CN109749328B - 可逆交联反应组合物 - Google Patents
可逆交联反应组合物 Download PDFInfo
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Abstract
本公开提供一种可逆交联反应组合物。该可逆交联反应组合物包括至少一种具有式(I)所示结构的低聚物和一具有式(II)所示结构的双马来酰亚胺:
Description
【技术领域】
本公开涉及一种可逆交联反应组合物(组成物)。
【背景技术】
近年来,在2015年年底,欧盟发表了发表循环经济指令(Circular EconomyPackage,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年的巴黎协议中,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。
目前在电子产品组件中,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,再对金属和塑料进行纯化或掩埋处理。然而,回收率一般会低于3%。因此,目前业者通常仍采用燃烧的方式来处理,而这会产生大量的二氧化碳,造成温室效应。近年来随着金属纯化技术的成熟,已可从一吨的印刷电路板提炼出130公斤的铜、19公斤的锡、和大约16盎司的金。然而,在印刷电路板中,还有大约占了54.5%的塑料,这是二氧化碳的主要排放来源。印刷电路板中的塑料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。虽然也有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、热烈解温度、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合物,在对于回收废弃物的需求增加时,也面临类似的挑战。
【发明内容】
根据本公开实施例,本公开提供一种可逆交联反应组合物。该可逆交联反应组合物包括至少一种具有式(I)所示结构的低聚物和具有式(II)所示结构的双马来酰亚胺:
其中,该具有式(I)所示结构的低聚物的呋喃基和具有式(II)所示结构的双马来酰亚胺的马来酰亚胺基的当量比为0.5:1~1:0.5
在式(I)中,x为1~5的整数,A为包含胺、酰胺、酰亚胺、酯基、苯醚或烯醇醚的重复基团,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-O-(CH2)b-或-(CH2)a-CH(OH)-(CH2)b-NH-,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。该具有式(I)所示结构的低聚物的数均分子量为1000~12000。
在式(II)中,E为经取代或未经取代的C6-C25亚芳基、C5-C25烷基芳基、C5-C25芳基烷基、C6-C25亚杂芳基、C1-C25酰基芳基、C2-C25烷氧基芳基、C5-C25酰氧基芳基、C6-C25亚芳基醚基或C6-C25亚芳醚基。
根据本公开实施例,本公开更提供一种可逆交联反应组合物。该可逆交联反应组合物包括(a)一种低聚物,其中该低聚物的数均分子量为1000~12000,其中该低聚物为具有式(IV)所示结构的低聚物、具有式(V)所示结构的低聚物、或具有-第一重复单元及-第二重复单元的低聚物,其中第一重复单元具有式(VI)所示结构、以及第二重复单元具有式(VII)所示结构,且第一重复单元及第二重复单元以无规方式或嵌段方式重复,
其中R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11及R12独立地为氢、C1-6烷基、C1-6烷氧基、或卤素;R13、R14、R15、R18、R19及R20独立地为氢、或C1-6烷基;R16及R17独立地为氢、C1-6烷基、C5-8环烷基、C6-12芳香基、C5-10杂芳基或卤素;R21、R22、R23、R24及R25独立地为氢、C1-6烷基或卤素;q为5~50的整数;以及,z为5~20的整数;以及(b)具有式(II)所示结构的双马来酰亚胺:
其中,E为经取代或未经取代的C6-C25亚芳基、C7-C25烷基芳基、C7-C25芳基烷基、C6-C25亚杂芳基、C7-C25酰基芳基、C7-C25烷氧基芳基、C7-C25酰氧基芳基、C6-C25亚芳基醚基或C6-C25亚芳醚基。
【具体实施方式】
本公开实施例提供一种可逆交联反应组合物。
当组合物中低聚物的呋喃基和双马来酰亚胺的马来酰亚胺基在适当温度下会发生1,2加成反应形成交联,而交联形成的键结在适当的温度下会发生逆反应,使得含呋喃基低聚物/化合物和双马来酰亚胺化合物的桥接断掉,回复成原本的未交联状态,从而有利于回收再利用。当含呋喃基低聚物具有特殊结构时,其和双马来酰亚胺的交联反应可被控制在80-150℃,且于大于200℃以上发生逆交联反应,使得该组合物可适用于需该温度制程的光电或通讯产品相关原物料。
根据本公开实施例,本公开提供一种可逆交联反应组合物。该可逆交联反应组合物包括至少一种具有式(I)所示结构的低聚物和具有式(II)所示结构的双马来酰亚胺:
其中,该至少一种具有式(I)所示结构的低聚物的呋喃基和具有式(II)所示结构的双马来酰亚胺的马来酰亚胺基的当量比为0.5:1~1:0.5。
在式(I)中,x为1~5的整数,A为包含胺、酰胺、酰亚胺、酯基、苯醚或烯醇醚的重复基团,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-O-(CH2)b-或-(CH2)a-CH(OH)-(CH2)b-NH-,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。该具有式(I)所示结构的低聚物的数均分子量为1000~12000。
在式(II)中,E为经取代或未经取代的C6-C25亚芳基、C5-C25烷基芳基、C5-C25芳基烷基、C6-C25亚杂芳基、C1-C25酰基芳基、C2-C25烷氧基芳基、C5-C25酰氧基芳基、C6-C25亚芳基醚基或C6-C25亚芳醚基。
根据本公开实施例,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(thienylene group)、亚吲哚基(indolylene)、亚菲基(phenanthrenylene)、亚茚基(indenylene)、亚蒽基(anthracenylene)、或亚芴基(fluorenylene)。更具体地说,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)。
根据本公开实施例,A可以为 (重复单元及重复单元以有序或无规方式排列)、 A以星号(*)所标示位置与G连接,m、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 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。
根据本公开实施例,该可逆交联反应组合物可还包括具有式(III)所示结构的含呋喃基化合物:
在式(III)中,y为1~5的整数,B为包含酮基、酰胺基、酰亚胺基、胺基、亚胺基、苯醚基或烯醇醚的基团,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-O-(CH2)d-或-(CH2)c-CH(OH)-(CH2)d-NH-,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。
根据本公开实施例,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)。更具体地说,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(naphthylene group)、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)。
根据本公开实施例,B可以为 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,B以星号(*)所标示位置与D连接。更具体地说,B可为 B以星号(*)所标示位置与D连接,,其中R8为CH3或C2H5,t为1~5的整数,e为1~5的整数。
根据本公开实施例,该组合物中该至少一种具有式(I)所示结构的含呋喃基低聚物和具有式(III)所示结构的含呋喃基化合物的重量比可为20:80~80:20。
根据本公开实施例,该组合物中该至少一种具有式(I)所示结构的含呋喃基低聚物和该具有式(III)所示结构的含呋喃基化合物的呋喃基和具有式(II)所示结构的双马来酰亚胺的马来酰亚胺基的当量比为0.7:1~1:0.5。
根据本公开实施例,本公开还提供一种可逆交联反应组合物。该可逆交联反应组合物包括(a)一种低聚物,其中该低聚物的数均分子量为1000~12000,其中该低聚物为具有式(IV)所示结构的低聚物、具有式(V)所示结构的低聚物、或具有-第一重复单元及-第二重复单元的低聚物,其中第一重复单元具有式(VI)所示结构、以及第二重复单元具有式(VII)所示结构,且第一重复单元及第二重复单元以无规方式或嵌段方式重复,
其中R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11及R12独立地为氢、C1-6烷基、C1-6烷氧基、或卤素;R13、R14、R15、R18、R19及R20独立地为氢、或C1-6烷基;R16及R17独立地为氢、C1-6烷基、C5-8环烷基、C6-12芳香基、C5-10杂芳基或卤素;R21、R22、R23、R24及R25独立地为氢、C1-6烷基或卤素;q为5~50的整数;以及,z为5~20的整数;以及(b)具有式(II)所示结构的双马来酰亚胺:
其中,E为经取代或未经取代的C6-C25亚芳基、C7-C25烷基芳基、C7-C25芳基烷基、C6-C25亚杂芳基、C7-C25酰基芳基、C7-C25烷氧基芳基、C7-C25酰氧基芳基、C6-C25亚芳基醚基或C6-C25亚芳醚基。
根据本公开实施例,该可逆交联反应组合物,还包括(c)具有式(III)所示结构的化合物:
其中,y为1~5的整数,B为包含酮基、酰胺基、酰亚胺基、胺基、亚胺基、苯醚基或烯醇醚的基团,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-O-(CH2)d-或-(CH2)c-CH(OH)-(CH2)d-NH-,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。
根据本公开实施例,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。
根据本公开实施例,其中该(a)低聚物和该(c)具有式(III)所示结构的化合物的重量比为20:80~80:20。
根据本公开实施例,其中该(a)低聚物和该(c)具有式(III)所示结构的化合物的呋喃基和具有式(II)所示结构的双马来酰亚胺的马来酰亚胺基的当量比为0.7:1~1:0.5。
根据本公开实施例,本公开的该组合物可用于铜箔基板或印刷电路板制程。本公开的该组合物可作为黏着剂、涂层、封装、复合材料或功能性膜层,亦可用于各种光学及电子产品。
为了让本公开的上述和其他目的、特征、和优点能更明显易懂,下文特举多个实施例及比较例,作详细说明如下:
含呋喃基低聚物的制备例
具有如式(I-1)所示结构的低聚物(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(I-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(I-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(I-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,形成了马来酰亚胺官能基;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。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1~3的低聚物的玻璃态转变温度(Tg),列于表1。并且使用凝胶透析层析仪(凝胶渗透色谱仪,RI 830,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
具有如式(I-2)所示结构的低聚物(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(I-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(I-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2。并且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
具有如式(I-3)所示结构的低聚物(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(I-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
含呋喃基化合物制备例
具有如式(III-1)所示结构的化合物(T为-CH2-CH(OH)-官能基(T以CH2与N键结)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(III-1)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(III-1)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三(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
可逆交联反应组合物制备例
具有单一种类的含呋喃基低聚物的组合物
实施例9
取100.47克的在实施例1所合成的具有如式(I-1)所示的结构的低聚物和50克的双马来酰亚胺化合物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(可逆交联反应组合物)。将胶水放置在烘箱中并在170℃~190℃进行反应,以得到组合物I。
实施例10
取271.2克的在实施例4所合成的具有如式(I-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(可逆交联反应组合物)。将胶水放置烘箱中并在170℃~190℃进行反应,以得到交联组合物II。
实施例11
取40.18克的在实施例1所合成的具有如式(I-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(可逆交联反应组合物)。将胶水放置烘箱中并在170℃~190℃进行反应,以得到交联组合物III。
实施例12
取108.4克的在实施例4所合成的具有如式(I-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(可逆交联反应组合物)。将胶水放置烘箱中并在170℃~190℃进行反应,以得到交联组合物IV。
实施例13
取50.24克的在实施例1所合成的具有如式(I-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(可逆交联反应组合物)。将胶水放置烘箱中并在170℃~190℃进行反应,以得到交联组合物V。
实施例14
取135.6克的在实施例4所合成的具有如式(I-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(可逆交联反应组合物)。将胶水放置烘箱中并在170℃~190℃进行反应,以得到交联组合物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制得的交联组合物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。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9~14的交联组合物的玻璃态转变温度(Tg),列于表5。并且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的交联组合物的可逆温度(Tr),也列于表5。从表5列出的可逆温度(Tr)可知,实施例的交联组合物可稳定到160℃以上的高温。
表5
具有多种含呋喃基低聚物/化合物的组合物
实施例15
取54.24克的在实施例1所合成的具有如式(I-1)所示的结构的低聚物、135.6克的在实施例4所合成的具有如式(I-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(可逆交联反应组合物)。将胶水放置烘箱中并在170℃~190℃进行反应,以得到交联组合物VII。
实施例16
取54.24克的在实施例1所合成的具有如式(I-1)所示的结构的低聚物、42.38克的在实施例7所合成的具有如式(III-1)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(可逆交联反应组合物)。将胶水放置烘箱中并在170℃~190℃进行反应,以得到交联组合物VIII。
实施例17
取135.6克的在实施例4所合成的具有如式(I-2)所示的结构的低聚物、42.38克的在实施例7所合成的具有如式(III-1)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(可逆交联反应组合物)。将胶水放置烘箱中并在170℃~190℃进行反应,以得到交联组合物IX。
实施例18
取33.5克的在实施例1所合成的具有如式(I-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(I-2)所示的结构的低聚物、28.3克的在实施例7所合成的具有如式(III-1)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(可逆交联反应组合物)。将胶水放置在烘箱中并在170℃~190℃进行反应,以得到交联组合物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制得的交联组合物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。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15~18的交联组合物的玻璃态转变温度(Tg),列于表6。并且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的交联组合物的可逆温度(Tr),也列于表6。从表6列出的可逆温度(Tr)可知,实施例的交联组合物可稳定到160℃以上的高温。
表6
[可逆反应测试和结果]
将实施例9~18制得的交联组合物粉碎。之后通过将温度提高至大约250℃~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,表示交联组合物发生断链反应,回复成原本含呋喃基低聚物和/或化合物、和BMI-1000的组合物。
[分析结果的讨论]
对于根据实施例的可逆交联反应组合物而言,双马来酰亚胺化合物的二个马来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/化合物和双马来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,本公开可逆交联反应组合物结构稳定,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(I-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(I-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(III-1)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)为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℃,可通过将温度提高到约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、和双马来酰亚胺化合物,从而进行回收。
表6
[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。再把板材放入温度约250~300℃的溶液中,进行溶解和回收组合物。收集回收回来的树脂组合物,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,表示树脂组合物发生断链反应,回复成原本的含呋喃基低聚物或化合物和BMI-1000。此外,回收回来的树脂组合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合物相同(实施例18),进一步左证实施例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合物,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℃的组合物时,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,回收的组合物可重复使用,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 (20)
1.一种可逆交联反应组合物,包括:
至少一种具有式(I)所示结构的含呋喃基低聚物;以及
具有式(II)所示结构的双马来酰亚胺:
其中,该至少一种具有式(I)所示结构的含呋喃基低聚物的呋喃基和具有式(II)所示结构的双马来酰亚胺的马来酰亚胺基的当量比为0.5:1~1:0.5,
其中,x为1~5的整数,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-O-(CH2)b-或-(CH2)a-CH(OH)-(CH2)b-NH-,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,且该具有式(I)所示结构的含呋喃基低聚物的数均分子量为1000~12000,
其中,E为经取代或未经取代的C6-C25亚芳基、C7-C25烷基芳基、C7-C25芳基烷基、C6-C25亚杂芳基、C7-C25酰基芳基、C7-C25烷氧基芳基、C7-C25酰氧基芳基、C6-C25亚芳基醚基或C6-C25亚芳醚基,
其中A为
2.如权利要求1所述的可逆交联反应组合物,其中Ar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所述的可逆交联反应组合物,其中Ar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。
7.如权利要求6所述的可逆交联反应组合物,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。
8.如权利要求6所述的可逆交联反应组合物,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。
11.如权利要求6所述的可逆交联反应组合物,其中该至少一种具有式(I)所示结构的含呋喃基低聚物和该具有式(III)所示结构的含呋喃基化合物的重量比为20:80~80:20。
12.如权利要求6所述的可逆交联反应组合物,其中该具有式(I)所示结构的含呋喃基低聚物和该具有式(III)所示结构的含呋喃基化合物的总呋喃基当量数和具有式(II)所示结构的双马来酰亚胺的马来酰亚胺基的当量数比为0.7:1~1:0.5。
13.一种可逆交联反应组合物,包括:
一种低聚物,其中该低聚物的数均分子量为1000~12000,其中该低聚物为具有式(IV)所示结构的低聚物、具有式(V)所示结构的低聚物、或具有-第一重复单元及-第二重复单元的低聚物,其中第一重复单元具有式(VI)所示结构、以及第二重复单元具有式(VII)所示结构,且第一重复单元及第二重复单元以无规方式或嵌段方式重复,
其中R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11及R12独立地为氢、C1-6烷基、C1-6烷氧基、或卤素;R13、R14、R15、R18、R19及R20独立地为氢、或C1-6烷基;R16及R17独立地为氢、C1-6烷基、C5-8环烷基、C6-12芳香基、C5-10杂芳基或卤素;R21、R22、R23、R24及R25独立地为氢、C1-6烷基或卤素;q为5~50的整数;以及,z为5~20的整数;以及
具有式(II)所示结构的双马来酰亚胺:
其中,E为经取代或未经取代的C6-C25亚芳基、C7-C25烷基芳基、C7-C25芳基烷基、C6-C25亚杂芳基、C7-C25酰基芳基、C7-C25烷氧基芳基、C7-C25酰氧基芳基、C6-C25亚芳基醚基或C6-C25亚芳醚基。
16.如权利要求15所述的可逆交联反应组合物,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。
19.如权利要求15所述的可逆交联反应组合物,其中该低聚物和该具有式(III)所示结构的化合物的重量比为20:80~80:20。
20.如权利要求15所述的可逆交联反应组合物,其中该低聚物和该具有式(III)所示结构的化合物的总呋喃基当量数和具有式(II)所示结构的双马来酰亚胺的马来酰亚胺基的当量数比为0.7:1~1:0.5。
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US10894853B2 (en) | 2021-01-19 |
CN109748998A (zh) | 2019-05-14 |
CN109749328A (zh) | 2019-05-14 |
US20190144410A1 (en) | 2019-05-16 |
JP2019108524A (ja) | 2019-07-04 |
JP6869936B2 (ja) | 2021-05-12 |
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JP2019085409A (ja) | 2019-06-06 |
TW201918481A (zh) | 2019-05-16 |
JP6978107B2 (ja) | 2021-12-08 |
CN109748998B (zh) | 2021-08-31 |
US20190153139A1 (en) | 2019-05-23 |
US10858471B2 (en) | 2020-12-08 |
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