CN1325845A - 可固化的杂化含乙烯基醚的给电子体化合物 - Google Patents

可固化的杂化含乙烯基醚的给电子体化合物 Download PDF

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CN1325845A
CN1325845A CN01119527A CN01119527A CN1325845A CN 1325845 A CN1325845 A CN 1325845A CN 01119527 A CN01119527 A CN 01119527A CN 01119527 A CN01119527 A CN 01119527A CN 1325845 A CN1325845 A CN 1325845A
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O·M·穆萨
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Ingredion Inc
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Abstract

适用于粘合剂或作为粘合剂的一个组分的杂化的给电子体化合物,其包含一个连接到芳环上并与芳环中的不饱合部分共轭的碳碳双键和一个乙烯基醚部分。

Description

可固化的杂化含乙烯基醚的给电子体化合物
本发明涉及包含一种乙烯基醚基团的给电子体化合物以及包括这些给电子体化合物的可固化的粘合剂组合物。
粘合剂组合物，特别是导电粘合剂，广泛应用于半导体组合件及微电子装置的制造和装配中。更重要的用途是将集成电路芯片粘结到铅框架或其它基体上，把电路元件或组合件粘结到印刷电路板上。
目前用于低模量粘合剂，尤其是用于模片固定的快速固化粘合剂中，有人使用电子受体/给体粘合剂，其中乙烯基醚为给电子体。然而，许多合适的乙烯基醚在作为给体使用时由于其沸点低、挥发性高、制备困难，而受到了局限。因此，需要开发新的用于粘合剂的给电子体。
本发明涉及包含一种乙烯基醚和外接于芳环并与连接到一个分子(小分子)或聚合物基团上的芳环的不饱合键相共轭的碳碳双键的杂化给电子体化合物。乙烯基醚基团的存在使这些化合物相对于不含乙烯基醚基团的给电子体化合物具有更低的粘度。以双官能团杂化给电子体化合物为例，杂化的化合物比相应的含有相同给电子体基团作为各自官能团的双官能团给电子体化合物具有更低的粘度。
除了乙烯基醚基团外，给电子体官能团的活性可以通过添加芳环上的给电子取代基来增加或通过添加吸电子取代基来降低。该活性也会随立体效应而变化。碳碳双键上的烷基取代基的数量或大小的增加会使反应活性降低。优选碳碳双键上的任何取代基均为氢或除一个取代基为甲基外其他均为氢。
杂化体的每一个给电子体基团均通过一个连接基团连接到分子或聚合物本体上，该连接基团是给电子基团上的一个官能团与分子或聚合物基团上的一个共反应官能团反应的产物。另一方面，给电子体基团可以通过偶联反应连接到分子或聚合物基团上，其中在反应中形成了外接于(给电子体的)芳环的碳碳双键。
该分子或聚合物基团可以是环状的、支链的或线性的烷基、硅氧烷或聚硅氧烷、C1-C4的烷氧基封端的硅氧烷或聚硅氧烷、聚醚、聚酯、聚氨酯、(聚)丁二烯或芳环、多芳环或杂芳环基团。
本发明还涉及一种可固化组合物，其包括，一种或多种本发明的给电子体化合物和任选包括一种固化剂以及一种或多种填充剂。
本发明还涉及一种可固化组合物，其包括，一种或多种本发明的给电子体化合物和一种或多种可共聚的电子受体化合物，并可以包含一种固化剂和一种或多种填充剂。适合于共聚的电子受体化合物为富马酸酯和马来酸酯，例如，马来酸二辛酯、马来酸二丁酯、富马酸二辛酯、富马酸二丁酯。树脂或包含丙烯酸酯和马来酰亚胺官能团的化合物也适合作为电子受体物质。
本发明的给电子体化合物具有如下结构：
结构1：
结构2：
其中，m和n为1-6，优选为1-3，更优选为1；
Ar为一个环上含有3-10个碳原子的芳环或杂芳环，其中杂原子可以是N、O或S；
R1、R2和R3独立地为氢、如上所述的Ar或含有1-12个碳原子的烷基。优选R1、R2和R3为氢或含有1-4个碳原子的烷基，更优选为三者均为氢；
R4、R5和R6独立地为氢、甲基或乙基，优选为R4、R5和R6中的两个为氢，一个为甲基，更优选为三者均为氢；
G为-OR7、-SR7、-N(R1)(R2)、如上所述的Ar或含有1-12个碳原子的烷基，其中R7为如上所述的Ar或含有1-12个碳原子的烷基，优选为含有1-4个碳原子，R1和R2如上所述；
Q为一个含有1-12个碳原子的烷基；
X为：
Figure A0111952700111
Figure A0111952700121
-S-或-O-；
Z为烷基、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、或芳环、多芳环或杂芳环基团。这些化合物中用于制备Z基团的物质可以从许多渠道购得。例如，芳环和多芳环类物质可以从BASF或Bayer公司买到；硅氧烷和聚硅氧烷可以从Gelest公司买到；聚醚可以从BASF公司买到；聚酯可以从Uniqema或Bayer公司买到；(聚)丁二烯可以从Elf-Atochem公司买到；聚氨酯可以从Bayer或BASF公司买到；烷烃可以从Uniqema公司买到。其中一些化合物已经与乙烯基醚或其他给电子体原料上的共反应官能团反应进行了官能化得到了Z基团物质，另外一些化合物则需要用户将该物质与含有给电子体基团的原料官能化反应以进行制备。
Z基团可以包含环部分或杂原子，并且可以根据制备给电子体化合物的合成路线包含侧羟基或硫醇基。例如，如果原料之一含有与环氧官能团反应的侧羟基或硫醇基，Z基团将含有侧羟基或硫醇基。
对于本发明来说，Z的确切的组成或分子量并不是至关重要的，可以根据杂化给电子体化合物的最终用途的要求在大范围内变化。可以选择Z的组成以使最终的制剂具有特定材料性质，如：流变性、亲水或疏水性、硬度、韧度或挠曲性。例如：聚合物键的低交联度和自由旋转将使化合物具有挠曲性，硅氧烷部分的存在赋予化合物疏水性和挠曲性。分子量和链的长度将影响粘度，分子量越高，分子链越长，粘度越大。
正如本说明书所用，芳族化合物意味着一个满足芳族化合物传统定义的化合物，即，在分子平面上下包含离域π电子环状的云且该π电子云的总电子数为4n+2。
该芳环基团可以包含一个吸电子基如硝基，吸电子基将降低反应活性。但一般情况下，化合物反应活性越高，最终用途越大。
这些杂化的给电子体化合物可以通过标准的加成或缩合反应来制备或通过用标准的Wittig、Heck或Stille工艺的偶联反应来制备，加成和缩合反应在含有给电子体基团的原料上的一个官能团和含有分子或聚合物基团的原料上的一个共反应官能团和乙烯基醚官能团之间进行。例如，用于给电子体基团(除乙烯基醚外)的化合物原料为肉桂醇或肉桂基氯与3-异丙烯基-α,α-二甲基苄基异氰酸酯。尽管本领域技术人员可以通过官能团及其位置的选择对反应进行适当的变化，但这种变化实际上由原料的易得与否与合成路线的难易来决定。
具有代表性的合成路线包括：
1、异氰酸酯官能团与(ⅰ)羟基；或(ⅱ)胺基；或(ⅲ)硫醇官能团反应分别生成氨基甲酸酯、脲或硫代氨基甲酸酯；
2、卤素与(ⅰ)羟基；或(ⅱ)胺基；或(ⅲ)硫醇基发生取代反应，分别生成醚、胺或硫醚；
3、环氧官能团与(ⅰ)羟基；或(ⅱ)胺基；或(ⅲ)硫醇官能团反应，分别生成醚、胺或硫醚；
杂化的给电子体化合物可以与电子受体化合物如富马酸酯、马来酸酯、丙烯酸酯和马来酰亚胺混合，通过共聚形成具有广泛用途的固化粘合剂组合物。适合的富马酸酯和马来酸酯为，例如：马来酸二辛酯、马来酸二丁酯、富马酸二辛酯、富马酸二丁酯。适合的丙烯酸酯种类多且是市售的，如可以从Sartomer公司买到。适合的马来酰亚胺很容易制备，如可以用Dershem公司申请的US 6 034 194和6 034 195中描述的方法制得。
给电子体化合物可以制成粘合剂、涂料、适用于电子领域的浇注或密封组合物。这些制剂优选包含一种或多种固化剂和导电或非导电填充剂，也可以包含稳定剂、粘结促进剂或偶联剂。
典型的固化剂为热引发剂和光引发剂，用量为给电子体化合物重量的0.1％-10％，优选为0.1％-3.0％。优选的热引发剂包括过氧化物如过辛酸丁酯、二异丙苯基过氧化物，和偶氮化合物如2,2’-偶氮二(2-甲基丙腈)和2,2’-偶氮二(2-甲基丁腈)。优选的光引发剂系列为CibaSpecialty Chemicals以商标Irgacure出售的。在一些制备过程中，同时使用热引发和光引发是理想的。例如，固化过程开始于光的照射，之后用加热的方法完成热固化。
一般情况下，这些组合物在70℃-250℃的温度范围内固化并且在该范围内的一个温度下，固化时间从10秒到3小时不等。每一制剂的时间和温度固化分布将随特定的给电子体化合物和制剂中的其他组分而变化，但本领域专业技术人员可以无需过分的实验对固化分布的参数加以确定。
适当的导电填充剂为炭黑、石墨、金、银、铜、铂、钯、镍、铝、碳化硅、氮化硼、金刚石和氧化铝。适合的非导电性填充剂为蛭石粒子，云母，硅灰石、碳酸钙、二氧化钛、沙子、玻璃、熔融二氧化硅、发烟二氧化硅、硫酸钡以及卤化聚乙烯如四氟乙烯、三氟乙烯、亚乙烯基氟化物、乙烯基氟化物、偏氯乙烯和氯乙烯。填充剂存在时，其用量为制剂总重量的20％-90％。
适合的粘合促进剂或偶联剂为硅烷、硅酸酯、丙烯酸或甲基丙烯酸金属盐、钛酸盐以及含有一种螯合键的化合物如，膦、硫醇和乙酰乙酸酯。当偶联剂存在时，其用量可最高至杂化给电子体化合物重量的10％，优选为0.1％-3.0％。
另外，制剂中可以包含使最终固化的物质具有附加的挠曲性和韧性的化合物。这些化合物可以是Tg为150℃或更低的任何热固性或热塑性物质，一般为聚合物，如：聚丙烯酸酯、聚(丁二烯)、聚THF(四氢呋喃聚合物)、羧基封端的丁腈橡胶及聚丙二醇。这些化合物存在时，其用量可最高至杂化给电子体化合物重量的大约15％。
下面的实施例给出最具代表性的杂化的给电子体化合物及其制备反应。给电子体反应产物用1H NMR和FT-IR光谱进行了表征。这些实施例有助于阐述本发明但并不限制其范围。
在这些实施例中，fnc-C36-fnc代表一种异构体混合物，该异构体由油酸和亚油酸二聚后再转化为适当的官能团。其中当异构体为醇时，fnc为-OH，当异构体为胺时，fnc为-NH2，当异构体为异氰酸酯时，fnc为-NCO，和
Figure A0111952700151
代表一种异构体混合物，该异构体由油酸和亚油酸三聚后再转化为适当的官能团，其中当异构体为羧酸时，fnc为-COOH，当异构体为醇时，fnc为-CH2OH。实施例1
在装有机械搅拌、加料漏斗和氮气进/出口装置的1000ml三颈烧瓶中，将3-异丙烯基-α,α-二甲基苄基异氰酸酯(103.96g,0.517mol)溶于甲苯(150ml)中。反应在氮气保护下进行，将溶液加热到40℃，搅拌下加入二丁基锡二月桂酸酯(0.033g)。在加料漏斗中放置1,4-丁二醇乙烯基醚(60g,0.517mol)溶于甲苯(50ml)的溶液。在10分钟内将该溶液加入到异氰酸酯溶液中，得到的混合物在40℃下再反应3小时。冷却到室温之后，该混合物用蒸馏水洗涤三次，分离出的有机层用MgSO4干燥，过滤后减压除去溶剂，得到产物，收率94％。实施例2
在装有机械搅拌、加料漏斗和氮气进/出口装置的500ml三颈烧瓶中，将3-异丙烯基-α,α-二甲基苄基异氰酸酯(38.06g,0.189mol)溶于甲苯(100ml)中。反应在氮气保护下进行，将溶液加热到40℃，搅拌下加入二丁基锡二月桂酸酯(0.033g)。在加料漏斗中放置1,6-己二醇乙烯基醚(27.27g,0.189mol)溶于甲苯(50ml)的溶液。在10分钟内将该溶液加入到异氰酸酯溶液中，得到的混合物在40℃下再反应3小时。冷却到室温之后，该混合物用蒸馏水洗涤三次，分离出的有机层用MgSO4干燥，过滤后减压除去溶剂，得到产物，收率95％。实施例3
Figure A0111952700181
将1,4-丁二醇乙烯基醚(40.0g,0.344mol),50％的NaOH(300ml),硫酸四丁氢铵(50g,0.148mol)和甲苯中的肉桂基氯(52.56g,0.344mol)在53℃下搅拌反应5小时，75℃下搅拌15小时。冷却到室温之后，用盐水萃取和洗涤有机层三次。分离出的有机层用MgSO4干燥，过滤后减压除去溶剂，得到产物，收率95％。实施例4
在装有机械搅拌、加料漏斗和氮气进/出口装置的500ml三颈烧瓶中，将3-异丙烯基-α,α-二甲基苄基异氰酸酯(59.11g,0.294mol)溶于甲苯(100ml)中。反应在氮气保护下进行。将溶液加热到40℃，搅拌下加入二丁基锡二月桂酸酯(0.033g)。在加料漏斗中放置环己烷二甲醇单乙烯基醚(50.0g,0.294mol)溶于甲苯(50ml)的溶液，在10分钟内将该溶液加入到异氰酸酯溶液中，得到的混合物在40℃下再反应3小时。冷却到室温之后，该混合物用蒸馏水洗涤三次，分离出的有机层用MgSO4干燥，过滤后减压除去溶剂，得到产物，收率97％。实施例5
在装有机械搅拌、加料漏斗和氮气进/出口装置的三颈烧瓶中，将1摩尔当量的3-异丙烯基-α,α-二甲基苄基异氰酸酯溶于甲苯中。反应在氮气保护下进行，在加料漏斗中放置1摩尔当量的3-胺基-1-丙醇乙烯基醚的甲苯溶液。10分钟内将该溶液加入到异氰酸酯溶液中，得到的混合物在40℃下加热反应3小时。冷却到室温之后，该混合物用蒸馏水洗涤三次。分离出的有机层用MgSO4干燥，过滤后减压除去溶剂，得到产物。实施例6
Figure A0111952700211
1摩尔当量的3-胺基-1-丙醇乙烯基醚和1摩尔当量的三乙胺在室温下混合于干燥的氯乙烯中，加入1摩尔当量的4-乙烯基苄基氯的干燥二氯甲烷溶液。该混合物反应7小时。蒸去溶剂，粗产物用己烷/乙酸乙酯进行柱色谱分离纯化。
实施例7
Figure A0111952700212
1摩尔当量的3-胺基-1-丙醇乙烯基醚和1摩尔当量的三乙胺在室温下混合于干燥的氯乙烯中，加入1摩尔当量的肉桂基氯的干燥二氯甲烷溶液。该混合物反应7小时。蒸去溶剂，粗产物用己烷/乙酸乙酯进行柱色谱分离纯化。实施例8
Figure A0111952700221
在装有机械搅拌和氮气进/出口装置的500ml三颈烧瓶中，将异丁子香酚(20g,0.12mol)，表氯醇(38.8g,0.37mol)和碳酸钾(33.7g,0.244mol)溶于甲乙酮(100ml)中。反应在氮气保护下进行。加热到90℃下反应5小时。冷却到室温之后，过滤除去盐，滤液用10％的Na2SO4洗涤三次。分离出的有机层用MgSO4干燥，过滤后减压除去溶剂，得到产物。
Figure A0111952700222
1摩尔当量的异丁子香酚/表氯醇加成产物，1摩尔当量的1,4-丁二醇乙烯基醚和催化量的Amberlyst A-21离子交换树脂一起在90℃下加热20小时。从该反应混合物中分离除去Amberlyst树脂得到产物。实施例9
其他杂化的给电子体化合物可以通过类似的方法制备。下面的反应列出了其他芳环原料和含乙烯基醚的化合物以及得到的杂化的给电子体化合物。
实施例9-A
Figure A0111952700231
实施例9-B实施例9-C
Figure A0111952700241
实施例9-D实施例9-E
Figure A0111952700251
实施例9-F
Figure A0111952700252
实施例9-G
Figure A0111952700253
实施例9-H
Figure A0111952700261
实施例9-I
Figure A0111952700262
实施例9-J
实施例9-K
实施例9-L实施例9-M
实施例9-N实施例9-O
实施例10
用双马来酰亚胺作为电子受体，将实施例1、2和3的三种杂化的给电子体化合物制成粘合剂组合物。该双马来酰亚胺由胺基封端的聚氧丁烯(Versalink P650,Air Products)和马来酸酐根据US 4 745 197列出的方法，用USP-MD(Witco公司)作为引发剂制备得到。
这些粘合剂组合物用DSC固化(给电子体与电子受体共聚合)。定性地说，这些树脂中每一个的放热峰值看起来都类似，而且从峰值到开始反应的性质也类似。结果列于下表。
 模片固定粘合剂所用杂化的给电子体化合物来源  开始反应温度(℃)   最高温度(℃)  开始反应温度-最高温度之差(℃)   ΔH(J/g)
  实施例1    97.22    112.14     14.92     286.2
  实施例2    92.97    107.15     14.8     254.5
  实施例3    103.04    126.88     23.84     325.8
用相同的三种给电子体化合物制成模片固定粘合剂并检测其模片剪切强度。将这些粘合剂放置于一个铅框架(Pd、Ag或Cu)与一个120×120mil的硅模片之间，并在200℃的电加热板上固化大约60秒。室温下从模片的一端加压并将模片与铅框架组合件加热到240℃直到发生剪切。这些制剂及其检测结果列于下表。
模片固定制剂1
                组分                 质量(g)
双马来酰亚胺(VersalinkP650)(电子受体)                  1.65
实施例1的杂化的给电子体                  0.50
8％的马来酸酐(Ricon 131)(反应稀释剂)                  0.25
引发剂                  0.05
粘合促进剂混合物                  0.05
银片                  5.51
         室温下的模片剪切(Kg)             热(240℃)模片剪切(Kg)
    Pd     Ag     Cu 铅框架     Pd     Ag     Cu
   18.0    12.0    17.0     2.6     1.4     1.3
模片固定制剂2
                 组分                 质量(g)
双马来酰亚胺(VersalinkP650)(电子受体)                  0.68
实施例2的杂化的给电子体                  0.50
 8％的马来酸酐(Ricon 131)(反应稀释剂)                  0.14
引发剂                  0.028
粘合促进剂混合物                  0.028
银片                  4.13
          室温下的模片剪切(Kg)            热(240 ℃)模片剪切(Kg)
    Pd     Ag     Cu  铅框架     Pd     Ag     Cu
   16.0    19.0    16.0     3.2     1.8     0.8
模片固定制剂3
                组分              质量(g)
双马来酰亚胺(VersalinkP650)(电子受体)                2.26
实施例3的杂化的给电子体                0.50
 8％的马来酸酐(Ricon 131)(反应稀释剂)                0.32
引发剂                0.064
粘合促进剂混合物                0.064
银片                9.63
         室温下的模片剪切(Kg)           热(240℃)模片剪切(Kg)
    Pd     Ag     Cu  铅框架     Pd     Ag     Cu
    7.1     7.4     5.6     2.2     1.6     1.4

Claims (9)

1．一种具有如下结构的化合物：
Figure A0111952700021
其中，m和n独立地为1-6；
Ar为环上含有3-10个碳原子的芳环或杂芳环，其中杂原子可以是N、O或S；
R1,R2和R3独立地为氢、如上所述的Ar或一个含有1-12个碳原子的烷基；
R4、R5和R6独立地为氢、甲基或乙基；
G为-OR7、-SR7、-N(R1)(R2)、如上所述的Ar或含有1-12个碳原子的烷基，其中R7为如上所述的Ar或含有1-12个碳原子的烷基，R1和R2如上所述；
Q为含有1-12个碳原子的烷基；
X为：
Figure A0111952700022
-S-或-O-；
和
Z为烷基、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、丁二烯或聚丁二烯，或芳环、多芳环或杂芳环基团。
2．根据权利要求1的化合物，其选自具有如下结构的化合物：
Figure A0111952700041
Figure A0111952700051
和
3．一种具有如下结构的化合物
Figure A0111952700053
其中，m和n独立地为1-6；
Ar为环上含有3-10个碳原子的芳环或杂芳环，其中杂原子可以是N、O或S；
R1、R2独立地为氢、如上所述的Ar或含有1-12个碳原子的烷基；
R4、R5和R6独立地为氢、甲基或乙基；
G为-OR7、-SR7、-N(R1)(R2)、如上所述的Ar或含有1-12个碳原子的烷基，其中R7为如上所述的Ar或含有1-12个碳原子的烷基，R1和R2如上所述；
Q为含有1-12个碳原子的烷基；
X为：
Figure A0111952700061
-S-或-O-；
         和
Z为烷基、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、丁二烯或聚丁二烯、或芳环、多芳环或杂芳环基团。
4．根据权利要求3的具有如下结构的化合物：
5．一种可固化粘合剂组合物，其包含权利要求1-4中任一项的化合物。
6．一种可固化粘合剂组合物，其包含权利要求1-4中任一项的化合物和一种导电或非导电填充剂。
7．一种可固化粘合剂组合物，其包含权利要求1-4中任一项的化合物和至少一种可共聚的电子受体化合物，其选自富马酸酯、马来酸酯、丙烯酸酯和马来酰亚胺，并可任选包含一种导电或非导电填充剂。
8．一种半导体元件，其中的硅芯片用一种包含权利要求1-4中任一的化合物的粘合剂粘合到基体上。
9．一种半导体元件，其中的硅芯片用一种粘合剂粘结到基体上，该粘合剂包含：权利要求1-4中任一项的化合物、至少一种可共聚的电子受体化合物，其选自富马酸酯、马来酸酯、丙烯酸酯和马来酰亚胺基团的电子受体化合物，和可任选包含一种导电或非导电填充剂。
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CA2347901A1 (en) 2001-11-18
JP2002037752A (ja) 2002-02-06
KR100794634B1 (ko) 2008-01-14
DE60135062D1 (de) 2008-09-11
US6307001B1 (en) 2001-10-23
EP1158008A2 (en) 2001-11-28
JP4216490B2 (ja) 2009-01-28
EP1158008A3 (en) 2003-07-02
SG96221A1 (en) 2003-05-23
KR20020002201A (ko) 2002-01-09
CN101200620A (zh) 2008-06-18
HK1042471A1 (zh) 2002-08-16
EP1158008B1 (en) 2008-07-30
TW574335B (en) 2004-02-01

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