TWI705984B - (2,6-Dimethyl-1,4-phenylene ether) oligomers and cured products prepared therefrom - Google Patents

Abstract

A (2,6-dimethyl-1,4-phenylene ether) oligomer is represented by formula (I). The oligomer can make the subsequently prepared cured product have higher glass transition temperature (T _g ) and thermal stability, lower dielectric constant and dielectric loss, and higher elongation at break, and the oligomer It can be used for co-curing with epoxy resin.

Description

(2,6-Dimethyl-1,4-phenylene ether) oligomers and cured products prepared therefrom

The present invention relates to a (2,6-dimethyl-1,4-phenylene ether) oligomer and a cured product prepared therefrom, in particular to a (2,6 -Dimethyl-1,4-phenylene ether) oligomers and cured products prepared therefrom.

With the increasing development of semiconductor technology, the size of semiconductor components has also begun to move towards the micron area. However, the current single-layer wires are no longer sufficient and need to be developed in three dimensions. Therefore, multilayer metal interconnections must be constructed to meet current needs. In the multilayer metal interconnection process, there are two main problems that affect its performance. One of the problems is the signal transmission delay (RC delay) caused by the metal wire and the dielectric layer, and the other is the metal wire wiring. Signal interference (cross talk) in which the signal transmission speed is inversely proportional to the square root of the dielectric constant (D _k ), and the lower the dielectric loss (dissipation factor; D _f ), the easier it is to maintain the signal Integrity, so the development of materials with low dielectric constant and low dielectric loss has become the most important topic at present.

In 1956, General Electric Company developed a kind of thermoplastic polymer poly(2,6-dimethyl-1,4-phenylene oxide) [poly(2,6-dimethyl-1,4-phenylene oxide; PPO)] . Due to the rigid structure of PPO, it has the characteristics of high glass transition temperature (T _g ), low coefficient of thermal expansion (CTE) and high tensile strength. In addition, PPO also has low dielectric strength. The electrical characteristics of the electrical constant and low dielectric loss meet the requirements of the current multilayer metal interconnection process. However, PPO has a high molecular weight, and therefore has a relatively high viscosity, resulting in poor solubility and limited application range. US 6,995,195 B2 is aimed at improving PPO. Example 1 (Example 1) discloses a (2,6-dimethyl-1,4-phenylene ether) oligomer (trade name) with the following formula (A) structure OPE-2St), where t1 and t2 of formula (A) are integers from 0 to 300, respectively. [Formula (A)]

However, if the thermal, dielectric, and mechanical properties of the cured product of OPE-2St obtained by self-curing of OPE-2St are tested, it is found that the glass transition temperature (T _g ) and thermal stability of the cured product are low. Both the electric constant and the dielectric loss are relatively high, and because of the excessively brittle characteristics after the double bond is cured, the elongation at break of the cured OPE-2St is also relatively low. In addition, if the oligomer and epoxy resin are to be co-cured to improve the brittleness of the cured product, the double bond on OPE-2St cannot be combined with the epoxy group of epoxy resins. Therefore, OPE-2St cannot be co-cured with epoxy resin.

Therefore, in order to solve the various shortcomings of the aforementioned OPE-2St, how to find a cured product that can have higher glass transition temperature (T _g ) and thermal stability, lower dielectric constant and dielectric loss, and Oligomers that have higher elongation at break and can be co-cured with epoxy resin have become the main research direction at present.

In view of the various shortcomings of the aforementioned OPE-2St, the applicant in this case first found out from the various possible oligomer structures listed in the US 6,995,195 B2 patent case, and even further improved a kind that can make the subsequent cured product also have Higher glass transition temperature (T _g ) and thermal stability, lower dielectric constant and dielectric loss and higher elongation at break, and can be used as an oligomer co-cured with epoxy resin.

Therefore, the first objective of the present invention is to provide a (2,6-dimethyl-1,4-phenylene ether) oligomer.

其中， X為

或

， Y為單鍵、− CH₂ − 、− C(CH₃ )₂ − 、− C(CF₃ )₂ − 、− SO₂ − 、− O− 、− C(O)− 或

， R¹ 與R² 分別為氫、C₁ ~C₆ 烷基或苯基， m、n分別為0至50的整數， q為1至3的整數。Thus, the (2,6-dimethyl-1,4-phenylene ether) oligomer of the present invention is represented by the following formula (I): [Formula (I)]

Where X is

or

, Y is a single bond, − CH ₂ − , − C(CH ₃ ) ₂ − , − C(CF ₃ ) ₂ − , − SO ₂ − , − O − , − C(O) − or

, R ¹ and R ² are hydrogen, C ₁ to C ₆ alkyl or phenyl, m and n are integers from 0 to 50, and q is an integer from 1 to 3.

Therefore, the second object of the present invention is to provide a cured product. The cured product has both higher glass transition temperature (T _g ) and thermal stability, lower dielectric constant and dielectric loss, and higher elongation at break.

Therefore, the cured product of the present invention is prepared by curing a resin composition in the presence of a peroxide initiator, the resin composition containing the (2,6-dimethyl-) represented by the aforementioned formula (I) 1,4-phenylene ether) oligomers.

The effect of the present invention is: because the (2,6-dimethyl-1,4-phenylene ether) oligomer of the formula (I) of the present invention has vinyl phenyl ester at the end, the subsequent cured product can be simultaneously It has the characteristics of higher glass transition temperature (T _g ) and thermal stability, lower dielectric constant and dielectric loss, and higher elongation at break, and because the terminal vinyl phenyl ester is an active ester group, the formula of the present invention (I) (2,6-Dimethyl-1,4-phenylene ether) oligomers can also be used for co-curing with epoxy resin.

The content of the present invention will be described in detail below:

[(2,6- Dimethyl -1,4- Phenyl ether ) Oligomer ]

The (2,6-dimethyl-1,4-phenylene ether) oligomer of the present invention is represented by the above formula (I).

或

。Preferably, in formula (I), X is

or

.

Preferably, in formula (I), Y is _{- C (CH 3) 2 -} .

Preferably, in formula (I), R ¹ is hydrogen.

Preferably, in formula (I), R ² is hydrogen.

Preferably, in formula (I), m is an integer of 0-30.

Preferably, in formula (I), n is an integer of 0-30.

Preferably, in formula (I), q is 1 or 2.

[ Preparation method of oligomer ]

[式(III)]

[式(IV)]

其中， Y、m、n與q的定義分別同前所述。The (2,6-dimethyl-1,4-phenylene ether) oligomer of the present invention is prepared by the esterification reaction between a compound of the following formula (II) and an acid. The acid is a compound represented by the following formula (III) or the following formula (IV). [Formula (II)]

[Formula (III)]

[Formula (IV)]

Among them, the definitions of Y, m, n and q are the same as those described above.

It should be noted that the conditions of the esterification reaction can be any existing conditions that can cause the esterification reaction of alcohol and acid. The esterification reaction is, for example, but not limited to, the compound of formula (II) and acid in a solvent, dicyclohexyl Carbodiimide (N,N'-dicyclohexylcarbodiimide; DCC for short) is esterified in the presence of 4-dimethylaminopyridine (DMAP). The solvent is, for example, but not limited to, dichloromethane (DCM for short).

[ Cured ]

The cured product of the present invention is prepared by curing a resin composition in the presence of a peroxide initiator. The resin composition contains (2,6-dimethyl-1, 4-phenylene ether) oligomer.

The peroxide initiator is any existing peroxide that can initiate the polymerization reaction of the (2,6-dimethyl-1,4-phenyl ether) oligomer represented by the formula (I). The peroxide initiator is, for example, but not limited to, di-tert-butyl peroxide (DTBP), benzoyl peroxide (BPO), tert-butyl peroxide (tert-butyl peroxide), butyl hydroperoxide; TBHP), tert-butyl cumyl peroxide (TBCP) or a combination of the foregoing.

Preferably, based on the weight of the (2,6-dimethyl-1,4-phenylene ether) oligomer being 100 wt%, the weight range of the peroxide initiator is 0.1-5 wt%. More preferably, the weight range of the peroxide initiator is 0.1-2 wt%. More preferably, the weight range of the peroxide initiator is 0.5 to 1.5 wt%.

Preferably, the resin composition further contains epoxy resin, and the cured product is prepared by curing the resin composition in the presence of a peroxide initiator and a catalyst.

The epoxy resin can be any known epoxy resin. The epoxy resin is, for example, but not limited to, diglycidyl ether of bisphenol A, phenol novolac epoxy, cresol novolac epoxy, dicyclopentadiene Dicyclopentadiene-phenol epoxy, naphthalene-containing epoxy, or a combination of the foregoing. In the specific embodiment of the present invention, the epoxy resin is dicyclopentadiene phenol epoxy resin.

The catalyst can be any existing catalyst that can catalyze the co-curing of the (2,6-dimethyl-1,4-phenylene ether) oligomer represented by the formula (I) and epoxy resin. The catalyst is, for example, but not limited to, 4-dimethylaminopyridine (DMAP), imidazole, 2-ethyl-4-methylimidazole, 2 -2-methylimidazole, triphenylphosphine or a combination of the foregoing.

Preferably, based on the weight of the epoxy resin being 100 wt%, the weight of the catalyst ranges from 0.1 to 5 wt%. More preferably, the weight of the catalyst ranges from 0.1 to 2 wt%. More preferably, the weight of the catalyst ranges from 0.1 to 1.5 wt%.

The present invention will be further described with reference to the following embodiments, but it should be understood that this embodiment is only illustrative and should not be construed as a limitation of the implementation of the present invention.

(m為0至30的整數；n為0至30的整數) 見反應式I，於一個100 mL的三頸反應器中，加入0.4 g (2.86 mmol)的苯乙烯酸(4-carboxystyrene)、0.57 g (2.86 mmole)的二環己基碳二亞胺(DCC)、0.15 g (0.65 mmol)的4-二甲胺基吡啶(DMAP)與10 mL的二氯甲烷(DCM)後，於氮氣環境下冷卻至0℃攪拌30分鐘。接著，先另取2 g (1.3 mmol)末端基為酚的(2,6-二甲基-1,4-苯醚)寡聚物(SA90)溶於10 mL的二氯甲烷中，並將該含有SA90的二氯甲烷溶液逐滴加入三頸反應器中並攪拌2小時，再移除冰浴，並於室溫下反應12小時。待反應結束後，以抽氣過濾方式移除大部分二環己基脲(N,N'-dicyclohexylurea；簡稱DCU)，最後將濾液倒入甲醇中析出粗產物，並以甲醇清洗該粗產物後進行抽氣過濾，所得到的濾餅再於60℃下進行真空乾燥，即得到白色粉末產物(即實施例1的OPE-E-2St；產率約90 wt%)。實施例1之OPE-E-2St的核磁共振氫譜(¹ H-NMR，見圖1)、傅里葉轉換紅外光譜(FTIR)及凝膠滲透層析(GPC)分析結果： ¹ H-NMR (ppm, CDCl₃ ) ： δ=1.69 (6H, H¹⁰ )；2.08 (Ar-CH₃ , H⁶ , H⁸ )；5.40, 5.42 (2H, H^b )；5.88, 5.91 (2H, H^a )； 6.46 (Ar-H, H⁷ , H⁹ )；6.75, 6.77, 6.78, 6.80 (2H, H² )；6.95 (4H, H⁹ )；7.51, 7.53 (4H, H³ )；8.15, 8.17 (4H, H⁴ )。FTIR (KBr, cm^-1 ) ： ν= 1730 (C=O)；1607 (Ar-ring)；1311, 1185 (C-O-C)；988, 916 (=C-H)。GPC (NMP) ： M_n = 4268； M_w = 5799。 實施例 2 OPE-E-4St( 寡聚物 ) 實施例2之OPE-E-4St的製備方法包含下列步驟(1)至(3)：[ 反應式 II]

(1) 製備化合物 BS-Mba ： 見反應式II，在一個100 mL三頸反應器中，加入1 g (5.94 mmol)的3,5-二羥基苯甲酸甲酯(3,5-dihydroxybenzoic acid methyl ester)、2 g (13 mmol)的氯甲基苯乙烯[1-(chloromethyl)-4-ethenylbenzene]、1.8 g (13 mmol)的碳酸鉀(K₂ CO₃ )及10 mL的二甲基乙醯胺(dimethylacetamide；簡稱DMAc)後，於氮氣環境下升溫至85℃並進行反應12小時，待反應結束後，倒入甲醇水溶液(甲醇與水的重量比值為1)析出粗產物。接著，以甲醇水溶液(甲醇與水的重量比值為1)清洗該粗產物數次後，先將清洗後得到的黃色油狀粗產物溶於乙酸乙酯(ethyl acetate)中並以純水萃取三次，再取有機層以無水硫酸鎂除水，最後進行減壓濃縮除去乙酸乙酯後，得到黃色透明油狀產物(即化合物BS-Mba；產率約90 wt%)。化合物BS-Mba的¹ H-NMR及FTIR分析結果： ¹ H-NMR (ppm, DMSO-d₆ ) ： δ=3.83 (3H, H¹⁵ )；5.13 (4H, H⁹ )；5.25, 5.27, 5.29 (2H, H^b )；5.82, 5.84, 5.85, 5.87 (2H, H^a )；6.73, 6.76 (2H, H² )；6.97 (1H, H¹⁰ )；7.18, 7.20 (2H, H¹² )；7.42, 7.47 (8H, H⁴ , H⁵ )。FTIR (KBr, cm^-1 ) ： ν= 1721 (C=O)；1600 (Ar-ring)；1165, 1058 (C-O-C)；990, 910 (=C-H)。[ 反應式 III]

(2) 製備化合物 BS-Acid ： 見反應式III，在一個100 mL三頸反應器中，加入1 g (2.49 mmol)的BS-Mba與10 mL乙醇後，於氮氣環境下升溫至80℃並攪拌1小時。另取0.35 g (6.2 mmol)氫氧化鉀(KOH)溶於10 mL乙醇中，逐滴加入三頸反應器中並於80℃下反應16小時，待反應結束後，以減壓濃縮方法除去乙醇。接著，先加入30 mL乙酸乙酯並依序以1N鹽酸萃取三次、鹽水萃取二次及純水萃取二次，再取有機層以無水硫酸鎂除水後，進行減壓濃縮除去乙酸乙酯，得到固體。最後，先使該固體溶於二氯甲烷，且逐滴加入正己烷至析出粗產物，並經攪拌過夜後進行抽氣過濾，再將所得到的濾餅於60℃下進行真空乾燥，得白色粉末狀產物(即化合物BS-Acid；產率約80 wt%)。化合物BS-Mba的¹ H-NMR及FTIR分析結果： ¹ H-NMR (ppm, DMSO-d₆ ) ： δ=5.14 (4H, H⁹ )；5.26, 5.28, 5.29 (2H, H^b )；5.82, 5.84, 5.85, 5.87 (2H, H^a )；6.71, 6.73, 6.76, 6.78 (2H, H² )；6.93 (1H, H¹⁰ )；7.15, 7.17 (2H, H¹² )；7.42, 7.48 (8H, H⁴ , H⁵ )；13.00 (1H, COOH)。FTIR (KBr, cm^-1 ): ν=3200-2400 (COO-H)；1692 (C=O)；1595 (Ar-ring)；1165, 1058 (C-O-C)；990, 910 (=C-H)。[ 反應式 IV]

(m為0至30的整數；n為0至30的整數)製備 OPE-E-4St ： 見反應式IV，在一個100 mL三頸反應器中，加入1.06 g (2.86 mmol)的BS-Acid、0.57 g (2.86 mmol)的二環己基碳二亞胺(DCC)、0.15 g (0.65 mmol)的4-二甲胺基吡啶及10 mL的二氯甲烷後，於氮氣環境下冷卻至0℃並攪拌30分鐘。另取2 g (1.3 mmol)的SA90溶於10 mL的二氯甲烷，並將該含有SA90的二氯甲烷溶液逐滴加入三頸反應器中並攪拌2小時，再於室溫下反應12小時，待反應結束後，以抽氣過濾方式移除大部分二環己基脲(DCU)。接著，先取濾液倒入甲醇/丙酮中析出粗產物，再以甲醇/丙酮清洗該粗產物後進行抽氣過濾，所得到的濾餅於60℃下進行真空乾燥，得到白色粉末產物(即實施例2的OPE-E-4St；產率約90 wt%)。實施例2之OPE-E-4St的¹ H-NMR(見圖2)、FTIR及GPC分析結果： ¹ H-NMR (ppm, CDCl₃ ) ： δ =1.68 (6H, H¹³ )；2.07 (Ar-CH₃ , H⁹ , H¹¹ )；5.08 (8H, H⁵ )；5.24, 5.25, 5.26, 5.27 (4H, H^b )；5.73, 5.75, 5.76, 5.77(4H, H^a )；6.46 (Ar-H, H¹⁰ , H¹² )；6.71 (4H, H² )；6.86 (2H, H⁶ )；6.95 (4H, H¹² )；7.32-7.46 (H⁴ ,  H⁵ )。FTIR (KBr, cm^-1 ) ： ν= 1738 (C=O)；1607 (Ar-ring)；1311, 1185(C-O-C)；988, 916 (=C-H)。GPC (NMP) ： M_n = 4535, M_w = 6969。 比較例 1 OPE-4St( 寡聚物 ) 比較例1之OPE-4St的製備方法包含下列步驟(1)至(3)：[ 反應式 V]

(1) 製備化合物 BS-OH ： 見反應式V，在一個100 mL三頸反應器中，加入0.5 g (3.6 mmol)的二烴基苯甲醇、氯甲基苯乙烯1.2 g (7.92 mmol)、碳酸鉀1.09 g (7.92 mmol)及10毫升之DMAc後，於氮氣環境下升溫至85℃並反應12小時，待反應結束後，倒入甲醇水溶液(甲醇與水的重量比值為1)析出粗產物。接著，以甲醇水溶液(甲醇與水的重量比值為1)清洗該粗產物數次後，先將清洗後得到的黃色油狀粗產物溶於乙酸乙酯中並以純水萃取三次，再取有機層以無水硫酸鎂除水，最後進行減壓濃縮除去乙酸乙酯後，得到黃色透明油狀產物(即化合物BS-OH；產率約90 wt%)。化合物BS-OH的¹ H-NMR及FTIR分析結果： ¹ H-NMR (ppm, DMSO-d₆ ) ： δ=4.46 (2H, H¹⁴ )；5.07(4H, H⁹ )；5.23 (OH)；5.26, 5.28, 5.30 (2H, H^b )；5.83, 5.84, 5.86, 5.87 (2H, H^a )；6.56 (1H, H¹⁰ )； 6.63, 6.61 (2H, H¹² )；6.72-6.78 (2H, H² )；7.41, 7.48 (8H, H⁴ , H⁵ )。FTIR (KBr, cm^-1 ) ： ν=3377 (OH)；1600 (Ar-ring)；1165, 1048 (C-O-C)；990, 910 (=C-H)。[ 反應式 VI]

(2) 製備化合物 BS-Cl ： 見反應式VI，在一個100 mL的三頸反應器中，加入1 g (2.68 mmol)的BS-OH及10 mL的二氯甲烷，於室溫下與氮氣環境中分批且逐滴加入0.76 g (6.44 mmol)氯化亞碸(SOCl₂ )與數滴吡啶(pyridine)進行反應3小時。待反應結束後，緩慢滴入純水並以純水萃取三次，取有機層以無水硫酸鎂除水後，以減壓濃縮方式除去二氯甲烷，得黃色透明油狀產物(即化合物BS-Cl；產率約80 wt%)。化合物BS-Cl的¹ H-NMR及FTIR分析結果： ¹ H-NMR (ppm, DMSO-d₆ ) ： δ=4.67 (2H, H¹⁴ )；5.08 (4H, H⁹ )；5.26, 5.28, 5.29 (2H, H^b )；5.83, 5.84, 5.86, 5.87 (2H, H^a )；6.66 (1H, H¹⁰ )；6.73 (2H, H¹² )；6.74-6.78 (2H, H² )；7.42, 7.48 (8H, H⁴ , H⁵ )。FTIR (KBr, cm^-1 ) ： ν= 1600 (Ar-ring)；1257 (CH₂ -Cl)； 1165, 1048 (C-O-C)；990, 910 (=C-H)。[ 反應式 VII]

(m為0至30的整數；n為0至30的整數)製備 OPE-4St ： 見反應式VII，在一個100 mL的三頸反應器中，加入1 g (0.62 mmol)的SA90、0.58 g (1.5 mmol)的BS-Cl、0.2 g (1.5 mmol)的碳酸鉀(K₂ CO₃ )及15 mL的DMAc後，於氮氣環境下升溫至100℃並進行反應24小時。待反應結束後，滴入甲醇析出粗產物，並以甲醇/丙酮混合液清洗數次，最後進行抽氣過濾後，將所得到的濾餅於60℃進行真空乾燥，得到白色粉末狀產物(即比較例1的OPE-4St；產率約85 wt%)。比較例1之OPE-4St的¹ H-NMR、FTIR及GPC分析結果： ¹ H-NMR (ppm, CDCl₃ ) ： δ=1.69 (6H, H¹³ )；2.08 (Ar-CH₃ , H⁹ , H¹¹ )；4.68 (4H, H⁸ )；5.03 (8H, H⁵ )；5.23, 5.24, 5.26, 5.27 (4H, H^b )；5.73, 5.74, 5.76, 5.77 (4H, H^a )；6.46 (Ar-H, H¹⁰ , H¹² )；6.57 (2H, H⁶ )；6.71 (4H, H⁷ )；6.74 (4H, H² )；6.95 (4H, H¹² )；7.29-7.45 (16H, H⁴ , H⁵ )。FTIR (KBr, cm^-1 ) ： ν=1605 (Ar-ring)；1311, 1185 (C-O-C)；990, 910 (=C-H)。GPC (NMP) ： M_n = 5041；M_w = 6818。 應用例 1 OPE-E-2St 的自身交聯固化物 應用例1之OPE-E-2St的自身交聯固化物製備方法如下： 先將0.5 g實施例1的OPE-E-2St與5 mg [1 wt%(以OPE-E-2St的重量為100 wt%計)]的二叔丁基過氧化物(過氧化物起始劑)加入4.5 mL(使固含量為10 wt%)的DMAc中並攪拌2小時，再以0.44 µm的針頭過濾器進行過濾後，倒入鋁盤，使其於氮氣環境下進行升溫固化，得到該OPE-E-2St的自身交聯固化物。其中，升溫固化的條件如下：80℃ (12小時)、120℃ (2小時)、180℃ (2小時)、200℃ (2小時)、220℃ (2小時)。 應用例 2 OPE-E-4St 的自身交聯固化物 應用例2之OPE-E-4St的自身交聯固化物製備方法如下： 先將0.5 g實施例2的OPE-E-4St與5 mg [1 wt%(以OPE-E-4St的重量為100 wt%計)]的二叔丁基過氧化物(過氧化物起始劑)加入4.5 mL(使固含量為10 wt%)的DMAc中並攪拌2小時，再以0.44 µm的針頭過濾器進行過濾後，倒入鋁盤，使其於氮氣環境下進行升溫固化，得到該OPE-E-4St的自身交聯固化物。其中，升溫固化的條件如下：80℃ (12小時)、120℃ (2小時)、180℃ (2小時)、200℃ (2小時)、220℃ (2小時)。 應用例 3 OPE-E-2St 與環氧樹脂共固化的固化物 應用例3之OPE-E-2St與環氧樹脂共固化的固化物製備方法如下： 先將1 g (1 mmol)實施例1的OPE-E-2St、0.28 g (1 mmol)的環氧樹脂(商品名:HP7200)、0.01 g [1 wt%(以OPE-E-2St的重量為100 wt%計)]的二叔丁基過氧化物(過氧化物起始劑)、1.4 mg [0.5 wt%(以環氧樹脂的重量為100 wt%計)]的DMAP(觸媒)加入11.4 mL(使固含量為10 wt%)的DMAc中並攪拌2小時，再以0.44 µm的針頭過濾器進行過濾後，倒入鋁盤，使其於氮氣環境下進行升溫固化，得到該OPE-E-2St與環氧樹脂共固化的固化物。其中，升溫固化的條件如下：80℃ (12小時)、120℃ (2小時)、180℃ (2小時)、200℃ (2小時)、220℃ (2小時)。 應用例 4 OPE-E-4St 與環氧樹脂共固化的固化物 應用例4之OPE-E-4St與環氧樹脂共固化的固化物製備方法如下： 先將1 g (0.86 mmol)實施例2的OPE-E-4St、0.22 g (0.86 mmol)的環氧樹脂(商品名:HP7200)、0.01 g [1 wt%(以OPE-E-4St的重量為100 wt%計)]的二叔丁基過氧化物(過氧化物起始劑)、1.1 mg [0.5 wt%(以環氧樹脂的重量為100 wt%計)]的DMAP(觸媒)加入11 mL(使固含量為10 wt%)的DMAc中並攪拌2小時，再以0.44 µm的針頭過濾器進行過濾後，倒入鋁盤，使其於氮氣環境下進行升溫固化，得到該OPE-E-4St與環氧樹脂共固化的固化物。其中，升溫固化的條件如下：80℃ (12小時)、120℃ (2小時)、180℃ (2小時)、200℃ (2小時)、220℃ (2小時)。 比較應用例 1 OPE-2St 的自身交聯固化物 比較應用例1之OPE-2St的自身交聯固化物製備方法如下： 先將0.5 g的OPE-2St(廠商:Mitsubishi Gas Chemical Company, Inc.)與5 mg [1 wt%(以OPE-2St的重量為100 wt%計)]的二叔丁基過氧化物(過氧化物起始劑)加入4.5 mL(使固含量為10 wt%)的DMAc中並攪拌2小時，再以0.44 µm的針頭過濾器進行過濾後，倒入鋁盤，使其於氮氣環境下進行升溫固化，得到該OPE-2St的自身交聯固化物。其中，升溫固化的條件如下：80℃ (12小時)、120℃ (2小時)、180℃ (2小時)、200℃ (2小時)、220℃ (2小時)。 比較應用例 2 OPE-4St 的自身交聯固化物 比較應用例2之OPE-4St的自身交聯固化物製備方法如下： 先將0.5 g比較例1的OPE-4St與5 mg [1 wt%(以OPE-4St的重量為100 wt%計)]的二叔丁基過氧化物(過氧化物起始劑)加入4.5 mL(使固含量為10 wt%)的DMAc中並攪拌2小時，再以0.44 µm的針頭過濾器進行過濾後，倒入鋁盤，使其於氮氣環境下進行升溫固化，得到該OPE-4St的自身交聯固化物。其中，升溫固化的條件如下：80℃ (12小時)、120℃ (2小時)、180℃ (2小時)、200℃ (2小時)、220℃ (2小時)。The preparation methods of the oligomers of Examples 1 to 2 and Comparative Example 1, and the cured products of Application Examples 1 to 4 and Comparative Application Examples 1 to 2 mentioned in this embodiment are respectively described in detail below. Example 1 OPE-E-2St ( oligomer ) The preparation method of OPE-E-2St in Example 1 is as follows: [ Reaction Formula I]

(m is an integer from 0 to 30; n is an integer from 0 to 30) See Reaction Formula I, in a 100 mL three-necked reactor, add 0.4 g (2.86 mmol) of 4-carboxystyrene, After 0.57 g (2.86 mmole) of dicyclohexylcarbodiimide (DCC), 0.15 g (0.65 mmol) of 4-dimethylaminopyridine (DMAP), and 10 mL of dichloromethane (DCM), place it in a nitrogen atmosphere Cool down to 0°C and stir for 30 minutes. Next, first take another 2 g (1.3 mmol) of (2,6-dimethyl-1,4-phenylene ether) oligomer (SA90) with a phenol end group and dissolve it in 10 mL of dichloromethane, and The dichloromethane solution containing SA90 was added dropwise to a three-necked reactor and stirred for 2 hours, then the ice bath was removed, and the reaction was carried out at room temperature for 12 hours. After the reaction is over, remove most of the dicyclohexylurea (N,N'-dicyclohexylurea; DCU) by suction filtration, and finally pour the filtrate into methanol to precipitate the crude product, and wash the crude product with methanol. After suction filtration, the obtained filter cake was vacuum dried at 60° C. to obtain a white powder product (ie, the OPE-E-2St of Example 1; the yield was about 90 wt%). The proton nuclear magnetic resonance spectrum ( ¹ H-NMR, see Figure 1), Fourier transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC) analysis results of OPE-E-2St in Example 1: ¹ H-NMR (ppm, CDCl ₃ ) : δ=1.69 (6H, H ¹⁰ ); 2.08 (Ar-CH ₃ , H ⁶ , H ⁸ ); 5.40, 5.42 (2H, H ^b ); 5.88, 5.91 (2H, H ^a ) ; 6.46 (Ar-H, H ⁷ , H ⁹ ); 6.75, 6.77, 6.78, 6.80 (2H, H ² ); 6.95 (4H, H ⁹ ); 7.51, 7.53 (4H, H ³ ); 8.15, 8.17 ( 4H, H ⁴ ). FTIR (KBr, cm ^-1 ) : ν= 1730 (C=O); 1607 (Ar-ring); 1311, 1185 (COC); 988, 916 (=CH). GPC (NMP) : M _n = 4268; M _w = 5799. Example 2 OPE-E-4St ( oligomer ) The preparation method of OPE-E-4St in Example 2 includes the following steps (1) to (3): [ Reaction formula II]

(1) Preparation of compound BS-Mba : see reaction formula II, in a 100 mL three-neck reactor, add 1 g (5.94 mmol) of 3,5-dihydroxybenzoic acid methyl ester (3,5-dihydroxybenzoic acid methyl ester), 2 g (13 mmol) of chloromethyl styrene [1-(chloromethyl)-4-ethenylbenzene], 1.8 g (13 mmol) of potassium carbonate (K ₂ CO ₃ ) and 10 mL of dimethyl ethyl After dimethylacetamide (DMAc for short), the temperature is raised to 85° C. under a nitrogen atmosphere and the reaction is carried out for 12 hours. After the reaction is completed, an aqueous methanol solution (the weight ratio of methanol to water is 1) is poured into the crude product to precipitate. Next, after washing the crude product several times with a methanol aqueous solution (the weight ratio of methanol to water is 1), the yellow oily crude product obtained after washing is dissolved in ethyl acetate and extracted with pure water three times After removing the water from the organic layer with anhydrous magnesium sulfate, and finally concentrating under reduced pressure to remove ethyl acetate, a yellow transparent oily product (ie compound BS-Mba; yield is about 90 wt%) is obtained. ¹ H-NMR and FTIR analysis results of compound BS-Mba: ¹ H-NMR (ppm, DMSO-d ₆ ) : δ=3.83 (3H, H ¹⁵ ); 5.13 (4H, H ⁹ ); 5.25, 5.27, 5.29 (2H, H ^b ); 5.82, 5.84, 5.85, 5.87 (2H, H ^a ); 6.73, 6.76 (2H, H ² ); 6.97 (1H, H ¹⁰ ); 7.18, 7.20 (2H, H ¹² ); 7.42 , 7.47 (8H, H ⁴ , H ⁵ ). FTIR (KBr, cm ^-1 ) : ν= 1721 (C=O); 1600 (Ar-ring); 1165, 1058 (COC); 990, 910 (=CH). [ Reaction formula III]

(2) Preparation of compound BS-Acid : see reaction formula III, in a 100 mL three-necked reactor, add 1 g (2.49 mmol) of BS-Mba and 10 mL of ethanol, then heat to 80°C under a nitrogen atmosphere and Stir for 1 hour. Another 0.35 g (6.2 mmol) of potassium hydroxide (KOH) was dissolved in 10 mL of ethanol, added dropwise to a three-necked reactor and reacted at 80°C for 16 hours. After the reaction was completed, the ethanol was removed by concentration under reduced pressure . Then, first add 30 mL of ethyl acetate and sequentially extract three times with 1N hydrochloric acid, two times with brine, and two times with pure water, and then take the organic layer to remove water with anhydrous magnesium sulfate, and concentrate under reduced pressure to remove ethyl acetate. A solid is obtained. Finally, the solid was dissolved in dichloromethane, and n-hexane was added dropwise until the crude product precipitated. After stirring overnight, it was filtered with suction, and then the resulting filter cake was vacuum dried at 60°C to obtain a white Powdered product (ie compound BS-Acid; yield is about 80 wt%). ¹ H-NMR and FTIR analysis results of compound BS-Mba: ¹ H-NMR (ppm, DMSO-d ₆ ) : δ=5.14 (4H, H ⁹ ); 5.26, 5.28, 5.29 (2H, H ^b ); 5.82 , 5.84, 5.85, 5.87 (2H, H ^a ); 6.71, 6.73, 6.76, 6.78 (2H, H ² ); 6.93 (1H, H ¹⁰ ); 7.15, 7.17 (2H, H ¹² ); 7.42, 7.48 (8H , H ⁴ , H ⁵ ); 13.00 (1H, COOH). FTIR (KBr, cm ^-1 ): ν=3200-2400 (COO-H); 1692 (C=O); 1595 (Ar-ring); 1165, 1058 (COC); 990, 910 (=CH). [ Reaction formula IV]

(m is an integer from 0 to 30; n is an integer from 0 to 30) Preparation of OPE-E-4St : See Reaction Formula IV, in a 100 mL three-necked reactor, add 1.06 g (2.86 mmol) of BS-Acid , 0.57 g (2.86 mmol) of dicyclohexylcarbodiimide (DCC), 0.15 g (0.65 mmol) of 4-dimethylaminopyridine and 10 mL of dichloromethane, then cool to 0°C under nitrogen And stir for 30 minutes. Another 2 g (1.3 mmol) of SA90 was dissolved in 10 mL of dichloromethane, and the dichloromethane solution containing SA90 was added dropwise to a three-necked reactor and stirred for 2 hours, and then reacted at room temperature for 12 hours After the reaction is over, most of the dicyclohexylurea (DCU) is removed by suction filtration. Then, first take the filtrate and pour it into methanol/acetone to precipitate the crude product, and then wash the crude product with methanol/acetone and perform suction filtration. The resulting filter cake is vacuum dried at 60°C to obtain a white powder product (ie, Example 2 OPE-E-4St; the yield is about 90 wt%). ¹ H-NMR (see Figure 2), FTIR and GPC analysis results of OPE-E-4St in Example 2: ¹ H-NMR (ppm, CDCl ₃ ) : δ = 1.68 (6H, H ¹³ ); 2.07 (Ar -CH ₃ , H ⁹ , H ¹¹ ); 5.08 (8H, H ⁵ ); 5.24, 5.25, 5.26, 5.27 (4H, H ^b ); 5.73, 5.75, 5.76, 5.77 (4H, H ^a ); 6.46 (Ar -H, H ¹⁰ , H ¹² ); 6.71 (4H, H ² ); 6.86 (2H, H ⁶ ); 6.95 (4H, H ¹² ); 7.32-7.46 (H ⁴ , H ⁵ ). FTIR (KBr, cm ^-1 ) : ν = 1738 (C=O); 1607 (Ar-ring); 1311, 1185 (COC); 988, 916 (=CH). GPC (NMP) : M _n = 4535, M _w = 6969. Comparative Example 1 OPE-4St ( oligomer ) The preparation method of OPE-4St in Comparative Example 1 includes the following steps (1) to (3): [ Reaction formula V]

(1) Preparation of compound BS-OH : see reaction formula V, in a 100 mL three-necked reactor, add 0.5 g (3.6 mmol) of dihydrocarbyl benzyl alcohol, 1.2 g (7.92 mmol) of chloromethyl styrene, carbonic acid After potassium 1.09 g (7.92 mmol) and 10 ml of DMAc, the temperature was raised to 85° C. and reacted for 12 hours under a nitrogen atmosphere. After the reaction was completed, the methanol solution was poured into the solution (the weight ratio of methanol to water was 1) to precipitate a crude product. Next, after washing the crude product several times with methanol aqueous solution (the weight ratio of methanol to water is 1), the yellow oily crude product obtained after washing is dissolved in ethyl acetate and extracted with pure water three times, and then the organic The layer was dehydrated with anhydrous magnesium sulfate, and finally concentrated under reduced pressure to remove ethyl acetate to obtain a yellow transparent oily product (ie, compound BS-OH; the yield was about 90 wt%). ¹ H-NMR and FTIR analysis results of compound BS-OH: ¹ H-NMR (ppm, DMSO-d ₆ ) : δ=4.46 (2H, H ¹⁴ ); 5.07 (4H, H ⁹ ); 5.23 (OH); 5.26, 5.28, 5.30 (2H, H ^b ); 5.83, 5.84, 5.86, 5.87 (2H, H ^a ); 6.56 (1H, H ¹⁰ ); 6.63, 6.61 (2H, H ¹² ); 6.72-6.78 (2H, H ² ); 7.41, 7.48 (8H, H ⁴ , H ⁵ ). FTIR (KBr, cm ^-1 ) : ν=3377 (OH); 1600 (Ar-ring); 1165, 1048 (COC); 990, 910 (=CH). [ Reaction formula VI]

(2) Preparation of compound BS-Cl : see reaction formula VI, in a 100 mL three-necked reactor, add 1 g (2.68 mmol) of BS-OH and 10 mL of dichloromethane, and mix with nitrogen at room temperature Add 0.76 g (6.44 mmol) of sulfite chloride (SOCl ₂ ) and a few drops of pyridine to the environment in batches and dropwise to react for 3 hours. After the reaction is over, pure water is slowly dropped and extracted with pure water three times, the organic layer is removed with anhydrous magnesium sulfate to remove water, and the dichloromethane is removed by concentration under reduced pressure to obtain a yellow transparent oily product (ie, compound BS-Cl ; The yield is about 80 wt%). ¹ H-NMR and FTIR analysis results of compound BS-Cl: ¹ H-NMR (ppm, DMSO-d ₆ ) : δ=4.67 (2H, H ¹⁴ ); 5.08 (4H, H ⁹ ); 5.26, 5.28, 5.29 (2H, H ^b ); 5.83, 5.84, 5.86, 5.87 (2H, H ^a ); 6.66 (1H, H ¹⁰ ); 6.73 (2H, H ¹² ); 6.74 to 6.78 (2H, H ² ); 7.42, 7.48 (8H, H ⁴ , H ⁵ ). FTIR (KBr, cm ^-1 ) : ν= 1600 (Ar-ring); 1257 (CH ₂ -Cl); 1165, 1048 (COC); 990, 910 (=CH). [ Reaction formula VII]

(m is an integer from 0 to 30; n is an integer from 0 to 30) Preparation of OPE-4St : see reaction formula VII, in a 100 mL three-necked reactor, add 1 g (0.62 mmol) of SA90, 0.58 g After (1.5 mmol) of BS-Cl, 0.2 g (1.5 mmol) of potassium carbonate (K ₂ CO ₃ ) and 15 mL of DMAc, the temperature was raised to 100° C. under a nitrogen atmosphere and the reaction was carried out for 24 hours. After the reaction is over, methanol is added dropwise to precipitate the crude product, which is washed several times with a methanol/acetone mixture, and finally after suction filtration, the resulting filter cake is vacuum dried at 60°C to obtain a white powdery product (ie OPE-4St of Comparative Example 1; the yield is about 85% by weight). ¹ H-NMR, FTIR and GPC analysis results of OPE-4St of Comparative Example 1: ¹ H-NMR (ppm, CDCl ₃ ) : δ=1.69 (6H, H ¹³ ); 2.08 (Ar-CH ₃ , H ⁹ , H ¹¹ ); 4.68 (4H, H ⁸ ); 5.03 (8H, H ⁵ ); 5.23, 5.24, 5.26, 5.27 (4H, H ^b ); 5.73, 5.74, 5.76, 5.77 (4H, H ^a ); 6.46 ( Ar-H, H ¹⁰ , H ¹² ); 6.57 (2H, H ⁶ ); 6.71 (4H, H ⁷ ); 6.74 (4H, H ² ); 6.95 (4H, H ¹² ); 7.29-7.45 (16H, H ⁴ , H ⁵ ). FTIR (KBr, cm ^-1 ) : ν=1605 (Ar-ring); 1311, 1185 (COC); 990, 910 (=CH). GPC (NMP) : M _n = 5041; M _w = 6818. Application Example 1 OPE-E-2St self-crosslinked cured product Application Example 1 OPE-E-2St self-crosslinked cured product was prepared as follows: First, 0.5 g of OPE-E-2St of Example 1 and 5 mg [ 1 wt% (based on the weight of OPE-E-2St as 100 wt%)] di-tert-butyl peroxide (peroxide initiator) is added to 4.5 mL (to make the solid content 10 wt%) of DMAc It was stirred for 2 hours, and then filtered with a 0.44 µm syringe filter, poured into an aluminum pan, and allowed to heat up and solidify in a nitrogen environment to obtain the self-crosslinked cured product of OPE-E-2St. Among them, the conditions for heating and curing are as follows: 80°C (12 hours), 120°C (2 hours), 180°C (2 hours), 200°C (2 hours), 220°C (2 hours). Application Example 2 OPE-E-4St self-crosslinked cured product Application Example 2 OPE-E-4St self-crosslinked cured product was prepared as follows: First, 0.5 g of OPE-E-4St of Example 2 and 5 mg [ 1 wt% (based on the weight of OPE-E-4St as 100 wt%)] di-tert-butyl peroxide (peroxide initiator) was added to 4.5 mL (to make the solid content 10 wt%) of DMAc It was stirred for 2 hours, and then filtered with a 0.44 µm syringe filter, then poured into an aluminum pan and allowed to heat up and cure in a nitrogen environment to obtain the self-crosslinked cured product of OPE-E-4St. Among them, the conditions for heating and curing are as follows: 80°C (12 hours), 120°C (2 hours), 180°C (2 hours), 200°C (2 hours), 220°C (2 hours). Application Example 3 OPE-E-2St co-cured with an epoxy resin cured Application Example OPE-E-2St co-cured with an epoxy resin 3 of the cured product prepared as follows: Example 1 First 1 g (1 mmol) embodiment OPE-E-2St, 0.28 g (1 mmol) epoxy resin (trade name: HP7200), 0.01 g [1 wt% (based on the weight of OPE-E-2St as 100 wt%)] di-tert-butyl Base peroxide (peroxide initiator), 1.4 mg [0.5 wt% (based on the weight of epoxy resin as 100 wt%)] DMAP (catalyst) was added to 11.4 mL (to make the solid content 10 wt% ) In DMAc and stirred for 2 hours, then filtered with a 0.44 µm syringe filter, poured into an aluminum pan, and allowed to heat up and cure in a nitrogen environment to obtain the OPE-E-2St and epoxy resin co-cured Cured matter. Among them, the conditions for heating and curing are as follows: 80°C (12 hours), 120°C (2 hours), 180°C (2 hours), 200°C (2 hours), 220°C (2 hours). The method of preparing a cured product OPE-E-4St with the epoxy resin of Example 4 Application Example 4 OPE-E-4St co-cured with an epoxy resin cured co-curing was applied as follows: first 1 g (0.86 mmol) of Example 2 OPE-E-4St, 0.22 g (0.86 mmol) epoxy resin (trade name: HP7200), 0.01 g [1 wt% (based on the weight of OPE-E-4St as 100 wt%)] di-tert-butyl Base peroxide (peroxide initiator), 1.1 mg [0.5 wt% (based on the weight of epoxy resin as 100 wt%)] DMAP (catalyst) was added 11 mL (to make the solid content 10 wt% ) In the DMAc and stirred for 2 hours, then filtered with a 0.44 µm syringe filter, poured into an aluminum pan, and allowed to heat up and cure in a nitrogen environment to obtain the OPE-E-4St and epoxy resin co-cured Cured matter. Among them, the conditions for heating and curing are as follows: 80°C (12 hours), 120°C (2 hours), 180°C (2 hours), 200°C (2 hours), 220°C (2 hours). Comparative Application Example 1 OPE-2St self-crosslinked cured product Comparative Application Example 1 OPE-2St self-crosslinked cured product was prepared as follows: First, 0.5 g of OPE-2St (manufacturer: Mitsubishi Gas Chemical Company, Inc.) And 5 mg [1 wt% (based on the weight of OPE-2St as 100 wt%)] of di-tert-butyl peroxide (peroxide initiator) added to 4.5 mL (to make the solid content 10 wt%) Stir in DMAc for 2 hours, then filter with a 0.44 µm syringe filter, pour it into an aluminum pan, and allow it to heat up and cure in a nitrogen environment to obtain a self-crosslinked cured product of OPE-2St. Among them, the conditions for heating and curing are as follows: 80°C (12 hours), 120°C (2 hours), 180°C (2 hours), 200°C (2 hours), 220°C (2 hours). Comparative Application Example 2 OPE-4St self-crosslinked cured product Comparative Application Example 2 OPE-4St self-crosslinked cured product The preparation method of the self-crosslinked cured product of OPE-4St is as follows: First, 0.5 g of OPE-4St of Comparative Example 1 and 5 mg [1 wt%( The weight of OPE-4St is 100 wt%)] di-tert-butyl peroxide (peroxide initiator) is added to 4.5 mL (to make the solid content 10 wt%) of DMAc and stirred for 2 hours, then After filtering with a 0.44 µm syringe filter, it was poured into an aluminum pan and heated and cured in a nitrogen atmosphere to obtain a self-crosslinked cured product of the OPE-4St. Among them, the conditions for heating and curing are as follows: 80°C (12 hours), 120°C (2 hours), 180°C (2 hours), 200°C (2 hours), 220°C (2 hours).

In particular, the existing OPE-2St and the OPE-4St oligomers of Comparative Example 1 have no active ester groups at their ends, so they cannot be used for co-curing with epoxy resins.

＜ Thermal properties analysis of cured products ＞

A. Analytical method:

The thermal property analysis is for the glass transition temperature (T _g ), coefficient of thermal expansion (CTE), 5wt% thermogravimetric loss temperature (T _d5 ) and 800℃ coke of the cured products of Application Examples 1 to 4 and Comparative Application Examples 1 to 2 The residual rate (char yield) is analyzed, and the analysis methods are as follows. 1. Dynamic Mechanical Analyzer (dynamic mechanical analyzer; DMA) measurement of glass transition temperature (T _g): using a dynamic mechanical analyzer (Model: Perkin-Elmer Pyris Diamond) for 1 to 4 and Comparative Application Example 1 Application Example 2 The glass transition temperature of the cured product is measured. Among them, the aforementioned dynamic mechanical analysis conditions are measured at a heating rate of 5°C/min. 2. thermomechanical analysis (thermo-mechanical analysis; TMA) Measurement of glass transition temperature (T _g) and the coefficient of thermal expansion (CTE): thermal mechanical analysis (TMA) for Application Examples 1 to 4 and Comparative Application Example 1 ~2 The glass transition temperature (T _g ) and thermal expansion coefficient of the cured product are measured. Among them, the aforementioned thermomechanical analysis conditions are measured at a heating rate of 5°C/min. 3. Thermogravimetric Analysis (thermo-gravimetric analysis; TGA) weight measurement 5wt% heat loss temperature (T _d5) of 800 deg.] C and coke residue: A thermogravimetric analyzer (Model: Thermo Cahn VersaTherm) for Application Example The 5wt% thermogravimetric loss temperature and the coke residual rate of 800°C of the cured products of 1~4 and Comparative Application Examples 1~2 were measured. Among them, the aforementioned thermogravimetric analysis conditions are performed under a nitrogen atmosphere and a heating rate of 20°C/min. It should be noted that the 5wt% thermogravimetric loss temperature refers to the temperature at which the weight loss of the cured product reaches 5wt%, and the higher the 5wt% thermogravimetric loss temperature, the higher the thermal stability of the cured product; 800°C coke The residual rate refers to the residual weight ratio of the cured product when the heating temperature reaches 800°C, and the higher the coke residual rate at 800°C, the higher the thermal stability of the cured product.

The glass transition temperature (T _g ), coefficient of thermal expansion (CTE), 5wt% thermogravimetric loss temperature (T _d5 ) of the cured products of application examples 1 to 4 and comparative application examples 1 to 2 and coke residual rate at 800°C, and curing The hardeners (oligomer/epoxy resin) used are listed in Table 1 below. Table 1 Hardener used for curing T _g (DMA) ( ℃) T _g (TMA) ( ℃) CTE (ppm/ ℃) T _d5 ( ℃) Residual coke rate (wt%) Comparative application example 1 OPE-2St 229 204 76 394 27 Application example 1 OPE-E-2St 258 223 62 504 32 Application example 3 OPE-E-2St and epoxy resin 214 182 65 417 twenty one Comparative application example 2 OPE-4St 246 221 61 426 33 Application example 2 OPE-E-4St 257 225 62 488 36 Application example 4 OPE-E-4St and epoxy resin 218 185 59 421 26

B. Results and discussion:

From the data of the cured product obtained by self-crosslinking and curing in Table 1, it can be found that compared to the cured product formed by OPE-2St without any ester group at the end (Comparative Application Example 1), the OPE- with ester group at the end The cured product formed by E-2St (application example 1) will have a higher glass transition temperature, 5wt% thermogravimetric loss temperature and coke residual rate, compared to the one formed by OPE-4St without any ester group at the end Cured product (Comparative Application Example 2), the cured product formed by OPE-E-4St with an ester group at the end (Application Example 2) will also have higher glass transition temperature, 5wt% thermal weight loss temperature and coke residual rate . Therefore, in terms of the thermal properties of the cured product, compared to the existing oligomers without any ester groups at the ends, the oligomers with vinyl phenyl ester at the ends of the present invention [formula (I)] can make subsequent preparations The cured product has a higher glass transition temperature, and at the same time also has a higher thermogravimetric loss temperature (T _d5 ) and coke residual rate (that is, higher thermal stability).

It is added that the aforementioned increase in thermal stability is due to the fact that the cured product obtained by self-crosslinking and curing of the oligomer of the present invention will have an ester group that can resonate with the benzene ring, so that the structure of the cured product is more stable and can Improve the thermal stability of the cured product.

In addition, comparing the data of Application Example 3 and Application Example 4 obtained by co-curing with epoxy resin, it can be found that the cured product obtained by co-curing OPE-E-4St and epoxy resin will have a higher glass transition temperature and a lower The coefficient of thermal expansion (that is, it has higher dimensional stability), and at the same time it will have a higher thermogravimetric loss temperature and coke residual rate (that is, it has higher thermal stability).

＜ Analysis of the dielectric properties of the cured product ＞

A. Analytical method:

The analysis of dielectric properties is to analyze the dielectric constant (D _k ) and dielectric loss (D _f ) of the cured products of application examples 1 to 4 and comparative application examples 1 to 2. The analysis method is to use a dielectric analyzer to analyze The dielectric constant and dielectric loss of the cured products of Application Examples 1 to 4 and Comparative Application Examples 1 to 2.

The dielectric constant (D _k ) and dielectric loss (D _f ) of the cured products of application examples 1 to 4 and comparative application examples 1 to 2 at 1 GHz, and the hardener used for curing (oligomer/epoxy resin) ) And the thickness of the cured product test piece are listed in Table 2 below. Table 2 Hardener used for curing Thickness (µm) D _k (U) D _f (mU) Comparative application example 1 OPE-2St 237 2.69±0.001 6.9±0.5 Application example 1 OPE-E-2St 190 2.54±0.001 5.9±0.5 Application example 3 OPE-E-2St and epoxy resin 220 2.47±0.002 7.0±0.3 Comparative application example 2 OPE-4St 184 2.64±0.002 9.0±0.2 Application example 2 OPE-E-4St 140 2.52±0.002 7.0±0.2 Application example 4 OPE-E-4St and epoxy resin 170 2.46±0.001 8.1±0.2

B. Results and discussion:

From the data of the cured product obtained by self-crosslinking and curing in Table 2, it can be found that compared to the cured product formed by OPE-2St without any ester group at the end (Comparative Application Example 1), the OPE- with an ester group at the end is The cured product formed by E-2St (application example 1) will have lower dielectric constant and dielectric loss, and compared to the cured product formed by OPE-4St without any ester groups at the end (comparative application example 2) ), the cured product (Application Example 2) formed by OPE-E-4St with an ester group at the end will also have a lower dielectric constant and dielectric loss. Therefore, from the perspective of the dielectric properties of the cured product, compared to the existing oligomers without any ester groups at the ends, the oligomers with vinyl phenyl ester at the ends of the present invention [formula (I)] can make subsequent preparations The cured product obtained has a lower dielectric constant and dielectric loss.

It is added that the aforementioned decrease in dielectric constant is due to the fact that the cured product obtained by self-crosslinking and curing of the oligomer of the present invention will have ester groups. Therefore, compared with the cured product having only fatty groups, the present invention has ester groups. The cured product will have a higher three-dimensional obstacle and more free volume, which can lower the dielectric constant.

＜ Analysis of the mechanical properties of the cured product ＞

A. Analytical method:

The mechanical property analysis is to analyze the Young's modulus, tensile strength and elongation at break of the cured products of Application Examples 1 to 4 and Comparative Application Examples 1 to 2. The analysis methods are all analyzed by using a tensile machine.

The Young's modulus, tensile strength and elongation at break of the cured products of Application Examples 1 to 4 and Comparative Application Examples 1 to 2, as well as the curing agent (oligomer/epoxy resin) used for curing and the thickness of the cured product test piece They are summarized in Table 3 below. table 3 Hardener used for curing Thickness (µm) Young's modulus (GPa) Tensile strength (MPa) Elongation at break (%) Comparative application example 1 OPE-2St 110 1.565 67.33 5.67 Application example 1 OPE-E-2St 140 1.376 67.23 8.69 Application example 3 OPE-E-2St and epoxy resin 140 1.573 98.89 8.71 Comparative application example 2 OPE-4St 165 0.888 50.93 4.81 Application example 2 OPE-E-4St 160 0.965 62.82 7.22 Application example 4 OPE-E-4St and epoxy resin 175 1.275 90.27 8.15

B. Results and discussion:

From the data of the cured product obtained by self-crosslinking and curing in Table 3, it can be found that compared with the cured product formed by OPE-2St without any ester group at the end (Comparative Application Example 1), the OPE- with ester group at the end The cured product formed by E-2St (application example 1) will have higher elongation at break, and compared to the cured product formed by OPE-4St without any ester group at the end (comparative application example 2), the end has The cured product formed by ester-based OPE-E-4St (application example 2) also has a higher elongation at break. Therefore, in terms of the mechanical properties of the cured product, compared with the existing oligomers without any ester groups at the ends, the oligomers with vinyl phenyl ester at the ends of the present invention [formula (I)] can make subsequent preparations The cured product has a higher elongation at break (that is, it is less likely to be brittle due to stretching). It is added that the increase in elongation at break is due to the fact that the cured product obtained by self-crosslinking and curing of the oligomer of the present invention will have ester groups. Therefore, compared with the cured product having only fatty groups, the cured product of the present invention has ester groups. The object will have a higher steric barrier and a higher molecular chain swing space, which can increase the elongation at break.

In addition, the cured product obtained by co-curing the oligomer and epoxy resin of the present invention (application examples 3 to 4) not only has higher elongation at break, but also higher Young's modulus and tensile strength. This is because the cured product after co-curing with the epoxy resin will have a network structure, so its overall mechanical properties can be improved, and the cured product is less prone to brittle cracking.

＜ Analysis of the crosslink density and air permeability of the cured product ＞

A. Analytical method:

The analysis of mechanical properties is to analyze the crosslink density and air permeability of the cured products of application examples 1 to 4 and comparative application examples 1 to 2. The analysis methods are all analyzed by gas permeability analysis (GTR) . Among them, the conditions of the aforementioned analysis are set to a pressure of 1.0 atm, a temperature of 35.5°C, and the measurement gas is oxygen.

The crosslinking density and air permeability of the cured products of Application Examples 1 to 4 and Comparative Application Examples 1 to 2, and the hardener (oligomer/epoxy resin) used for curing are listed in Table 4 below. Table 4 Hardener used for curing Crosslink density (mmol • cm ^-3 ) Air permeability (barrer) Comparative application example 1 OPE-2St 1.46 8.7 Application example 1 OPE-E-2St 1.54 10.0 Application example 3 OPE-E-2St and epoxy resin 1.53 7.7 Comparative application example 2 OPE-4St 2.99 6.0 Application example 2 OPE-E-4St 3.25 4.8 Application example 4 OPE-E-4St and epoxy resin 2.99 5.6

B. Results and discussion:

It can be seen from Table 4 that whether OPE-E-4St is cross-linked and cured by itself or co-cured with epoxy resin (Application Examples 2 and 4), the cured product has a lower air permeability, that is, it will have a better Oxygen barrier.

In summary, because the (2,6-dimethyl-1,4-phenylene ether) oligomer of formula (I) of the present invention has vinyl phenyl ester at the end, the cured product obtained subsequently can have both Higher glass transition temperature (T _g ) and thermal stability, lower dielectric constant and dielectric loss, and higher elongation at break characteristics, and because the terminal vinyl phenyl ester is an active ester group, the formula of the present invention ( The (2,6-dimethyl-1,4-phenylene ether) oligomer of I) can also be used for co-curing with epoxy resin, so it can indeed achieve the purpose of the invention.

However, the above are only examples of the present invention. When the scope of implementation of the present invention cannot be limited by this, all simple equivalent changes and modifications made in accordance with the scope of the patent application of the present invention and the content of the patent specification still belong to Within the scope of the patent for the present invention.

Other features and effects of the present invention will be clearly presented in the embodiment with reference to the drawings, in which: Figure 1 is a ¹ H-NMR spectrum of Example 1 of the present invention; and Figure 2 is a view of Example 1 of the present invention ¹ H-NMR spectrum.

Claims (9)

A (2,6-dimethyl-1,4-phenylene ether) oligomer, as shown in the following formula (I):

Where X is

, Y is -C(CH ₃ ) ₂ -, R ¹ is hydrogen, C ₁ to C ₆ alkyl or phenyl, m and n are each an integer from 0 to 50, and q is an integer from 1 to 3. The (2,6-dimethyl-1,4-phenylene ether) oligomer according to claim 1, wherein X is

. A cured product is prepared by curing a resin composition in the presence of a peroxide initiator, the resin composition containing (2,6-dimethyl-1,4 -Phenyl ether) oligomers. The cured product according to claim 3, wherein the peroxide initiator is selected From di-tert-butyl peroxide, benzyl peroxide, tert-butanol peroxide, tert-butyl cumene peroxide or a combination of the foregoing. The cured product according to claim 3, wherein, based on the weight of the (2,6-dimethyl-1,4-phenylene ether) oligomer being 100% by weight, the weight range of the peroxide initiator It is 0.1~5wt%. The cured product according to claim 3, wherein the resin composition further contains an epoxy resin, and the cured product is prepared by curing the resin composition in the presence of a peroxide initiator and a catalyst . The cured product according to claim 6, wherein the epoxy resin is selected from the group consisting of bisphenol A epoxy resin, novolac epoxy resin, methyl novolac epoxy resin, dicyclopentadiene phenol epoxy resin, and Naphthalene epoxy resin or a combination of the foregoing. The cured product according to claim 6, wherein the catalyst is selected from 4-dimethylaminopyridine, imidazole, 2-methyl-4-methylimidazole, 2-methylimidazole, triphenyl Phosphine or a combination of the foregoing. The cured product according to claim 6, wherein, based on the weight of the epoxy resin being 100 wt%, the weight of the catalyst ranges from 0.1 to 5 wt%.

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