CN113773603A - 一种含磷乙烯基苯聚苯醚及其树脂组合物和应用 - Google Patents
一种含磷乙烯基苯聚苯醚及其树脂组合物和应用 Download PDFInfo
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- CN113773603A CN113773603A CN202111125676.XA CN202111125676A CN113773603A CN 113773603 A CN113773603 A CN 113773603A CN 202111125676 A CN202111125676 A CN 202111125676A CN 113773603 A CN113773603 A CN 113773603A
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 48
- 239000011574 phosphorus Substances 0.000 title claims abstract description 48
- 239000011342 resin composition Substances 0.000 title claims abstract description 30
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229920013636 polyphenyl ether polymer Polymers 0.000 title description 12
- -1 vinyl benzene compound Chemical class 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 18
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- 239000003431 cross linking reagent Substances 0.000 claims abstract description 8
- 229920001955 polyphenylene ether Polymers 0.000 claims description 32
- 239000003063 flame retardant Substances 0.000 claims description 25
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 10
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- XSHWKULGRFTYIT-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C XSHWKULGRFTYIT-UHFFFAOYSA-N 0.000 claims description 3
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 claims description 3
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- JCRCPEDXAHDCAJ-UHFFFAOYSA-N ethoxy(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(OCC)C1=CC=CC=C1 JCRCPEDXAHDCAJ-UHFFFAOYSA-N 0.000 description 2
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Abstract
本发明公开了一种含磷乙烯基苯聚苯醚及其树脂组合物和应用。含磷乙烯基苯聚苯醚由含磷乙烯基苯化合物及乙烯基聚苯醚反应得到，本发明的另一目的在于提供一种树脂组合物，包含上述含磷乙烯基苯聚苯醚及至少一种交联剂。该树脂组合物制成的树脂膜、半固化片、层压板或印刷电路板，具有热膨胀系数低耐热性高、阻燃性优异、介电常数低、介电损耗低等特性。
Description
技术领域
本发明属于新材料技术领域，涉及聚苯醚树脂，具体涉及一种含磷乙烯基苯聚苯醚及其树脂和应用。
背景技术
随着电子科技的高速发展，尤其是5G技术在全世界范围内的普及，移动通讯、自动驾驶等领域的电子产品的信息处理要求高频化和高速数字化。高频高速基板目前主要的研发方向是开发低介电性树脂材料。考虑到铜箔基板等树脂材料制品的要求，需要同时满足低介电常数、低介电损耗、高可靠性、高耐湿热性、高尺寸稳定性等。基于以上考虑，目前商业化路线包括聚四氟乙烯基板、改性环氧基板、聚苯醚材料基板、碳氢树脂基板等。聚四氟乙烯基板造价过高，改性环氧基板的介电常数很难进一步降低、碳氢树脂体系阻燃性能较差。相比之下，聚苯醚树脂因其良好的力学性能、介电常数及介电损耗较小、自身具备一定阻燃性能等特点，逐渐成为当今高频低介电印刷电路板中较理想的材料。
商业化的聚苯醚，例如Sabic开发的双羟基聚苯醚SA90、双乙烯基改性聚苯醚树脂SA9000、三菱瓦斯开发的双(乙烯基苄基)聚苯醚Ope-2st，在某些特性尤其是阻燃性能上，并无法达到印刷电路板产业的要求。为解决此问题，通常的方案为：
(1)在聚苯醚树脂组合物中添加各类阻燃剂，例如缩合磷酸酯、DOPO化合物(例如Di-DOPO等产品)、有机次磷酸盐(例如OP-930、OP-935等产品)等各类阻燃剂，这一类的添加型阻燃剂因极性较强、吸湿性强等特点，会劣化介电特性，并降低聚苯醚树脂组合物制品的耐热性；
(2)引入可聚合型的含磷单体，例如引入烯丙基磷酸二乙酯、烯丙基膦腈阻燃剂、丙烯酸酯DOPO阻燃剂等具有可聚合双键的化合物，以期兼顾所需的阻燃性、耐热性与介电特性。加入烯丙基磷酸二乙酯的体系在耐热性能、变形性上远不及烯丙基膦腈阻燃剂丙烯酸酯DOPO阻燃剂体系，但后两者则因制造难度大，价格高，很难商业化。
(3)目前，人们还注意到在高频高速体系中，引入含P-C键阻燃剂体系可以在实现阻燃性能的同时，不会影响材料的介电性能。例如人们开发的PQ-60,BPE-3等化合物。该类化合物具有超过300℃的熔点，但，几乎不溶于常见溶剂，带来分散不均、相容性差的问题。
因此，亟需开发出兼顾介电特性、相容性、耐热性及低造价的新一代含磷阻燃剂及对应的聚苯醚化合物。
发明内容
为了解决现有技术中存在的上述问题，本发明提供了一种由含磷乙烯基苯化合物及乙烯基聚苯醚反应得到的含磷乙烯基苯聚苯醚。
其中，所述的含磷乙烯基苯化合物：为具有下述结构的化合物：
所述含磷乙烯基苯化合物按如下路线合成：
所述乙烯基聚苯醚为任一种至少一末端含有不饱和双键的聚苯醚化合物，如：甲基丙烯酸酯聚苯醚、乙烯基苄基聚苯醚中的一种或多种。
本发明的另一目的在于提供一种树脂组合物，包含上述含磷乙烯基苯聚苯醚及至少一种交联剂。
所述交联剂包括二乙烯基苯、三烯丙基异氰脲酸酯、二乙烯基苯醚、异氰酸酯、聚苯醚树脂、马来酰亚胺、聚酰胺、聚酰亚胺、苯乙烯马来酸酐共聚物、苯乙烯-丁二烯共聚物、苯乙烯-丁二烯-二乙烯基苯三聚物、聚酯、烯烃聚合物、三环癸烷二甲醇二丙烯酸酯、聚丁二烯、三乙烯环己烷、及酸酐硬化剂中的一种或多种。
进一步的，所述的树脂组合物，还包括含磷阻燃剂、硬化促进剂、无机填料、溶剂中的一种或多种。
优选的，磷阻燃剂为2-(二苯基膦酰基)-1,4-苯二酚、烯丙基磷酸二乙酯阻燃剂、磷腈阻燃剂等中的一种或多种。
优选的，无机填料包括二氧化硅、氧化铝、二氧化钛、氧化锌、氧化锆、云母、煅烧高岭土等中的一种或多种的组合。
优选的，无机填料为球型或纤维状型。
优选的，所述硬化促进剂包括过氧化二异丙苯、过氧苯甲酸叔丁酯、二叔丁基过氧化二异丙基苯、2,5-二(叔丁基过氧)-2,5-二甲基-3-己炔中的一种或多种。
优选的，溶剂为乙二醇单甲醚、丙酮、丁酮、甲基异丁基酮、环己酮、甲苯、二甲苯、二甲基甲酰胺、丙二醇甲基醚中的一种或多种的组合。
所述硬化促进剂包括过氧化二异丙苯、过氧苯甲酸叔丁酯、二叔丁基过氧化二异丙基苯、2,5-二(叔丁基过氧)-2,5-二甲基-3-己炔中的一种或多种。
本发明所述的含磷乙烯基苯聚苯醚在制备树脂膜、半固化片、背胶铜箔、层压板或印刷电路板中的应用。
本发明的再一目的在于提供一种由上述树脂组合物制得的制品，其包括树脂膜、半固化片、背胶铜箔、层压板或印刷电路板。
与现有技术相比，本发明的有益效果在于：
1.本发明开发出兼顾介电特性、相容性、耐热性及低造价的新一代含磷阻燃剂，及采用合成的乙烯基苄基二苯基氧磷化合物(EPO)与乙烯基聚苯醚在过氧化物的作用下获得对应的含磷乙烯基苯聚苯醚预聚体。
2.本发明的EPO合成原料均为市售工业化产品，合成一步反应就可以得到产品；在聚合过程中，因多个苯环存在，刚性较强，对体系的玻璃化转变温度有很好的提升作用。此外，P-C键化合物极性小，不水解，不会提高制品的介电常数，制品的耐候性提高，不吸湿。
3.本发明由含有含磷乙烯基苯聚苯醚的树脂组合物制得的树脂膜、半固化片、层压板或印刷电路板，具有热膨胀系数低、热膨胀率低、耐热性高、阻燃性优异、介电常数低、介电损耗低等特性。
4.本发明由含有含磷乙烯基苯聚苯醚的树脂组合物制品阻燃性可达到UL94标准的V0或V1等级。
附图说明
图1.为本发明的EPO 31P NMR核磁谱图；
图2.为本发明的EPO质谱图。
具体实施方式
以下结合实施例对本发明作进一步的说明，但本发明不仅限于这些实施例，在未脱离本发明宗旨的前提下，所作的任何改进均落在本发明的保护范围之内。
一种含磷乙烯基苯聚苯醚，由含磷乙烯基苯化合物、乙烯基聚苯醚及过氧化物在升温条件下进行反应获得，具体为：将含磷乙烯苯基化合物、乙烯基聚苯醚及溶剂加入搅拌槽中，再加入过氧化物，将其混合均匀后升温至80-110℃后，持续搅拌3-6h，减压蒸馏去除溶剂，即得到含磷乙烯基苯化合物与乙烯基聚苯醚的预聚物，即本发明的含磷乙烯基苯聚苯醚。
上述含磷乙烯基苯化合物：为具有以下单元结构的对乙烯基苄基二苯基氧磷化合物(EPO)：
所述化合物按照如下路线合成：
上述乙烯基聚苯醚，可为任一种至少一末端含有不饱和双键的聚苯醚化合物，可以选择市售的甲基丙烯酸酯聚苯醚(例如沙比克公司生产的SA-9000)、乙烯基苄基聚苯醚(三菱瓦斯化学生产的乙烯基苄基聚苯醚树脂OPE-2st)。
另一方面，本发明提出了一种树脂组合物，其包括上述含磷乙烯基苯聚苯醚及至少一种交联剂，所述交联剂与含磷乙烯基苯聚苯醚的重量比为5％-30％。
所述交联剂，为二乙烯基苯、三烯丙基异氰脲酸酯、二乙烯基苯醚异氰酸酯、聚苯醚树脂、马来酰亚胺、聚酰胺、聚酰亚胺、苯乙烯马来酸酐共聚物、苯乙烯-丁二烯共聚物、苯乙烯-丁二烯-二乙烯基苯三聚物、聚酯、烯烃聚合物、酸酐硬化剂、三环癸烷二甲醇二丙烯酸酯、聚丁二烯、三乙烯环己烷中的一种或多种的组合。
除此之外，本发明所述树脂组合物，还包括含磷阻燃剂、硬化促进剂、无机填料、溶剂中的一种或多种的组合。
其中，含磷阻燃剂，可以为2-(二苯基膦酰基)-1,4-苯二酚、烯丙基磷酸二乙酯阻燃剂、磷腈阻燃剂等中的一种或多种，但并非仅限于此。
硬化促进剂，包括可产生自由基的过氧化物硬化促进剂，包括但不限于，过氧化二异丙苯、过氧苯甲酸叔丁酯、二叔丁基过氧化二异丙基苯、2,5-二(叔丁基过氧)-2,5-二甲基-3-己炔等中的一种或多种。
无机填料，包括但不限于二氧化硅、氧化铝、二氧化钛、氧化锌、氧化锆、云母、煅烧高岭土等中的一种或多种的组合。优选无机填料为球型或纤维状型。
溶剂为乙二醇单甲醚、丙酮、丁酮、甲基异丁基酮、环己酮、甲苯、二甲苯、二甲基甲酰胺、丙二醇甲基醚中的一种或多种的组合。
实施例1-5
采用以下来源的各种原料，依照表1用量分别调配各实施例及对比例，并进一步制作成各类测试样本或制品。
原料：
甲基丙烯酸酯聚苯醚：产品名SA-9000，购自沙比克。
乙烯基苄基聚苯醚：产品名0PE-2st，购自三菱瓦斯化学。
乙烯基苯二苯氧磷阻燃剂：产品名EPO，按本专利方法合成。
过氧化二异丙苯(DCP)：购自Sigma Aldrich。
球型二氧化硅：产品名SC-2050，购自Admatechs。
DPO-HQ：产品名2-(二苯基膦酰基)-1,4-苯二酚,购自青岛富斯林华工科技有限公司。
三环癸烷二甲醇二丙烯酸酯：沙多玛SR833s，购自上海凯茵化工。
聚丁二烯：产品名Ricon142，购自上海凯茵化工。
1,2,4-三乙烯基环己烷(1,2,4-trivinylcyclohexane resin，TVCH)：购自Evonik。
苯乙烯-丁二烯共聚物：产品名G1657，购自Kraton。
2,5-二(叔丁基过氧)-2,5-二甲基-3-己炔：产品名25B，购自Aldrich。
二苯甲酰过氧化物(BPO)：购自Sigma Aldrich。
1、含磷乙烯基苯化合物EPO的制备：
二苯基乙氧基膦(719-80-2)230g溶解于500mL氯苯中，分批加入对氯甲基苯乙烯(1592-20-7)155g，升温至135℃，反应3-5h后，得淡黄色溶液，蒸除溶剂，得到淡黄色粘稠状液体，即为含磷乙烯基苯化合物EPO。
2、预聚物的制备：
参照以下说明制备本发明实施例及本发明对比例树脂组合物中所采用的聚苯醚预聚物。
预聚体YJT：将70g的乙烯基苄基聚苯醚OPE-2st、30g的含磷乙烯基苯化合物EPO、0.05g的BPO及150g的甲苯加入搅拌槽中，将混合均匀的溶液升温至95℃后，持续搅拌4h，然后加入水搅拌并去除废液，并减压蒸馏去除溶剂，所得产物称为预聚体YJT。
3、预浸料树脂组合物的制备：
如下表1所示，分别将各个实施例或对比例依照表中的用量，将各组分加入搅拌槽中进行搅拌，均匀混合后形成预浸料树脂组合物。
表1实施例及对比例树脂组合物的组成(单位：重量份)
4、半固化片的制备，包括如下步骤：
按照实施例的组分及配比制备预浸料树脂组合物；
将玻璃纤维布浸渍在预浸料树脂组合物中，烘烤，得到半固化片。
根据本发明的一个方面，所述烘烤的温度为150-180℃，烘烤的时间为3-8min。
5、层压板的制备，包括如下步骤：
采用所述的半固化片的制备方法制备半固化片；将两张金属箔叠放在半固化片的上下两面；和对金属箔和半固化片进行层压，得到层压板。所述层压在真空环境中进行。所述层压的升温速率为1.1-2.5℃/min。在半固化片的温度达到90-120℃时，对金属箔和半固化片施加最大压力；优选最大压力为350-450psi。固化时，控制半固化片的温度在195-210℃，保温90-140min。
6、树脂组合物制品铜箔基板：
半固化片：将南亚2116玻璃纤维布浸入到树脂槽中，使树脂组合物附着于玻璃纤维布上，再在150-180℃烘箱中加热烘烤成半固化态，得到半固化片。再使用两张铜箔、六张各待测样品所制得的半固化片按顺序叠合，在真空条件、200℃下压合2小时形成各铜箔基板。
表2.实施例及对照例性能测试表
由实施例及对比例可知，使用含磷乙烯基化合物与乙烯基聚苯醚进行预聚，相较于使用其他含磷化合物进行预聚可达成较高的Tg、较低的热膨胀系数、较低的热膨胀率、较佳的T288耐热性、较低的介电特性及较佳的阻燃性。
Claims (13)
1.一种由含磷乙烯基苯化合物及乙烯基聚苯醚反应得到的含磷乙烯基苯聚苯醚。
2.如权利要求1所述的含磷乙烯基苯聚苯醚，其特征在于：其中，所述的含磷乙烯基苯化合物：为具有下述结构的化合物：
3.如权利要求1或2所述的含磷乙烯基苯聚苯醚，其特征在于：所述含磷乙烯基苯化合物按如下路线合成：
4.如权利要求1所述的含磷乙烯基苯聚苯醚，其特征在于：所述乙烯基苯聚苯醚为任一种至少一末端含有不饱和双键的聚苯醚化合物。
5.一种树脂组合物，其特征在于：包含权利要求1-4中任一项所述含磷乙烯基苯聚苯醚及至少一种交联剂。
6.如权利要求5所述的树脂组合物，其特征在于：所述交联剂包括二乙烯基苯、三烯丙基异氰脲酸酯、二乙烯基苯醚、异氰酸酯、聚苯醚树脂、马来酰亚胺、聚酰胺、聚酰亚胺、苯乙烯马来酸酐共聚物、苯乙烯-丁二烯共聚物、苯乙烯-丁二烯-二乙烯基苯三聚物、聚酯、烯烃聚合物、三环癸烷二甲醇二丙烯酸酯、聚丁二烯、三乙烯环己烷、及酸酐硬化剂中的一种或多种。
7.如权利要求5或6所述的树脂组合物，其特征在于：还包括含磷阻燃剂、硬化促进剂、无机填料、溶剂中的一种或多种。
8.如权利要求7所述的树脂组合物，其特征在于：磷阻燃剂为2-(二苯基膦酰基)-1,4-苯二酚、烯丙基磷酸二乙酯阻燃剂、磷腈阻燃剂等中的一种或多种。
9.如权利要求8所述的树脂组合物，其特征在于：无机填料包括二氧化硅、氧化铝、二氧化钛、氧化锌、氧化锆、云母、煅烧高岭土等中的一种或多种的组合。
10.如权利要求9所述的树脂组合物，其特征在于：所述硬化促进剂包括过氧化二异丙苯、过氧苯甲酸叔丁酯、二叔丁基过氧化二异丙基苯、2,5-二(叔丁基过氧)-2,5-二甲基-3-己炔中的一种或多种。
11.如权利要求8-10任一项所述的树脂组合物，其特征在于：溶剂为乙二醇单甲醚、丙酮、丁酮、甲基异丁基酮、环己酮、甲苯、二甲苯、二甲基甲酰胺、丙二醇甲基醚中的一种或多种的组合。
12.如权利要求1所述的含磷乙烯基苯聚苯醚在制备树脂膜、半固化片、背胶铜箔、积层板或印刷电路板中的应用。
13.一种由权利要求12所述的树脂组合物制得的制品，其包括树脂膜、半固化片、背胶铜箔、层压板或印刷电路板。
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| CN115873403A (zh) * | 2022-12-30 | 2023-03-31 | 江苏蔚观新材料科技有限公司 | 一种高gwit无卤阻燃玻璃纤维增强尼龙 |
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| EP0147724A2 (en) * | 1983-12-28 | 1985-07-10 | General Electric Company | Flame resistant alkenyl aromatic compounds and polymers containing chemically bonded phosphorus and blends with polyphenylene ether |
| CN107868188A (zh) * | 2016-09-23 | 2018-04-03 | 台光电子材料股份有限公司 | 含磷乙烯聚苯醚、含有该含磷乙烯聚苯醚的树脂组合物及其制品 |
| CN112126212A (zh) * | 2019-06-24 | 2020-12-25 | 台光电子材料股份有限公司 | 含磷树脂组合物及由其制成的制品 |
| WO2020262089A1 (ja) * | 2019-06-27 | 2020-12-30 | パナソニックＩｐマネジメント株式会社 | 樹脂組成物、プリプレグ、樹脂付きフィルム、樹脂付き金属箔、金属張積層板、及び配線板 |
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| EP0147724A2 (en) * | 1983-12-28 | 1985-07-10 | General Electric Company | Flame resistant alkenyl aromatic compounds and polymers containing chemically bonded phosphorus and blends with polyphenylene ether |
| CN107868188A (zh) * | 2016-09-23 | 2018-04-03 | 台光电子材料股份有限公司 | 含磷乙烯聚苯醚、含有该含磷乙烯聚苯醚的树脂组合物及其制品 |
| CN112126212A (zh) * | 2019-06-24 | 2020-12-25 | 台光电子材料股份有限公司 | 含磷树脂组合物及由其制成的制品 |
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| CN115873403A (zh) * | 2022-12-30 | 2023-03-31 | 江苏蔚观新材料科技有限公司 | 一种高gwit无卤阻燃玻璃纤维增强尼龙 |
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