CN109748998B - 呋喃改性的化合物及低聚物 - Google Patents

呋喃改性的化合物及低聚物 Download PDF

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CN109748998B
CN109748998B CN201811299735.3A CN201811299735A CN109748998B CN 109748998 B CN109748998 B CN 109748998B CN 201811299735 A CN201811299735 A CN 201811299735A CN 109748998 B CN109748998 B CN 109748998B
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庄贵贻
邱国展
曾峰柏
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Abstract

本发明提供一种呋喃改性的化合物或低聚物，化合物具有如化学式I所表示的结构：[化学式I]
Figure DDA0001852043640000011
x为1～5的整数，A为包含酮基、酰胺基、酰亚胺基、亚胺基、苯醚基或烯醇醚的基团，G为直接键、‑O‑、‑N‑、‑Ar‑NH‑(CH2)b‑、‑Ar‑O‑(CH2)b‑、‑Ar‑O‑(CH2)a‑NH‑(CH2)b‑、‑(CH2)a‑NH‑(CH2)b‑或‑(CH2)a‑O‑(CH2)b‑，Ar为具取代基或未取代的亚芳基，a为1～5的整数，b为0～5的整数。

Description

呋喃改性的化合物及低聚物
【技术领域】
本发明是关于一种化合物及低聚物，特别是关于一种呋喃改性的化合物及低聚物。
【背景技术】
在2015年年底，欧盟发表了循环经济指令(Circular Economy Package,CEP)，未来的产品组成和零件需符合可修理(repaired)、耐久(durable)、易回收(recycled)等要件以达成循环经济。此外，在2016年的巴黎协定中，提出减少温室气体排放以及把全球平均气温升高幅度控制在工业革命前水平以上低于2℃之内。
目前在电子产品元件中，占最大二氧化碳(CO2)排放量的是印刷电路板(PrintedCircuit Board,PCB)，其排放量大于10万kg CO2/10000m2PCB。因此，相关业者正面临如何有效回收废弃的印刷电路板来降低二氧化碳排放量并同时遵守能源相关产品生态设计指令(Ecodesign Directive)的挑战。目前回收废弃印刷电路板的做法是先将其碾碎，再对金属和塑胶进行纯化或掩埋处理。近年来随着金属纯化技术的成熟，已可从一吨印刷电路板提炼出130公斤铜、19公斤锡、和大约16盎司金。然而，在印刷电路板中，还有大约占了54.5％的塑胶，这是二氧化碳的主要排放来源。印刷电路板中的塑胶包括绝缘树脂和玻璃纤维布，而目前用于印刷电路板的树脂系统都是属于热固型聚合物，性质相当稳定，因此在回收方面便相当困难。虽然也提出使用可分解的热塑性高分子的做法，但仍需进一步地改善热塑性高分子的玻璃态转变温度、热裂解温度、和耐燃特性，才能达到与目前的印刷电路板绝缘树脂相当的特性。
除了印刷电路板之外，应用在其他需在制程或使用上忍受高温的产品中的树脂组成物(组合物)，在对于回收废弃物的需求增加时，也面临类似的挑战。因此，存在着对类似树脂组成物中的成分作进一步的调整以达成使其既可维持在高温应用又能被回收的目的。
【发明内容】
根据本发明的实施例，本发明提供一种呋喃改性的化合物，其具有如下列化学式I所表示的结构：
[化学式I]
Figure BDA0001852043630000021
其中，x为1～5的整数，A为包含酮基、酰胺基、酰亚胺基、亚胺基、苯醚基或烯醇醚的基团，G为直接键、-O-、-N-、-Ar-NH-(CH2)b-、-Ar-O-(CH2)b-、-Ar-O-(CH2)a-NH-(CH2)b-、-(CH2)a-NH-(CH2)b-、或-(CH2)a-CH(OH)-(CH2)b-NH-或-(CH2)a-O-(CH2)b-，Ar为具取代基或未取代的亚芳基，a为1～5的整数，b为0～5的整数。
根据本发明的实施例，本发明提供一种呋喃改性的低聚物，其具有如下列化学式II所表示的结构：
[化学式II]
Figure BDA0001852043630000022
其中，y为1～5的整数，B为包含胺、酰胺、马来酰亚胺、酯基、苯醚或或烯醇醚的重复基团，D为直接键、-O-、-N-、-Ar2-NH-(CH2)d-、-Ar2-O-(CH2)d-、-Ar2-O-(CH2)c-NH-(CH2)d-、-(CH2)c-NH-(CH2)d-、-(CH2)c-CH(OH)-(CH2)d-NH-或-(CH2)c-O-(CH2)d-，Ar2为具取代基或未取代的亚芳基，c为1～5的整数，d为0～5的整数。该呋喃改性的低聚物的数均分子量为1000～12000。
为了对本发明的上述及其他方面有更佳的了解，下文特举实施方案和实施例，并配合所附图式详细说明如下：
【具体实施方式】
本发明的一实施例提供呋喃改性的化合物，其具有如下列化学式I所表示的结构：
[化学式I]
Figure BDA0001852043630000031
其中，x为1～5的整数，A为包含酮基、酰胺基、酰亚胺基、亚胺基、苯醚基烯醇醚的基团，G为直接键、-O-、-N-、-Ar-NH-(CH2)b-、-Ar-O-(CH2)b-、-Ar-O-(CH2)a-NH-(CH2)b-、-(CH2)a-NH-(CH2)b-、-(CH2)a-CH(OH)-(CH2)b-NH-或-(CH2)a-O-(CH2)b-，Ar为具取代基或未取代的亚芳基，a为1～5的整数，b为0～5的整数。
具体地说，A可为
Figure BDA0001852043630000032
Figure BDA0001852043630000033
Figure BDA0001852043630000034
R为氢、卤素、C1～C8烷基、C1～C8卤烷基、C5～C10环烷基、或C6～C12芳香基，A以星号(*)所标示位置与G连接。更具体地说，R可为氢、氟、甲基、乙基、丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、戊基、己基、氟甲基、氟乙基、环戊基、环己基、苯基、联苯基、或萘基。举例来说，A可为
Figure BDA0001852043630000041
Figure BDA0001852043630000042
A以星号(*)所标示位置与G连接，q为1～5的整数，，其中R8为CH3或C2H5，t为1～5的整数，e为1～5的整数。
根据本公开的实施例，Ar可为具取代基或未取代的亚苯基(phenylene group)、亚联苯基(biphenylene group)、亚萘基(naphthylene group)、亚噻吩基(thienylenegroup)、亚吲哚基(indolylene)、亚菲基(phenanthrenylene)、亚茚基(indenylene)、亚蒽基(anthracenylene)、或亚芴基(fluorenylene)。具体地说，Ar可为具1～4个C1～C6烷基取代基的亚苯基(phenylene group)、亚联苯基(biphenylene group)、亚萘基(naphthylenegroup)、亚噻吩基(thienylene group)、亚吲哚基(indolylene)、亚菲基(phenanthrenylene)、亚茚基(indenylene)、亚蒽基(anthracenylene)、或亚芴基(fluorenylene)。
本发明的一实施例提供呋喃改性的低聚物，其具有如下列化学式II所表示的结构：
[化学式II]
Figure BDA0001852043630000043
其中，y为1～5的整数，B为包含胺、酰胺、马来酰亚胺、酯基、苯醚或或烯醇醚的重复基团，D为直接键、-O-、-N-、-Ar2-NH-(CH2)d-、-Ar2-O-(CH2)d-、-Ar2-O-(CH2)c-NH-(CH2)d-、-(CH2)c-NH-(CH2)d-、-(CH2)c-CH(OH)-(CH2)d-NH-或-(CH2)c-O-(CH2)d-，Ar2为具取代基或未取代的亚芳基，c为1～5的整数，d为0～5的整数。该呋喃改性的低聚物的数均分子量为1000～12000。
举例来说，B可为
Figure BDA0001852043630000051
Figure BDA0001852043630000052
B以星号(*)所标示位置与D连接，m为7～200的整数，n为7～200的整数，p、r及s为1～5的整数，q为5～50的整数，z为5～20的整数，R1、R2、R3、R4各自独立地为C1-C5烷基，T1为直接键、C1～C12的直链或支链烷基、-O-、-S-或-NH-，Q为
Figure BDA0001852043630000053
其中，R9、R10及R11各自独立地为CH3或C2H5，T2为C1～C12的直链或支链烷基，i、j及k为1～5的整数。
根据本公开的实施例，Ar2可为具取代基或未取代的亚苯基(phenylene group)、亚联苯基(biphenylene group)、亚萘基(naphthylene group)、亚噻吩基(thienylenegroup)、亚吲哚基(indolylene)、亚菲基(phenanthrenylene)、亚茚基(indenylene)、亚蒽基(anthracenylene)、或亚芴基(fluorenylene)。具体地说，Ar2可为具1～4个C1～C6烷基取代基的亚苯基(phenylene group)、亚联苯基(biphenylene group)、亚萘基(naphthylenegroup)、亚噻吩基(thienylene group)、亚吲哚基(indolylene)、亚菲基(phenanthrenylene)、亚茚基(indenylene)、亚蒽基(anthracenylene)、或亚芴基(fluorenylene)。
以下提供具体的实施例和比较例，以使得对于根据实施例的呋喃改性的化合物和/或低聚物及其应用有更进一步的了解。在此，提出以其在可逆交联反应组成物及进而由该可逆交联反应组成物形成的复合材料的材料为例。
[呋喃改性的化合物和/或低聚物的合成]
[具有如化学式1-1所表示的结构的低聚物]
[化学式1-1]
Figure BDA0001852043630000061
化学式1-1中的m为7～200、n为7～200，且由其表示的低聚物的数均分子量为2000～12000。
实施例1
将60克的苯乙烯马来酸酐(styrene maleic anhydride,SMA，购自Polyscope，重均分子量(Mw)：7500)放入到80克的二甲基乙酰胺(DMAc，购自景明化工)溶剂中，进行预溶解。再加入29.6克的呋喃甲胺(糠胺，furfurylamine,FA，购自ALDRICH)，升温至100℃～160℃，搅拌进行反应。待完全反应后，将温度降至室温，即可获得具有如式(1-1)所表示的结构的低聚物。接着，测量低聚物各项物理特性，结果如表1所示。
实施例2
将60克的苯乙烯马来酸酐(SMA，购自Polyscope，重均分子量(Mw)：9000)放入到80克的二甲基乙酰胺(DMAc)溶剂中，进行预溶解。再加入22.33克的呋喃甲胺(FA，购自ALDRICH)，升温至100℃～160℃，搅拌进行反应。待完全反应后，将温度降至室温，即可获得具有如式(1-1)所表示的结构的低聚物。接着，测量低聚物各项物理特性，结果如表1所示。
实施例3
将83克的苯乙烯马来酸酐(SMA，购自Polyscope，重均分子量(Mw)：10000)放入到115克的二甲基乙酰胺(DMAc)溶剂中，进行预溶解。再加入40克的呋喃甲胺(FA，购自ALDRICH)，升温至100℃～160℃，搅拌进行反应。待完全反应后，将温度降至室温，即可获得具有如式(1-1)所表示的结构的低聚物。接着，测量低聚物各项物理特性，结果如表1所示。
[特性分析和结果]
使用反射式红外线光谱分析仪(Spectrum One-54415，PERLIN ELMER)对实施例1～3制得的低聚物进行IR光谱分析。所得的光谱信息包括：1701cm-1和1776cm-1的-(CO)2NH特征峰，表示呋喃甲胺接枝上了苯乙烯马来酸酐，形成了酰亚胺官能基；以及1006cm-1、1068cm-1的C-O-C特征峰、和1491cm-1的C＝C特征峰，为呋喃甲胺上的呋喃官能基的信号。使用示差扫描热分析仪(Q10，TA仪器股份有限公司)依照IPC-TM-650.2.4.24规范测量实施例1～3的低聚物的玻璃态转变温度(Tg)，列于表1。使用凝胶透析层析仪(凝胶渗透色谱仪，RI830，JASCO)测量实施例1～3的低聚物的重均分子量(Mw)，列于表1。
表1
Figure BDA0001852043630000071
[具有如化学式1-2所表示的结构的低聚物]
[化学式1-2]
Figure BDA0001852043630000081
化学式1-2中的x为5～47，且由其表示的低聚物的数均分子量为1000～6000。
实施例4
将60克的聚苯醚(polyphenylene ether,PPE，购自Sabic，Mn：1600)放入到60克的二甲基乙酰胺(DMAc)溶剂中，进行预溶解。再加入6.9克的呋喃甲胺(FA，购自ALDRICH)，升温至100℃～160℃，搅拌进行反应。待完全反应后，将温度降至室温，即可获得具有如式(1-2)所表示的结构的低聚物。接着，测量低聚物各项物理特性，结果如表2所示。
实施例5
将60克的聚苯醚(PPE，购自Sabic，Mn：2350)放入到60克的二甲基乙酰胺(DMAc)溶剂中，进行预溶解。再加入8克的呋喃甲胺(FA，购自ALDRICH)，升温至100℃～160℃，搅拌进行反应。待完全反应后，将温度降至室温，即可获得具有如式(1-2)表示的结构的低聚物。接着，测量低聚物各项物理特性，结果如表2所示。
[特性分析和结果]
使用反射式红外线光谱分析仪(Spectrum One-54415，PERLIN ELMER)对实施例4～5制得的低聚物进行IR光谱分析。所得的光谱信息包括：3200～3400cm-1的NH特征峰，表示呋喃甲胺接枝上了聚苯醚；以及1006cm-1、1068cm-1的C-O-C特征峰、和1491cm-1的C＝C特征峰，为呋喃甲胺上的呋喃基的信号。使用示差扫描热分析仪(Q10，TA仪器股份有限公司)依照IPC-TM-650.2.4.24规范测量实施例4～5制得的低聚物的玻璃态转变温度(Tg)，列于表2。使用凝胶透析层析仪(RI 830，JASCO)测量实施例4～5的低聚物的重均分子量(Mw)，列于表2。
表2
Figure BDA0001852043630000082
Figure BDA0001852043630000091
[具有如化学式1-3所表示的结构的低聚物]
[化学式1-3]
Figure BDA0001852043630000092
化学式1-3中的z为5～20，且由其表示的低聚物的数均分子量为900～3000。
实施例6
将50克的环氧树脂压克力低聚物(环氧丙烯酸酯低聚物，Epoxy acrylateoligomer，DOUNLEMER1730，购自Double Bond chemical)放入到60克的二甲基乙酰胺(DMAc)溶剂中。再加入10克的呋喃甲胺(FA，购自ALDRICH)，升温至100℃～140℃，搅拌进行反应。待完全反应后，将温度降至室温，即可获得具有如式(1-3)所表示的结构的低聚物。接着，测量低聚物各项物理特性，结果如表3所示。
[特性分析和结果]
使用反射式红外线光谱分析仪(Spectrum One-54415，PERLIN ELMER)对实施例6制得的低聚物进行IR光谱分析。所得的光谱信息包括：3200～3400cm-1的NH特征峰，表示呋喃甲胺接枝上了聚苯醚；以及1006cm-1、1068cm-1的C-O-C特征峰、和1491cm-1的C＝C特征峰，为呋喃甲胺上的呋喃官能基的信号。此外，使用示差扫描热分析仪(Q10，TA仪器股份有限公司)依照IPC-TM-650.2.4.24规范测量实施例4～5制得的低聚物的玻璃态转变温度(Tg)，列于表3。并且使用凝胶透析层析仪(RI 830，JASCO)测量实施例6的低聚物的重均分子量(Mw)，列于表3。
表3
Figure BDA0001852043630000093
[具有如化学式1-4所表示的结构的化合物]
[化学式1-4]
Figure BDA0001852043630000101
化学式1-4中的T为-CH2-CH(OH)-官能基或-CH2-CH2-官能基。
实施例7
将50克的三烯丙基异氰脲酸酯(triallyl isocyanurate,TAIC，购自ALDRICH)放入到60克的二甲基乙酰胺(DMAc)溶剂中。再加入19.48克的的呋喃甲胺(FA，购自ALDRICH)，升温至100℃～160℃，搅拌至完全反应后，将温度降至室温，即可获得具有如式(1-4)所示的结构的化合物。
实施例8
将50克的三(2,3-环氧丙基)异氰脲酸酯(tris(2,3-epoxy propyl)isocyanurate,TEPIC，购自Nissan Chemical)放入到60克的二甲基乙酰胺(DMAc)溶剂中。再加入23克的呋喃甲胺(FA，购自ALDRICH)，升温至100℃～160℃，搅拌至完全反应后，将温度降至室温，即可获得具有如式(1-4)所示的结构的化合物。
特性分析和结果
使用反射式红外线光谱分析仪(Spectrum One-54415，PERLIN ELMER)对实施例7～8制得的化合物进行IR光谱分析。所得的光谱信息包括：3200～3400cm-1的NH特征峰，表示呋喃甲胺接枝上了三烯丙基异氰脲酸酯或参(2,3-环氧丙基)异氰脲酸酯；以及1006cm-1、1068cm-1的C-O-C特征峰、和1491cm-1的C＝C特征峰，为呋喃甲胺上的呋喃基的信号。此外，使用示差扫描热分析仪(Q10，TA仪器股份有限公司)依照IPC-TM-650.2.4.24规范测量实施例7～8制得的化合物的玻璃态转变温度(Tg)，列于表4。
表4
Figure BDA0001852043630000111
[可回收树脂组成物的合成和分析]
[具有单一种类的呋喃改性的低聚物的可回收树脂组成物]
实施例9
取100.47克的实施例1所合成的具有如式(1-1)所示的结构的低聚物和50克的双酰亚胺化合物BMI-1000(购自K.I.Chemical Industry，分子量：358.35)，在50℃～60℃下反应30分钟，形成胶水(可逆交联反应组成物)。将胶水放置在烘箱中并在170℃～190℃进行反应，以得到交联组成物I。
实施例10
取271.2克的实施例4所合成的具有如式(1-2)所示的结构的低聚物和50克的BMI-1000(购自K.I.Chemical Industry)，在50℃～60℃下反应30分钟，形成胶水(可逆交联反应组成物)。将胶水放置烘箱中并在170℃～190℃进行反应，以得到交联组成物II。
实施例11
取40.18克的实施例1所合成的具有如式(1-1)所示的结构的低聚物和10克的BMI-1000(购自K.I.Chemical Industry)，在50℃～60℃反应30分钟，形成胶水(可逆交联反应组成物)。将胶水放置烘箱中并在170℃～190℃进行反应，以得到交联组成物III。
实施例12
取108.4克的实施例4所合成的具有如式(1-2)所示的结构的低聚物和10克的BMI-1000(购自K.I.Chemical Industry)，在50℃～60℃反应30分钟，形成胶水(可逆交联反应组成物)。将胶水放置烘箱中并在170℃～190℃进行反应，以得到交联组成物IV。
实施例13
取50.24克的实施例1所合成的具有如式(1-1)所表示的结构的低聚物和50克的BMI-1000(购自K.I.Chemical Industry)，在50℃～60℃反应30分钟，形成胶水(可逆交联反应组成物)。将胶水放置烘箱中并在170℃～190℃进行反应，以得到交联组成物V。
实施例14
取135.6克的实施例4所合成的具有如式(1-2)所示的结构的低聚物和50克的BMI-1000(购自K.I.Chemical Industry)，在50℃～60℃反应30分钟，形成胶水(可逆交联反应组成物)。将胶水放置烘箱中并在170℃～190℃进行反应，以得到交联组成物VI。
特性分析和结果
使用反射式红外线光谱分析仪(Spectrum One-54415，PERLIN ELMER)对实施例9～14制得的交联组成物I-VI进行IR光谱分析。所得的光谱信息包括：原本在822cm-1的BMI-1000的特征峰在反应后消失，且1068cm-1的呋喃官能基的C-O-C的特征峰的信号强度明显下降，表示形成了交联产物。使用示差扫描热分析仪(Q10，TA仪器股份有限公司)依照IPC-TM-650.2.4.24规范测量实施例9～14制得的组成物的玻璃态转变温度(Tg)，列于表5。使用示差扫描热分析仪(Q10，TA仪器股份有限公司)，取至少5mg的样品，以5℃/min的速率升温至350℃，测量实施例9～17的组成物的可逆温度(Tr)，列于表5。从表5列出的可逆温度(Tr)可知，实施例的交联组成物稳定于160℃以上的高温，甚至在260℃的温度保持稳定。
表5
Figure BDA0001852043630000121
[具有多个种类的呋喃改性的化合物和/或低聚物的组成物]
实施例15
取54.24克的实施例1所合成的具有如式(1-1)所示的结构的低聚物、135.6克的实施例4所合成的具有如式(1-2)所示的结构的低聚物、和50克的BMI-1000(购自K.I.Chemical Industry)，在50℃～60℃下反应30分钟，形成胶水(可逆交联反应组成物)。将胶水放置烘箱中并在170℃～190℃进行反应，以得到交联组成物VII。
实施例16
取54.24克的实施例1所合成的具有如式(1-1)所示的结构的低聚物、42.38克的实施例7所合成的具有如式(1-4)所表示的结构的化合物、和50克的BMI-1000(购自K.I.Chemical Industry)，在50℃～60℃下反应30分钟，形成胶水(可逆交联反应组成物)。将胶水放置烘箱中并在170℃～190℃进行反应，以得到交联组成物VIII。
实施例17
取135.6克的实施例4所合成的具有如式(1-2)所示的结构的低聚物、42.38克的实施例7所合成的具有如式(1-4)所示的结构的化合物、和50克的BMI-1000(购自K.I.Chemical Industry)，在50℃～60℃下反应30分钟，形成胶水(可逆交联反应组成物)。将胶水放置烘箱中并在170℃～190℃进行反应，以得到交联组成物IX。
实施例18
取33.5克的实施例1所合成的具有如式(1-1)所示的结构的低聚物、90.4克的实施例4所合成的具有如式(1-2)所示的结构的低聚物、28.3克的实施例7所合成的具有如式(1-4)所示的结构的化合物、和50克的BMI-1000(购自K.I.Chemical Industry)，在50℃～60℃下反应30分钟，形成胶水(可逆交联反应组成物)。将胶水放置在烘箱中并在170℃～190℃进行反应，以得到交联组成物X。
[特性分析和结果]
使用反射式红外线光谱分析仪(Spectrum One-54415，PERLIN ELMER)对实施例15～18制得的交联组成物VII-X进行IR光谱分析。所得的光谱信息包括：原本在822cm-1的BMI-1000的特征峰在反应后消失，且1068cm-1的呋喃官能基上的C-O-C的特征峰的信号强度明显下降，表示形成了交联产物。使用示差扫描热分析仪(Q10，TA仪器股份有限公司)依照IPC-TM-650.2.4.24规范测量实施例15～18的组成物的玻璃态转变温度(Tg)，列于表6。使用示差扫描热分析仪(Q10，TA仪器股份有限公司)，取至少5mg的样品，以5℃/min的速率升温至350℃，测量实施例18～21的交联组成物的可逆温度(Tr)，也列于表6。从表6列出的可逆温度(Tr)可知，实施例的组成物可稳定于160℃以上的高温，甚至在300℃的温度保持稳定。
表6
Figure BDA0001852043630000141
[可逆反应测试和结果]
将实施例9～18制得的交联组成物粉碎。之后通过提高温度至大于300℃的温度使其断链回到胶水状态。将温度降回60℃～70℃，其再度硬化变成块材形状。使用反射式红外线光谱分析仪(Spectrum One-54415，PERLIN ELMER)对该块材进行IR光谱分析。所得的光谱信息包括：822cm-1的BMI-1000上的C＝C的特征峰重新出现，且1068cm-1的呋喃官能基上的C-O-C的特征峰的信号强度明显提高，表示交联组成物发生断链反应，回复成原本含呋喃基低聚物和/或化合物、和BMI-1000的组成物。
[分析结果的讨论]
对于根据实施例的可逆交联反应组成物而言，双酰亚胺化合物的二个酰亚胺官能基能够分别和二个含呋喃基低聚物或化合物的呋喃官能基发生1,2加成反应，而此立体结构在达到特定温度时，由1,2加成反应形成的键结会断链，使得含呋喃基低聚物/化合物和双酰亚胺化合物的桥接断掉，回复成原本的反应物，从而有利于回收再利用。此外，根据实施例结果，本公开的可逆交联反应组成物结构稳定，耐热性高，且高可逆温度有利于高温制程的应用，举例来说，应用在印刷电路板作为树脂绝缘材料时，需在回焊制程中保持完好，因此可逆温度最好大于等于250℃。
[复合材料的合成和分析]
实施例19
取33.5克的在实施例1所合成的具有如式(1-1)所示的结构的低聚物、90.4克的在实施例4所合成的具有如式(1-2)所示的结构的低聚物、28.3克的在实施例7所合成的具有如化学式(1-4)所表示的结构的化合物、和50克的BMI-1000(购自K.I.ChemicalIndustry)，再加入75克的二甲基乙酰胺(DMAc)，在50℃～60℃下反应30分钟，形成胶水。将胶水含浸在玻璃纤维布中，经过140℃～170℃的烘烤制成胶片(prepreg)，再和铜箔压合制成铜箔基板材。
[比较例]
取环氧树脂828(BE-188，购自长春化工)，100wt％、5phr的二氰二胺(dicyandiamide，购自景明化学)、和500ppm的2-甲基咪唑(2-MI，购自景明化学)，再加入丁酮(MEK，购自景明化学)溶剂，配制成固含量为70％的胶水。将胶水含浸在玻璃纤维布中，经过170℃的烘烤制成胶片，再和铜箔压合制成铜箔基板材。压合条件为温度170℃～190℃、反应1小时～2小时、压力350psi～450psi。由此制成的铜箔基板材为一般用于印刷电路板的FR-4板材。
[特性分析和结果]
使用示差扫描热分析仪(Q10，TA仪器股份有限公司)依照IPC-TM-650.2.4.24规范测量实施例19和比较例的铜箔基板材的玻璃态转变温度(Tg)，列于表7。使用热机械分析仪(Q400，TA仪器股份有限公司)依照IPC-TMC-650.2.4.24规范测量实施例19和比较例的铜箔基板材的热膨胀系数(CTE)，列于表7。使用热重分析仪(Q500，TA仪器股份有限公司)依照IPC-TM-650 2.3.40规范测量实施例19和比较例的铜箔基板材的裂解温度(Td)，列于表7。使用示差扫描热分析仪(Q10，TA仪器股份有限公司)，取至少5mg的样品，以5℃/min的速率升温至350℃，测量实施例19和比较例的铜箔基板材的可逆温度(Tr)，列于表7。并且使用共振腔式微波介质仪(Resonant Cavity Type Microwave Dielectrometer，日本AET公司)依照JIS-compliant 1641规范测量实施例21和比较例的铜箔基板材在10GHz的介电常数(Dk)和介电损失系数(Df)，也列于表7。从表7可以看出，实施例19的铜箔基板材和比较例的铜箔基板材(亦即一般用于印刷电路板的FR-4板材)具有相近的介电常数和介电损失系数。但相较于比较例的铜箔基板材，实施例19的铜箔基板材具有可逆温度300℃，可通过提高温度到约300℃来使得其中的树脂逆反应成呋喃改性的化合物和/或低聚物、和双酰亚胺化合物，从而进行回收。
表7
Figure BDA0001852043630000161
[可逆反应测试和结果]
对实施例19的铜箔基板材进行蚀刻，除去铜箔。再把板材放入温度大于300℃的溶液中，进行溶解和回收组成物。收集回收回来的树脂组成物，使用反射式红外线光谱分析仪(Spectrum One-54415，PERLIN ELMER)对其进行IR光谱分析。所得的光谱信息包括：822cm-1的BMI-1000上的C＝C的特征峰重新出现，且1068cm-1的呋喃官能基上的C-O-C的特征峰的信号强度明显提高，表示树脂组成物发生断链反应，回复成原本的含呋喃基低聚物或化合物和BMI-1000。此外，回收回来的树脂组成物在经过硬化后测量出来的玻璃态转变温度和原本的树脂组成物相同(实施例18)，进一步佐证实施例19的复合材料可回收再利用。
[分析结果的讨论]
由根据实施例的制造方法所制造而成的复合材料包括可逆交联反应组成物，从而可提高复合材料的回收率。举例来说，使用可逆温度大于等于250℃的组成物时，可改善印刷电路板的回收率，进而降低二氧化碳的排放量。此外，回收的组成物可重复使用，作为印刷电路板制程中的绝缘树脂，或者作为次等原物料，而达成循环经济。
综上所述，虽然本发明已以实施方案和实施例揭露如上，然其并非用以限定本发明。本发明所属技术领域中的技术人员在不脱离本发明的精神和范围内，应可作各种的更改与润饰。因此，本发明的保护范围应以所附权利要求书所界定的范围为准。

Claims (3)

1.一种呋喃改性的低聚物，其具有如下列化学式II所表示的结构：
[化学式II]
Figure FDA0003107686320000011
其中，y为1～3的整数，D为直接键、-O-、-N-、-Ar2-NH-(CH2)d-、-Ar2-O-(CH2)d-、-Ar2-O-(CH2)c-NH-(CH2)d-、-(CH2)c-NH-(CH2)d-、-(CH2)c-CH(OH)-(CH2)d-NH-或-(CH2)c-O-(CH2)d-，Ar2为具取代基或未取代的亚芳基，c为1～5的整数，d为0～5的整数，B为
Figure FDA0003107686320000012
Figure FDA0003107686320000013
Figure FDA0003107686320000021
B以星号(*)所标示位置与D连接，m为7～200的整数，n为7～200的整数，p、r及s为1～5的整数，q为5～50的整数，z为5～20的整数，R1、R2、R3、R4各自独立地为C1～C5的烷基，T1为直接键、C1～C12的直链或支链烷基、-O-、-S-或-NH-，Q为
Figure FDA0003107686320000022
其中，R9、R10及R11各自独立地为CH3或C2H5，T2为C1～C12的直链或支链烷基，i、j及k为1～5的整数，
其中该呋喃改性的低聚物的数均分子量为1000～12000。
2.如权利要求1所述的呋喃改性的低聚物，其中Ar2为具取代基或未取代的亚苯基、亚联苯基、亚萘基、亚噻吩基、亚吲哚基、亚菲基、亚茚基、亚蒽基、或亚芴基。
3.如权利要求1所述的呋喃改性的低聚物，其中Ar2为具1～4个C1～C6烷基取代基的亚苯基、亚联苯基、亚萘基、亚噻吩基、亚吲哚基、亚菲基、亚茚基、亚蒽基、或亚芴基。
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