sulfur-containing compounds, sulfur-containing polyphenylene ethers, functionalized sulfur-containing polyphenylene ethers, compositions, film materials

Abstract

The functionalized sulfur-containing polyphenylene ethers provided have a chemical structure wherein each R 1 each independently H or F; Z is,, or, each R 3 each independently H, F, C 1‑6 a linear alkyl of 1 to 10 carbon atoms, C 1‑6 a fluorinated linear alkyl of 1 to 10 carbon atoms, C 3‑6 a cyclic alkyl of 3 to 10 carbon atoms, C 3‑6 a fluorinated cyclic alkyl of 3 to 10 carbon atoms, C 3‑6 a branched alkyl of 3 to 10 carbon atoms, or C 3‑6 a fluorinated branched alkyl of 3 to 10 carbon atoms, and n is an integer from 0 to 10; each R 4 each independently H, F, C each independently 1 to 60.

Description

Technical Field

[0001] This invention relates to sulfur-containing compounds, sulfur-containing polyphenylene ethers, functionalized sulfur-containing polyphenylene ethers, compositions, and membrane materials. Background Technology

[0002] With the advancement of semiconductor technology and the strong demand from fields such as AI servers, low-orbit satellites, and automotive electronics, the requirements for the dielectric and mechanical properties of high-frequency circuit boards are becoming increasingly stringent.

[0003] Polyphenylene oxide (PPO) is an engineering plastic with good dielectric properties, which can be used as a copper foil substrate material for printed circuit boards (PCBs).

[0004] However, PPO is difficult to simultaneously possess good dielectric properties and other related properties (such as dimensional stability or flame retardancy). Adding large amounts of phosphorus-containing flame retardants to improve flame retardancy may affect the dielectric properties and / or dimensional stability of PPO in subsequent applications. Therefore, PPO that balances dielectric properties with other related properties (such as dimensional stability or flame retardancy) is a key development direction for manufacturers. Summary of the Invention

[0005] One embodiment of the present invention provides a sulfur-containing compound having the following chemical structure: , where each R 1 Each is independently H or F; each R 2 Each independently is C 1-10 Alkyl or substituted with C 1-10 alkyl aryl; Z is , ,or Each R 3 Each is independently H, F, C 1-6 straight-chain alkyl, C 1-6 Fluorinated straight-chain alkyl, C 3-6 Cycloalkyl, C 3-6 Fluorinated cyclic alkyl groups, C 3-6 Branched alkyl groups, or C 3-6 Fluorinated branched alkyl groups, and n is an integer from 0 to 10.

[0006] Some embodiments of the present invention provide sulfur-containing polyphenylene ethers having the following chemical structure: , where each R 1 Each is independently H or F; Z is , ,or Each R 3 Each is independently H, F, C1-6 straight-chain alkyl, C 1-6 Fluorinated straight-chain alkyl, C 3-6 Cycloalkyl, C 3-6 Fluorinated cyclic alkyl groups, C 3-6 Branched alkyl groups, or C 3-6 The fluorinated branched alkyl group, and n is an integer from 0 to 10; each x is an integer from 1 to 60 independently.

[0007] The functionalized sulfur-containing polyphenylene ether provided in one embodiment of the present invention has the following chemical structure:

[0008] ,

[0009] Each R 1 Each is independently H or F; Z is , ,or Each R 3 Each is independently H, F, C 1-6 straight-chain alkyl, C 1-6 Fluorinated straight-chain alkyl, C 3-6 Cycloalkyl, C 3-6 Fluorinated cyclic alkyl groups, C 3-6 Branched alkyl groups, or C 3-6 Fluorinated branched alkyl groups, and n being an integer from 0 to 10; each R 4 Each independently , , ,or Each x is an independent integer from 1 to 60.

[0010] The composition provided in one embodiment of the present invention comprises 100 parts by weight of the above-described functionalized sulfur-containing polyphenylene ether and 10 to 50 parts by weight of bismaleimide resin.

[0011] The membrane material provided in one embodiment of the present invention is formed by curing the above composition. Detailed Implementation

[0012] One embodiment of the present invention provides a sulfur-containing compound having the following chemical structure: , where each R 1 Each is independently H or F; each R 2 Each independently is C 1-10 Alkyl or substituted with C 1-10 alkyl aryl; Z is , ,or Each R 3 Each is independently H, F, C 1-6straight-chain alkyl, C 1-6 Fluorinated straight-chain alkyl, C 3-6 Cycloalkyl, C 3-6 Fluorinated cyclic alkyl groups, C 3-6 Branched alkyl groups, or C 3-6 Fluorinated branched alkyl groups, and n is an integer from 0 to 10.

[0013] In some embodiments, the above-mentioned sulfur-containing compounds are synthesized as follows. It is understood that the following synthetic methods are only possible methods and not the only methods. Those skilled in the art can choose any feasible synthetic steps to synthesize the sulfur-containing compounds. For example, ketones, phenyl sulfides, and 3-mercaptopropionic acid can be reacted as follows: Next, the sulfide group is oxidized to form a sulfoxide group as follows: .

[0014] In some embodiments, the sulfur-containing compound has the following chemical structure: , ,or .

[0015] Some embodiments of the present invention provide sulfur-containing polyphenylene ethers having the following chemical structure: , where each R 1 Each is independently H or F; Z is , ,or Each R 3 Each is independently H, F, C 1-6 straight-chain alkyl, C 1-6 Fluorinated straight-chain alkyl, C 3-6 Cycloalkyl, C 3-6 Fluorinated cyclic alkyl groups, C 3-6 Branched alkyl groups, or C 3-6 The fluorinated branched alkyl group, and n is an integer from 0 to 10; each x is an integer from 1 to 60 independently. In some embodiments, each x is an integer from 1 to 35 independently.

[0016] In some embodiments, the above-mentioned sulfur-containing polyphenylene ether is synthesized as follows. It is understood that the following synthesis methods are only possible methods and not the only methods. Those skilled in the art can choose any feasible synthesis steps to synthesize the sulfur-containing polyphenylene ether. For example, a sulfur-containing compound, a polyphenylene ether oligomer, and Eaton reagent can be reacted, followed by reflux to produce the sulfur-containing polyphenylene ether as follows:

[0017] .

[0018] In some embodiments, the sulfur-containing polyphenylene ether has the following chemical structure: , ,or .

[0019] The functionalized sulfur-containing polyphenylene ether provided in one embodiment of the present invention has the following chemical structure:

[0020] ,

[0021] Each R 1 Each is independently H or F; Z is , ,or Each R 3 Each is independently H, F, C 1-6 straight-chain alkyl, C 1-6 Fluorinated straight-chain alkyl, C 3-6 Cycloalkyl, C 3-6 Fluorinated cyclic alkyl groups, C 3-6 Branched alkyl groups, or C 3-6 Fluorinated branched alkyl groups, and n being an integer from 0 to 10; each R 4 Each independently , , ,or Each x is an independent integer from 1 to 60. In some implementations, each x is an independent integer from 1 to 35.

[0022] In some embodiments, the above-described functionalized sulfur-containing polyphenylene ether is synthesized as follows. It is understood that the following synthesis methods are only possible methods and not the only methods. Those skilled in the art can choose any feasible synthesis steps to synthesize the functionalized sulfur-containing polyphenylene ether. For example, the sulfur-containing polyphenylene ether can be esterified with an acrylic acid compound or its anhydride as follows:

[0023] .

[0024] On the other hand, sulfur-containing polyphenylene ethers and R can be used. 4 -X(R 4 for , , ,or The substitution reaction (where X is Cl, Br, or I) is as follows:

[0025] .

[0026] In some embodiments, the functionalized sulfur-containing polyphenylene ether has the following chemical structure: , , , , , , , ,or .

[0027] The composition provided in one embodiment of the present invention comprises 100 parts by weight of the above-described functionalized sulfur-containing polyphenylene ether and 10 to 50 parts by weight of bismaleimide resin. If the amount of bismaleimide resin is too low, incomplete curing will result in insufficient mechanical strength and poor thermal stability of the cured product. If the amount of bismaleimide resin is too high, the cured product will be too hard and brittle, and there may even be concerns about resin exudates.

[0028] In some embodiments, the composition further comprises 1 to 50 parts by weight of a functionalized polyphenylene ether having the following chemical structure: , where R 5 for , , ,or ; and y is an integer from 1 to 60. In some embodiments, y is an integer from 1 to 20. Functionalized polyphenylene ether can further improve the mechanical strength of the cured product. If the amount of functionalized polyphenylene ether is too high, it may affect the dielectric properties of the cured product.

[0029] In some embodiments, the composition further comprises 1 to 5 parts by weight of a free radical initiator; 10 to 70 parts by weight of an inorganic filler; and 30 to 60 parts by weight of a solvent. If the amount of inorganic filler is too low, the cured product will have high thermal expansion and insufficient dimensional stability. If the amount of inorganic filler is too high, the composition will have insufficient flowability and will be brittle and hard after curing. If the amount of solvent is too low, the composition will have insufficient flowability and uneven resin dispersion. If the amount of solvent is too high, the drying and curing time will be too long, and there may even be concerns about solvent residue.

[0030] In some embodiments, the inorganic filler includes glass, quartz, ceramic, or combinations thereof. In some embodiments, the solvent includes toluene, xylene, methyl ethyl ketone (MEK), or N-methylpyrrolidone. In some embodiments, the free radical initiator includes initiators such as azobisisobutyronitrile (AIBN), benzoyl peroxide (BPO), or ammonium persulfate.

[0031] The membrane material provided in one embodiment of the present invention is formed by curing the above-described composition. For example, the composition can be impregnated with fiberglass cloth, subsequently stacked between copper foils, and heated and pressed to form a copper foil substrate. Alternatively, the composition can be formed into a membrane material by any means, such as spraying, blade coating, molding, or other methods, and then cured (e.g., dried) to obtain the membrane material.

[0032] It is understood that sulfur-containing compounds can be used to form sulfur-containing polyphenylene ethers, but are not limited thereto. Sulfur-containing polyphenylene ethers can be used to form functionalized sulfur-containing polyphenylene ethers, but are not limited thereto. Functionalized sulfur-containing polyphenylene ethers can be used to form compositions, but are not limited thereto. Compositions can be used to form membranes, but are not limited thereto. Sulfur-containing compounds, sulfur-containing polyphenylene ethers, functionalized sulfur-containing polyphenylene ethers, and compositions can be used individually in any feasible field.

[0033] To make the above-mentioned and other objects, features and advantages of the present invention more apparent and understandable, embodiments are provided below for detailed description:

[0034] [Example]

[0035] Example 1

[0036] Fluorenone (93.7 g, 520 mmol), anisole (258 g, 2080 mmol), and 3-mercaptopropionic acid (5 g, 52 mmol) were dissolved in trifluoroacetic acid (400 g), and the mixture was heated to 60 °C for 24 hours under nitrogen atmosphere. After the reaction was completed, the mixture was cooled, poured into dichloromethane, and extracted multiple times with water. The organic layer was collected and the solvent was removed to obtain a precipitated solid product. The above reaction is as follows:

[0037]

[0038] The above product (82 g, 200 mmol) was placed in a mixed solvent of dichloromethane (400 mL) and acetonitrile (50 mL) and placed in an ice bath (0 °C) under nitrogen atmosphere. Concentrated nitric acid (72 g) was added dropwise, and after the addition was complete, the temperature was raised to 25 °C and the reaction was carried out for 4 hours. Then, the mixture was poured into an aqueous NaOH solution and stirred for one hour. The mixture was then extracted multiple times with dichloromethane, the organic layer was collected, and the solvent was removed. After washing several times with ethyl acetate, the mixture was filtered and dried to obtain sulfur-containing compound S1 (81 g, yield approximately 92%). The 1H NMR spectrum of sulfur-containing compound S1 is as follows: 1 ¹H-NMR (400MHz, CDCl₃): δ 2.73 (s, 6H), 7.34–7.36 (m, 8H), 7.41–7.45 (t, 2H), 7.53–7.55 (d, 4H), 7.81–7.83 (d, 2H). The above reactions are as follows:

[0039] .

[0040] Example 2

[0041] The sulfur-containing compound S1 (0.5 g, 1.25 mmol) from Example 1 and the polyphenylene ether oligomer (4.7 g, 2.5 mmol, synthesized according to CN10872379A, Mn=1584, Mw=3524, PDI=2.22) were dissolved in 100 mL of dichloromethane at 15 °C, and Eaton's reagent (25 mL) was slowly added dropwise. The reaction was carried out at 12 °C for 24 hours. After the reaction was completed, the solution was slowly poured into deionized water at 10 °C, and the mixture was extracted several times with dichloromethane. The organic layer was collected and the solvent was removed under vacuum to obtain the solid product.

[0042] The above product was added to dimethylacetamide (DMAc, 100 mL) and heated under reflux for 6 hours. After the reaction was complete, the mixture was poured into deionized water, filtered under vacuum, and the filter cake was collected. The cake was dried in a vacuum oven (50 °C) for 6 hours to obtain sulfur-containing polyphenylene ether P1. The GPC analysis results of sulfur-containing polyphenylene ether P1 are as follows: Mn = 4343, Mw = 6027, and PDI = 1.38, with the measurement standard being ASTM D3593. The 1H NMR spectrum of sulfur-containing polyphenylene ether P1 is as follows: 1 ¹H-NMR (400MHz, CDCl₃): δ 2.06 (s, 1H), 2.13 (s, 6H), 2.19 (s, 1H), 6.37 (s, 0.4H), 6.46 (s, 0.4H), 6.48 (s, 2H), 7.09–7.13 (m, 0.6H), 7.36 (m, 0.2H), 7.76–7.78 (d, 0.1H). The above reactions are as follows:

[0043] .

[0044] In the above formula, x ranges from 2 to 22.

[0045] Example 3

[0046] The sulfur-containing polyphenylene ether P1 (5 g, 1.25 mmol), methacrylic anhydride (3.3 g, 21.5 mmol), sodium acetate (0.01 g, 1.25 mmol), and DMAc (50 mL) from Example 2 were stirred until homogeneous and heated to 75°C. After reacting for 2 hours, 500 mL of saturated brine was added dropwise to precipitate a solid. After filtration under vacuum, the filter cake was dried in a vacuum oven at 80°C for 2 hours to obtain functionalized sulfur-containing polyphenylene ether P1a. The 1H NMR spectrum of functionalized sulfur-containing polyphenylene ether P1a is as follows: 1¹H-NMR (400MHz, CDCl₃): δ 2.10 (s, 1H), 2.15 (s, 6H), 2.18 (s, 1H), 5.75 (s, 0.1H), 6.46 (s, 0.4H), 6.48 (s, 2H), 7.08–7.11 (m, 0.6H), 7.36 (m, 0.2H), 7.76–7.78 (d, 0.1H). GPC analysis of P₁a showed: Mn = 4377, Mw = 6030, PDI = 1.45. The above reaction is as follows:

[0047]

[0048] In the above formula, x ranges from 2 to 22.

[0049] Example 4

[0050] The sulfur-containing compound S1 (5 g, 12.5 mmol) from Example 1 and 2,6-dimethylphenol (3 g, 25 mmol) were dissolved in 50 mL of dichloromethane at 15 °C, and Eaton's reagent (50 mL) was slowly added dropwise. The reaction was carried out at 12 °C for 24 hours. After the reaction was completed, the solution was slowly poured into deionized water at 10 °C, and the mixture was extracted several times with dichloromethane. The organic layer was collected and the solvent was removed under vacuum to obtain the solid product.

[0051] The above product was added to DMAc (100 mL) and heated under reflux for 6 hours. After the reaction was complete, the mixture was poured into deionized water, filtered under vacuum, and the filter cake was collected. The cake was dried in a vacuum oven (50 °C) for 6 hours to obtain sulfur-containing polyphenylene ether P2. The 1H NMR spectrum of sulfur-containing polyphenylene ether P2 is as follows: 1 ¹H-NMR (400MHz, CDCl₃): δ 2.21 (s, ¹²H), 6.94–6.96 (d, ⁴H), 7.02–7.04 (d, ⁴H), 7.13 (s, ⁴H), 7.22–7.26 (m, ⁴H), 7.32–7.34 (m, ⁴H), 7.72–7.74 (d, ⁴H). The above reactions are as follows:

[0052] .

[0053] Example 5

[0054] The sulfur-containing polyphenylene ether P2 (2g, 27.3mmol), methacrylic anhydride (8.4g, 54.7mmol), sodium acetate (0.2g, 25mmol), and DMAc (20mL) from Example 4 were stirred until homogeneous and heated to 75°C. After reacting for 2 hours, 500mL of saturated brine was added dropwise to precipitate a solid. After filtration under vacuum, the filter cake was dried in a vacuum oven at 80°C for 2 hours to obtain functionalized sulfur-containing polyphenylene ether P2a. The 1H NMR spectrum of functionalized sulfur-containing polyphenylene ether P2a is as follows: 1 ¹H-NMR (400MHz, CDCl₃): δ 2.09 (s, 6H), 2.10 (s, 12H), 6.38 (s, 2H), 7.10 (s, 8H), 7.13 (s, 4H), 7.29–7.35 (m, 2H), 7.35–7.38 (m, 4H), 7.75–7.77 (d, 2H). The above reactions are as follows:

[0055] .

[0056] Comparative Example 1

[0057] SA90, purchased from Sabic, was used to measure its Mn (measurement standard: ASTM D3593), Tg (measurement standard: ASTM D3418), Td (5wt%, measurement standard: ASTM E2550), solubility in toluene (40wt%), and solubility in toluene and xylene (40wt%). The chemical structure of Sabic's SA90 is as follows: SA90 has a Mn of 2200, a Tg of 156℃, and a Td (5wt%) of 402℃, and exhibits good solubility in toluene and xylene.

[0058] Example 6

[0059] The sulfur-containing polyphenylene ether P1 in Example 2 has a Mn of 4343, a Tg of 180°C, and a Td (5wt%) of 422°C, and exhibits good solubility in toluene and xylene. As can be seen from Comparative Example 1 and Example 6, the thermal stability of sulfur-containing polyphenylene ether P1 is superior to that of SA90.

[0060] Comparative Example 2

[0061] SA9000, purchased from Sabic, was used to form a dielectric substrate. The dielectric constant (10kHz, measurement standard ASTM D150), dielectric loss (10kHz, measurement standard ASTM D150), and coefficient of thermal expansion (150℃, measurement standard ASTM E831) of the substrate were measured. The chemical structure of SA9000 is as follows: The sheet material properties were measured using Changchun phosphorus-containing polyphenylene ether (hereinafter referred to as Changchun phosphorus-containing polyphenylene ether) as referenced in TWI537281B, and Jin Yi Chemical PQ-60 (hereinafter referred to as PQ-60) as referenced in TWI678390B. The chemical structure of Changchun phosphorus-containing polyphenylene ether is as follows: The chemical structure of PQ-60 is as follows: .

[0062] The substrate formed from SA9000 has a dielectric constant (10kHz) of 2.52, a dielectric loss (10kHz) of 0.0036, and a coefficient of thermal expansion of 47.8ppm. The substrate formed from Changchun phosphorus-containing polyphenylene ether has a dielectric constant (10kHz) of 2.78, a dielectric loss (10kHz) of 0.0060, and a coefficient of thermal expansion of 48.0ppm. The substrate formed from PQ-60 has a dielectric constant (10kHz) of 3.81 and a dielectric loss (10kHz) of 0.0044.

[0063] Example 7

[0064] The substrate formed by curing functionalized sulfur-containing polyphenylene ether P1a with bismaleimide resin (BMI, purchased from K.I. Chemical) (P1a and bismaleimide resin weight ratio approximately 100:15) exhibits a dielectric constant (10 kHz) of 2.72, a dielectric loss (10 kHz) of 0.0033, and a coefficient of thermal expansion of 34.8 ppm. Compared to the substrate of Comparative Example 2, the substrate of Example 7 demonstrates superior dielectric properties and dimensional stability.

[0065] Although the present invention has been disclosed above with several embodiments, it is not intended to limit the present invention. Anyone skilled in the art can make any modifications and refinements without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be determined by the appended claims.

Claims

1. A sulfur-containing compound having the following chemical structure: ， Each R 1 Each can be H or F independently; Each R 2 Each independently is C 1-10 Alkyl or substituted with C 1-10 alkyl aryl; and Z is , ,or ; Each R 3 Each is independently H, F, C 1-6 straight-chain alkyl, C 1-6 Fluorinated straight-chain alkyl, C 3-6 Cycloalkyl, C 3-6 Fluorinated cyclic alkyl groups, C 3-6 Branched alkyl groups, or C 3-6 Fluorinated branched alkyl groups, and n is an integer from 0 to 10.

2. The sulfur-containing compound according to claim 1, having the following chemical structure: , ,or .

3. A sulfur-containing polyphenylene ether having the following chemical structure: ， Each R 1 Each can be H or F independently; Z is , ,or , Each R 3 Each is independently H, F, C 1-6 straight-chain alkyl, C 1-6 Fluorinated straight-chain alkyl, C 3-6 Cycloalkyl, C 3-6 Fluorinated cyclic alkyl groups, C 3-6 Branched alkyl groups, or C 3-6 Fluorinated branched alkyl groups, and n is an integer from 0 to 10; and Each x is an independent integer from 1 to 60.

4. The sulfur-containing polyphenylene ether according to claim 3 has the following chemical structure: , ,or .

5. A functionalized sulfur-containing polyphenylene ether having the following chemical structure: ， Each R 1 Each can be H or F independently; Z is , ,or , Each R 3 Each is independently H, F, C 1-6 straight-chain alkyl, C 1-6 Fluorinated straight-chain alkyl, C 3-6 Cycloalkyl, C 3-6 Fluorinated cyclic alkyl groups, C 3-6 Branched alkyl groups, or C 3-6 Fluorinated branched alkyl groups, and n is an integer from 0 to 10; Each R 4 Each independently , , ,or ;as well as Each x is an independent integer from 1 to 60.

6. The functionalized sulfur-containing polyphenylene ether according to claim 5 has the following chemical structure: 、 、 、 、 、 、 、 ,or 。 7. A composition comprising: 100 parts by weight of the functionalized sulfur-containing polyphenylene ether of claim 5; as well as 10 to 50 parts by weight of bismaleimide resin.

8. The composition according to claim 7, further comprising 1 to 50 parts by weight of a functionalized polyphenylene ether having the following chemical structure: , Where R 5 for , , ,or ;as well as y is an integer from 1 to 60.

9. A membrane material cured from the composition of claim 7.

Images