CN110892033B - 高温环氧粘合剂配制品 - Google Patents

高温环氧粘合剂配制品 Download PDF

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CN110892033B
CN110892033B CN201880040279.2A CN201880040279A CN110892033B CN 110892033 B CN110892033 B CN 110892033B CN 201880040279 A CN201880040279 A CN 201880040279A CN 110892033 B CN110892033 B CN 110892033B
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A·卢茨
D·施耐德
B·A·哈格
I·梅德
M·阿希旺登
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Abstract

本发明是可用作高温应用的粘合剂的环氧树脂体系。所述体系是30‑70重量％的量的二缩水甘油醚双酚环氧树脂、与1‑10重量％的环氧酚醛清漆树脂、10‑30重量％的聚氨酯增韧剂(其优选具有被封闭的末端异氰酸酯官能团)、1‑8重量％的硬化剂、0.1‑重量％的固化促进剂(优选潜伏的脲固化促进剂)的组合，提供了所希望的机械强度和弹性模量的平衡。所述环氧酚醛清漆树脂的特征在于以下特征中的至少一个：(i)具有根据ASTM D‑445在25℃下小于3000mPa·s的粘度，(ii)多于2但少于3.7的环氧基团平均数/分子，以及(iii)小于750g/mol的分子量。

Description

高温环氧粘合剂配制品
技术领域
本发明总体上涉及可用于粘合预期经受热应力的各种表面，包括特别用于粘合运输车辆中的部件的环氧配制品。
背景技术
在运输车辆，尤其包括汽车和卡车的制造中，设计中使用了不同的材料以减轻车身重量。除钢之外，还使用了轻质材料，如铝或碳纤维增强复合材料。此外，更常用的是粘合剂，而不仅仅是焊接部件。由于车身在制造过程中被加热(例如，在温度可能在160至210C的范围内的用于腐蚀保护的电泳涂层(e-coat)烘箱中)，并且在使用中还可能经受大的温度范围变化，因此不同材料的不同热膨胀率可能在材料之间的连接处造成明显的机械应力。
现今的结构增韧的环氧基车身修理厂粘合剂不能完全胜任抵抗由不同材料制成的部件的不同线性热膨胀系数(CLTE)引起的热应力。它们在较高的温度下失去较高的强度值，并且在升高的温度下内聚失效模式。具有所希望的较低弹性模量的粘合剂在高温下不具有所需的高机械强度。试图增加在高温下的机械强度通常对弹性模量产生不希望的影响。因此，存在对于一种结构环氧粘合剂配制品的需要，所述配制品既实现相对较低的弹性模量(例如600-1200MPa)，同时保持在升高的温度下的机械强度。
发明内容
诸位发明人已经发现了一种配制品，其提供所希望的在高温下的机械强度和所希望的弹性模量的平衡。
具体地，诸位发明人已经发现了一种环氧树脂体系，其是30-70重量％的量的二缩水甘油醚双酚环氧树脂、与1-10重量％的环氧酚醛清漆树脂、10-30重量％的聚氨酯增韧剂(其优选具有被封闭的末端异氰酸酯官能团)、1-8重量％的硬化剂、0.1-重量％的固化促进剂(优选潜伏的脲固化促进剂)的组合，提供了所希望的机械强度和弹性模量的平衡。所述环氧酚醛清漆树脂的特征在于以下特征中的至少一个：(i)根据ASTM D-445在25℃下小于3000mPa·s的粘度，(ii)多于2但少于3.7的环氧基团平均数/分子，以及(iii)小于750g/mol的分子量。
因此，本发明是上述环氧树脂体系和上述成分的固化反应产物。根据一个优选的实施例，所述体系包含上述成分的单一组分，其中所述聚氨酯增韧剂是封闭的使得其对环氧是稳定的，并且其中所述固化促进剂是潜伏的并且固化通过加热开始，优选地加热至高于150℃并且优选160℃至210℃的温度。根据第二实施例，本发明还是一种体系，其包含第一反应组分和第二反应组分，所述第一反应组分是包括双酚A的二缩水甘油醚和环氧酚醛清漆树脂的环氧树脂组分，所述第二反应组分包含硬化剂和固化促进剂。
具体实施方式
可用于本发明的二缩水甘油醚双酚环氧树脂可以是呈液体或固体形式。可以使用此类树脂的共混物。优选地，此组分是双酚A、双酚F、双酚K、或双酚M的二缩水甘油醚。最优选地，它是双酚A的二缩水甘油醚。
如果使用共混物，则其可以是以下项的混合物：至少一种多元酚(优选双酚-A或双酚-F)的二缩水甘油醚，其具有170至299、尤其170至225的环氧当量重量；和至少一种第二多元酚(再次优选双酚-A或双酚-F)的二缩水甘油醚，这一种二缩水甘油醚具有至少300、优选310至600的环氧当量重量。两种类型的树脂的比例优选地使得两种树脂的混合物具有225至400的平均环氧当量重量。混合物可任选地还含有最高达20％、优选最高达10％的一种或多种其他环氧树脂。
合适的二缩水甘油醚包括双酚A二缩水甘油醚树脂，如由奥林公司(OlinCorporation)以名称D.E.R.330、D.E.R.331、D.E.R.332、D.E.R.383、D.E.R.661和D.E.R.662树脂销售的。此类树脂的示例混合物包括固体和液体树脂的混合物，如来自奥林公司的D.E.R.671和D.E.R.331，其量为40重量百分比的固体树脂和60重量百分比的液体树脂以及。
基于体系的组分的总重量，所使用的双酚A二缩水甘油醚树脂的量为至少30重量百分比、并且更优选至少40重量百分比但不超过70重量百分比、优选不超过60重量百分比。优选地，双酚A二缩水甘油醚(DGEBA)树脂是固体和液体环氧树脂的混合物，其中固体DGEBA基于体系的组分的总重量占至少1重量百分比、更优选至少2重量百分比但优选不超过10重量百分比、更优选不超过6重量百分比，并且液体DGEBA基于体系的组分的总重量占至少30重量百分比、并且更优选至少40重量百分比但不超过60重量百分比。
可用于本发明的环氧酚醛清漆树脂的特征在于相对较低的粘度和/或较低的分子量。优选的环氧酚醛清漆树脂具有以下结构
Figure GDA0003251722970000031
其中n是重复单元的平均数并且n小于1.7。可替代地或另外地，优选的环氧酚醛清漆树脂具有根据ASTM D-445在25℃下小于3000mPa·s、优选小于2500mPa·s、并且最优选不大于2000mPa·s的粘度。可替代地或另外地，优选的环氧酚醛清漆树脂具有小于700g/mol、优选小于650g/mol、更优选还小于600g/mol、还更优选小于550g/mol并且最优选小于500g/mol的分子量，但具有至少250g/mol、优选至少300g/mol的分子量。合适的环氧酚醛清漆树脂的实例包括D.E.N.354、D.E.N.431和D.E.N.438，全部来自奥林公司。
本发明的体系包含聚氨酯增韧剂。优选的增韧剂通过使用多酚、优选ODBA(o,o’-二烯丙基双酚A)，使用PTMEG(聚四亚甲基二醇)和PBD(聚丁二烯二醇)的组合扩链，并通过使用单酚封端。实例F没有任何PBD并使用多酚作为封端基团。优选地，特别是对于通过热活化的单组分体系，增韧剂具有封闭的官能团以防止过早反应。优选使用单酚进行封闭。聚氨酯增韧剂优选是聚合的聚四亚甲基醚二醇(PTMEG)，其中末端已用异氰酸酯和酚类化合物改性以在获得固化条件时允许所述末端与环氧树脂反应。在单组分可热固化的粘合剂中，异氰酸酯预聚物需要受到当暴露于热(固化条件)时从PU增韧剂解离的封端基团的保护。优选地，增韧剂包括具有通过异氰酸酯残基连接的软单元(例如来自PTMEG)和橡胶状单元(例如来自聚丁二烯醇)的二醇残基。聚氨酯增韧剂还可以使用多酚，如o,o’二烯丙基双酚a(OBDA)扩链。封端基团优选为单酚基团，如腰果酚(来自腰果壳油“CNSL”)或烯丙基苯酚。优选的聚氨酯增韧剂是PTMEG(10-95重量％、优选20-90重量％、更优选45-85重量％)与聚丁二烯-二醇(2-55重量％、优选5-40重量％、更优选10-30重量％)、二异氰酸酯如1,6-六亚甲基二异氰酸酯(2-40重量％、优选5-30重量％、更优选10-20重量％)和CNSL(0.1-50重量％、优选0.1-20重量％、最优选0.1-15重量％)的反应产物，全部基于增韧剂的重量。合适的封闭的聚氨酯增韧剂的实例是在WO/2017/044402和U.S.8,404,787实例2中传授的那些，其中每一个通过引用并入本文。
基于环氧体系的总重量，所使用的增韧剂的量为优选至少10重量百分比、更优选至少15重量百分比但优选不超过30重量百分比、更优选不超过25重量百分比。
可用于本发明的硬化剂可以是本领域中已知有用的任何的双氰胺、咪唑、胺、酰胺、多元酚和多元酸酐，但优选基于胺或酰胺的硬化剂。这些硬化剂优选地是潜伏的，使得它们在环境条件下不会引起硬化，而是必须被加热或暴露于比正常光照辐射暴露更多的辐射以引起硬化。合适的硬化剂包括双氰胺，如来自空气产品公司(Air Products)的AmicureTMCG 1200或来自阿兹肯化工公司(Alzchem)的Dyhard 100SF。基于体系的总重量，硬化剂的量为优选至少1重量百分比、更优选至少2重量百分比但优选不超过8重量百分比、更优选不超过6重量百分比。
可用于本发明的固化促进剂是芳族脲基固化促进剂。这些可以通过使亚甲基二苯基二异氰酸酯(MDI)与二甲胺反应来形成。此类芳族脲基固化促进剂的可商购实例包括来自埃默拉尔德公司(Emerald)的OmnicureTM52M和405M。基于苯基-二-甲基的脲是优选的。基于体系的总重量，固化促进剂的量为优选至少0.1、更优选至少0.3重量百分比但优选不超过3、更优选不超过1重量百分比。
除上述以外，成分还包括软化剂。合适的软化剂包括羧基封端的丙烯腈丁二烯(CTBN)环氧加合物或多胺环氧加合物。此类产品的实例包括来自希纶赛勒赫公司(S&SSchill&Seilacher)的Strutkol 3604或来自奥林公司的D.E.R.如D.E.R.330与来自亨斯迈公司(Huntsman Corporation)的聚醚胺如Jeffamine D-2000的组合。基于体系中的组分的总重量，软化剂优选以至少5重量百分比、更优选至少8重量百分比但不超过20重量百分比并且更优选不超过15重量百分比的量存在。
当需要时，也可以使用填充剂。合适的填充剂包括碳酸钙、氧化钙、滑石、硅灰石、玻璃珠等。填充剂的量为优选小于30重量百分比、更优选小于20重量百分比。当使用时，填充剂的量为优选大于5重量百分比。
成分还可任选地包括着色剂、活性稀释剂、粘合促进剂和/或润湿剂。合适的着色剂的实例是来自亨斯迈公司Araldite DY系列的环氧着色剂。活性稀释剂的实例包括己烷、丁基二缩水甘油基及其。粘合促进剂可以是环氧硅烷，例如像Sylquest A 187。
可以通过在混合器如行星式混合器中组合所有的流体和糊剂和固体来配制单组分体系。对于双组分体系，可以将包括双酚A二缩水甘油醚和环氧酚醛清漆树脂的环氧树脂组分组合并混合，并且可以将包括硬化剂和固化促进剂的第二组分组合并混合。然后，当需要使用粘合剂时，将两种组分原位组合。
然后将体系加热到至少150℃、优选至少160℃、但优选不超过210℃的温度以进行固化。
可以根据任何已知方法使用粘合剂体系。例如，混合物可以填充在筒中。为了试验目的，粘合剂通常通过使用筒枪从筒中通过喷嘴手动施用。如果粘合剂配制品的粘度那么高，则在室温下不容易进行手动施用，可以将筒优先加热到40℃至60℃，以获得更好的适用性。
本发明的体系显示出在升高的温度下高机械强度，同时具有相对较低的弹性模量的良好平衡。具体地，当根据DIN EN ISO 527-1测试时，这些体系示出大于600但小于1200MPa的弹性模量。哑铃试样5a。它们还具有高搭接剪切强度，如由在130℃下60CF或更高和在140℃下40CF或更高的内聚失效证明的。
实例
通过以下非限制性实例进一步说明本发明。
表1：粘合剂成分的原料清单
Figure GDA0003251722970000061
*将DER 330 54.8重量份和Jeffamin D-2000 45.2重量份添加到实验室反应器中并加热到100℃。在真空下在100℃下将混合物混合60分钟。然后将混合物冷却至60℃并敲击它。
表2：增韧剂A成分的原料清单
Figure GDA0003251722970000071
通用增韧剂A(优选增韧剂)合成：
1.第一反应步骤：将x wt％的组分[a]和[b]添加到实验室反应器中并加热至120℃。在真空下在120℃下将混合物混合30分钟。然后将混合物冷却至60℃。如果温度达到60℃，则添加x wt％的组分[c]并将其混合2分钟。然后添加x wt％的组分[d]，并使混合物在氮气下在85℃(浴温)下反应45分钟。
2.第二反应步骤：添加x wt％的组分[e]，并将混合物
在氮气下在95℃[浴温]下搅拌60分钟。
3.第三反应步骤：添加x wt％的组分[f]，并将混合物在氮气下搅拌120分钟。最后，将混合物在真空下搅拌20分钟。
表3示出了制成的不同配制品。这些配制品是按照通用程序制造的：将所有流体、糊剂和着色剂在罐中组合并在50℃下混合五分钟，然后在真空下再混合30分钟。刮下，添加气相二氧化硅，将温度设定为35℃，混合三分钟，并且然后在真空下再混合20分钟。添加所有其他颜料，在真空下混合三分钟，并且然后在刮下后在真空下再混合十五分钟。
表3：
Figure GDA0003251722970000072
Figure GDA0003251722970000081
根据以下程序测试配制品：
流变学
-旋转粘度/屈服应力：Bohlin CS-50流变仪，C/P 20，上/下0.1-20s/1；根据卡森模式(Casson model)评估
DSC：梅特勒托利多(Mettler Toledo)25℃-250℃，10℃/min斜升；第二轮测量的TG
机械试验
所用的钢：热浸镀锌钢：420LAD+Z100MB，厚度1.2mm和电解镀锌钢HC 340LAD+ZE50-50厚度1.0mm，如由奥地利钢铁联合公司(Voest Alpine)提供。
-按照DIN EN 1465的搭接剪切强度：10x 25mm粘合区域，0.2mm粘合剂层厚度。LS基底＝H420 Z100 LAD 1.2mm//H340 ZE 50/50 1.0mm组合，由奥地利钢铁联合公司提供。试验速度10mm/min。
-搭接剪切强度在23℃、130℃和140℃下测试
-按照ISO 11343的冲击剥离强度：20x 30mm粘合区域，0.3mm粘合剂层厚度。IP基底＝H420 Z100 LAD 1.0mm，由奥地利钢铁联合公司提供。试验速度2m/s。
-模量按照DIN EN ISO 527-1测试。哑铃试样5a。
表4示出了试验结果：
Figure GDA0003251722970000101

Claims (13)

1. 一种粘合剂环氧树脂体系，其包含
a.30-70重量%的一种或多种二缩水甘油醚双酚A树脂
b.1-10重量%的环氧酚醛清漆树脂，其中所述环氧酚醛清漆树脂的特征在于以下特征中的至少一个：(i) 具有根据ASTM D-445在25°C下小于3000 mPa·s的粘度，(ii) 多于2但少于3.7的环氧基团平均数/分子，以及 (iii) 小于750 g/mol的分子量
c.10-30重量%的聚氨酯增韧剂，前提是如果所述体系是单组分体系，则所述聚氨酯增韧剂用单官能封端剂封闭，
d.5-20重量%的软化剂
e.1-8重量%的硬化剂，以及
f.0.1-3重量%的芳族脲基固化促进剂，
其中所述重量百分比是基于所述体系的总重量。
2.如权利要求1所述的粘合剂环氧树脂体系，其中，所述体系是单组分体系，并且所述固化促进剂是潜伏的固化促进剂。
3.如权利要求1或2所述的粘合剂环氧树脂体系，其中，所述一种或多种二缩水甘油醚双酚A树脂包含所述体系的30-60重量%的量的液体环氧树脂组分和所述体系的1至10重量%的量的固体环氧树脂组分。
4. 如权利要求1或2所述的粘合剂环氧树脂体系，其进一步包含5至30重量%的量的填充剂。
5.如权利要求1或2所述的粘合剂环氧树脂体系，其中，所述环氧酚醛清漆树脂具有下式
Figure DEST_PATH_IMAGE001
其中，n是重复单元的平均数，并且n小于1.7。
6.如权利要求1或2所述的粘合剂环氧树脂体系，其中，所述聚氨酯增韧剂是由聚四亚烷基醚二醇与聚二烯二醇和二异氰酸酯的反应产物形成的。
7.如权利要求6所述的粘合剂环氧树脂体系，其中，所述增韧剂通过与多酚扩链剂反应扩链。
8.如权利要求7所述的粘合剂环氧树脂体系，其中，所述扩链剂是o,o’-二烯丙基双酚A。
9.如权利要求1或2所述的粘合剂环氧树脂体系，其中，所述软化剂是羧基封端的丙烯腈丁二烯环氧加合物或多胺环氧加合物。
10.如权利要求1或2所述的粘合剂环氧树脂体系，其中，所述硬化剂是双氰胺。
11.如权利要求1或2所述的粘合剂环氧树脂体系，其中，所述环氧酚醛清漆树脂具有根据ASTM D-445在25°C下不大于2000 mPa·s的粘度。
12.如权利要求1或2所述的粘合剂环氧树脂体系，其中，所述环氧酚醛清漆树脂具有至少250 g/mol的分子量。
13.如权利要求1所述的粘合剂环氧树脂体系，其为两组分体系，其中，第一组分包括所述一种或多种二缩水甘油醚双酚A树脂和所述环氧酚醛清漆树脂，并且第二组分包括所述聚氨酯增韧剂、所述硬化剂和所述固化促进剂。
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