CN104736621A - 四甲基锡氧基化合物 - Google Patents

四甲基锡氧基化合物 Download PDF

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CN104736621A
CN104736621A CN201380042290.XA CN201380042290A CN104736621A CN 104736621 A CN104736621 A CN 104736621A CN 201380042290 A CN201380042290 A CN 201380042290A CN 104736621 A CN104736621 A CN 104736621A
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alkyl
tin
thiazolinyl
oxygen base
compound
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M·艾兹尔斯多夫
C·玛内戈尔德
M·科尔
R·葛
M·普罗布斯特
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Dow Europe GmbH
Dow Global Technologies LLC
Rohm and Haas Co
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Abstract

一种式(I)的化合物，其中R是C9-C11烷基、C9-C11烯基、C17烷基或C17烯基。

Description

四甲基锡氧基化合物
本发明涉及新的锡化合物，其可用作各种反应的催化剂。
现有技术已经公开了四烷基锡氧基(tetraalkylstannoxy)化合物。例如，欧洲专利第446,171号公开了具有如下所示记作的“(D)”的结构的四烷基锡氧基化合物：
其中，Z是C1-C20烷基，Z1是氢、C1-C20烷基、C3-C20烯基、C5-C8环烷基、苯基、C7-C18烷基苯基或C7-C9苯基烷基。但是，该参考文献并未揭示或建议本文所述的化合物。本发明解决的问题是发现其它有用的锡催化剂。
发明内容
本发明提供式(I)的化合物
其中R是C9-C11烷基、C9-C11烯基、C17烷基或C17烯基。
发明详述
除非另外说明，否则，百分数为重量百分数(重量％)，温度的单位为℃。“烷基”是包含1-22个碳原子的饱和烃基，可以是直链或支化的形式。“烯基”是具有至少一个碳碳双键的烷基。较佳的是，烯基是直链的。较好的是，烯基包含不超过三个碳碳双键，优选包含一个或两个碳碳双键，优选仅有一个碳碳双键。较好的是，烯基中的碳碳双键是顺(Z)式构型。
较好的是，R是C9-C11烷基、C17烷基或C17烯基；优选C9-C11烷基或C17烯基；优选C9烷基、C11烷基、C17烷基或C17烯基；优选C9烷基、C11烷基或C17烯基；优选C9支化烷基、C11烷基或C17烯基；优选C9支化烷基、C11烷基或仅有一个双键的C17烯基；优选1-乙基-1,4-二甲基戊基(新癸酸的烷基)、正十一烷基(月桂酸的烷基)或顺-8-十七碳烯基(油酸的烷基)。R的其它合适选择包括15-甲基十六烷基(异硬脂酸的烷基)、3-庚基(2-乙基己酸的烷基)和十三烷基(肉豆蔻酸(十四烷酸)的烷基)。
本发明的化合物可通过以下方法制备：使二甲基二氧化锡与脂肪酸接触并加热，然后除去水，以制备二聚锡氧基化合物。
本发明的化合物可用于由异氰酸酯和多元醇组分制备聚氨酯，特别是用于由多异氰酸酯和多元醇组分制备聚氨酯泡沫。
实施例
实施例1：四甲基锡氧基二-(C 12 -C 18 羧酸盐)
在1L旋转蒸发仪烧瓶中将658.8g二甲基氧化锡(DMTO)(4mol)和801.2g(3.6-3.8mol)椰子油脂肪酸(RADIACID 0600,欧利安公司(Oleon))(1mol)混合，以形成浆液。在旋转蒸发仪上将该浆液加热至约80℃，并在该温度下保持2小时。
然后，在温度最高达110℃/10毫巴的条件下在真空下通过蒸馏除去反应水。除去理论量的水(36.6g,2.03mol)。最后，加入1％硅藻土(过滤助剂)，并过滤产物。
产量：342.6g催化剂,(理论值的95.3％)。13C NMR(CDCl3):6.32,8.74,14.05,22.64,25.66,29.33,29.50,29.58,31.88,36.26,180.19ppm。1H NMR(CDCl3):0.76-1.55(m,25H)；2.13-2.20(t,2H)。由于分子是对称的，因而仅有一组质子和碳NMR信号。119Sn NMR(CDCl3):-186.0和-207.3。锡NMR显示了2个特征峰，这是由于RCOOSnMe2-O-SnMe2OCOR形成了具有外和内Sn对称性的二聚体,这解释了两个不同的化学位移。Sn是sp3d杂化的，其是三角双椎型，可以是梯形结构。这种性质对于二锡化合物是已知的：1,3-二氯-和1,3-二乙酰氧基四-正丁基二锡氧烷二元体系的119Sn-NMR光谱研究(119Sn-NMR spectroscopic study of the 1,3-dichloro-and1,3-diacetoxytetra-n-butyldistannoxane binary system.)Journal ofOrganometallic(2001),620,296-302。ESI质谱(300V):C16H35O3Sn2 +[515.06]。这证实了在分子中存在Sn-O-Sn键。
还通过大气压固体分析探针-质谱(ASAP-MS)来分析该物质。该分析在未经任何溶解的样品上进行。将样品放置在毛细管的一端并直接导入至离子化源。使用的碎裂电压为50V。基于ASAP-MS分析，样品形成分子离子。由于从母体复合物中提取了氢化物，从而形成分子离子。在离子化过程中，氢化物提取很可能发生在脂肪酸链基团上。ASAP质谱(50V):C28H57O5Sn2 +[713.224]。这证实了存在所需的材料。
对于月桂酸，方程式如下(制备中使用的椰子油脂肪酸是52-59％二月桂酸根,<1.5％二-C6-C10羧酸根，19-23％二-C14羧酸根,8-12％二-C15羧酸根,5-10％二-单-不饱和的C18羧酸根和<3％双-二-不饱和的C18羧酸根)
实施例2：四甲基锡氧基二油酸盐
使用实施例1中相同的步骤，使164.7g DMTO(1mol)和282.5g油酸(1mol)反应。除去理论量的水(7.9g,0.44mol)。
产量：426.8g催化剂,(理论值的95.4％)。液体，固化点-10℃。13C NMR(CDCl3):6.27,8.69,14.00,22.52,25.57,27.08,29.06,29.21,29.43,29.63,31.81,35.78,129.61,129.82,180.84ppm。1H NMR(CDCl3):0.69-2.20(m,37H)；5.32-5.37(t,2H)。119Sn NMR(CDCl3):-185和-205。ESI质谱(300V):C22H45O3Sn2 +[597.14]。这证实了在分子中存在Sn-O-Sn键。
还通过大气压固体分析探针-质谱(ASAP-MS)来分析该物质。该分析在未经任何溶解的样品上进行。将样品放置在毛细管的一端并直接导入至离子化源。使用的碎裂电压为50V。基于Metatin催化剂1282的ASAP-MS分析，样品形成分子离子。由于从母体复合物中提取了氢化物，从而形成分子离子。在离子化过程中，氢化物提取很可能发生在脂肪酸链基团上。ASAP质谱(50V):C40H77O5Sn2 +[877.381]。这证实了存在所需的材料。
实施例3：四甲基锡氧基二月桂酸盐
使用实施例1中相同的步骤，使164.7g DMTO(1mol)和200.3g月桂酸99％(1mol)反应。除去理论量的水(8.9g,0.49mol)。
固体，熔点60℃。13C NMR(CDCl3):6.38,8.74,14.08,22.66,25.65,29.34,29.51,29.59,31.89,36.21,180.32ppm。1H NMR(CDCl3):0.76-1.57(m,25H)；2.17(br,2H)。ESI质谱(300V):C16H35O3Sn2 +[515.06]。这证实了在分子中存在Sn-O-Sn键。
实施例4：四甲基锡氧基二新癸酸盐
使用实施例1中相同的步骤，使666.4g DMTO(4mol)和698g新癸酸(4mol)(以下异构体的混合物：2,2,3,5-四甲基己酸；2,4-二甲基-2-异丙基戊酸；2,5-二甲基-2-乙基己酸；2,2-二甲基辛酸；2,2二乙基己酸)反应。除去理论量的水(37.3g,2.07mol)。
高度黏稠的液体。虽然异构烷基的数量使得不可能有完全的峰归属，但NMR信号与结构大体一致。
2,5-二甲基-2-乙基己酸的方程式
催化剂测试
主要使用以下物质：
VORALASTTM GE 128  异氰酸酯聚醚预聚物，以MDI和聚醚二元醇和三元醇为基准计，其平均NCO含量为20.8重量％(购自陶氏化学公司(The Dow ChemicalCompany))。
VORANOLTM EP 1900  聚氧基丙烯-聚氧基乙烯多元醇，其是环氧乙烷封端的，其理论OH官能度为2，其平均分子量约为4000，其标称平均羟值为28mgKOH/g(购自陶氏化学公司)
VORANOLTM CP 6001  丙三醇引发的聚氧基丙烯-聚氧基乙烯多元醇，其是环氧乙烷封端的，其理论OH官能度为3，其平均分子量约为6000，其标称平均羟值为26-29mg KOH/g(购自陶氏化学公司)
SPECFLEXTM NC 138  丙三醇引发的聚氧基丙烯-聚氧基乙烯多元醇，其理论OH官能度为3，其平均分子量约为5700，其标称平均羟值为29.5mg KOH/g(购自陶氏化学公司)
NIAXTM L-6900  稳定剂，其是平均羟值为49mg KOH/g的不可水解的硅酮共聚物(购自迈图性能材料有限公司(Momentive Performance Materials Inc))。
33LB  催化剂，其是33重量％三亚乙基二胺(TEDA)稀释在67％1,4-丁二醇中的溶液，其标称平均羟值为821mg KOH/g(购自空气产品和化学品公司(Air Products&Chemicals,Inc.)。
77  催化剂，其是基于二(二甲基氨基丙基)甲基胺的溶液，其在25℃下的比重为0.85(g/cm3)，在25℃下的粘度为3mPa*s(购自空气产品和化学品公司)。
SA-1/10催化剂，其是基于1,8-二偶氮二环[5,4,0]十一碳-7-烯(DBU)的溶液，其标称平均羟值为83.5mg KOH/g(购自空气产品和化学品公司)。
HFA 134a       发泡剂，其是1,1,1,2-四氟乙烷。
TEGOSTABTM B 2114 硅基表面活性剂(购自伊夫尼克工业公司(EvonikIndustries))。
FOMREZTM UL 38  二辛基锡羧酸盐催化剂(购自迈图性能材料有限公司)。
METATINTM 1213  二甲基锡-二-2-乙基己基(ethylexyl)巯基乙酸盐催化剂(购自阿西马专业化学品公司(Acima Speciality Chemicals,Inc.)，陶氏化学公司的子公司)。
METATINTM 1215  二甲基双十二烷基硫醇锡催化剂(购自阿西马专业化学品公司，陶氏化学公司的子公司)。
根据实施例5和6的示例性实施方式的以下配制的多元醇分别与VORALASTTM GE 128异氰酸酯组分反应，形成聚氨酯泡沫。具体而言，将100重量份的实施例5和6的配制多元醇分别与54重量份的VORALASTTM GE 128异氰酸酯组分反应。实施例5和6的配制多元醇包括催化剂组分，所述催化剂组分具有基于四烷基锡氧基的催化剂(例如，代替基于二辛基锡催化剂，例如FOMREZ UL 38)。如下表1所示，实施例5和6在催化剂组分中分别包含0.01重量％和0.02重量％的四甲基锡氧基二新癸酸盐。
表1
对于实施例7的配制多元醇，用0.02重量％FOMREZTM UL 38代替实施例6中的0.02重量％的四甲基锡氧基二新癸酸盐。实施例7的配制多元醇与VORALASTTM GE 128异氰酸酯组分反应，形成聚氨酯泡沫。具体而言，将100重量份的实施例7的配制多元醇与54重量份的VORALASTTM GE 128异氰酸酯组分反应。
比较例8和9的配制多元醇分别用0.01重量％和0.02重量％的METATINTM1213催化剂代替实施例5和6中的0.01重量％和0.02重量％的四甲基锡氧基二新癸酸盐。比较例10和11的配制多元醇分别用0.01重量％和0.02重量％的METATINTM 1215催化剂代替实施例5和6中的0.01重量％和0.02重量％的四甲基锡氧基二新癸酸盐。比较例8-11的配制多元醇分别单独地与VORALASTTMGE128异氰酸酯组分反应，形成聚氨酯泡沫。具体而言，将100重量份的实施例8-11的配制多元醇分别与54重量份的VORALASTTM GE 128异氰酸酯组分反应。
分别制备实施例5-11的所得反应产物的样本(使用模具形成测试板，每个测试板的尺寸为200x 200x 10mm)，评估样本的反应性和物理-机械性质，如下表2所示。具体而言，分别测量实施例5-11的乳白时间(ASTM D7487-8),凝胶时间(ASTM D2471),收紧时间(ASTM D7487-8),可印压性(imprintability)(ASTMD7487-8),细根密度(fine root density)(ISO 845),最少脱模时间(在50℃下用脱模温度使用狗耳测试(Dog Ear Test)),抗撕裂强度(DIN 53543),拉伸强度(DIN 53543),伸长率(DIN 53543),挠曲疲劳(DIN 53543,“De Mattia”挠曲试验机),以及硬度(根据ISO 868)。
表2
对于最终的聚氨酯泡沫，在聚氨酯体系中用基于二甲基锡二羧酸盐的催化剂或者用基于含硫二甲基锡的催化剂(实施例8-11)来代替基于二辛基锡的催化剂(实施例7)显示了增加的挠曲疲劳和较长的最少脱模时间，这会为最终终端用户带来生产率问题。但是，根据以上实施方式，相对于基于二甲基锡二羧酸盐的催化剂和基于含硫二甲基锡的催化剂而言，使用基于四烷基锡氧基的催化剂，例如四甲基锡氧基二新癸酸盐(实施例5和6)提供了降低的挠曲疲劳和较短的最少脱模时间。因此，这表明基于四烷基锡氧基的催化剂可作为更可行的二取代的有机锡化合物(例如二辛基锡基催化剂)的代替。

Claims (9)

1.一种式(I)的化合物
其中R是C9-C11烷基、C9-C11烯基、C17烷基或C17烯基。
2.如权利要求1所述的化合物，其特征在于，R是C9-C11烷基、C17烷基或C17烯基。
3.如权利要求2所述的化合物，其特征在于，R是C9烷基、C11烷基或C17烯基。
4.如权利要求3所述的化合物，其特征在于，R是C9支链烷基、C11烷基或只有一个双键的C17烯基。
5.如权利要求4所述的化合物，其特征在于，R是1-乙基-1,4-二甲基戊基、正十一烷基或顺-8-十七碳烯基。
6.四甲基锡氧基二油酸盐。
7.四甲基锡氧基二新癸酸盐。
8.四甲基锡氧基二月桂酸盐。
9.四甲基锡氧基二异硬脂酸盐。
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