CN117946313A - 含乙烯基芳香脂环族共聚合物、树脂组成物及其制品 - Google Patents
含乙烯基芳香脂环族共聚合物、树脂组成物及其制品 Download PDFInfo
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Abstract
本发明提供一种含乙烯基芳香脂环族共聚合物、树脂组成物及其制品,树脂组成物包括含乙烯基芳香脂环族共聚合物,由树脂组成物制成的制品,其Tg大于200℃、介电常数Dk(10GHz)为3.0以下且介电损耗Df(10GHz)为0.0014以下。
Description
技术领域
本发明涉及一种共聚合物、树脂组成物及其制品,且涉及一种含乙烯基芳香脂环族共聚合物、树脂组成物及其制品。
背景技术
一般低介电树脂例如液态橡胶因具有优异介电特性,如介电常数Dk以及介电损耗Df,因此,成为了高频印刷电路板的基板材料首选树脂之一。
然而,液态橡胶为热塑性树脂,即使改质反应基也偏少,将其直接应用于铜箔基板容易存在以下缺点:1.Tg过低、2.反应性不佳、3.难以加工成型、4.融熔黏度高,因此,需要设计新型改质结构才能符合印刷电路板的使用需求。
基于上述,如何开发出具有优异电性并符合印刷电路板其他特性需求,例如高Tg、低膨胀系数、低吸水率的特性材料,并将其应于高频基板制造,为本领域技术人员亟欲发展的目标。
发明内容
本发明提供一种含乙烯基芳香脂环族共聚合物、树脂组成物及其制品,使其具备高玻璃转移温度、低介电常数Dk及介电耗损Df。
本发明的含乙烯基芳香脂环族共聚合物包括下述式(1)所示的化学结构:
在式(1)中,x为1至10的整数,y为1至20的整数,z为为1至20的整数,
R1为
R2为
R3为选自下述化学式的一种
I为选自下述化学式的一种
在本发明的一实施例中,含乙烯基芳香脂环族共聚合物的分子量Mn为2000至6000。
在本发明的一实施例中,在含乙烯基芳香脂环族共聚合物中,脂环族的摩尔比为10%至40%,乙烯基的摩尔比为10%至40%,苯乙烯的摩尔比为20%至90%。
本发明的树脂组成物包括上述含乙烯基芳香脂环族共聚合物、聚苯醚树脂、三烯丙基异三聚氰酸酯、双马来酰亚胺树脂、耐燃剂以及无机填料。
在本发明的一实施例中,耐燃剂包括磷系阻燃剂。
在本发明的一实施例中,无机填料包括二氧化硅。
在本发明的一实施例中,以树脂组成物的总重量计,含乙烯基芳香脂环族共聚合物的含量为5wt%至20wt%,聚苯醚树脂的含量为5wt%至30wt%,三烯丙基异三聚氰酸酯的含量为5wt%至20wt%,双马来酰亚胺树脂的含量为5wt%至20wt%,耐燃剂的含量为5wt%至20wt%,无机填料的含量为30wt%至60wt%。
本发明的制品,由上述树脂组成物进行加工方法而制成,加工方法包括含浸及热压成型。
在本发明的一实施例中,制品的Tg大于200℃、介电常数Dk(10GHz)为3.0以下且介电损耗Df(10GHz)为0.0014以下。
基于上述,本发明提供一种含乙烯基芳香脂环族共聚合物,含有可反应双键,藉由分子间交联,不仅改善其反应性、耐热性、耐化学性、耐寒性、低温柔韧性和电性并提高溶剂溶解度,更由于本发明的乙烯基芳香脂环族共聚合物含有非极性骨干结构,在电场中不易受到极化,可大幅降低介电常数Dk(10GHz)及介电损耗Df(10GHz),且丙酮中的溶剂溶解性为40%。
具体实施方式
以下,将详细描述本发明的实施例。然而,这些实施例为例示性,且本发明揭露不限于此。
在本文中,由“一数值至另一数值”表示的范围,是一种避免在说明书中一一列举该范围中的所有数值的概要性表示方式。因此,某一特定数值范围的记载,涵盖该数值范围内的任意数值以及由该数值范围内的任意数值界定出的较小数值范围,如同在说明书中说明文写出该任意数值和该较小数值范围一样。
本发明的含乙烯基芳香脂环族共聚合物,包括下述式(1)所示的化学结构:
在式(1)中,x为1至10的整数,y为1至20的整数,z为为1至20的整数,
R1为
R2为
R3为选自下述化学式的一种
I为选自下述化学式的一种
在本实施例中,含乙烯基芳香脂环族共聚合物的分子量Mn例如是2000至6000。在含乙烯基芳香脂环族共聚合物中,脂环族的摩尔比例如是10%至40%,乙烯基的摩尔比例如是10%至40%,苯乙烯的摩尔比例如是20%至90%。
在本实施例中,含乙烯基芳香脂环族共聚合物的制造方法可包括合成反应制程及析出纯化制程,方法可包括以下步骤。首先,准备反应容器,内部设有搅拌混合器。选取自由基控制剂、自由基起始剂以及可反应乙烯基结构原料,自由基控制剂可包括2,2,6,6-四甲基哌啶-1-氧化物(TEMPO)或4-羟基-2,2,6,6-四甲基-1-氧化哌啶,自由基起始剂可包括过氧苯甲酰(Benzoyl peroxide,BPO)或偶氮二异丁腈(AIBN),可反应乙烯基结构原料可包括2-乙烯基萘、苯乙烯、二乙烯基苯(DVB)、丁二烯、4-乙烯基联苯、双环戊二烯DCPD)、降冰片烯等等,其中I、X、Y、Z的摩尔比例如是1:2至5:2至10:2至10,I为自由基捕捉剂,X、Y、Z为不同种类可反应乙烯基结构。在温度0℃至150℃下,于非质子溶剂中反应1小时至5小时,非质子溶剂可包括甲苯、二甲基甲酰胺(Dimethylformamide,DMF)。反应液加甲醇析出固体、过滤,经真空干燥,即可得到本发明的含乙烯基芳香脂环族共聚合物。
本发明也提供一种树脂组成物,包括上述含乙烯基芳香脂环族共聚合物、聚苯醚树脂、三烯丙基异三聚氰酸酯、双马来酰亚胺树脂、耐燃剂以及无机填料。在本实施例中,耐燃剂可包括磷系耐燃剂,无机填料可包括二氧化硅。以树脂组成物的总重量计,含乙烯基芳香脂环族共聚合物的含量例如是5至20wt%,聚苯醚树脂的含量例如是5wt%至30wt%,三烯丙基异三聚氰酸酯的含量例如是5wt%至20wt%,双马来酰亚胺树脂的含量例如是5wt%至20wt%,耐燃剂的含量例如是5wt%至20wt%,无机填料的含量例如是30wt%至60wt%。
本发明也提供一种制品,由上述树脂组成物进行加工方法而制成,所述加工方法可包括含浸及热压成型。在本实施例中,制品的Tg可大于200℃、介电常数Dk(10GHz)可为3.0以下且介电损耗Df(10GHz)可为0.0014以下。
以下,藉由实验例来详细说明上述本发明的含乙烯基芳香脂环族共聚合物、树脂组成物及其制品。然而,下述实验例并非用以限制本发明。
实验例
为了本发明的含乙烯基芳香脂环族共聚合物可改善制品的反应性、耐热性、耐化学性、耐寒性、低温柔韧性和电性并提高溶剂溶解度,以下特别作此实验例。
测试方法
(1)玻璃转移温度:使用热重量分析仪(Thermogravimetric Analyzer,TGA),测试橡胶树脂材料的玻璃转移温度。
(2)介电常数(10GHz):使用介电分析仪(Dielectric Analyzer)(型号HP AgilentE5071C),测试橡胶树脂材料在频率10G Hz时的介电常数。
(3)介电损耗(10GHz):使用介电分析仪(Dielectric Analyzer)(型号HP AgilentE5071C),测试橡胶树脂材料在频率10G Hz时的介电损耗。
(4)剥离强度测试:根据IPC-TM-650-2.4.8测试方法,测试金属基板的剥离强度。
(5)耐热性:将金属基板于温度为120℃、压力为2atm的高压锅中加热120分钟,再浸入288℃焊锡炉中,并记录爆板的所需时间,爆板时间超过10min以“OK”表示,爆板时间短于10min以“NG”表示。
含乙烯基芳香脂环族共聚合物的制备
以下表1中列出本发明含乙烯基芳香脂环族共聚合物的合成条件,以此制造制备例1至制备例6的乙烯基芳香脂环族共聚合物。
表1
制备例1
依照摩尔比1:40:2:1:1,取3.9g(等同0.025mol)自由基控制剂TEMPO、104g(等同1mol)苯乙烯、6.6g(等同0.05mol)DCPD、3.3g(等同0.025mol)DVB以及6g(等同0.025mol)BPO起始剂。将上述原料溶于500ml甲苯中,投入设有搅拌混合器的1L四颈圆底反应烧瓶,对反应烧瓶通入氮气以去除空气及水气,在常压下,启动搅拌混合器,在300rpm下对反应溶液均匀混合。当反应温度达到120℃时,反应溶液的所有固含量溶解成清澈红褐色溶液,反映条件设定在反应温度120℃下反应3小时,使得清澈红褐色溶液改变为黏稠红褐色溶液,将溶液滴至甲醇中沉淀聚合物,将所得到的聚合物过滤及真空干燥,即可得到本发明的含乙烯基芳香脂环族共聚合物。
制备例2至制备例6
将表1所制成的制备例1至制备例6的含乙烯基芳香脂环族共聚合物以及市售取得的B1000、B2000及RI257树脂,以树脂组成物形式制成铜箔基板,加工方法可包括含浸及热压成型。将一玻璃纤维布,分别浸入实施例1至实施例4以及比较例1至比较例10的橡胶树脂材料中,经含浸、干燥与成型的步骤之后,可获得一预浸片(prepreg)。树脂组成物的成分比例以及铜箔基板的测试结果列于以下表2中。由表2可得知,使用本发明含乙烯基芳香脂环族共聚合物的合成方法,可使树脂PDI介于1至1.4,且适合制成高Tg大于200℃、介电常数Dk(10GHz)为3.0以下且介电损耗Df(10GHz)为0.0014以下的铜箔基板。
耐燃剂DE60H的化学结构如下所示:
表2
综上所述,基于上述,本发明提供一种含乙烯基芳香脂环族共聚合物,含有可反应双键,藉由分子间交联,不仅改善其反应性、耐热性、耐化学性、耐寒性、低温柔韧性和电性并提高溶剂溶解度,更由于本发明的乙烯基芳香脂环族共聚合物含有非极性骨干结构,在电场中不易受到极化,可大幅降低介电常数Dk(10GHz)及介电损耗Df(10GHz),介电常数Dk(10GHz)为3.0以下,介电损耗Df(10GHz)为0.0014以下,且丙酮中的溶剂溶解性为40%,因此,具有优异电性并符合印刷电路板其他特性需求。相较于一般低介电芳香族树脂,本发明的含乙烯基芳香脂环族共聚合物可改善脆性、提高韧性、提高耐热性及对溶剂提高溶解量,适合制成高Tg大于200℃、介电常数Dk(10GHz)为3.0以下且介电损耗Df(10GHz)为0.0014以下的铜箔基板,更具备多样使用用途,与其他树脂混合硬化后,其特性仍具备高的玻璃转化温度(Tg)、更低的介电常数Dk及介电损耗Df。
Claims (9)
1.一种含乙烯基芳香脂环族共聚合物,其特征在于,包括下述式(1)所示的化学结构:
在式(1)中,x为1至10的整数,y为1至20的整数,z为为1至20的整数,
R1为
R2为
R3为选自下述化学式的一种
I为选自下述化学式的一种
2.根据权利要求1所述的含乙烯基芳香脂环族共聚合物,其特征在于,所述含乙烯基芳香脂环族共聚合物的分子量Mn为2000至6000。
3.根据权利要求1所述的含乙烯基芳香脂环族共聚合物,其特征在于,在所述含乙烯基芳香脂环族共聚合物中,脂环族的摩尔比为10%至40%,乙烯基的摩尔比为10%至40%,苯乙烯的摩尔比为20%至90%。
4.一种树脂组成物,其特征在于,包括:
根据权利要求1至3中任一项所述的含乙烯基芳香脂环族共聚合物;
聚苯醚树脂;
三烯丙基异三聚氰酸酯;
双马来酰亚胺树脂;
耐燃剂;以及
无机填料。
5.根据权利要求4所述的树脂组成物,其特征在于,所述耐燃剂包括磷系耐燃剂。
6.根据权利要求4所述的树脂组成物,其特征在于,所述无机填料包括二氧化硅。
7.根据权利要求4所述的树脂组成物,其特征在于,以所述树脂组成物的总重量计,所述含乙烯基芳香脂环族共聚合物的含量为5至20wt%,所述聚苯醚树脂的含量为5wt%至30wt%,所述三烯丙基异三聚氰酸酯的含量为5wt%至20wt%,所述双马来酰亚胺树脂的含量为5wt%至20wt%,所述耐燃剂的含量为5wt%至20wt%,所述无机填料的含量为30wt%至60wt%。
8.一种制品,其特征在于,由权利要求4至7中任一项所述的树脂组成物进行加工方法而制成,所述加工方法包括含浸及热压成型。
9.根据权利要求8所述的制品,其特征在于,所述制品的Tg大于200℃、介电常数Dk(10GHz)为3.0以下且介电损耗Df(10GHz)为0.0014以下。
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