CN115385962A - 一种具有线性聚硅氧烷骨架的环保型磷氮协同催化剂的合成方法 - Google Patents
一种具有线性聚硅氧烷骨架的环保型磷氮协同催化剂的合成方法 Download PDFInfo
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Abstract
本发明公开了一种具有线性聚硅氧烷骨架的磷氮协同催化剂的合成方法,属于化学、材料技术领域。本发明以线性聚硅氧烷作为分子骨架,通过加成、取代等反应,直接与含磷氮的基团反应制备得到氨基乙基哌嗪螺环季戊四醇双膦酸酯官能化的七甲基三硅氧烷,该技术反应条件温和,产物无需进一步重结晶提纯,缩短了制备流程,大大降低了生产成本,且该催化剂可以显著提高苯并噻唑类染料的合成效率。
Description
技术领域
本发明涉及一种具有线性聚硅氧烷骨架的磷氮协同催化剂的合成方法,属于化学、材料技术领域。
背景技术
线性聚硅氧烷骨架的磷氮化合物是一类重要的合成中间体,其在医学、化学以及工业生产中都有着广泛的应用。现阶段,硅磷氮协同化合物在染料合成催化领域取得了较大的突破,并衍生出了诸多从简单到复杂的硅磷氮化合物;同时硅磷氮类化合物拥有较多孤电子对,电子转移、分子重排比较活跃,被广泛地应用于染料合成中不对称Diels Alder反应、偶合反应、Mannich反应等。线性硅磷氮协同催化剂具有更多的活性位点,具有反应速度快、高收率、高选择性等优势,使其具有更高的实用价值。
目前,分散染料合成工艺大多是以单体直接反应,不使用催化剂,这样的反应制备过程极为繁琐,且得到的产品纯度较低,副产物较多,因此需进一步重结晶提纯,导致效率降低,产品收率降低。
发明内容
针对上述问题,本发明提供了一种具有线性聚硅氧烷骨架的磷氮协同催化剂的合成方法。本发明以线性聚硅氧烷作为分子骨架,通过加成、取代等反应,直接与含磷氮的基团反应制备得到氨基乙基哌嗪螺环季戊四醇双膦酸酯官能化的七甲基三硅氧烷,该技术反应条件温和,产物无需进一步重结晶提纯,缩短了制备流程,大大降低了生产成本,且该催化剂可以显著提高苯并噻唑类染料的合成效率。
本发明的具体技术方案为:提供一种具有线性聚硅氧烷骨架的磷氮协同催化剂的合成方法,具体步骤如下:
(1)向三颈烧瓶中加入七甲基三硅氧烷(HMTS),甲苯和催化剂量的H2PtCl6,并开始用磁力搅拌器搅拌。然后将烯丙基缩水甘油醚(AGE)溶于甲苯,一并逐滴加入到烧瓶中。接通氮气并将该混合溶液加热至70℃,反应7h,提纯获得透明液体(GHMTS)。
(2)向三颈烧瓶中加入氨基乙基哌嗪(AEP),GHMTS和适量甲苯,接通氮气并加热至75℃,开启磁力搅拌反应6h,提纯最终得到浅黄色油状液体(AHMTS)。
(3)使用三氯氧磷与季戊四醇合成了季戊四醇二膦酸酯二氯化物(SPDPC),然后向三颈烧瓶中加入适量乙腈,并将SPDPC分散其中。接下来,将AHMTS缓慢加入上述溶液中,加入Et3N,接通氮气保护,并在80℃下反应7h,最终通过过滤获得目标产物黄色固体(SiPNBH)。
本发明制备方法的化学反应过程示意如下:
在本发明的一种实施方式中,步骤(1)中,所述HMTS与AGE摩尔比为1:1 1:1.2;步骤(2)中,所述AEP与GHMTS摩尔比为1:1 1:1.2;步骤(3)中,SPDPC与AHMTS 摩尔比为1:2。
在本发明的一种实施方式中,步骤(1)(2)(3)中,所述反应物和有机溶剂的用量比为 1g:(3.0~8.0)mL。
在本发明的一种实施方式中,步骤(3)中,所述缚酸剂为三乙胺、氢氧化钠和氢氧化钾中的一种;所述缚酸剂的摩尔质量为SPDPC的2倍。
在本发明的一种实施方式中,步骤(1)(2)(3)在无氧无水条件下进行。
在本发明的一种实施方式中,步骤(1)(2)(3)中所述提纯方法为旋蒸,旋蒸温度40 80℃,真空度状态小于<-0.1MPa。
与现有技术相比,本发明的有益效果为:
(1)本发明以线性聚硅氧烷作为分子骨架,通过加成、取代等反应,直接与含磷氮的基团反应制备得到氨基乙基哌嗪螺环季戊四醇双膦酸酯官能化的七甲基三硅氧烷,该技术反应条件温和,产物无需进一步重结晶提纯,缩短了制备流程,大大降低了生产成本。
(2)本发明方法制得的产物收率高(>90.0%)、纯度高(>95%)。
(3)本发明整个反应过程不涉及危险化学品,操作环境更好更安全,适合工业化生产。
附图说明:
图1为合成目标产物ASPBH的核磁共振氢谱图;
具体实施方式
下面结合具体实例对本发明作进一步地说明,所举实例只用于解释本发明,并非用于限定本发明的范围。
实施例1
一种结构式如下所示的具有线性聚硅氧烷骨架的磷氮协同催化剂,
其合成路线为:
(1)搭建回流反应装置,向100mL三颈烧瓶中加入4.45g七甲基三硅氧烷(HMTS),10mL甲苯和催化剂量的H2PtCl6,并开始用磁力搅拌器搅拌。然后将2.28g烯丙基缩水甘油醚(AGE)溶于10mL甲苯,一并逐滴加入到烧瓶中。接通氮气并将该混合溶液加热至70℃,反应7h。通过旋转蒸发仪蒸除掉溶剂,获得透明液体(3-缩水甘油基丙氧基)七甲基三硅氧烷(GHMTS)。
(2)在另一个装有相同装置的三颈烧瓶中,加入2.58g氨基乙基哌嗪(AEP),6.73gGHMTS和适量甲苯,接通氮气并加热至75℃,开启磁力搅拌反应6h。然后通过旋转蒸发仪蒸出溶剂,最终得到浅黄色油状液体氨基乙基哌嗪官能化的七甲基三硅氧烷(AHMTS)。
(3)使用三氯氧磷与季戊四醇合成了季戊四醇二膦酸酯二氯化物(SPDPC)。然后向250 mL三颈烧瓶中加入适量的乙腈,并将SPDPC分散其中。接下来,将AHMTS缓慢加入上述溶液中(SPDPC与AHMTS摩尔比为1:2)。加入Et3N,接通氮气保护,并在80℃下反应7 h,最终通过过滤获得黄色固体氨基乙基哌嗪螺环季戊四醇双膦酸酯官能化的七甲基三硅氧烷(ASPBH)。
以上所述,仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (6)
1.一种具有线性聚硅氧烷骨架的磷氮协同催化剂制备方法,其特征在于,包括以下步骤:
(1)向三颈烧瓶中加入七甲基三硅氧烷(HMTS),甲苯和催化剂量的H2PtCl6,并开始用磁力搅拌器搅拌。然后将烯丙基缩水甘油醚(AGE)溶于甲苯,一并逐滴加入到烧瓶中。接通氮气并将该混合溶液加热至70℃,反应7h,提纯获得透明液体(GHMTS)。
(2)向三颈烧瓶中加入氨基乙基哌嗪(AEP),GHMTS和适量甲苯,接通氮气并加热至75℃,开启磁力搅拌反应6h,提纯最终得到浅黄色油状液体(AHMTS)。
(3)使用三氯氧磷与季戊四醇合成了季戊四醇二膦酸酯二氯化物(SPDPC),然后向三颈烧瓶中加入适量乙腈,并将SPDPC分散其中。接下来,将AHMTS缓慢加入上述溶液中,加入Et3N,接通氮气保护,并在80℃下反应7h,最终通过过滤获得目标产物黄色固体(ASPBH)。
2.如权利要求1所述的制备方法,其特征在于:
HMTS与AGE摩尔比为1:1 1:1.2
AEP与GHMTS摩尔比为1:1 1:1.2
SPDPC与AHMTS摩尔比为1:2。
3.如权利要求1所述的制备方法,其特征在于:步骤中,所述反应物和有机溶剂的用量比为1g:(3.0~8.0)mL。
4.如权利要求1所述的制备方法,其特征在于:步骤(3)中,所述缚酸剂为三乙胺、氢氧化钠和氢氧化钾中的一种;所述缚酸剂的摩尔质量为SPDPC的2倍。
5.如权利要求1所述的制备方法,其特征在于:步骤(1)-(3)在无氧无水条件下进行。
6.如权利要求1所述的制备方法,其特征在于:步骤中,所述提纯方法为旋蒸,旋蒸温度40 80℃,真空度状态小于<-0.1MPa。
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