TWI621679B - 聚苯醚寡聚物及高頻銅箔基板 - Google Patents

聚苯醚寡聚物及高頻銅箔基板 Download PDF

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TWI621679B
TWI621679B TW105142422A TW105142422A TWI621679B TW I621679 B TWI621679 B TW I621679B TW 105142422 A TW105142422 A TW 105142422A TW 105142422 A TW105142422 A TW 105142422A TW I621679 B TWI621679 B TW I621679B
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polyphenylene ether
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independently hydrogen
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郭政柏
陳泊如
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財團法人工業技術研究院
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Abstract

本發明實施例提供一種聚苯醚(polyphenylene ether)寡聚物及高頻銅箔基板。該聚苯醚寡聚物係具有如式(I)所示之結構：
其中，每一R1係獨立地為氫、C1-6的烷基或苯基；每一R2係獨立地為氫、C1-6的烷基或苯基；a：(a+b)係介於0.05：1至1：1之間；n：(a+b)係介於0.05：1至5：1之間；Q係或，m係0至4之整數，Ra係C1-6的烷撐基，Rb係C1-6的烷撐基；每一X係獨立地為氫、丙烯醯基(acryloyl group)、丙烯基(allyl group)、乙烯基苯基(vinylbenzyl group)、環氧丙基(epoxypropyl group)、甲基丙烯醯基(methacryloyl group)、丙炔基(propargyl group)或丙 烯腈基(cyanol group)；以及該聚苯醚寡聚物之數目平均分子量(Mn)係介於400至2000之間。

Description

聚苯醚寡聚物及高頻銅箔基板
本發明係有關於一種聚苯醚寡聚物及高頻銅箔基板。
現今通訊電子產業發展迅速，並朝向高速、高頻、高密度發展，因此具高耐熱性、低介電係數、高堅韌結構特性之高分子是下一世代電子構裝及高頻基板材料開發之主要方向。聚苯醚(polyphenylene ether)即為一種高性能材料。然而，聚苯醚的應用中，在加工製程方面，還需要開發具備良好溶解度的材料。因此，聚苯醚的設計開發是相當重要的研究。
本發明實施例提供一種聚苯醚(polyphenylene ether)寡聚物，聚苯醚寡聚物係具有如式(I)所示之結構：
其中，每一R1係獨立地為氫、C1-6的烷基或苯基；每一R2 係獨立地為氫、C1-6的烷基或苯基；a：(a+b)係介於0.05：1至1：1之間；n：(a+b)係介於0.05：1至5：1之間；Q係或，m係0至4之整數，Ra係C1-6的烷撐基，Rb係C1-6的烷撐基；每一X係獨立地為氫、丙烯醯基(acryloyl group)、丙烯基(allyl group)、乙烯基苯基(vinylbenzyl group)、環氧丙基(epoxypropyl group)、甲基丙烯醯基(methacryloyl group)、丙炔基(propargyl group)或丙烯腈基(cyanol group)；以及該聚苯醚寡聚物之數目平均分子量(Mn)係介於400至2000之間。
一種高頻銅箔基板，包含銅箔基板以及黏著層，黏著層位於銅箔基板之上，其中黏著層由一組成物製備而得，組成物包含上述的聚苯醚寡聚物。
為讓本發明之上述和其他目的、特徵、和優點能更明顯易懂，下文特舉出較佳實施例，作詳細說明如下：
本發明提供一種聚苯醚(polyphenylene ether)寡聚物，具有良好的溶解度有利於加工，以聚苯醚寡聚物製得之製品可呈現良好的電性。
本發明提供一種聚苯醚(polyphenylene ether)寡聚物，具有如式(I)所示之結構：
其中，每一R1可以獨立地為氫、C1-6的烷基或苯基；每一R2可以獨立地為氫、C1-6的烷基或苯基；a：(a+b)約介於0.05：1至1：1之間；n：(a+b)約介於0.05：1至5：1之間。
Q可以是或 ，m可以是0至4之整數，Ra可以是C1-6的烷撐基，Rb可以是C1-6的烷撐基；以及每一X可以獨立地為氫、丙烯醯基(acryloyl group)、丙烯基(allyl group)、乙烯基苯基(vinylbenzyl group)、環氧丙基(epoxypropyl group)、甲基丙烯醯基(methacryloyl group)、丙炔基(propargyl group)或丙烯腈基(cyanol group)。
在本發明一實施例中，聚苯醚寡聚物的數目平均分子量(Mn)約介於400至2000之間，例如約介於500至2000之間或約介於800至2000之間，也可以是介於1000至2000之間，又或是介於900至1700之間。若聚苯醚寡聚物的數目平均分子量過低，則易造成熱穩定性不佳。若聚苯醚寡聚物的重量平均分 子量過高，則易造成加工性不佳。
值得說明的是，於本揭露中，介於某兩數值之間亦包含某兩數值，例如約介於500至2000之間亦包含500與2000。
在本發明一實施例中，Q可以是
在本發明一實施例中，每一X可以獨立地為氫、 或，其中R3可以獨立地為氫或C1-3烷基，p可以是1至4之整數，W可以是環氧基、羥基或乙烯基，R4可以是C1-12烷撐基，g係0或1之整數，s係0或1之整數，R5可以是獨立地為氫或C1-12烷基。
在本發明一實施例中，每一X可以獨立地為
在本發明一實施例中，聚苯醚寡聚物可具有如式(II)所示之結構：
其中a：(a+b)約介於0.05：1至1：1之間；n：(a+b)約介於0.05：1至5：1之間。
在本發明一實施例中，聚苯醚寡聚物可具有如式(III)所示之結構：
其中a：(a+b)約介於0.05：1至1：1之間；n：(a+b)約介於0.05：1至5：1之間。
在本發明一實施例中，聚苯醚寡聚物可具有如式(IV)所示之結構：
其中a：(a+b)約介於0.05：1至1：1之間；n：(a+b)約介於0.05：1至5：1之間。
在本發明一實施例中，聚苯醚寡聚物可具有如式(V)所示之結構：
其中a：(a+b)約介於0.05：1至1：1之間；n：(a+b)約介於0.05：1 至5：1之間。
在本發明一實施例中，係利用第一反應物(例如 )與第二反應物(例如 、或上述之組合)作為起始物合成雙酚單體，接著，將雙酚單體與第三反應物(例如 )進行聚合反應，以形成聚苯醚寡聚物。每一R1可以獨立地為氫、C1-6的烷基或苯基；每一R2可以獨立地為氫、C1-6的烷基或苯基；m可以是0至4之整數，Ra可以是C1-6的烷撐基，Rb可以是C1-6的烷撐基，X可以是氫、丙烯醯基(acryloyl group)、丙烯基(allyl group)、乙烯基苯基(vinylbenzyl group)、環氧丙基(epoxypropyl group)、甲基丙烯醯基(methacryloyl group)、丙炔基(propargyl group)或丙烯腈基(cyanol group)。
在本發明一實施例中，係利用第一反應物(例如 )與第二反應物(例如 、或上述之組合)作為起始物合成雙酚單體，接著，將雙酚單體與第三反應物(例如 )進行聚合反應後再與第四反應物(例如 )進行取代反應，以形成聚苯醚寡聚物。每一R1可以獨立地為氫、C1-6的烷基或苯基；每一R2可以獨立地為氫、C1-6的烷基或苯基；m可以是0至4之整數，Ra可以是C1-6的烷撐基，Rb可以是C1-6的烷撐基，X可以是氫、丙烯醯基(acryloyl group)、丙烯基(allyl group)、乙烯基苯基(vinylbenzyl group)、環氧丙基(epoxypropyl group)、甲基丙烯醯基(methacryloyl group)、丙炔基(propargyl group)或丙烯腈基(cyanol group)，R4可以是C1-12烷撐基，g係0或1之整數，s係0或1之整數，R5可以是獨立地為氫或C1-12烷基。
在本發明一實施例中，第一反應物(例如 )與第二反應物(例如 、或上述之組合)的莫耳比約介於2：1至3：1之間。
在本發明一實施例中，第三反應物(例如 )對第二反應物(例如 、或上述之組合)的莫耳比約介於0.2：1至20：1之間。若上述莫耳比過低，則可能造成熱穩定性不佳。若上述莫耳比過高，則可能造成材料韌性不足。
在本發明一實施例中，聚苯醚寡聚物可應用於高頻銅箔基板的製作，例如高頻銅箔基板可包含銅箔基板以及黏著層，黏著層位於銅箔基板，其中黏著層由組成物製備而得，組成物包含上述的聚苯醚寡聚物。
以下藉由下列實施例來說明本發明所述之聚苯醚寡聚物的合成方式，用以進一步闡明本發明之技術特徵。
【實施例1】合成聚苯醚寡聚物1
取102.97克(0.84mol)2,6-二甲基苯酚(2,6-dimethylphenol,DMP)和2.36克(0.018mol)氯化鋁(aluminium chloride)加入至反應器中，在氮氣系統下加熱至120℃。接著，在120℃下，加入15.6克(0.12mol)雙環戊二烯(dicyclopentadiene)，再持續攪拌反應。待反應結束後，加入5wt%氫氧化鈉(0.06mol)水溶液中和觸媒，並加入甲苯攪拌1小時後將反應液過濾除去鹽類與觸媒，所得之濾液利用水洗數次，取有機層並減壓蒸餾純化即可得40.61克的深棕色雙酚單體(DCPD-DIDMP)，產率為90%。
混合16.22克(43.08mmol)DCPD-DIDMP、15.66克(128.36mmol)2,6-二甲基苯酚、1.33克(13.14mmol)N,N’-二甲基 丁胺(N,N’-dimethylbutylamine)、1.05克(8.14mmol)二正丁胺(di-n-butylamine)與208克甲醇形成單體混合溶液。
在氧氣系統下於反應器中混合0.253克(1.13mmol)溴化銅(CuBr2)、0.71克(7.02mmol)N,N’-二甲基丁胺(N,N’-dimethylbutylamine)、0.55克(4.26mmol)二正丁胺(di-n-butylamine)和235克甲苯，加熱至45℃。而後，在氧氣系統下將單體混和溶液加入至反應器中。
待反應結束後，將1.2克(3.16mmol)乙二胺四乙酸四鈉溶解於200克水中，加入反應器中，以終止反應。分離水層和有機層。將有機層溶液減壓濃縮，獲得28克之聚酚醚寡聚物1，上述反應可表示如下式：
DCPD-DIDMP的氫核磁共振(1H-NMR)光譜(400MHz，氘-二甲基亞碸(DMSO-d 6 )，化學位移2.54ppm)1H-NMR分析結果：δ7.93ppm(-OH)，δ6.87-6.55ppm(Aromatic H of DMP)，δ2.19-1.05ppm(Aliphatic H of DMP and DCPD)。在δ 7.93ppm訊號為DCPD-DIDMP之DMP苯環上羥基吸收位置。聚苯醚寡聚物1的氫核磁共振(1H-NMR)光譜(400MHz，溶劑為氘-丙酮(acetone-d 6 )，化學位移2.05ppm)， 1H-NMR分析結果：δ7.20-7.15ppm(5H)，δ7.09-6.99ppm(4H)，δ6.86-6.81ppm(3H)，δ6.53-6.50ppm(2H)，δ6.34ppm(1H)。聚苯醚寡聚物1的FT-IR圖譜測得3600cm-1為聚苯醚寡聚物1末端之酚羥基吸收峰。
由膠透層析儀(Gel Permeation Chromatography,GPC)鑑定，聚苯醚寡聚物1之數目平均分子量(Mn)約為1044，而分子量分佈值(polydispersity,PDI)約為1.41，相關溶解度測試結果請參閱表2。
聚苯醚寡聚物1之溶解度測試方式：聚苯醚寡聚物與溶劑混合後溶液為澄清無沉澱物則為可溶，反之為不可溶，聚苯醚寡聚物與溶劑混合之重量比為1：1。本揭露所有聚苯醚寡聚物之溶解度測試皆同上述方式。
【實施例2】合成聚苯醚寡聚物2
取25克聚苯醚寡聚物1、1.17克(9.58mmol)4-二甲氨基吡啶(4-dimethylaminopyridine,DMAP)、16.65克(107mmol)甲基丙烯酸酐(methacrylic anhydride)和63.8克甲苯，加熱至80℃反應。待反應結束後，回至常溫加入甲苯63.8克，將此反應溶液沉澱於大量甲醇中，所得沉澱粗產物以抽氣過濾收集，再以300ml甲醇清洗攪拌30分鐘後再以抽氣過濾收集得到固體產物，然後在減壓下乾燥，以獲得17克之聚苯醚寡聚物2，上述反應可表示如下式：
聚苯醚寡聚物2的FT-IR圖譜中顯示在3600cm-1(聚苯醚寡聚物1末端之酚羥基吸收位置)吸收峰消失，然而在1734cm-1為聚苯醚寡聚物2末端之甲基丙烯醯基(methylacryloy group)吸收峰。聚苯醚寡聚物2的氫核磁共振(1H-NMR)光譜(400MHz，溶劑為氘-丙酮(acetone-d 6 )，化學位移2.05ppm)，1H-NMR分析結果：δ7.09-6.99ppm(4)，δ6.53-6.48ppm(3)，δ6.33ppm(2)，δ5.83ppm(1)。
由膠透層析儀(Gel Permeation Chromatography；GPC)鑑定，聚苯醚寡聚物2之數目平均分子量(Mn)約為1594，而分子量分佈值(PDI)約為1.29，相關溶解度測試結果請參閱表2。
【實施例3】合成聚苯醚寡聚物3
取2克(1.92mmol)聚苯醚寡聚物1至100ml的雙頸瓶中，加入20ml四氫呋喃(THF)作為溶劑，在氮氣系統下加熱至60℃。接著，加入8克濃度為25%的氫氧化鈉水溶液，緊接著緩慢加入20ml(27.5mmol)對氯甲基苯乙烯(4-chloromethylstyrene)。待反應結束後，回至常溫後加入甲苯與 去離子水進行萃取，所得有機層溶液迴旋濃縮後再溶解於甲苯並於甲醇中沉澱，以抽氣過濾收集固體產物，然後在減壓下乾燥，以獲得1.2克之聚苯醚寡聚物3；上述反應可表示如下式：
聚苯醚寡聚物3的氫核磁共振(1H-NMR)光譜(400MHz，溶劑為氘-氯仿(CDCl3)，化學位移7.24ppm)1H-NMR分析結果：δ7.44-7.34ppm(4H)，δ7.06-6.89ppm(6H)，δ6.77-6.73ppm(2H)，δ6.47-6.46ppm(2H)，δ6.39ppm(2H)，δ5.79-5.74ppm(1H)，δ5.29-5.25ppm(1H)，δ4.76ppm(2H)，δ4.58ppm(1H)。聚苯醚寡聚物3的FT-IR圖譜中顯示3600cm-1(聚苯醚寡聚物1末端之酚羥基吸收位置)吸收峰消失，官能基已改變。
由膠透層析儀(Gel Permeation Chromatography；GPC)鑑定，聚苯醚寡聚物3之數目平均分子量約為1953，PDI值為1.33。
【實施例4】合成聚苯醚寡聚物4
聚苯醚寡聚物1(2g,1.92mmol)至100ml的雙頸瓶中，並加入環氧氯丙烷(11.7g,117mmol)，在氮氣系統下加熱至100℃。接著，緩慢滴加入乙氧化鈉(0.36g,5.44mmol)溶解 於乙醇(1.6g)中而製得之溶液。待反應結束後，回至常溫後加入甲苯與去離子水進行萃取，所得有機層溶液迴旋濃縮後再溶解於甲苯並於甲醇中沉澱，以抽氣過濾收集固體產物，然後在減壓下乾燥，以獲得1.1g之聚苯醚寡聚物4；上述反應可表示如下式：
聚苯醚寡聚物4的氫核磁共振(1H-NMR)光譜(400MHz，溶劑為氘-丙酮(acetone-d 6 )，化學位移2.05ppm)。1H-NMR詳細分析結果如下：δ7.26-7.05ppm(6H)，δ6.96-6.91ppm(2H)，δ6.54-6.52ppm(2H)，δ6.40ppm(2H)，δ4.08-4.05ppm(2H)，δ3.63-3.59ppm(1H)，δ3.30ppm(2H)。聚苯醚寡聚物4的FT-IR圖譜中顯示3600cm-1(聚苯醚寡聚物1末端之酚羥基吸收位置)吸收峰消失，官能基已改變。
由膠透層析儀(Gel Permeation Chromatography；GPC)鑑定，聚苯醚寡聚物4之數目平均分子量約為1916，PDI值為1.38。
【實施例5】量測介電特性
將上述聚苯醚寡聚物2製備所得之黏著層與銅箔 進行高溫壓合硬化，形成銅箔基板材料後，以介電分析儀量測其相關電氣特性數據，請參閱表1。
由表1可知本發明實施例之聚苯醚寡聚物具有相當優異的介電常數(dielectric constant,Dk)與介電損耗(dissipation factor,Df)。
【比較例1】聚苯醚寡聚物A
混合16.22克(43.08mmol)DCPD-DIDMP、52.55克(430.8mmol)2,6-二甲基苯酚、3.19克(31.54mmol)N,N’-二甲基丁胺(N,N’-Dimethylbutylamine)、2.52克(19.54mmol)二正丁胺(di-n-butylamine)與208克甲醇形成單體混合溶液。
在氧氣系統下於反應器中混合0.61克(2.71mmol)溴化銅(CuBr2)、1.70克(16.85mmol)N,N’-二甲基丁胺(N,N’-dimethylbutylamine)、1.32克(10.22mmol)二正丁胺(di-n-butylamine)和235克甲苯，加熱至45℃。而後，在氧氣系統下將單體混和溶液加入至反應器中。
待反應結束後，將2.88克(7.58mmol)乙二胺四乙酸四鈉溶解於200克水中，加入反應器中，以終止反應。分離水層和有機層。將有機層溶液減壓濃縮，以獲得62g之聚苯醚寡聚物A；數目平均分子量約為2,009，PDI為1.54。相關溶解度測試結果請參閱表2。
由表2可知本發明實施例之聚苯醚寡聚物可溶於多種溶劑，有利於加工應用，尤其對丙酮具有良好的溶解度。
雖然本發明已以數個較佳實施例揭露如上，然其並非用以限定本發明，任何所屬技術領域中具有通常知識者，在不脫離本發明之精神和範圍內，當可作任意之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。

Claims (10)

  1. 一種聚苯醚(polyphenylene ether)寡聚物，係具有如式(I)所示之結構： 其中，每一R1係獨立地為氫、C1-6的烷基或苯基；每一R2係獨立地為氫、C1-6的烷基或苯基；a：(a+b)係介於0.05：1至1：1之間；n：(a+b)係介於0.05：1至5：1之間；Q係或m係0至4之整數，Ra係C1-6的烷撐基，Rb係C1-6的烷撐基；每一X係獨立地為氫、丙烯醯基(acryloyl group)、丙烯基(allyl group)、乙烯基苯基(vinylbenzyl group)、環氧丙基(epoxypropyl group)、甲基丙烯醯基(methacryloyl group)、丙炔基(propargyl group)或丙烯腈基(cyanol group)；以及該聚苯醚寡聚物之數目平均分子量(Mn)係介於400至2000之間。
  2. 如申請專利範圍第1項所述之聚苯醚寡聚物，其中Q係
  3. 如申請專利範圍第1項所述之聚苯醚寡聚物，其中每一X係獨立地為氫、或 其中R3係獨立地為氫或C1-3烷基，p係1至4之整數，W係環氧基、羥基或乙烯基，R4係C1-12烷撐基，g係0或1之整數，s係0或1之整數，R5係獨立地為氫或C1-12烷基。
  4. 如申請專利範圍第1項所述之聚苯醚寡聚物，其中每一X係獨立地為或
  5. 如申請專利範圍第1項所述之聚苯醚寡聚物，其中該聚苯醚寡聚物的數目平均分子量介於500至2000之間。
  6. 如申請專利範圍第1項所述之聚苯醚寡聚物，其係具有如式(II)所示之結構： 其中a：(a+b)係介於0.05：1至1：1之間；n：(a+b)係介於0.05：1至5：1之間。
  7. 如申請專利範圍第1項所述之聚苯醚寡聚物，其係具有 如式(III)所示之結構： 其中a：(a+b)係介於0.05：1至1：1之間；n：(a+b)係介於0.05：1至5：1之間。
  8. 如申請專利範圍第1項所述之聚苯醚寡聚物，其係具有如式(IV)所示之結構： 其中a：(a+b)係介於0.05：1至1：1之間；n：(a+b)係介於0.05：1至5：1之間。
  9. 如申請專利範圍第1項所述之聚苯醚寡聚物，其係具有如式(V)所示之結構： 其中a：(a+b)係介於0.05：1至1：1之間；n：(a+b)係介於0.05：1至5：1之間。
  10. 一種高頻銅箔基板，包含：一銅箔基板；以及一黏著層，黏著層位於銅箔基板，其中該黏著層由一組成物製備而得，該組成物包含如申請專利範圍第1項的聚苯醚寡聚物。
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