CN101213017A - 制备双金属氰化物催化剂的方法 - Google Patents
制备双金属氰化物催化剂的方法 Download PDFInfo
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- CN101213017A CN101213017A CNA2006800242038A CN200680024203A CN101213017A CN 101213017 A CN101213017 A CN 101213017A CN A2006800242038 A CNA2006800242038 A CN A2006800242038A CN 200680024203 A CN200680024203 A CN 200680024203A CN 101213017 A CN101213017 A CN 101213017A
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/26—Cyanides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2663—Metal cyanide catalysts, i.e. DMC's
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/48—Ring-opening reactions
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Abstract
本发明公开了一种制备通式M2 a[M1(CN)rXt]b的双金属氰化物催化剂的方法,其中M2优选为Co(Ⅲ)或Fe(Ⅲ),和M1优选为Zn(Ⅱ),X为除氰根之外的与M1形成配位键的基团和选自羰基、氰酸根、异氰酸根、腈基、硫氰酸根和亚硝酰基,a、b、r、t为经选择使得满足电中性条件的整数。该双金属氰化物催化剂通过使a)与b)进行反应而制得,a)通式Hw [M1(CN)r(X)t]的氰基合金属酸,其中M1和X如上所定义,r和t如上所定义,和选择w使得满足电中性条件,b)易于质子传递的金属化合物M2Rw和/或M2RuYv,其中M2如上所定义,基团R独立地为pKa≥20的非常弱的质子酸的阴离子,和Y为具有-10~+10的pKa的中等强至强的有机酸或无机酸的阴离子,w对应M2的化合价,u+v对应M2的化合价,并且u与v各自至少为1,所述反应在非水的非质子溶剂中进行。
Description
本发明涉及用于制备双金属氰化物催化剂(DMC催化剂)的方法、所述DMC催化剂本身以及它们的用途。
为了制备具有宽范围性能的聚氨酯泡沫体,需要具有经过设计的聚醚多元醇。例如,长链多元醇被用于柔性泡沫体,和较短链多元醇被用于刚性泡沫体。
在起始物和多种催化剂如氢氧化钾、疏水双层氧化物、Lewis酸体系和DMC化合物的存在下,从环氧烷制得聚醚多元醇。具有低含量不饱和成分的长链聚醚多元醇的经济重要性日益增加。特别地,已发现DMC化合物可用作制备所述聚醚多元醇的催化剂。
根据F.E.Bailey,Jr,J.V.Koleske,Alkylene Oxides and theirPlolymers,Vol.35,1991,通过在水中使氯化锌与六氰合钴酸钾或六氰合钴酸钙相结合而制得DMC催化剂。当用有机溶剂如乙二醇或二甘醇代替水时,可得到具有增大活性的催化剂。
WO 99/16775公开了通过使氰基合金属酸如六氰合钴(III)酸的水溶液与金属羧酸盐、优选甲酸锌、乙酸锌和丙酸锌的水溶液反应而制备结晶DMC催化剂的制备。当合并所述水溶液之后,可向所得的含水悬浮液中加入可与水混溶的含杂原子的组分作为配体。
然而,现有技术中已知的DMC催化剂就其诱导性能而言仍然能够有所改进。
本发明的目的是提供改进的DMC催化剂。
本发明的另一个目的是提供制备DMC催化剂的可供选择的方法。
通过制备通式(I)的双金属氰化物催化剂的方法而实现了所述目的
M2 a[M1(CN)rXt]b (I)
其中
M1为选自Zn(II)、Fe(II)、Co(III)、Ni(II)、Mn(II)、Co(II)、Sn(II)、Pb(II)、Fe(III)、Mo(IV)、Mo(VI)、Al(III)、V(IV)、V(V)、Sr(II)、W(IV)、W(IV)、Cu(II)和Cr(III)的金属离子,
M2为选自Sr(I)、Mg(II)、Zn(II)、Fe(II)、Fe(III)、Co(III)、Cr(III)、Mn(II)、Mn(III)、Ir(III)、Rh(III)、Ru(II)、V(IV)、V(IV)、Co(II)、Cr(II)、Ti(IV)的金属离子,
X为除氰根之外的与M1形成配位键的基团和选自羰基、氰酸根、异氰酸根、腈基(nitrile)、硫氰酸根和亚硝酰基,
a、b、r、t为经选择使得所述化合物呈电中性的整数,
该制备通过使
a)通式(II)的氰基合金属酸
Hw[M1(CN)r(X)t]
其中M1和X如上所定义,
r和t如上所定义,和选择w使得所述化合物呈电中性,
与
b)易于质子传递(protolyzable)的金属化合物(IIIa)
M2Rw
和/或(IIIb)
M2RuYv
进行反应,
其中M2如上所定义,
基团R相同或不同并各自为pKa≥20的非常弱的质子酸的阴离子,和
Y为具有-10~+10的pKa的中等强至强的有机酸或无机酸(inorganicmineral acid)的阴离子,
w对应M2的化合价,
u+v对应M2的化合价,并且u与v各自至少为1,
所述反应在非水的非质子溶剂中进行。
本发明的所述方法在非水介质中进行。根据本发明制备的所述DMC催化剂可作为可泵送的凝胶得到以及还可按照其原样使用。这省略了过滤和干燥步骤以及固体的处理。
在所述氰基合金属酸(II)中,优选
r=4-6,
t=0-2。
在所述金属化合物(IIIa)或(IIIb)中,优选
w=2或u+v=2。
特别优选的金属离子M2为Co(III)和Fe(III)。
特别优选的金属离子M1为Zn(II)。
氰基合金属酸(II)是在水溶液中可容易地进行处理的化合物。已知制备氰基合金属酸的多种方法。例如,如在W.Klemm等,Z.Anorg.Allg.Chem.308(1961)179中所描述,可通过氰基金属化银(silver cyanometalate)从氰基金属化碱金属(alkali metal cyanometalate)来制备氰基合金属酸。此外,可借助于酸性离子交换剂将氰基金属化碱金属或碱土金属转化为所述氰基合金属酸,参见F.Hein,H.Lilie,Z.Anorg.Allg.Chem.270(1952)45,A.Ludi等,Helv.Chim.Acta 50(1967)2035。在G.Brauer(编者)“Handbuch der prparativen anorganischen Chemie”,Ferdinand EnkeVerlag,Stuttgart 1981中描述了其他可能的合成方法。
优选的氰基合金属酸(II)为六氰合钴(III)酸和六氰合铁(III)酸。
合适的金属化合物(IIIa)和(IIIb)例如为二甲基锌、二乙基锌、二正丁基锌、二异丙基锌、二异丁基锌、二乙基氰化铝、三甲基铝、三异丁基铝、三乙基铝、三正丙基铝、三正辛基铝、三正癸基铝、三正己基铝、二(四甲基环戊二烯基)锰、二乙基镁、二正丁基镁、正丁基乙基镁、2,2,6,6-四甲基-3,5-庚二酮酸锶、二(五甲基环戊二烯基)锶、1,1’-二甲基二茂铁、二茂铁、苯甲酰基二茂铁、环戊二烯基二羰基铁二聚体、联茚基铁、二(五甲基环戊二烯基)铁、二茂镍、环戊二烯基羰基镍二聚体、二(五甲基环戊二烯基)镍、二茂钴、二(乙基环戊二烯基)钴、二(五甲基环戊二烯基)钴、二(环戊二烯基)锰、二(五甲基环戊二烯基)锰、二(环戊二烯基)二氯化钛、二(五甲基环戊二烯基)二氯化钛、二(环戊二烯基)二羰基钛(II)和二(环戊二烯基)二甲基钛。
特别优选的金属化合物(IIIa)为二烷基锌化合物,如二甲基锌、二乙基锌、二正丁基锌、二异丙基锌和二异丁基锌,特别为二乙基锌。
所述氰基合金属酸(II)与所述金属化合物(IIIa)或(IIIb)的反应通常在非水的偶极或非极性的非质子溶剂中进行。合适的非质子溶剂例如为二甲基亚砜(DMSO)、二甲基甲酰胺(DMF)、环丁砜、二硫化碳、乙二醇二甲醚、二甘醇二甲醚和N-甲基吡咯烷酮(NMP),优选DMSO、DMF和NMP。
所述反应可在一种或多种其它有机组分存在下进行,所述有机组分充当用于控制所述催化剂形态的表面活性组分和/或充当化学结合的配体。同样可将这种其它有机组分添加到反应之后包含所述DMC化合物(I)的产物溶液或悬浮液中。优选的其它有机组分选自聚醚、聚酯、聚碳酸酯、聚亚烷基二醇脱水山梨糖醇酯、聚亚烷基二醇缩水甘油醚、聚丙烯酰胺、聚(丙烯酰胺-共-丙烯酸)、聚丙烯酸、聚(丙烯酰胺-共-马来酸)、聚丙烯腈、聚丙烯酸烷基酯、聚甲基丙烯酸烷基酯、聚乙烯基甲基醚、聚乙烯基乙基醚、聚醋酸乙烯酯、聚乙烯醇、聚N-乙烯基吡咯烷酮、聚(N-乙烯基吡咯烷酮-共-丙烯酸)、聚乙烯基甲基酮、聚(4-乙烯基苯酚)、聚(丙烯酸-共-苯乙烯)、唑啉聚合物、聚亚烷基亚胺、马来酸和马来酸酐共聚物、羟乙基纤维素、聚醋酸酯、离子型表面-活性和界面-活性化合物、胆汁酸和盐、酯和其酰胺、苷和多元醇的羧酸酯。
所述反应可间歇、半连续或连续进行。
根据本发明制备的所述DMC催化剂(I)可用作催化剂或用于负载催化剂的制备。
例如,所述DMC催化剂(I)可通过常规固/液分离法从所述反应中得到的溶液分离出来,并可作为湿沉淀物用作催化剂,或可不经从所述溶剂中在先分离而作为悬浮液或凝胶使用。
可借助环氧烷、优选环氧乙烷、环氧丙烷和/或环氧丁烷将所述DMC催化剂用于具有活性H原子的化合物的烷氧基化。活性氢原子例如存在于羟基或伯氨基和仲氨基中。根据本发明制备的所述DMC催化剂优选用于通过使二元醇或多元醇与环氧乙烷、环氧丙烷、环氧丁烷或它们的混合物反应而制备聚醚多元醇。
根据本发明制备的所述DMC催化剂显示出特别优异的“诱导性能”,即当向待烷氧基化的具有活性H原子的化合物中加入所述环氧烷时立即开始烷氧基化反应。这一点从在加入环氧烷后非常迅速的压力下降显见,其由于通过所述反应而立即开始消耗环氧烷。
本发明还提供了根据本发明制备的所述DMC催化剂本身,及其用于具有活性H原子的化合物的烷氧基化的用途,优选用于借助环氧乙烷、环氧丙烷、环氧丁烷或它们的混合物使得二元醇或多元醇的烷氧基化的用途。基于所得产物的量,通常以5-5000ppm、优选10-1000ppm、特别优选15-500ppm的量使用本发明的所述DMC催化剂。可以使用现有技术中已知的所有操作方式以间歇、半间歇或连续工艺进行所述烷氧基化。
通过下面实施例来解释本发明。
实施例
DMC催化剂的制备
实施例1
在45℃下将3.98g(17.5mmol)的H3Co(CN)6·0.5H2O(六氰合钴(III)酸)溶解在250ml干燥DMF中,与3.24g ZnEt2(26.3 mmol;27.35g在甲苯中的11.97%重量浓度溶液),将该混合物在45℃下搅拌2小时并在室温下放置过夜。这形成了未经进一步处理的白色悬浮液(267g)。
实施例2
在40℃下将3.97g(17.5mmol)的H3Co(CN)6·0.5H2O溶解在250ml干燥DMF中,与5.4g ZnEt2(43.8mmol;45.4g在甲苯中的11.97%重量浓度溶液),将该混合物在45℃下搅拌2小时并在室温下放置过夜。这形成了未经进一步处理的混浊流体凝胶(269g)。
实施例3
在室温下,将3.97g(17.5mmol)的H3Co(CN)6·0.5H2O溶解在150ml干燥DMSO中,与4.44g ZnEt2(36mmol;36.15g在甲苯中的11.97%重量浓度溶液),将该混合物在45℃下搅拌1小时并在室温下放置过夜。这形成了未经进一步处理的粉色凝胶(208g)。
实施例4
在45℃下,将3.97g(17.5mmol)的H3Co(CN)6·0.5H2O溶解在100ml水中,得到淡黄色溶液。经30分钟将4.40g ZnEt2(35mmol;36.8g在甲苯中的11.97%重量浓度溶液)加入到该溶液中,将该混合物在45℃下搅拌2小时并在室温下放置过夜。形成了粉色沉淀物。对该反应混合物进行离心分离并将所述沉淀物用80ml水洗涤一次,用80ml MeOH洗涤一次和用80ml Et2O洗涤一次,每一洗涤步骤包括10分钟的超声处理。在降低的压力下于60℃干燥所述沉淀物至恒重。
产量:6.88g的固体产物。
实施例5
将100ml MeOH(无水)加入到13.29g(20mmol)的2-乙基己酸锆中。形成了粘稠的赭色沉淀物并将其通过超声处理和随后的剧烈搅拌进行分散。加热到40℃后,加入40℃下的在200ml MeOH(无水)中的六氰合钴酸(4.50g,20mmol)溶液,并将该混合物在40℃下搅拌30分钟。形成了一些沉淀物,但大部分的所述赭色固体并未发生反应。对所述反应混合物超声处理2.5小时,在40℃下搅拌8小时,并超声处理另外2小时。过滤出固体,用MeOH洗涤两次并在降低的压力下于60℃进行干燥,得到3.65g固体产物。
实施例6
将3.28g六氰合钴酸溶解在220ml干燥甲醇中,并在室温下剧烈搅拌的同时,经5分钟加入23.31g在甲苯中的11.97%重量浓度的二乙基锌溶液,形成了白色沉淀物并剧烈放出气体。将该混合物另外搅拌约12小时。随后离心分离出沉淀物,用甲醇洗涤并在降低的压力下干燥。产量:4.1g晶体。
实施例7
在室温下将3.97g六氰合钴酸溶解在250ml干燥二甲基甲酰胺中,与36.15g在甲苯中11.97%的二乙基锌溶液进行混合,将该混合物在45℃下搅拌1小时并在室温下放置过夜。形成了乳状凝胶。在未经进一步处理的情况下将所述凝胶用作催化剂。
实施例8
在45℃下将4.00g六氰合钴酸溶解在250ml干燥二甲基甲酰胺中,并经15分钟加入49.6g在甲苯中的11.0%重量浓度的二乙基锌溶液和20ml二甲氧基乙烷的混合物,将该混合物在45℃下搅拌1小时并在室温下放置过夜。形成了乳状凝胶。在未经进一步处理的情况下将所述凝胶用作催化剂。
对比实施例1
将7.0g六氰合钴酸钾溶于300ml乙二醇中,并在搅拌下与4.09g二氯化锌在150ml乙二醇中的混合物进行混合。形成了白色沉淀。在未经进一步处理的情况下使用所述悬浮液。
对比实施例2
在搅拌下经10分钟将13.74g 4.8%重量浓度的六氰合钴酸(3.01mmolH3Co(CN)6)溶液缓慢加入到0.82g(6mmol)ZnCl2在10ml甲醇中的溶液中。形成了精细的白色沉淀物。添加完成后,将该分散液另外搅拌1小时。乙氧基化
一般方法
将10g相应起始物与25-5000ppm相应催化剂(基于批料量的金属含量)在约15mbar和75℃下脱气75分钟。随后使用氮气鼓泡所述反应混合物。称取2.0g的所述起始物/催化剂悬浮液装入装配有压力和温度测量装置的5ml实验反应器中。所述实验反应器使用氮气进行吹扫并加热到140℃。随后从分开连接的环氧乙烷存储容器中以1ml/min的计量速度连续计量加入1.0g环氧乙烷。
实施例9
将作为起始物的2-丙基庚醇和来自实施例8的5000ppm催化剂的1.81g混合物装入实验反应器中。经1分钟计量加入1g环氧乙烷(起始物∶环氧烷的摩尔比=约1∶3)。图1和2显示用于两个不同实验的压力和温度曲线。这里,将温度℃(上面的曲线;左轴)和压力bar(下面的曲线;右轴)绘制成相对时间min的曲线。在图中可看到在开始加入环氧乙烷之后压力非常迅速的下降(下面的曲线)。
对比实施例3
将作为起始物的2-丙基庚醇和来自对比实施例1的5000ppm催化剂的2.26g混合物装入实验反应器中。经1分钟计量加入1 g环氧乙烷(起始物∶环氧烷的摩尔比=约1∶3.3)。图3和4显示用于两个不同实验的压力和温度曲线。这里,将温度℃(上面的曲线;左轴)和压力bar(下面的曲线;右轴)绘制成相对时间min的曲线。在图中可看到在开始加入环氧乙烷之后压力的显著延迟下降(下面的曲线)。
实施例10
将作为起始物的2-丙基庚醇和来自实施例2的4000ppm催化剂的1.94g混合物装入实验反应器中。经1分钟计量加入1g环氧乙烷(起始物∶环氧烷的摩尔比=约1∶3)。图5显示了压力和温度曲线。这里,将温度℃(上面的曲线;左轴)和压力bar(下面的曲线;右轴)绘制成相对时间min的曲线。在图中可看到在开始加入环氧乙烷之后压力的迅速下降(下面的曲线)。
实施例11
将200.0g(1.0mol)三癸醇N和基于批料量相当于500ppm的18.2g来自实施例7的所述催化剂悬浮液装入2l钢反应器中。将该混合物加热到100℃并在10mbar下脱气2小时。随后引入氮气打破真空。将所述混合物加热到135℃,并在于0.2-1.6bar之间波动的压力下,经50分钟计量加入200.0g(3.45mol)环氧丙烷。完成环氧丙烷的加入后,使得所述混合物进行反应直至压力恒定并冷却到100℃。随后在1mbar下使其进一步反应30分钟。随后使用Seitz-Supradur 200过滤器过滤出反应产物。
产量:411.8g(理论产量:418.2g)
残留醇含量:0.8重量%
OH数:127mg KOH/g
实施例12
将200.0g(1.0mol)三癸醇N和基于批料量相当于500ppm的0.2g来自实施例6的干燥催化剂装入2l钢反应器中。将该混合物加热到100℃并在10mbar下脱气2小时。随后引入氮气打破真空。将所述混合物加热到135℃,并在于0.4-8bar之间波动的压力下,经50分钟计量加入200.0g(3.45mol)环氧丙烷。完成环氧丙烷的加入后,使得所述混合物进行反应直至压力恒定并冷却到100℃。随后在1mbar下使其进一步反应30分钟。随后使用Seitz-Supradur 200过滤器过滤出反应产物。
产量:373.7g(理论产量:400.2g)
残留醇含量:4.0重量%
OH数:150mg KOH/g
Claims (10)
1.制备通式(I)的双金属氰化物催化剂的方法
M2 a[M1(CN)rXt]b (I)
其中
M1为选自Zn(II)、Fe(II)、Co(III)、Ni(II)、Mn(II)、Co(II)、Sn(II)、Pb(II)、Fe(III)、Mo(IV)、Mo(VI)、Al(III)、V(IV)、V(V)、Sr(II)、W(IV)、W(VI)、Cu(II)和Cr(III)的金属离子,
M2为选自Sr(I)、Mg(II)、Zn(II)、Fe(II)、Fe(III)、Co(III)、Cr(III)、Mn(II)、Mn(III)、Ir(III)、Rh(III)、Ru(II)、V(IV)、V(V)、Co(II)、Cr(II)、Ti(IV)的金属离子,
X为除氰根之外的与M1形成配位键的基团和选自羰基、氰酸根、异氰酸根、腈基、硫氰酸根和亚硝酰基,
a、b、r、t为经选择使得所述化合物呈电中性的整数,该制备通过使
a)通式(II)的氰基合金属酸
Hw[M1(CN)r(X)t]
其中M1和X如上所定义,
r和t如上所定义,和选择w使得所述化合物呈电中性,
与
b)易于质子传递的金属化合物(IIIa)
M2Rw
和/或(IIIb)
M2RuYv
进行反应,
其中M2如上所定义,
基团R相同或不同并各自为pKa≥20的非常弱的质子酸的阴离子,和
Y为具有-10~+10的pKa的中等强至强的有机酸或无机酸的阴离子,
w对应M2的化合价,
u+v对应M2的化合价,并且u与v各自至少为1,
所述反应在非水的非质子溶剂中进行。
2.根据权利要求1的方法,其中在所述氰基合金属酸(II)中,r=4-6,t=0-2。
3.根据权利要求1或2的方法,其中在所述金属化合物(IIIa)或(IIIb)中,w=2或u+v=2。
4.根据权利要求1-3任一项的方法,其中所述金属离子M2选自Co(III)和Fe(III),和所述金属离子M1为Zn(II)。
5.根据权利要求1-4任一项的方法,其中所述氰基合金属酸(II)选自六氰合钴(III)酸和六氰合铁(III)酸。
6.根据权利要求1-5任一项的方法,其中所述金属化合物(IIIa)为二烷基锌化合物。
7.根据权利要求1-5任一项的方法,其中所述金属化合物(IIIa)为二乙基锌。
8.根据权利要求1-7任一项的方法,其中所述溶剂选自二甲基亚砜、二甲基甲酰胺和N-甲基吡咯烷酮。
9.可通过根据权利要求1-8任一项的方法得到的DMC催化剂。
10.根据权利要求9的所述DMC催化剂的用途,其用于具有活性H原子的化合物的烷氧基化。
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DE102005020347A DE102005020347A1 (de) | 2005-05-02 | 2005-05-02 | Verfahren zur Herstellung von Doppelmetallcyanidkomplex-Katalysatoren |
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EP (1) | EP1937408A2 (zh) |
JP (1) | JP2008540080A (zh) |
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WO2017156797A1 (zh) | 2016-03-18 | 2017-09-21 | 淮安巴德聚氨酯科技有限公司 | 一种利用dmc催化剂循环制备聚醚多元醇的方法 |
CN114133416A (zh) * | 2020-09-03 | 2022-03-04 | 万华化学集团股份有限公司 | 一种dmc催化剂的制备方法及由其制备的dmc催化剂 |
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MX2009008311A (es) * | 2007-02-05 | 2009-08-12 | Basf Se | Catalizadores de dmc, metodo para la produccion de los mismos y uso de los mismos. |
WO2010072769A1 (de) | 2008-12-23 | 2010-07-01 | Basf Se | Verfahren zur herstellung von polyether-blockcopolymeren |
PT2408841E (pt) | 2009-03-17 | 2014-12-11 | Basf Se | Corpo moldado de poliuretano com resistência ao rasgamento melhorada e comportamento de fadiga a flexões repetidas melhorado |
BR112019023481B1 (pt) * | 2017-05-10 | 2023-10-31 | Dow Global Technologies Llc | Processo para a produção de um poliéter |
WO2020084046A1 (de) | 2018-10-26 | 2020-04-30 | Basf Se | Verfahren zur herstellung von propylenoxy-haltigen hydrophob assoziierenden monomeren mittels dmc-katalyse |
WO2020084033A1 (de) | 2018-10-26 | 2020-04-30 | Basf Se | Hydrophob assoziierende copolymere für die tertiäre erdölförderung umfassend monomere mit propylenoxy-einheiten |
CN112194178B (zh) * | 2020-10-20 | 2021-06-01 | 福州大学 | 一种二氧化钛和普鲁士蓝有序组装态介晶纳米材料及其制备方法 |
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US3365282A (en) * | 1968-01-23 | Du Pont | Process for preparing amino derivatives of polyhedral boron compounds | |
JPS62294636A (ja) * | 1986-05-21 | 1987-12-22 | Eisai Co Ltd | 2−メチル−1,4−ナフトキノンの製造法 |
US6642423B2 (en) * | 1999-07-09 | 2003-11-04 | Dow Global Technologies, Inc. | Polymerization of ethylene oxide using metal cyanide catalysts |
CN100391999C (zh) * | 1999-07-09 | 2008-06-04 | 陶氏环球技术公司 | 利用金属氰化物催化剂和不饱和引发剂化合物的烯化氧的聚合 |
JP2003525328A (ja) * | 2000-02-29 | 2003-08-26 | ビーエーエスエフ アクチェンゲゼルシャフト | 多金属シアニド化合物の製造方法 |
AU2003220309B2 (en) * | 2002-03-19 | 2008-09-25 | Dow Global Technologies, Inc. | Method for preparing metal cyanide catalysts using insoluble metal salts |
CN100450616C (zh) * | 2003-05-22 | 2009-01-14 | 陶氏环球技术公司 | 纳米级dmc催化剂颗粒 |
JP4928271B2 (ja) * | 2004-11-05 | 2012-05-09 | 株式会社日本触媒 | ビニルピロリドン系重合体粉体およびその製造方法 |
JP5151480B2 (ja) * | 2005-08-17 | 2013-02-27 | 旭硝子株式会社 | ポリエステルエーテルポリ(モノ)オールの製造方法およびポリウレタンの製造方法 |
DE102007002555A1 (de) * | 2007-01-17 | 2008-07-24 | Bayer Materialscience Ag | Doppelmetallcyanid-Katalysatoren für die Herstellung von Polyetherpolyolen |
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- 2006-05-02 CN CNA2006800242038A patent/CN101213017A/zh active Pending
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CN114133416A (zh) * | 2020-09-03 | 2022-03-04 | 万华化学集团股份有限公司 | 一种dmc催化剂的制备方法及由其制备的dmc催化剂 |
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US20080292526A1 (en) | 2008-11-27 |
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