CN107022075B - 聚苯醚寡聚物及高频铜箔基板 - Google Patents

聚苯醚寡聚物及高频铜箔基板 Download PDF

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CN107022075B
CN107022075B CN201611192062.2A CN201611192062A CN107022075B CN 107022075 B CN107022075 B CN 107022075B CN 201611192062 A CN201611192062 A CN 201611192062A CN 107022075 B CN107022075 B CN 107022075B
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polyphenylene oxide
oxide oligomer
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郭政柏
陈泊如
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Abstract

本发明涉及一种聚苯醚寡聚物及高频铜箔基板。该聚苯醚寡聚物具有如式(I)所示的结构：式(I)；其中，每一R1独立地为氢、C1‑6的烷基或苯基；每一R2独立地为氢、C1‑6的烷基或苯基；a:(a+b)是介于0.05:1至1:1之间；n:(a+b)是介于0.05:1至5:1之间；Q是或m是0至4的整数，Ra是C1‑6的烷撑基，Rb是C1‑6的烷撑基；每一X是独立地为氢、丙烯酰基、烯丙基、乙烯基苯基、环氧丙基、甲基丙烯酰基、丙炔基或丙烯腈基；以及该聚苯醚寡聚物的数目平均分子量(Mn)是介于400至2000之间。本发明的聚苯醚寡聚物，具有良好的溶解度，有利于加工。

Description

聚苯醚寡聚物及高频铜箔基板
技术领域
本发明是有关于一种聚苯醚寡聚物及高频铜箔基板。
背景技术
现今通讯电子产业发展迅速，并朝向高速、高频、高密度发展，因此具高耐热性、低介电系数、高坚韧结构特性的高分子是下一代电子构装及高频基板材料开发的主要方向。
聚苯醚(polyphenylene ether)即为一种高性能材料。然而，聚苯醚的应用中，在加工制程方面，还需要开发具备良好溶解度的材料。因此，聚苯醚的设计开发是相当重要的研究。
发明内容
本发明的目的在于提供一种具备良好溶解度的聚苯醚。
本发明实施例提供一种聚苯醚(polyphenylene ether)寡聚物，聚苯醚寡聚物是具有如式(I)所示的结构：
其中，每一R1独立地为氢、C1-6的烷基或苯基；每一R2独立地为氢、C1-6的烷基或苯基；a:(a+b)是介于0.05:1至1:1之间；n:(a+b)是介于0.05:1至5:1之间；Q是m是0至4的整数，Ra是C1-6的烷撑基，Rb是C1-6的烷撑基；每一X独立地为氢、丙烯酰基(acryloyl group)、烯丙基(allylgroup)、乙烯基苯基(vinylbenzyl group)、环氧丙基(epoxypropyl group)、甲基丙烯酰基(methacryloyl group)、丙炔基(propargyl group)或丙烯腈基(cyanol group)；以及该聚苯醚寡聚物的数目平均分子量(Mn)是介于400至2000之间。
一种高频铜箔基板，包含铜箔基板以及粘着层，粘着层位于铜箔基板之上，其中粘着层由一组合物制备而得，组合物包含上述的聚苯醚寡聚物。
与现有技术相比，本发明的优点在于：本发明的聚苯醚寡聚物，具有良好的溶解度，有利于加工。并且，以本发明的聚苯醚寡聚物制备所得的粘着层与铜箔进行高温压合硬化，形成铜箔基板材料后，可呈现良好的电性，例如，相当优异的介电常数与介电损耗。
为让本发明的上述和其他目的、特征、和优点能更明显易懂，下文特举出较佳实施例，作详细说明如下：
具体实施方式
本发明提供一种聚苯醚寡聚物，具有良好的溶解度有利于加工，以聚苯醚寡聚物制得的制品可呈现良好的电性。
本发明提供一种聚苯醚寡聚物，具有如式(I)所示的结构：
其中，每一R1可以独立地为氢、C1-6的烷基或苯基；每一R2可以独立地为氢、C1-6的烷基或苯基；a:(a+b)约介于0.05:1至1:1之间；n:(a+b)约介于0.05:1至5:1之间；
Q可以是m可以是0至4的整数，Ra可以是C1-6的烷撑基，Rb可以是C1-6的烷撑基；以及每一X可以独立地为氢、丙烯酰基、烯丙基、乙烯基苯基、环氧丙基、甲基丙烯酰基、丙炔基或丙烯腈基。
在本发明一实施例中，聚苯醚寡聚物的数目平均分子量(Mn)约介于400至2000之间，例如约介于500至2000之间或约介于800至2000之间，也可以是介于1000至2000之间，又或是介于900至1700之间。若聚苯醚寡聚物的数目平均分子量过低，则易造成热稳定性不佳。若聚苯醚寡聚物的重量平均分子量过高，则易造成加工性不佳。
需要说明的是，于本揭露中，介于某两数值之间亦包含某两数值，例如约介于500至2000之间亦包含500与2000。
在本发明一实施例中，Q可以是
在本发明一实施例中，每一X可以独立地为氢、 其中R3可以独立地为氢或C1-3烷基，p可以是1至4的整数，W可以是环氧基、羟基或乙烯基，R4可以是C1-12烷撑基，g是0或1的整数，s是0或1的整数，R5可以是独立地为氢或C1-12烷基。
在本发明一实施例中，每一X可以独立地为
在本发明一实施例中，聚苯醚寡聚物可具有如式(II)所示的结构：
其中a:(a+b)约介于0.05:1至1:1之间；n:(a+b)约介于0.05:1至5:1之间。
在本发明一实施例中，聚苯醚寡聚物可具有如式(III)所示的结构：
其中a:(a+b)约介于0.05:1至1:1之间；n:(a+b)约介于0.05:1至5:1之间。
在本发明一实施例中，聚苯醚寡聚物可具有如式(IV)所示的结构：
其中a:(a+b)约介于0.05:1至1:1之间；n:(a+b)约介于0.05:1至5:1之间。
在本发明一实施例中，聚苯醚寡聚物可具有如式(V)所示的结构：
其中a:(a+b)约介于0.05:1至1:1之间；n:(a+b)约介于0.05:1至5:1之间。
在本发明一实施例中，是利用第一反应物(例如)与第二反应物(例如或上述的组合)作为起始物合成双酚单体，接着，将双酚单体与第三反应物(例如)进行聚合反应，以形成聚苯醚寡聚物。每一R1可以独立地为氢、C1-6的烷基或苯基；每一R2可以独立地为氢、C1-6的烷基或苯基；m可以是0至4的整数，Ra可以是C1-6的烷撑基，Rb可以是C1-6的烷撑基，X可以是氢、丙烯酰基、烯丙基、乙烯基苯基、环氧丙基、甲基丙烯酰基、丙炔基或丙烯腈基。
在本发明一实施例中，是利用第一反应物(例如)与第二反应物(例如或上述的组合)作为起始物合成双酚单体，接着，将双酚单体与第三反应物(例如)进行聚合反应后再与第四反应物(例如)进行取代反应，以形成聚苯醚寡聚物。每一R1可以独立地为氢、C1-6的烷基或苯基；每一R2可以独立地为氢、C1-6的烷基或苯基；m可以是0至4的整数，Ra可以是C1-6的烷撑基，Rb可以是C1-6的烷撑基，X可以是氢、丙烯酰基、烯丙基、乙烯基苯基、环氧丙基、甲基丙烯酰基、丙炔基或丙烯腈基，R4可以是C1-12烷撑基，g是0或1的整数，s是0或1的整数，R5可以是独立地为氢或C1-12烷基。
在本发明一实施例中，第一反应物(例如)与第二反应物(例如或上述的组合)的摩尔比约介于2:1至3:1之间。
在本发明一实施例中，第三反应物(例如)对第二反应物(例如或上述的组合)的摩尔比约介于0.2:1至20:1之间。若上述摩尔比过低，则可能造成热稳定性不佳。若上述摩尔比过高，则可能造成材料韧性不足。
在本发明一实施例中，聚苯醚寡聚物可应用于高频铜箔基板的制作，例如高频铜箔基板可包含铜箔基板以及粘着层，粘着层位于铜箔基板，其中粘着层由组合物制备而得，组合物包含上述的聚苯醚寡聚物。
以下藉由下列实施例来说明本发明所述的聚苯醚寡聚物的合成方式，用以进一步阐明本发明的技术特征。
【实施例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)氯化铝(aluminium chloride)加入至反应器中，在氮气系统下加热至120℃。接着，在120℃下，加入15.6克(0.12mol)双环戊二烯(dicyclopentadiene)，再持续搅拌反应。待反应结束后，加入5wt％氢氧化钠(0.06mol)水溶液中和催化剂，并加入甲苯搅拌1小时后将反应液过滤除去盐类与催化剂，所得的滤液利用水洗数次，取有机层并减压蒸馏纯化即可得40.61克的深棕色双酚单体(DCPD-DIDMP)，产率为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)与208克甲醇形成单体混合溶液。
在氧气系统下于反应器中混合0.253克(1.13mmol)溴化铜(CuBr2)、0.71克(7.02mmol)N,N’-二甲基丁胺、0.55克(4.26mmol)二正丁胺和235克甲苯，加热至45℃。而后，在氧气系统下将单体混和溶液加入至反应器中。
待反应结束后，将1.2克(3.16mmol)乙二胺四乙酸四钠溶解于200克水中，加入反应器中，以终止反应。分离水层和有机层。将有机层溶液减压浓缩，获得28克的聚酚醚寡聚物1，上述反应可表示如下式：
DCPD-DIDMP的氢核磁共振(1H-NMR)光谱(400MHz，氘-二甲基亚砜(DMSO-d6)，化学位移2.54ppm)1H-NMR分析结果：δ7.93ppm(-OH)，δ6.87-6.55ppm(Aromatic H of DMP)，δ2.19-1.05ppm(Aliphatic H of DMP and DCPD)。在δ7.93ppm信号为DCPD-DIDMP的DMP苯环上羟基吸收位置。聚苯醚寡聚物1的氢核磁共振(1H-NMR)光谱(400MHz，溶剂为氘-丙酮(acetone-d6)，化学位移2.05ppm)，1H-NMR分析结果：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图谱测得3600cm-1为聚苯醚寡聚物1末端的酚羟基吸收峰。
由胶透层析仪(Gel Permeation Chromatography,GPC)鉴定，聚苯醚寡聚物1的数目平均分子量(Mn)约为1044，而分子量分布值(polydispersity,PDI)约为1.41，相关溶解度测试结果请参阅表2。
聚苯醚寡聚物1的溶解度测试方式：聚苯醚寡聚物与溶剂混合后溶液为澄清无沉淀物则为可溶，反之为不可溶，聚苯醚寡聚物与溶剂混合的重量比为1：1。本揭露所有聚苯醚寡聚物的溶解度测试皆同上述方式。
【实施例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(methacrylicanhydride)和63.8克甲苯，加热至80℃反应。待反应结束后，回至常温加入甲苯63.8克，将此反应溶液沉淀于大量甲醇中，所得沉淀粗产物以抽气过滤收集，再以300ml甲醇清洗搅拌30分钟后再以抽气过滤收集得到固体产物，然后在减压下干燥，以获得17克的聚苯醚寡聚物2，上述反应可表示如下式：
聚苯醚寡聚物2的FT-IR图谱中显示在3600cm-1(聚苯醚寡聚物1末端的酚羟基吸收位置)吸收峰消失，然而在1734cm-1为聚苯醚寡聚物2末端的甲基丙烯酰基(methylacryloygroup)吸收峰。聚苯醚寡聚物2的氢核磁共振(1H-NMR)光谱(400MHz，溶剂为氘-丙酮(acetone-d6)，化学位移2.05ppm)，1H-NMR分析结果：δ7.09-6.99ppm(4)，δ6.53-6.48ppm(3)，δ6.33ppm(2)，δ5.83ppm(1)。
由胶透层析仪(Gel Permeation Chromatography；GPC)鉴定，聚苯醚寡聚物2的数目平均分子量(Mn)约为1594，而分子量分布值(PDI)约为1.29，相关溶解度测试结果请参阅表2。
【实施例3】合成聚苯醚寡聚物3
取2克(1.92mmol)聚苯醚寡聚物1至100ml的双颈瓶中，加入20ml四氢呋喃(THF)作为溶剂，在氮气系统下加热至60℃。接着，加入8克浓度为25％的氢氧化钠水溶液，紧接着缓慢加入20ml(27.5mmol)对氯甲基苯乙烯(4-chloromethylstyrene)。待反应结束后，回至常温后加入甲苯与去离子水进行萃取，所得有机层溶液回旋浓缩后再溶解于甲苯并于甲醇中沉淀，以抽气过滤收集固体产物，然后在减压下干燥，以获得1.2克的聚苯醚寡聚物3；上述反应可表示如下式：
聚苯醚寡聚物3的氢核磁共振(1H-NMR)光谱(400MHz，溶剂为氘-氯仿(CDCl3)，化学位移7.24ppm)1H-NMR分析结果：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图谱中显示3600cm-1(聚苯醚寡聚物1末端的酚羟基吸收位置)吸收峰消失，官能基已改变。
由胶透层析仪(Gel Permeation Chromatography；GPC)鉴定，聚苯醚寡聚物3的数目平均分子量约为1953，PDI值为1.33。
【实施例4】合成聚苯醚寡聚物4
聚苯醚寡聚物1(2g,1.92mmol)至100ml的双颈瓶中，并加入环氧氯丙烷(11.7g,117mmol)，在氮气系统下加热至100℃。接着，缓慢滴加入乙氧化钠(0.36g,5.44mmol)溶解于乙醇(1.6g)中而制得的溶液。待反应结束后，回至常温后加入甲苯与去离子水进行萃取，所得有机层溶液回旋浓缩后再溶解于甲苯并于甲醇中沉淀，以抽气过滤收集固体产物，然后在减压下干燥，以获得1.1g的聚苯醚寡聚物4；上述反应可表示如下式：
聚苯醚寡聚物4的氢核磁共振(1H-NMR)光谱(400MHz，溶剂为氘-丙酮(acetone-d6)，化学位移2.05ppm)。1H-NMR详细分析结果如下：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图谱中显示3600cm-1(聚苯醚寡聚物1末端的酚羟基吸收位置)吸收峰消失，官能基已改变。
由胶透层析仪(Gel Permeation Chromatography；GPC)鉴定，聚苯醚寡聚物4的数目平均分子量约为1916，PDI值为1.38。
【实施例5】量测介电特性
将上述聚苯醚寡聚物2制备所得的粘着层与铜箔进行高温压合硬化，形成铜箔基板材料后，以介电分析仪量测其相关电气特性数据，请参阅表1。
表1
Dk(5GHz) Df(5GHz)
实施例5 3.94 0.004
由表1可知本发明实施例的聚苯醚寡聚物具有相当优异的介电常数(dielectricconstant,Dk)与介电损耗(dissipation factor,Df)。
【比较例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、2.52克(19.54mmol)二正丁胺与208克甲醇形成单体混合溶液。
在氧气系统下于反应器中混合0.61克(2.71mmol)溴化铜(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，加热至45℃。而后，在氧气系统下将单体混和溶液加入至反应器中。
待反应结束后，将2.88克(7.58mmol)乙二胺四乙酸四钠溶解于200克水中，加入反应器中，以终止反应。分离水层和有机层。将有机层溶液减压浓缩，以获得62g的聚苯醚寡聚物A；数目平均分子量约为2,009，PDI为1.54。相关溶解度测试结果请参阅表2。
表2
由表2可知本发明实施例的聚苯醚寡聚物可溶于多种溶剂，有利于加工应用，尤其对丙酮具有良好的溶解度。
虽然本发明已以数个较佳实施例揭露如上，然其并非用以限定本发明，任何所属技术领域中具有通常知识者，在不脱离本发明的精神和范围内，当可作任意的更动与润饰，因此本发明的保护范围当视后附的权利要求书界定的范围为准。

Claims (10)

1.一种聚苯醚寡聚物，具有如式(I)所示的结构：
其中，每一R1独立地为氢、C1-6的烷基或苯基；
每一R2独立地为氢、C1-6的烷基或苯基；a:(a+b)是介于0.05:1至1:1之间；n:(a+b)是介于0.05:1至5:1之间；
Q是
m是0至4的整数，Ra是C1-6的烷撑基，Rb是C1-6的烷撑基；
每一X独立地为氢、 乙烯基苯基、丙炔基或丙烯腈基，
其中R3独立地为氢或C1-3烷基，p是1至4的整数，W是环氧基、羟基或乙烯基，R4是C1-12烷撑基，g是0或1的整数，s是0或1的整数，R5是独立地为氢或C1-12烷基；以及
该聚苯醚寡聚物的数目平均分子量(Mn)是介于400至2000之间。
2.如权利要求1所述的聚苯醚寡聚物，其中Q是
3.如权利要求1所述的聚苯醚寡聚物，其中
每一X独立地为丙烯酰基、烯丙基、环氧丙基或甲基丙烯酰基。
4.如权利要求1所述的聚苯醚寡聚物，其中每一X独立地为
5.如权利要求1所述的聚苯醚寡聚物，其中该聚苯醚寡聚物的数目平均分子量介于500至2000之间。
6.如权利要求1所述的聚苯醚寡聚物，其具有如式(II)所示的结构：
其中a:(a+b)是介于0.05:1至1:1之间；n:(a+b)是介于0.05:1至5:1之间。
7.如权利要求1所述的聚苯醚寡聚物，其是具有如式(III)所示的结构：
其中a:(a+b)是介于0.05:1至1:1之间；n:(a+b)是介于0.05:1至5:1之间。
8.如权利要求1所述的聚苯醚寡聚物，其具有如式(IV)所示的结构：
式(IV)
其中a:(a+b)是介于0.05:1至1:1之间；n:(a+b)是介于0.05:1至5:1之间。
9.如权利要求1所述的聚苯醚寡聚物，其具有如式(V)所示的结构：
其中a:(a+b)是介于0.05:1至1:1之间；n:(a+b)是介于0.05:1至5:1之间。
10.一种高频铜箔基板，包含
铜箔基板；以及
粘着层，所述粘着层位于铜箔基板上，其中该粘着层由组合物制备而得，该组合物包含如权利要求1的聚苯醚寡聚物。
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