CN1798784A - 聚醚多元醇组合物 - Google Patents

聚醚多元醇组合物 Download PDF

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CN1798784A
CN1798784A CNA2004800153177A CN200480015317A CN1798784A CN 1798784 A CN1798784 A CN 1798784A CN A2004800153177 A CNA2004800153177 A CN A2004800153177A CN 200480015317 A CN200480015317 A CN 200480015317A CN 1798784 A CN1798784 A CN 1798784A
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polyether glycol
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cyanide complex
bimetallic cyanide
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H·P·B·杜耶胡森
M·B·埃利维尔德
P·A·舒特
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Shell Internationale Research Maatschappij BV
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Abstract

聚醚多元醇组合物，该组合物包括：(a)聚醚多元醇，(b)双金属氰化物络合催化剂，和(c)以聚醚多元醇的重量为基准100－10,000ppm的胺抗氧化剂。

Description

聚醚多元醇组合物
技术领域
本发明涉及一种聚醚多元醇组合物。
背景技术
聚醚多元醇是公知的。它们可用于多种目的。通过在适宜条件下。使聚醚多元醇与聚异氰酸酯反应，可用于制备聚氨酯。可制备的聚氨酯产品包括聚氨酯涂料、弹性体、密封剂、泡沫以及粘合剂。另外，聚醚多元醇还可用于其它应用如润滑剂的基础流体和操作液体如压缩机润滑剂、汽车润滑剂、齿轮油、油脂、航空涡轮机润滑剂、金属切割液和液压流体。
通常，在氢氧化钾催化剂存在下，通过含有活性氢原子的含羟基引发剂与亚烷基氧化物如环氧丙烷和环氧乙烷反应产生聚醚多元醇，从而制备聚醚多元醇，亦称为聚(亚烷基氧化物)聚合物。
现在，可用双金属氰化物(DMC)络合催化剂替代氢氧化钾催化剂。这些化合物是公知的用于环氧化物聚合反应的催化剂，即用于聚合亚烷基氧化物。该催化剂活性高，同利用强碱性催化剂如氢氧化钾制备的类似聚醚多元醇相比，其制备的聚醚多元醇具有低的不饱和度。
为提高聚醚多元醇组合物的储存稳定性，其通常含有抗氧化剂。EP-A-759450教导了如果聚醚多元醇组合物中含有50-250ppm或更高的双金属氰化物复合物，则使用500ppm的酚类抗氧化剂如丁基化羟基甲苯。
令人惊讶的是，我们已发现了一种用于含双金属氰化物络合催化剂的聚醚多元醇组合物的更有效的抗氧化剂。
发明内容
本发明涉及一种聚醚多元醇组合物，该组合物包括：(a)聚醚多元醇，(b)双金属氰化物络合催化剂，和(c)以聚醚多元醇重量为基准100-10,000ppm的胺抗氧化剂。
具体实施方式
本发明的聚醚多元醇组合物含有双金属氰化物络合催化剂。该催化剂通常源自聚醚多元醇制备过程。双金属氰化物复合物的存在形式可以为以下情况：其加入聚醚多元醇制备过程时的形式；或在聚醚多元醇制备过程中有活性的形式；或者以衍生物的形式存在。如果双金属氰化物催化剂失活，则可以得到这种衍生物。为了制备具有聚(环氯乙烷)终端嵌段的聚醚多元醇，失活是必须的。本发明的组合物含有双金属氰化物络合催化剂或双金属氰化物络合催化剂的衍生物或残余物。
针对本发明给出的量均以本发明组合物中存在的聚醚多元醇的重量为基准。
本发明组合物中存在的聚醚多元醇是在双金属氰化物(DMC)络合催化剂存在下通过使含羟基的引发剂与亚烷基氧化物接触而制备的。亚烷基氧化物原则上可以是任何亚烷基氧化物。优选地，该亚烷基氧化物含2-10个碳原子，优选为2-6个碳原子，更优选为2-4个碳原子。优选的用于本发明的亚烷基氧化物是环氧乙烷、环氧丙烷、环氧丁烷、氧化苯乙烯等以及它们的混合物。最优选地，该亚烷基氧化物是环氧乙烷和/或环氧丙烷。
多种含羟基引发剂均可用于制备用于本发明的聚醚多元醇。该含羟基的引发剂可以是水、乙二醇、二甘醇、三甘醇、丙二醇、二丙二醇、三丙二醇、1，2-、1，3-和1，4-丁二醇、新戊二醇、丙三醇、三羟甲基丙烷、三羟乙基丙烷、季戊四醇、α-甲基葡糖苷、羟甲基、羟乙基和羟丙基葡糖苷、山梨醇、甘露醇、蔗糖以及其它常用的含羟基引发剂。另外适用的是单官能的含羟基的引发剂如甲醇、乙醇、1-丙醇、2-丙醇、正丁醇、2-丁醇、2-乙基己醇等以及苯酚、邻苯二酚、4，4′-二羟基联苯、4，4′-二羟基二苯基甲烷。
通常使用的含羟基引发剂为含有至少1个活性氢原子的化合物，更优选为至少2个活性氢原子。优选的含羟基引发剂为平均含至少1个羟基的有机化合物，更优选平均含1个以上羟基，更优选地，含羟基引发剂是含2-6个羟基的有机化合物。优选这类醇的例子有二醇如二甘醇、二丙二醇、丙三醇、二丙三醇和聚丙三醇、季戊四醇、三羟甲基丙烷、三乙醇胺、山梨醇和甘露醇。
通常，含羟基引发剂在大气压下在50-150℃的温度，尤其是80-130℃的温度下与亚烷基氧化物反应。也可以应用更高的压力，但该压力一般不超过20bar，优选为1-5bar。该方法可在惰性溶剂存在下或无惰性溶剂条件下进行。合适的惰性溶剂有环己烷、甲苯、二甲苯、二乙醚、二甲氧基乙烷和/或氯代烃(如二氯甲烷、氯仿或1，2-二氯丙烷)。如果使用溶剂，其用量通常为10-30wt％。
双金属氰化物络合催化剂在现有技术中是公知的。已经发现在本发明中原则上可以应用任何已知可用于使亚烷基氧化物与含羟基引发剂反应的过程的双金属氰化物催化剂。本发明组合物中存在的双金属氰化物络合催化剂优选含叔丁醇配体。
通常，用于本发明的双金属氰化物催化剂显示粉末x-射线衍射图，其在约5.07(d-间距，埃)处没有对应高晶态六氰基钴酸锌的可检测信号。更具体地，这类双金属氰化物催化剂通常在(d-间距，埃)4.82(br)和3.76(br)处显示粉末X-射线衍射图案，而在(d-间距，埃)约5.07、3.59、2.54和2.28处没有对应高晶态六氰基钴酸锌的可检测信号。
日本申请4-145123中描述了一种可以制备用于本发明的双金属氰化物催化剂的方法。所制备的催化剂是含有作为有机配体配合的叔丁醇的双金属氰化物复合物。
另一种可以制备双金属氰化物催化剂的方法在PCT专利申请PCT/EP01/03498中有述。所描述的该方法包括如下步骤：
(a)将金属盐水溶液与金属氰化物水溶液混合，并使这些溶液反应，其中该反应至少部分是在有机络合剂的存在下发生的，从而形成固体双金属氰化物复合物在含水介质中的分散体；
(b)将步骤(a)中得到的分散体与一种液体混合，该液体基本不溶于水，并且能将步骤(a)中形成的固体双金属氰化物复合物从含水介质中萃取出来，并形成由第一含水层和含双金属氰化物复合物和所加入的液体的层组成的两相系统；
(c)除去第一含水层；和
(d)从含有双金属氰化物催化剂的层中回收双金属氰化物催化剂。
通常，存在于本发明组合物中的双金属氰化物催化剂具有通式Zn2[Co(CN)6]Cl.nC.mH2O.pA，其中C为所使用的配体，A是所使用的通式(I)的化合物。优选地，C为叔丁醇，A为甲基叔丁基醚、二乙醚、二异丙醚、叔戊基甲基醚或二丁醚。优选地，n为0-10，m为0-20，和p为0-10。
聚醚多元醇组合物中双金属氰化物络合催化剂的含量可以在很宽范围内变化。以聚醚多元醇的量为基准，DMC催化剂的含量优选少于150ppm，更优选少于100ppm，更优选少于50ppm，更优选至多25ppm，更优选少于25ppm，更优选至多10ppm，更优选少于10ppm。
特别适用于本发明的胺抗氧化剂为具有如下通式的胺抗氧化剂：
Figure A20048001531700061
其中，R1、R2和R3各自独立地为氢或含有1-30个碳原子的烃，优选为氢或具有1-30个碳原子的烷基，环烷基或芳基。已证明有效的抗氧化剂为N，N-二甲基-N-环己胺和辛基化二苯胺。优选地，R1为氢，R2和R3各自独立地为含5-25个碳原子的烷基、环烷基或芳基，优选环烷基或芳基。更具体地，优选R2和R3各自独立地为烷基取代的苯基，其中烷基取代基含5-10个碳原子。最优选地，胺抗氧化剂是辛基化二苯胺。一种可商购的辛基化二苯胺是Irganox 5057。
所存在的胺抗氧化剂的量受其它条件影响。通常，小于100ppm的量不能充分稳定聚醚多元醇组合物，而大于10,000ppm的量则不能明显提高稳定性。针对不同应用，抗氧化剂的具体优选含量一般不同。本发明的聚醚多元醇组合物优选用于粘稠原料应用中。对于这种应用，本发明的多元醇组合物优选含1000-10,000ppm的胺抗氧化剂，更具体地，抗氧化剂的含量优选为1000-8000ppm。
本发明的组合物中可包含其它抗氧化剂，如为苯酚衍生物的化合物。
本发明的聚醚多元醇组合物中可包含其它的添加剂，如填料、阻燃剂、泡沫稳定剂(表面活性剂)和着色剂。阻燃剂可以是液体和/或固体阻燃剂。有机硅氧烷表面活性剂是聚氨酯生产中最常用的泡沫稳定剂。大量的这种有机硅氧烷表面活性剂是可商购的。
一种优选的组合物是可商购于Osi的化合物L2100。通常，以多元醇反应物和聚异氰酸酯反应物的反应混合物的重量为基准，这种泡沫稳定剂的用量可至多为5wt％。常用助剂的量可以在很高范围内变化。通常，以多元醇的量为基准，其量为0-50重量份，更具体为0-40重量份。
另外，本发明的聚醚多元醇组合物可用于其它用途，如润滑剂的基础流体和操作液体。
对本发明举例如下。
实施例
程序A
向5升搅拌反应器中装入379克平均分子量400的1，2-丙二醇/环氧丙烷的加合物(PPG400)。另外，加入32克含3wt％双金属氰化物络合催化剂的PPG400溶液。双金属氰化物络合催化剂按WO 01/72418中所述制备。
反应器在真空下用氮气气提以脱除痕量水，并加热到105℃。将少量环氧丙烷加入反应器中，并仔细监控反应器压力。直到反应器中发生加速压力下降时，才加入附加的环氧丙烷。压降表明催化剂已被活化。当确定催化剂具有活性时，在2小时内逐步加入足量的环氧丙烷，以得到平均分子量为4000的多元醇。双金属氰化物络合催化剂在多元醇中的浓度为275ppm。
程序B
在与程序A类似的实验中，得到的多元醇平均分子量为4000，但含有30ppm双金属氰化物络合催化剂。
程序C
从程序B中得到的含30ppm催化剂的多元醇中脱除双金属氰化物络合催化剂，得到基本不含双金属氰化物络合催化剂的多元醇。
样品
在实验中加入以下抗氧化剂：
Iohol：2，6-双(1，1-二甲基乙基)-4-甲基苯酚、丁基化羟基甲苯(BHT)
Irganox 5057：辛基化二苯胺
制备的样品包括上述多元醇(分别含0、30和275ppm的双金属氰化物络合催化剂)和不同量的Ionol或Irganox 5057抗氧化剂(500、1500和5000ppm)。
储存稳定性试验
利用顶隙气相色谱和滴定对样品进行分析，以获得其总羰基含量和酸值，随后将样品放置在烤箱中，在100℃下避光储存7天。该处理之后，再次测量样品的总羰基含量和酸值。样品的总羰基含量和酸值的变化(在储存稳定性试验前后)见表1和表2。
                           表1
  DMC(ppm)   Ionol(ppm)   酸值降低(mg KOH/g多元醇)   羰基含量增加(ppm)
  0   500   0.04   45
  30   500   0.01   35
  275   500   0.04   31
  0   1500   0.01   4
  30   1500   0.01   2
  275   1500   0.01   4
  0   5000   0.00   1
  30   5000   0.01   2
  275   5000   0.00   2
                              表2
  DMC(ppm)   Irganox5057(ppm)   酸值降低(mg KOH/g多元醇)   羰基含量增加(ppm)
  0   500   *   0
  30   500   0.01   2
  275   500   0.03   3
  0   1500   *   3
  30   1500   0.00   2
  275   1500   0.01   2
  0   5000   *   0
  30   5000   0.01   3
  275   5000   0.02   3
*：未测定

Claims (6)

1.聚醚多元醇组合物，该组合物包括：(a)聚醚多元醇，(b)双金属氰化物络合催化剂，和(c)以聚醚多元醇的重量为基准100-10,000ppm的胺抗氧化剂。
2.权利要求1的聚醚多元醇组合物，其中胺抗氧化剂具有如下通式(I)：
其中R1、R2和R3各自独立地为氢或含有1-30个碳原子的烃。
3.权利要求2的聚醚多元醇组合物，其中R1为氢，R2和R3各自独立地为含5-25个碳原子的环烷基或芳基。
4.前述权利要求任一项的聚醚多元醇组合物，其中双金属氰化物络合催化剂含叔丁醇配位体。
5.前述权利要求任一项的聚醚多元醇组合物，其中双金属氰化物络合催化剂的含量低于150ppm。
6.权利要求4的聚醚多元醇组合物，其中双金属氰化物络合催化剂的含量低于50ppm。
CNA2004800153177A 2003-06-04 2004-06-04 聚醚多元醇组合物 Pending CN1798784A (zh)

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DE602004002484T2 (de) 2007-06-14
ATE340202T1 (de) 2006-10-15
WO2004108789A1 (en) 2004-12-16
JP2006526679A (ja) 2006-11-24
EP1629022B1 (en) 2006-09-20
ES2268665T3 (es) 2007-03-16
US20050014637A1 (en) 2005-01-20
KR20060013427A (ko) 2006-02-09
EP1629022A1 (en) 2006-03-01
DE602004002484D1 (de) 2006-11-02

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