CN114144452A - 具有低含量的环状低聚物的聚醚多元醇 - Google Patents
具有低含量的环状低聚物的聚醚多元醇 Download PDFInfo
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Abstract
本发明涉及以低含量的环状副产物为特征的聚醚多元醇，以及用于制备该聚醚多元醇的方法和包含该聚醚多元醇的粘合剂组合物。
Description
技术领域
本发明涉及以低含量的环状副产物为特征的聚醚多元醇，以及用于制备该聚醚多元醇的方法和包含该聚醚多元醇的粘合剂组合物。
背景技术
聚醚多元醇是公知的适合于各种应用的化合物。一种常见的应用是在粘合剂体系、特别是聚氨酯粘合剂的制备中使用聚醚多元醇，其中所述聚醚多元醇与异氰酸酯组分反应以得到所期望的聚氨酯。特别是对于聚醚多元醇在粘合剂体系中的应用，高含量的线性OH封端的聚合物链是理想的。然而，在大多数情况下，聚醚多元醇还含有一定量的环状低聚副产物，这导致粘合剂或热塑性聚氨酯的机械性能下降。因此，理想的是保持环状低聚物的含量尽可能低。
已经做了许多尝试以得到合适的聚醚多元醇，其中所述尝试之一是环醚的聚合。虽然三元环醚和四元环醚由于高的环张力而容易进行聚合反应，但是热力学上稳定的五元环状体系和六元环状体系的聚合仍然具有挑战性。
A.Ishigaki在Die Makromolekulare Chemie 1964,79,第170页中描述了使用BF3·(C2H5)2O作为引发剂的2-取代的四氢呋喃与一些环醚的共聚合反应。发现已知不均聚的2-甲基四氢呋喃(MTHF)与诸如环氧氯丙烷和3,3-双(氯甲基)氧杂环丁烷(BCMO)这样的单体共聚合。该报告特别地强调了2-取代的四氢呋喃的低反应性，发现其仅与卤化的共聚单体进行聚合反应。
然而，发现根据已知方法所制备的聚醚多元醇仍然含有大量的环状副产物，这损害了由该聚醚多元醇得到的任何产品的性能。
鉴于上述情况，本发明的一个目的是提供聚醚多元醇，该聚醚多元醇允许生产产品显示出良好的机械性能。
发明内容
出人意料地发现，具有减少量的环状副产物的聚醚多元醇得到了机械稳定的产品，例如粘合剂和涂料体系。出人意料地发现，如果通过在具有弱配位的且非亲核的阴离子的布朗斯台德酸的存在下含环氧基的化合物与能够进行开环反应的另一化合物的聚合反应来制备相应的聚醚多元醇，那么可以显著地减少不期望的环状副产物的量。
因此，本发明的第一主题是聚醚多元醇，其通过含有至少一个环氧化物部分的化合物A与能够进行开环反应的化合物B的共聚合反应得到，其中化合物A和化合物B彼此不同，并且其中所述共聚合反应在具有弱配位的且非亲核的阴离子的布朗斯台德酸的存在下进行。
出人意料地发现本发明的聚醚多元醇可以以良好的产率并且以适合于粘合剂应用的链长获得。
具体实施方式
优选避免存在环状副产物(特别是环状低聚物)，这是由于其对最终产品(例如粘合剂、密封剂(sealing)或涂料)的机械性能具有负面影响。出人意料地发现，在制备本发明的聚醚多元醇期间几乎没有观测到环状副产物的形成。作为不期望的环状副产物的存在的量度，使用以凝胶渗透色谱法(GPC)测定的本发明的聚醚多元醇的数均分子量Mn与以端基滴定法测定的本发明的聚醚多元醇的数均分子量Mn的差。以GPC测定的数均分子量与由端基滴定法测定的数均分子量之间的显著的差被解释为：由于以端基滴定法的测定无法记录环状副产物的存在，从而导致所提及的分子量差。因此，优选这样的本发明的实施方案，其中，基于以GPC测定的本发明的聚醚多元醇的数均分子量Mn，以GPC测定的本发明的聚醚多元醇的数均分子量Mn与以端基滴定法测定的本发明的聚醚多元醇的数均分子量Mn之间的差小于50％，优选地小于40％，特别地小于20％。
在优选的实施方案中，化合物A是低分子量环氧化合物，特别是具有40至200g/mol、优选地50至160g/mol的分子量的环氧化合物。在特别优选的实施方案中，化合物A选自环氧乙烷(EO)、环氧丙烷(PO)和以下所示的化合物。
在特别优选的实施方案中，化合物A是环氧丙烷(PO)。
出人意料地发现，通常不进行共聚合反应的环状体系可用作本发明的聚醚多元醇中的共聚单体。
在优选的实施方案中，化合物B选自五元杂环和六元杂环。在特别优选的实施方案中，化合物B选自任选地被取代的五元环醚和六元环醚。在另外优选的实施方案中，化合物B选自取代的五元环醚和取代的六元环醚，其中一个或多个取代基独立地选自甲基、乙基、丙基、异丙基、丁基、异丁基和叔丁基。在特别优选的实施方案中，化合物B是2-甲基四氢呋喃。
本发明中所使用的具有弱配位的且非亲核的阴离子的布朗斯台德酸优选地选自：H3PW12O40*xH2O，其中10≤x≤44，优选地15≤x≤30；H3PMo12O40；HBF4；CF3COOH；CF3SO3H；三氟甲磺酰亚氨酸(triflimidic acid)和HSbF6。
鉴于资源有限的意识，可持续性和用由可再生资源得到的化合物(所谓的生物基化合物)对常用的石油基化合物的替代已成为关注的焦点。本发明的聚醚多元醇具有以下优点：该共聚合反应中所使用的单体可以由可再生资源例如植物得到，从而有助于资源友好型化学化合物的不断增长的部分。因此，在本发明的优选实施方案中，化合物A和/或化合物B由可再生资源得到。
进一步出人意料地发现，可以通过选择合适的单体比率来单独地设计聚醚多元醇的聚合物主链。以此方式，可以得到其中链中的单体开环单元具有完美交替的聚醚多元醇，其中烯烃封端的链仅以低于定量限的量形成。在优选的实施方案中，化合物A与化合物B的初始单体重量比为1:20至1:1.3，优选地1:5至1:1.5。
可根据具体应用调整本发明的聚醚多元醇的分子量。然而，特别是考虑到在粘合剂中的应用，如果分子量不超过某个限度则是有利的。因此，在本发明的优选实施方案中，聚醚多元醇具有以GPC测定的500至5000g/mol、优选地700至3000g/mol的数均分子量Mn。
具有窄的分子量分布也是理想的。因此，在优选的实施方案中，本发明的聚醚多元醇具有根据GPC所测定的1.1至5.0、优选地1.1至2.5的多分散指数(PDI)。在本发明中，PDI是指聚醚多元醇的重均分子量与数均分子量的比率(Mw/Mn)。
在优选的实施方案中，本发明的聚醚多元醇具有根据DIN 53240所测定的10至200mg KOH/g、优选地50至150mg KOH/g的羟值(OH值)。
本发明的另一主题是用于制备根据本发明的聚醚多元醇的方法。该方法包括通过在具有弱配位的且非亲核的阴离子的布朗斯台德酸的存在下提供装有化合物B的反应容器并且随后在时间段tA内添加化合物A而进行的化合物A与化合物B的聚合反应。出人意料地发现，如果在某时间段内逐滴加入化合物A，那么可以进一步减小以GPC测定的分子量与以端基滴定法测定的分子量之间的差。时间段tA根据待加入的化合物A的量的不同而不同，并且可以从几分钟到几小时不等。
出人意料地发现，具有显示出亲核行为的官能团的化合物——例如水、醇、胺、硫醇等——在聚合反应期间的存在也抑制了环状低聚物的形成。这些化合物可被称为引发剂。因此，优选在一种或多种引发剂的存在下进行聚合反应。然而，观测到，如果存在太多引发剂，那么聚醚多元醇的分子量降低。因此，在优选的实施方案中，相对于化合物A，引发剂的量为1至15摩尔％，优选地为2至10摩尔％。
具有弱配位的且非亲核的阴离子的布朗斯台德酸优选以0.005至10摩尔％、优选地0.01至1摩尔％的量用于反应中。具有弱配位的且非亲核的阴离子的布朗斯台德酸优选地选自：H3PW12O40*xH2O，其中10≤x≤44，优选地15≤x≤30；H3PMo12O40；HBF4；CF3COOH；CF3SO3H；三氟甲磺酰亚氨酸和HSbF6。
可以将本发明的聚醚多元醇用许多不同的反应搭档(partner)进一步官能化，从而产生丙烯酸酯、异氰酸酯、环氧化物、乙烯基醚、硫醇、胺封端等。因此，它特别适合应用于涂料、粘合剂、密封剂和弹性体(CASE)领域中，特别是粘合剂领域中。因此，本发明的另一主题是包含本发明的聚醚多元醇的粘合剂组合物。在优选的实施方案中，粘合剂组合物是聚氨酯粘合剂组合物或基于硅烷的粘合剂。
此外，本发明的一个主题是本发明的聚醚多元醇用于制备粘合剂的用途，其中所述粘合剂优选为聚氨酯粘合剂和基于硅烷的体系。
将参考以下实施例更详细地解释本发明，这些实施例决不应被理解为限制本发明的范围和精神。
实施例：
实施例A(参比)
将2-甲基THF装入反应容器并且加入BF3·2H2O。将环氧丙烷逐滴加入到反应混合物中，并且将所产生的内容物搅拌。然后，加入氢氧化钠的水溶液。将所产生的水相用有机溶剂萃取。将所得到的有机相洗涤并干燥。去除有机溶剂后，得到聚醚多元醇。
实施例B(根据本发明)
将2-甲基THF装入反应容器并且加入磷钨酸(H3PW12O40*24H2O)，接着加入醇。将环氧丙烷逐滴加入到反应混合物中，并且将所产生的内容物搅拌。然后，加入碳酸钠的水溶液。在减压下蒸发任何过量的2-甲基THF。将所得到的聚醚多元醇溶解在有机溶剂中并且经过二氧化硅滤料(pad)过滤。去除滤液中的挥发物后，得到本发明的聚醚多元醇。
经由GPC-APC和以端基滴定的方式来测定所得到的聚醚多元醇的分子量。结果总结在表1中。
表1
可从沃特世公司(美国)获得的带有RI和PDA探测器的Acquity超高效聚合物色谱系统上进行样品的GPC分析。使用流速为0.5ml/分钟的THF作为洗脱液，并且采用266道尔顿至1210000道尔顿的聚苯乙烯标准品(PSS)测定分子量。使用五阶校准曲线(“Streifenmethode”)进行平均分子量数值的评估。
通过用吡啶溶剂中的乙酸酐对样品的游离羟基的乙酰化作用，根据如DIN 53240中所描述的标准步骤进行端基滴定。在反应完成后，加入水，剩余的未反应的乙酸酐转化为乙酸并且通过用氢氧化钾滴定来测量。
本发明的聚醚多元醇与二异氰酸酯(4,4’-亚甲基二苯基二异氰酸酯)以2.2(NCO/OH)的比例反应以得到聚氨酯粘合剂。将膜流延(13cm x 5cm，厚2mm)并在23℃和50％相对湿度下储存7天。分别使用PPG 2000和pTHF作为可比较的聚醚多元醇，应用相同的步骤。然后，通过应力-应变测试，对所得到的膜进行表征。结果汇总于表2中。出人意料地发现，在50％的伸长率下，基于本发明的聚醚多元醇的粘合剂达到了比常用的PPG更高的拉伸强度(2.18n/mm2相比于1.54n/mm2)。
表2
使用来自Zwick-Roell的配有500N探头的Z010测试系统进行应力-应变测试。根据DIN 535049，样品伸长的速度为50mm/分钟。
Claims (13)
1.聚醚多元醇，其由含有至少一个环氧化物部分的化合物A与能够进行开环反应的化合物B的共聚合反应得到，其中化合物A和化合物B彼此不同，并且其中在具有弱配位的且非亲核的阴离子的布朗斯台德酸的存在下进行所述共聚合反应。
2.根据权利要求1的聚醚多元醇，其特征在于化合物B选自任选地被取代的五元杂环和六元杂环，特别是五元环醚和六元环醚。
3.根据前述权利要求中任一项的聚醚多元醇，其特征在于化合物A具有40至200g/mol、优选地50至160g/mol的分子量。
4.根据前述权利要求中任一项的聚醚多元醇，其特征在于化合物A和/或化合物B由可再生资源得到。
5.根据前述权利要求中任一项的聚醚多元醇，其特征在于，其中，基于以GPC测定的本发明的聚醚多元醇的数均分子量Mn，以GPC测定的本发明的聚醚多元醇的数均分子量Mn与以端基滴定法测定的所述聚醚多元醇的数均分子量Mn之间的差小于50％，优选地小于40％，特别是小于20％。
6.根据前述权利要求中任一项的聚醚多元醇，其特征在于具有弱配位的且非亲核的阴离子的布朗斯台德酸选自：H3PW12O40*xH2O，其中10≤x≤44，优选地15≤x≤30；H3PMo12O40；HBF4；CF3COOH；CF3SO3H；三氟甲磺酰亚氨酸和HSbF6。
7.根据前述权利要求中任一项的聚醚多元醇，其特征在于所述聚醚多元醇具有以GPC测定的500至5000g/mol、优选地700至3000g/mol的数均分子量Mn。
8.根据前述权利要求中任一项的聚醚多元醇，其特征在于所述聚醚多元醇具有根据DIN 53240测定的10至200mg KOH/g、优选地50至150mg KOH/g的羟值(OH值)。
9.用于制备根据权利要求1至8中任一项的聚醚多元醇的方法，所述方法包括：通过在具有弱配位的且非亲核的阴离子的布朗斯台德酸的存在下提供装有化合物B的反应容器并且随后在时间段tA内加入化合物A而进行的化合物A与化合物B的聚合反应。
10.根据权利要求9的方法，其特征在于在亲核引发剂的存在下进行所述聚合反应。
11.根据权利要求1的方法，其特征在于，相对于化合物A，所述引发剂的量为1至15摩尔％，优选地2至10摩尔％。
12.粘合剂组合物，所述粘合剂组合物包含根据权利要求1至8中任一项的聚醚多元醇。
13.根据权利要求1至8中任一项的聚醚多元醇用于制备粘合剂的用途，其中所述粘合剂优选地为聚氨酯粘合剂和基于硅烷的粘合剂。
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