A polyarylene ether resin and its preparation method

Abstract

This application discloses a novel polyarylene ether resin, wherein its number average molecular weight is 1000-4000, preferably 2000-3000, and its structural formula is shown in formula (1) below. In formula (1), R1, R2, R3, and R4 are selected from hydrogen, halogens, and C1-C4. 12 Alkyl; R5 and R6 are selected from hydrogen or methyl; R7-R9 are selected from hydrogen or C1-C2. 18 Alkyl groups; m and n are integers from 1 to 50. This application also discloses a method for preparing a novel polyarylene ether resin, comprising the following steps: adding polyarylene ether and polyphenol compound to a good solvent of polyarylene ether, then adding peroxide, and carrying out a first reaction; after the first reaction is completed, cooling down, and pouring the obtained first reaction solution into a poor solvent to precipitate dihydroxy polyarylene ether; then adding a capping agent and a catalyst, and carrying out a second reaction; after the second reaction is completed, pouring the obtained reaction solution into a poor solvent to precipitate the novel polyarylene ether resin shown in formula (1).

Description

[0001] This case is a divisional application of the application filed on December 31, 2019, entitled "A Novel Polyarylene Ether Resin and Its Preparation Method Thereof", with application number CN201911409978.2. Technical Field

[0002] This application relates to the field of polymer synthesis, specifically to a novel polyarylene ether resin and its preparation method. Background Technology

[0003] In recent years, with the continuous development of the information industry, the requirements for signal transmission speed and transmission loss have become increasingly higher. In the traditional copper clad laminate manufacturing industry, the most widely used matrix resin is epoxy resin. However, due to its poor dimensional stability at low temperatures and excessively high dielectric constant in the high-frequency range, traditional epoxy resin can no longer meet the needs of the technological development of electronic products. Therefore, the development of copper clad laminates with low dielectric constant and dielectric loss has become one of the research hotspots of major copper clad laminate manufacturers.

[0004] Thermoplastic polyarylene ethers (PPEs) possess excellent density-to-weight (Dk) and flame-retardant (Df) properties. Furthermore, given their low moisture absorption and good flame retardancy, thermoplastic PPEs are promising substrates for copper-clad laminates. High-molecular-weight PPEs are themselves thermoplastic engineering plastics with excellent heat resistance, good mechanical properties, and dimensional stability. However, high-molecular-weight PPEs require high processing temperatures and exhibit high viscosity during processing, thus limiting their direct application in the copper-clad laminate field.

[0005] To address these issues, a common approach is to reduce the molecular weight of polyarylene ethers (PLEs) and simultaneously attach reactive groups to both ends of the PLE, transforming it into a thermosetting resin. This allows for cross-linking reactions with other resins, thereby maximizing the excellent Dk and Df properties of PLEs.

[0006] Chinese patent CN109161014A discloses a method for preparing low molecular weight double-hydroxyl-terminated polyarylene ethers. The two hydroxyl groups at both ends can react with acid, acid anhydride, epoxy group, cyanate ester and other groups. However, the reaction with these active groups cannot fully utilize the excellent dielectric properties of polyarylene ether resin.

[0007] Chinese patent CN100402582C provides an epoxy-functionalized polyarylene ether resin, which can only react with acid anhydrides, acids, cyanate esters, etc., and cannot fully utilize the excellent dielectric properties of polyarylene ether. Summary of the Invention

[0008] To address the aforementioned issues, this application provides a novel polyarylene ether resin and its preparation method. This novel polyarylene ether, while having a low molecular weight, contains unsaturated aliphatic groups, allowing it to be blended with unsaturated resins such as styrene, polybutadiene, and allyl without introducing highly polar groups, thus fully utilizing the excellent dielectric properties of polyarylene ether.

[0009] The specific technical solution of this application is as follows:

[0010] 1. A novel polyarylene ether resin, wherein its number-average molecular weight is 1000-4000, preferably 2000-3000, and its structural formula is shown in the following formula (1):

[0011]

[0012] In formula (1), R1, R2, R3, and R4 are selected from hydrogen, halogens, and C1-C. 12 Alkyl; R5 and R6 are selected from hydrogen or methyl; R7-R9 are selected from hydrogen or C1-C2. 18 Alkyl groups; m and n are integers from 1 to 50.

[0013] 2. The novel polyarylene ether resin according to item 1, wherein the halogen is bromine or chlorine; C1-C 12 Alkyl groups are C1-C 12 Straight-chain alkyl or branched alkyl

[0014] Preferably, the C1-C 12 The alkyl group is methyl.

[0015] 3. The novel polyarylene ether resin according to item 1 or 2, wherein R7 is a C1-C6 alkyl group; preferably R7 is a C1-C4 alkyl group.

[0016] 4. The novel polyarylene ether resin according to any one of items 1 to 3, wherein R5 and R6 are methyl.

[0017] 5. The novel polyarylene ether resin according to any one of items 1 to 4, wherein the intrinsic viscosity of the resin is 0.04 to 0.20 dL / g, preferably 0.06 to 0.14 dL / g.

[0018] 6. A method for preparing a novel polyarylene ether resin, comprising the following steps:

[0019] Polyarylene ether and polyphenol compound are added to a good solvent for polyarylene ether, and then peroxide is added to carry out the first reaction. After the first reaction is completed, the temperature is lowered, and the resulting first reaction solution is poured into a poor solvent to precipitate dihydroxy polyarylene ether.

[0020] Then, a capping agent and a catalyst are added to the dihydroxy polyarylene ether to carry out a second reaction. After the second reaction is completed, the resulting second reaction solution is poured into a poor solvent to precipitate the novel polyarylene ether resin shown in formula (1).

[0021]

[0022] In equation (1), R1, R2, R3, and R4 are selected from hydrogen, halogens, and Cl-C. 12 Alkyl; R5 and R6 are selected from hydrogen or methyl; R7-R9 are selected from hydrogen or C1-C2. 18 Alkyl groups; m and n are integers from 1 to 50.

[0023] 7. The preparation method according to item 6, wherein the halogen is bromine or chlorine; C1-C 12 Alkyl groups are C1-C 12 Straight-chain alkyl or branched alkyl

[0024] Preferably, the C1-C 12 The alkyl group is methyl.

[0025] 8. The preparation method according to item 7 or 8, wherein R7 is a C1-C6 alkyl group; preferably R7 is a C1-C4 alkyl group.

[0026] 9. The preparation method according to any one of items 6 to 8, wherein R5 and R6 are methyl groups.

[0027] 10. The preparation method according to any one of items 6 to 9, wherein the intrinsic viscosity of the resin is 0.04 to 0.20 dL / g, preferably 0.06 to 0.14 dL / g.

[0028] 11. The preparation method according to any one of items 6 to 10, wherein after adding polyarylene ether and polyphenol compound to a good solvent of polyarylene ether, a peroxide is added at 50 to 110°C, preferably at 70 to 100°C, to carry out a first reaction, and after the first reaction is completed, the temperature is lowered to 0 to 60°C, and the obtained first reaction solution is poured into a poor solvent to precipitate dihydroxy polyarylene ether.

[0029] 12. The preparation method according to any one of items 6 to 11, wherein the first reaction time is 1 to 4 hours, preferably 3 hours; more preferably, the second reaction time is 1 to 40 hours, more preferably 4 to 24 hours.

[0030] 13. The preparation method according to any one of items 6 to 12, wherein when the obtained first reaction solution is poured into a poor solvent to precipitate dihydroxy polyarylene ether, the volume ratio of the first reaction solution to the poor solvent is 1:(1 to 10), preferably 1:(3 to 6);

[0031] Preferably, when the obtained second reaction solution is poured into a poor solvent to precipitate the novel polyarylene ether resin, the volume ratio of the second reaction solution to the poor solvent is 1:(1-10), more preferably 1:(3-6).

[0032] 14. The preparation method according to any one of items 6 to 13, wherein after heating the good solvent of the polyarylene ether to 80 to 110°C, the polyarylene ether and the polyphenol compound are added to the good solvent of the polyarylene ether, and then a peroxide is added at 50 to 110°C, preferably at 70 to 100°C, to carry out the first reaction.

[0033] 15. The preparation method according to any one of items 6 to 14, wherein the good solvent is selected from any one or more of toluene, chlorobenzene, chloroform, and xylene.

[0034] 16. The preparation method according to any one of items 6 to 15, wherein the undesirable solvent is selected from any one or more fatty alcohols.

[0035] 17. The preparation method according to any one of items 6 to 16, wherein the polyphenol compound is selected from any one of bisphenol A, tetramethylbisphenol A, tetramethylbiphenyl, dihydroxydiphenyl ether, and phenolic varnish.

[0036] 18. The preparation method according to any one of items 6 to 17, wherein the peroxide is selected from one or more of dicumyl peroxide, tert-butylcumyl peroxide, di-tert-butyl peroxide, diisopropylbenzene hydrogen peroxide, tert-butyl hydrogen peroxide, tert-butyl acetate peroxide, tert-butyl benzene peroxide, diisobutyryl peroxide, tert-hexyl isopropyl peroxide monocarbonate, dilauroyl peroxide, tert-butyl peroxyisopropyl monocarbonate, tert-butyl acetate peroxide, tert-butyl peroxide, benzoyl peroxide, or benzoyl peroxide derivatives.

[0037] 19. The preparation method according to any one of items 6 to 18, wherein the capping agent is selected from any one or more of fumaric acid, fumaric anhydride, maleic anhydride, monomethyl fumaric acid, dimethyl fumaric acid, diethyl fumaric acid, and dibutyl fumaric acid.

[0038] 20. The preparation method according to any one of items 6 to 19, wherein the catalyst is selected from any one or more of N-ethylmorpholine, N,N'-diethylpiperazine, N,N-dimethylcyclohexylamine, bis(2-dimethylaminoethyl) ether, triethylamine, N,N-dimethylbenzylamine, N-ethylmorpholine, triethanolamine, pyridine, 4-dimethylaminopyridine, N,N'-dimethylaniline, dicyclohexylcarbodiimide, and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride; preferably, the catalyst comprises 4-dimethylaminopyridine.

[0039] 21. The preparation method according to any one of items 6 to 20, wherein the mass ratio of the polyphenol compound to the polyarylene ether is 1:100 to 25:100, preferably 5:100 to 20:100.

[0040] 22. The preparation method according to any one of items 6 to 21, wherein the mass ratio of the peroxide to the polyarylene ether is 1:100 to 15:100, preferably 1:100 to 10:100.

[0041] 23. The preparation method according to any one of items 6 to 22, wherein the mass ratio of the capping agent to the polyarylene ether is 5:100 to 40:100, preferably 15:100 to 30:100.

[0042] 24. The preparation method according to any one of items 6 to 23, wherein the mass ratio of the catalyst to the polyarylene ether is 10:100 to 50:100, preferably 15:100 to 30:100.

[0043] The effects of the invention

[0044] The novel polyarylene ether resin provided in this application contains unsaturated aliphatic groups, which can be blended with unsaturated resins such as styrene, polybutadiene, and allyl without introducing highly polar groups, thus fully utilizing the excellent dielectric properties of polyarylene ethers. Using the preparation method of this application to prepare the novel polyarylene ether resin, by controlling the reaction temperature, reaction time, the content and type of undesirable solvents added, and the types of good solvents, peroxides, capping agents, and catalysts, and within the range of the added substances, the end-capping degree of the obtained polyarylene ether resin is above 80%, and can reach up to 99.9%. Detailed Implementation

[0045] The following will provide a detailed description of this application.

[0046] It should be noted that the terms "comprising" or "including" as used throughout the specification and claims are open-ended and should be interpreted as "comprising but not limited to". The following descriptions in the specification are preferred embodiments for carrying out this application; however, these descriptions are for the purpose of understanding the general principles of the specification and are not intended to limit the scope of this application. The scope of protection of this application shall be determined by the appended claims.

[0047] <Novel Polyarylene Ether Resins>

[0048] The structural formula, number-average molecular weight, and intrinsic viscosity of the novel polyarylene ether resin of this application are as follows.

[0049] (Structural formula)

[0050] The structural formula (1) of the novel polyarylene ether resin of this application is:

[0051]

[0052] In formula (1), R1-R9 are hydrogen or substituents, and m and n are repeating units.

[0053] R1, R2, R3, and R4 are individually or simultaneously hydrogen, halogen, or C1-C. 12 Alkyl group; R5 and R6 are each or simultaneously hydrogen or methyl; R7-R9 are each or simultaneously hydrogen or C1-C 18 Alkyl groups.

[0054] The halogen may be chlorine, bromine or iodine, preferably chlorine or bromine.

[0055] C1-C 12 Alkyl groups are C1-C 12 Straight-chain alkyl or branched-chain alkyl.

[0056] Preferably, the C1-C 12 The alkyl group is methyl.

[0057] Preferably, R5 and R6 are both methyl groups.

[0058] Preferably, R7 is an alkyl group of C1-C6 independently or simultaneously; more preferably, R7 is an alkyl group of C1-C4 independently or simultaneously, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, etc.

[0059] m is an integer from 1 to 50, for example, it can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 18, 20, 22, 25, 27, 30, 32, 35, 37, 40, 42, 45, 47, 50, etc.; n is an integer from 1 to 50, for example, it can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 18, 20, 22, 25, 27, 30, 32, 35, 37, 40, 42, 45, 47, 50, etc.

[0060] (Number average molecular weight)

[0061] This application describes the determination of the molecular weight distribution of a novel polyarylene ether resin using gel permeation chromatography (GPC). The chromatographic system consisted of an Agilent Series 1100 system, including an isobaric pump, an autosampler, a temperature-controlled column compartment, and a multi-wavelength detector. The elution solvent was chloroform containing 50 ppm di-n-butylamine. The sample solution was filtered through a Gelman 0.45 μm injection filter prior to GPC analysis; no further sample preparation was performed. The injection volume was 50 mL, and the eluent flow rate was set to 1 mL / min. The detection wavelength was set to 280 nm. Data were acquired and processed using an Agilent ChemStation with integrated GPC data analysis software. The molecular weight distribution results were calibrated using polystyrene standards. Without any corrections, the results are reported as Mn / Mw. The number-average molecular weight Mn of the novel polyarylene ether resin was measured to be 1000–4000 g / mol, for example, 1000–3500 g / mol, 1500–3200 g / mol, 1800–3000 g / mol, 2000–3000 g / mol, 2050–2800 g / mol, 2100–2500 g / mol, etc.

[0062] (Intrinsic viscosity)

[0063] In this application, the intrinsic viscosity of a novel polyarylene ether resin that had been dried under vacuum at 125°C for 1 hour was measured in chloroform at 25°C. The concentration of the novel polyarylene ether resin in chloroform was 0.008 g / mL. The intrinsic viscosity of the novel polyarylene ether resin of this application is 0.04–0.20 dL / g, preferably 0.06–0.14 dL / g, more preferably 0.07–0.13 dL / g, more preferably 0.08–0.125 dL / g, and most preferably 0.1–0.12 dL / g. For example, it can be 0.04 dL / g, 0.05 dL / g, 0.06 dL / g, 0.07 dL / g, 0.08 dL / g, 0.09 dL / g, 0.1 dL / g, 0.11 dL / g, 0.12 dL / g, 0.13 dL / g, 0.14 dL / g, 0.15 dL / g, 0.16 dL / g, 0.17 dL / g, 0.18 dL / g, 0.19 dL / g, 0.20 dL / g, etc. The intrinsic viscosity of the novel polyarylene ether resin within the scope of this application allows for better miscibility with epoxy resins and hydrocarbon resins, making it suitable for printed circuit board manufacturing processes.

[0064] <Preparation Method of Novel Polyarylene Ether Resin>

[0065] The preparation method of the novel polyarylene ether resin of this application includes the following two steps.

[0066] (1) Add polyarylene ether and polyphenol compound to a good solvent of polyarylene ether, then add peroxide to carry out the first reaction. After the first reaction is completed, cool down and pour the obtained first reaction solution into a poor solvent to precipitate dihydroxy polyarylene ether.

[0067] (2) Add a capping agent and a catalyst to the dihydroxy polyarylene ether to carry out a second reaction. After the second reaction is completed, pour the resulting second reaction solution into a poor solvent to precipitate the novel polyarylene ether resin shown in formula (1).

[0068]

[0069] In equation (1), R1, R2, R3, and R4 are selected from hydrogen, halogens, and Cl-C. 12 Alkyl; R5 and R6 are selected from hydrogen or methyl; R7-R9 are selected from hydrogen or C1-C2. 18 Alkyl groups; m and n are integers from 1 to 50.

[0070] (Steps for generating dihydroxy polyarylene ethers)

[0071] In this application, "good solvent" refers to a solvent that has a strong dissolving ability for polymeric solutes and whose interaction parameter χ with the polymeric solute is less than 0.5. Specifically, the good solvent may be selected from any one or more of toluene, chlorobenzene, chloroform, and xylene, but is not limited thereto. Preferably, it contains one or two of toluene and xylene; more preferably, it contains toluene.

[0072] The polyphenol compound may be selected from any one of bisphenol A, tetramethylbisphenol A, tetramethylbiphenyl, dihydroxydiphenyl ether, and phenolic varnish, but is not limited thereto. Phenolic varnish includes condensates of phenol and formaldehyde and condensates of cresol and formaldehyde. Tetramethylbisphenol A or bisphenol A is preferred; bisphenol A is more preferred.

[0073] Preferably, the mass ratio of the polyphenol compound to the polyarylene ether is 1:100 to 25:100, for example, it can be 1:100, 2:100, 3:100, 4:100, 5:100, 6:100, 7:100, 8:100, 9:100, 10:100, 11:100, 12:100, 13:100, 14:100, 15:100, 16:100, 17:100, 18:100, 19:100, 20:100, 21:100, 22:100, 23:100, 24:100, 25:100, etc., and more preferably 5:100 to 20:100.

[0074] The peroxide is selected from one or more of dicumyl peroxide, tert-butylcumyl peroxide, di-tert-butyl peroxide, diisopropylbenzene hydroperoxide, tert-butyl hydroperoxide, tert-butyl acetate peroxide, tert-butyl benzene peroxide, diisobutyryl peroxide, tert-hexyl isopropyl peroxide monocarbonate, dilauryl peroxide, tert-butyl isopropyl peroxide monocarbonate, tert-butyl acetate peroxide, tert-butyl peroxide, benzoyl peroxide, or benzoyl peroxide derivatives, but is not limited thereto. Preferably, it is selected from one or more of diisopropylbenzene hydroperoxide, tert-butyl hydroperoxide, dilauryl peroxide, and benzoyl peroxide; more preferably, it contains dilauryl peroxide.

[0075] Preferably, the mass ratio of the peroxide to the polyarylene ether is 1:100 to 15:100, for example, it can be 1:100, 2:100, 3:100, 4:100, 5:100, 6:100, 7:100, 8:100, 9:100, 10:100, 11:100, 12:100, 13:100, 14:100, 15:100, etc., and more preferably 1:100 to 10:100.

[0076] Preferably, after adding polyarylene ether and polyphenol compound to a good solvent of polyarylene ether, the peroxide is added at 50-110°C, for example, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, etc., more preferably 70-100°C, to carry out the first reaction. After the first reaction is completed, the temperature is lowered to 0-60°C, for example, 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, etc., more preferably lowered to room temperature, and then the obtained first reaction solution is poured into a poor solvent to precipitate dihydroxy polyarylene ether.

[0077] Preferably, the first reaction time is 1 to 4 hours, for example, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, etc., and more preferably 3 hours.

[0078] Preferably, the obtained first reaction solution is poured into a poor solvent to precipitate the substance, then filtered and dried to obtain dihydroxy polyarylene ether.

[0079] In this application, "poor solvent" refers to a solvent that has a weak dissolving ability for polymeric solutes and whose interaction parameter χ with the polymeric solute is close to or greater than 0.5. Specifically, the poor solvent may be selected from any one or more combinations of fatty alcohols; it may be further selected from any one or more of methanol, ethanol, propanol, and isobutanol.

[0080] The volume ratio of the first reaction solution to the undesirable solvent is 1:(1 to 10), for example, it can be 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, etc., preferably 1:(3 to 6).

[0081] This application measures the molecular weight distribution of the dihydroxy polyarylene ether using gel permeation chromatography (GPC). The measurement method is the same as that used for measuring the molecular weight distribution of the novel polyarylene ether resin described above. The number-average molecular weight Mn of the dihydroxy polyarylene ether is measured to be 1000–4000 g / mol, for example, 1000–3500 g / mol, 1500–3200 g / mol, 1800–3000 g / mol, 2000–3000 g / mol, 2050–2800 g / mol, 2100–2500 g / mol, etc.

[0082] In this application, the intrinsic viscosity of dihydroxy polyarylene ether, which had been dried under vacuum at 125°C for 1 hour, was measured in chloroform at 25°C. The concentration of dihydroxy polyarylene ether in chloroform was 0.008 g / mL. The intrinsic viscosity of the dihydroxy polyarylene ether of this application is 0.04 to 0.20 dL / g, for example, it can be 0.04 dL / g, 0.05 dL / g, 0.06 dL / g, 0.07 dL / g, 0.08 dL / g, 0.09 dL / g, 0.1 dL / g, 0.11 dL / g, 0.12 dL / g, 0.13 dL / g, 0.14 dL / g, 0.15 dL / g, 0.16 dL / g, 0.17 dL / g, 0.18 dL / g, 0.19 dL / g, 0.20 dL / g, etc., preferably 0.06 to 0.14 dL / g, more preferably 0.07 to 0.13 dL / g, more preferably 0.08 to 0.125 dL / g, and most preferably 0.1 to 0.12 dL / g.

[0083] (End sealing steps)

[0084] In this application, "capping" refers to the functionalization of the terminal hydroxyl groups of the uncapped dihydroxy polyarylene ether generated above through a reaction with a capping agent, ultimately yielding a novel capped polyarylene ether resin. The degree of capping (capping rate) of the novel polyarylene ether resin is determined by characterizing both the number of terminal hydroxyl groups in the dihydroxy polyarylene ether before capping and the content of terminal hydroxyl groups in the novel polyarylene ether resin obtained after capping. The number of terminal hydroxyl groups is measured using Fourier transform infrared spectroscopy (FT-IR). A dihydroxy polyarylene ether sample is prepared by weighing 0.30 g of dihydroxy polyarylene ether powder and dissolving it in 25 mL of carbon disulfide. The dihydroxy polyarylene ether-carbon dioxide solution is measured at 3610 cm⁻¹. -1 The absorbance value was calculated to determine the terminal hydroxyl content A of the dihydroxy polyarylene ether. A novel polyarylene ether resin sample was prepared by weighing 0.30 g of the resin and dissolving it in 25 mL of carbon disulfide. The absorbance of the novel polyarylene ether resin-carbon dioxide solution was measured at 3610 cm⁻¹. -1 The absorbance value was used to calculate the terminal hydroxyl content B of the novel polyarylene ether resin. The end-capping rate of the prepared novel polyarylene ether resin is calculated as (AB) / A*100%, where A is the terminal hydroxyl content of the dihydroxy polyphenylene ether (ppm) and B is the hydroxyl content of the novel polyarylene ether resin obtained after the end-capping reaction (ppm).

[0085] The capping agent may be selected from any one or more of fumaric acid, maleic anhydride, fumaric anhydride, monomethyl fumaric acid, dimethyl fumaric acid, diethyl fumaric acid, and dibutyl fumaric acid, but is not limited thereto. Preferably, it contains maleic anhydride.

[0086] Preferably, the mass ratio of the capping agent to the polyarylene ether is 5:100 to 40:100, for example, 5:100, 8:100, 10:100, 12:100, 14:100, 16:100, 18:100, 20:100, 22:100, 24:100, 26:100, 28:100, 30:100, 32:100, 34:100, 36:100, 40:100, etc., and more preferably 15:100 to 30:100.

[0087] The catalyst may be selected from any one or more of N-ethylmorpholine, N,N'-diethylpiperazine, N,N-dimethylcyclohexylamine, bis(2-dimethylaminoethyl) ether, triethylamine, N,N-dimethylbenzylamine, N-ethylmorpholine, triethanolamine, pyridine, 4-dimethylaminopyridine, N,N'-dimethylaniline, dicyclohexylcarbodiimide, and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, but is not limited thereto.

[0088] Preferably, it contains pyridine, more preferably 4-dimethylaminopyridine, and even more preferably 4-dimethylaminopyridine and N,N-dimethylcyclohexylamine.

[0089] Preferably, the mass ratio of the catalyst to the polyarylene ether is 10:100 to 50:100, for example, 10:100, 12:100, 14:100, 16:100, 18:100, 20:100, 22:100, 24:100, 26:100, 28:100, 30:100, 32:100, 34:100, 36:100, 38:100, 40:100, 42:100, 44:100, 46:100, 48:100, 50:100, etc.; more preferably, it is 15:100 to 30:100.

[0090] The second reaction time is 1 to 40 hours, for example, it can be 1 hour, 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, 24 hours, 26 hours, 28 hours, 30 hours, 32 hours, 34 hours, 36 hours, 38 hours, 40 hours, etc., preferably 4 to 24 hours.

[0091] Preferably, under conditions of 0–60°C, such as 0°C, 10°C, 20°C, 30°C, 40°C, 50°C, 60°C, etc., a capping agent and a catalyst are added to the dihydroxy polyarylene ether to carry out a second reaction. After the second reaction is completed, the resulting second reaction solution is poured into a poor solvent to precipitate the novel polyarylene ether resin of formula (1).

[0092] In formula (1), R1-R9 are hydrogen or substituents, and m and n are repeating units.

[0093] R1, R2, R3, and R4 are individually or simultaneously hydrogen, halogen, or C1-C. 12 Alkyl group; R5 and R6 are each or simultaneously hydrogen or methyl; R7-R9 are each or simultaneously hydrogen or C1-C 18 Alkyl groups.

[0094] The halogen may be chlorine, bromine or iodine, preferably chlorine or bromine.

[0095] C1-C 12 Alkyl groups are C1-C 12 Straight-chain alkyl or branched-chain alkyl.

[0096] Preferably, the C1-C 12 The alkyl group is methyl.

[0097] Preferably, R5 and R6 are both methyl groups.

[0098] Preferably, R7 is an alkyl group of C1-C6 independently or simultaneously; more preferably, R7 is an alkyl group of C1-C4 independently or simultaneously, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl, etc.

[0099] m is an integer from 1 to 50, for example, it can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 18, 20, 22, 25, 27, 30, 32, 35, 37, 40, 42, 45, 47, 50, etc.; n is an integer from 1 to 50, for example, it can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 18, 20, 22, 25, 27, 30, 32, 35, 37, 40, 42, 45, 47, 50, etc.

[0100] This application measures the intrinsic viscosity of a novel polyarylene ether resin that has been dried under vacuum at 125°C for 1 hour in chloroform at 25°C. The concentration of the novel polyarylene ether resin in chloroform is 0.008 g / mL. The intrinsic viscosity of the novel polyarylene ether resin prepared by the method of this application is 0.04–0.20 dL / g, preferably 0.06–0.14 dL / g, more preferably 0.07–0.13 dL / g, more preferably 0.08–0.125 dL / g, and most preferably 0.1–0.12 dL / g. For example, it can be 0.04 dL / g, 0.05 dL / g, or 0. The intrinsic viscosity of the novel polyarylene ether resin prepared by the method of this application is within the range of this application, allowing for better miscibility with epoxy resins and hydrocarbon resins, making it suitable for printed circuit board manufacturing processes. The intrinsic viscosity ranges from 0.06 dL / g, 0.07 dL / g, 0.08 dL / g, 0.09 dL / g, 0.1 dL / g, 0.11 dL / g, 0.12 dL / g, 0.13 dL / g, 0.14 dL / g, 0.15 dL / g, 0.16 dL / g, 0.17 dL / g, 0.18 dL / g, 0.19 dL / g, and 0.20 dL / g.

[0101] The unsuitable solvent can be selected from any one or a combination of methanol, ethanol, propanol, and isobutanol. The volume ratio of the second reaction solution to the unsuitable solvent is 1:(1 to 10), for example, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, etc., preferably 1:(3 to 6).

[0102] Example

[0103] In the following specific embodiments, all materials and reagents are commercially available unless otherwise specified.

[0104] Synthesis of dihydroxy polyarylene ethers

[0105] Refer to Example 1

[0106] In a four-necked reactor, 500 g of toluene was added as a solvent. After heating to 90°C, 100 g of polyarylene ether (Sabic, trade name: PPO646) with a number-average molecular weight of 21000 g / mol and 6 g of bisphenol A (BPA) as a polyphenolic compound were dissolved. The mixture was cooled to 80°C, and 12 g of a 50% (w / w) toluene solution of diisopropylbenzene peroxide was added dropwise over 60 min. The reaction time was 3 h. After the reaction was completed, the mixture was cooled to room temperature, and a small amount of the reaction solution was precipitated with methanol, filtered, and dried in a vacuum oven at 60°C for 2 h to obtain dihydroxy polyarylene ether.

[0107] Refer to Example 2

[0108] In a four-necked reactor, 500 g of toluene was added as a solvent. After heating to 90 °C, 100 g of polyarylene ether (Sabic, trade name: PPO646) with a number-average molecular weight of 21000 g / mol and 6 g of bisphenol A (BPA) as a polyphenolic compound were dissolved. The mixture was cooled to 80 °C, and a 50% (w / w) toluene solution of 12 g of tert-butyl hydroperoxide was added dropwise over 60 min. The reaction time was 3 h. After the reaction was completed, the mixture was cooled to room temperature, a small amount of the reaction solution was precipitated with methanol, filtered, and dried in a vacuum oven at 60 °C for 2 h to obtain dihydroxy polyarylene ether.

[0109] Reference Example 3

[0110] In a four-necked reactor, 500 g of toluene was added as a solvent. After heating to 90 °C, 100 g of polyarylene ether (Sabic, trade name: PPO646) with a number-average molecular weight of 21000 g / mol and 6 g of bisphenol A (BPA) as a polyphenolic compound were dissolved. The mixture was cooled to 80 °C, and 12 g of a 50% (w / w) toluene solution of bislauroyl peroxide was added dropwise over 60 min. The reaction time was 3 h. After the reaction was completed, the mixture was cooled to room temperature, a small amount of the reaction solution was precipitated with methanol, filtered, and dried in a vacuum oven at 60 °C for 2 h to obtain dihydroxy polyarylene ether.

[0111] Refer to Example 4

[0112] 500g of toluene was added as a solvent to a four-necked reactor. After heating to 90°C, 100g of polyarylene ether (Sabic, trade name: PPO646) with a number-average molecular weight of 21000g / mol and 6g of bisphenol A (BPA) as a polyphenolic compound were dissolved. The mixture was cooled to 80°C, and 12g of a 50% by mass toluene solution of benzoyl peroxide was added dropwise over 60min. The reaction time was 3h. After the reaction was completed, the mixture was cooled to room temperature, a small amount of the reaction solution was precipitated with methanol, filtered, and dried in a vacuum oven at 60°C for 2h to obtain dihydroxy polyarylene ether.

[0113] Refer to Example 5

[0114] In a four-necked reactor, 500 g of toluene was added as a solvent. After heating to 90 °C, 100 g of polyarylene ether (Sabic, trade name: PPO646) with a number-average molecular weight of 21000 g / mol and 3 g of bisphenol A (BPA) as a polyphenolic compound were dissolved. The mixture was cooled to 80 °C, and 6 g of a 50% (w / w) toluene solution of bislauroyl peroxide was added dropwise over 60 min. The reaction time was 3 h. After the reaction was completed, the mixture was cooled to room temperature, and a small amount of the reaction solution was precipitated with methanol, filtered, and dried in a vacuum oven at 60 °C for 2 h to obtain dihydroxy polyarylene ether.

[0115] Reference Example 6

[0116] In a four-necked reactor, 500 g of toluene was added as a solvent. After heating to 90 °C, 100 g of polyarylene ether (Sabic, trade name: PPO646) with a number-average molecular weight of 21000 g / mol and 9 g of bisphenol A (BPA) as a polyphenolic compound were dissolved. The mixture was cooled to 80 °C, and 18 g of a 50% (w / w) toluene solution of bislauroyl peroxide was added dropwise over 60 min. The reaction time was 3 h. After the reaction was completed, the mixture was cooled to room temperature, and a small amount of the reaction solution was precipitated with methanol, filtered, and dried in a vacuum oven at 60 °C for 2 h to obtain dihydroxy polyarylene ether.

[0117] Refer to Example 7

[0118] In a four-necked reactor, 500 g of toluene was added as a solvent. After heating to 90 °C, 100 g of polyarylene ether (Sabic, trade name: PPO646) with a number-average molecular weight of 21000 g / mol and 15 g of bisphenol A (BPA) as a polyphenolic compound were dissolved. The mixture was cooled to 80 °C, and 18 g of a 50% (w / w) toluene solution of bislauroyl peroxide was added dropwise over 60 min. The reaction time was 3 h. After the reaction was completed, the mixture was cooled to room temperature, a small amount of the reaction solution was precipitated with methanol, filtered, and dried in a vacuum oven at 60 °C for 2 h to obtain dihydroxy polyarylene ether.

[0119] Reference Comparative Example 1

[0120] In a four-necked reactor, 500 g of toluene was added as a solvent. After heating to 90 °C, 100 g of polyarylene ether (Sabic, trade name: PPO646) with a number-average molecular weight of 21000 g / mol and 30 g of bisphenol A (BPA) as a polyphenolic compound were dissolved. The mixture was cooled to 80 °C, and 35 g of a 50% (w / w) toluene solution of bislauroyl peroxide was added dropwise over 60 min. The reaction time was 3 h. After the reaction was completed, the mixture was cooled to room temperature, a small amount of the reaction solution was precipitated with methanol, filtered, and dried in a vacuum oven at 60 °C for 2 h to obtain dihydroxy polyarylene ether.

[0121] Reference Comparative Example 2

[0122] In a four-necked reactor, 500 g of toluene was added as a solvent. After heating to 120 °C, 100 g of polyarylene ether (Sabic, trade name: PPO646) with a number-average molecular weight of 21000 g / mol and 15 g of bisphenol A (BPA) as a polyphenolic compound were dissolved. A 50% (w / w) toluene solution of 18 g of bislauroyl peroxide was added dropwise at 115 °C over 60 min, with a reaction time of 3 h. After the reaction was completed, the temperature was lowered to 70 °C, a small amount of the reaction solution was precipitated with methanol, filtered, and dried in a vacuum oven at 60 °C for 2 h to obtain dihydroxy polyarylene ether.

[0123] The experimental conditions of Reference Examples 1-7 and Reference Comparative Examples 1-2, as well as the parameters of the synthesized dihydroxy polyarylene ethers, are listed in Table 1 below.

[0124] Table 1

[0125]

[0126]

[0127] End capping experiment

[0128] End capping example 1

[0129] Based on Reference Example 6, the end-capping experiment was continued. The temperature was lowered to 50°C, and 25g of maleic anhydride and 2.5g of pyridine were added to the reaction vessel. 30g of a 50% N,N-dimethylcyclohexylamine toluene solution was added dropwise to the reactor. The reaction time was 24h. Then, the reaction solution was added to ethanol to precipitate, filtered, and dried in a vacuum oven at 60°C for 2h to obtain a novel polyarylene ether resin.

[0130] End capping example 2

[0131] Setting the reaction time to 12 hours is equivalent to Example 1 of the end-capping reaction;

[0132] End capping example 3

[0133] Setting the reaction time to 6 hours is equivalent to the end-capping reaction in Example 1;

[0134] End capping example 4

[0135] Setting the reaction temperature to 30°C is equivalent to the end-capping reaction in Example 1;

[0136] End capping example 5

[0137] Based on Reference Example 6, the end-capping experiment was continued. The temperature was lowered to 30°C, and 25g of maleic anhydride and 2.5g of dimethylaminopyridine were added to the reaction vessel. 30g of a 50% N,N-dimethylcyclohexylamine toluene solution was added dropwise to the reactor. The reaction time was 6h. Then the reaction solution was added to ethanol to precipitate, filtered, and dried in a vacuum oven at 60°C for 2h to obtain a novel polyarylene ether resin.

[0138] End capping example 6

[0139] Based on Reference Example 6, the end-capping experiment was continued. The temperature was lowered to 30°C, and 25g of fumaric acid and 2.5g of 4-dimethylaminopyridine were added to the reaction vessel. 30g of a 50% N,N-dimethylcyclohexylamine toluene solution was added dropwise to the reactor. The reaction time was 6h. Then the reaction solution was added to ethanol to precipitate, filtered, and dried in a vacuum oven at 60°C for 2h to obtain a novel polyarylene ether resin.

[0140] End capping example 7

[0141] Based on Reference Example 6, the end-capping experiment was continued. The temperature was lowered to 30°C, and 25g of dimethyl fumarate and 2.5g of 4-dimethylaminopyridine were added to the reaction vessel. 30g of a 50% N,N-dimethylcyclohexylamine toluene solution was added dropwise to the reactor. The reaction time was 6h. Then, the reaction solution was added to ethanol to precipitate, filtered, and dried in a vacuum oven at 60°C for 2h to obtain a novel polyarylene ether resin.

[0142] End capping example 8

[0143] Based on Reference Example 6, the end-capping experiment was continued. The temperature was lowered to 30°C, and 25g of dimethyl fumarate and 2.5g of dicyclohexylcarbodiimide were added to the reaction vessel. 30g of a 50% N,N-dimethylcyclohexylamine toluene solution was added dropwise to the reactor. The reaction time was 6h. Then, the reaction solution was added to ethanol to precipitate, filtered, and dried in a vacuum oven at 60°C for 2h to obtain a novel polyarylene ether resin.

[0144] End capping example 9

[0145] Based on Reference Example 6, the end-capping experiment was continued. The temperature was lowered to 30°C, and 10g of dimethyl fumarate and 2.5g of dicyclohexylcarbodiimide were added to the reaction vessel. 16g of a 50% N,N-dimethylcyclohexylamine toluene solution was added dropwise to the reactor. The reaction time was 6h. Then, the reaction solution was added to ethanol to precipitate, filtered, and dried in a vacuum oven at 60°C for 2h to obtain a novel polyarylene ether resin.

[0146] End capping example 10

[0147] Based on Reference Example 7, the end-capping experiment was continued. The temperature was lowered to 30°C, and 25g of maleic anhydride and 2.5g of 4-dimethylaminopyridine were added to the reaction vessel. 30g of a 50% N,N-dimethylcyclohexylamine toluene solution was added dropwise to the reactor. The reaction time was 6h. Then the reaction solution was added to ethanol to precipitate, filtered, and dried in a vacuum oven at 60°C for 2h to obtain a novel polyarylene ether resin.

[0148] End-sealing Example 11

[0149] Based on Comparative Example 1, the end-capping experiment was continued. The temperature was lowered to 30°C, and 25g of maleic anhydride and 2.5g of 4-dimethylaminopyridine were added to the reaction vessel. 30g of a 50% N,N-dimethylcyclohexylamine toluene solution was added dropwise to the reactor. The reaction time was 6h. Then, the reaction solution was added to ethanol to precipitate, filtered, and dried in a vacuum oven at 60°C for 2h to obtain a novel polyarylene ether resin.

[0150] End capping example 12

[0151] Based on Comparative Example 2, the end-capping experiment was continued. The temperature was lowered to 30°C, and 25g of maleic anhydride and 2.5g of 4-dimethylaminopyridine were added to the reaction vessel. 30g of a 50% N,N-dimethylcyclohexylamine toluene solution was added dropwise to the reactor. The reaction time was 6h. Then the reaction solution was added to ethanol to precipitate, filtered, and dried in a vacuum oven at 60°C for 2h to obtain a novel polyarylene ether resin.

[0152] End capping comparison example 1

[0153] Based on Reference Example 6, the end-capping experiment was continued. The temperature was lowered to 30°C, and 25g of acrylic acid and 17.5g of dimethylbutylamine were added to the reaction vessel. The reaction time was 6h. Then the reaction solution was added to ethanol to precipitate, filtered, and dried in a vacuum oven at 60°C for 2h to obtain a novel polyarylene ether resin.

[0154] The experimental conditions of end-capping Examples 1-12 and End-capping Comparative Example 1, as well as the end-capping rates of the resulting novel polyarylene ether resins, are listed in Table 2 below.

[0155] Table 2

[0156]

[0157]

[0158] The data in Table 2 show that the catalyst containing 4-dimethylaminopyridine exhibits high catalytic efficiency and completes the reaction within 6 hours. Using a capping agent containing maleic anhydride can achieve an even higher capping rate.

[0159] The structural formulas of the final end-capping embodiments and end-capping comparison examples are shown below.

[0160] Among them, end-capping examples 1-6 and 10-12 have the structure shown in formula (I) below, wherein R1-R4 are all hydrogen:

[0161]

[0162] End-capping examples 7-9 have the structure shown in formula (II) below, wherein R1-R4 are all hydrogen:

[0163]

[0164] The end cap comparison example 1 has the structure shown in equation (III) below:

[0165]

[0166] The above description is merely a preferred embodiment of this application and is not intended to limit the application in any other way. Any person skilled in the art may make changes or modifications to the disclosed technical content to create equivalent embodiments. However, any simple modifications, equivalent changes, and modifications made to the above embodiments based on the technical essence of this application without departing from the scope of the technical solution of this application shall still fall within the protection scope of this application.

Claims

1. A method for preparing a polyarylene ether resin, wherein, Includes the following steps: Polyarylene ether and polyphenol compound are added to a good solvent for polyarylene ether, and then peroxide is added to carry out the first reaction. After the first reaction is completed, the temperature is lowered, and the resulting first reaction solution is poured into a poor solvent to precipitate dihydroxy polyarylene ether. Then, a capping agent and a catalyst are added to the dihydroxy polyarylene ether to carry out a second reaction. After the second reaction is completed, the resulting second reaction solution is poured into a poor solvent to precipitate the polyarylene ether resin shown in formula (1). Equation (1); In formula (1), R1, R2, R3, and R4 are hydrogen; R5 and R6 are selected from hydrogen or methyl; R7 is selected from hydrogen or methyl; R8-R9 are hydrogen; m and n are integers from 1 to 50. The number-average molecular weight of the polyarylene ether resin is 1000~4000; The catalyst contains 4-dimethylaminopyridine.

2. The preparation method according to claim 1, wherein, R5 and R6 are methyl groups.

3. The preparation method according to claim 1, wherein, The intrinsic viscosity of the resin is 0.04~0.20 dL / g.

4. The preparation method according to claim 1, wherein, The intrinsic viscosity of the resin is 0.06~0.14 dL / g.

5. The preparation method according to claim 1, wherein, After adding polyarylene ether and polyphenol compound to a good solvent for polyarylene ether, peroxide is added at 50~110℃ to carry out the first reaction. After the first reaction is completed, the temperature is lowered to 0~60℃, and the resulting first reaction solution is poured into a poor solvent to precipitate dihydroxy polyarylene ether.

6. The preparation method according to claim 1, wherein, After adding polyarylene ether and polyphenol compound to a good solvent of polyarylene ether, peroxide is added at 70~100℃ to carry out the first reaction.

7. The preparation method according to claim 1, wherein, The first reaction takes 1 to 4 hours.

8. The preparation method according to claim 1, wherein, The first reaction took 3 hours.

9. The preparation method according to claim 1, wherein, The second reaction takes 1 to 40 hours.

10. The preparation method according to claim 1, wherein, The second reaction takes 4 to 24 hours.

11. The preparation method according to claim 1, wherein, When the obtained first reaction solution is poured into a poor solvent to precipitate dihydroxy polyarylene ether, the volume ratio of the first reaction solution to the poor solvent is 1:(1~10).

12. The preparation method according to claim 1, wherein, When the obtained first reaction solution is poured into a poor solvent to precipitate dihydroxy polyarylene ether, the volume ratio of the first reaction solution to the poor solvent is 1:(3~6).

13. The preparation method according to claim 1, wherein, When the obtained second reaction solution is poured into a poor solvent to precipitate polyarylene ether resin, the volume ratio of the second reaction solution to the poor solvent is 1:(1~10).

14. The preparation method according to claim 1, wherein, When the obtained second reaction solution is poured into a poor solvent to precipitate polyarylene ether resin, the volume ratio of the second reaction solution to the poor solvent is 1:(3~6).

15. The preparation method according to claim 1, wherein, After heating the good solvent of the polyarylene ether to 80~110°C, the polyarylene ether and polyphenol compound are added to the good solvent of the polyarylene ether, and then peroxide is added at 50~110°C to carry out the first reaction.

16. The preparation method according to claim 15, wherein, The peroxide is added at 70~100℃ to carry out the first reaction.

17. The preparation method according to claim 1, wherein, The good solvent is selected from any one or more of toluene, chlorobenzene, chloroform, and xylene.

18. The preparation method according to claim 1, wherein, The undesirable solvent is selected from any one or more fatty alcohols.

19. The preparation method according to claim 1, wherein, The polyphenol compound is selected from any one of bisphenol A, tetramethylbisphenol A, tetramethylbiphenyl, dihydroxydiphenyl ether, and phenolic varnish.

20. The preparation method according to claim 1, wherein, The peroxide is selected from one or more of the following: dicumyl peroxide, tert-butylcumyl peroxide, di-tert-butyl peroxide, diisopropylbenzene hydrogen peroxide, tert-butyl hydrogen peroxide, tert-butylbenzene peroxide, diisobutyryl peroxide, tert-hexylisopropyl peroxide monocarbonate, dilauryl peroxide, tert-butylperoxyisopropyl monocarbonate, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, benzoyl peroxide, or benzoyl peroxide derivatives.

21. The preparation method according to claim 1, wherein, The capping agent is selected from any one or more of fumaric acid, fumaric anhydride, maleic anhydride, monomethyl fumaric acid, dimethyl fumaric acid, diethyl fumaric acid, and dibutyl fumaric acid.

22. The preparation method according to claim 1, wherein, The catalyst further comprises any one or more of the following: N-ethylmorpholine, N,N'-diethylpiperazine, N,N-dimethylcyclohexylamine, bis(2-dimethylaminoethyl) ether, triethylamine, N,N-dimethylbenzylamine, N-ethylmorpholine, triethanolamine, pyridine, N,N'-dimethylaniline, dicyclohexylcarbodiimide, and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride.

23. The preparation method according to claim 1, wherein, The mass ratio of the polyphenol compound to the polyarylene ether is 1:100 to 25:

100.

24. The preparation method according to claim 1, wherein, The mass ratio of the polyphenol compound to the polyarylene ether is 5:100 to 20:

100.

25. The preparation method according to claim 1, wherein, The mass ratio of the peroxide to the polyarylene ether is 1:100 to 15:

100.

26. The preparation method according to claim 1, wherein, The mass ratio of the peroxide to the polyarylene ether is 1:100 to 10:

100.

27. The preparation method according to claim 1, wherein, The mass ratio of the capping agent to the polyarylene ether is 5:100 to 40:

100.

28. The preparation method according to claim 1, wherein, The mass ratio of the capping agent to the polyarylene ether is 15:100 to 30:

100.

29. The preparation method according to claim 1, wherein, The mass ratio of the catalyst to the polyarylene ether is 10:100 to 50:

100.

30. The preparation method according to claim 1, wherein, The mass ratio of the catalyst to the polyarylene ether is 15:100 to 30:100.

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