CN1283136A - 制备聚醚多元醇用的改进型双金属氰化物催化剂 - Google Patents
制备聚醚多元醇用的改进型双金属氰化物催化剂 Download PDFInfo
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- CN1283136A CN1283136A CN98812517A CN98812517A CN1283136A CN 1283136 A CN1283136 A CN 1283136A CN 98812517 A CN98812517 A CN 98812517A CN 98812517 A CN98812517 A CN 98812517A CN 1283136 A CN1283136 A CN 1283136A
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Abstract
本发明涉及制备聚醚多元醇用的新的改进型双金属氰化物(DMC )催化剂,制备聚醚多元醇的方法是使烯化氧与含活泼氢原子的引发剂化合物进行加聚反应。该催化剂包含一种双金属氰化合物、一种有机配位体和以催化剂量为基准计的2~80wt%的聚碳酸酯。这类新的改进型催化剂在用于制备聚醚多元醇时能显著缩短诱导时间并显著提高活性。
Description
本发明涉及用于制备聚醚多元醇的新的改进型双金属氰化物(DMC)催化剂,该聚醚多元醇的制备是通过烯化氧加聚到含活泼氢原子的引发剂化合物上的。
烯化氧加聚到含活泼氢原子的引发剂化合物上的反应所用的双金属氰化物(DMC)催化剂是已知的(例如可参阅美国专利3,404,109、3,829,505、3,941,849和5,158,922)。采用DMC催化剂制备聚醚多元醇的作用在于,同采用碱金属催化剂如碱金属氢氧化物的聚醚多元醇的常规制备方法相比较,前者能显著降低含双键端基的单官能团聚醚即称之为一元醇的比例。所制得的聚醚多元醇可以加工成高质量的聚氨酯(例如弹性体、泡沫塑料、涂料)。DMC催化剂通常的制备方法是,使一种金属盐的水溶液在低分子量有机配位体例如一种醚的存在下与一种金属氰化物盐的水溶液反应。例如,在一种典型的催化剂制备方法中,将氯化锌水溶液(过量)与六氰钴酸钾混合,随后向所生成的悬浮液中加入二甲氧基乙烷(甘醇二甲醚)。经过滤并用甘醇二甲醚水溶液洗涤催化剂之后,便制得通式如下的活性催化剂(参阅欧洲专利700 949):
Zn3[Co(CN)6]2·xZnCl2·yH2O·z甘醇二甲醚分子式(Ⅰ)
日本专利4 145 123、美国专利5 470 813、欧洲专利700 949、欧洲专利743 093和欧洲专利761 708公开了改进型的DMC催化剂,该催化剂采用叔丁醇作为有机配位体(其自身单独成为配位体或与聚醚配合(欧洲专利700 949、欧洲专利761 708)成为配位体),在制备聚醚多元醇中能够进一步降低含双键端基的单官能团聚醚的比例。此外,采用改进型DMC催化剂能缩短烯化氧与适当引发剂化合物加聚反应的诱导时间并提高催化剂活性。
因此,本发明的目的在于提供用于将烯化氧加聚到适当引发剂化合物上的进一步改进的DMC催化剂,该催化剂较之迄今为止所知的催化剂类型更能显著地缩短诱导时间,同时更能显著提高催化剂的活性。由于缩短了制备聚醚多元醇总的反应时间,因而提高了该方法的经济效益。毫无疑问,由于活性的提高,于是可以使用低浓度的催化剂,因而也就省去高成本的催化剂分离步骤,同时,所制得的产物也就能够直接用于制备聚氨酯。令人惊奇的是,现已发现,以催化剂量为基准计,含2~80wt%的聚碳酸酯的DMC催化剂在聚醚多元醇的制备中能显著缩短诱导时间,同时能极大提高活性。
本发明所提供的新的改进型双金属氰化物(DMC)催化剂包含:
a)一种双金属氰化物;和
b)一种有机配位体;其特征在于:该催化剂含有2~80wt%以成品催化剂量为基准计的聚碳酸酯。
按照本发明的催化剂还可含有来自双金属氰化物制备过程中的水,其优选含量为1~10wt%,和/或水溶性金属盐,其优选含量为5~25wt%。
适用于按照本发明的催化剂的双金属氰化物a)是水溶性金属盐与水溶性金属氰化物盐的反应产物。
水溶性金属盐优选的通式为M(X)n,M选自金属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)。Zn(Ⅱ),Fe(Ⅱ),Co(Ⅱ)和Ni(Ⅱ)是特别优选的。X是阴离子,优先选自包含卤离子、氢氧根、硫酸根、碳酸根、氰酸根、硫氰酸根、异氰酸根、异硫氰酸根、羧酸根、草酸根和硝酸根这一组中的阴离子。n的值为1、2或3。
适用的金属盐的实例有:氯化锌、溴化锌、醋酸锌、乙酰丙酮化锌、苯甲酸锌、硝酸锌、硫酸亚铁、溴化亚铁、氯化亚铁、氯化亚钴、硫氰酸亚钴、氯化亚镍和硝酸亚镍。也可以使用不同金属盐的混合物。
水溶性金属氰化物盐优选的通式为(Y)aM'(CN)b(A)c,M'选自金属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)。M'特别优选Co(Ⅱ),Co(Ⅲ),Fe(Ⅱ),Fe(Ⅲ),Cr(Ⅲ),Ir(Ⅲ)和Ni(Ⅱ)。水溶性金属氰化物盐可含有一种或多种这些金属。Y是碱金属离子或碱土金属离子。A是阴离子,选自包含卤离子、氢氧根、硫酸根、碳酸根、氰酸根、硫氰酸根、异氰酸根、异硫氰酸根、羧酸根、草酸根和硝酸根这一组中的阴离子。a和b均为整数(≥1),a、b和c之值的选择应确保金属氰化物盐的电中性;c的优选值为0。适用的水溶性金属氰化物盐的实例是六氰钴(Ⅲ)酸钾,六氰亚铁(Ⅱ)酸钾、六氰铁(Ⅲ)酸钾、六氰钴(Ⅲ)酸钙和六氰钴(Ⅲ)酸锂。
可用于作为本发明催化剂的合适的双金属氰化物a)的实例有六氰钴(Ⅲ)酸锌、六氰亚铁(Ⅱ)酸锌、六氰铁(Ⅲ)酸锌、六氰亚铁(Ⅱ)酸镍(Ⅱ)和六氰钴(Ⅲ)酸钴(Ⅱ)。合适的双金属氰化物的其它实例可在例如美国专利5158922(第8栏第29~66行)中查到。优选使用的是六氰钴(Ⅲ)酸锌。
按照本发明的DMC催化剂含有有机配位体b),因为它能提高例如催化活性。合适的有机配位体原则上是已知的,且在上述的专利(参阅例如美国专利5158922第6栏第9~65行)中作了详尽叙述。配位体可在制备催化剂的过程中加入,也可在催化剂沉淀出来后立即加入。所使用的配位体是过量的。优选的配位体是含杂原子如氧、氮、磷或硫的水溶性有机化合物,这些杂原子能与双金属氰化物生成配合物。合适的有机配位体的实例有醇类、醛类、酮类、醚类、酯类、酰胺类、脲类、腈类、硫醚类以及它们的混合物。优选的有机配位体是水溶性的脂族醇,例如乙醇、异丙醇、正丁醇、异丁醇、仲丁醇和叔丁醇。叔丁醇是特别优选的。
按照本发明的DMC催化剂所含的双金属氰化物的量为以成品催化剂量为基准计的20~90wt%,优选为25~80wt%,而有机配位体的含量为以成品催化剂量为基准计的1~30wt%,优选为3~25wt%。
按照本发明的DMC催化剂所含的聚碳酸酯的量为以催化剂量为基准计的2~80wt%。优选的催化剂含有5~50wt%的聚碳酸酯。
适合于制备本发明催化剂的聚碳酸酯是高分子量物质,其结构特征是以碳酸酯基团-O-CO-O-作为链的重复单元。聚碳酸酯通常是由多官能团羟基化合物(一般为双羟基化合物,如链烷二醇类或双酚类)与碳酸衍生物如光气或双〔氯羰基氧〕化合物、碳酸二酯或脲缩聚而成的。还有可能是由多官能团羟基化合物(如双酚类)和碳酸衍生物与例如乙烯基单体或聚合物、卤代双酚或双〔4-羟苯基〕硫烷、环氧乙烷、二羧酸或二酰氯、膦酸或膦酸衍生物,或有机硅化合物进行三组分或多组分的缩聚反应而制得。制备聚碳酸酯的其它常规方法包括(大)环碳酸二酯、螺环原碳酸四酯和不饱和碳酸二酯的聚合;包括环状羧酸二酯与其它环状碳酸二酯、内酯或内酰胺的共聚合;以及包括二氧化碳与环氧乙烷或氧杂环丁烷的共聚合。
制备聚碳酸酯的方法通常是已知的,且例如在“有机化学方法,Houben-Weyl”(卷E20,大分子物质,第四版,1987,第1443~1457页)、“乌尔曼工业化学大全”(卷A21,第5版,1992,第207~215页)和“聚合物科学与工程大全”(卷11,第2版,1988,第648~718页)中均有详尽叙述。
优选使用含羟端基且平均分子量低于12,000(按照OH值测定法测得的)的脂族聚碳酸酯,该聚碳酸酯通常的制备方法是用多官能团脂族羟基化合物(通常为二元醇)与碳酸二芳酯、碳酸二烷酯、二氧杂环戊酮、光气、双氯碳酸酯或脲进行反应。
特别优选使用平均分子量为400~6000(按照OH值测定法测得的)的脂族碳酸酯-二醇,该化合物通常是由非相邻的二醇与碳酸二芳酯、碳酸二烷酯、二氧杂环戊酮、光气、双氯碳酸酯或脲反应而制得的(参阅例如欧洲专利292772,及其中所引用的文献)。
下述的非相邻二醇尤其适用于此目的:1,4-丁二醇、新戊二醇、1,5-戊二醇、2-甲基-1,5-戊二醇、3-甲基-1,5-戊二醇、1,6-己二醇、双(6-羟已基)醚、1,7-庚二醇、1,8-辛二醇、2-甲基-1,8-辛二醇、1,9-壬二醇、1,10-癸二醇、1,4-双羟甲基环己烷、二甘醇、三甘醇、四甘醇、二缩丙二醇、三缩丙二醇、四缩丙二醇,以及二元醇与环氧乙烷和/或环氧丙烷和/或四氢呋喃的烷氧基化产物,其分子量可达1000、优选为200~700;还有时采用叫做“二聚二醇”的化合物,系由所谓的“二聚酸”的两个羧基经还原后制得的,而该二聚酸又是由不饱和的植物脂肪酸经二聚化反应而制得的。
这些二元醇可单独使用,也可以混合物形式使用。
可以使用少量高沸点的单官能团醇类,例如苯乙醇、癸醇、硬脂醇或月桂醇。
也可使用少量三官能团或更多官能团的醇,例如三羟甲基乙烷、三羟甲基丙烷或季戊四醇作为支化反应用。
下述化合物可用于与非相邻二醇的反应:诸如碳酸二苯酯、二甲苯酯、二二甲苯酯和二萘酯之类的碳酸二芳酯,诸如碳酸二甲酯、二乙酯、二丙酯、二丁酯、二戊酯和二环己酯之类的碳酸二烷酯,诸如碳酸乙烯酯和碳酸丙烯酯之类的二氧杂环戊酮,1,6-双氯代碳酸己二醇酯,光气以及脲。
上述反应可采用常规方法即用碱或过渡金属化合物进行催化。
为了制备具有缩短诱导时间和提高活性性能的DMC催化剂,必须同时使用有机配位体和聚碳酸酯(参阅实施例7~8和对比例6与9)。采用常规方法即元素分析法和热重分析法对催化剂组成进行分析。
按照本发明的催化剂可以是结晶的、部分结晶的或无定形的。分析结晶度采用常规的X射线粉末衍射法。
按照本发明的改进型DMC催化剂系采用常规的方法制备的,即在水溶液中,在有机配位体和聚碳酸酯存在下使金属盐(过量)与金属氰化物盐反应。
该方法的第一步最好使金属盐水溶液(例如氯化锌,使用过量的化学计量比(至少为金属氰化物盐的50摩尔%))与金属氰化物盐水溶液(例如六氰钴酸钾)在有机配位体(例如叔丁醇)存在下进行反应,以便制成一种含双金属氰化物(例如六氰钴酸锌)、过量金属盐、水和有机配位体的悬浮液。
有机配位体即可存在于上述的一种水溶液中,也可存在于上述的两种水溶液中,或者在双金属氰化物沉淀之后所得到的悬浮液中立即将其加入。现已发现,在剧烈搅拌下将上述水溶液与有机配位体混合是有利的。
随后,用聚碳酸酯处理所制得的悬浮液,所用的聚碳酸酯最好以与水和有机配位体的混合物形式提供。
采用例如离心或过滤等已知技术将含聚碳酸酯的催化剂从悬浮液中分离出来。
为提高催化剂活性,如果随后用有机配位体水溶液洗涤分离出来的催化剂(例如采用再分散方法并接着用过滤或离心方法进行再分离),这样做则是有利的。这种操作有可能从本发明的催化剂中除去例如水溶性的副产物如氯化钾,该副产物对于加聚反应会产生不利影响。
水洗涤液中的有机配位体含量优选为40~80wt%。向该水洗涤液中加入一些聚碳酸酯,其量优选为0.5~5wt%,则更为有利。
多次洗涤催化剂也是有利的。例如可以按照第一次的洗涤方法重复操作来完成多次洗涤。但是,进一步的洗涤最好采用非水溶液,例如有机配位体与聚碳酸酯的混合物。
最后,在研磨之后任选将洗涤后的催化剂置于20~100℃和0.1毫巴~常压(1013毫巴)的条件下进行干燥。
本发明还提供了本发明改进型的DMC催化剂用于制备聚醚多元醇的用途,该制备是通过使烯化氧加聚到含活泼氢原子的引发剂化合物上而实现的。
优选使用的烯化氧是环氧乙烷、环氧丙烷、环氧丁烷及其混合物。用烷氧基化法合成聚醚链可以只用一种单聚合环氧化合物来完成,但也可以用2种或3种不同的单聚合环氧化合物进行无规的或嵌段的反应。更详尽的叙述可参阅“乌尔曼工业化学大全”(英文版,1992,卷A21,第670~671页)。
用分子量为18~2000且含有1~8个羟基的化合物作为含活泼氢的引发剂化合物,可提及的实例有乙二醇、二甘醇、三甘醇、1,2-丙二醇、1,4-丁二醇、六亚甲基二醇、双酚A、三羟甲基丙烷、甘油、季戊四醇、山梨醇、蔗糖、降解淀粉和水。
作为含活泼氢原子的引发剂化合物,使用那些例如由常见碱金属催化剂和上述低分子引发剂所制备的并相当于分子量为200~2000的低聚烷氧基化的化合物是很有利的。
采用本发明催化剂催化的烯化氧加聚到含活泼氢原子引发剂化合物上的反应,其一般的反应温度为20~200℃,优选的反应温度为40~180℃,特别优选的反应温度为50~150℃。该反应可在0~20巴的总压下进行。加聚反应可在无溶剂条件下或在如甲苯和/或THF等惰性有机溶剂中进行。溶剂用量一般为以待制备的聚酯多元醇为基准计的10~30wt%。
催化剂浓度应作如下选择,即在给定条件下能对加聚反应进行良好的控制。催化剂浓度一般为以待制备聚醚多元醇为基准计的0.0005wt%~1wt%,优选的为0.001wt%~0.1wt%。
加聚反应的反应时间为几分钟至若干天。
按照本发明方法所制备的聚醚多元醇的分子量为500~100,000克/摩尔,优选的为1000~50,000克/摩尔,特别优选的为2000~20,000克/摩尔。
加聚反应可以连续地、分批地或半分批地进行。
按照本发明的催化剂通常要求几分钟至若干小时的诱导时间。
借助按照本发明的新型催化剂,制备聚醚多元醇的诱导时间较之迄今为止已知的DMC催化剂要显著地缩短。
烷氧基化时间也同时显著地缩短,这是因为实质上提高了活性。
这样就使整个反应时间(诱导时间和烷氧基化时间之和)比起迄今为止已知的DMC催化剂的反应时间一般缩短65~80%,因而提高了本方法的经济效益。
由于反应活性的显著提高,本发明的催化剂可以低浓度使用(15ppm或更低,参阅实施例10),因此在应用于制备聚氨酯时,一般可以不必从多元醇中除去催化剂,这样做不会对产品质量产生不良影响。
实施例
催化剂的制备
对比例1
用叔丁醇作为有机配位体且不使用聚碳酸酯制备DMC催化剂(催化剂A,按照日本专利4145123方法进行合成)。
将10g(73.3毫摩尔)氯化锌溶于15ml蒸馏水的溶液在剧烈搅拌下加入到4g(12毫摩尔)六氰钴酸钾溶于75ml蒸馏水的溶液中。然后将50g叔丁醇和50g蒸馏水的混合物立即加入到所制成的悬浮液中,随后对该制成的混合物剧烈搅拌10分钟。过滤分离出固体,然后加入125g叔丁醇与蒸馏水的混合物(70/30w/w)剧烈搅拌10分钟,再次滤出固体。最后再用125g叔丁醇搅拌该固体10分钟、过滤后,将催化剂在50℃和常压下干燥至恒重。
干燥的粉末状催化剂的产量:3.08g
元素分析:
钴=13.6%,锌=27.35%,叔丁醇=14.2%,(聚碳酸酯=0%)。
实施例2
用叔丁醇作为有机配位体并使用脂族聚碳酸酯制备DMC催化剂(催化剂B)
将12.5g(91.5毫摩尔)氯化锌溶于20ml蒸馏水的溶液在剧烈搅拌下(24,000rpm)加入到4g(12毫摩尔)六氰钴酸钾溶于70ml蒸馏水的溶液中。然后立即向所制得的悬浮液中加入50g叔丁醇和50g蒸馏水的混合物,并随后将所得的混合物剧烈搅拌(24000rpm)10分钟。然后加入由1g平均分子量为1972(按OH值测量法测得的)的三甘醇/四甘醇聚碳酸酯(三甘醇/四甘醇摩尔比=1/1)、1g叔丁醇和100g蒸馏水组成的混合物,并将所得混合物搅拌(1000rpm)3分钟。过滤分离出固体,然后用由70g叔丁醇、30g蒸馏水和1g上述聚碳酸酯组成的混合物搅拌(10,000rpm)10分钟并再次过滤。最后用100g叔丁醇和0.5g上述聚碳酸酯的混合物将固体又搅拌(10,000rpm)10分钟。过滤后,将该催化剂置于50℃和常压下干燥至恒重。
干燥的粉末状催化剂产量:5.42g
元素分析和热重分析:
钴=10.5%,锌=24.2%,叔丁醇=13.3%,聚碳酸酯=21.2%。
实施例3
用叔丁醇作为有机配位体并使用脂族聚碳酸酯制备DMC催化剂(催化剂C)
同实施例2的方法,所不同的是:
使用平均分子量1968(按照OH值测定法测得的)的一缩丙二醇聚碳酸酯代替实施例2中的聚碳酸酯。
干燥的粉末状催化剂产量:5.33g
元素分析和热重分析:
钴=10.8%,锌=24.4%,叔丁醇=20.2%,聚碳酸酯=15.0%。
对比例4
使用聚碳酸酯而不使用叔丁醇作为有机配位体来制备DMC催化剂(催化剂D)。
将12.5g(91.5毫摩尔)氯化锌溶于20ml蒸馏水的溶液在剧烈搅拌(24,000rpm)下加入到4g(12毫摩尔)六氰钴酸钾溶于70ml蒸馏水的溶液中。然后立即将1g实施例3的聚碳酸酯与100g蒸馏水的混合物加入到所制成的悬浮液中,随后将所得混合物剧烈搅拌(24,000rpm)10分钟。过滤分离出固体,然后用1g聚碳酸酯与100g蒸馏水的混合物搅拌(10,000rpm)10分钟并再次过滤。最后用0.5g聚碳酸酯与100g蒸馏水的混合物将固体再搅拌(10,000rpm)10分钟。过滤后,将催化剂置于50℃和常压下干燥至恒重。
干燥的粉末状催化剂的产量:4.72g
元素分析和热重分析:
钴=10.7%,锌=18.2%,聚碳酸酯=28.6%,(叔丁醇=0%)。
对比例5
使用叔丁醇作为有机配位体并使用聚醚来制备DMC催化剂(催化剂E,按照欧洲专利700949的方法合成)。
将12.5g(91.5毫摩尔)氯化锌溶于20ml蒸馏水的溶液在剧烈搅拌(24,000rpm)下加入到4g(12毫摩尔)六氰钴酸钾溶于70ml蒸馏水的溶液中。然后立即向所制成的悬浮液中加入50g叔丁醇与50g蒸馏水的混合物,随后将所得混合物剧烈搅拌(24,000rpm)10分钟。然后加入1g平均分子量为2000(OH值=56mg KOH/g)的多缩丙二醇、1g叔丁醇和100g蒸馏水的混合物,并将所得混合物搅拌(1000rpm)3分钟。过滤分离出固体,然后用70g叔丁醇、30g蒸馏水和1g上述聚醚搅拌(10,000rpm)10分钟,并再次过滤。最后用100g叔丁醇和0.5g上述聚醚的混合物将固体又搅拌(10,000rpm)10分钟。过滤后,将催化剂置于50℃和常压下干燥至恒重。
干燥的粉末状催化剂的产量:6.23g
元素分析和热重分析:
钴=11.6%,锌=24.6%,叔丁醇=3.0%,聚醚=25.8%。
聚醚多元醇的制备
通用方法
在一个惰性气体(氩气)保护下的500ml的压力反应器中加入50g聚丙二醇引发剂(分子量=1000g/摩尔)和3~20mg催化剂(以待制备多元醇量为基准计,15~100ppm),并在搅拌下加热至105℃。然后计量一次性加入环氧丙烷(约5g)直至总压力升至2.5巴。然后只当观察到反应器内出现加速的压力降时才又计量注入环氧丙烷。这种加速的压力降表明催化剂是活化的。然后在恒定的2.5巴总压下连续地计量注入剩余的环氧丙烷(145g)。当计量注入环氧丙烷的操作完成且在105℃下经过5小时的后反应之后,在90℃(1毫巴)下蒸出挥发性组分,然后冷却至室温。
所得的聚醚多元醇通过测定OH值、双键含量和分子量分布Mw/Mn(MALDI-TOF-MS)来表征。
反应过程借助转化率/时间曲线(环氧丙烷消耗[g]对反应时间[分钟])来跟踪。
由转化率/时间曲线最低点的切线与曲线的处延基线的交点求得诱导时间。
对催化剂活性有决定意义的丙氧基化时间对应于催化剂活化(诱导期结束)与环氧丙烷计量注入结束之间的时间长度。
总的反应时间是诱导时间与丙氧基化时间之和。
对比例6
用催化剂A(100ppm)制备聚醚多元醇
诱导时间: 290分钟
丙氧基化时间: 165分钟
总反应时间: 455分钟
聚醚多元醇: OH值(mg KOH/g): 28.5
双键含量(毫摩尔/kg):6
Mw/Mn: 1.12
实施例7
用催化剂B(100ppm)制备聚醚多元醇
诱导时间: 95分钟
丙氧基化时间: 40分钟
总反应时间: 135分钟
聚醚多元醇: OH值(mgKOH/g): 28.8
双键含量(毫摩尔/kg): 6
Mw/Mn: 1.05
实施例8
用催化剂C(100ppm)制备聚醚多元醇
诱导时间: 65分钟
丙氧基化时间: 35分钟
总反应时间: 100分钟
聚醚多元醇: OH值(mgKOH/g): 28.7
双键含量(毫摩尔/kg): 6
Mw/Mn: 1.04
对比例9
用催化剂D(100ppm)制备聚醚多元醇
诱导时间: >700分钟
丙氧基化时间: 无活性
实施例7~8与对比例6之间的比较显而易见,使用按照本发明的DMC催化剂因其中含有有机配位体(叔丁醇)和聚碳酸酯,在制备聚醚多元醇时,所得到的诱导时间较之使用只含有机配位体(叔丁醇)的DMC催化剂的诱导时间有显著的缩短;同时还明显发现,按照本发明的催化剂同时还具有显著提高的活性(可由实际上缩短的丙氧基化时间检测到)。
对比例9表明,只含聚碳酸酯而不含有机配位体的DMC催化剂是无活性的。
实施例10
用催化剂C(15ppm)制备聚醚多元醇
总反应时间: 310分钟
聚醚多元醇: OH值(mg KOH/g): 29.6
双键含量(毫摩尔/kg): 6
Mw/Mn: 1.06
不除去催化剂,多元醇中的金属含量如下:Zn=4ppm,Co=2ppm。
实施例10表明,在制备聚醚多元醇中由于本发明的新型DMC催化剂具有显著提高的活性,故而可以低浓度使用,这就有可能略去从多元醇中分离催化剂的步骤。
对比例11
用催化剂E(15ppm)制备聚醚多元醇
总反应时间: 895分钟
聚醚多元醇: OH值(mgKOH/g): 29.8
双键含量(毫摩尔/kg): 6
Mw/Mn: 1.04
实施例10与对比例11之间的比较表明,按照本发明的含有机配位体(叔丁醇)和聚碳酸酯的新型DMC催化剂较之迄今为止已知的含有机配位体(叔丁醇)和聚醚(其分子量与本发明催化剂中所用的聚碳酸酯的分子量相当)的高活性DMC催化剂具有明显更高的活性。因此,使用按照本发明的新型催化剂制备聚醚多元醇有可能显著缩短总反应时间。
Claims (8)
1.一类双金属氰化物(DMC)催化剂,包含:
a)一种双金属氰化合物;和
b)一种有机配位体,其特征在于:这类催化剂含有以成品催化剂量为基准计的2~80wt%的聚碳酸酯。
2.按照权利要求1的DMC催化剂,其特征在于所说的双金属氰化合物是六氰钴(Ⅲ)酸锌。
3.按照权利要求1的DMC催化剂,其特征在于所说的有机配位体是叔丁醇。
4.按照权利要求1~3的DMC催化剂,其特征在于所说的催化剂含有5~50wt%的聚碳酸酯。
5.按照权利要求1~4的DMC催化剂,其特征在于所说的催化剂包含具有端羟基且其按照OH值测定法测得的平均分子量低于12,000的脂族聚碳酸酯,该聚碳酸酯系由多官能团脂族羟基化合物与碳酸二芳酯、碳酸二烷酯、二氧杂环戊酮、光气、双氯碳酸酯或脲反应而制得的。
6.按照权利要求1~5的DMC催化剂,其特征在于所说的催化剂包含具有按照OH值测定法测得的平均分子量为400~6000的脂族聚碳酸酯-二醇,该脂族聚碳酸酯-二醇系由非相邻二醇与碳酸二芳酯、碳酸二烷酯、二氧杂环戊酮、光气、双氯碳酸酯或脲反应而制得的。
7.一种制备按照权利要求1的DMC催化剂的方法,其特征在于使过量的金属盐在水溶液中、在有机配位体和聚碳酸酯存在下与金属氰化物盐反应,并将所制得的催化剂分离出来、进行洗涤,然后干燥。
8.按照权利要求1的DMC催化剂用于制备聚醚多元醇的用途,该多元醇是由烯化氧加聚到含活泼氢原子的引发剂化合物上去而制得的。
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---|---|---|---|---|
CN101424058B (zh) * | 2007-10-30 | 2011-04-13 | 王擎昊 | 纸品包装树脂强渗剂的生产工艺 |
CN110964191A (zh) * | 2018-09-29 | 2020-04-07 | 杭州普力材料科技有限公司 | 一种混合酸改性的锌钴双金属氰化物催化剂及其制备方法 |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19817676A1 (de) | 1998-04-21 | 1999-10-28 | Bayer Ag | Verfahren zur aufarbeitungsfreien Herstellung langkettiger Polyetherpolyole |
DE19928156A1 (de) | 1999-06-19 | 2000-12-28 | Bayer Ag | Aus Polyetherpolyolen hergestellte Polyurethan-Weichschäume |
DE19945351C2 (de) * | 1999-09-22 | 2002-04-18 | Lohmann Therapie Syst Lts | Verfahren zum Auffinden und zur Isolierung pharmakologisch wirksamer Verbindungen aus Substanzgemischen |
US6642171B2 (en) | 2000-04-28 | 2003-11-04 | Synuthane International, Inc. | Double metal cyanide catalysts containing polyglycol ether complexing agents |
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 |
EP2548908A1 (de) * | 2011-07-18 | 2013-01-23 | Bayer MaterialScience AG | Verfahren zur Herstellung von Polyetherpolyolen |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AR243911A1 (es) * | 1988-11-18 | 1993-09-30 | Dow Chemical Co | Un proceso para la preparacion de un poliol que tiene un peso equivalente de 200 a 4000 mediante la reaccion de un compuesto monoepoxi. |
US5545601A (en) * | 1995-08-22 | 1996-08-13 | Arco Chemical Technology, L.P. | Polyether-containing double metal cyanide catalysts |
US5714428A (en) * | 1996-10-16 | 1998-02-03 | Arco Chemical Technology, L.P. | Double metal cyanide catalysts containing functionalized polymers |
-
1997
- 1997-12-23 DE DE19757574A patent/DE19757574A1/de not_active Withdrawn
-
1998
- 1998-12-10 HU HU0004519A patent/HUP0004519A2/hu unknown
- 1998-12-10 WO PCT/EP1998/008073 patent/WO1999033562A1/de active IP Right Grant
- 1998-12-10 CN CN98812517A patent/CN1107542C/zh not_active Expired - Fee Related
- 1998-12-10 BR BR9814402-2A patent/BR9814402A/pt not_active IP Right Cessation
- 1998-12-10 EP EP98966294A patent/EP1051253B1/de not_active Expired - Lifetime
- 1998-12-10 PT PT98966294T patent/PT1051253E/pt unknown
- 1998-12-10 KR KR1020007006951A patent/KR100566842B1/ko not_active IP Right Cessation
- 1998-12-10 CA CA002315766A patent/CA2315766C/en not_active Expired - Fee Related
- 1998-12-10 JP JP2000526299A patent/JP2001527132A/ja active Pending
- 1998-12-10 ES ES98966294T patent/ES2207029T3/es not_active Expired - Lifetime
- 1998-12-10 DE DE59809600T patent/DE59809600D1/de not_active Expired - Lifetime
- 1998-12-10 AU AU22705/99A patent/AU2270599A/en not_active Abandoned
- 1998-12-11 TW TW087120578A patent/TW568799B/zh active
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2001
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101424058B (zh) * | 2007-10-30 | 2011-04-13 | 王擎昊 | 纸品包装树脂强渗剂的生产工艺 |
CN110964191A (zh) * | 2018-09-29 | 2020-04-07 | 杭州普力材料科技有限公司 | 一种混合酸改性的锌钴双金属氰化物催化剂及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CA2315766A1 (en) | 1999-07-08 |
HUP0004519A2 (hu) | 2001-04-28 |
EP1051253B1 (de) | 2003-09-10 |
WO1999033562A1 (de) | 1999-07-08 |
CA2315766C (en) | 2007-07-17 |
DE59809600D1 (de) | 2003-10-16 |
EP1051253A1 (de) | 2000-11-15 |
HK1034687A1 (en) | 2001-11-02 |
KR20010024804A (ko) | 2001-03-26 |
JP2001527132A (ja) | 2001-12-25 |
DE19757574A1 (de) | 1999-06-24 |
ES2207029T3 (es) | 2004-05-16 |
PT1051253E (pt) | 2004-02-27 |
KR100566842B1 (ko) | 2006-04-03 |
BR9814402A (pt) | 2000-10-10 |
CN1107542C (zh) | 2003-05-07 |
AU2270599A (en) | 1999-07-19 |
TW568799B (en) | 2004-01-01 |
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