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CN105542128A - 一种环氧树脂固化剂及其制备方法和用途 - Google Patents

一种环氧树脂固化剂及其制备方法和用途 Download PDF

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Publication number
CN105542128A
CN105542128A CN201510936667.7A CN201510936667A CN105542128A CN 105542128 A CN105542128 A CN 105542128A CN 201510936667 A CN201510936667 A CN 201510936667A CN 105542128 A CN105542128 A CN 105542128A
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CN
China
Prior art keywords
unsubstituted
replace
replacement
epoxy resin
substituted
Prior art date
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Pending
Application number
CN201510936667.7A
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English (en)
Inventor
潘庆崇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
GUANG SHAN NEW MATERIALS Co Ltd
Original Assignee
GUANG SHAN NEW MATERIALS Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Application filed by GUANG SHAN NEW MATERIALS Co Ltd filed Critical GUANG SHAN NEW MATERIALS Co Ltd
Priority to CN201510936667.7A priority Critical patent/CN105542128A/zh
Priority to JP2016039625A priority patent/JP2017110176A/ja
Priority to TW105111540A priority patent/TWI585119B/zh
Priority to US15/130,085 priority patent/US20170166513A1/en
Priority to EP16167206.8A priority patent/EP3181608A1/en
Publication of CN105542128A publication Critical patent/CN105542128A/zh
Priority to KR1020160084993A priority patent/KR101830511B1/ko
Pending legal-status Critical Current

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    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/94—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of polycyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of six-membered aromatic rings
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Abstract

本发明涉及一种环氧树脂固化剂及其制备方法和用途，该环氧树脂固化剂具有式Ⅰ所示的分子结构。本发明通过采用特定结构的环氧树脂固化剂，使得由其组成的树脂组合物具有良好的低介电性能，其固化物具有低的介电常数和介电损耗，具有良好的耐热性，是一种还具有较大的经济性及环保友好型的低介电材料。

Description

一种环氧树脂固化剂及其制备方法和用途
技术领域
本发明属于低介电材料技术领域，尤其涉及一种环氧树脂固化剂及其制备方法和用途。
背景技术
以手机、电脑、摄像机、电子游戏机为代表的电子产品、以空调、冰箱、电视影像、音响用品等为代表的家用、办公电器产品以及其他领域使用的各种产品，为了安全，很大部分的产品都要求其具备低介电性和耐热性。
就电气性质而言，主要需考虑的因素还包括材料的介电常数以及介电损耗。一般而言，由于基板的讯号传送速度与基板材料的介电常数的平方根成反比，故基板材料的介电常数通常越小越好；另一方面，由于介电损耗越小代表讯号传递的损失越少，故介电损耗较小的材料所能提供的传输质量也较为良好。
因此，如何开发出具有低介电常数以及低介电损耗的材料，并将其应用于高频印刷电路板的制造，乃是现阶段印刷电路板材料供货商亟欲解决的问题。
发明内容
有鉴于此，本发明第一方面提供一种环氧树脂固化剂，该环氧树脂固化剂具有低介电性，并且具有良好耐热性和机械性能，而且，该环氧树脂固化剂具有成本低的优势。
为了实现上述目的，本发明采用了如下技术方案：
一种环氧树脂固化剂，其具有如式Ⅰ所示的分子结构：
式Ⅰ中，R独立地为满足其化学环境的任意有机基团，R1、R2、R3、R4和R5独立地为H或满足其化学环境的任意有机基团，Ra、Rb独立地为芳香基团；n为大于等于零的整数。例如n可以为0、1、2、3、4、5、6、7、8、9、10等，优选为1-6。
R为取代的或未取代的直链或支链烷基、取代的或未取代的环烷基、取代的或未取代的芳基、取代的或未取代的杂芳基、取代的或未取代的烷基芳基、取代的或未取代的环烷基芳基、取代的或未取代的烷基杂芳基或取代的或未取代的烷基杂芳基中的任意一种；
优选地，R1、R2、R3、R4和R5独立地为为H、取代的或未取代的直链或支链烷基、取代的或未取代的环烷基、取代的或未取代的芳基、取代的或未取代的杂芳基、取代的或未取代的烷基芳基、取代的或未取代的环烷基芳基、取代的或未取代的烷基杂芳基、取代或未取代的烷氧基、取代的或未取代的环烷氧基、取代的或未取代的芳氧基、取代的或未取代的杂芳基氧基、取代的或未取代的芳基烷氧基、取代或未取代的烷基芳氧基、取代或未取代的杂芳基烷氧基、取代或未取代的烷基杂芳氧基、取代或未取代的羧酸酯基、取代或未取代的碳酸酯基、取代或未取代的磺酸酯基或取代或未取代的膦酸酯基中的任意一种或至少两种的组合。
优选地，Ra、Rb独立地为取代的或未取代的苯基、取代的或未取代的联苯基、取代的或未取代的苯基烷基、取代的或未取代的烷基苯基、取代的未取代的苯基烷基苯基、取代的或未取代的吡啶基、取代的或未取代的呋喃基或取代的或未取代的吗啉基中的任意一种。
优选地，所述环氧树脂固化剂具有如下式I或式II所示的分子结构：
式Ⅰ中，R为为满足其化学环境的任意有机基团，R1、R2、R3、R4、R5、R6、R7、R8和R9独立地为满足其化学环境的任意有机基团，n为大于等于零的整数；例如n可以为0、1、2、3、4、5、6、7、8、9、10等，优选为1-6。
式II中，R独立地为满足其化学环境的任意有机基团，R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12和R13独立地为H、或者满足其化学环境的任意有机基团；X为不存在或满足其化学环境的任意有机基团；n为大于等于零的整数；例如n可以为0、1、2、3、4、5、6、7、8、9、10等，优选为1-6。
在本发明中，所述满足其化学环境是指能够与其相邻的原子相连，得到稳定的化学连接键。
在本发明中，式I中片段部分中，苯环上的与氧相连的两个取代位置可以是对位、邻位或间位，优选为间位。
优选地，所述环氧树脂固化剂具有如下式III或式IV所示的分子结构：
式III中，R为满足其化学环境的任意有机基团，R1、R2、R3、R4、R5、R6、R7、R8和R9独立地为为H或满足其化学环境的任意有机基团，n为大于等于零的整数；例如n可以为0、1、2、3、4、5、6、7、8、9、10等，优选为1-6。
式IV中，R独立地为满足其化学环境的任意有机基团，R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12和R13独立地为H、或者满足其化学环境的任意有机基团；X为不存在或满足其化学环境的任意有机基团；n为大于等于零的整数；例如n可以为0、1、2、3、4、5、6、7、8、9、10等，优选为1-6。
优选地，R为取代的或未取代的直链或支链烷基、取代的或未取代的环烷基、取代的或未取代的芳基、取代的或未取代的杂芳基、取代的或未取代的烷基芳基、取代的或未取代的环烷基芳基、取代的或未取代的烷基杂芳基或取代的或未取代的烷基杂芳基中的任意一种。
具体地，R可以为但不限于-CH2CH2-、-CH2CH2CH2-、
优选地，R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12和R13独立地为H、取代的或未取代的直链或支链烷基、取代的或未取代的环烷基、取代的或未取代的芳基、取代的或未取代的杂芳基、取代的或未取代的烷基芳基、取代的或未取代的环烷基芳基、取代的或未取代的烷基杂芳基、取代的或未取代的烷基杂芳基、取代或未取代的烷氧基、取代的或未取代的环烷氧基、取代的或未取代的芳氧基、取代的或未取代的杂芳基氧基、取代的或未取代的芳基烷氧基、取代或未取代的烷基芳氧基、取代或未取代的杂芳基烷氧基、取代或未取代的烷基杂芳氧基、取代或未取代的羧酸酯基、取代或未取代的碳酸酯基、取代或未取代的磺酸酯基或取代或未取代的膦酸酯基中的任意一种或至少两种的组合。
在本发明中，所述的取代基为不含有卤素的任意有机基团，例如烷基、环烷基、烷氧基、换烷氧基、芳基、杂芳基、烷基芳基、杂芳基烷基、羧酸酯基、碳酸酯基、磺酸酯基或膦酸酯基等。
具体地，R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12和R13可独立地为但不限于-CH3、-CH2CH3、-OCH3、-OCH2CH3、-SH、-SCH3、-CONH2、-COOH或-OOCCH3中的任意一种或至少两种的组合。
在本发明中，取代或未取代的直链或支链烷基优选为取代或未取代的C1～C12(例如C1、C2、C3、C4、C5、C6、C7、C8、C9、C10或C11)直链或支链烷基，进一步优选C1～C8直链烷基或支链烷基，当碳原子数为1时即为甲基，碳原子数为2时，即为乙基。
取代或未取代的环烷基优选为取代或未取代的C3～C12(例如C4、C5、C6、C7、C8、C9、C10或C11)的环烷基。
取代的或未取代的烷氧基优选为取代或未取代的C1～C12(例如C2、C3、C4、C5、C6、C7、C8、C9、C10或C11)的烷氧基。
取代的或未取代的环烷氧基优选为取代或未取代的C3～C12(例如C4、C5、C6、C7、C8、C9、C10或C11)的环烷氧基。
取代或未取代的芳基优选为C7-C13(例如C8、C9、C10、C11或C12)烷基芳基。优选为苯基、萘基、或等。苯基的实例包括联苯基、三联苯基、苯甲基、苯乙基或苯丙基等。
取代或未取代的杂芳基优选为C7-C13(例如C8、C9、C10、C11或C12)杂芳烷基，优选为五元或六元杂芳基，进一步优选为取代的或未取代的呋喃基或吡啶基。
取代或未取代的烷基杂芳基优选为C7-C13(例如C8、C9、C10、C11或C12)烷基杂芳基。
取代或未取代的芳氧基优选为C7-C13(例如C8、C9、C10、C11或C12)芳氧基。
取代或未取代的杂芳基氧基优选为C5-C13(例如C6、C7、C8、C9、C10、C11或C12)杂芳基氧基。
取代的或未取代的芳基烷氧基优选为C7-C13(例如C8、C9、C10、C11或C12)芳基烷氧基。
取代或未取代的烷基芳氧基优选为C6-C13(例如C7、C8、C9、C10、C11或C12)烷基芳氧基。
取代或未取代的烷基杂芳氧基优选为C6-C13(例如C7、C8、C9、C10、C11或C12)烷基杂芳氧基。
本发明所使用的术语“取代的”是指指定原子上的任何一个或多个氢原子被选自指定组的取代基取代，条件是所述指定原子不超过正常价态，并且取代的结果是产生稳定的化合物。当取代基是氧代基团或酮基(即＝O)时，那么原子上的2个氢原子被取代。酮取代基在芳香环上不存在。“稳定的化合物”是指能够足够强健地从反应混合物中分离至有效的纯度并配制成有效的化合物。
优选地，本发明所述环氧树脂固化剂为具有以下结构的化合物中的一种或至少两种的组合：
或n为大于等于零的整数；例如n可以为0、1、2、3、4、5、6、7、8、9、10等，优选为1-6。
另一方面，本发明提供一种所述环氧树脂固化剂的制备方法，由该方法制备的环氧树脂固化剂具有低介电性，并且具有良好耐热性和机械性能。
一种制备上述述环氧树脂固化剂的方法，将酚类化合物与多元酰氯化合物或多元酸化合物反应制备得到所述环氧树脂固化剂。
在本发明中多元酰氯化合物是指二元酰氯或二元以上酰氯化合物，所述多元酸化合物是指二元酸或二元以上酸化合物。例如典型的，在本发明中，利用酚类化合物与二元酸化合物进行酯化反应，用浓硫酸或固体酸作催化剂，反应得到相应酯。还可以利用酚类化合物与酰氯反应脱除氯化氢来得到相应酯。
本发明的酯类环氧树脂固化剂的制造方法为公知的酯类的制造方法，本发明对此并无特别规定，例如，在熔融或者溶解状态下的二元酸或多元酸化合物中，使用硫酸、磷酸、固体酸化合物等常用的脱水剂当作催化剂，或以二元酰氯多元酰氯化合物代替二元酸或多元酸，使用公知的脱氯化氢催化剂在一定温度条件下，一边搅拌，一边加入酚类物质，经过脱水聚合反应完成后，通过物理方法出去溶剂、副产物或其他杂质，即可得到本发明所述的新规酯类环氧树脂化合物。
酚类化合物指与式Ⅰ中Ra或Rb基团所对应的酚类化合物，例如带有Ra或Rb的酚类化合物可以为苯二酚，即可以为对苯二酚、邻苯二酚或间苯二酚。所述二元羧酸是指与式Ⅰ中的具有R基团的二元羧酸，即为HOOC-R-COOH，所述酚类化合物与二元羧酸发生缩合反应，生成酯，从而得到式Ⅰ所示环氧树脂固化剂。所述反应以及反应所需条件是本领域技术人员所熟知的。
另一方面，本发明提供一种具有低介电性、良好耐热性、良好的机械性能的环氧树脂组合物。
该环氧树脂组合物包含环氧树脂和以上所述的环氧树脂固化剂。
优选地，所述环氧树脂为液态双酚A型环氧树脂、液态双酚F型环氧树脂、固态双酚A型环氧树脂、固态双酚F型环氧树脂、双酚S型环氧树脂、环异戊二烯型环氧树脂或联苯型环氧树脂中的一种或至少两种的组合。
优选地，所述环氧树脂组合物还包含固化促进剂。
优选地，所述固化促进剂为咪唑类固化促进剂、有机膦固化促进剂、三级胺固化促进剂、季铵盐、DBU及其衍生物、吡啶及其衍生物中的任意一种或至少两种的混合物。
优选地，所述环氧树脂组合物还包含无机填料。
优选地，所述无机填料选自氢氧化铝、勃姆石、二氧化硅、滑石粉、云母、硫酸钡、立德粉、碳酸钙、硅灰石、高岭土、水镁石、硅藻土、膨润土或浮石粉中的任意一种或至少两种的混合物。
优选地，所述环氧树脂组合物还包含阻燃剂。所述阻燃剂为本领域已知的有机阻燃剂和/或无机阻燃剂。
上述环氧树脂固化剂可根据实际需要制成塑封料和预浸板。
一种塑封料，其包含本发明所述环氧树脂组合物。
一种预浸板，其由如上述的环氧树脂组合物含浸或涂布于基材而成。
基材可以为玻璃纤维基材、聚酯基材、聚酰亚胺基材、陶瓷基材或碳纤维基材等。
这里，其含浸或涂布的具体工艺条件无特别限定。“预浸板”也为本领域技术人员所熟知的“粘结片”。
一种复合金属基板，其包括一张以上如上述预浸板依次进行表面覆金属层重叠、压合而成。
这里，表面覆金属层的材质为铝、铜、铁及其任意组合的合金。
复合金属基板的具体实例有CEM-1覆铜板、CEM-3覆铜板、FR-4覆铜板、FR-5覆铜板、CEM-1铝基板、CEM-3铝基板、FR-4铝基板或FR-5铝基板。
一种线路板，于上述的复合金属基板的表面加工线路而成。
环氧树脂组合物的原料通过固化在复合金属基板上形成具有良好低介电性能的涂层，可提高线路板，例如电子产业、电气、电器产业、交通运输、航空航天、玩具产业等需要线路板的机器、设备、仪器、仪表等产业的广泛应用。
上述术语“×××基或基团”指×××化合物分子结构中脱去一个或多个氢原子或其它原子或原子团后剩余的部分。
本发明通过采用特定结构的环氧树脂固化剂，使得由其组成的树脂组合物具有良好的低介电性能，其固化物具有良好耐热性、机械性能以及低的介电常数和介电损耗，是一种还具有较大的经济性及环保友好型的低介电材料。采用该树脂组合物得到的覆铜板的介电常数(1GHz)为3.25-3.32，介电损耗(1GHz)为0.005-0.006，Tg可达到158℃及以上，T-剥离强度可达到1.97kg/mm2及以上，层间剥离强度可达到1.62kg/mm2及以上，饱和吸水率可达到0.34％以下。
具体实施方式
下面结合实施例来进一步说明本发明的技术方案。
在以下实施例中，所用原料均可通过商业购买得到。
实施例1
本实施例的环氧树脂固化剂具有以下结构：
制备方法如下：
在带有搅拌器的1000mL玻璃反应器中加入2,6-二甲基对苯二酚1mol，以二氯甲烷为溶剂，搅拌溶解，滴入3mL98％的浓硫酸作为催化剂，而后缓慢滴加对苯二甲酸(1.1mol)的二氯甲烷溶液，滴加完毕，在室温下搅拌反应10小时，而后加入1.1mol邻二甲基苯酚，继续搅拌反应8小时，用物理的方法除去体系中副产物、蒸发溶剂，得到酯当量为100g/eq的目的物100g，将此目的物命名为环氧树脂固化剂A。
通过核磁共振氢谱对得到的环氧树脂固化剂A进行了表征，结果如下：
1HNMR(CDCl3,500MHz):δppm6.92-6.96(m,苯环上氢),6.81-6.83(m,苯环上氢),2.32(s,CH3)。
红外谱图特征峰的位置：酯羰基1730-1740cm-1，酯基的C-O-C1200cm-1，邻位取代苯环750cm-1，对位取代苯环860-790cm-1，甲基的吸收峰2995cm-1。
利用该环氧树脂固化剂与其他组分组成环氧树脂组合物，并制成覆铜板，步骤如下：
环氧当量187g/eq双酚A环氧树脂100g、环氧当量为120g/eq的邻甲酚醛环氧树脂100g，加入上述环氧树脂固化剂136g，固化促进剂DBU0.1g。采用该环氧树脂组合物按照通用的覆铜板制作程序制得符合国标、UL等标准的标准覆铜板样品，命名为a覆铜板，测试a覆铜板的性能，其结果在表-1中表示。
实施例2
本实施例的环氧树脂固化剂具有以下结构：
制备方法如下：
在带有搅拌器的1000mL玻璃反应器中加入2,3-二甲基对苯二酚1mol，搅拌溶解，滴入3mL98％的浓硫酸作为催化剂，而后缓慢滴加2,3-二甲基对苯二甲甲酸1.1mol，滴加完毕，在室温下搅拌反应15小时，而后加入1.2mol邻二甲基苯酚，继续搅拌反应6小时，用物理的方法除去体系中副产物、蒸发溶剂，得到酯当量为180g/eq的目的物180g，将此目的物命名为环氧树脂固化剂B。
通过核磁共振氢谱对得到的环氧树脂固化剂B进行了表征，结果如下：
1HNMR(CDCl3,500MHz):δppm7.7-7.9(m,中苯环上氢),6.91-6.94(m,中苯环上氢),2.32(s,CH3)。
红外谱图特征峰的位置：酯羰基1730-1740cm-1，酯基的C-O-C1200cm-1，邻位取代苯环750cm-1，对位取代苯环860-790cm-1，甲基的吸收峰2995cm-1。
利用该环氧树脂固化剂与其他组分组成环氧树脂组合物，并制成覆铜板，步骤如下：
环氧当量187g/eq双酚A环氧树脂100g、环氧当量为120g/eq的邻甲酚醛环氧树脂100g，加入上述环氧树脂固化剂245g，固化促进剂DBU0.1g。采用该环氧树脂组合物按照通用的覆铜板制作程序制得符合国标、UL等标准的标准覆铜板样品，命名为b覆铜板，测试b覆铜板的性能，其结果在表-1中表示。
实施例3
本实施例的环氧树脂固化剂具有以下结构：
制备方法如下：
在带有搅拌器的1000mL玻璃反应器中加入2,6,2’,6’-四甲基双酚A1mol，以二氯甲烷为溶剂，搅拌溶解，滴入3mL98％的浓硫酸作为催化剂，而后缓慢滴加2,3-二甲基对苯二甲酸(1.1mol)的二氯甲烷溶液，滴加完毕，在室温下搅拌反应10小时，而后加入1.2mol邻二甲基苯酚，继续搅拌反应8小时，用物理的方法除去体系中副产物、蒸发溶剂，得到酯当量为220g/eq的目的物220g，将此目的物命名为环氧树脂固化剂C。
通过核磁共振氢谱对得到的环氧树脂固化剂C进行了表征，结果如下：
1HNMR(CDCl3,500MHz):δppm7.7-7.9(m,中苯环上氢),6.4-6.9(m,中苯环上氢),3.7(m,基团中甲基上的氢),2.35(s,与苯环相连的甲基上的氢),1.65(m,基团中不与苯环相连的甲基上的氢)。
红外谱图特征峰的位置：酯羰基1730-1740cm-1，酯基的C-O-C1200cm-1，邻位取代苯环750cm-1，基团中苯环的骨架振动吸收峰1611cm-1、1509cm-1、1446cm-1，中-CH3的弯曲振动吸收峰1435cm-1、1382cm-1。
利用该环氧树脂固化剂与其他组分组成环氧树脂组合物，并制成覆铜板，步骤如下：
环氧当量187g/eq双酚A环氧树脂100g、环氧当量为120g/eq的邻甲酚醛环氧树脂100g，加入上述环氧树脂固化剂299g，固化促进剂DBU0.1g。采用该环氧树脂组合物按照通用的覆铜板制作程序制得符合国标、UL等标准的标准覆铜板样品，命名为c覆铜板，测试c覆铜板的性能，其结果在表-1中表示。
实施例4
本实施例的环氧树脂固化剂具有以下结构：
制备方法如下：
在带有搅拌器的1000mL玻璃反应器中加入双酚B1mol，以二氯甲烷为溶剂，搅拌溶解，滴入3mL98％的浓硫酸作为催化剂，而后缓慢滴加对苯二甲酰氯(1.1mol)的二氯甲烷溶液，滴加完毕，在室温下搅拌反应10小时，而后加入1.2mol邻二甲基苯酚，继续搅拌反应8小时，用物理的方法除去体系中副产物、蒸发溶剂，得到酯当量为190g/eq的目的物190g，将此目的物命名为环氧树脂固化剂D。
通过核磁共振氢谱对得到的环氧树脂固化剂D进行了表征，结果如下：
1HNMR(CDCl3,500MHz):δppm8.29(s,中苯环上氢),7.1-7.2(m,中苯环上氢),6.8-6.9(m,8H,中苯环上氢),3.7(m,基团中甲基上的氢),1.91(m,中亚甲基上氢),1.72(m,中连接季碳原子的甲基上的氢),1.0(m,中与亚甲基相连的甲基上的氢)。
红外谱图特征峰的位置：酯羰基1730-1740cm-1，酯基的C-O-C1200cm-1，邻位取代苯环750cm-1，基团中苯环的骨架振动吸收峰1641cm-1、1500cm-1、1446cm-1，-CH3的弯曲振动吸收峰1435cm-1、1382cm-1,甲基醚的吸收峰2995cm-1。
利用该环氧树脂固化剂与其他组分组成环氧树脂组合物，并制成覆铜板，步骤如下：
环氧当量187g/eq双酚A环氧树脂100g、环氧当量为120g/eq的邻甲酚醛环氧树脂100g，加入上述环氧树脂固化剂258g，固化促进剂DBU0.1g。采用该环氧树脂组合物按照通用的覆铜板制作程序制得符合国标、UL等标准的标准覆铜板样品，命名为d覆铜板，测试d覆铜板的性能，其结果在表-1中表示。
比较例1
在该对比例中利用常用的酚羟基当量105g/eq的线性酚醛树脂来替代本发明的环氧树脂固化剂作为固化剂，利用实施例1中相同的方法制备得到覆铜板e，测试e覆铜板的性能，其结果在表-1中表示。
比较例2
取市场销售的环氧当量为380.0g/eq的MDI改性环氧树脂100g,加入具有如式(1)结构的树脂化合物57.9g，酯当量为220，和0.2g的吡啶，用适当的丙酮溶解成溶液，用标准玻璃纤维布、以公知的方法做成覆铜板，将此覆铜板命名为覆铜板f。测得覆铜板f的性能如表-1所示。
实施例和比较例的测试结果如下表-1所示(鉴于具体测试方法已为本领域技术人员所熟知，在此对方法不再详述)。
实施例和比较例的测试结果如下表-1所示(鉴于具体测试方法已为本领域技术人员所熟知，在此对方法不再详述)：
表-1
由表1可以看出，本发明采用含有式Ⅰ所示的分子结构的化合物作为固化剂制备的树脂组合物，使得由其制备得到的覆铜板的介电常数(1GHz)为3.25-3.32，介电损耗(1GHz)为0.005-0.006，Tg可达到158℃及以上，T-剥离强度可达到1.97kg/mm2及以上，层间剥离强度可达到1.62kg/mm2及以上，饱和吸水率可达到0.34％以下，明显优于对比例覆铜板的性能。
申请人声明，本发明通过上述实施例来说明本发明的环氧树脂固化剂及其制备方法和用途，但本发明并不局限于上述实施例，即不意味着本发明必须依赖上述实施例才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (10)

1.一种环氧树脂固化剂，其特征在于，其具有如式Ⅰ所示的分子结构：
式Ⅰ中，R独立地为满足其化学环境的任意有机基团，R1、R2、R3、R4和R5独立地为H或满足其化学环境的任意有机基团，Ra、Rb独立地为芳香基团；n为大于等于零的整数。
2.根据权利要求1所述的环氧树脂固化剂，其特征在于，R为取代的或未取代的直链或支链烷基、取代的或未取代的环烷基、取代的或未取代的芳基、取代的或未取代的杂芳基、取代的或未取代的烷基芳基、取代的或未取代的环烷基芳基、取代的或未取代的烷基杂芳基或取代的或未取代的烷基杂芳基中的任意一种；
优选地，R1、R2、R3、R4和R5独立地为H、取代的或未取代的直链或支链烷基、取代的或未取代的环烷基、取代的或未取代的芳基、取代的或未取代的杂芳基、取代的或未取代的烷基芳基、取代的或未取代的环烷基芳基、取代的或未取代的烷基杂芳基、取代或未取代的烷氧基、取代的或未取代的环烷氧基、取代的或未取代的芳氧基、取代的或未取代的杂芳基氧基、取代的或未取代的芳基烷氧基、取代或未取代的烷基芳氧基、取代或未取代的杂芳基烷氧基、取代或未取代的烷基杂芳氧基、取代或未取代的羧酸酯基、取代或未取代的碳酸酯基、取代或未取代的磺酸酯基或取代或未取代的膦酸酯基中的任意一种；
优选地，Ra、Rb独立地为取代的或未取代的苯基、取代的或未取代的联苯基、取代的或未取代的苯基烷基、取代的或未取代的烷基苯基或取代的未取代的苯基烷基苯基中的任意一种。
3.根据权利要求1或2所述的环氧树脂固化剂，其特征在于，所述环氧树脂固化剂具有如下式I或式II所示的分子结构：
式Ⅰ中，R为为满足其化学环境的任意有机基团，R1、R2、R3、R4、R5、R6、R7、R8和R9独立地为满足其化学环境的任意有机基团，n为大于等于零的整数；
式II中，R为满足其化学环境的任意有机基团，R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12和R13独立地为H、或者满足其化学环境的任意有机基团；X为不存在或满足其化学环境的任意有机基团；n为大于等于零的整数；
优选地，所述环氧树脂固化剂具有如下式III或式IV所示的分子结构：
式III中，R为满足其化学环境的任意有机基团，R1、R2、R3、R4、R5、R6、R7、R8和R9独立地为为H或满足其化学环境的任意有机基团，n为大于等于零的整数；
式IV中，R独立地为满足其化学环境的任意有机基团，R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12和R13独立地为H、或者满足其化学环境的任意有机基团；X为不存在或满足其化学环境的任意有机基团；n为大于等于零的整数；
优选地，R为取代的或未取代的直链或支链烷基、取代的或未取代的环烷基、取代的或未取代的芳基、取代的或未取代的杂芳基、取代的或未取代的烷基芳基、取代的或未取代的环烷基芳基、取代的或未取代的烷基杂芳基或取代的或未取代的烷基杂芳基中的任意一种；
优选地，R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12和R13独立地为H、取代的或未取代的直链或支链烷基、取代的或未取代的环烷基、取代的或未取代的芳基、取代的或未取代的杂芳基、取代的或未取代的烷基芳基、取代的或未取代的环烷基芳基、取代的或未取代的烷基杂芳基、取代或未取代的烷氧基、取代的或未取代的环烷氧基、取代的或未取代的芳氧基、取代的或未取代的杂芳基氧基、取代的或未取代的芳基烷氧基、取代或未取代的烷基芳氧基、取代或未取代的杂芳基烷氧基、取代或未取代的烷基杂芳氧基、取代或未取代的羧酸酯基、取代或未取代的碳酸酯基、取代或未取代的磺酸酯基或取代或未取代的膦酸酯基中的任意一种或至少两种的组合。
4.根据权利要求1-3中任一项所述的环氧树脂固化剂，其特征在于，所述环氧树脂固化剂为具有以下结构的化合物中的一种或至少两种的组合：
5.一种环氧树脂组合物，其特征在于，所述环氧树脂组合物包含环氧树脂和如权利要求1-4中任一项所述的环氧树脂固化剂；
优选地，所述环氧树脂为液态双酚A型环氧树脂、液态双酚F型环氧树脂、固态双酚A型环氧树脂、固态双酚F型环氧树脂、双酚S型环氧树脂、环异戊二烯型环氧树脂或联苯型环氧树脂中的一种或至少两种的组合；
优选地，所述环氧树脂组合物还包含固化促进剂；
优选地，所述固化促进剂为咪唑类固化促进剂、有机膦固化促进剂、三级胺固化促进剂、季铵盐、DBU及其衍生物、吡啶及其衍生物中的任意一种或至少两种的混合物；
优选地，所述环氧树脂组合物还包含无机填料；
优选地，所述环氧树脂组合物还包含阻燃剂。
6.一种预浸板，其特征在于，其由如权利要求5所述环氧树脂组合物含浸或涂布于基材而成。
7.根据权利要求6所述的预浸板，其特征在于，所述基材为玻璃纤维基材、聚酯基材、聚酰亚胺基材、陶瓷基材或碳纤维基材。
8.一种复合金属基板，其特征在于，其包括一张以上如权利要求6或7所述预浸板依次进行表面覆金属层、重叠、压合而成。
9.根据权利要求8所述的复合金属基板，其特征在于，所述表面覆金属层的材质为铝、铜、铁及其任意组合的合金；
优选地，所述复合金属基板为CEM-1覆铜板、CEM-3覆铜板、FR-4覆铜板、FR-5覆铜板、CEM-1铝基板、CEM-3铝基板、FR-4铝基板或FR-5铝基板。
10.一种线路板，其特征在于，于权利要求8或9所述的复合金属基板的表面加工线路而成。
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