CN105482075A - 一种异氰酸酯改性环氧树脂及用途 - Google Patents
一种异氰酸酯改性环氧树脂及用途 Download PDFInfo
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Abstract
本发明涉及一种异氰酸酯改性环氧树脂,具有式(I)所示结构:式(I)中,R选自亚有机基团;n为大于或等于零的整数;Y所述R1、R2、R3、R4、R18、R19、R20、R21各自独立地选自有机基团;X不存在或选自亚有机基团;且R1、R2、R3、R4、R18、R19、R20、R21不同时为氢原子。本发明提供的环氧树脂采用含有2个以上的多异氰酸酯为原料制备,与具有环氧基的树脂单体反应,达到在环氧树脂单体中引入噁唑烷酮基的目的,且本发明提供的环氧树脂以环氧基封端,使提供的环氧树脂组分具有高耐热、低介电的性能。
Description
技术领域
本发明属于环氧树脂制备领域,涉及一种环氧树脂及用途。
背景技术
环氧树脂是泛指分子中含有两个或两个以上环氧基团的有机化合物,除个别外,它们的相对分子质量都不高。环氧树脂的分子结构是以分子链中含有活泼的环氧基团为其特征,环氧基团可以位于分子链的末端、中间或成环状结构。由于分子结构中含有活泼的环氧基团,使它们可与多种类型的固化剂发生交联反应而形成不溶的具有三向网状结构的高聚物。凡分子结构中含有环氧基团的高分子化合物统称为环氧树脂。固化后的环氧树脂具有良好的物理、化学性能,它对金属和非金属材料的表面具有优异的粘接强度,介电性能良好,变定收缩率小,制品尺寸稳定性好,硬度高,柔韧性较好,对碱及大部分溶剂稳定,因而广泛应用于国防、国民经济各部门,作浇注、浸渍、层压料、粘接剂、涂料等用途。
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。
就电器性质而言,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领域亟欲解决的问题。
发明内容
本发明的目的在于提供一种异氰酸酯改性环氧树脂,具有式(I)所示结构:
式(I)中,R选自亚有机基团;
n为大于或等于零的整数;
Y选自所述R1、R2、R3、R4、R18、R19、R20、R21各自独立地选自有机基团;X不存在或选自亚有机基团;且R1、R2、R3、R4、R18、R19、R20、R21不同时为氢原子。
作为优选方案之一,所述环氧树脂具有式(II)所示结构:
式(II)中,R选自亚有机基团;
R1、R2、R3、R4各自独立地选自有机基团,且R1、R2、R3、R4不同时为氢原子;
n为大于或等于零的整数。
作为优选方案之二,所述环氧树脂具有式(III)所示结构:
式(III)中,X不存在或选自亚有机基团;
R选自亚有机基团;
R1、R2、R3、R4、R18、R19、R20、R21各自独立地选自有机基团,且R1、R2、R3、R4、R18、R19、R20、R21不同时为氢原子;
n为大于或等于零的整数。
优选地,所述环氧树脂具有式(IV)所示结构:
式(IV)中,R选自亚有机基团;
所述R1、R2、R3、R4各自独立地选自有机基团,且R1、R2、R3、R4不同时为氢原子;
所述n为大于或等于零的整数。
或者优选地,所述环氧树脂具有式(V)所示结构:
式(V)中,X、R选自亚有机基团;
所述R1、R2、R3、R4、R18、R19、R20、R21各自独立地选自有机基团,且R1、R2、R3、R4、R18、R19、R20、R21不同时为氢原子;
所述n为大于或等于零的整数。
优选地,R选自取代或未取代的直链亚烃基、取代或未取代的支链亚烃基、取代或未取代的亚芳香基;优选C1~C30的取代或未取代的直链亚烃基、C1~C30取代或未取代的支链亚烃基、C6~C30取代或未取代的亚芳香基;进一步优选
其中,所述R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R17各自独立地选自有机基团,优选自H、取代或未取代的直链烃基、取代或未取代的支链烃基或取代或未取代的芳香基;优选C1~C30的取代或未取代的直链烃基、C1~C30取代或未取代的支链烃基或C6~C30取代或未取代的芳香基;
所述R16各自独立地选自有机基团,优选自取代或未取代的直链亚烃基、取代或未取代的支链亚烃基或取代或未取代的亚芳香基;优选C1~C30的取代或未取代的直链亚烃基、C1~C30取代或未取代的支链亚烃基或C6~C30取代或未取代的亚芳香基;
所述m为大于或等于零的整数。
进一步优选地,所述R5、R6、R7、R8、R9、R10、R11、R12为H;
优选地,所述R13、R14、R15、R17各自独立地选自取代或未取代的N-噁唑烷酮基;
优选地,所述R16选自C1~C5的取代或未取代的直链亚烃基,优选亚甲基、亚乙基或亚正丙基中的任意1种。
优选地,所述X不存在或选自取代或未取代的直链亚烃基、取代或未取代的支链亚烃基、取代或未取代的亚芳香基;优选不存在或C1~C30的取代或未取代的直链亚烃基、C1~C30取代或未取代的支链亚烃基、C6~C30取代或未取代的亚芳香基;进一步优选不存在或亚甲基、亚异丙基、亚异丁基、亚环己基、羰基中的任意1种;特别优选不存在或亚甲基或亚异丙基;
优选地,所述R选自
优选地,所述R1、R2、R3、R4、R18、R19、R20、R21各自独立地选自H、取代或未取代的直链烃基、取代或未取代的支链烃基或取代或未取代的芳香基;优选C1~C30的取代或未取代的直链烃基、C1~C30取代或未取代的支链烃基或C6~C30取代或未取代的芳香基,优选甲基、乙基、正丙基、异丙基、正丁基或叔丁基中的任意1种或至少2种的组合。
本发明提供的异氰酸酯改性环氧树脂的典型的制备方法为:将至少含有2个氰酸根的多异氰酸酯与具有双酚醚结构的物质反应,得到噁唑烷酮环。
所述具有双酚结构的物质的通式为:其中,Y具有前述的选择范围。
典型但非限制性的包括双酚A环氧基醚、双酚F环氧基醚、双酚Z环氧基醚中的任意1种或至少2种的组合。
作为非限制性的实例,所述异氰酸酯改性环氧树脂的制备方法包括:
(1)将具有双酚结构的物质投入反应釜,加热,优选加热至60~190℃更加优选地为120~160℃;
(2)加入至少含有2个氰酸根的多异氰酸酯,搅拌;
(3)加入咪唑类、胺类及其盐、三苯基膦及其衍生物等公知的催化剂,反应完毕,得到本发明提供的异氰酸酯改性环氧树脂。
本发明的目的之二是提供一种环氧树脂组合物,所述环氧树脂组合物包括环氧树脂和固化剂;所述环氧树脂部分或全部为目的之一所述的异氰酸酯改性环氧树脂;
优选地,所述环氧树脂还包括液态双酚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任意1种或至少2种的组合;
优选地,所述固化剂包括优选胺类、多元酚化合物、酯类化合物、酸类、酸酐类中的任意1种或至少2种的组合;
优选地,所述环氧树脂组合物中还包含固化促进剂,所述固化促进剂为咪唑类固化促进剂、有机膦固化促进剂、三级胺固化促进剂或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;
优选地,所述环氧树脂组合物还包含脱模剂。
本发明目的之三是提供一种预浸板,其由目的之二所述环氧树脂组合物含浸或涂布于基材而成;
优选地,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。
本发明目的之四是提供一种复合金属基板,其包括一张以上如目的之四所述预浸板依次进行表面覆金属层、重叠、压合而成;
优选地,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。
本发明目的之五是提供一种线路板,由目的之五所述的复合金属基板的表面加工线路而成。
与现有技术相比,本发明具有以下有益效果:
本发明提供的环氧树脂采用含有2个以上的多异氰酸酯为原料制备,与具
有环氧基的树脂单体反应,达到在环氧树脂单体中引入噁唑烷酮基的目的,且本发明提供的环氧树脂以环氧基封端,使提供的环氧树脂组分具有高耐热、低介电的性能。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。
本领域技术人员应该明了,所述实施例仅仅是帮助理解本发明,不应视为
对本发明的具体限制。
实施例1
化合物1具有如下结构:
制备方法为:
(1)在装有搅拌机的三口1000mL的玻璃反应器中投入环氧当量为153g/eq的如下结构所示的环氧树脂230g(1.5eq)、和四甲基氯化铵0.1g,一边通入氮气、一边搅拌溶解、一边升温到105℃,然后用240min时间均匀滴入62.5g的4,4’-MDI(0.5eq)后升温到130℃继续反应640min,得到环氧当量为320g/eq的环氧树脂292.5g,将此生成物环氧树脂命名为环氧树脂C。
性能表征:
红外:环氧基913~916cm-1;醚基1230~1010cm-1;噁唑烷酮基1755cm-1;甲基2960cm-1、2870cm-1;
核磁1H-NMR(DMSO-d6,ppm):6.45~6.49(s,O-Ar-O苯上的氢);6.50~6.60(s,O-Ar-O苯上的氢);7.50~7.55(m,N-Ar-C苯上的氢);7.00~7.10(m,N-Ar-C苯上的氢);2.47~2.52(m,亚甲基的氢);3.00~3.10(m,中甲基的氢);5.05~5.12(噁唑烷酮基基上中甲基的氢);4.03~4.10(与环氧基连接的CH2的氢);4.18(与噁唑烷酮基连接的CH2的氢);3.81(连接两个苯环的碳上的氢);2.3~2.4(苯环上的甲基上的氢);2.35(甲基的氢)。
实施例2
化合物2具有如下结构:
(1)在装有搅拌机的三口1000ml的玻璃反应器中投入环氧当量为195g/eq的如下结构所示的环氧树脂273g(1.4eq)、和四甲基氯化铵0.1g,一边通入氮气、一边搅拌溶解、一边升温到105℃,然后用240min时间均匀滴入62.5g的4,4’-MDI(0.5eq)后升温到130℃继续反应640min,得到环氧当量为373g/eq的环氧树脂335.5g,将此生成物环氧树脂命名为环氧树脂B。
性能表征:
红外:环氧基913~916cm-1;醚基1230~1010cm-1;噁唑烷酮基1755cm-1;
经测定,n为10;
核磁1H-NMR(DMSO-d6,ppm):1.6~1.7(Ar-C(CH3)2-Ar的氢);7.0~7.1(N-Ar-C苯上的氢);7.50~7.55(N-Ar-C苯上的氢);6.65~6.72(O-Ar-C苯上的氢);7.00~7.05(O-Ar-C苯上的氢);2.47~2.52(m,亚甲基的氢);3.00~3.10(m,中甲基的氢);5.05~5.12(噁唑烷酮基基上中甲基的氢);4.03~4.10(与环氧基连接的CH2的氢);4.18(与噁唑烷酮基连接的CH2的氢)。
实施例3
取实施例1得到的环氧树脂A100g,加入酚羟基当量为105g/eq的线型酚醛树脂25.0g和0.1g的2-苯基咪唑,用适当的丙酮溶解成溶液,用标准玻璃纤维布上胶,压合成覆铜板,将此覆铜板命名为覆铜板a。测得覆铜板a的性能如表-1所示。
实施例4
取实施例2得到的环氧树脂B100g,加入具有如下结构的树脂化合物63.7g,酯当量为220,和0.2g的吡啶,用适当的丙酮溶解成溶液,用标准玻璃纤维布上胶,压合成覆铜板,将此覆铜板命名为覆铜板b。测得覆铜板b的性能如表-1所示。
比较例1
取市场销售的环氧当量为380.0g/eq的MDI改性环氧树脂100g,加入酚羟基当量为105g/eq的线型酚醛树脂27.3g和0.1g的2-苯基咪唑,用适当的丙酮溶解成溶液,用标准玻璃纤维布上胶,压合成覆铜板,将此覆铜板命名为覆铜板c。测得覆铜板c的性能如表-1所示。
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,加入具有如下结构的树脂化合物57.9g,酯当量为220,和0.2g的吡啶,用适当的丙酮溶解成溶液,用标准玻璃纤维布上胶,压合成覆铜板,将此覆铜板命名为覆铜板d。测得覆铜板d的性能如表-1所示。
性能测试
将覆铜板a、覆铜板b、覆铜板c和覆铜板d进行如下性能测试:
(1)介电常数/介电损耗
制备大小为50mm×50mm的试样,试样表面蒸镀上厚度约为的铜层,之后将试样置于两测试平板电极之间,测定其在指定频率范围内的介电常数。
(2)吸水率
将100mm×100mm×1.6mm板材置于105℃的烘箱中干燥1h,冷却后称重并放置在105kPa的蒸汽压下蒸煮120min,最后擦干称重并计算出吸水率。
(3)玻璃化转变温度
制备测试样品的宽度约为8-12mm,长度为60mm,测量玻璃化转变温度Tg。
(4)弯曲强度与弯曲模量
制备25mm×65m的试样,使用游标卡尺测量其厚度,将材料万能试验机的测试模式调为弯曲测试模式,测量弯曲强度与弯曲模量。
(5)拉伸强度
制备250mm×25m的试样,使用游标卡尺测量其厚度,将材料万能试验机的测试模式调为拉伸测试模式,测量拉伸强度。
(6)剥离强度测定
将覆铜层叠板切成100mm×3mm的试验片,使用抗剥仪试验装置,以速度50.8mm/min对铜箔进行剥离分层,测试铜箔与树脂的剥离强度。
实施例制备的铜箔基板的性能测试结果如表1所示;
表1实施例制备的铜箔基板的性能测试结果
项目 | 覆铜板a | 覆铜板b | 覆铜板c | 覆铜板d |
介电常数(5MHz) | 3.0 | 3.3 | 4.8 | 5.2 |
介电损耗(5MHz) | 0.003 | 0.006 | 0.036 | 0.038 |
吸水率(%) | 0.38 | 0.35 | 0.65 | 0.74 |
Tg(℃) | 170 | 158 | 136 | 132 |
剥离强度(N·mm-1) | 2.03 | 2.05 | 1.46 | 1.52 |
申请人声明,本发明通过上述实施例来说明本发明的工艺方法,但本发明并不局限于上述工艺步骤,即不意味着本发明必须依赖上述工艺步骤才能实施。所属技术领域的技术人员应该明了,对本发明的任何改进,对本发明所选用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 (9)
1.一种异氰酸酯改性环氧树脂,具有式(I)所示结构:
式(I)中,R选自亚有机基团;
n为大于或等于零的整数;
Y选自所述R1、R2、R3、R4、R18、R19、R20、R21各自独立地选自有机基团;X不存在或选自亚有机基团;且R1、R2、R3、R4、R18、R19、R20、R21不同时为氢原子。
2.如权利要求1所述的环氧树脂,其特征在于,所述环氧树脂具有式(II)所示结构:
式(II)中,R选自亚有机基团;
R1、R2、R3、R4各自独立地选自有机基团,且R1、R2、R3、R4不同时为氢原子;
n为大于或等于零的整数;
或者,所述环氧树脂具有式(III)所示结构:
式(III)中,X不存在或选自亚有机基团;
R选自亚有机基团;
R1、R2、R3、R4、R18、R19、R20、R21各自独立地选自有机基团,且R1、R2、R3、R4、R18、R19、R20、R21不同时为氢原子;
n为大于或等于零的整数。
3.如权利要求1所述的环氧树脂,其特征在于,所述环氧树脂具有式(IV)所示结构:
式(IV)中,R选自亚有机基团;
所述R1、R2、R3、R4各自独立地选自有机基团,且R1、R2、R3、R4不同时为氢原子;
所述n为大于或等于零的整数;
或者,所述环氧树脂具有式(V)所示结构:
式(V)中,X、R选自亚有机基团;
所述R1、R2、R3、R4、R18、R19、R20、R21各自独立地选自有机基团,且R1、R2、R3、R4、R18、R19、R20、R21不同时为氢原子;
所述n为大于或等于零的整数。
4.如权利要求1~3之一所述的环氧树脂,其特征在于,R选自取代或未取代的直链亚烃基、取代或未取代的支链亚烃基、取代或未取代的亚芳香基;优选C1~C30的取代或未取代的直链亚烃基、C1~C30取代或未取代的支链亚烃基、C6~C30取代或未取代的亚芳香基;进一步优选
其中,所述R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R17各自独立地选自有机基团,优选自H、取代或未取代的直链烃基、取代或未取代的支链烃基或取代或未取代的芳香基;优选C1~C30的取代或未取代的直链烃基、C1~C30取代或未取代的支链烃基或C6~C30取代或未取代的芳香基;
所述R16各自独立地选自有机基团,优选自取代或未取代的直链亚烃基、取代或未取代的支链亚烃基或取代或未取代的亚芳香基;优选C1~C30的取代或未取代的直链亚烃基、C1~C30取代或未取代的支链亚烃基或C6~C30取代或未取代的亚芳香基;
所述m为大于或等于零的整数。
优选地,所述R5、R6、R7、R8、R9、R10、R11、R12为H;
优选地,所述R13、R14、R15、R17各自独立地选自取代或未取代的N-噁唑烷酮基;
优选地,所述R16选自C1~C5的取代或未取代的直链亚烃基,优选亚甲基、亚乙基或亚正丙基中的任意1种。
5.如权利要求1~3之一所述的环氧树脂,其特征在于,所述X不存在或选自取代或未取代的直链亚烃基、取代或未取代的支链亚烃基、取代或未取代的亚芳香基;优选不存在或C1~C30的取代或未取代的直链亚烃基、C1~C30取代或未取代的支链亚烃基、C6~C30取代或未取代的亚芳香基;进一步优选不存在或亚甲基、亚异丙基、亚异丁基、亚环己基、羰基中的任意1种;特别优选不存在或亚甲基或亚异丙基;
优选地,所述R选自
优选地,所述R1、R2、R3、R4、R18、R19、R20、R21各自独立地选自H、取代或未取代的直链烃基、取代或未取代的支链烃基或取代或未取代的芳香基;优选C1~C30的取代或未取代的直链烃基、C1~C30取代或未取代的支链烃基或C6~C30取代或未取代的芳香基,优选甲基、乙基、正丙基、异丙基、正丁基或叔丁基中的任意1种或至少2种的组合。
6.一种环氧树脂组合物,其特征在于,所述环氧树脂组合物包括环氧树脂和固化剂;所述环氧树脂部分或全部为权利要求1~5之一所述的异氰酸酯改性环氧树脂;
优选地,所述环氧树脂还包括液态双酚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任意1种或至少2种的组合;
优选地,所述固化剂包括优选胺类、多元酚化合物、酯类化合物、酸类、酸酐类中的任意1种或至少2种的组合;
优选地,所述环氧树脂组合物中还包含固化促进剂,所述固化促进剂为咪唑类固化促进剂、有机膦固化促进剂、三级胺固化促进剂或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;
优选地,所述环氧树脂组合物还包含脱模剂。
7.一种预浸板,其特征在于,其由如权利要求6所述环氧树脂组合物含浸或涂布于基材而成;
优选地,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7所述预浸板依次进行表面覆金属层、重叠、压合而成;
优选地,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。
9.一种线路板,其特征在于,由权利要求8所述的复合金属基板的表面加工线路而成。
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CN105566613A (zh) * | 2016-03-08 | 2016-05-11 | 广东广山新材料有限公司 | 一种异氰酸酯改性环氧树脂及用途 |
CN107652943A (zh) * | 2017-09-05 | 2018-02-02 | 复旦大学 | 一种耐紫外光耐高低温有机硅胶黏剂及其制备方法 |
CN107652943B (zh) * | 2017-09-05 | 2020-12-22 | 复旦大学 | 一种耐紫外光耐高低温有机硅胶黏剂及其制备方法 |
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