CN1190419C - 带有电子给体和电子受体官能团的化合物 - Google Patents

带有电子给体和电子受体官能团的化合物 Download PDF

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CN1190419C
CN1190419C CNB011195258A CN01119525A CN1190419C CN 1190419 C CN1190419 C CN 1190419C CN B011195258 A CNB011195258 A CN B011195258A CN 01119525 A CN01119525 A CN 01119525A CN 1190419 C CN1190419 C CN 1190419C
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O·M·穆萨
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Abstract

同时含有电子给体和电子受体官能团的化合物适用于粘合剂，电子给体基团是连接于芳环的碳-碳双键，并与环中的不饱和键共轭。电子受体基团是马来酰亚胺、丙烯酸酯、富马酸酯或马来酸酯。

Description

带有电子给体和电子受体官能团的化合物
本发明涉及电子给体/受体化合物和含有这些电子给体/受体化合物的可固化的粘合剂组合物。
粘合剂组合物，尤其是导电粘合剂在制造和装配半导体组合件和微电子装置中用于各种用途。更突出的用途是集成电路芯片与铅框架或其它基质的粘合和电路组合件或装置与印刷线路板的粘合。
现有的使用乙烯基醚作为给体的电子受体/给体粘合剂用于低模量粘合剂，尤其是小片连接(die attach)应用的快速固化粘合剂。然而，用作给体的乙烯基醚的数量由于其高挥发和难以制备而被限制。因此，人们仍需要开发用于粘合剂应用的新电子给体/受体化合物。
本发明涉及同时含有电子给体基团和电子受体基团的化合物(电子给体/受体化合物)。电子给体基团是连接于芳环和与环中的不饱和键共轭的碳-碳双键。电子受体基团是马来酸酯、富马酸酯、马来酰亚胺或丙烯酸酯。本发明还涉及含有一种或多种本发明的电子给体/受体化合物、固化剂和任意选择性地一种或多种填料的粘合剂组合物。
本发明的电子给体/受体化合物将具有如下所示的结构之一：
结构I：
Figure C0111952500081
结构II：
其中
Ar是在环结构中含有3-10个碳原子的芳香或杂芳环或稠合环，其中杂原子可以是N、O或S；
R1、R2和R3分别是H、含有1-12个碳原子的支链、环或直链烷基或如上所述的Ar；优选R1、R2和R3是H或甲基或乙基；
G是-OR4、-SR4、-N(R1)(R2)、如上所述的Ar或含有1-12个碳原子的烷基，其中R1和R2是如上所述的，和R4是如上所述的Ar或含有1-12个碳原子，优选1-4个碳原子的烷基；
Q是含有1-12个碳原子的烷基；
X是：
Figure C0111952500091
Figure C0111952500101
-S-或-O-；
Z是烷基、硅氧烷、聚硅氧烷、C1-C4烷氧基封端的硅氧烷或聚硅氧烷、聚醚、聚酯、聚氨酯、聚丁二烯或芳香、多芳香或杂芳基团；
和
E是
Figure C0111952500102
或
其中Y是O或N(R1)和R1、R2和R3和Q是如上所述的。
电子给体基团是碳-碳双键，它直接连接于芳环和与芳环中的不饱和键共轭。芳环可以是满足芳香化合物的经典定义的任何分子部分，即它在分子平面之上和之下含有环状的非定域π电子云，π电子云总共含有(4n+2)个电子。
芳环还可含有供电子取代基，它将增加碳-碳双键上的电子密度，产生更高的反应性。电子给体基团的反应性还受空间相互作用的影响。在碳-碳双键上烷基取代基数量的增加将降低反应性。优选碳-碳双键上的所有取代基是H或是H与作为唯一其它取代基的甲基。
用于Z基团部分的起始物料在商业上可由许多来源获得，例如芳香和多芳香物质可由BASF或Bayer得到；硅氧烷或聚硅氧烷由Gelest得到；聚醚由BASF得到；聚酯由Uniqema或Bayer得到；聚丁二烯由Elf-Atochem得到；聚氨酯由Bayer或BASF得到和支链或直链烷烃由Uniqema得到。
Z基团可含有环状部分或杂原子，根据制备电子给体化合物的合成途径，可含有羟基或硫醇侧基；例如如果起始化合物之一含有与环氧官能团反应的羟基或硫醇官能团，则Z基团将含有羟基或硫醇侧基。
Z的确切组成或分子量对于本发明不是关键的，可根据电子给体化合物的最终用途的需要广泛地变化。例如Z可以是亚甲基或高分子聚合体。可选择Z的组成以得到在最终配方中的特殊材料性质，例如流变性、亲水或疏水性质、韧性、强度或柔韧性。例如，低含量的交联和围绕聚合键的自由旋转将赋予化合物柔韧性，存在硅氧烷部分将赋予疏水性和柔韧性。分子量和链长将影响粘度，分子量越高和链长度越长，粘度越高。
电子受体起始化合物可以是富马酸酯、马来酸酯、丙烯酸酯和马来酰亚胺。合适的丙烯酸酯是无数的，是商业上可获得的，例如由Satomer得到。合适的马来酰亚胺是容易制备的，例如根据Dershem的US6034194和6034195中描述的方法。通常在丙烯酸酯、马来酸酯和富马酸酯化合物中的羧基将是将电子给体连接到Z基团上的辅助活性官能团上的活性官能团。如实施例中所示，马来酰亚胺将含有一单独的官能团，它与Z基团上的辅助活性官能团反应。
合适的反应途径可通过决定特殊的加成或缩合反应，随后选择起始电子给体化合物和起始电子受体化合物参与该反应的官能团而设计。虽然本领域的技术人员通过选择和定位官能团(在起始电子给体或起始电子受体化合物上)可设计合适的变化，但应理解在实践中选择将受起始物料的可获得性或合成途径的容易度的制约。
代表性的合成途径包括：
1.异氰酸酯官能团与(i)羟基或(ii)胺或(iii)硫醇官能团反应以分别产生氨基甲酸酯链、脲或硫代氨基甲酸酯；
2.用(i)羟基或(ii)胺或(iii)硫醇官能团取代卤素以分别产生醚键、胺或硫醚；
3.环氧官能团与(i)羟基或(ii)胺或(iii)硫醇官能团反应以分别产生醚键、胺或硫醚。
电子给体/受体化合物可配制入粘合剂、涂料、封装或密封剂(potting or encapsulant)组合物中。除电子给体/受体化合物之外，配方将含有一种或多种固化剂和可含有导电或非导电填料。
举例性固化剂是热引发剂和光引发剂，将以按电子给体化合物重量计0.1％-10％，优选0.1％-3.0％的数量存在。优选的热引发剂包括过氧化物，例如过辛酸丁基酯和二枯基过氧化物和偶氮化合物，例如2，2’-偶氮双(2-甲基-丙腈)和2，2’-偶氮双(2-甲基-丁腈)。光引发剂的优选系列是由Ciba Speciatly Chemicals以商标Irgacure出售的物质。在某些配方中，热引发和光引发均是需要的，例如固化过程可通过照射开始，在随后的加工步骤中，固化可通过采用加热完成以实现热固化。
通常，这些组合物将在70℃-250℃的温度下固化，固化将进行10秒钟-3小时。每种配方的时间和温度固化曲线(profile)将随特定的电子给体化合物和配方的其它组分变化，但固化曲线的参数可以由本领域中已知该技术教导的技术人员确定。
合适的导电填料是碳黑、石墨、金、银、铜、铂、钯、镍、铝、碳化硅、氮化硼、金刚石和氧化铝。合适的非导电填料是蛭石、云母、硅灰石、碳酸钙、氧化钛、沙土、玻璃、熔凝硅石、热解法二氧化硅、硫酸钡粒子和卤代乙烯聚合物，例如四氟乙烯、三氟乙烯、1，1-二氟乙烯、氟乙烯、1，1-二氯乙烯和氯乙烯。如果存在，填料的数量为按配方重量计的20％-90％。
合适的粘合促进剂或偶联剂是硅烷、硅酸盐酯、金属丙烯酸盐或甲基丙烯酸盐、钛酸盐和含有螯合配位体的化合物，例如膦、硫醇和乙酰乙酸酯。如果存在，偶联剂的数量为按电子给体化合物重量计至多10％，优选为按重量计0.1％-3.0％。
此外，配方可含有给生成的固化物质增添附加柔韧性和韧性的化合物，该化合物可以是任何具有Tg为150℃或以下的热固性或热塑性物质，典型地为聚合物，例如聚丙烯酸酯、聚丁二烯、聚THF(聚四氢呋喃)、羧基封端的丁腈橡胶和聚丙二醇。如果存在，这些化合物可以按电子给体化合物重量计至多约15％的数量存在。
如下实施例显示代表性的电子给体/受体化合物和它们制备过程的反应。电子给体/受体反应产物用1H-NMR和FT-IR光谱表征，实施例是发明的举例说明，不用来限制发明。
                         实施例1
将1摩尔当量的马来酸酐在乙腈中的溶液加入到1摩尔当量在乙酸中的6-氨基己酸中，使混合物在室温下反应3小时直至由溶液中沉淀出酰胺酸加合物的白色结晶。过滤出白色结晶，用冷乙腈洗涤和干燥。
将酰胺酸与2摩尔当量在甲苯中的三乙胺混合，混合物加热到130℃2小时，直至蒸馏出水。蒸发有机溶剂，加入2M盐酸达到pH2。混合物用乙酸乙酯提取，用硫酸镁干燥，蒸发溶剂得到6-马来酰亚氨基己酸。
将6-马来酰亚氨基己酸与过量亚硫酰氯在50℃下反应3小时，蒸馏出过量亚硫酰氯得到6-马来酰亚氨基己酰氯。
在0℃将各1摩尔当量的肉桂醇和三乙胺在无水二氯甲烷中混合，向其中加入溶解在无水二氯甲烷中的6-马来酰亚氨基己酰氯。使混合物反应4小时，蒸发溶剂，粗产物通过使用梯度己烷/乙酸乙酯的柱色谱法纯化。
                       实施例2
Figure C0111952500141
在0℃将1摩尔当量的异丁子香酚和1摩尔当量的三乙胺在无水二氯甲烷中混合，向其中加入溶解在无水二氯甲烷中的1摩尔当量的6-马来酰亚氨基己酰氯。使混合物反应4小时，蒸发溶剂，粗产物通过使用梯度己烷/乙酸乙酯的柱色谱法纯化。
                   实施例3
在0℃将1摩尔当量的肉桂基胺和1摩尔当量的三乙胺在无水二氯甲烷中混合，向其中加入溶解在无水二氯甲烷中的1摩尔当量的6-马来酰亚氨基己酰氯。使混合物反应4小时，蒸发溶剂，粗产物通过使用梯度己烷/乙酸乙酯的柱色谱法纯化。
                   实施例4
Figure C0111952500152
在0℃将1摩尔当量的4-乙烯基苄胺和1摩尔当量的三乙胺在无水二氯甲烷中混合，向其中加入溶解在无水二氯甲烷中的1摩尔当量的6-马来酰亚氨基己酰氯。使混合物反应4小时，蒸发溶剂，粗产物通过使用梯度己烷/乙酸乙酯的柱色谱法纯化。
                      实施例5
将1摩尔当量的马来酸酐和1摩尔当量的5-氨基戊醇溶解在无水乙酸中，将溶液回流加热8小时。蒸馏出乙酸，残余物溶解在乙醚中。乙醚溶液用1N氢氧化钠洗涤1次，用水洗涤2次，随后用硫酸镁干燥。蒸发乙醚，残余物由异丙基醚结晶得到N-(5-羟基戊基)马来酰亚胺。
在带有机械搅拌器、添加漏斗和氮气入口/出口的三颈烧瓶中将1摩尔当量的3-异丙烯基-α，α-二甲基苄基异氰酸酯(m-TMI)在甲苯中溶剂化。将反应混合物置于氮气下，当溶液加热到90℃时在搅拌下加入0.01摩尔当量的二丁基锡二月桂酸盐(催化剂)。通过添加漏斗加入溶解在甲苯中的1摩尔当量的N-(5-羟基戊基)马来酰亚胺，将溶液在10分钟内加入异氰酸酯溶液中，得到的混合物在90℃下再加热3小时。使反应混合物冷却到室温，混合物用蒸馏水洗涤3次。分离出有机层，用硫酸镁干燥，过滤和真空蒸发溶剂得到产物。
                      实施例6
将1摩尔当量N-(5-羟基戊基)马来酰亚胺、过量50％氢氧化钠、0.43摩尔当量四丁基铵硫酸氢盐和1摩尔当量肉桂基氯在甲苯中在53℃下搅拌5小时，随后在75℃下搅拌15小时。使反应混合物冷却到室温，提取有机层和用盐水洗涤3次。分离的有机层随后用硫酸镁干燥、过滤和真空除去溶剂得到肉桂基氯/戊醇马来酰亚胺加合物。
                      实施例7
将1摩尔当量马来酸酐和对氨基苯甲酸溶解在N，N-二甲基甲酰胺(DMF)中，混合物在氮气气氛中在室温下搅拌5小时。将得到的溶液倾入足够的水中以沉淀粗N-(4-羧基苯基)马来酰胺酸，将其过滤、干燥和由水中重结晶3次得到纯N-(4-羧基苯基)马来酰胺酸。
将1摩尔当量的N-(4-羧基苯基)马来酰胺酸、乙酸酐和乙酸钠的混合物在60℃下搅拌2小时，将反应混合物倾入足够的水中以沉淀粗N-(4-羧基苯基)马来酰亚胺，将其过滤、干燥和由水中重结晶3次得到纯N-(4-羧基苯基)马来酰亚胺。
将1摩尔当量的N-(4-羧基苯基)马来酰亚胺的混合物与过量亚硫酰基氯在50℃下反应3小时，蒸馏出过量的亚硫酰基氯，残余的产物由苯中重结晶得到纯N-(4-(氯羰基)苯基)马来酰亚胺。
在0℃将1摩尔当量的肉桂基醇和1摩尔当量的三乙胺在无水二氯甲烷中混合，向其中加入溶解在无水二氯甲烷中的N-(4-(氯羰基)苯基)马来酰亚胺。使混合物反应4小时，蒸发溶剂，粗产物通过使用梯度己烷/乙酸乙酯的柱色谱法纯化。
                      实施例8
在0℃将1摩尔当量的肉桂基胺和1摩尔当量的三乙胺在无水二氯甲烷中混合，向其中加入溶解在无水二氯甲烷中的1摩尔当量的N-(4-(氯羰基)苯基)马来酰亚胺。使混合物反应4小时，蒸发溶剂，粗产物通过使用梯度己烷/乙酸乙酯的柱色谱法纯化。
                      实施例9
Figure C0111952500192
在0℃将1摩尔当量的4-乙烯基苄胺和1摩尔当量的三乙胺在无水二氯甲烷中混合，向其中加入溶解在无水二氯甲烷中的1摩尔当量的N-(4-(氯羰基)苯基)马来酰亚胺。使混合物反应4小时，蒸发溶剂，粗产物通过使用梯度己烷/乙酸乙酯的柱色谱法纯化。
                      实施例10
Figure C0111952500201
在圆底烧瓶中，在剧烈搅拌下，将在水和甲苯中的1摩尔当量的叠氮化钠和催化量的苄基三乙基氯化铵冷却到10℃，在约40分钟的时间内向该溶液中滴加1摩尔当量的6-马来酰亚氨基己酰氯。将溶液在15℃下搅拌1小时，随后在20℃下搅拌1小时。分离出有机相，用2N碳酸氢钠水溶液和水洗涤。有机相用硫酸镁干燥并过滤。将滤液加入圆底烧瓶中，缓慢加热到回流。保持回流直至氮气释放停止。再将溶液回流加热30分钟，在冷却后在旋转蒸发器中浓缩。残余物在高真空下蒸馏以产生带有异氰酸酯官能团的马来酰亚胺。
在带有机械搅拌器、添加漏斗和氮气入口/出口的三颈烧瓶中将1摩尔当量的带有异氰酸酯官能团的马来酰亚胺在甲苯中溶剂化。将反应混合物置于氮气下，当溶液加热到70℃时在搅拌下加入0.01摩尔当量的二丁基锡二月桂酸盐(催化剂)。通过添加漏斗加入溶解在甲苯中的1摩尔当量的肉桂基醇，将溶液在10分钟内加入异氰酸酯溶液中，得到的混合物在70℃下再加热3小时。在反应混合物冷却到室温后，混合物用蒸馏水洗涤3次。分离出有机层，用硫酸镁干燥，过滤和真空蒸发溶剂得到产物。
                      实施例11
在带有机械搅拌器、添加漏斗和氮气入口/出口的三颈烧瓶中将1摩尔当量的带有异氰酸酯官能团的马来酰亚胺在甲苯中溶剂化。将反应混合物置于氮气下，当溶液加热到70℃时在搅拌下加入0.01摩尔当量的二丁基锡二月桂酸盐(催化剂)。通过添加漏斗加入溶解在甲苯中的1摩尔当量的异丁子香酚，将溶液在10分钟内加入异氰酸酯溶液中，得到的混合物在70℃下加热3小时。在反应混合物冷却到室温后，混合物用蒸馏水洗涤3次。分离出有机层，用硫酸镁干燥，过滤和真空蒸发溶剂得到产物。
                      实施例12
Figure C0111952500221
在带有机械搅拌器、添加漏斗和氮气入口/出口的三颈烧瓶中将1摩尔当量的带有异氰酸酯官能团的马来酰亚胺在甲苯中溶剂化。通过添加漏斗加入溶解在甲苯中的1摩尔当量的4-乙烯基苄胺，将溶液在10分钟内加入异氰酸酯溶液中，得到的混合物在70℃下再加热3小时。在反应混合物冷却到室温后，混合物用蒸馏水洗涤3次。分离出有机层，用硫酸镁干燥，过滤和真空蒸发溶剂得到产物。
                      实施例13
Figure C0111952500222
在带有机械搅拌器、添加漏斗和氮气入口/出口的三颈烧瓶中将1摩尔当量的3-异丙烯基-α，α-二甲基苄基异氰酸酯(m-TMI)在甲苯中溶剂化。将反应混合物置于氮气下，当溶液加热到70℃时在搅拌下加入0.01摩尔当量的二丁基锡二月桂酸盐(催化剂)。通过添加漏斗加入溶解在甲苯中的1摩尔当量的丁二醇单丙烯酸酯，将溶液在10分钟内加入异氰酸酯溶液中，得到的混合物在70℃下加热3小时。在反应混合物冷却到室温后，混合物用蒸馏水洗涤3次。分离出有机层，用硫酸镁干燥，过滤和真空蒸发溶剂得到产物。
                      实施例14
将1摩尔当量丁二醇单丙烯酸酯、过量50％氢氧化钠、0.43摩尔当量四丁基铵硫酸氢盐和1摩尔当量肉桂基氯在甲苯中在53℃下搅拌5小时，随后在75℃下搅拌15小时。使反应混合物冷却到室温，随后提取有机层和用盐水洗涤3次。分离的有机层用硫酸镁干燥、过滤和真空除去溶剂得到产物。
                      实施例15
Figure C0111952500232
在0℃将1摩尔当量的肉桂基醇和1摩尔当量的三乙胺在无水二氯甲烷中混合，向其中加入溶解在无水二氯甲烷中的1摩尔当量的丙烯酰氯。使混合物反应4小时，蒸发溶剂，粗产物通过使用梯度己烷/乙酸乙酯的柱色谱法纯化。
                      实施例16
Figure C0111952500241
在0℃将各1摩尔当量的肉桂基胺和三乙胺在无水二氯甲烷中混合，向其中加入溶解在无水二氯甲烷中的1摩尔当量的丙烯酰氯。使混合物反应4小时，蒸发溶剂，粗产物通过使用梯度己烷/乙酸乙酯的柱色谱法纯化。
                      实施例17
在0℃将各1摩尔当量的4-乙烯基胺和三乙胺在无水二氯甲烷中混合，向其中加入溶解在无水二氯甲烷中的1摩尔当量的丙烯酰氯。使混合物反应4小时，蒸发溶剂，粗产物通过使用梯度己烷/乙酸乙酯的柱色谱法纯化。
                      实施例18
在带有机械搅拌器、添加漏斗和氮气入口/出口的三颈烧瓶中将1摩尔当量的3-异丙烯基-α，α-二甲基苄基异氰酸酯(m-TMI)在甲苯中溶剂化。将反应混合物置于氮气下，当溶液加热到70℃时在搅拌下加入0.01摩尔当量的二丁基锡二月桂酸盐(催化剂)。在10分钟内将溶解在甲苯中的1摩尔当量的羟基酰胺酸酯溶液加入异氰酸酯溶液中，得到的混合物在70℃下加热另外3小时。在反应混合物冷却到室温后，混合物用蒸馏水洗涤3次。分离出有机层，用硫酸镁干燥，过滤和真空蒸发溶剂得到产物。
                      实施例19
将1摩尔当量羟基酰胺酸酯、过量50％氢氧化钠、0.43摩尔当量四丁基铵硫酸氢盐和1摩尔当量肉桂基氯在甲苯中在53℃下搅拌5小时，随后在75℃下搅拌15小时。使反应混合物冷却到室温，随后提取有机层和用盐水洗涤3次。分离的有机层用硫酸镁干燥、过滤和真空除去溶剂得到产物。
                      实施例20
Figure C0111952500261
将1摩尔当量羟基酰胺酸酯、过量50％氢氧化钠、0.43摩尔当量四丁基铵硫酸氢盐和1摩尔当量4-乙烯基苄基氯在甲苯中在53℃下搅拌5小时，随后在75℃下搅拌15小时。使反应混合物冷却到室温，提取有机层和用盐水洗涤3次。分离的有机层用硫酸镁干燥、过滤和真空除去溶剂得到产物。
                      实施例21
其它电子给体/受体化合物可根据类似方法制备，如下反应方案显示其它起始电子给体化合物和起始电子受体化合物，得到电子给体/受体化合物。
                      实施例21-A
                      实施例21-B
                      实施例21-C
Figure C0111952500273
                      实施例21-D
TYZOR TOT是由Aldrich得到的钛催化剂。
                      实施例21-E
Figure C0111952500282
                      实施例21-F
Figure C0111952500283

Claims (4)

1.具有如下结构的化合物：
其中
Ar是在环结构中含有3-10个碳原子的芳香环，其中杂原子可以是N、O或S；
R1、R2和R3分别是H、含有1-12个碳原子的支链或直链烷基；
G是-OR4、-SR4、-N(R1)(R2)或含有1-12个碳原子的烷基，其中R1和R2是如上所述的，和R4是含有1-12个碳原子的烷基；
Q是含有1-12个碳原子的烷基；
X是：
-S-，或-O-：
Z是烷基；和
E是
Figure C011195250003C2
或
Figure C011195250003C3
其中Y是O或N(R1)和R1、R2和Q是如上所述的。
2.权利要求1的化合物，其选自如下化合物：
Figure C011195250004C1
和
Figure C011195250004C2
3.具有如下结构的化合物：
Figure C011195250004C3
其中
Ar是在环结构中含有3-10个碳原子的芳香环，其中杂原子可以是N、O或S；
R1、R2和R3分别是H、含有1-12个碳原子的支链或直链烷基；
G是-OR4、-SR4、-N(R1)(R2)或含有1-12个碳原子的烷基，其中R1和R2是如上所述的，和R4是含有1-12个碳原子的烷基；
Q是含有1-12个碳原子的烷基；
X是：
Figure C011195250005C1
-S-或-O-；
Z是烷基；和
E是
或
其中Y是O或N(R1)和R1、R2和Q是如上所述的。
4.权利要求3的化合物，其选自如下化合物：
Figure C011195250007C1
和
Figure C011195250007C2
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JP2002030041A (ja) 2002-01-29
KR20010105229A (ko) 2001-11-28
CN1325847A (zh) 2001-12-12
HK1042492A1 (en) 2002-08-16
KR100794635B1 (ko) 2008-01-14
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