product 11 «, 5.2g (88%) 〇Rf (EAC: Hexane = 1: 20): 0.64 〇 monomer M4- 2F Synthetic Weighing Compound U 3.4g and 4-fluoro-3-trifluoromethyl phenyl boronic acid 2.1g into a 250ml reactor, add toluene 60ml and 1M Na2C03 sol'n 48ml and Pd (PPh3) 4 0.15g (0.14mmol), heated to 110 ° C, reacted for 5 days, cooled, poured into a separatory funnel to extract the upper liquid with EAC, filtered and concentrated by removing water, and then purifying the product by column chromatography, extracting the solvent It was n-hexane, and the collection range was checked with a TLC film to obtain a white solid product M4-2F, 3.5 g (80%). Rf (EAC: Hexane = 1: 20): 0.45 〇 Example 5: Synthesis of compound JJ_3.5g (4.58mmol) and 4-fluoro-3-trifluoromethyl phenyl boronic Acid 2.1 g (10.l mmol) was placed in a 250 ml reactor. Toluene 60 ml and the prepared 1M Na2C03 sol, 48 ml and Pd (PPh3) 4 0.15 g (0.14 mmol) were added. The mixture was heated to 110 ° C and reacted for 5 days. , Cool, pour into the separatory funnel to extract the upper liquid with EAC, remove the water, filter and concentrate, then purify the product by column chromatography, extract the solvent as n-hexane, and cooperate with the TLC film to check the collection range to obtain white solid product M4 -4F, 3.53g (83%). Rf (EAC: Hexane = 1: 20): 0_44. UV (THF, log ε = 4.84): 257.8 nm 〇 (Please read the precautions on the back before filling this page) Binding and binding The paper size applies the Chinese National Standard (CNS) A4 specification (210X 297 public envy) 22 572922 A7 __ B7 V. Description of the invention (19) Example 6: Synthesis of diol monomers Synthesis of a single 2,2 A (ZJ'-Dihydroxydiphenyl adamantine)

Weigh out 2-adamantanone 1 Og (0.0667mol) and phenol 42g (0.446mol) in a 100ml reactor, add C6H13SH 0.5m to heat to 58 ° C, pass in HC1 gas, react for 3-4 hours, add water to filter and It was washed several times with water and recrystallized with alcohol to obtain a single white solid product of 2,2A, 20.3g (95%). Rf (EAC: Hexane = 1: 1) = 0.4. MS (FAB) [m / z (rel. Intensity)]: 320.1 (M +, 80); 227.1 ([M-C6H50] +, 30); 154 ([M-C12H10O2] +, 100). Synthesis of Single 1,1C (1,1 ′ -Dihydroxydiphenyl cyclododecane)

(Please read the notes on the back before filling this page)

1. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the 1T line printed a scale and took 5 g (0.0274 mol) and 20 g (0.213 mol) of cyclododecanone into a 100 ml reactor, added C6H13SH 0.2 m to heat to 58 ° C, and passed HC1 After 2 days of reaction, it was filtered by adding water and washed several times with water. The filter cake was stirred and filtered with Hexane, and then recrystallized with alcohol to obtain the white solid product Cuixiang 1,1C, 5.02g (52%). Rf (EAC: Hexane = l: This paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 23 572922 A7 __B7_ V. Description of the invention (20) 1): 0.35 〇MS (FAB) [m / z (rel. intensity)]: 352.2 (M +, 100). Synthesis of monomer 1,3 A (1,3'-Dihydroxydiphenyl adamantane) Weigh out compound 1,3-Dibromoadamantane 6g (0.0204mol) and phenol 60g (0.63 8mol) in a 250ml reactor, and add FeCl3 l.lg ( 0.00678mol), heated to 80 ° C, reacted overnight, added water to the furnace, washed with water several times, and recrystallized with methanol to obtain the white solid product monomer MA, 3.26g (50%). Rf (EAC: Hexane = 1: 1): 0.3. MS (EI, 20 eV) [m / z (rel. Intensity)]: 320 · 1 (M +, 100) 0 Example 7: Synthesis of polymer (please refer to the flowchart in Figure 3) Polymer P2-2, 2A P2-4, 4F P2-4, 40 P2-1, 3A P2-1, 1C Synthesis-binding · (Please read the precautions on the back before filling this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

This paper size applies to Chinese National Standard (CNS) A4 (210X297 mm) 24 572922 A7 ____B7 V. Description of Invention (21) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs P2-2, 2A as an example, take the order Body Ml 0.5g (0.7074mmol) and 2,29-dihydroxydiphenyl adamantane 0.2238g (0.7074mmol) and K2C〇3 0.215g (1.56mmol) into a 50ml reactor, and a Dean-Stark trap, and after adding nitrogen, add 5ml of DMAc and 10m of anhydrous toluene are heated to 140 ~ 150 ° C and the toluene is discharged to remove the water. After the water is removed, heat to 180 ° C for 3 days. After the reaction is completed, cool down. Add 8ml of THF to dilute the polymer. Into a conical flask filled with 100ml methanol, filaments are generated, filtered, dried, and washed with boiling water several times, filtered, dried, and then dissolved in THF. It was then poured into a conical flask containing 100 ml of methanol, filtered, and dried to give a white silky product, 0.68 g (91%). iH-NMR (CDC13; 500Hz): 5 (ppm) = 6.92-7.66 (m, 34H), 1.71-3.19 (m, 14H). 13C-NMR (CDC13; 300Hz): δ (ppm) = 121_8 (m, CVC〗, Q-; Q_-F3), 154.1 (s, C3, CO), 119.3 (s, C4), 132.0 (s, C5 ), 136.7 (d, C6), 125.3 (s, C7), 137.5 (d, C8), 132.1 (s, C9), 132.18 (s, C10), 142.8 (d, Cn), 142-2 (s, C12), 141_8 (s, C13), 141-0 (d, C14), 132.3 (s, C15), 132.1 (d, C16), * 127 · 4 (d, C17), 130.1 (s, C18), 154.6 (d, C19, CO), 119.3 (s, C20), 127.4 (s, C21), 144.4 (s, C22), 49.8 (s, C23), 3 2.6 (s, C24), 33.3 (s, C25 ), 27.5 (s, C26) '37.8 (s, C27). 19F-NMR (CDC13; 400Hz): 5 (ppm) =-62.83 (s, 6F, FA). Synthesis of polymer P3-2, 2A P3-4, 4F P3-4, 40 P3-1, 3A P3-l, lc (Please read the precautions on the back before filling this page)-Packing. Thread paper size is applicable China National Standard (CNS) A4 specification (21 × 297 mm) 25 572922 A7 B7 V. Description of invention (22 23 16

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, taking P3-2,2A as an example, taking 0.5g (0.6387mmOl) and 2,2'-dihydroxydiphenyl adamantane (0.2046g) (0.6387mmol) and K2C03 0.194g ( (1.41mmol) into a 50ml reactor, and a Dean-Stark trap. After introducing nitrogen, add 5ml of DMAc and 10m of anhydrous toluene to heat to 140 ~ 150 ° C and discharge toluene to remove water. After removing water, Heat to 180 ° C for 3 days. After the reaction is completed, cool down. Add thF 8ml diluted polymer to the cone-shaped tincture filled with 100ml methanol. Then, filaments are generated, filtered, dried, and then The silk was washed several times with boiling water, filtered, dried, and then dissolved in THF, and then poured into a conical flask containing 100 ml of methanol, filtered, and dried to obtain a white silk product. 634g (90%). ! H-NMR (CDC13; 500Hz): 5 (ppm) = 6.88- 7.86 (m5 40H), 1.68-3.21 (m, 14H). 13C-NMR (CDC13; 300Hz): 6 (ppm) = 121.2 (m, Ci / C2, CC-F3) »153.8 (s, C3, CO) ^ 120.1 (s, C4), 131.8 (s, C5), 136.2 (d, C6), 125.1 (s, c7), 137.4 (d, C8), 131.8 (s, C9), 132.1 (s, C10), 142_7 (d, C "), 142.5 (s, C12), 142.1 (s, C13), 141.5 (d, C14), 132.1 (s, c15), 132.8 (d, C16), 126.2 (d, C17), 130.4 (s, C18) 141.95 (d, C19), this paper Standards are applicable to Chinese National Standard (CNS) A4 specifications (21 OX297 mm) (Please read the precautions on the back before filling out this page}. Installation ·-Thread 26 572922 A7 B7 V. Description of the invention (23) 141.74 (d, C20), 132.19 (s, C21), 132.1 (s, C22), 137.42 (s5 C23), 140.2 (s, C24), 140.3 (s, C25), 132.6 (s, C26,), 132.2 (s, C27 ) '126.3 (s, C28)' 154.2 (d, C29, CO) '119.1 (s, C30)' 127-5 (s, C31), 144.6 (s, C32), 49.4 (s5 C33), 32 · 4 (s, C34), 33.1 (s, C35), 27.3 (s, C36), 37.4 (s, C37) 〇19F-NMR (CDC13; 400Hz): 5 (ppm) =-62.81 (s, 6F, Fa) Polymer P4_2,2A P4_4,4F P4-4,40 P4-1,3A Synthesis of P4-1, 1C (Please read the precautions on the back before filling this page) • Packing · 17

2,84 dihydroxydiphenyl adamantane 0.184g (0.5822mmol) and K2C03 〇.177g (1.28mmol) into a 50ml reactor, and set up a Dean-Stark trap. After aeration, add 5ml DMAc and 10ml anhydrous toluene Toluene was discharged to 140 ~ 150 ° C for water removal. After the water was removed, it was heated to 180 ° C and reacted for 3 days. After the reaction was completed, it was cooled down. 8 ml of THF was added to dilute the polymer. In the conical flask, filaments are generated, filtered, dried, and the filaments are washed with boiling water several times. The thread is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. This paper is printed in accordance with Chinese national standards (CNS ) M size (210X297 public envy) 27 572922 A7 B7 V. Description of the invention (24) Filter, dry, and then dissolve with THF, then pour into a conical flask containing 100ml methanol, filter, and dry to get white Filamentary product, 616 g (90%). b-NMR (CDC13; 500Hz): 6 (ppm) = 6.58— 7.76 (m, 42H), 1_71-3.19 (m, 14H). 13C-NMR (CDC13; 300Hz): 5 (ppm) = 121.3 (m, C "., £-£ -F3), 152.85 (s, C3, C_0), 119.21 (s5 C4), 131.25 (s, C5) , 135.98 (d, C7), 134.80 (s, C8), 125.41 (s, C9), 131.32 (s, C10), 139.54 (s, C " / C14), 140.24 (s, C12), 139_41 (s, C13), 132.24 (d, C15), 114.58 (d, C16), 154.82 (d, C17), 1 54.83 (s3 C18), 119.41 (s, C19), 127.21 (s, C20), 144.24 (s, C21 ), 49.35 (s, C22), 32.32 (s, C23), 33.35 (s, C24), 27.75 (s, C25), 37.84 (s, C26). 19F-NMR (CDC13; 400Hz): 5 (ppm) =-62.84 (s, 6F, FA). Polymer Synthesis of P4-2CF3-2, 2A P4-2CF3-1, 3A P4-2CF3-CF3 (Please read the precautions on the back before filling out this page) Order Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

Taking P4-2CF3-2,2A as an example, take 0.5g (0.503mmol) of monomer M4-2CF3 and 2,29-dihydroxydiphenyl adamantane 0.159g (0.503mmol) and K2C03 0.153g (1.1ml) to 50ml reaction Dean-Stark trap, and after adding nitrogen, DMAc 5ml thread is added. Paper size is applicable to Chinese National Standard (CNS) A4 specification (2IOX297 mm) 28 572922 Employees ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs printed A7 ___ ___B7 V. Description of the invention (25) and 10m of anhydrous toluene are heated to 140 ~ 150 ° C and the toluene is discharged to remove water. After removing the water, heat to 180 ° C and react for 3 days. After the reaction, cool and add THF. After 8ml of diluted polymer was placed in a conical flask filled with 100ml methanol, filaments were generated, filtered, and dried. After the filaments were washed with boiling water several times, filtered and dried After being dissolved in THF, it was poured into a conical flask containing 100 ml of methanol and filtered and dried to obtain a white silky product, 0.6 g (91%). ^ -NMR (CDC13; 500Hz): 5 ( ppm) = 6.84- 7.64 (m, 40H), 1.70— 3.17 (m, 14H). 13C-NMR (CDC13; 300Hz): 5 (ppm) = 121.1 (m, C " C2, £ __Q-F3), 152_8 (s, C3, CO), 119.18 (s, C4), 132.1 (s, C5) , 125.1 (d, C6), 136.45 (s, C7), 135.21 (s, C8), 130_8 (s, C10), 138-46 (d, Cu), 141.0 (d, C12), 140.86 (d, C13 ), 139.29 (s, C14), 134-3 (d, C15), 122.4 (s, C17), 127-45 (d, C18), 128.35 (m, C19, Q-CF3), 129_5 (m, C20 , C-F3), 141.34 (s, C2i), 139.83 (s, C22), 131.72 (s, C23), 126.91 (s, C24), 125.3 (s, C25), 154.77 (s, C26, CO), 119.5 (s, C27), 127.3 (s, C28), 144.33 (s, C29) '49-91 (s, C30), 32.22 (s, C31), 33.26 (s, C32), 27.47 (s, C33) , 3 7.93 (s, C34). 19F-NMR (CDCI3; 400Hz): δ (ppm) = ~ 64.07 (d, J = 83 · 2Ηζ, 6F, FA), 62.86 (s, 6F, FB) 0 polymer P4-2F2CF3-2, 2A P4 -2F2CF3-1, 3A P4-2F2CF3-CF3 synthesis (Please read the precautions on the back before filling this page).

、 TT line This paper size is applicable to Chinese National Standard (CNS) A4 specification (21 〇X 297 mm) 29 572922 A7 ____B7 V. Description of invention (26)

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, taking P4-2F2CF3_2,2A as an example, taking the monomer M4-2F2CF3 0.4g (0.3 883mmol) 2,2'-dihydroxydiphenyl adamantine 0.1244g (0.3883mmol) and K2C03 〇 · 11 8g (0.86mmol) into a 50ml reactor, and a Dean-Stark trap. After introducing nitrogen, add 5ml of DMAc and 10m of anhydrous toluene and heat to 140 ~ 150 ° C to discharge the toluene to remove water. After removing the water, heat Allow to react for 3 days at 180 ° C. After the reaction, cool down. Add 8 ml of THF to dilute the polymer and place it in a conical flask filled with 100 mi of methanol. Filaments are generated, filtered, dried, and then The silk was washed several times with boiling water, filtered, dried, and then dissolved in THF, and then poured into a conical flask filled with 100m methanol and filtered and dried to obtain a white silky product. 47 g (90%) O-NMR (CDCI3; 500 Hz): δ (ppm) = 6.61-7.66 (m, 38H), 1.70-3.17 (m, 14H). 13C-NMR (CDC13; 300Hz): 5 (ppm) = 121.5 (m, (VC〗, £ _-e_-F3), 153.25 (s, C3, CO), 119.14 (s, C4), 3 1.75 (d , C5), 125.4 (d, C6), 135.68 (d, C7), 134.85 (s, C8), 131-59 (s, C10), 138.96 (s, Cn / C14), 140.39 (s, C12), 140.6 (d, C13), 132.55 (d, C15), 114.15 (d, C16),! 61 (d, C17), 139_3 (d, C18), 136-63 (s, C19), 134.2 (d, C20 ), 131.25 (s, C21) ,: 122_54 (s5 C22), 127.52 (d5 C23), 128.25 (Please read the precautions on the back before filling out this page) A4 specifications (210X 297 mm) 30 572922 A7 B7 V. Description of the invention (27) (Please read the notes on the back before filling this page) (m, C24, Q-CF3), 129.52 (m, C25, C- F3), 154.88 (s, C26, CO), 119.5 2 (s, C27), 127.3 (s, C28), 144.36 (s, C29), 49.91 (s5 C30), 32-21 (s, C31), 33.26 (s, C32), 27.46 (s, C33), 37.93 (s, C34 "19F-NMR (CDC13; 400Hz): 5 (PPm) =-64.10 (d, J = 84Hz, 6F, FA), 62.87 ( s, 6F, FB), — 116.98 (s, 2F , Fc) Synthesis of polymer P4_4F-2, 2A P4-4F-1, 3A P4-4F-CF3

Taking P4-4F-2,2A as an example, take the monomer M4-4F 0.4g (0.4297mmol) printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and 2,2,2,2,2-dihydroxydiphenyl adamantine 0.1377g (0.4297mmol) and K2C03 0.131g (0_95mmol) into a 50ml reactor, and set up a Dean-Stark trap. After introducing nitrogen, add 4ml of DMAc and 10m of anhydrous toluene and heat to 140 ~ 1 50 ° C. The toluene is removed to remove water. After removing the water, heat Reaction to 180 ° C for 3 days. After the reaction, cool down. After adding 8ml of THF to dilute the polymer, put it into a conical flask filled with 100ml of methanol. Then filaments are generated, filtered, dried, and then the filaments. After washing with boiling water several times, it was filtered, dried, and then dissolved in THF, and then poured into a conical flask filled with 100 mi methanol and filtered and dried to obtain a white silky product, 0.48 (90%) . This paper is suitable for 81 national standards (CNS) A4 specifications (210X297 public envy) 31 572922 A7 B7 V. Description of the invention (28) ^ -NMR (CDCI3; 500Hz): (5 (ppm) = 6.56-7.7 (m5 38H ), 1_70-3.17 (m, 14H). 13C-NMR (CDC13; 300Hz): 5 (ppm) = 121.5 (m, CXIC2, CC-F3) ^ 153 · 35 (s, C3, CO), 119.26 (s, C4), 131.18 (s, C5), 136.08 (d, C7), 134.88 (s5 C8), 125.20 (s, C9), 131.79 (s5 C10), 139-6 (s, Ch / Cm), 140.36 (s, C12), 139.87 (s, C13), 132.65 (d, C15), 114.05 (d, C16), 160.82 (d, Ci7, CF), 154-83 (s, C18), 119.47 (s, C19), 127.31 (s, C20), 144.34 (s, C21), 49.93 (s, C22), 32.24 (s, C23), 33.28 (s, C24), 27.48 (s5 C25), 37.95 (s5 C26). 19F-NMR (CDCI3; 400Hz): δ (ppm) =-62.84 (s, 6F, FB), -117.32 (s, 4F, FA) 〇 Polymer P4-4CF3-2, 2A P4-4CF3-1, 3A Synthesis of P4-4CF3-CF3 (Please read the precautions on the back before filling this page)

, 1T

Taking P4-4CF3_2,2A as an example, take monomers M4-4CF3 0.4g (0.354mmt) l) and 2,2, dihydroxydiphenyl adamantine 0.1134g (0.354mmol) and K2CO3 0.18g (0.78mmol) to 50ml reaction Dean-Stark trap, and after introducing nitrogen, add 4ml of DMAc and 10m of anhydrous toluene, and heat to 140 ~ 15 (TC discharges toluene to remove water. After removing water, heat to 1 80 ° C Response for 3 days, cooling after reaction, printed by Consumer Cooperative of Intellectual Property Bureau of Ministry of Economic Affairs

32 572922 A7 B7 V. Description of the invention (29 After adding 8ml of THF diluted polymer, put it into a conical flask filled with 100mi methanol, filaments are generated, filtered, dried, and then the filaments After washing with boiling water several times, it was filtered, dried, and then dissolved in THF, and then poured into a conical flask containing 100 mj of methanol, and filtered and dried to obtain a white silky product, 46 g (90%) ). H-NMR (CDC13; 500Hz): 5 (ppm) = 6.78- 7.63 (m5 38H), 1.70 — 3.17 (m, 14H). 13C-NMR (CDC13; 300Hz): 5 (ppm) = 153.19 (s, C3, CO), 119.06 (s, C4), 131.4 (m, C5 / Ci〇 / C16), 137.1 (m9 C7 / C8) * 125.65 (m5 C9 / C6) 5 138.36 (s, C ") '140.29 (m, C12 / C13), 139-84 (d, C14), 134.12 (d, C15), 122.79 (s, C17), 127.72 (d, C18), 128.15 (m, C19, CC-F3) ^ 154.97 (s, C21, CO), 119.59 (s, c22), 127.33 (s, C23), 144.42 (s, C24), 49.93 (s, C25), 32.23 (s, C26), 33.27 (s, C27 ), 27.47 (s, C28). 19F-NMR (CDC13; 400Hz) · 5 (ppm) = -64_1 (d, J = 86_4Hz, 12F, FA),-62.92 (s, 6F, FB) 〇 (Please Read first Note on the back, please fill in this page again) Printed by Ding-S · Mouth, Ministry of Economic Affairs, Intellectual Property Bureau, Employees' Cooperatives The following is the analysis of the polymer properties of the polyaromatic ethers of the present invention Example 8: Molecular weight and solubility analysis of the polyaromatics of the present invention Ether polymers have a high conversion rate and a high number average molecular weight (Μη) 3.14 × 104 to 1.47 × 105 g / mol; and they will all be dissolved in NMP, DMAc, DMF, THF, Chloroform, The fluorinated polymer with a central stupid ring is more soluble in Acetone, and both have good solubility. Therefore, the polyaromatic ether polymer of the present invention can be easily made into a transparent film of good quality. The paper size is applicable to Chinese national standards (CNS) A4 specification (210X297 mm) Line 33 572922 A7 __V. Description of the invention (30) Example 9: Thermal stability analysis of polyaromatic ether The present invention uses a differential scanning calorimeter (DSC) And thermogravimetric analysis (TGA) to identify the thermal stability of the polymer of the present invention. Figures 4 and 5 are examples of standard thermal analysis spectra. The thermal properties of some polyether polymers are listed in Table 1. The analysis results show (Table 1) that all polymer Tgs are concentrated between 265 ° C and 334 ° C, which is higher than the literature of 210 ° C and 300 ° C, and the temperature at a weight loss of 5% (Td5%) Most of them are concentrated between 454 ° C ~ 671 ° C. At the same time, DSC analysis showed that all polymers did not have obvious crystal peaks, which indicates that the polyaromatic ether polymer of the present invention is an amorphous material. (Please read the precautions on the back before filling out this page) Order the printed form of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Thermal analysis results of some polyether polymers of this invention Polymer Tg · (° C) Ύά5% (° C) P2-2, 2A 294 602 P2-4, 4F 294 658 P2-4, 40 285 497 P2-1, 3A 276 525 P2-1, 1C 267 454 P3-252A 310 527 P3-4, 4F 305 657 P3 -4,40 294 512 P3-1? 3A 284 514 P3-1, 1C 277 496 P4-2,2A 334 540 P4-4,4F 332 671 The paper size of this paper applies the Chinese National Standard (CNS) A4 specification (210X297 male) 34) 572922 A7 B7 V. Description of the invention (31) P4-4, 40 318 528 P4-1, 3A 310 537 P4-1, 1C 298 471 P4-2CF3-2, 2A 300 523 P4-2CF3-1, 3A 276 521 P4-2CF3-CF3 242 568 P4-2F2CF3-2, 2A 302 513 P4-2F2CF3-1, 3A 275 521 P4-2F2CF3-CF3 250 641 P4-4F-2, 2A 329 523 P4-4F-U3A 313 514 P4-4F-CF3 286 627 P4-4CF3-2, 2A 286 545 P4-4CF3-1, 3A 265 514 P4-4CF3-CF3 233 628 The polyaromatic ether polymer P4-Y of the present invention and the comparison object PO-Y The thermal property results are listed in Table 2: (Please read the precautions on the back before filling in this ) Line Ministry of Economic Affairs Intellectual Property Office employees consumer cooperatives printed

The paper size is applicable to Chinese National Standard (CNS) A4 (210X29 * 7mm) 35 572922 5. Description of the invention (32)

〇 ～ γ ～ 丨 Table 2 · Comparison of P4_γ series polymers of the present invention with similar high scores γ Thermal properties Y of Tg Td5X PO-Y --- P4-Y (° C) (° C) Tg (° C) Td5r ^^ (° C) __ (> b 332 670 0¾ 300 534 262 643 2l〇— 510 ~ QrQr 299 635 ~ ----- 257 549 (Please read the precautions on the back before filling this page j 、 · = " R Industrial Consumption Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

Hard Y From the results of thermal property analysis, the glass transition temperature (Tg) of the polyaromatic ether polymer υ of the present invention and the cracking temperature (Td5 X) at a thermal weight loss of 5% are much higher than those of PO-Y polymer. This is because compared to PO-Y, the central clumsy ring of the molecular structure of 1 > 4_γ has increased, thus increasing the stiffness of the polymer main chain and making it difficult to freely rotate, so the Tg point of P4-Υ is higher than the Tg of P0- At the same time, the Td5x of P4-Y is also higher than the Td5x of ρo-γ. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 36 572922 A7 __B7 V. Description of the invention (33) Example 10: Dielectric analysis In terms of dielectric analysis (DEA), the present invention is The polymer was dissolved in THF to form a film in a petri dish with a diameter of 5 cm. After drying at 8 ° C for 12 hours and 12 ° C for 24 hours, it was cut into 2.5cm x 2.5cm squares and plated with a thin film holder. After the gold film is applied, different frequency voltage values (Frequency; 1Hz, 10Hz, 100Hz, 1000Hz, 10000Hz) are applied at a constant temperature (room temperature), and the dielectric constant (Dielectric) is measured using a dielectric analyzer (DEA). permittivity) 〇 The measurement results show that at a frequency of 1000 Hz, the dielectric constant of the fluoropolymer is between 2.70 and 2.40, and the more fluorine atoms on the benzene ring, the lower the dielectric constant. This is Because the fluorine atom has a strong anion property, it can attract nearby electrons and prevent it from moving freely under the action of the electric field to cause resonance. This makes the molecule difficult to be polarized; when the number of electrons is equivalent, Occupied by fluorine-containing functional groups The larger free volume makes the dielectric constant lower. Therefore, considering the electron polarizability and free volume, the fluoropolymer has a lower dielectric constant. Example 11: Analysis of light absorption properties As shown in FIG. 6, the maximum aromatic absorption wavelength of the polyaromatic ether polymer P4-4, 4F of the present invention is between 350nm and 370nm. This shows that the polyaromatic polymer does not absorb visible light. At the same time, as in Example 9 The confirmed polyaromatic ether polymers of the present invention are all amorphous materials, so they can all be made into transparent films with a penetration of more than 80%. This paper standard is applicable to China National Standard (CNS) A4 Specifications (210X 297mm) (Please read the notes on the back before filling this page)

1T printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 37 572922 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (34) Example 12: Measurement of contact angle in the analysis of affinity with water In the present invention, a contact angle is measured using a dsssile drop tensiometry apparatus and the video digitization equipment; thus, the hydrophilic and hydrophobic properties of a polymer can be identified. The results show that the contact angles of fluoropolymers are all above 97 degrees, and the more fluorine atoms on the benzene ring, the larger the contact angle, indicating that the fluoropolymer has better hydrophobicity. From the above experimental results, it is verified that the polyaromatic ether series novel material of the present invention can be used as a highly functional engineering plastic. Especially in applications with high glass transition temperature (Tg), good thermal stability, low dielectric, and low water absorption, it has very good potential. The present invention has been described in detail with specific examples, and any conceivable related derivative will be encompassed within the spirit and scope of the present invention.

(Please read the notes on the back before filling this page)

38

Claims (1)

572922 (Formula II) ο—Υ—ο—— cf3 wherein Υ is the same as the structure defined in application scope 1; R3, R4, R5, and R6 each independently represent a hydrogen atom, a fluorine atom, an aliphatic alkyl group containing 1 to 2 carbon atoms, or fluorine An alkyl group; and R7 and Rs represent a hydrogen atom, a phenyl group, a fluorinated phenyl group, a tolyl group, or a trifluorotolyl group. 3.—A kind of polyaromatic ether polymer, which conforms to a chemical material represented by application scope 2; R3 and R4 each represent a hydrogen atom, which is a substance represented by the chemical formula IΠ (Formula III) wherein Y is the same as the structure defined in application scope 1; R5 and R6 each independently represent a hydrogen atom, a fluorine atom, an aliphatic alkyl group or a fluoroalkyl group containing 1 to 2 carbon atoms; and R7, R8 It represents a hydrogen atom, a phenyl group, a fludnated phenyl group, a tolyl group, or a trifluorotolyl group. 40 572922 4. A polyaromatic ether polymer conforming to a chemical material represented by application scope 2; wherein R3, R4, R5, and R6 each represent a hydrogen atom, which is a substance represented by chemical formula IV: (Formula IV) 0—Y-0—— CF3 wherein γ has the same structure as defined in application scope 1; R7 and R8 each independently represent a hydrogen atom, a phenyl group, a fluorinated phenyl group, a tolyl group or a trifluorotolyl group. 5. A kind of polyaromatic ether polymer, which conforms to a chemical material represented by application scope 2; wherein R3 and R4 represent fluorine atoms and R5 and R6 represent hydrogen atoms, that is, a substance represented by chemical formula V: Y is the same as the structure defined in application scope 1; and R7 and 仏 represent a hydrogen atom, 41 572922 phenyl, fluorinated phenyl, tolyl, or trifluorotolyl. 6. A kind of polyaromatic ether polymer, which conforms to a chemical material represented by application scope 2; wherein R3 and R4 represent hydrogen atoms and R5 and R6 represent 3-trifluoromethylphenyl, that is, as in formula VI One substance represented: (Formula VI) —Y-0— CF3 where γ has the same structure as defined in application scope 1; and R7 and R8 represent hydrogen atom phenyl, fluorinate / (^ henyl), tolyl, or trioxytolyl. Cap range Alas, > Ο—Υ—0—— cf3 42 572922 F F 43 572922 44 572922 Where Y z 8. A kind of polyaromatic ether monomer, such as a substance represented by Chemical Formula VIII: (Formula VIII) wherein Ri, R2, R3, R4, R5, and R6 each independently represent a hydrogen atom, a fluorine atom, an aliphatic alkyl group or a fluoroalkyl group containing 45 572922 1 to 2 carbon atoms; and R7, It represents a hydrogen atom, a phenyl group, a fluorinated phenyl group, a tolyl group, or a trivinyl group. 9. A polyaromatic ether monomer, which conforms to a chemical material represented by the scope of application 8; Ri represents trifluoromethyl and R2 is a hydrogen atom, which is a substance represented by chemical formula IX: (Formula IX) wherein R3, R4, R5, and R6 each independently represent a hydrogen atom, a fluorine atom, an aliphatic alkyl group or a fluoroalkyl group containing 1 to 2 carbon atoms; and R7, R8 represent a hydrogen atom, benzene Radical, fluorinated phenyl, tolyl or trifluorotolyl. 10. A kind of polyaromatic ether monomer, which conforms to a chemical material represented by application scope 9; wherein R3 and R4 each represent a hydrogen atom, which is a substance represented by chemical formula X: Is R7 CF3 (Formula X) 46 572922 wherein R5 and R6 each independently represent a hydrogen atom, a fluorine atom, an aliphatic alkyl group or a fluoroalkyl group containing 1 to 2 carbon atoms; and R7 and R8 represent a hydrogen atom, Phenyl, fluorinated phenyl, tolyl or trifluorotolyl. 11. A polyaromatic ether monomer, which conforms to a chemical material represented by application scope 9; wherein R3, R4, R5 and respectively represent hydrogen atoms, that is, a substance represented by chemical formula XI: (Formula XI) F CF3 wherein R5 and R6 each independently represent a hydrogen atom, a fluorine atom, an aliphatic alkyl group or a fluoroalkyl group containing 1 to 2 carbon atoms; and R7 and R8 represent a hydrogen atom, a phenyl group, and a fluorinated phenyl group (fluorinated phenyl), tolyl, or trifluorotolyl. 12. A kind of polyaromatic ether monomer, which conforms to a chemical material represented by application scope 9; wherein R3 and R4 represent fluorine atoms and R5 and R6 represent hydrogen atoms, that is, a substance represented by chemical formula XII: F F 47 572922 (Formula χπ) where 7, is represented by a hydrogen atom, phenyl, fluorinated phenyl fluorene 11 (^ 1 ^ to? 1 ^ 1 ^ 1), tolyl or trifluorotolyl. 13 = —A kind of polyaromatic ether monomer, which conforms to one of the chemical materials represented by application scope 9: where R3 and R4 represent hydrogen atoms and R5 and R6 represent 3-trifluoromethylphenyl, that is, as in formula XIII One substance represented: (Formula XIII) F cf3 where R7 and R8 represent hydrogen atom, phenyl, fluorinated phenyl, tolyl or trifluorotolyl. ,.Eight 48 572922 F F 49 572922 F F 50 572922 51