CN1072687C - 固体双金属氰化物催化剂及其制法和环氧化物聚合方法 - Google Patents
固体双金属氰化物催化剂及其制法和环氧化物聚合方法 Download PDFInfo
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Abstract
本发明公开了高活性双金属氰化物(DMC)催化剂。该催化剂包含DMC配合物和有机配位剂,以及约5-80wt%(基于催化剂量)数均分子量大于约500的聚醚。还公开了制备该催化剂的方法。该催化剂易于制备,具有较优的活性,并且如有需要可以很容易地从聚合产物中分离出来。
Description
本发明涉及用于环氧化物聚合的双金属氰化物(DMC)配合物催化剂。特别是,本发明的DMC催化剂易于制备,具有较优活性,并且如果需要易于从聚合产物中除去。
双金属氰化物(DMC)配合物是已知用于环氧化物聚合的催化剂。这种活性催化剂产生的聚醚多元醇与用碱性(KOH)催化剂制备的类似多元醇比较具有较低的不饱和性。该催化剂可用于制备许多聚合物产品,包括聚醚、聚酯、和聚醚酯多元醇。该多元醇可用于聚氨酯涂料、高弹体、密封胶、泡沫和粘合剂。
DMC催化剂通常是通过金属盐和金属氰化物盐水溶液反应以生成DMC化合物沉淀而制成的。一种低分子量配位剂,有代表性的是醚或醇,被包括在该催化剂的制备过程中。对于催化剂活性起促进作用来说配位剂是必须的。
在一种常用的制备方法中,使氯化锌(过量)和六氰合高钴酸钾水溶液混合在一起,再往所得的浆料中加入二甲氧基乙烷(glyme:甘醇二甲醚)。过滤后用含水的甘醇二甲醚洗涤催化剂,获得的活性催化剂具有通式:
Zn3〔CO(CN)6〕2·xZnCl2·yH2O·zGlyme另外一些已知的配位剂包括醇类、酮类、酯类、酰胺类、脲类等(例如参见US专利3,427,256、3,427,334、3,278,459和日本专利申请公开号4-145123、3-281529和3-149222)。用甘醇二甲醚制成的催化剂已被广泛地使用。所用配位剂通常是水溶性的、且分子量低于500。例如参见US专利4,477,589(3栏)、US专利3,829,505(12栏)和US专利5,158,922(6栏)。
尽管低分子量的聚醚如甘醇二甲醚、二甘醇二甲醚、三甘醇二甲醚和乙二醇一甲基醚都可以作为配位剂而用于DMC催化剂中,但没人教导采用含5-80wt%分子量大于500的聚醚的固体催化剂。US专利4,477,589描述了一种催化剂的制备方法,其中,DMC催化剂在水中的悬浮液与高比例的300分子量的丙氧基化甘油混合。解吸出这种混合物中的挥发性物质(水、甘醇二甲醚),留下DMC催化剂在丙氧基化甘油中的3.7wt%悬浮液。该催化剂/丙氧基化甘油悬浮液可用于制造高分子量的聚醚多元醇。
通常双金属氰化物催化剂用于环氧化物聚合时具有高活性,该活性经常高于常规碱性催化剂(如KOH)。但由于DMC催化剂相当贵,所以希望具有改进活性的催化剂,使所用的催化剂含量降低。
不管是用KOH还是DMC催化剂去制备聚醚多元醇,但都必须有分离催化剂的步骤。当使用KOH制取多元醇时,粗产品一般需用吸附剂如硅酸镁进行处理,水洗,或离子交换以便除去多元醇中残留的钾离子。从多元醇中除去双金属氰化物催化剂经常是比较麻烦的,人们已研究出许多适于这些催化剂的用于分离催化剂的方法,其中大多涉及一些化学处理。这些方法中有些被描述于US专利4,355,188、4,877,906和5,248,833中。优选的DMC催化剂通过普通的过滤应当很容易从多元醇产物中分离出来而且不需要化学处理。
任何一种催化剂分离方法都是昂贵的。这些工艺步骤费时,劳动强度大,并且需要处理材料。使用价格经常很高。多元醇处理会产生废物:水洗时产生的废水,吸附剂滤饼,废离子交换树脂。
理想的催化剂应产生低饱和的聚醚多元醇并且其活性应足以能使其在很低的浓度下使用,优选的浓度应低到足以能克服任何需要从多元醇中除去催化剂。对于许多成品使用的用途来说,能消除催化剂分离步骤的环氧聚合催化剂,对聚醚多元醇制造商来说无疑是有价值的。
本发明是一种适用于环氧化物聚合的固体双金属氰化物(DMG)催化剂。该催化剂含有DMC化合物、有机配位剂、和约为5-80重量%(基于催化剂量)、数均分子量大于约500的聚醚。本发明催化剂与在没有聚醚情况下制备的类似催化剂相比具有较高的环氧化物聚合活性。所述催化剂特别适用于制备具有特别低的不饱和性的聚醚多元醇。
本发明包括制备适用于环氧化物聚合的双金属氰化物(DMC)催化剂的方法。该方法包括在有数均分子量大于约500的聚醚存在的情况下制备固体DMC催化剂,其中固体DMC催化剂含有约5-80wt%聚醚。
本发明人意外地发现了含有约5-8wt%(按催化剂量)数均分子量大于约500的聚醚的固体DMC催化剂易于制备,有较优的活性,而且如果需要很容易与聚合产物分离。事实上,该催化剂的活性已高到足够使其能在很低的浓度下使用,以致对于许多产品使用用途来说能有效免去分离催化剂的要求。
图1表示在100ppm的本发明催化剂之一存在下,聚合反应过程中环氧丙烷消耗量与时间的关系曲线。催化剂的活性(在本申请中通常描述为每克钴每分钟所转化的环氧丙烷的千克数)是根据曲线最陡点的曲线斜率确定的。
用于本发明的双金属氰化物(DMC)化合物是水溶性金属盐和水溶性金属氰化物盐的反应产物。水溶性金属盐优选具有通式为M(Ⅹ)n,其中M选自由Zn(Ⅱ)、Fe(Ⅱ)、Ni(Ⅱ)、Mn(Ⅱ)、Co(Ⅱ)、Sn(Ⅱ)、Pb(Ⅱ)、Fe(Ⅲ)、Mo(Ⅳ)、Mo(Ⅵ)、Al(Ⅲ)、V(Ⅴ)、V(Ⅳ)、Sr(Ⅱ)、W(Ⅳ)、W(Ⅵ)、Cu(Ⅱ)和Cr(Ⅲ)组成的组中。最好M选自由Zn(Ⅱ)、Fe(Ⅱ)、Co(Ⅱ)和Ni(Ⅱ)组成的组中。在该通式中,最好X是选自由卤化物、氢氧化物、硫酸盐、碳酸盐、氰化物、草酸盐、硫氰酸盐、异氰酸盐、异硫氰酸盐、羧酸盐和硝酸盐组成的组中的阴离子。n值从1到3并符合M的价态。合适的金属盐实例包括但不限于氯化锌、溴化锌、乙酸锌、丙酮基丙酮酸锌、苯甲酸锌、硝酸锌、硫酸亚铁(Ⅱ)、溴化亚铁(Ⅱ)、氯化钴(Ⅱ)、硫氰酸钴(Ⅱ)、甲酸镍(Ⅱ)、硝酸镍(Ⅱ)等及其混合物。
用于制造双金属氰化物化合物的水溶液性金属氰化物盐最好具有通式(Y)aM’(CN)b(A)c,其中M’选自由Fe(Ⅱ)、Fe(Ⅲ)、Co(Ⅱ)、Co(Ⅲ)、Cr(Ⅱ)、Cr(Ⅲ)、Mn(Ⅱ)、Mn(Ⅲ)、Ir(Ⅲ)、Ni(Ⅱ)、Rh(Ⅲ)、Ru(Ⅱ)、V(Ⅳ)、和V(Ⅴ)组成的组。最好M’选自由Co(Ⅱ)、Co(Ⅲ)、Fe(Ⅱ)、Fe(Ⅲ)、Cr(Ⅲ)、Ir(Ⅲ)和Ni(Ⅱ)组成的组。该水溶性金属氰化物盐可含一种或多种这种金属。在该通式中,Y是碱金属离子或碱土金属离子。A是选自由卤化物、氢氧化物、硫酸盐、碳酸盐、氰化物、草酸盐、硫氰酸盐、氰酸盐、异硫氰酸盐、羧酸盐、和硝酸盐组成的组中的离子。a和b是大于或等于1的整数;a、b和c电荷总数与M’电荷相等。合适的水溶性金属氰化物盐包括但不限于六氰合高钴(Ⅲ)酸钾、六氰合亚铁(Ⅱ)酸钾、六氰合高铁(Ⅲ)酸钾、六氰合高钴(Ⅲ)酸钙、六氰合高钴(Ⅲ)酸锂等。
能用于本发明的双金属氰化物化合物实例包括例如六氰合高钴(Ⅲ)酸锌、六氰合高铁(Ⅲ)酸锌、六氰合亚铁(Ⅱ)酸镍、六氰合高钴(Ⅲ)酸钴等。另外的合适双金属氰化物配合物实例列于US专利5,158,922中,该专利的教导作为参考文献列入本文。六氰合高钴(Ⅲ)酸锌是优选的。
本发明的固体DMC催化剂包括有机配位剂。通常配位剂必须是较溶于水的。合适的配位剂是现有技术中通常已知的配位剂,例如在U.S 5,158,922中所述的。配位剂即可在制备过程中加入,也可在催化剂沉淀后立即加入。通常,使用过量的配位剂。优选配位剂是水溶性含杂原子的有机化合物,它可与双金属氰化物化合物配合。合适的配位剂包括但不限于醇类、醛类、酮类、醚类、酯类、酰胺类、脲、腈、硫化物及其混合物。最佳配位剂选自由乙醇、异丙醇、正丁醇、异丁醇、仲丁醇和叔丁醇组成的组中的水溶性脂肪醇。特别优选叔丁醇。
本发明的固体DMC催化剂含有根据催化剂量为约5-80wt%聚醚,该聚醚的数均分子量大于约500。优选的催化剂含有约10-70wt%的聚醚。最好的催化剂含有约15-60wt%聚醚。对比在无聚醚条件下所制得的催化剂,必须有至少约5wt%的聚醚才能显著改进催化剂的活性。当催化剂含有多于约80wt%的聚醚时,通常活性不会更高,而且不能用于分离和使用,因为它们通常是很粘的膏状物而不是粉末状固体。
合适的聚醚包括由环状醚开环聚合所产生的聚醚,并且包括环氧化物聚合物、氧杂环丁烷聚合物、四氢呋喃聚合物等。任何催化方法都可用于制造该聚醚。该聚醚可具有任何想要的末端基团,包括例如羟基、胺、酯、醚或诸如此类的基团。优选聚醚是具有平均羟基官能度约2-8和数均分子量范围在约1000-10,000,优选地在约1000-5000的聚醚多元醇。这样的聚醚通常是通过将环氧化物在含活泼氢的引发剂和碱、酸或有机金属催化剂(包括DMC催化剂)存在下聚合而制成的。有效聚醚多元醇包括聚(氧化丙烯)多元醇、EO-封端聚(氧化丙烯)多元醇、混合EO-PO多元醇、环氧丁烷聚合物、与环氧乙烷和/或环氧丙烷的环氧丁烷共聚物、聚亚丁基醚二元醇等。聚乙二醇一般不用于本发明。最好的是聚(氧化丙烯)多元醇,特别是数均分子量在约2000-4000范围内的二元醇和三元醇。
本发明人发现有机配位剂和聚醚在双金属氰化物催化剂中均是必须的。与在没有聚醚情况下制备的类似催化剂的活性相比,除了有机配位剂以外还含有聚醚能意外地提高催化剂活性(见实例1-3和对比例4)。有机配位剂同样是必要的:在有聚醚但没有有机配位剂如叔丁醇的情况下制成的催化剂,将不会使环氧化物聚合(见对比例5)。
本发明的催化剂可以用任何手段来表征。聚醚和有机配位剂可以用常规方法来鉴定和定量分析,如用热重法和质谱法分析,金属很容易用元素分析来定量分析。
本发明的催化剂还可用粉末X-射线衍射表征。该催化剂所显示的宽谱线集中在特征性d-间隔上。例如,使用叔丁醇和分子量约4000的聚(氧化丙烯)二醇制成的六氰合高钴酸锌催化剂在d-间隔约5.75和4.82上集中了两个宽信号,而在d-间隔约3.76上集中了有些狭窄的信号。(见表2)。这个衍射图谱另外的特征在于在约5.07、3.59、2.54和2.28的d-间隔上缺少与高晶态六氰合高钴酸锌对应的尖陡谱线。
本发明包括制备用于环氧化物聚合的固体DMC催化剂的方法。该方法包括在数均分子量大于约500的聚醚存在的情况下制备DMC催化剂,其中该固体DMC催化剂含有约5-80wt%的聚醚。
一般来说,该方法是通过在聚醚和有机配位剂存在的情况下使金属盐(过量)和金属氰化物盐在水溶液中起反应而实现。使用足够的聚醚来产生含有约5-80wt%聚醚的固体DMC催化剂。使用本发明方法制备的催化剂与在没有聚醚下制备的类似催化剂相比提高了环氧化物聚合的活性。
在本发明的一个最佳方法中(用下文实例1-3和7说明),首先使金属盐(如氯化锌)和金属氰化物盐(如六氰合高钴酸钾)的水溶液在有机配位剂(如叔丁醇)存在的情况下利用充分搅拌而反应,产生一种催化剂浆料。使用过量的金属盐。该催化剂浆料含有金属盐和金属氰化物盐的反应产物,该产物是一种双金属氰化物的化合物。还有过量的金属盐、水和有机配位剂;各种化合物在某种程度上被引入到催化剂的结构中。
该有机配位剂可以包括在这两种盐水溶液中一种或两种中,或在DMC化合物沉淀后立即加到催化剂浆料中。通常优选地使配位剂和任何一种水溶液,或两种水溶液在混合反应物前预混。
含水的金属盐和金属氰化物盐溶液(或其DMC反应产物)需要与配位剂充分地混合以产生最有活性的催化剂。为了实现充分的混合,常常采用均化器或高剪切搅拌器。
然后使第一步产生的催化剂浆料与数均分子量大于500的聚醚混合。第二步优选地在低剪切混合条件下完成。当该步骤使用非常有效的混合时,混合物倾向于增稠和凝结,从而使催化剂的分离复杂化。另外,该催化剂经常缺乏所要求的高活性。
第三步,从催化剂浆料中分离出含聚醚的固体催化剂。这一步的完成可通过任何常规方法,如过滤、离心或类似方法。
分离出来的含聚醚固体催化剂用含附加有机配位剂的水溶液洗涤。洗涤一般是通过把催化剂重新在有机配合剂的水溶液中制成浆料,接着进行催化剂分离步骤而完成的。所述洗涤步骤用于去除催化剂中的杂质,例如KCl,假若它们不被除去,则将使催化剂失活。优选的是用于该水溶液中的有机配位剂量在约40%-70wt%范围内,此外优选的是有机配位剂的水溶液中含一些聚醚。洗涤溶液中聚醚的量优选的范围为约2wt%-8wt%。洗涤步骤中含有聚醚通常能提高催化剂的活性。
尽管一次洗涤步骤就可以得到具有提高活性的催化剂,但是最好把催化剂洗涤一次以上。后续的洗涤可以是第一次洗涤的重复。最好是后来的洗涤是不含水的,即它仅含有机配位剂或有机配位剂和聚醚的混合物。多次洗涤对催化剂活性的好处描述于下文的例7中。
在把催化剂洗涤过后,通常最好是将其置于真空下(26英寸Hg-约30英寸Hg)干燥直到催化剂重量恒定。催化剂干燥温度范围约40℃-90℃。
在本发明第二种优选方法中,在制备过程中通过稀释法除去催化剂中的杂质,该法消除了用配位剂水溶液洗涤分离出的含聚醚催化剂的需要。下面的实例6说明该方法。
首先,使金属盐(过量)和金属氰化物盐的水溶液在有机配位剂存在下利用充分的混合(如上所述)起反应以便产生催化剂浆料。第二步,使催化剂浆料与一种稀释剂充分混合,该稀释剂含有附加有机配位剂的水溶液。该稀释剂的使用量要对溶解水相中的杂质(即过量反应物KCl等)有效。
用配位剂水溶液稀释后,使催化剂浆料与数均分子量大于约500的聚醚混合。通常在这步骤中最好使用低剪切混合。然后通过任意常规方法(如前所述),包括过滤、离心等从浆料中把含聚醚的固体催化剂分离出来。分离后,该催化剂优选地用附加有机配位剂或附加聚醚和有机配位剂混合物洗涤。完成这种洗涤步骤无须把固体放在洗涤溶剂中再次制浆或再次悬浮(见例6)。最后,分离出含约5-80wt%聚醚的固体DMC催化剂。
本发明催化剂较现有技术已知的DMC催化剂具有明显高的活性。事实上,本发明催化剂的活性足以使其能在很低的催化剂浓度下使用,如25ppm或以下(见下文例8)。在这样低的催化剂浓度下,催化剂经常能被留在聚醚多元醇产物中而不会对产品质量有坏的影响。例如,残留在多元醇中来自本发明六氰合高钴酸锌催化剂的Zn和Co量在对多元醇进行任何纯化前都能在产品技术要求内(各为<5ppm)。当需要纯度较高的产品时,简单的过滤一般就能适于除去多元醇产品中最后痕量的催化剂,该催化剂似乎是多相的。这些催化剂能留在多元醇中的性能是一个重要的优点,因为现在所有制造的聚醚多元醇(其中大多数是用KOH催化剂制造的)都需要催化剂分离步骤。
下列实例仅仅说明本发明,所属技术领域的技术人员将会认识到许多在本发明的精神和权利要求范围内的变更方案。
实例1
催化剂制备把六氰合高钴酸钾(8.0g)溶解在烧杯中的去离子(DI)水(140ml)内(溶液1)。把氯化锌(25g)溶解于第二个烧杯中的DI水(40ml)内(溶液2)。第三个烧杯含有溶液3:DI水(200ml)、叔-丁醇(2ml)、和多元醇(2g分子量为4000的聚(氧化丙烯)二醇,是通过双金属氰化物催化剂采用对比例4的方法制备的)的混合物。
使用均化器把溶液1和2混合在一起。立即将叔丁醇和DI水50/50(体积计)的混合物(总200ml)加到六氰合高钴酸锌混合物中,产物被均化10分钟。
把溶液3(多元醇/水/叔丁醇混合物)加入到六氰合高钴酸锌含水浆料中,将产物磁搅拌3分钟。在压力下通过5μm滤器过滤混合物以分离固体。
固体滤饼再于叔丁醇(140ml)、DI水(60ml)、和附加的4000分子量聚(氧化丙烯)二醇(2.0g)中制浆,然后使混合物均化10分钟再如上所述过滤。
使固体滤饼在叔丁醇(200ml)和附加4000分子量聚(氧化丙烯)二醇(1.0g)中再次制浆,均化10分钟,再过滤。使所得到的固体催化剂在真空50℃下(30英寸Hg)干燥至恒重。干燥的、粉末状催化剂产量为10.7g。
对固体催化剂的元素、热解重量和质谱分析显示:多元醇=21.5wt%;叔丁醇=7.0wt%;钴=11.5wt%。
聚醚多元醇的合成和催化剂活性的测量
按如上所述制备的催化剂样品用于制备具有羟基数约30mgKOH/g的聚醚三醇。
向1升搅拌反应器装入70g 700分子量聚(氧化丙烯)三醇起动多元醇和0.057g六氰合高钴酸锌/叔丁醇/聚醚多元醇催化剂(最终多元醇产物中100ppm催化剂)。该混合物经搅拌后在真空中加热至105℃以除去痕量残留水。把环氧丙烷(PO)(10g)加到反应器中,再将反应器中的压力从真空提高到4Psig(磅表压/英寸2)。不久反应器中的压力很快下降,表明催化剂已经开始活化。在催化剂的引发得到证实后,缓慢地往反应器中加入附加的环氧丙烷(总计500g)以维持反应器压力在约10Psig。
该催化剂的活性是由PO转化率对时间曲线的最陡点处的斜率测量的(见样品曲线图1),其值为3.31KgPO/克Co/分钟。在PO加完后,反应混合物保温在105℃直到获得恒压,这表明PO转化已完成。将该混合物在60℃下真空解吸0.5小时以便除去反应器中任意痕量的未反应PO。产物经冷却后回收。产物是具有29.8mgKOH/g羟值和0.0055meq/g(毫当量/克)不饱和度的聚(氧化丙烯)三醇。
实例2
催化剂制备向1加仑玻璃压力反应器中装入六氰合高钴酸钾(40g)在DI水(700ml)中的溶液(溶液1)。把氯化锌(125g)溶解于盛DI水(200ml)的烧杯中(溶液2)。将叔丁醇(500ml)溶于盛DI水(500ml)的烧杯中(溶液3)。通过把4000分子量聚(氧化丙烯)二醇(60g,与用于实例1的相同)悬浮于DI水(1000ml)和叔丁醇(10ml)中制备第四种混合物(溶液4)。
把溶液1和2在300rpm(转/分)搅拌下混合,随后立即缓慢地将溶液3加入到所得到的六氰合高钴酸锌混合物中。将搅拌的速度提高到900rpm,再将混合物在室温下搅拌2小时。搅拌速度降至300rpm,再加入溶液4。使产物混合5分钟,再按例1所述在压力下过滤以分离固体催化剂。把一份这种催化剂(催化剂A)留出用于例7中以说明洗涤对催化活性的影响。
剩余的固体放入叔丁醇(700ml)和DI水(300ml)中重新制浆,并于900rpm下搅拌2小时。将搅拌速度降至300rpm,再加入60g的4000分子量聚(氧化丙烯)二醇。将该混合物搅拌5分钟,再按上述过滤。
把该固体放入叔丁醇(1000ml)中重新制浆再于900rpm下搅拌2小时。搅拌速度降至300rpm,再加入30g的4000分子量聚(氧化丙烯)二醇。搅拌该混合物5分钟,再按上述过滤。把所得到的固体催化剂在50℃真空下(30英寸Hg)干燥至恒重。该催化剂很容易被破碎成细而干的粉末。
对所述固体催化剂的元素、热解重量、和质谱分析显示:多元醇=45.8wt%;叔丁醇=7.4wt%;钴=6.9wt%。
聚醚多元醇合成和催化剂活性的测量
将按在本例中所述制备而成的催化剂样品用于按实例1所述方法制备羟值约30mg KOH/g的聚醚三醇。按实例1所述测量的催化剂活性为每克钴每分钟6.69kg PO。产物是具有羟值29.1mg KOH/g和0.0042meq/g不饱和度的聚(氧化丙烯)三醇。
实例3
催化剂制备
按实例1程序,除了用2000分子量聚(氧化丙烯)二醇(也用双金属氰化物催化剂制造)代替4000分子量聚(氧化丙烯)二醇。
对固体催化剂的元素、热解重量、和质谱分析表示:多元醇=26.5wt%;叔丁醇=3.2wt%;钴=11.0wt%。
聚醚多元醇的合成和催化剂活性的测量
将按本例所述制备的催化剂样品用于通过实例1的方法制备羟值约为30mg KOH/g的聚醚三醇。按实例1所述测出的催化剂的活性为每克钴每分钟2.34kg PO。产品是羟值为30.8mgKOH/g和0.0037meq/g不饱和度的聚(氧化丙烯)三醇。
对比例4
本例说明使用叔丁醇作配位剂制备六氰合高钴酸锌催化剂,但在催化剂制备中省去了聚醚多元醇。
催化剂制备
把六氰合高钴酸钾(24g)溶于烧杯中的DI水(450ml)内(溶液1)。氯化锌(60g)溶于第二个烧杯中的DI水(90ml)内(溶液2)。采用混合用的均化器使溶液1和2混合。在此之后立即缓慢加入叔丁醇和水(按50/50体积计,600ml)混合物,然后使所得的浆料均化10分钟。浆料经离心以后,倒出液体部分。把固体放入叔丁醇和水(按70/30体积计,600ml)混合物内重新制浆,再使该混合物均化10分钟,然后离心再按上述滗析以分离出洗涤过的固体。使固体于100%的叔丁醇(600ml)中重新制浆,并使混合物均化10分钟,离心再倒出。固体催化剂在真空烘箱(50℃,30英寸Hg)内干燥至恒重。
对固体催化剂的元素,热解重量,和质谱分析显示:叔丁醇=14.1wt%;钴=12.5wt%;(多元醇=0wt%)。
聚醚多元醇的合成和催化剂活性的测量
将如本例所述制备的催化剂样品按实例1的方法制备羟值约为30mg KOII/g的聚醚多元醇。按实例1所述测出的催化剂活性为每克钴每分钟1.75kg PO。该产品是具有羟值29.8mg KOH/g和0.0052meq/g不饱和度的聚(氧化丙烯)三醇。
本例的结果证实当在该催化剂制备中不加聚醚多元醇时,用叔丁醇作配位剂制备的六氰合高钴酸锌催化剂作为环氧化物聚合催化剂活性低。
对比例5
本例说明在本发明六氰合高钴酸锌催化剂的制备中省略有机配位剂(叔丁醇)的影响,即只在多元醇存在下制备该催化剂。
催化剂的制备
把六氰合高钴酸钾(8.0g)溶于烧杯中的去离子(DI)水(140ml)内(溶液1)。使氯化锌(25g)溶于第二个烧杯中的DI水(40ml)内(溶液2)。第三个烧杯含溶液3:DI水(200ml)和多元醇(8g采用对比例4的方法借助双金属氰化物催化剂制备的4000分子量聚(氧化丙烯)二醇)的混合物。
采用均化器使溶液1和2混合在一起。之后马上缓慢加入溶液3(水/多元醇混合物),使混合过的混合物均化10分钟。使该混合物在压力下通过5μm过滤器过滤分离固体。使固体在DI水(200ml)和同样的多元醇(2.0g)混合物内重新制浆,将混合物均化10分钟,使固体通过过滤再次分离。固体再次于DI水(200ml)和同样的多元醇(1.0g)的混合物中制浆,将混合物均化10分钟,固体通过过滤再次分离。将固体催化剂置于真空烘箱内(50℃,30英寸Hg)干燥至恒重。
对固体催化剂的元素、热解重量和质谱分析显示:多元醇=61.7wt%;钴=7.0wt%;(叔丁醇=0wl%)。
催化剂活性的测量
当用实例1所述方法试验时该催化剂不是活性的。
本例证实有必要在除了聚醚成分外还有配位剂的情况下制备催化剂;如果省略配位剂,就会产生失活的催化剂。
实例6在催化剂制备过程中杂质的去除:稀释法
本例说明制备DMC催化剂的方法,在该法中杂质是用稀释法在制备过程中除去的。稀释作用排除了用有机配位剂水溶液洗涤分离后的含聚醚催化剂的需要。
使六氰合高钴酸钾(40g)溶解于1加仑玻璃压力反应器中的DI水(700ml)内(溶液1)。在烧杯中制备氯化锌(125g)在DI水(200ml)中的溶液(溶液2)。在另外一个烧杯中制备叔丁醇(500ml)和水(500ml)的混合物(溶液3)。在300rpm搅拌下把溶液2加到玻璃反应器中的溶液1中。继之立即把溶液3缓慢加到反应器中。搅拌速度提高到900rpm,再使混合物在室温下搅拌2小时。
反应混合物用叔丁醇(700ml)和DI水(300ml)的混合物稀释,再于500rpm下使混合持续1小时。
使一部分(1200ml)催化剂浆料收集在烧杯中,加入30g 4000分子量聚(氧化丙烯)二醇并用搅拌棒混合5分钟。产物用5μm滤纸离心过滤。滤饼变硬前,向滤饼加另外的叔丁醇,再使过滤持续到完全。不要将固体催化剂在洗涤溶液中重新制浆。使催化剂在50℃,30英寸(Hg)的真空烘箱内干燥至恒重。该催化剂易破碎成为细而干的粉末。对催化剂的分析表明:多元醇=66.0wt%;叔丁醇=1.7wt.%;钴=4.9wt%。该催化剂所测出的活性为4.73kgPO/g Co/分,并可得到羟值约为30mg KOH/g和具有0.0059meq/g不饱和度的聚醚三醇。
从反应器收集第二份催化剂浆料(800ml)放入烧杯中。不用加入多元醇,过滤该产品。在滤饼变硬之前,往滤饼加另外的叔丁醇(100ml),再使过滤持续到完全。产物如上所述被干燥。这种催化剂含有9.8wt%钴和12.9wt%叔丁醇(0wt%多元醇),其所测量的活性为1.99kg PO/g Co/分,并得到羟值为约30mg KOH/g和具有0.0104meq/g的不饱和度的聚醚三醇。
实例6还表明,在单个例子中,在催化剂制备中含有聚醚多元醇的优点:催化剂活性超过两倍且多元醇产物的不饱和度由于在聚醚多元醇存在下制备催化剂而大大降低。
实例7洗涤对催化剂活性的影响
采用催化剂A(实例2中所获得的未冲洗的六氰合高钴酸锌样品)来评价洗涤对催化剂活性的影响。当使用实例1的方法检测活性时,发现催化剂A(未冲洗)对于环氧丙烷聚合完全失活。
把催化剂A样品用含有70%叔丁醇的含水混合物洗涤一次。样品在真空下干燥,并按实例1所述测量活性。该催化剂以13.2gPO/分的速度活性聚合环氧丙烷。由这种催化剂制备的聚醚三醇的羟值为30.0mg KOH/g,不饱和度为0.0040meq/g。
另外的催化剂A样品用70%叔丁醇含水混合物洗涤一次,再用100%叔丁醇洗第二次。将样品在真空下干燥后测量活性。聚合速度为26.3g PO/分。由该催化剂制取的聚醚三醇的羟值为29.1mg KOH/g,不饱和度为0.0042meq/g。
本例证实洗涤步骤对获得活性催化剂是必须的。还说明多次洗涤步骤可得到活性较高的催化剂。
实例8使用25ppm催化剂制备4K聚(氧化丙烯)二醇
本例说明本发明催化剂的活性足够在低催化剂浓度下制备聚醚多元醇。这一点有效地消除了就许多多元醇成品使用来说进行催化剂分离的必要。
使用实例1制备的催化剂样品,在按实例1所述装配的多元醇合成用1升反应器内,通过使425分子量聚(氧化丙烯)二醇(通常由丙二醇、KOH和环氧丙烷制造)(500g)与15wt%环氧丙烷(75g)和200ppm(0.117g)实例1的六氰合高钴酸锌/叔丁醇/多元醇催化剂混合而使该聚(氧化丙烯)二醇预活化。该混合物被加热至约105℃持续90分钟,在此温度下催化剂变成活性的,而且环氧丙烷完全反应,产生预活化的二(元)醇引发剂。
然后把预活化的二元醇引发剂(550g)转移到按实例1装配的2加仑反应器内,再于105℃下2小时内向其中加入环氧丙烷(3850g)。聚合结束时催化剂浓度为25ppm。混合物于80℃下真空解吸0.5小时以除去反应器中任何痕量的未反应PO。将产物冷却后回收。产物是羟值为30.1mg KOH/g和不饱和度为0.0034meq/g的聚(氧化丙烯)二醇。在进行任何催化剂除去之前,多元醇中金属的测定量为:Zn=7ppm;Co=3ppm。
用粉末X-射线衍射对催化剂的表征
表2列出多种六氰合高钴酸锌催化剂的典型粉末X-射线衍射的结果。对比例5(在多元醇存在下制备的催化剂,但没有叔丁醇配位剂)的X-射线图与高晶态六氰合高钴酸锌水合物的图相类似。所述的高晶态六氰合高钴酸锌水合物是在没有任何多元醇或有机配位剂存在的条件下制备的。这两种“催化剂”对于环氧化物聚合都是失活的。
本发明的催化剂(实例1)是在叔丁醇和多元醇都存在的情况下制成的,它在5.75的d-间隔处显示出宽信号。该信号是由叔丁醇但无多元醇制备的催化剂所缺少的(对比例4)。尽管实例1和C4的催化剂均可以活性聚合环氧丙烷,但由叔丁醇和多元醇(实例1)制成的催化剂具有更高的活性(见表1)。
前述实例仅作为说明。下列权利要求限定本发明的范围。
表1.催化剂组成和活性,以及由该催化剂制成的聚醚三醇性质六氰合高钴酸锌/叔-丁醇/聚醚多元醇作催化剂 | ||||||
实例# | 催化剂组成(wt%)多元醇* 钴 叔·丁醇 | 催化剂活性(kg PO/g Co/分) | 6K分子量聚(PO)三醇产物OH#(mg KOH/g) 不饱和度(meq/g) | |||
1 | 21.5 | 11.5 | 7.0 | 3.31 | 29.8 | 0.0055 |
2 | 45.8 | 6.9 | 7.4 | 6.69 | 29.1 | 0.0042 |
3 | 26.5 | 11.0 | 3.2 | 2.34 | 30.8 | 0.0037 |
C4 | 0 | 12.5 | 14.1 | 1.75 | 29.8 | 0.0052 |
C5 | 61.7 | 7.0 | 0 | 0 | --- | --- |
*实例1-2使用4K分子量聚(PO)二醇;实例3使用2K分子量聚(PO)二醇6K分子量聚(PO)三醇产物是用100ppm催化剂制成的。 |
表2.用X-射线衍射表征DMC催化剂 | ||||||||
实例# | 催化剂含量 | X-射线衍射图(d-间隔,)1 | ||||||
5.75(br) | 5.07(s) | 4.82(br) | 3.76 | 3.59(s) | 2.54(s) | 2.28(s) | ||
--- | 晶体Zn-Co2 | 不存在 | × | 不存在 | 不存在 | × | × | × |
C5 | 多元醇但无TBA2 | 不存在 | × | 不存在 | 不存在 | × | × | × |
C4 | TBA,但无多元醇2 | 不存在 | 不存在 | × | × | 不存在 | 不存在 | 不存在 |
1 | TBA和多元醇3 | × | 不存在 | × | × | 不存在 | 不存在 | 不存在 |
X=存在的X-射线衍射线;(br)=宽谱带;(s)=狭窄谱线。样品用单色的CuKα1辐射(λ=1.54059)通过X-射线衍射进行分析。功率为40KV和30mA的Seimens D500 Kristalloflex衍射仪以0.02°2θ的步进扫描方式(计时为2秒/步)进行操作。发散缝为1°,而单色器和检测器开孔各为0.05°和0.15°。每个样品中都从5°运行至70°2θ。1水合水能引起所测量的d-间隔发生微小变化2对比例3本发明催化剂 |
Claims (23)
1.一种用于环氧化物聚合的固体双金属氰化物催化剂,其与在没有聚醚存在情况下制备的催化剂相比对于环氧化物聚合具有强活性,所述催化剂包含:
(a)双金属氰化物化合物;
(b)有机配位剂;和
(c)基于催化剂量计为5-80wt%的数均分子量大于500的聚醚。
2.权利要求1的催化剂,其特征在于双金属氰化物化合物是六氰合高钴酸锌。
3.权利要求1的催化剂,其特征在于有机配位剂是叔丁醇。
4.权利要求1的催化剂,其特征在于聚醚是数均分子量范围在1000-10,000的聚醚多元醇。
5.权利要求1的催化剂,其特征在于含有约10-70wt%的聚醚。
6.一种固体双金属氰化物催化剂,所述催化剂含有:
(a)六氰合高钴酸锌化合物;
(b)叔丁醇;和
(c)基于催化剂量计为10-70wt%的聚醚多元醇,所述多元醇的数均分子量范围在1000-5000。
7.权利要求6的催化剂,具有d-间隔,10-10m:5.75(br)、4.82(br)、3.76的X-射线衍射图,并且在d-间隔,10-10m:5.07、3.59、2.54、2.28处未显示出与高晶态六氰合高钴酸锌对应的可检测信号。
8.权利要求7的催化剂,具有的钴含量范围在5-10wt%。
9.权利要求1-8任一项的催化剂,其特征在于聚醚是数均分子量范围在2000-4000的聚(氧化丙烯)二醇。
10.权利要求1-8任一项的催化剂,其特征在于含有15-60wt%的聚醚。
11.一种包括在有机配位剂和数均分子量大于500的聚醚存在的情况下制备固体双金属氰化物催化剂的方法,其中该固体催化剂含5-80wt%的聚醚。
12.权利要求11的方法,其特征在于聚醚是数均分子量在1000-10,000范围内的聚醚多元醇。
13.权利要求12的方法,其特征在于聚醚是数均分子量在2000-4000范围内的聚(氧化丙烯)二醇。
14.权利要求11的方法,其特征在于催化剂是六氰合高钴酸锌。
15.权利要求11的方法,其特征在于催化剂含有15-60wt%的聚醚多元醇。
16.权利要求11-15任一项的方法,其特征在于有机配位剂是叔丁醇。
17.权利要求16的方法,所述方法包括:
(a)将过量金属盐和金属氰化物盐的水溶液在有机配位剂存在下利用充分混合起反应以产生催化剂浆料;
(b)将该催化剂浆与所述聚醚混合;
(c)分离浆料中的含聚醚固体催化剂;
(d)用含有附加有机配位剂的水溶液洗涤该含聚醚固体催化剂;和
(e)回收该固体催化剂。
18.权利要求17的方法,其特征在于在步骤(d)的该有机配位剂水溶液还包含附加的聚醚。
19.权利要求18的方法,其特征在于,在步骤(d)之后,已洗涤过的含聚醚固体催化剂用附加的有机配位剂或用聚醚和有机配位剂的混合物再次洗涤。
20.权利要求16的方法,所述方法包括:
(a)将过量金属盐和金属氰化物盐水溶液在有机配位剂存在的条件下利用充分混合起反应以产生催化剂浆料;
(b)将该催化剂浆料与含有附加有机配位剂水溶液的稀释剂充分混合;
(c)将来自步骤(b)的催化剂浆料与所述聚醚混合;
(d)从浆料中分离出含聚醚的催化剂;和
(e)回收该固体催化剂。
21.权利要求20的方法,其特征在于,在步骤(d)之后,含聚醚的固体催化剂用附加的有机配位剂或用附加聚醚和有机配位剂的混合物洗涤。
22.权利要求17至20任一项所述的方法,其特征在于该催化剂浆料利用低剪切混合与聚醚混合。
23.一种用于聚合环氧化物的方法,所述方法包括将环氧化物和含羟基的引发剂在权利要求1-10任一项的催化剂或按权利要求11-21任一项的方法制备的催化剂存在的情况下起反应。
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JP2595766B2 (ja) * | 1990-05-25 | 1997-04-02 | 旭硝子株式会社 | ポリオキシアルキレンアルコールの製造方法 |
JPH04314728A (ja) * | 1991-04-12 | 1992-11-05 | Asahi Glass Co Ltd | ポリエーテル類の製造方法 |
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- 1994-09-08 US US08/302,296 patent/US5482908A/en not_active Expired - Lifetime
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- 1995-05-30 US US08/453,194 patent/US5536883A/en not_active Expired - Lifetime
- 1995-08-29 EP EP95305994A patent/EP0700949B1/en not_active Expired - Lifetime
- 1995-08-29 ES ES95305994T patent/ES2127997T3/es not_active Expired - Lifetime
- 1995-08-29 AT AT95305994T patent/ATE177123T1/de not_active IP Right Cessation
- 1995-08-29 DK DK95305994T patent/DK0700949T3/da active
- 1995-08-29 DE DE69508009T patent/DE69508009T2/de not_active Expired - Lifetime
- 1995-08-31 CA CA002157312A patent/CA2157312C/en not_active Expired - Lifetime
- 1995-09-05 JP JP25012195A patent/JP3479175B2/ja not_active Expired - Lifetime
- 1995-09-06 ZA ZA957474A patent/ZA957474B/xx unknown
- 1995-09-07 AU AU30487/95A patent/AU688548B2/en not_active Ceased
- 1995-09-07 KR KR1019950029366A patent/KR100355336B1/ko not_active IP Right Cessation
- 1995-09-07 RO RO95-01576A patent/RO111742B1/ro unknown
- 1995-09-07 HU HU9502619A patent/HU215551B/hu active IP Right Revival
- 1995-09-08 TW TW084109401A patent/TW401429B/zh not_active IP Right Cessation
- 1995-09-08 CN CN95118425A patent/CN1072687C/zh not_active Expired - Lifetime
- 1995-09-08 BR BR9503975A patent/BR9503975A/pt not_active IP Right Cessation
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EP0090444A2 (en) * | 1982-03-31 | 1983-10-05 | Shell Internationale Researchmaatschappij B.V. | Novel catalysts for the polymerization of epoxides and process for the preparation of such catalysts |
JPH04145123A (ja) * | 1990-10-05 | 1992-05-19 | Asahi Glass Co Ltd | ポリエーテル化合物の製造方法 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103534029A (zh) * | 2011-05-17 | 2014-01-22 | 雷普索尔有限公司 | 高活性双金属氰化物催化剂的制备方法及其在聚醚多元醇的合成中的用途 |
CN103534029B (zh) * | 2011-05-17 | 2016-05-11 | 雷普索尔有限公司 | 高活性双金属氰化物催化剂的制备方法及其在聚醚多元醇的合成中的用途 |
CN106084197A (zh) * | 2016-06-22 | 2016-11-09 | 青神鑫统领建材有限公司 | 一种窄分布聚醚的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
ATE177123T1 (de) | 1999-03-15 |
KR100355336B1 (ko) | 2003-01-24 |
EP0700949A3 (en) | 1996-08-07 |
BR9503975A (pt) | 1996-09-24 |
TW401429B (en) | 2000-08-11 |
HU215551B (hu) | 1999-01-28 |
CA2157312C (en) | 2008-02-19 |
DE69508009D1 (de) | 1999-04-08 |
US5482908A (en) | 1996-01-09 |
HU9502619D0 (en) | 1995-10-30 |
JPH08104741A (ja) | 1996-04-23 |
EP0700949A2 (en) | 1996-03-13 |
EP0700949B1 (en) | 1999-03-03 |
DE69508009T2 (de) | 1999-08-12 |
HUT73052A (en) | 1996-06-28 |
ZA957474B (en) | 1996-04-09 |
JP3479175B2 (ja) | 2003-12-15 |
AU3048795A (en) | 1996-03-21 |
KR960010719A (ko) | 1996-04-20 |
US5536883A (en) | 1996-07-16 |
CN1133300A (zh) | 1996-10-16 |
ES2127997T3 (es) | 1999-05-01 |
DK0700949T3 (da) | 1999-09-27 |
AU688548B2 (en) | 1998-03-12 |
RO111742B1 (ro) | 1997-01-30 |
CA2157312A1 (en) | 1996-03-09 |
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