CN104910205A - 二乙烯基倍半硅氧烷的新型官能化不饱和双层衍生物 - Google Patents
二乙烯基倍半硅氧烷的新型官能化不饱和双层衍生物 Download PDFInfo
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Abstract
本发明的主题是通式1所示的二乙烯基倍半硅氧烷的新型官能化不饱和双层衍生物:(1)-R1 相同且代表含1至2个环的芳基;-R2 相同且代表含碳原子C1到C2的烷基,含1至2个环的被取代的或未被取代的芳基;-R3 相同且代表含1至2个环的被取代的或未被取代的芳基,或式-R4-R5-所示组,其中,R4 代表含碳原子C1到C3的烷基,而R5 代表含1至2个环的芳基。
Description
技术领域
本发明的对象是二乙烯基倍半硅氧烷的新型官能化不饱和双层衍生物。
背景技术
双层二乙烯基取代的倍半硅氧烷的结构不同于式(RSiO3/2)n n=8(T8)所描述的立方笼对称体系的结构,且其包括在平行平面内的两个环硅氧烷环,并具有8个惰性R1基团位于每个环中的硅原子上。所述环由两种类型的桥的接合:第一种类型接合相对的氧原子,而第二种类型是通过O2SiCH=CH2基团。在该结构中,硅原子上的乙烯基在分子的两相对侧,并决定了相对于位于硅氧烷环中的硅原子的R3基团不对称(WO2003/024870)。
二乙烯基倍半硅氧烷的双层官能化不饱和衍生物,是由能够结合广泛范围的官能团的无机硅氧烷骨架构建,制成合适的基质以用于混合材料的合成,并可以用作新一代复合材料的纳米填料。不饱和碳-碳键的存在还改善了这些化合物的光物理特性。Miyashita描述了咔唑倍半硅氧烷衍生物及其可允许用作有机电致发光二极管的有趣的光电性能(M.Kohri,J.Matusi,A.Watanabe,T.Miyashita Chem.Lett.2010,39,1162)。Lee已提出使用倍半硅氧烷衍生物作为配体用于代表金属拉倍半硅氧烷配合低聚物的钛配位化合物的合成(M.T.Hay,B.Seurer,D.Holmes,A.Lee Macromolecules 2010,43,2108),而Basset报告了它们用于锆和铪络合物的合成,其中锆和铪络合物作为催化剂的型号用于烯烃固定于二氧化硅的聚合(J.Espinas,J.D.A.Pelletier,E.Abou-Hamad,L.Emsley,J.-M.Basset Organometallics 2012,31,7610)。倍半硅氧烷的不饱和胺和降冰片烯衍生物已被Kakimoto公开用于聚酰亚胺的修正,当其被构建在聚合物的主链上,聚合物的热学和光学性质会大大改善(S.Wu,T.Hayakawa,M.Kakimoto,H.Oikawa Macromolecules 2008,41)。
已知的双层二乙烯基倍半硅氧烷的合成方法已被专利EP.1428795公开,涉及乙烯基二氯甲基硅烷与包括四个反应性Si-OH基团的倍半硅氧烷的硅烷衍生物的缩合。在该方法中,在水分痕量存在下,有必要使用易水解的氯硅烷,因其会干扰所需产品的合成和分离。在(Seurer,B.;Vij,V.;Haddad,T.;Mabry,J.M.;Lee,A.Macromolecules 2010,43,9337–9347)文献中已发现含有不饱和键的倍半硅氧烷的芳基衍生物,但这些键是在芳基取代基的外部端。
另外一种已知的乙烯基倍半硅氧烷官能化的方法已被现有技术和波兰专利申请P.392166公开。此方法是基于单乙烯基和八乙烯基取代的倍半硅氧烷与烯烃在钌催化剂的存在下发生硅烷化耦合。上述反应的所述基质是对称的倍半硅氧烷体系(T8及芯Si8O8),具有单个反应性乙烯基或8个乙烯基取代基。导致单烯基或辛烯基取代的产物的所述硅烷化耦合反应设于对称的倍半硅氧烷芯上。
发明内容
本发明的对象是二乙烯基倍半硅氧烷的新型官能化不饱和双层衍生物,由通式1所示,
其中:
-R1相同且代表含1至2个环的芳基;
-R2相同且代表:
含碳原子C1到C2的烷基,
含1至2个环的未被取代的芳基,
含1至2个环的和在环的任意位点被包括含碳原子C1到C3的烷基的烷氧基取代的单取代芳基;
-R3相同且代表:
式2所示组
-R4-R5-(2),
其中,R4代表含碳原子C1到C3的烷基,而R5代表含1至2个环的芳基,
含1至2个环的未取代芳基,
含1至2个环的和在任意位点被以下基团取代的芳基:
含碳原子C1到C2的烷基,
包括含碳原子C1至C2的烷基的烷氧基,
卤素X=F、Cl、Br,
含碳原子C1至C2和F或Cl的被完全取代的卤代烷基。
通式1所示的二乙烯基倍半硅氧烷的官能化不饱和双层衍生物的合成为,
其中,R1、R2和R3由如上定义,基于通式3所示的双层二乙烯基倍半硅氧烷的硅烷化耦合,
其中,R1和R2由如上定义,具有通式4所示的烯烃,
其中,R3由如上定义,为一种钌配合物,以作为催化剂存在。
作为催化剂的钌配合物如通式5所示
RuHCl(CO)[P(R5)3]n (5)。
其中,n代表2或3,;如果n=3,那么R5代表三苯基膦,而如果n=2,则R5代表三环或三异丙基。
所述催化剂的用量为每摩尔参与通式3所示二乙烯基倍半硅氧烷与通式4所示烯烃反应的不饱和基团,使用1x10-3到1x10-1摩尔Ru,优选为使用所述催化剂的量从0.5x10-2到2x10-2摩尔,更优选为使用1x 10-2摩尔。在反应过程中的有利的影响是添加铜(I)或铜(II)盐作为助催化剂,尤其是添加铜(I)盐,最有利的影响是使用10-1–10摩尔的铜,更优选为每摩尔Ru使用5摩尔铜。
所述反应在溶剂中、惰性气体环境下、开放或封闭的系统中进行,优选为使用不含水分和氧的气体。在开放系统中,该反应不得在高于反应混合物沸点的温度下进行。在封闭系统中,该反应不得在高于200℃的温度下进行。优选的,但非必要的是,使用相对于二乙烯基倍半硅氧烷来说过量的烯烃以加速该反应。优选的,每摩尔通式3所示二乙烯基倍半硅氧烷中的CH2=CH基,使用1.1-2摩尔的过量烯烃,最有利的是使用接近1.5的过量烯烃。
所述反应的反应溶剂选自:芳族有机化合物,优选为甲苯、苯、二甲苯,最优选为甲苯;氯代脂族化合物及它们的混合物。优选的,该反应在1,2-二氯乙烷、氯仿、一氯甲烷中进行,最优选的为使用二氯甲烷或甲苯。优选的,通过以下方式进行该反应:适量的二乙烯基倍半硅氧烷、溶剂、烯烃和催化剂在惰性气体环境下被置于反应器中;搅拌反应混合物并将其加热至40℃或更高的温度,在温度40℃时继续该过程直到反应混合物的沸点。优选的,在整个过程中保持恒定温度。该反应需要1至48小时。
如果使用助催化剂,在混合物已被加热到40℃以上的温度后,其被加入到试剂和催化剂的混合物中。所述助催化剂被加入时的温度必须不低于40℃,但不得超过反应混合物的沸点。助催化剂的存在增强了反应速率和产物的产率,并减少了形成副产物的数量。优选的,,在反应之前全部试剂进行干燥和脱氧。该反应在封闭系统和开放系统中的反应条件相同。
该粗产物从反应混合物中分离是通过沉淀操作,其以一种溶剂发起,所述溶剂选自含碳原子C5到C10的脂族烃族、甲醇、乙腈,最优选的是己烷,或以去除溶剂发起。如果使用第二操作,在溶剂蒸发后,将催化剂用一种含碳原子C5到C10的,选择性地仅溶解催化剂的脂族烃的溶剂洗涤。该初级产品通过具有洗脱液的色谱柱进一步纯化,使用的洗脱液是由脂族烃和脂族烃的氯代衍生物的混合物制备得到,优选地,使用己烷:二氯甲烷的比例为10-0:0-10的洗脱液,最优选为5:5。纯化后的洗脱液蒸发,得到纯的产品。
具体实施方式
本发明的二乙烯基倍半硅氧烷的双层衍生物的合成可通过以下实施例进行说明。
该产物通过采取下列光谱进行分析:
1H和13C-NMR,在分光计VarianGemini300上,在300兆赫和75兆赫的频率;
29Si NMR,在色谱仪VarianAvance600上,在119兆赫和203兆赫的频率;
质谱,在4000Q TRAP仪器上,由Applied Biosystems公司生产。
实施例1
一5毫升容量的反应器,装有一磁力搅拌器、一回流冷凝器和一盖子以允许将反应系统连接至一真空气体管线,在氩气环境下加入0.1g(8.29×10-5mol)的二[9,19-甲基乙烯基]-1,3,5,7,11,13,15,17-八(苯基)五环-[11.7.1.13,11.15,17.17,15]-癸硅氧烷(DDSQ-Me),随后加入2mL二氯甲烷和17×10-3g(1.66×10-4mole)苯乙烯。反应混合物在连续搅拌下加热至45℃。然后加入0.0012g(1,66×10-6mole)的carbonylchlorohydridebis(三环己基膦)合钌(II),5分钟后加入0.0008g(8.29×10-6mole)的氯化铜。反应混合物在45℃下加热18小时。然后,在真空下蒸发溶剂并加入2毫升正己烷以洗出催化剂。过滤后,将沉淀物溶解于正己烷与二氯甲烷的体积比为1:2的混合物,并沉积到装有硅胶的色谱柱以从产物中除去催化剂留下的杂质。得到的产品为白色粉末,产率为95%。
实施例2
以实施例1所述的相同方式,在0.0012g(1.66×10-6mole)carbonylchlorohydridebis(三环己基膦)钌(II)和0.0008g(8.29×10-6mole)氯化铜存在的情况下,实施0.1g(8.29×10-5mole)二乙烯基倍半硅氧烷(DDSQ-ME)与31×10-3g(1.66×10-4mole)4-溴苯乙烯之间的反应。得到的产品为白色粉末,产率为93%。
实施例3
以实施例1所述的相同方式,在0.0018g(2.49×10-6mole)carbonylchlorohydridebis(三环己基膦)钌(II)和0.0012g(1.24×10-5mole)氯化铜存在的情况下,实施0.15g(1.24×10-4mole)二乙烯基倍半硅氧烷(DDSQ-ME)与35×10-3g(2.49×10-4mole)4-氯苯乙烯之间的反应。得到的产品为白色粉末,产率为94%。
实施例4
以实施例1所述的相同方式,并在0.0014g(1.99×10-6mole)carbonylchlorohydridebis(三环己基膦)钌(II)和0.0010g(9.95×10-6mole)氯化铜存在的情况下,实施0.12g(9.95×10-5mole)二乙烯基倍半硅氧烷(DDSQ-ME)与27×10-3g(1.99×10-4mole)4-甲氧基苯乙烯之间的反应。得到的产品为白色粉末,产率为91%。
实施例5
以实施例1所述的相同方式,在0.0012g(1.66×10-6mole)carbonylchlorohydridebis(三环己基膦)钌(II)和0.0008g(8.29×10-6mole)氯化铜存在的情况下,实施0.1g(8.29×10-5mole)二乙烯基倍半硅氧烷(DDSQ-ME)与28×10-3g(1.66×10-4mol)4-(三氟甲基)苯乙烯之间的反应。得到的产品为白色粉末,产率为90%。
实施例6
以实施例1所述的相同方式,在0.0011g(1.50×10-6mole)carbonylchlorohydridebis(三环己基膦)钌(II)和0.0007g(7.52×10-6mole)氯化铜存在的情况下,实施0.1g(7.52×10-5mole)二[9.19-苯基乙烯基]-(1,3,5,7,11,13,15,17)-八(苯基)五环-[11.7.1.13,11.15,17.17,15]癸硅氧烷(DDSQ-Ph)与15×10-3g(1.50×10-4mole)苯乙烯之间的反应。得到的产品为白色粉末,产率为90.3%。
实施例7
以实施例1所述的相同方式,在0.0015g(2.10×10-6mole)carbonylchlorohydridebis(三环己基膦)钌(II)和0.0010g(1.05×10-5mole)氯化铜存在的情况下,实施0.14g(1.05×10-4mole)二乙烯基倍半硅氧烷(DDSQ-PH)与36×10-3g(2.10×10-4mole)4-(三氟甲基)苯乙烯之间的反应。得到的产品为白色粉末,产率为88%。
实施例8
以实施例1所述的相同方式,在0.0012g(1.65×10-6mol)carbonylchlorohydridebis(三环己基膦)钌(II)和0.0008g(8.27×10-6mole)氯化铜存在的情况下,实施0.11g(8,27×10-5mole)二乙烯基倍半硅氧烷(DDSQ-PH)与20×10-3g(1.65×10-4mole)4-甲基苯乙烯之间的反应。得到的产品为白色粉末,产率为91%。
实施例9
以实施例1所述的相同方式,在0.0011g(1.50×10-6mole)carbonylchlorohydridebis(三环己基膦)钌(II)和0.0007g(7.52×10-6mole)氯化铜存在的情况下,实施0.1g(7.52×10-5mole)二乙烯基倍半硅氧烷(DDSQ-PH)与28×10-3g(1,50×10-4mole)四溴苯乙烯之间的反应。得到的产品为白色粉末,产率为95%。
实施例10
以实施例1所述的相同方式,在0.0015g(2.10×10-6mole)carbonylchlorohydridebis(三环己基膦)钌(II)和0.0010g(1.05×10-5mole)氯化铜存在的情况下,实施0.14g(1.05×10-4mole)二乙烯基倍半硅氧烷(DDSQ-PH)与29×10-3g(2.10×10-4mol)4-氯苯乙烯之间的反应。得到的产品为白色粉末,产率为91%。
实施例11
以实施例1所述的相同方式,在0.0010g(1.44×10-6mole)carbonylchlorohydridebis(三环己基膦)钌(II)和0.0007g(7.19×10-6mole)氯化铜存在的情况下,实施0.1g(7.19×10-5mol)二[9,19-(4--甲氧基苯基)乙烯基]-(1,3,5,7,11,13,15,17)-八(苯基)五环[11.7.1.13,11.15,17.17,15]癸硅氧烷(DDSQ-4-MeOPh)与14.5×10-3g(1.44×10-4mole)苯乙烯之间的反应。得到的产品为白色粉末,产率为87%。
实施例12
以实施例1所述的相同方式,在0.0012g(1.72×10-6mole)carbonylchlorohydridebis(三环己基膦)钌(II)和0.0008g(8.63×10-6mole)氯化铜存在的情况下,实施0.12g(8.63×10-5mole)二乙烯基倍半硅氧烷(DDSQ-4-MeOPh)与31.5×10-3g(1.72×10-4mole)四溴苯乙烯之间的反应。得到的产品为白色粉末,产率为85%。
实施例13
以实施例1所述的相同方式,在0.0010g(1.44×10-6mole)carbonylchlorohydridebis(三环己基膦)钌(II)和0.0007g(7.19×10-6mole)氯化铜存在的情况下,实施0.1g(7.19×10-5mole)二乙烯基倍半硅氧烷(DDSQ-4-MeOPh)与19.6×10-3g(1.44×10-4mole)4-氯苯乙烯之间的反应。得到的产品为白色粉末,产率为90%。
表
以上对本发明的具体实施例进行了详细描述,但其只是作为范例,本发明并不限制于以上描述的具体实施例。对于本领域技术人员而言,任何对本发明进行的等同修改和替代也都在本发明的范畴之中。因此,在不脱离本发明的精神和范围下所作的均等变换和修改,都应涵盖在本发明的范围内。
Claims (1)
1.通式1所示的二乙烯基倍半硅氧烷的新型官能化不饱和双层衍生物
(1),
其中:
-R1 相同且代表含1至2个环的芳基;
-R2 相同且代表:
含碳原子C1到C2的烷基,
含1至2个环的未被取代的芳基,
含1至2个环的和在环的任意位点被包括含碳原子C1到C3的烷基的烷氧基取代的单取代芳基;
-R3 相同且代表:
式2所示组
-R4-R5- (2),
其中,R4 代表含碳原子C1到C3的烷基,而R5 代表含1至2个环的芳基,
含1至2个环的未取代芳基,
含1至2个环的和在任意位点被以下基团取代的芳基:
含碳原子C1到C2的烷基,
包括含碳原子C1至C2的烷基的烷氧基,
卤素X= F、Cl、Br,
含碳原子C1至C2和F或Cl的被完全取代的卤代烷基。
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EP1428795A1 (en) * | 2001-09-18 | 2004-06-16 | Chisso Corporation | Silsesquioxane derivatives and process for production thereof |
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CN103052645A (zh) * | 2010-08-20 | 2013-04-17 | 亚当密茨凯维奇大学 | 官能化的多面体八乙烯基硅倍半氧烷 |
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CN103052645A (zh) * | 2010-08-20 | 2013-04-17 | 亚当密茨凯维奇大学 | 官能化的多面体八乙烯基硅倍半氧烷 |
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