CN1133300A - 高活性双金属氰化物催化剂 - Google Patents
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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(DMC)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5-80wt%(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.S5,158,922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3.76A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。
合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3.31Kg PO/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 KOH/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:DT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=0wt%)。
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/gCo/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/gCo/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)进行振作。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 (35)
1.一种用于环氧化物聚合的固体双金属氰化物(DMC)催化剂,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)约5-80wt%(基于催化剂量)的数均分子量大于约500的聚醚;其中该催化剂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。
2.权利要求1的催化剂,其中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,其中有机配位剂是叔丁醇。
4.权利要求1的催化剂,其中聚醚是数均分子量范围在约1000-10,000的聚醚多元醇。
5.权利要求1的催化剂,其中聚醚是数均分子量范围在约2000-4000的聚(氧化丙烯)二醇。
6.权利要求1的催化剂,含有约10-70wt%的聚醚。
7.权利要求1的催化剂,含有约15-60wt%的聚醚。
8.一种可用于环氧化物聚合的固体双金属氰化物(DMC)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)约10-70wt%(基于催化剂量)的聚醚多元醇,所述多元醇的数均分子量范围在约1000-5000;
其中催化剂与在没有聚醚多元醇存在的情况下制备的催化剂比较对于环氧化物聚合具有强活性。
9.权利要求8的催化剂,其中聚醚多元醇是数均分子量范围在约2000-4000的聚(氧化丙烯)二醇。
10.权利要求8的催化剂,含有约15-60wt%的聚醚多元醇。
11.权利要求8的催化剂,具有(d-间隔,)5.75(br)、4.82(br)、3.76的X-射线衍射图,并且在约(d-间隔,):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。
12.权利要求8的催化剂,具有的钴含量范围约5-10wt%。
13.一种包括在数均分子量大于约500的聚醚存在的情况下制备固体双金属氰化物(DMC)催化剂的方法,其中该固体DMC催化剂含约5-80wt%的聚醚。
14.权利要求13的方法,其中聚醚是数均分子量在约1000-约10,000范围内的聚醚多元醇。
15.权利要求13的方法,其中的聚醚是数均分子量在约2000-约4000范围内的聚(氧化丙烯)二醇。
16.权利要求13的方法,其中DMC催化剂是六氰合高钴酸锌。
17.权利要求14的方法,其中DMC催化剂含有约15-60wt%的聚醚多元醇。
18.权利要求13的方法,其中催化剂是在一种有机配位剂存在的情况下制备的。
19.权利要求18的方法,其中有机配位剂是叔丁醇。
20.一种制备可用于环氧化物聚合的固体双金属氰化物(DMC)催化剂的方法,所述方法包括:
(a)将金属盐(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混合起反应以产生催化剂浆料;
(b)将该催化剂浆与数均分子量大于约500的聚醚混合;
(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)回收含约5-80wt%(基于固体DMC催化剂量)聚醚的固体DMC催化剂。
21.权利要求20的方法,其中该双金属氰化物催化剂是六氰合高钴酸锌。
22.权利要求20的方法,其中该有机配位剂是叔丁醇。
23.权利要求20的方法,其中该聚醚是数均分子量在约1000-10,000范围内的聚醚多元醇。
24.权利要求20的方法,其中该聚醚是数均分子量在约2000-4000范围内的聚(氧化丙烯)二醇。
25.权利要求20的方法,其中该催化剂浆料是在步骤(b)利用低剪切混合与聚醚混合的。
26.权利要求20的方法,其中该有机配位剂水溶液在步骤(d)还包含附加的聚醚。
27.权利要求26的方法,其中,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再次洗涤。
28.权利要求26的方法,其中,在步骤(d)以后,已洗涤过的含聚醚固体催化剂是用聚醚和有机配位剂的混合物再次洗涤。
29.一种制备可用于环氧化物聚合的固体双金属氰化物(DMC)催化剂的方法,所述方法包括:
(a)将金属盐(过量)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)的催化剂浆料与数均分子量大于约500的聚醚混合;
(d)从浆料中分离出含聚醚的催化剂;和
(e)回收含约5-80wt%(基于固体DMC催化剂)聚醚的固体DMC催化剂。
30.权利要求29的方法,其中,在步骤(d)之后,含聚醚的固体催化剂用附加的有机配位剂洗涤。
31.权利要求29的方法,其中,在步骤(d)之后,含聚醚的固体催化剂用附加聚醚和有机配位剂的混合物洗涤。
32.一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的催化剂的存在下起反应。
33.一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8的催化剂存在的情况下起反应。
34.一种使用权利要求1的催化剂制备的聚醚多元醇。
35.一种用权利要求8的催化剂制备的聚醚多元醇。
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Families Citing this family (469)
Publication number | Priority date | Publication date | Assignee | Title |
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US6624286B2 (en) | 1997-10-13 | 2003-09-23 | Bayer Aktiengesellschaft | Double-metal cyanide catalysts containing polyester for preparing polyether polyols |
ID24172A (id) * | 1997-10-13 | 2000-07-13 | Bayer Ag | Katalis logam ganda yang sangat aktif untuk memproduksi poliol-poliol poliester |
US5962619A (en) * | 1998-03-16 | 1999-10-05 | Arco Chemical Technology, L.P. | Process for making clear polyurethane/urea elastomers |
US5952261A (en) * | 1998-03-20 | 1999-09-14 | Arco Chemical Technology, L.P. | Double metal cyanide complex catalysts modified with Group IIA compounds |
US6008263A (en) * | 1998-04-03 | 1999-12-28 | Lyondell Chemical Worldwide, Inc. | Molded and slab polyurethane foam prepared from double metal cyanide complex-catalyzed polyoxyalkylene polyols and polyols suitable for the preparation thereof |
US6066683A (en) * | 1998-04-03 | 2000-05-23 | Lyondell Chemical Worldwide, Inc. | Molded and slab polyurethane foam prepared from double metal cyanide complex-catalyzed polyoxyalkylene polyols and polyols suitable for the preparation thereof |
DE19817676A1 (de) | 1998-04-21 | 1999-10-28 | Bayer Ag | Verfahren zur aufarbeitungsfreien Herstellung langkettiger Polyetherpolyole |
AR019107A1 (es) | 1998-04-27 | 2001-12-26 | Dow Global Technologies Inc | Polioles de alto peso molecular, proceso para su preparacion y uso de los mismos. |
US6063897A (en) * | 1998-05-05 | 2000-05-16 | Arco Chemical Technology, L.P. | Acid-treated double metal cyanide complex catalysts |
US6013596A (en) * | 1998-05-18 | 2000-01-11 | Arco Chemical Technology, L.P. | Double metal cyanide catalysts containing cyclic, bidentate complexing agents |
US6028230A (en) * | 1998-06-05 | 2000-02-22 | Arco Chemical Technology, L.P. | Epoxide polymerization process |
US6051680A (en) * | 1998-06-08 | 2000-04-18 | Arco Chemical Technology, L.P. | Silylated double metal cyanide complex catalysts |
US6022903A (en) * | 1998-07-09 | 2000-02-08 | Arco Chemical Technology L.P. | Permanent gas blown microcellular polyurethane elastomers |
US6299715B1 (en) | 1998-07-14 | 2001-10-09 | Bayer Antwerp N.V. | Urethane adhesive-laminated carpeting |
US6171678B1 (en) * | 1998-07-14 | 2001-01-09 | Bayer Antwerp N.V. | Polyurethane carpet backings with improved tuft bind |
DE19834572A1 (de) | 1998-07-31 | 2000-02-03 | Bayer Ag | Doppelmetallcyanid-Katalysatoren für die Herstellung von Polyetherpolyolen |
DE19842383A1 (de) * | 1998-09-16 | 2000-03-23 | Bayer Ag | Doppelmetallcyanid-Katalysatoren für die Herstellung von Polyetherpolyolen |
US6051622A (en) * | 1998-09-17 | 2000-04-18 | Arco Chemical Technology, L.P. | Low resilience, low frequency molded polyurethane foam |
US6100310A (en) * | 1998-09-25 | 2000-08-08 | Bayer Antwerp N.V. | Process for making microcellular polyurethane elastomers |
US6264775B1 (en) | 1998-12-22 | 2001-07-24 | Bayer Antwerp N.V. | Face-up coating of carpet backs with polyurethane |
DE19903274A1 (de) | 1999-01-28 | 2000-08-03 | Basf Ag | Verfahren zur Herstellung von Polyetherpolyolen |
DE19913260C2 (de) | 1999-03-24 | 2001-07-05 | Bayer Ag | Doppelmetallcyanid-Katalysatoren für die Herstellung von Polyetherpolyolen |
DE19905611A1 (de) | 1999-02-11 | 2000-08-17 | Bayer Ag | Doppelmetallcyanid-Katalysatoren für die Herstellung von Polyetherpolyolen |
BR0008108A (pt) | 1999-02-11 | 2001-11-13 | Bayer Ag | Catalisadores de cianeto de duplo metal paraprodução de polióis poliéter |
DE19906985A1 (de) | 1999-02-19 | 2000-08-31 | Bayer Ag | Doppelmetallcyanid-Katalysatoren für die Herstellung von Polyetherpolyolen |
DE19918727A1 (de) | 1999-04-24 | 2000-10-26 | Bayer Ag | Langkettige Polyetherpolyole mit hohem Anteil primärer OH-Gruppen |
HUP0201002A3 (en) * | 1999-05-05 | 2003-08-28 | Bayer Ag | Double metal cyanide catalysts for the production of polyether polyols |
US6800583B2 (en) * | 1999-06-02 | 2004-10-05 | Basf Aktiengesellschaft | Suspension of multimetal cyanide compounds, their preparation and their use |
US6613714B2 (en) * | 1999-06-02 | 2003-09-02 | Basf Aktiengesellschaft | Multimetal cyanide compounds, their preparation and their use |
DE19928156A1 (de) | 1999-06-19 | 2000-12-28 | Bayer Ag | Aus Polyetherpolyolen hergestellte Polyurethan-Weichschäume |
US6384183B1 (en) | 1999-07-09 | 2002-05-07 | The Dow Chemical Company | Metal hexacyanocobaltate nitroferricyanide complexes |
US6423662B1 (en) | 1999-07-09 | 2002-07-23 | Dow Global Technologies Inc. | Incipient wetness method for making metal-containing cyanide catalysts |
US6376645B1 (en) | 1999-07-09 | 2002-04-23 | The Dow Chemical Company | Complexing agent-modified hexacyanometallate hexanitrometallate catalysts |
US20040266982A1 (en) * | 1999-07-09 | 2004-12-30 | Clement Katherine S | Polymerization of alkylene oxides onto functionalized initiators |
DE19937114C2 (de) | 1999-08-06 | 2003-06-18 | Bayer Ag | Verfahren zur Herstellung von Polyetherpolyolen |
US6358877B1 (en) | 1999-09-10 | 2002-03-19 | The Dow Chemical Company | Metal catalysts complexed with sulfone or sulfoxide compounds |
DE19953546A1 (de) | 1999-11-08 | 2001-05-10 | Bayer Ag | Doppelmetallcyanid-Katalysatoren für die Herstellung von Polyetherpolyolen |
DE19958355A1 (de) | 1999-12-03 | 2001-06-07 | Bayer Ag | Verfahren zur Herstellung von DMC-Katalysatoren |
US6359101B1 (en) | 1999-12-15 | 2002-03-19 | Synuthane International, Inc. | Preparing polyether polyols with DMC catalysts |
WO2001057106A1 (en) * | 2000-02-04 | 2001-08-09 | Ppg Industries Ohio, Inc. | Photochromic coated articles |
DE10008635A1 (de) † | 2000-02-24 | 2001-09-06 | Basf Ag | Verfahren zur Herstellung von Polyetherpolyolen |
JP2003528213A (ja) | 2000-03-30 | 2003-09-24 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | Dmc錯体触媒及びその製造方法 |
HU226653B1 (en) * | 2000-04-20 | 2009-05-28 | Bayer Ag | Method for producing double metal cyanide (dmc) catalysts |
AU2001255735A1 (en) | 2000-04-28 | 2001-11-12 | Synuthane International, Inc. | Double metal cyanide catalysts containing polyglycol ether complexing agents |
US6429166B1 (en) | 2000-05-19 | 2002-08-06 | Dow Global Technologies Inc. | Method for preparing metal cyanide catalyst/polyol initiator slurries |
US6388048B1 (en) * | 2000-05-19 | 2002-05-14 | The Dow Chemical Company | Complexing agent-modified trimetal cyanide catalyst |
US6955772B2 (en) * | 2001-03-29 | 2005-10-18 | Agfa-Gevaert | Aqueous composition containing a polymer or copolymer of a 3,4-dialkoxythiophene and a non-newtonian binder |
US6890584B2 (en) * | 2000-06-28 | 2005-05-10 | Agfa-Gevaert | Flexographic ink containing a polymer or copolymer of a 3,4-dialkoxythiophene |
DE10108485A1 (de) | 2001-02-22 | 2002-09-05 | Bayer Ag | Verbessertes Verfahren zur Herstellung von Polyetherpolyolen |
DE10108484A1 (de) | 2001-02-22 | 2002-09-05 | Bayer Ag | Verbessertes Verfahren zur Herstelung von Polyetherpolyolen |
DE10117273A1 (de) * | 2001-04-06 | 2002-10-17 | Basf Ag | Verfahren zur Herstellung von Hydroxyalkylcarbonsäureestern |
KR100418058B1 (ko) * | 2001-04-18 | 2004-02-14 | 에스케이씨 주식회사 | 폴리올 제조용 복금속 시안계 착화합물 촉매 |
US6833431B2 (en) * | 2001-05-02 | 2004-12-21 | Bayer Aktiengesellschaft | Double-metal cyanide catalysts for preparing polyether polyols |
DE10122020A1 (de) | 2001-05-07 | 2002-11-14 | Bayer Ag | Doppelmetallcyanid-Katalysatoren für die Herstellung von Polyetherpolyolen |
DE10122019A1 (de) * | 2001-05-07 | 2002-11-14 | Bayer Ag | Doppelmetallcyanid-Katalysatoren für die Herstellung von Polyetherpolyolen |
US6596842B2 (en) | 2001-07-16 | 2003-07-22 | Shell Oil Company | Polymerizing alkylene oxide with sound or radiation treated DMC |
DE10138216A1 (de) | 2001-08-03 | 2003-02-20 | Bayer Ag | Aliphatische Polycarbonathomo- und -copolymere durch DMC-Katalyse |
DE10137628A1 (de) * | 2001-08-03 | 2003-02-27 | Basf Ag | Verfahren zur Herstellung von Polyurethan-Weichschaumstoffen |
DE10142746A1 (de) | 2001-08-31 | 2003-03-20 | Bayer Ag | Doppelmetallcyanid-Katalysatoren für die Herstellung von Polyetherpolyolen |
DE10142747A1 (de) | 2001-08-31 | 2003-03-20 | Bayer Ag | Doppelmetallcyanid-Katalysatoren für die Herstellung von Polyetherpolyolen |
US20070142604A1 (en) * | 2005-12-16 | 2007-06-21 | Nina Bojkova | Polyurethanes and sulfur-containing polyurethanes and methods of preparation |
US20030096935A1 (en) * | 2001-11-16 | 2003-05-22 | Nagpal Vidhu J. | Impact resistant polyureaurethane and method of preparation |
US8017720B2 (en) * | 2005-12-16 | 2011-09-13 | Ppg Industries Ohio, Inc. | Sulfur-containing oligomers and high index polyurethanes prepared therefrom |
US20060241273A1 (en) * | 2001-11-16 | 2006-10-26 | Bojkova Nina V | High impact poly (urethane urea) polysulfides |
US6541673B1 (en) * | 2001-11-30 | 2003-04-01 | Arco Chemical Technology, L.P. | Process for oxyalkylating phenolic compounds |
ES2199666B1 (es) | 2002-02-25 | 2005-06-01 | Repsol Quimica, S.A. | Procedimiento de produccion de polioleteres. |
KR20040091768A (ko) * | 2002-03-21 | 2004-10-28 | 다우 글로벌 테크놀로지스 인크. | 부분 혼화성 착물화제를 사용하는 금속 시아나이드 촉매착물의 제조 방법 |
US6797665B2 (en) | 2002-05-10 | 2004-09-28 | Bayer Antwerpen | Double-metal cyanide catalysts for preparing polyether polyols |
US6835801B2 (en) * | 2002-07-19 | 2004-12-28 | Bayer Antwerp, N.V. | Activated starter mixtures and the processes related thereto |
US20040021133A1 (en) * | 2002-07-31 | 2004-02-05 | Nagpal Vidhu J. | High refractive index polymerizable composition |
DE10235130A1 (de) * | 2002-08-01 | 2004-02-19 | Bayer Ag | Doppelmetallcyanid-Katalysatoren für die Herstellung von Polyetherpolyolen |
US6696383B1 (en) * | 2002-09-20 | 2004-02-24 | Bayer Polymers Llc | Double-metal cyanide catalysts which can be used to prepare polyols and the processes related thereto |
DE10246707A1 (de) * | 2002-10-07 | 2004-04-15 | Bayer Ag | Zweikomponenten-Systeme für die Herstellung elastischer Beschichtungen |
DE10246708A1 (de) * | 2002-10-07 | 2004-04-15 | Bayer Ag | Zweikomponenten-Systeme für die Herstellung elastischer Beschichtungen |
US7001634B2 (en) * | 2002-11-07 | 2006-02-21 | Bayer Materialscience Llc | Process for suppressing the foaming of an aqueous system |
US7009032B2 (en) * | 2002-12-20 | 2006-03-07 | Ppg Industries Ohio, Inc. | Sulfide-containing polythiols |
US6806348B2 (en) * | 2003-02-11 | 2004-10-19 | Basf Corporation | Process for removing and regenerating a double metal cyanide (DMC) catalyst from a polymer polyol |
ZA200506576B (en) * | 2003-03-07 | 2006-12-27 | Dow Global Technologies Inc | Continuous process and system of producing polyether polyols |
US6713599B1 (en) | 2003-03-31 | 2004-03-30 | Basf Corporation | Formation of polymer polyols with a narrow polydispersity using double metal cyanide (DMC) catalysts |
US20040197570A1 (en) * | 2003-04-02 | 2004-10-07 | Slack William E. | Prepolymers of allophanate-modified MDI and polyoxypropylene polyol |
US20050014637A1 (en) * | 2003-06-04 | 2005-01-20 | Duijghuisen Henricus Petrus Bernardus | Polyether polyol composition |
US6884826B2 (en) * | 2003-06-09 | 2005-04-26 | Bayer Antwerp, N.V. | Process for preparing double metal cyanide catalyzed polyols |
US20050070682A1 (en) * | 2003-09-30 | 2005-03-31 | Lawrey Bruce D. | Polyetherurethaneurea elastomers and thin-walled articles prepared therefrom |
DE602004025022D1 (de) | 2003-10-06 | 2010-02-25 | Kaneka Corp | Haftklebemittel |
US7223890B2 (en) * | 2003-10-10 | 2007-05-29 | Bayer Materialscience Llc | Isocyanate reactive mixture and process for preparing same |
US7005552B2 (en) * | 2003-11-03 | 2006-02-28 | Bayer Materialscience Llc | Single reactor synthesis of KOH-capped polyols based on DMC-synthesized intermediates |
US20050101477A1 (en) * | 2003-11-07 | 2005-05-12 | George Combs | Unsaturated tertiary alcohols as ligands for active dmc catalysts |
US20050107486A1 (en) * | 2003-11-17 | 2005-05-19 | Bi Le-Khac | UV-curable polyols |
US20050281977A1 (en) * | 2004-01-23 | 2005-12-22 | Mashburn Larry E | Method of carpet construction |
US8470927B2 (en) | 2004-02-26 | 2013-06-25 | Bayer Materialscience Llc | Process for production of polymer polyols |
ES2298705T3 (es) * | 2004-02-27 | 2008-05-16 | Repsol Quimica S.A. | Catalizadores de cianuros dobles metalicos (dmc) con esteres-corona, procedimiento para su obtencion y aplicaciones. |
US20050209438A1 (en) * | 2004-03-19 | 2005-09-22 | Browne Edward P | Starter feed stream acidification in DMC-catalyzed process |
US7060750B2 (en) * | 2004-04-28 | 2006-06-13 | Bayer Materialscience Llc | Moisture-curable, polyether urethanes and their use in sealant, adhesive and coating compositions |
US11149107B2 (en) | 2004-09-01 | 2021-10-19 | Ppg Industries Ohio, Inc. | Polyurethanes, articles and coatings prepared therefrom and methods of making the same |
US20090280709A1 (en) | 2004-09-01 | 2009-11-12 | Ppg Industries Ohio, Inc. | Polyurethanes, Articles and Coatings Prepared Therefrom and Methods of Making the Same |
US9598527B2 (en) | 2004-09-01 | 2017-03-21 | Ppg Industries Ohio, Inc. | Polyurethanes, articles and coatings prepared therefrom and methods of making the same |
US9464169B2 (en) | 2004-09-01 | 2016-10-11 | Ppg Industries Ohio, Inc. | Polyurethanes, articles and coatings prepared therefrom and methods of making the same |
US20090280329A1 (en) | 2004-09-01 | 2009-11-12 | Ppg Industries Ohio, Inc. | Polyurethanes, Articles and Coatings Prepared Therefrom and Methods of Making the Same |
US11591436B2 (en) | 2004-09-01 | 2023-02-28 | Ppg Industries Ohio, Inc. | Polyurethane article and methods of making the same |
US11008418B2 (en) | 2004-09-01 | 2021-05-18 | Ppg Industries Ohio, Inc. | Polyurethanes, articles and coatings prepared therefrom and methods of making the same |
US20060058182A1 (en) * | 2004-09-13 | 2006-03-16 | Combs George G | Processes for the preparation of double metal cyanide (DMC) catalysts |
BRPI0516890A (pt) * | 2004-10-26 | 2008-09-23 | Dow Global Technologies Inc | processo para preparar um poliéter, composição de poliéter e composição iniciadora |
CN1308079C (zh) * | 2004-11-29 | 2007-04-04 | 黎明化工研究院 | 一种氰化物络合物催化剂及其制备方法和用途 |
US20060229375A1 (en) * | 2005-04-06 | 2006-10-12 | Yu-Ling Hsiao | Polyurethane foams made with alkoxylated vegetable oil hydroxylate |
US7609773B2 (en) * | 2005-04-18 | 2009-10-27 | Qualcomm Incorporated | Method of determining the location of the FFT window and the delay spread for the platinum broadcast channel estimator |
US7842653B2 (en) * | 2005-06-16 | 2010-11-30 | Council Of Scientific & Industrial Research | Process for the preparation of lubricants |
US7754643B2 (en) * | 2005-10-07 | 2010-07-13 | Council Of Scientific & Industrial Research | Transesterification catalyst and a process for the preparation thereof |
US7323605B2 (en) * | 2005-11-09 | 2008-01-29 | Bayer Materialscience Llc | Double metal cyanide-catalyzed, low unsaturation polyethers from boron-containing starters |
US7482495B2 (en) * | 2005-12-22 | 2009-01-27 | Lyondell Chemical Technology, L.P. | Process for making alkylene glycol ether compositions useful for metal recovery |
DE102006006696A1 (de) * | 2006-02-14 | 2007-08-23 | Clariant International Limited | Polyalkylenglykol-Schmiermittelbasisöle mit enger Molmassenverteilung |
EP2559721B1 (en) | 2006-05-05 | 2015-01-07 | PPG Industries Ohio, Inc. | Compositions and articles prepared from thioether functional oligomeric polythiols |
DE102006024025A1 (de) * | 2006-05-23 | 2007-11-29 | Bayer Materialscience Ag | Verfahren zur Herstellung von Polyetherpolyolen |
US20070299242A1 (en) * | 2006-06-21 | 2007-12-27 | Bayer Materialscience Llc | Pendant acrylate and/or methacrylate-containing polyether monols and polyols |
US20080021191A1 (en) * | 2006-07-20 | 2008-01-24 | Reese Jack R | High water content tolerant process for the production of polyethers |
US7977501B2 (en) | 2006-07-24 | 2011-07-12 | Bayer Materialscience Llc | Polyether carbonate polyols made via double metal cyanide (DMC) catalysis |
US8093351B2 (en) | 2006-08-24 | 2012-01-10 | Cornell Research Foundation, Inc. | Copolymerization of propylene oxide and carbon dioxide and homopolymerization of propylene oxide |
US20080132729A1 (en) | 2006-12-01 | 2008-06-05 | Mcdaniel Kenneth G | Continuous process for the production of ethoxylates |
US20080132728A1 (en) | 2006-12-01 | 2008-06-05 | Mcdaniel Kenneth G | Continuous processes for the production of alkylphenol ethoxylates |
CN100415800C (zh) * | 2007-01-05 | 2008-09-03 | 南通汇科聚氨酯研发有限公司 | 环氧化物开环聚合用双金属氰化物催化剂 |
US20080167501A1 (en) | 2007-01-08 | 2008-07-10 | Bayer Materialscience Llc. | High productivity alkoxylation processes |
DE102007002555A1 (de) * | 2007-01-17 | 2008-07-24 | Bayer Materialscience Ag | Doppelmetallcyanid-Katalysatoren für die Herstellung von Polyetherpolyolen |
US7834082B2 (en) | 2007-01-17 | 2010-11-16 | Bayer Materialscience Llc | Polyether-polysiloxane polyols |
JP2010516871A (ja) | 2007-01-29 | 2010-05-20 | ザ ルブリゾル コーポレイション | 潤滑組成物 |
ES2705482T3 (es) | 2007-01-29 | 2019-03-25 | Lubrizol Corp | Composiciones lubricantes |
DE102007005960A1 (de) | 2007-02-07 | 2008-08-14 | Bayer Materialscience Ag | Ruß-gefüllte Polyurethane mit hoher Dielektrizitätskonstante und Durchschlagsfestigkeit |
US20080255378A1 (en) | 2007-04-16 | 2008-10-16 | Bayer Materialscience Llc | High productivity process for non-phenolic ethoxylates |
US7473677B2 (en) | 2007-04-16 | 2009-01-06 | Bayer Materialscience Llc | High productivity process for alkylphenol ethoxylates |
DE102007038436A1 (de) * | 2007-08-16 | 2009-02-19 | Bayer Materialscience Ag | Verfahren zur Herstellung von Polyolen |
DE102007057146A1 (de) | 2007-11-28 | 2009-06-04 | Evonik Goldschmidt Gmbh | Verfahren zur Herstellung von Polyetheralkoholen mit DMC-Katalysatoren unter Verwendung von speziellen Additiven mit aromatischer Hydroxy-Funktionalisierung |
DE102007057145A1 (de) | 2007-11-28 | 2009-06-04 | Evonik Goldschmidt Gmbh | Verfahren zur Herstellung von Polyetheralkoholen mit DMC-Katalysatoren unter Verwendung von SiH-Gruppen tragenden Verbindungen als Additive |
DE102008000360A1 (de) | 2008-02-21 | 2009-08-27 | Evonik Goldschmidt Gmbh | Neue Alkoxysilylgruppen tragende Polyetheralkohole durch Alkoxylierung epoxidfunktioneller Alkoxysilane an Doppelmetallcyanid (DMC)-Katalysatoren, sowie Verfahren zu deren Herstellung |
DE102008011683A1 (de) | 2008-02-28 | 2009-09-03 | Bayer Materialscience Ag | Verfahren zur Herstellung von Polyolen |
DE102008000903A1 (de) | 2008-04-01 | 2009-10-08 | Evonik Goldschmidt Gmbh | Neue Organosiloxangruppen tragende Polyetheralkohole durch Alkoxylierung epoxidfunktioneller (Poly)Organosiloxane an Doppelmetallcyanid (DMC)-Katalysatoren, sowie Verfahren zu deren Herstellung |
KR100941637B1 (ko) * | 2008-05-21 | 2010-02-11 | 에스케이씨 주식회사 | 반응성이 제어된, 폴리올 제조용 복금속 시안계 촉매 및이의 제조방법 |
DE102008028555A1 (de) | 2008-06-16 | 2009-12-17 | Bayer Materialscience Ag | Verfahren zur Herstellung von Polyolen |
US8124801B2 (en) * | 2008-06-24 | 2012-02-28 | Benefuel Inc. | Process of manufacturing of fatty acid alkyl esters |
DE102008002713A1 (de) | 2008-06-27 | 2009-12-31 | Evonik Goldschmidt Gmbh | Neue Polyethersiloxane enthaltende Alkoxylierungsprodukte durch direkte Alkoxylierung organomodifizierter alpha, omega-Dihydroxysiloxane an Doppelmetallcyanid (DMC)-Katalysatoren, sowie Verfahren zu deren Herstellung |
IL200997A0 (en) | 2008-10-01 | 2010-06-30 | Bayer Materialscience Ag | Special polyether-based polyurethane formulations for the production of holographic media |
IL200995A0 (en) | 2008-10-01 | 2010-06-30 | Bayer Materialscience Ag | Polyether-based polyurethane formulations for the production of holographic media |
IL200996A0 (en) | 2008-10-01 | 2010-06-30 | Bayer Materialscience Ag | Photopolymer formulations having a low crosslinking density |
DE102008051882A1 (de) | 2008-10-16 | 2010-04-29 | Bayer Materialscience Ag | Verfahren zur Herstellung von Polyetheresterpolyolen |
DE102008043245A1 (de) | 2008-10-29 | 2010-05-06 | Evonik Goldschmidt Gmbh | Siliconpolyether-Copolymersysteme sowie Verfahren zu deren Herstellung durch Alkoxylierungsreaktion |
DE102008043343A1 (de) | 2008-10-31 | 2010-05-06 | Evonik Goldschmidt Gmbh | Silikonpolyetherblock-Copolymere mit definierter Polydispersität im Polyoxyalkylenteil und deren Verwendung als Stabilisatoren zur Herstellung von Polyurethanschäumen |
EP2350191B1 (en) * | 2008-11-14 | 2013-09-11 | Dow Global Technologies LLC | Modified natural oils and products made therefrom |
US10239985B2 (en) | 2008-12-23 | 2019-03-26 | Covestro Llc | Polymer polyols comprising a natural oil base polyol, polyurethane foams comprising these polymer polyols and processes for their preparation |
DE102009002371A1 (de) | 2009-04-15 | 2010-10-21 | Evonik Goldschmidt Gmbh | Verfahren zur Herstellung von geruchlosen Polyetheralkoholen mittels DMC-Katalysatoren und deren Verwendung in kosmetischen und/oder dermatologischen Zubereitungen |
US20100324340A1 (en) | 2009-06-23 | 2010-12-23 | Bayer Materialscience Llc | Short chain polyether polyols prepared from ultra-low water-content starters via dmc catalysis |
DE102009031584A1 (de) | 2009-07-03 | 2011-01-05 | Bayer Materialscience Ag | Verfahren zur Herstellung von Polyetherpolyolen mit primären Hydroxyl-Endgruppen |
EP2451768A1 (en) | 2009-07-10 | 2012-05-16 | Dow Global Technologies LLC | Esters of secondary hydroxy fatty acid oligomers and preparation thereof |
US8362304B2 (en) * | 2009-07-15 | 2013-01-29 | Lyondell Chemical Technology, L.P. | Process for making glycol ether compositions useful for metal recovery |
DE102009042190A1 (de) | 2009-09-18 | 2011-03-24 | Bayer Materialscience Ag | Silangruppenhaltige Reaktivverdünner |
DE102009042201A1 (de) | 2009-09-18 | 2011-04-14 | Bayer Materialscience Ag | Silangruppenhaltige Polyether |
DE102009043616A1 (de) | 2009-09-29 | 2011-03-31 | Bayer Materialscience Ag | Verfahren zur Herstellung von aminogruppenhaltigen Polyolen |
HUE044164T2 (hu) | 2009-10-19 | 2019-10-28 | Basf Se | Kettõs fém-cianid katalizátorok kondicionálása |
EP2490728A1 (de) | 2009-10-21 | 2012-08-29 | Bayer Materialscience AG | Bioabbaubares hydrogel |
WO2011067057A1 (de) | 2009-11-03 | 2011-06-09 | Bayer Materialscience Ag | Verfahren zur herstellung eines holographischen films |
IN2012DN03891A (zh) | 2009-11-03 | 2015-09-04 | Bayer Materialscience Ag | |
ATE548730T1 (de) | 2009-11-03 | 2012-03-15 | Bayer Materialscience Ag | Photopolymerformulierungen mit einstellbarem mechanischem modul guv |
EP2497083B1 (de) | 2009-11-03 | 2013-12-25 | Bayer Intellectual Property GmbH | Photopolymer-formulierung mit verschiedenen schreibcomonomeren |
KR101746886B1 (ko) | 2009-11-03 | 2017-06-27 | 코베스트로 도이칠란드 아게 | 홀로그래픽 매체의 제조 방법 |
WO2011071492A1 (en) | 2009-12-09 | 2011-06-16 | Dow Global Technologies Llc | Polyether derivatives of secondary hydroxy fatty acids and derivatives thereof |
WO2011075343A1 (en) | 2009-12-17 | 2011-06-23 | Dow Global Technologies Inc. | Ethylene oxide capping of secondary hydroxyl polyols |
SG182437A1 (en) | 2010-01-20 | 2012-08-30 | Bayer Ip Gmbh | Method for activating double metal cyanide catalysts for producing polyether carbonate polyols |
DE102010008410A1 (de) | 2010-02-18 | 2011-08-18 | Bayer MaterialScience AG, 51373 | Verfahren zur Herstellung von Polyethercarbonatpolyolen |
CN102782100A (zh) * | 2010-02-26 | 2012-11-14 | 陶氏环球技术有限责任公司 | 可用作生物润滑剂的酸酐衍生物 |
EP2365019A1 (de) | 2010-03-13 | 2011-09-14 | Bayer MaterialScience AG | Verfahren zur Herstellung von Polyetherpolyolen |
US20110230581A1 (en) | 2010-03-17 | 2011-09-22 | Bayer Materialscience Llc | Process for the production of polyether polyols with a high ethylene oxide content |
ES2587257T3 (es) | 2010-03-24 | 2016-10-21 | Covestro Deutschland Ag | Procedimiento para la preparación de polioletercarbonatos |
EP2372454A1 (de) | 2010-03-29 | 2011-10-05 | Bayer MaterialScience AG | Photopolymer-Formulierung zur Herstellung sichtbarer Hologramme |
ES2719589T3 (es) | 2010-04-29 | 2019-07-11 | Dow Global Technologies Llc | Polioles híbridos de poliéster y poliéter |
EP2563838A1 (en) | 2010-04-29 | 2013-03-06 | Dow Global Technologies LLC | Oligomerized ester alkoxylate compositions |
US9115246B2 (en) | 2010-04-30 | 2015-08-25 | Basf Se | Polyether polyols, process for preparing polyether polyols and their use for producing polyurethanes |
MX2012012596A (es) | 2010-04-30 | 2013-05-06 | Basf Se | Polioles de polieter, proceso para preparar polioles de polieter y su uso para producir poliuretanos. |
DE102010019504A1 (de) | 2010-05-06 | 2011-11-10 | Bayer Materialscience Ag | Polyisocyanatprepolymere und deren Verwendung |
KR101902018B1 (ko) | 2010-05-18 | 2018-09-27 | 바이엘 인텔렉쳐 프로퍼티 게엠베하 | 폴리에테르 카르보네이트 폴리올의 제조 방법 |
SA111320500B1 (ar) | 2010-06-04 | 2015-06-17 | داو جلوبال تكنولوجيز ال ال سي | معلقات لاستعادة محسنة للزيت |
WO2011160296A1 (en) | 2010-06-23 | 2011-12-29 | Basf Se | Modified double metal cyanide catalyst |
ES2534519T5 (es) | 2010-06-30 | 2020-12-29 | Dow Global Technologies Llc | Polímeros terminados en sililo |
WO2012004209A1 (de) | 2010-07-05 | 2012-01-12 | Bayer Materialscience Ag | Verfahren zur herstellung von polyolgemischen |
DE102010038774A1 (de) | 2010-08-02 | 2012-02-02 | Evonik Goldschmidt Gmbh | Modifizierte Alkoxylierungsprodukte, die zumindest eine nicht-terminale Alkoxysilylgruppe aufweisen, mit erhöhter Lagerstabilität und erhöhter Dehnbarkeit der unter deren Verwendung hergestellten Polymere |
DE102010038768A1 (de) | 2010-08-02 | 2012-02-02 | Evonik Goldschmidt Gmbh | Modifizierte Alkoxylierungsprodukte mit mindestens einer nicht-terminalen Alkoxysilylgruppe mit erhöhter Lagerstabilität und erhöhter Dehnbarkeit der unter deren Verwendung hergestellten Polymere |
DE102010039090A1 (de) | 2010-08-09 | 2012-02-09 | Basf Se | Verfahren zur Herstellung von Polyetheralkoholen |
DE102010039140A1 (de) | 2010-08-10 | 2012-02-16 | Evonik Goldschmidt Gmbh | Dispergiermittel und Verfahren zu deren Herstellung |
WO2012022048A1 (en) | 2010-08-20 | 2012-02-23 | Basf Se | Process for the preparation of polyetherester polyols |
DE102010040517A1 (de) | 2010-09-09 | 2012-03-15 | Bayer Materialscience Aktiengesellschaft | Verfahren zur Herstellung von Polyetherpolyolen |
EP2441788A1 (de) | 2010-10-14 | 2012-04-18 | Bayer MaterialScience AG | Verfahren zur Herstellung von Polyetherpolyolen |
AP3677A (en) | 2010-10-25 | 2016-04-16 | Stepan Co | Fatty amines, amidoamines, and their derivatives from natural oil metathesis |
AU2011323770B2 (en) | 2010-10-25 | 2015-07-16 | Stepan Company | Glyphosate formulations based on compositions derived from natural oil metathesis |
CN103201254B (zh) | 2010-10-25 | 2016-01-20 | 斯特潘公司 | 来自天然油复分解的酯胺及衍生物 |
SG189516A1 (en) | 2010-10-25 | 2013-05-31 | Stepan Co | Fatty amides and derivatives from natural oil metathesis |
BR112013009946B1 (pt) | 2010-10-25 | 2019-04-30 | Stepan Company | Composição de sulfobetaina, betaina ou amônio quaternário, derivado; formulação de glifosato, composição de herbicida solúvel em água ou composição antimicrobiana, limpador de superfície áspera, formulação de detergente para vestuário sujo, xampu ou condicionador de cabelo ou produto de limpeza pessoal ou sabonete, inibidor de corrosão, dispersante de parafina, espumante de poço de gás, espumante, aditivo de espuma ou dispersante e emulsificante aniônico para composições agrícolas |
US9598359B2 (en) | 2010-10-25 | 2017-03-21 | Stepan Company | Sulfonates from natural oil metathesis |
MX341184B (es) | 2010-10-25 | 2016-08-09 | Stepan Co | Detergentes liquidos de trabajo ligero basados en composiciones derivadas de la metatesis de aceite natural. |
DK2633022T3 (en) | 2010-10-25 | 2019-04-23 | Stepan Co | DIFFICULT SURFACE CLEANERS BASED ON COMPOSITIONS DERIVED FROM NATURAL OIL METHODS |
ES2726054T3 (es) | 2010-10-25 | 2019-10-01 | Stepan Co | Esteres grasos alcoxilados y derivados de la metátesis del aceite natural |
WO2012061108A1 (en) | 2010-10-25 | 2012-05-10 | Stepan Company | Laundry detergents based on compositions derived from natural oil metathesis |
DE102010043409A1 (de) | 2010-11-04 | 2012-05-10 | Bayer Materialscience Aktiengesellschaft | Verfahren zur Herstellung von Polycarbonatpolyolen durch immortale Polymerisation von cyclischen Carbonaten |
EP2450387A1 (de) | 2010-11-08 | 2012-05-09 | Bayer MaterialScience AG | Photopolymer-Formulierung für die Herstellung holographischer Medien |
CN103314031B (zh) | 2010-11-09 | 2014-12-31 | 巴斯夫欧洲公司 | 聚醚酯多元醇 |
EP2465890A1 (de) | 2010-12-17 | 2012-06-20 | Bayer MaterialScience AG | Verfahren zur Herstellung von Polyethercarbonatpolyolen mit primären Hydroxyl-Endgruppen und daraus hergestellte Polyurethanpolymere |
MX345793B (es) | 2010-12-20 | 2017-02-16 | Bayer Ip Gmbh | Procedimiento para la preparacion de polioleteres. |
WO2012084760A1 (de) | 2010-12-20 | 2012-06-28 | Bayer Materialscience Ag | Verfahren zur herstellung von polyetheresterpolyolen |
CN103403061B (zh) | 2010-12-27 | 2016-06-01 | 陶氏环球技术有限责任公司 | 使用双金属氰化物催化剂络合物和镁、第3族-第15族金属或镧系金属化合物的环氧烷烃聚合反应 |
WO2012121997A1 (en) | 2011-03-04 | 2012-09-13 | Ppg Industries Ohio, Inc. | Polythiourethan based composite articles |
KR101404702B1 (ko) | 2011-03-08 | 2014-06-17 | 에스케이이노베이션 주식회사 | 에테르 결합 단위체를 함유한 이산화탄소/에폭사이드 공중합체의 제조 방법 |
MY163273A (en) | 2011-03-09 | 2017-08-30 | Benefuel Inc | Systems and methods for making bioproducts |
CN103764703A (zh) | 2011-03-28 | 2014-04-30 | 拜耳知识产权有限责任公司 | 制造聚氨酯-软质泡沫材料的方法 |
WO2012136658A1 (de) | 2011-04-04 | 2012-10-11 | Henkel Ag & Co. Kgaa | Katalysator zur epoxidpolymerisation und zur copolymerisation von epoxid mit kohlendioxid |
EP2511314A1 (de) | 2011-04-12 | 2012-10-17 | Bayer MaterialScience AG | Polyurethanpolymer und dessen Verwendung in elektromechanischen Wandlern |
WO2012158645A1 (en) | 2011-05-16 | 2012-11-22 | Stepan Company | Surfactants for enhanced oil recovery |
SA112330512B1 (ar) | 2011-05-17 | 2016-11-17 | ريبسول، اس. ايه. | عملية لتحضير مُحفِّز من مُعقَّد سيانيدي مزدوج المعدن |
DE102011076019A1 (de) | 2011-05-18 | 2012-11-22 | Evonik Goldschmidt Gmbh | Alkoxylierungsprodukte und Verfahren zu ihrer Herstellung mittels DMC-Katalysatoren |
EP2530101A1 (de) | 2011-06-01 | 2012-12-05 | Bayer MaterialScience AG | Verfahren zur Herstellung von Polyetherpolyolen |
CA2840520A1 (en) | 2011-06-30 | 2013-01-03 | Bayer Intellectual Property Gmbh | Process for preparing high molecular weight polyether polyols |
PT2543689T (pt) | 2011-07-04 | 2016-09-22 | Repsol Sa | Método contínuo para a síntese de polióis |
EP2548906A1 (de) | 2011-07-18 | 2013-01-23 | Bayer MaterialScience AG | Verfahren zur Aktivierung von Doppelmetallcyanidkatalysatoren zur Herstellung von Polyetherpolyolen |
EP2548908A1 (de) | 2011-07-18 | 2013-01-23 | Bayer MaterialScience AG | Verfahren zur Herstellung von Polyetherpolyolen |
EP2548905A1 (de) | 2011-07-18 | 2013-01-23 | Bayer MaterialScience AG | Verfahren zur Aktivierung von Doppelmetallcyanidkatalysatoren zur Herstellung von Polyetherpolyolen |
EP2548907A1 (de) | 2011-07-18 | 2013-01-23 | Bayer MaterialScience AG | Verfahren zur Herstellung von Polyetherpolyolen |
WO2013014126A1 (de) | 2011-07-26 | 2013-01-31 | Bayer Intellectual Property Gmbh | Veretherte laktatester, verfahren zu ihrer herstellung und ihre verwendung zur verbesserung der wirkung von pflanzenschutzmitteln |
DE102011109541A1 (de) | 2011-08-03 | 2013-02-07 | Evonik Goldschmidt Gmbh | Verwendung von Polysiloxanen enthaltend verzweigte Polyetherreste zur Herstellung von Polyurethanschäumen |
DE102011109545A1 (de) | 2011-08-03 | 2013-02-07 | Evonik Goldschmidt Gmbh | Verfahren zur Herstellung von Polyethersiloxanen enthaltend Polyethercarbonatgrundstrukturen |
KR101909320B1 (ko) | 2011-08-25 | 2018-10-17 | 다우 글로벌 테크놀로지스 엘엘씨 | 이중 금속 시아니드 촉매의 존재 하에 에틸렌 카르보네이트의 중합에 의한 옥시에틸렌 단위를 갖는 폴리에테르 알콜의 제조 방법 |
US20140255824A1 (en) | 2011-10-12 | 2014-09-11 | Bayer Intellectual Property Gmbh | Sulphur-containing chain transfer reagents in polyurethane-based photopolymer formulations |
EP2766903A1 (de) | 2011-10-12 | 2014-08-20 | Bayer Intellectual Property GmbH | Kettenübertragungsreagenzien in polyurethan-basierten photopolymer-formulierungen |
US9650588B2 (en) | 2011-10-28 | 2017-05-16 | Dow Global Technologies Llc | Compositions of hydrocarbon oils and oil soluble PAGS produced by DMC catalysts |
EP2604642A1 (de) | 2011-12-16 | 2013-06-19 | Bayer Intellectual Property GmbH | Verfahren zur Herstellung von Polyethercarbonatpolyolen |
EP2604641A1 (de) | 2011-12-16 | 2013-06-19 | Bayer Intellectual Property GmbH | Verfahren zur Herstellung von Polyetherestercarbonatpolyolen |
ES2846300T3 (es) | 2011-12-20 | 2021-07-28 | Adhesys Medical Gmbh | Prepolímero con funcionalidad isocianato para un adhesivo de tejido biodegradable |
EP2794798B1 (de) | 2011-12-20 | 2015-11-25 | Medical Adhesive Revolution GmbH | Hydroxy-aminopolymer und dessen verwendung in polyharnstoffpolyurethan-gewebeklebstoffen |
WO2013092501A1 (de) | 2011-12-20 | 2013-06-27 | Bayer Intellectual Property Gmbh | Hydroxy-aminopolymere und verfahren zu deren herstellung |
EP2802612B1 (de) | 2012-01-09 | 2016-04-06 | Medical Adhesive Revolution GmbH | Beta-aminosäureester modifizierte (aspartat-)härter und dessen verwendung in polyharnstoff-gewebeklebstoffen |
DE102012203737A1 (de) | 2012-03-09 | 2013-09-12 | Evonik Goldschmidt Gmbh | Modifizierte Alkoxylierungsprodukte, die zumindest eine nicht-terminale Alkoxysilylgruppe aufweisen und mehrere Urethangruppen enthalten und deren Verwendung |
AR090330A1 (es) | 2012-04-24 | 2014-11-05 | Stepan Co | Derivados de alcoholes grasos insaturados de la metatesis del aceite natural |
MY169208A (en) | 2012-04-24 | 2019-03-18 | Stepan Co | Unsaturated fatty alcohol alkoxylates from natural oil metathesis |
EP2846935B1 (en) * | 2012-05-10 | 2017-07-26 | Basf Se | Alkoxylated alcohols and their use in formulations for hard surface cleaning |
EP2671893A1 (de) | 2012-06-06 | 2013-12-11 | Bayer MaterialScience AG | Verfahren zur Herstellung von Omega-Hydroxy-Aminopolymeren |
US9035105B2 (en) | 2012-07-20 | 2015-05-19 | Bayer Materialscience Llc | Process for the in situ production of polyether polyols based on renewable materials and their use in the production of flexible polyurethane foams |
EP2703426A1 (de) | 2012-08-27 | 2014-03-05 | Bayer MaterialScience AG | Verfahren zur Herstellung von Polyethercarbonatpolyolen |
EP2703425A1 (de) | 2012-08-27 | 2014-03-05 | Bayer MaterialScience AG | Verfahren zur Herstellung von Polyethercarbonatpolyolen |
DE102012218846A1 (de) | 2012-10-16 | 2014-04-17 | Bayer Materialscience Ag | Herstellung und Verwendung neuer thermoplastischer Polyurethan-Elastomere auf Basis von Polyethercarbonatpolyolen |
DE102012218848A1 (de) | 2012-10-16 | 2014-04-17 | Bayer Materialscience Ag | Herstellung und Verwendung neuer thermoplastischer Polyurethan-Elastomere auf Basis von Polyethercarbonatpolyolen |
EP2725044B1 (de) | 2012-10-24 | 2017-06-21 | Covestro Deutschland AG | Alkoxysilanterminiertes Präpolymer auf Basis von Polyethercarbonatpolyolen für Sprühschäume |
EP2730602A1 (de) | 2012-11-09 | 2014-05-14 | Bayer MaterialScience AG | Verfahren zur Herstellung von Polyethercarbonatpolyolen |
KR20150084820A (ko) | 2012-11-09 | 2015-07-22 | 바이엘 머티리얼사이언스 아게 | 폴리에테르 카르보네이트 폴리올의 제조 방법 |
US9568643B2 (en) | 2012-12-13 | 2017-02-14 | Ppg Industries Ohio, Inc. | Polyurethane urea-containing compositions and optical articles and methods for preparing them |
US9562134B2 (en) | 2013-03-12 | 2017-02-07 | Covestro Llc | Catalyst for the production of polyols having lower amounts of high molecular weight tail |
PL2967033T3 (pl) | 2013-03-13 | 2020-01-31 | Stepan Company | Środki powierzchniowo czynne na bazie jednonienasyconych pochodnych alkoholi tłuszczowych |
US9051412B2 (en) | 2013-03-14 | 2015-06-09 | Bayer Materialscience Llc | Base-catalyzed, long chain, active polyethers from short chain DMC-catalyzed starters |
US9890100B2 (en) | 2013-03-14 | 2018-02-13 | Covestro Llc | Continuous process for the production of low molecular weight polyethers with a DMC catalyst |
US10669368B2 (en) | 2013-03-15 | 2020-06-02 | Covestro Llc | Method to increase the resistance of double metal cyanide catalysts to deactivation |
US8987396B2 (en) | 2013-03-15 | 2015-03-24 | Bayer Materialscience Llc | Active polymer polyols and a process for their production |
DE102013206175A1 (de) | 2013-04-09 | 2014-10-09 | Evonik Industries Ag | Polysiloxan-Polyether-Copolymere mit Amino- und/oder quaternären Ammoniumgruppen im Polyetherteil und Verfahren zu deren Herstellung |
US10513667B2 (en) | 2013-04-17 | 2019-12-24 | The Lubrizol Corporation | 2-stroke internal combustion engine cylinder liner lubricating composition |
DE102013208328A1 (de) | 2013-05-07 | 2014-11-13 | Evonik Industries Ag | Polyoxyalkylene mit seitenständigen langkettigen Acyloxyresten und Verfahren zu ihrer Herstellung mittels DMC-Katalysatoren |
ES2627002T3 (es) | 2013-06-13 | 2017-07-26 | Covestro Deutschland Ag | Copolímeros de bloques de polietercarbonato-polioximetileno |
US9815965B2 (en) | 2013-08-02 | 2017-11-14 | Covestro Deutschland Ag | Method for producing polyether carbonate polyols |
DE102013216751A1 (de) | 2013-08-23 | 2015-02-26 | Evonik Industries Ag | Modifizierte Alkoxylierungsprodukte, die Alkoxysilylgruppen aufweisen und Urethangruppen enthalten und deren Verwendung |
EP2845871A1 (de) | 2013-09-05 | 2015-03-11 | Bayer MaterialScience AG | Vernetzung von Doppelbindungen enthaltenden Polyethercarbonatpolyolen durch Addition von Mercaptanen |
EP2845872A1 (de) | 2013-09-05 | 2015-03-11 | Bayer MaterialScience AG | Niederviskose Polyethercarbonatpolyole mit Seitenketten |
EP2845873A1 (de) | 2013-09-05 | 2015-03-11 | Bayer MaterialScience AG | Radikalische Vernetzung von Polyethercarbonatpolyolen enthaltend elektronenarme und elektronenreiche Doppelbindungen |
CN105473638B (zh) | 2013-09-05 | 2018-01-26 | 科思创德国股份公司 | 使用支化剂分子获得的较高官能的聚醚碳酸酯多元醇 |
EP2851384A1 (de) | 2013-09-20 | 2015-03-25 | Bayer MaterialScience AG | Verzweigte Polyethercarbonatpolyole und Verfahren zu deren Herstellung |
EP2865700A1 (de) | 2013-10-23 | 2015-04-29 | Bayer MaterialScience AG | Verfahren zur Herstellung von Polyethercarbonatpolyolen |
US20160237367A1 (en) | 2013-10-29 | 2016-08-18 | Dow Brasil Sudeste Industrial Ltda. | Lubricant composition and a method to lubricate a mechanical device |
EP2876121A1 (de) | 2013-11-22 | 2015-05-27 | Bayer MaterialScience AG | Einsatz von Urethan-Alkoholen zur Herstellung von Polyetherpolyolen |
EP3077437A1 (de) | 2013-11-27 | 2016-10-12 | Covestro Deutschland AG | Mischungen von polyethercarbonatpolyolen und polyetherpolyolen zur herstellung von polyurethanweichschaumstoffen |
EP2886572A1 (de) | 2013-12-17 | 2015-06-24 | Bayer MaterialScience AG | Einsatz von Urethan-Alkoholen zur Herstellung von Polyethercarbonatpolyolen |
MX2016007549A (es) | 2013-12-18 | 2016-10-03 | Covestro Deutschland Ag | Metodo de elaboracion de polioles de polieter alcalinos. |
EP2894180A1 (en) | 2014-01-08 | 2015-07-15 | Bayer MaterialScience AG | Polymer Polyols comprising a Polyether Carbonate Polyol as the Base Polyol |
EP2910585B1 (de) | 2014-02-21 | 2018-07-04 | Covestro Deutschland AG | Schotterkörper sowie Verfahren zur Herstellung von Schotterkörpern |
SG11201608076RA (en) | 2014-04-07 | 2016-11-29 | Covestro Deutschland Ag | Process for the production of polyoxymethylene block copolymers |
WO2015162125A1 (de) | 2014-04-24 | 2015-10-29 | Bayer Material Science Ag | Polyurethanschaumstoffe basierend auf polyethercarbonatpolyolen |
US9527958B2 (en) | 2014-05-02 | 2016-12-27 | Covestro Llc | Process for purification of polyether carbonate polyols |
DE102014209355A1 (de) | 2014-05-16 | 2015-11-19 | Evonik Degussa Gmbh | Guanidinhaltige Polyoxyalkylene und Verfahren zur Herstellung |
DE102014209408A1 (de) | 2014-05-19 | 2015-11-19 | Evonik Degussa Gmbh | Ethoxylatherstellung unter Verwendung hoch aktiver Doppelmetallcyanid-Katalysatoren |
EP3152286B1 (en) | 2014-06-09 | 2020-01-22 | Stepan Company | Detergents for cold-water cleaning |
US10669380B2 (en) | 2014-07-30 | 2020-06-02 | Basf Se | Amphiphilic star-like polyether |
DE102014217790A1 (de) | 2014-09-05 | 2016-03-10 | Evonik Degussa Gmbh | Verfahren zur Herstellung von hydrosilylierbaren Eugenol-Polyethern und Eugenol-Polyethersiloxanen sowie deren Verwendung |
US10358526B2 (en) | 2014-09-23 | 2019-07-23 | Covestro Deutschland Ag | Moisture-curing polyether carbonate containing alkoxysilyl groups |
EP3023447A1 (de) | 2014-11-18 | 2016-05-25 | Covestro Deutschland AG | Verfahren zur Herstellung von Polyethercarbonatpolyolen |
CN107075158B (zh) | 2014-12-01 | 2021-01-01 | 陶氏环球技术有限责任公司 | 作为表面改性剂的聚烯烃多元醇 |
MX2017008863A (es) | 2015-01-08 | 2017-10-11 | Stepan Co | Detergentes para lavanderia con agua fria. |
EP3050907A1 (de) | 2015-01-28 | 2016-08-03 | Covestro Deutschland AG | Verfahren zur Herstellung von Polyethercarbonatpolyolen |
US20160244549A1 (en) | 2015-02-25 | 2016-08-25 | Bayer Materialscience Llc | Alkoxysilane-group modified polyurethanes and low modulus sealants formed therefrom |
EP3262090A1 (de) | 2015-02-27 | 2018-01-03 | Covestro Deutschland AG | Verwendung von polyethercarbonatpolyolen zur erzeugung farbstabiler polyurethanschaumstoffe |
EP3067376A1 (de) | 2015-03-11 | 2016-09-14 | Evonik Degussa GmbH | Herstellung von Polyurethansystemen unter Einsatz von Polyetherpolycarbonatpolyolen |
US9951174B2 (en) | 2015-05-20 | 2018-04-24 | Covestro Llc | Polyol compositions, a process for the production of these polyol compositions, and their use in the production of open celled polyurethane foams having high airflow |
EP3098251A1 (de) | 2015-05-26 | 2016-11-30 | Covestro Deutschland AG | Einsatz von alkoholen, die mindestens zwei urethangruppen enthalten, zur herstellung von polyetherpolyolen |
EP3098250A1 (de) | 2015-05-26 | 2016-11-30 | Covestro Deutschland AG | Verfahren zur herstellung von polyethercarbonatpolyolen |
DE102015108232A1 (de) | 2015-05-26 | 2016-12-01 | Franken Systems Gmbh | Verfahren zur feuchtigkeitsbeständigen Grundierung von mineralischen Untergründen |
EP3098252A1 (de) | 2015-05-26 | 2016-11-30 | Covestro Deutschland AG | Einsatz von alkoholen, die mindestens zwei urethangruppen enthalten, zur herstellung von polyethercarbonatpolyolen |
DE102015110841A1 (de) | 2015-07-06 | 2017-01-12 | Franken Systems Gmbh | Verwendung eines Reaktivsystems zur Bauwerksabdichtung und eine Bauwerksabdichtung |
SG11201801151YA (en) | 2015-08-26 | 2018-03-28 | Covestro Deutschland Ag | Method for producing high molecular weight polyoxyalkylene polyols |
GB201515350D0 (en) | 2015-08-28 | 2015-10-14 | Econic Technologies Ltd | Method for preparing polyols |
EP3138867B1 (de) | 2015-09-03 | 2019-10-02 | Evonik Degussa GmbH | Verwendung von eugenol-polyethern und eugenol-polyethersiloxanen als netzmittel |
CA3004385A1 (en) | 2015-11-19 | 2017-05-26 | Covestro Deutschland Ag | Polyurethane foams based on polyether carbonate polyols |
US9745259B2 (en) | 2015-12-04 | 2017-08-29 | Chevron U.S.A. Inc. | Process for preparing alcohol ether sulfates |
EP3178858A1 (de) | 2015-12-09 | 2017-06-14 | Covestro Deutschland AG | Polyurethanschaumstoffe basierend auf polyethercarbonatpolyolen |
US11345775B2 (en) | 2015-12-09 | 2022-05-31 | Covestro Deutschland Ag | Polyurethane foams based on polyethercarbonate polyols |
US9562135B1 (en) | 2015-12-21 | 2017-02-07 | Covestro Llc | Polyether carbonates by DMC catalysis |
EP3219741A1 (de) | 2016-03-18 | 2017-09-20 | Covestro Deutschland AG | Verfahren zur herstellung von polyethercarbonatpolyolen |
US9994506B2 (en) | 2016-04-20 | 2018-06-12 | Covestro Llc | Process for transitioning reactors from base-catalyzed polyol production to DMC-catalyzed polyol production |
US11312811B2 (en) | 2016-04-26 | 2022-04-26 | Covestro Llc | Flexible foam using polymer polyols produced via DMC catalyzed polyols |
WO2017194709A1 (de) | 2016-05-13 | 2017-11-16 | Covestro Deutschland Ag | Verfahren zur herstellung von polyoxyalkylenpolyolen |
WO2017200737A1 (en) | 2016-05-20 | 2017-11-23 | Stepan Company | Polyetheramine compositions for laundry detergents |
EP3260483A1 (de) | 2016-06-22 | 2017-12-27 | Covestro Deutschland AG | Verfahren zur herstellung von polyethercarbonatpolyolen |
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 |
US10119223B2 (en) | 2016-07-15 | 2018-11-06 | Covestro Llc | Carpet and synthetic turf backings prepared from a polyether carbonate polyol |
US10258953B2 (en) | 2016-08-05 | 2019-04-16 | Covestro Llc | Systems and processes for producing polyether polyols |
US11312812B2 (en) | 2016-10-12 | 2022-04-26 | Covestro Deutschland Ag | Process for producing elastomers |
US11098153B2 (en) | 2016-10-12 | 2021-08-24 | Covestro Deutschland Ag | Method for producing a multiple bond-containing prepolymer as elastomer precursor |
EP3330307A1 (de) | 2016-12-05 | 2018-06-06 | Covestro Deutschland AG | Verwendung von acrylsäureestern und amiden zur erniedrigung von emissionen eines polyurethanschaumstoffes |
EP3330308A1 (de) | 2016-12-05 | 2018-06-06 | Covestro Deutschland AG | Verfahren zur herstellung von tdi-basierten polyurethanweichschaumstoffen enthaltend organische säureanhydride und/oder organische säurechloride |
EP3336137A1 (de) | 2016-12-19 | 2018-06-20 | Covestro Deutschland AG | Verwendung von physikalischen treibmitteln zur erzeugung von polyethercarbonatpolyol-basierten polyurethanschaumstoffen mit reduzierter emission von cyclischem propylencarbonat |
EP3336130A1 (de) | 2016-12-19 | 2018-06-20 | Covestro Deutschland AG | Verfahren zur herstellung von polyetherthiocarbonatpolyolen |
EP3336115A1 (de) | 2016-12-19 | 2018-06-20 | Covestro Deutschland AG | Verfahren zur erniedrigung von emissionen eines polyurethanschaumstoffes |
GB201703324D0 (en) | 2017-03-01 | 2017-04-12 | Econic Tech Ltd | Method for preparing polyether carbonates |
CN110402263B (zh) | 2017-03-15 | 2022-06-07 | 科思创有限公司 | 具有降低的温度敏感性的粘弹性聚氨酯泡沫 |
EP3385295A1 (de) | 2017-04-05 | 2018-10-10 | Covestro Deutschland AG | Flammgeschützte phosphorfunktionelle polyethercarbonatpolyole und verfahren zu deren herstellung |
EP3409704A1 (de) | 2017-06-01 | 2018-12-05 | Covestro Deutschland AG | Polyurethanschaumstoffe basierend auf polyethercarbonatpolyolen |
EP3424967A1 (de) | 2017-07-07 | 2019-01-09 | Covestro Deutschland AG | Verfahren zur herstellung von funktionalisierten polyoxyalkylenpolyolen |
JP6948057B2 (ja) * | 2017-08-30 | 2021-10-13 | 公立大学法人大阪 | 有機リン化合物分解触媒 |
EP3461852A1 (de) | 2017-09-28 | 2019-04-03 | Covestro Deutschland AG | Verfahren zur herstellung eines mehrfachbindungen enthaltenden polymers als elastomer-vorstufe |
AU2018348031B2 (en) | 2017-10-10 | 2023-11-23 | Stepan Company | Polymeric dispersants from phenyl glycidyl ether |
AU2018346935A1 (en) | 2017-10-10 | 2020-04-16 | Stepan Company | Polymeric dispersants from aralkylated phenols |
WO2019076862A1 (de) | 2017-10-18 | 2019-04-25 | Covestro Deutschland Ag | Diblockcopolymere und deren verwendung als tenside |
EP3473658A1 (de) | 2017-10-18 | 2019-04-24 | Covestro Deutschland AG | Diblockcopolymere und deren verwendung als tenside |
GB201717441D0 (en) | 2017-10-24 | 2017-12-06 | Econic Tech Ltd | A polymerisation process |
GB201717459D0 (en) | 2017-10-24 | 2017-12-06 | Econic Tech Limited | Methods for forming polycarbonate ether polyols and high molecular weight polyether carbonates |
US20190119444A1 (en) | 2017-10-25 | 2019-04-25 | Covestro Llc | Process to remove dmc catalysts from polyether carbonate polyols |
US10766998B2 (en) | 2017-11-21 | 2020-09-08 | Covestro Llc | Flexible polyurethane foams |
EP3489278A1 (de) | 2017-11-23 | 2019-05-29 | Covestro Deutschland AG | Hochmolekulare polyoxyalkylene mit tiefer glastemperatur hergestellt nach der grafting-through-methode |
US11602740B2 (en) | 2017-12-19 | 2023-03-14 | Oriental Union Chemical Corp. | High-activity double-metal-cyanide catalyst |
US11919844B2 (en) | 2017-12-19 | 2024-03-05 | Oriental Union Chemical Corp. | Method for fabricating polyols |
EP3502162A1 (de) | 2017-12-19 | 2019-06-26 | Covestro Deutschland AG | Verfahren zur herstellung von polyetheresterpolyolen |
US20190185399A1 (en) | 2017-12-19 | 2019-06-20 | Oriental Union Chemical Corp. | High-activity double-metal-cyanide catalyst, method for fabricating the same, and applications of the same |
EP3527606A1 (de) | 2018-02-16 | 2019-08-21 | Covestro Deutschland AG | Verfahren zur herstellung von polyethercarbonatpolyolen |
EP3533815A1 (de) | 2018-02-28 | 2019-09-04 | Covestro Deutschland AG | Polyurethanweichschaumstoffe auf basis von polyoxymethylen-polyoxyalkylen-blockcopolymeren |
EP3536727A1 (de) | 2018-03-07 | 2019-09-11 | Covestro Deutschland AG | Polyurethanschaumstoffe basierend auf polyethercarbonatpolyolen |
US20200399466A1 (en) | 2018-03-07 | 2020-12-24 | Covestro Intellectual Property Gmbh & Co. Kg | Polyurethane foams based on polyethercarbonate polyols |
EP3543268A1 (de) | 2018-03-22 | 2019-09-25 | Covestro Deutschland AG | Verfahren zur herstellung von polyurethanweichschaumstoffen |
WO2019180156A1 (de) | 2018-03-22 | 2019-09-26 | Covestro Deutschland Ag | Verfahren zur herstellung von polyurethanweichschaumstoffen mit hoher rohdichte |
EP3549969A1 (de) | 2018-04-06 | 2019-10-09 | Covestro Deutschland AG | Polyurethanschaumstoffe basierend auf polyethercarbonatpolyolen |
JP2021522382A (ja) | 2018-04-25 | 2021-08-30 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンHenkel AG & Co. KGaA | ヒドロキシル官能化ポリエーテルポリシロキサンブロックコポリマーの調製用プロセス |
EP3567067A1 (de) | 2018-05-08 | 2019-11-13 | Covestro Deutschland AG | Abtrennung von doppelmetallcyanid-katalysator |
JP7485619B2 (ja) | 2018-06-19 | 2024-05-16 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン | 高活性複合金属シアン化物化合物 |
EP3587469A1 (de) | 2018-06-22 | 2020-01-01 | Covestro Deutschland AG | Verfahren zur herstellung von polyol |
EP3597690A1 (de) | 2018-07-19 | 2020-01-22 | Covestro Deutschland AG | Heterocyclen-funktionelle polyether oder polyethercarbonate und verfahren zu deren herstellung |
EP3604320A1 (de) | 2018-08-01 | 2020-02-05 | Covestro Deutschland AG | Phosphorfunktionelle polyoxyalkylenpolyole und verfahren zu deren herstellung |
EP3608348A1 (de) | 2018-08-07 | 2020-02-12 | Covestro Deutschland AG | Verfahren zur herstellung eines organooxysilyl-vernetzten polymers |
EP3608018A1 (de) | 2018-08-08 | 2020-02-12 | Covestro Deutschland AG | Verfahren zur herstellung von doppelmetallcyanid-katalysatoren |
EP3617248A1 (de) | 2018-08-30 | 2020-03-04 | Covestro Deutschland AG | Verfahren zur abtrennung von gasförmigen bestandteilen |
RU2677659C1 (ru) * | 2018-09-03 | 2019-01-18 | Публичное Акционерное Общество "Нижнекамскнефтехим" | Способ получения твердого двойного кобальтцианидного катализатора полимеризации пропиленоксида |
RU2687105C1 (ru) * | 2018-09-03 | 2019-05-07 | Публичное Акционерное Общество "Нижнекамскнефтехим" | Способ получения простого полиэфира с высокой молекулярной массой на основе пропиленоксида на двойном кобальтцианидном катализаторе |
GB201814526D0 (en) | 2018-09-06 | 2018-10-24 | Econic Tech Ltd | Methods for forming polycarbonate ether polyols and high molecular weight polyether carbonates |
US10793692B2 (en) | 2018-10-24 | 2020-10-06 | Covestro Llc | Viscoelastic flexible foams comprising hydroxyl-terminated prepolymers |
EP3643730A1 (de) | 2018-10-26 | 2020-04-29 | Covestro Deutschland AG | Verfahren zur herstellung von polyoxymethylen-polyoxyalkylen-blockcopolymeren |
EP3656797A1 (de) | 2018-11-22 | 2020-05-27 | Covestro Deutschland AG | Verfahren zur herstellung von polyoxymethylen-polyalkylenoxid-blockcopolymeren |
EP3663372B1 (en) | 2018-12-06 | 2024-03-13 | Henkel AG & Co. KGaA | Curable composition comprising polysiloxane polyalkyleneglycol brush copolymers |
EP3663371B1 (en) | 2018-12-06 | 2024-03-13 | Henkel AG & Co. KGaA | Preparation of polysiloxane polyalkyleneglycol brush copolymers |
US10738155B2 (en) | 2018-12-19 | 2020-08-11 | Covestro Llc | Product-to-product process for preparation of low viscosity polyoxyalkylene polyols |
US10961347B2 (en) | 2018-12-19 | 2021-03-30 | Covestro Llc | Process for preparing polyoxyalkylene polyols by the continuous addition of starter |
US10723829B2 (en) | 2018-12-19 | 2020-07-28 | Covestro Llc | Product-to-product process for preparation of low viscosity polyoxyalkylene polyols |
EP3670568A1 (de) | 2018-12-21 | 2020-06-24 | Covestro Deutschland AG | Verfahren zur herstellung eines polyesters |
EP3670571A1 (de) | 2018-12-21 | 2020-06-24 | Covestro Deutschland AG | Verfahren zur herstellung eines polyester-polyetherpolyol-blockcopolymers |
EP3670557A1 (de) | 2018-12-21 | 2020-06-24 | Covestro Deutschland AG | Verfahren zur herstellung eines polyoxyalkylenpolyesterpolyols |
EP3683251A1 (de) | 2019-01-15 | 2020-07-22 | Covestro Deutschland AG | Verfahren zur herstellung von diol |
CN113454134A (zh) | 2019-02-28 | 2021-09-28 | 科思创知识产权两合公司 | 用于生产聚氨酯整皮泡沫材料的异氰酸酯封端预聚物 |
EP3935038A1 (en) | 2019-03-08 | 2022-01-12 | Stepan Company | Reactive surfactants |
US10544158B1 (en) | 2019-03-14 | 2020-01-28 | Covestro Llc | Process for producing polycyclic polyether polyols |
US10723830B1 (en) | 2019-03-28 | 2020-07-28 | Covestro Llc | Product-to-product process for preparation of low viscosity polyoxyalkylene polyether polyols |
GB201906214D0 (en) | 2019-05-02 | 2019-06-19 | Econic Tech Ltd | A polyol block copolymer, compositions and processes therefor |
GB201906210D0 (en) | 2019-05-02 | 2019-06-19 | Econic Tech Limited | A polyol block copolymer, compositions and processes therefor |
EP3741788A1 (de) | 2019-05-24 | 2020-11-25 | Covestro Deutschland AG | Verfahren zur herstellung von polyoxyalkylenpolyol-mischungen |
EP3747927A1 (de) * | 2019-06-05 | 2020-12-09 | Covestro Deutschland AG | Verfahren zur kontinuierlichen herstellung von polyoxyalkylenpolyolen |
US20220227928A1 (en) | 2019-06-11 | 2022-07-21 | Covestro Intellectual Property Gmbh & Co. Kg | Method for preparing polyether carbonate polyols |
EP3750940A1 (de) | 2019-06-11 | 2020-12-16 | Covestro Deutschland AG | Verfahren zur herstellung von polyethercarbonatpolyolen |
EP3760663A1 (de) | 2019-07-05 | 2021-01-06 | Covestro Deutschland AG | Verfahren zur herstellung von polyetherestercarbonatpolyolen |
EP3763768A1 (de) | 2019-07-12 | 2021-01-13 | Covestro Deutschland AG | Polyethercarbonatpolyole mit enger segmentlängenverteilung |
CN114144451A (zh) | 2019-07-31 | 2022-03-04 | 科思创德国股份有限公司 | 制备聚醚碳酸酯多元醇的方法 |
EP3771724A1 (de) | 2019-07-31 | 2021-02-03 | Covestro Deutschland AG | Verfahren zur herstellung von polyethercarbonatpolyolen |
WO2021071808A1 (en) | 2019-10-09 | 2021-04-15 | Covestro Llc | Methods, systems and computer program products for producing polyurethane foam products using optical and infrared imaging |
EP3831867A1 (de) | 2019-12-04 | 2021-06-09 | Covestro Deutschland AG | Verfahren zur herstellung von polyethercarbonatpolyolen |
WO2021110691A1 (de) | 2019-12-04 | 2021-06-10 | Covestro Intellectual Property Gmbh & Co. Kg | Verfahren zur herstellung von polyethercarbonatpolyolen |
EP3838963A1 (de) | 2019-12-17 | 2021-06-23 | Covestro Deutschland AG | Verfahren zur herstellung von polyoxyalkylenpolyesterpolyolen |
EP3838938A1 (de) | 2019-12-18 | 2021-06-23 | Covestro Deutschland AG | Verfahren zur herstellung von polyoxymethylen-polyoxyalkylen-copolymeren |
EP3838964A1 (de) | 2019-12-18 | 2021-06-23 | Covestro Deutschland AG | Polyurethanschaumstoffe basierend auf polyethercarbonatpolyolen |
KR102395484B1 (ko) * | 2020-01-03 | 2022-05-06 | 부산대학교 산학협력단 | 이중금속시안염 촉매, 이의 제조방법 및 폴리올 제조 방법 |
EP4093539B1 (de) | 2020-01-21 | 2023-10-04 | Covestro Deutschland AG | Verfahren zur herstellung von doppelmetallcyanid-katalysatoren |
US20210238361A1 (en) | 2020-01-30 | 2021-08-05 | Evonik Operations Gmbh | Process for producing high-purity hydrosilylation products |
MX2022009296A (es) * | 2020-01-31 | 2022-08-15 | Dow Global Technologies Llc | Proceso de separacion de catalizadores. |
US20230046210A1 (en) | 2020-02-22 | 2023-02-16 | Covestro Deutschland Ag | Process for preparing double metal cyanide catalysts |
GB202003003D0 (en) | 2020-03-02 | 2020-04-15 | Econic Tech Ltd | A polyol block copolymer |
GB202003002D0 (en) | 2020-03-02 | 2020-04-15 | Crane Ltd | Method of preparation of a polyol block copolymer |
EP3878885A1 (de) | 2020-03-10 | 2021-09-15 | Covestro Deutschland AG | Verfahren zur herstellung von polyethercarbonatpolyolen |
EP3882297A1 (de) | 2020-03-17 | 2021-09-22 | Covestro Deutschland AG | Verfahren zur herstellung von polyethercarbonatpolyolen |
EP3885390A1 (de) | 2020-03-25 | 2021-09-29 | Covestro Deutschland AG | Verfahren zur herstellung eines etheresterols |
EP3889204A1 (de) | 2020-04-02 | 2021-10-06 | Covestro Deutschland AG | Verfahren zur herstellung eines polyoxyalkylencarbonatpolyols |
EP3892660A1 (de) | 2020-04-08 | 2021-10-13 | Covestro Deutschland AG | Polyurethanschaumstoffe basierend auf polyethercarbonatpolyolen |
EP3916055A1 (de) | 2020-05-26 | 2021-12-01 | Covestro Deutschland AG | Polycarbonat-zusammensetzungen enthaltend polyethercarbonatpolyole |
EP3922660A1 (de) | 2020-06-08 | 2021-12-15 | Covestro Deutschland AG | Verfahren zur herstellung von polyethercarbonatpolyolen |
EP3922659A1 (de) | 2020-06-08 | 2021-12-15 | Covestro Deutschland AG | Verfahren zur herstellung von polyethercarbonatpolyolen |
EP3922661A1 (de) | 2020-06-12 | 2021-12-15 | Covestro Deutschland AG | Verfahren zur herstellung von polyoxymethylen-polyoxyalkylen-copolymeren |
EP3932973A1 (en) | 2020-07-01 | 2022-01-05 | Henkel AG & Co. KGaA | Bi-functionalized polysiloxane brush copolymers |
EP3960783A1 (de) | 2020-09-01 | 2022-03-02 | Covestro Deutschland AG | Isocyanat-terminierte prepolymere auf basis von polyoxymethylen-polyoxyalkylen-blockcopolymeren, verfahren zur deren herstellung und deren verwendung |
EP3988600A1 (de) | 2020-10-20 | 2022-04-27 | Covestro Deutschland AG | Verfahren zur herstellung von polyethercarbonatalkoholen |
GB202017531D0 (en) | 2020-11-05 | 2020-12-23 | Econic Tech Limited | (poly)ol block copolymer |
WO2022096390A1 (de) | 2020-11-06 | 2022-05-12 | Covestro Deutschland Ag | Verfahren zur herstellung eines polyol-gemisches |
US11898007B2 (en) | 2021-02-12 | 2024-02-13 | Council Of Scientific & Industrial Research | Double metal cyanide catalyst for the production of polyether polyols and a process thereof |
US11572433B2 (en) | 2021-03-12 | 2023-02-07 | Covestro Llc | In-situ formed polyols, a process for their preparation, foams prepared from these in-situ formed polyols and a process for their preparation |
WO2022189318A1 (de) | 2021-03-12 | 2022-09-15 | Covestro Deutschland Ag | Verfahren zur aufreinigung von cyclischen carbonaten |
US11866543B2 (en) | 2021-05-06 | 2024-01-09 | Covestro Llc | Glycidyl (meth)acrylate polymer polyol stabilizers |
EP4089127A1 (en) | 2021-05-12 | 2022-11-16 | Covestro Deutschland AG | Cast polyurethane elastomers and production thereof |
WO2022258570A1 (de) | 2021-06-10 | 2022-12-15 | Covestro Deutschland Ag | Verfahren zur herstellung von polyoxymethylen-polyoxyalkylen-copolymeren |
EP4101873A1 (de) | 2021-06-11 | 2022-12-14 | Covestro Deutschland AG | Einsatz von bismut-katalysatoren zur verringerung von cyclischem propylencarbonat bei der herstellung von weichschaumstoffen basierend auf polyethercarbonatpolyolen |
EP4112674A1 (de) | 2021-06-30 | 2023-01-04 | Evonik Operations GmbH | Verfahren zur herstellung hochreiner hydrosilylierungsprodukte |
US11718705B2 (en) | 2021-07-28 | 2023-08-08 | Covestro Llc | In-situ formed polyether polyols, a process for their preparation, and a process for the preparation of polyurethane foams |
US20230039276A1 (en) | 2021-07-28 | 2023-02-09 | Covestro Llc | Novel polyether polyol blends, a process for their preparation, foams prepared from these polyether polyol blends and a process for their preparation |
KR20240036722A (ko) | 2021-08-11 | 2024-03-20 | 에코닉 테크놀로지 엘티디 | 거대고리형 이원금속 촉매 및 이중 금속 시아나이드 촉매의 혼합물을 사용한 에폭사이드 및 co2의 공중합에 의한 계면활성제 제조 방법 |
EP4151669A1 (de) | 2021-09-15 | 2023-03-22 | Covestro Deutschland AG | Verfahren zur herstellung von polyethercarbonatpolyolen |
WO2023057328A1 (de) | 2021-10-07 | 2023-04-13 | Covestro Deutschland Ag | Verfahren zur herstellung von polyoxyalkylenpolyesterpolyolen |
US11952454B2 (en) | 2021-10-18 | 2024-04-09 | Covestro Llc | Processes and production plants for producing polymer polyols |
GB202115335D0 (en) | 2021-10-25 | 2021-12-08 | Econic Tech Ltd | Surface-active agent |
US20230147479A1 (en) | 2021-11-05 | 2023-05-11 | Covestro Llc | Processes and production plants for producing polyols |
EP4194476A1 (de) | 2021-12-07 | 2023-06-14 | Covestro Deutschland AG | Polyurethanschaumstoffe basierend auf polyethercarbonatpolyolen |
WO2023104708A1 (en) | 2021-12-08 | 2023-06-15 | Covestro Deutschland Ag | Polyurethane elastomer with improved hydrolysis resistance |
EP4219578A1 (de) | 2022-01-28 | 2023-08-02 | Covestro Deutschland AG | Herstellung von aliphatischen polyurethan-weichschaumstoffe in einem präpolymerverfahren basierend auf aliphatischen oligomeren polyisocyanaten und monohydroxyfunktionellen verbindungen |
EP4219576A1 (de) | 2022-01-28 | 2023-08-02 | Covestro Deutschland AG | Herstellung von aliphatischen polyurethan-polyisocyanuratschaumstoffen (pur-pir) unter verwendung eines katalysatorgemischs aus salzen organischer carbonsäuren und 1,1,3,3-tetraalkylguanidinen |
EP4219579A1 (de) | 2022-01-28 | 2023-08-02 | Covestro Deutschland AG | Herstellung von aliphatischen polyurethan-weichschaumstoffe in einem präpolymerverfahren basierend auf aliphatischen oligomeren polyisocyanaten und monohydroxyfunktionellen verbindungen |
WO2023144058A1 (de) | 2022-01-28 | 2023-08-03 | Covestro Deutschland Ag | Herstellung von aliphatischen polyurethan-weichschaumstoffen mit verkürzten abbindezeiten (klebfreizeiten) und steigzeiten |
EP4273185A1 (en) | 2022-05-04 | 2023-11-08 | PCC Rokita SA | Method for the manufacture of a polyether diol product |
EP4279534A1 (en) | 2022-05-20 | 2023-11-22 | PCC ROKITA Spolka Akcyjna | A method for producing low unsaturation level oxyalkylates, an oxyalkylate, a use thereof and a polyurethane foam |
EP4302874A1 (de) | 2022-07-04 | 2024-01-10 | Covestro Deutschland AG | Verfahren zur herstellung von doppelmetallcyanid-katalysatoren |
CN115710164A (zh) * | 2022-12-26 | 2023-02-24 | 常州大学 | 一种异壬醇聚氧乙烯醚的制备方法及其应用方法 |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3278459A (en) * | 1963-02-14 | 1966-10-11 | Gen Tire & Rubber Co | Method of making a polyether using a double metal cyanide complex compound |
US3278458A (en) * | 1963-02-14 | 1966-10-11 | Gen Tire & Rubber Co | Method of making a polyether using a double metal cyanide complex compound |
US3427256A (en) * | 1963-02-14 | 1969-02-11 | Gen Tire & Rubber Co | Double metal cyanide complex compounds |
US3427334A (en) * | 1963-02-14 | 1969-02-11 | Gen Tire & Rubber Co | Double metal cyanides complexed with an alcohol aldehyde or ketone to increase catalytic activity |
US3829505A (en) * | 1970-02-24 | 1974-08-13 | Gen Tire & Rubber Co | Polyethers and method for making the same |
CA1155871A (en) * | 1980-10-16 | 1983-10-25 | Gencorp Inc. | Method for treating polypropylene ether and poly-1,2- butylene ether polyols |
AU551979B2 (en) * | 1982-03-31 | 1986-05-15 | Shell Internationale Research Maatschappij B.V. | Epoxy polymerisation catalysts |
US4877906A (en) * | 1988-11-25 | 1989-10-31 | Arco Chemical Technology, Inc. | Purification of polyols prepared using double metal cyanide complex catalysts |
US5010047A (en) * | 1989-02-27 | 1991-04-23 | Arco Chemical Technology, Inc. | Recovery of double metal cyanide complex catalyst from a polymer |
JPH03149222A (ja) | 1989-11-07 | 1991-06-25 | Asahi Glass Co Ltd | ポリエーテル化合物の製造方法 |
JP2960460B2 (ja) * | 1990-03-06 | 1999-10-06 | 旭硝子株式会社 | ポリエーテル類の製造方法 |
JPH03281529A (ja) | 1990-03-29 | 1991-12-12 | Asahi Glass Co Ltd | ポリエーテル化合物の製造方法 |
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 |
JP2653236B2 (ja) * | 1990-10-05 | 1997-09-17 | 旭硝子株式会社 | ポリエーテル化合物の製造方法 |
JPH04314728A (ja) * | 1991-04-12 | 1992-11-05 | Asahi Glass Co Ltd | ポリエーテル類の製造方法 |
US5158922A (en) * | 1992-02-04 | 1992-10-27 | Arco Chemical Technology, L.P. | Process for preparing metal cyanide complex catalyst |
US5248833A (en) * | 1992-09-22 | 1993-09-28 | Arco Chemical Technology, L.P. | Process for purifying polyols made with double metal cyanide catalysts |
CA2138063C (en) * | 1993-12-23 | 2007-02-20 | Bi Le-Khac | Polyurethane foam-supported double metal cyanide catalysts for polyol synthesis |
-
1994
- 1994-09-08 US US08/302,296 patent/US5482908A/en not_active Expired - Lifetime
-
1995
- 1995-05-30 US US08/453,194 patent/US5536883A/en not_active Expired - Lifetime
- 1995-08-29 ES ES95305994T patent/ES2127997T3/es not_active Expired - Lifetime
- 1995-08-29 DE DE69508009T patent/DE69508009T2/de not_active Expired - Lifetime
- 1995-08-29 DK DK95305994T patent/DK0700949T3/da active
- 1995-08-29 EP EP95305994A patent/EP0700949B1/en not_active Expired - Lifetime
- 1995-08-29 AT AT95305994T patent/ATE177123T1/de not_active IP Right Cessation
- 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 KR KR1019950029366A patent/KR100355336B1/ko not_active IP Right Cessation
- 1995-09-07 AU AU30487/95A patent/AU688548B2/en not_active Ceased
- 1995-09-07 HU HU9502619A patent/HU215551B/hu active IP Right Revival
- 1995-09-07 RO RO95-01576A patent/RO111742B1/ro unknown
- 1995-09-08 BR BR9503975A patent/BR9503975A/pt not_active IP Right Cessation
- 1995-09-08 CN CN95118425A patent/CN1072687C/zh not_active Expired - Lifetime
- 1995-09-08 TW TW084109401A patent/TW401429B/zh not_active IP Right Cessation
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
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CN1325165C (zh) * | 2002-05-17 | 2007-07-11 | 中国石化集团金陵石油化工有限责任公司 | 连续法制备双金属氰化物络合催化剂工艺 |
CN103025792A (zh) * | 2010-05-27 | 2013-04-03 | 陶氏环球技术有限责任公司 | 一种生产含可交联甲硅烷基的聚氧化烯聚合物的方法 |
CN105924637A (zh) * | 2010-05-27 | 2016-09-07 | 陶氏环球技术有限责任公司 | 一种生产含可交联甲硅烷基的聚氧化烯聚合物的方法 |
CN105924637B (zh) * | 2010-05-27 | 2019-04-19 | 陶氏环球技术有限责任公司 | 一种生产含可交联甲硅烷基的聚氧化烯聚合物的方法 |
CN102875796A (zh) * | 2012-10-16 | 2013-01-16 | 山东蓝星东大化工有限责任公司 | 一种提高聚醚多元醇生产用dmc催化剂活性的方法 |
CN107474237A (zh) * | 2017-09-05 | 2017-12-15 | 句容宁武新材料股份有限公司 | 一种通过三元复合催化剂合成聚醚多元醇的方法 |
CN112321815A (zh) * | 2020-10-28 | 2021-02-05 | 中国石油化工股份有限公司 | 一种低气味高活性聚醚多元醇的制备方法 |
CN112321815B (zh) * | 2020-10-28 | 2022-09-16 | 中国石油化工股份有限公司 | 一种低气味高活性聚醚多元醇的制备方法 |
CN116217913A (zh) * | 2022-12-29 | 2023-06-06 | 杭州普力材料科技有限公司 | 一种三配体双金属络合物催化剂及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
KR100355336B1 (ko) | 2003-01-24 |
TW401429B (en) | 2000-08-11 |
US5482908A (en) | 1996-01-09 |
HU9502619D0 (en) | 1995-10-30 |
KR960010719A (ko) | 1996-04-20 |
US5536883A (en) | 1996-07-16 |
JPH08104741A (ja) | 1996-04-23 |
EP0700949B1 (en) | 1999-03-03 |
AU688548B2 (en) | 1998-03-12 |
DE69508009D1 (de) | 1999-04-08 |
EP0700949A2 (en) | 1996-03-13 |
DK0700949T3 (da) | 1999-09-27 |
AU3048795A (en) | 1996-03-21 |
ATE177123T1 (de) | 1999-03-15 |
DE69508009T2 (de) | 1999-08-12 |
HUT73052A (en) | 1996-06-28 |
CN1072687C (zh) | 2001-10-10 |
JP3479175B2 (ja) | 2003-12-15 |
CA2157312C (en) | 2008-02-19 |
HU215551B (hu) | 1999-01-28 |
BR9503975A (pt) | 1996-09-24 |
EP0700949A3 (en) | 1996-08-07 |
ZA957474B (en) | 1996-04-09 |
ES2127997T3 (es) | 1999-05-01 |
RO111742B1 (ro) | 1997-01-30 |
CA2157312A1 (en) | 1996-03-09 |
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