A polyarylate containing polyphenylene ether structure and preparation method thereof

Abstract

The present invention discloses a polyarylate containing a polyphenylene ether structure and a preparation method thereof, comprising the following steps: configuring an aromatic diformyl chloride solution, adding dropwise under nitrogen protection, adding dropwise to a mixed solution of a dihydroxy-terminated polyphenylene ether, a bisphenol compound, a soluble solvent, an acid binding agent, and a catalyst, and reacting at room temperature for 6-9 hours to obtain a polymer solution; first dissolving with a soluble solvent, then precipitating in a large amount of insoluble solvents, standing, filtering, and drying to obtain a polymer solution. This method is simple to operate, the reaction conditions are easy to control, the prepared product has an ideal molecular weight, stable molecular weight control, good solubility in common organic solvents, a small dielectric constant, and excellent performance, and can be applied to fields such as 5G communications and microelectronics.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and particularly relates to a method for preparing polyarylate containing a polyphenylene ether structure in its molecular structure. Background Art

[0002] Polyarylates are a class of engineering plastics with excellent performance, boasting excellent thermal stability, mechanical properties, and optical transparency. They are often used as substrates for functional materials and are widely used in electronics, automotive components, medical devices, and other fields. With the advancement of science and technology, research on polyarylates is rapidly developing. By designing molecular structures and adjusting synthesis processes, novel polyarylate materials with diverse structural properties can be obtained.

[0003] In recent years, the rapid development of 5G communications has placed ever-more extensive and stringent requirements on materials. Polyphenylene ether (PPE) is a high-performance resin material with excellent heat resistance, solubility, dimensional stability, and a low dielectric constant. Incorporating PPE into the polyarylate backbone can further reduce its dielectric constant, enabling the preparation of new functional polyester materials with potential future applications in high-frequency communications and other fields. However, conventional polyarylates still fall short of meeting the low dielectric constant, high heat resistance, and easy processing requirements of 5G communications.

[0004] In order to meet the future needs of integrated circuit systems and expand the application areas of polyarylates, the preparation of polyarylate materials with low dielectric constants has far-reaching significance and broad economic prospects. However, there are no reports in the existing technology on the preparation of polyarylates using polyphenylene ether. Summary of the Invention

[0005] The present invention aims to provide a method for preparing polyarylate containing a polyphenylene ether structure in its molecular structure, so as to prepare a polyarylate having good heat resistance, strong processability and low dielectric constant.

[0006] To achieve the above object, the present invention provides a method for preparing a polyarylate containing a polyphenylene ether structure in its molecular structure, comprising the following steps:

[0007] S1, dissolving diformyl chloride in solvent A to prepare an acyl chloride solution;

[0008] S2, dissolving the dihydroxy-terminated polyphenylene ether, the bisphenol compound, the acid binding agent, and the catalyst in solvent A to obtain a reaction solution;

[0009] S3, at room temperature and under nitrogen protection, the acyl chloride solution obtained in step S1 was added dropwise to the reaction solution obtained in step S2 to react to obtain a polymer solution;

[0010] S4. Continue to add solvent A to dissolve, then precipitate in solvent B, let stand, filter, and dry to obtain polyarylate containing a polyphenylene ether structure.

[0011] Preferably, the diphthaloyl chloride comprises terephthaloyl chloride, isophthaloyl chloride or a mixture of terephthaloyl chloride and isophthaloyl chloride.

[0012] Preferably, the dosage ratio of diformyl chloride to solvent A is 0.02-0.25 g / ml; the ratio of the total molar number of the bisphenol compound and the dihydroxy-terminated polyphenylene ether to the molar number of diformyl chloride is 1:0.8-2; the molar amount of the acid binding agent is 0.5-3 times that of the diformyl chloride, and the molar amount of the catalyst is 0.5-10% of the diformyl chloride.

[0013] Preferably, the bisphenol compound is one or more of bisphenol A, tetramethyl bisphenol A, bisphenol F or tetramethyl bisphenol F.

[0014] Preferably, the acid binding agent is one or more of triethylamine, potassium tert-butoxide, pyridine, and diisopropylethylamine.

[0015] Preferably, the catalyst comprises 4-dimethylaminopyridine.

[0016] Preferably, the solvent A, i.e., the readily soluble solvent, is one or more of tetrahydrofuran, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, toluene, chloroform, chlorobenzene, and xylene.

[0017] Preferably, the solvent B, i.e., the insoluble solvent, is one or more of ethanol, butanol, methanol, acetonitrile, isopropanol, butanone, and acetone.

[0018] Preferably, the structure of the double-terminated hydroxyl polyphenylene ether is:

[0019]

[0020] wherein R1, R2, R3, R4, R5, and R6 are independently a hydrogen atom or an alkyl group, R1 to R6 are the same or different, and the value of m+n is 10 to 50.

[0021] The present invention provides a polyarylate containing a polyphenylene ether structure prepared by the preparation method of the polyarylate containing a polyphenylene ether structure.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] The present invention adopts double-terminal polyphenylene ether, general diphenol and common aromatic diformyl chloride for polycondensation. By adjusting the monomer ratio, a series of polyarylates containing polyphenylene ether structure can be obtained. The product molecular weight is ideal, and the number average relative molecular weight is 2.4×10 4 ~3.0×10 4 The weight average relative molecular weight is 8.5×10 4 ~10×10 4The dielectric constant is 2.0 to 2.4, significantly lower than that of traditional polyarylates (3.2 to 3.6). Aside from the byproduct salt, no other harmful substances are produced during the entire reaction process. During solution polymerization, the polymerization conditions are mild and require no heating, making the reaction environmentally friendly. Furthermore, the operation is simple, the reaction conditions are easily controlled, and the cost is low, making it suitable for industrial production and promising for applications in microelectronics, optoelectronics, and other fields. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is the hydrogen nuclear magnetic resonance spectrum of the polyarylate product 1 obtained in Example 1 of the present invention ( 1 HNMR) spectra;

[0025] Figure 2 This is a Fourier transform infrared spectrum (FT-IR) diagram of the polyarylate product 1 prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0026] The present invention will be further described below with reference to specific examples, but the present invention is not limited thereto in any way.

[0027] Example 1

[0028] (1) Add 0.62 g of isophthaloyl chloride and 8 ml of anhydrous THF (tetrahydrofuran) into a beaker and stir to dissolve to obtain an acyl chloride solution;

[0029] (2) 4.8 g of hydroxy polyphenylene ether (PPO, molecular weight 1600, purchased from Saudi Basic Industries (China) Co., Ltd., model No. Noryl SA90, m+n=10) was added to a three-necked flask equipped with a stirring device, and 8 ml of anhydrous THF was added. After dissolution, 0.02 g of DMAP (4-dimethylaminopyridine) and 0.9 ml of triethylamine were added, and nitrogen was introduced into the reaction solution for protection;

[0030] The acyl chloride solution was added dropwise to the three-necked flask at room temperature and the reaction was continued for 6 hours. As the reaction proceeded, the viscosity of the system increased significantly, from the initial clear solution to a viscous state. After the reaction was completed, the gas was stopped, and the polymerization solution was obtained.

[0031] (2) Add 20-80 ml of THF to the polymerization solution, stir evenly, and then pour into methanol. The product will precipitate in the solution and filter. The filtered product is washed with water and alcohol multiple times and then dried to obtain polyarylate product 1.

[0032] The polyarylate synthesis route prepared in this embodiment is as follows:

[0033]

[0034] like Figure 1As shown, it is the hydrogen nuclear magnetic resonance spectrum of the polyarylate product 1 prepared in Example 1. The chemical shift signals at δ = 9.04, 8.48, and 7.52 ppm are proton peaks on the benzene ring of isophthaloyl chloride, the chemical shift signals at δ = 6.96 and 6.47 ppm are proton peaks on the benzene ring of the polyphenylene ether chain segment, the chemical shift signal at δ = 2.12 ppm is the methyl peak on the benzene ring of the polyphenylene ether chain segment, and the chemical shift signal at δ = 1.69 ppm is the methyl peak on the main chain of the polyphenylene ether. The above signals all indicate the synthesis of polyarylate.

[0035] like Figure 2 The following is an infrared spectrum of the polyarylate product 1 obtained in Example 1. -1 and 1381cm -1 They are the stretching vibration peak and bending vibration peak of the polyphenylene ether main chain - CH3, 1605cm -1 and 1473cm -1 It is the skeleton vibration peak of the benzene ring of the polyphenylene ether main chain, 1188cm -1 It is the stretching vibration peak of the ether bond, 1744 cm -1 The peak at is C=O stretching vibration. The above results indicate that polyarylate containing polyphenylene ether structure in the molecular structure is synthesized.

[0036] Example 2

[0037] (1) Add 0.62 g of terephthaloyl chloride and 8 ml of anhydrous THF (tetrahydrofuran) into a beaker and stir to dissolve to obtain an acid chloride solution;

[0038] In a three-necked flask equipped with a stirring device, 4.8 g of hydroxy polyphenylene ether (PPO, molecular weight 1600, purchased from Saudi Basic Industries (China) Co., Ltd., model No. Noryl SA90, m+n=10) was added, and 8 ml of anhydrous THF was added. After dissolution, 0.02 g of DMAP (4-dimethylaminopyridine) and 0.9 ml of triethylamine were added, and nitrogen protection was introduced into the reaction solution.

[0039] The acyl chloride solution was added dropwise into the three-necked flask at room temperature and the reaction was continued for 6 h. After the reaction was completed, the gas was stopped to obtain a polymerization solution;

[0040] (2) Add 20-70 ml of THF to the polymerization solution, stir evenly, and then pour into methanol. The product will precipitate in the solution and filter. The filtered product is washed with water and alcohol multiple times and then dried to obtain polyarylate product 2.

[0041] The polyarylate synthesis route prepared in this embodiment is as follows:

[0042]

[0043] The polyarylate product 2 obtained in Example 2 was characterized by nuclear magnetic resonance. The chemical shift signal at δ = 8.36 ppm was a proton peak on the benzene ring of terephthaloyl chloride, the chemical shift signals at δ = 6.96 and 6.47 ppm were proton peaks on the benzene ring of the polyphenylene ether segment, the chemical shift signal at δ = 2.09 ppm was a methyl peak on the benzene ring of the polyphenylene ether segment, and the chemical shift signal at δ = 1.69 ppm was a methyl peak on the polyphenylene ether backbone chain. These signals all indicate the synthesis of the polyarylate.

[0044] The polyarylate product 2 obtained in Example 2 was characterized by infrared spectroscopy. -1 and 1381cm -1 They are the stretching vibration peak and bending vibration peak of the polyphenylene ether main chain - CH3, 1605cm -1 and 1473cm -1 It is the skeleton vibration peak of the benzene ring of the polyphenylene ether main chain, 1188cm -1 It is the stretching vibration peak of the ether bond, 1744 cm -1 The peak at is C=O stretching vibration. The above results indicate that polyarylate containing polyphenylene ether structure in the molecular structure is synthesized.

[0045] Example 3

[0046] (1) Add 0.78 g of isophthaloyl chloride, 0.54 g of terephthaloyl chloride, and 10 ml of anhydrous THF (tetrahydrofuran) into a beaker and stir to dissolve to obtain an acyl chloride solution;

[0047] In a three-necked flask equipped with a stirring device, 6 g of hydroxy polyphenylene ether (PPO, molecular weight 1600, purchased from Saudi Basic Industries (China) Co., Ltd., model No. Noryl SA90, m+n=10) was added, and 10 ml of anhydrous THF was added. After dissolution, 0.03 g of DMAP (4-dimethylaminopyridine) and 1.1 ml of triethylamine were added, and nitrogen protection was introduced into the reaction solution.

[0048] The acyl chloride solution was added dropwise into the three-necked flask at room temperature and the reaction was continued for 6 h. After the reaction was completed, the gas was stopped to obtain a polymerization solution;

[0049] (2) Add 25-75 ml of THF to the polymerization solution, stir evenly, and then pour into methanol. The product will precipitate in the solution and filter. The filtered product is washed with water and alcohol multiple times and then dried to obtain polyarylate product 3.

[0050] The polyarylate synthesis route prepared in this embodiment is as follows:

[0051]

[0052] The polyarylate product 3 obtained in Example 3 was characterized by nuclear magnetic resonance. Chemical shift signals at δ = 9.04, 8.49, and 7.52 ppm were proton peaks on the benzene ring of isophthaloyl chloride, a chemical shift signal at δ = 8.36 ppm was a proton peak on the benzene ring of terephthaloyl chloride, chemical shift signals at δ = 6.96 and 6.47 ppm were proton peaks on the benzene ring of the polyphenylene ether segment, a chemical shift signal at δ = 2.08 ppm was a methyl peak on the benzene ring of the polyphenylene ether segment, and a chemical shift signal at δ = 1.69 ppm was a methyl peak on the polyphenylene ether main chain. All of these signals indicate the synthesis of the polyarylate.

[0053] The polyarylate product 3 obtained in Example 3 was characterized by infrared spectroscopy. -1 and 1381cm -1 They are the stretching vibration peak and bending vibration peak of the polyphenylene ether main chain - CH3, 1605cm -1 and 1474cm -1 It is the skeleton vibration peak of the benzene ring of the polyphenylene ether main chain, 1188cm -1 It is the stretching vibration peak of the ether bond, 1744 cm -1 The peak at is C=O stretching vibration. The above results indicate that polyarylate containing polyphenylene ether structure in the molecular structure is synthesized.

[0054] Example 4

[0055] (1) Add 1.45 g of isophthaloyl chloride, 0.62 g of terephthaloyl chloride, and 12.5 ml of anhydrous THF (tetrahydrofuran) into a beaker and stir to dissolve to obtain an acyl chloride solution;

[0056] In a three-necked flask equipped with a stirring device, 4.8 g of hydroxy polyphenylene ether (PPO, molecular weight 1600, purchased from Saudi Basic Industries (China) Co., Ltd., model No. Noryl SA90, m+n=10) and 1.6 g of bisphenol A were added, and 12.5 ml of anhydrous THF was added. After dissolution, 0.06 g of DMAP (4-dimethylaminopyridine) and 2.8 ml of triethylamine were added, and nitrogen protection was introduced into the reaction solution.

[0057] The acyl chloride solution was added dropwise into the three-necked flask at room temperature and the reaction was continued for 6 h. After the reaction was completed, the gas was stopped to obtain a polymerization solution;

[0058] (2) Add 25-80 ml of THF to the polymerization solution, stir evenly, and then pour into methanol. The product will precipitate in the solution and filter. The filtered product is washed with water and alcohol multiple times and then dried to obtain polyarylate product 4.

[0059] The polyarylate synthesis route prepared in this embodiment is as follows:

[0060]

[0061] The polyarylate product 4 obtained in Example 4 was characterized by nuclear magnetic resonance. Chemical shift signals at δ = 9.02, 8.43, and 7.64 ppm were proton peaks on the benzene ring of isophthaloyl chloride, a chemical shift signal at δ = 8.32 ppm was a proton peak on the benzene ring of terephthaloyl chloride, chemical shift signals at δ = 7.31 and 7.14 ppm were proton peaks on the benzene ring of bisphenol A, chemical shift signals at δ = 6.96 and 6.47 ppm were proton peaks on the benzene ring of the polyphenylene ether chain segment, a chemical shift signal at δ = 2.08 ppm was a methyl peak on the benzene ring of the polyphenylene ether chain segment, and a chemical shift signal at δ = 1.73 ppm was a methyl peak on the main chain of polyphenylene ether and bisphenol A. All of the above signals indicate the synthesis of the polyarylate.

[0062] The polyarylate product 4 obtained in Example 4 was characterized by infrared spectroscopy. 2970 cm -1 and 1377cm -1 They are the stretching vibration peak and bending vibration peak of -CH3 on the main chain of polyphenylene ether and bisphenol A, 1605cm -1 and 1474cm -1 It is the skeleton vibration peak of the benzene ring of the polyphenylene ether main chain, 1188cm -1 It is the stretching vibration peak of the ether bond, 1744 cm -1 The peak at is C=O stretching vibration. The above results indicate that polyarylate containing polyphenylene ether structure in the molecular structure is synthesized.

[0063] Examples 1-3 show that whether terephthaloyl chloride, isophthaloyl chloride, or a mixture of the two chlorides can be reacted with hydroxyl polyphenylene ether to prepare a novel polyarylate material. Example 4 shows that adding a second bisphenol monomer to the polymerization system can also successfully prepare a polyarylate material. The number average relative molecular weight of the prepared polyarylate is 2.9×10 4 , 2.4×10 4 , 2.4×10 4 , 3.0×10 4 The results indicate that this method can be used to synthesize polyarylate materials with stable and considerable relative molecular weight. The dielectric constant of the polyarylate films prepared by solution casting is 2.1-2.4, which is significantly improved compared to the dielectric properties of traditional bisphenol A polyarylate.

[0064] Anyone skilled in the art will be able to utilize the above-disclosed technical content to make many possible changes and modifications to the technical solution of the present invention, or to modify it into equivalent embodiments with equivalent changes, without departing from the scope of the technical solution of the present invention. Therefore, any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of the present invention that do not depart from the content of the technical solution of the present invention shall still fall within the scope of protection of the technical solution of the present invention.

Claims

1. A method for preparing polyarylate containing a polyphenylene ether structure, characterized in that: The following steps are involved: (1) Add 1.45 g of isophthaloyl chloride, 0.62 g of terephthaloyl chloride, and 12.5 ml of anhydrous THF (tetrahydrofuran) into a beaker and stir to dissolve to obtain an acyl chloride solution; In a three-necked flask equipped with a stirring device, 4.8 g of hydroxy polyphenylene ether (molecular weight 1600, m+n=10) and 1.6 g of bisphenol A were added, and 12.5 ml of anhydrous THF was added. After dissolution, 0.06 g of DMAP and 2.8 ml of triethylamine were added, and nitrogen was introduced into the reaction solution for protection. The acyl chloride solution was added dropwise into the three-necked flask at room temperature and the reaction was continued for 6 h. After the reaction was completed, the gas was stopped to obtain a polymerization solution; (2) Add 25-80 ml of THF to the polymerization solution, stir evenly, and then pour into methanol. The product will precipitate in the solution, filter it, and wash the filtered product with water and alcohol several times before drying to obtain a polyarylate product; The synthetic route of polyarylate is as follows: ； Among them, m+n=10.

2. The polyarylate containing a polyphenylene ether structure prepared by the method for preparing the polyarylate containing a polyphenylene ether structure according to claim 1.

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