CN101360996B - 色谱用整体柱分离介质及其制造方法 - Google Patents
色谱用整体柱分离介质及其制造方法 Download PDFInfo
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Abstract
本发明提供一种非粒子凝集型的有机聚合物整体柱分离介质。其中,具备骨架相和以三维网状连续的细孔,在骨架相的表面具有可以导入新的官能团的官能团;骨架相具有超微到微米尺寸的平均直径,具有不是粒子凝集型的共连续结构,由来自二官能性以上的环氧化合物与二官能性以上的胺化合物的加聚物构成,富含有机物质,而且不含有来源于芳香族的碳原子。
Description
技术领域
本发明涉及一种具有由富含有机物质的骨架相和以三维网状连续的细孔构成的共连续结构的色谱用整体柱分离介质及其制造方法。
背景技术
贯通流道与骨架成为一体的多孔质体(称为整体柱)在用作高速液相色谱用的分离介质的情况下,被报道为表现出基于宽流道和细骨架而可以得到高柱性能或者基于低压降而即使在高流速下也可以抑制性能的降低的、在过去的粒子填充型的柱中未见的优越性(参照N.Ishizuka,H.Kobayashi,H.Minakuchi,K.Nakanishi,K.Hirao,K.Hosoya,T.Ikegami,and N.Tanaka,J.Chromatogr.A,960,85(2002)。)。
使用二氧化硅凝胶的整体柱主要基于微细的结构控制而表现出高性能,一部分也被市售。
还存在以有机高分子为基础的聚合物整体柱,但如后所述,过去的聚合物整体柱源于通常的自由基聚合的不均质性而不能冻结作为二相体系的相分离过程的过渡状态的旋量分解的结构,因而,通常成为相分离进一步发展的粒子凝集型。因此,尽管形成了贯通细孔,但结构的均一性低,成为粒子凝集型,不能实现以二氧化硅凝胶为基础的整体柱之类的高性能化。
过去的聚合物整体柱的配制如以Svec等的专利例(参照美国专利第5,453,185号公报。)为代表,基本上是在苯乙烯/二乙烯基苯之类的疏水性单体成分中,例如在单体中组合成为不良溶剂的苄醇等制孔剂来进行的。在这样的溶液体系中,基本上与成长的聚合物链的位阻相比,聚合物链间的范德华(van der Walls)力变大,聚合物链发生凝集。所以,发生聚合物链的缠绕引起的环生成和聚合物链凝集引起的微粒凝胶粒子的成长、体系的急剧的表面能上升,进而,微凝胶粒子发生凝集,凝胶继续相似的成长(不规则碎片形(fractal))从而粗化。因而,这样的单体与不良溶剂体系的特征在于,凝胶以粒子凝集的形态成长,同时相分离与凝胶化竞争从而极早地发生,大(macroporous)气孔的比表面积小的整体柱形态被固定化,成为粒子凝集型整体柱。所以,在过去的聚合物整体柱中本质上存在没有骨架结构、通孔(through pore)(贯通细孔)的经路因子大、在高流速下的背压上升、整体柱压缩性引起的形态变化等问题。
发明内容
本发明是为了解决所述的过去的有机聚合物整体柱的课题而提出的,其目的在于提供一种作为分离介质的非粒子凝集型的有机聚合物整体柱及其制造方法。
本发明人等为了解决这样的课题而进行了潜心研究,结果发现,将具有特定的分子结构的环氧化合物溶解于制孔剂中,向其中加入二官能性以上的胺化合物,通过进行加热聚合,使聚合物和制孔剂发生旋量分解,利用相分离的成长,在移行至粒子凝集结构之前,稳定地进行交联,由此冻结不是粒子凝集型的共连续结构,接着通过除去制孔剂而得到骨架结构极为均一的多孔体。另外,还发现可以成为下述分离介质,以至完成本发明,即,得到的多孔体源于其骨架的均一性而表现出极高的理论塔板数的分离介质。
即,本发明的有机高分子凝胶状色谱用整体柱分离介质具备骨架相、利用该骨架相形成的以三维网状连续的细孔和存在于骨架相的表面的可以导入新的官能团的官能团,该骨架相具有超微到微米尺寸的平均直径,具有不是粒子凝集型的共连续结构,由来自二官能性以上的环氧化合物与二官能性以上的胺化合物的加聚物构成,富含有机物质,而且不含有来源于芳香族的碳原子。
存在于骨架相的表面的可以导入新的官能团的官能团除了利用环氧基与氨基的反应生成的羟基以外,还包括未反应而残留的氨基或环氧基。
环氧化合物的优选例为2,2,2-三-(2,3-环氧丙基)-异氰尿酸酯(2,2,2-tri-(2,3-epoxypropyl)-isocyanurate)。2,2,2-三-(2,3-环氧丙基)-异氰尿酸酯为具有光学对映体的手性(chiral)化合物,在本发明中,可以使用消旋物和旋光物的任意一种。
作为胺化合物,也可以使用手性化合物,作为胺化合物,也可以使用消旋物和旋光物的任意一种。
由该分离介质构成的高速液相色谱用分离柱对应每1米柱长具有50000塔板以上的理论塔板数。
以利用液相色谱分离光学对映体的S体和R体为目的的光学离析用的分离介质是环氧化合物和胺化合物均使用旋光物来成为整体柱分离介质的。
过去利用旋光性的聚合物进行光学离析,但在主链具有光学活性点的物质是来源于作为天然物的“糖”的物质,另一方面,合成高分子不能在主链上含有光学活性点,而成为由主链吊成悬挂(pendant)状的结构。与此相对,环氧化合物及胺化合物均使用旋光物而成的本发明的聚合物虽为合成高分子但在主链中含有光学活性点,成为极稀的分离介质。而且,可以使其在环氧化合物和胺化合物的双方的单体单元上具有光学活性点,所以变化(variation)多样。
另外,本发明的制造方法是用于制造本发明的整体柱分离介质的方法,包括下面的工序(A)~(C)。
(A)在制孔剂中,在60℃~200℃的范围内加热二官能性以上的环氧化合物和二官能性以上的胺化合物,使其聚合,得到凝胶状体的工序,
(B)然后,用水等溶剂清洗该凝胶状体,除去制孔剂,残留骨架相的工序,以及
(C)然后,进行干燥的工序。
在制孔剂中的聚合温度是用于环氧化合物及胺化合物分别在制孔剂中溶解从而进行聚合反应的适当的温度,只要对应环氧化合物、胺化合物及制孔剂的种类适当地设定即可。
在制造工序中使用的环氧化合物的优选例是2,2,2-三-(2,3-环氧丙基)-异氰尿酸酯。该环氧化合物可以为消旋物,也可以为旋光物。
胺化合物是作为固化剂使用的,可以为消旋物或旋光物,可以举出乙二胺、二亚乙基三胺、三亚乙基四胺、三缩四乙二胺、亚氨基双丙胺、双(六亚甲基)三胺、1,3,6-三氨基甲基己烷、聚亚甲基二胺、三甲基六亚甲基二胺、聚醚二胺等脂肪族胺类,异佛尔酮二胺、薄荷烷二胺、N-氨基乙基哌嗪、3,9-双(3-氨丙基)2,4,8,10-四氧螺环、双(4-氨基环己基)甲烷或它们的改性品等脂环式聚胺类,此外还有由聚胺类与二聚酸构成的脂肪族聚酰胺胺类等。优选为在分子内具有2个以上伯胺的脂环族胺化合物,可以特别优选举出双(4-氨基环己基)甲烷、双(4-氨基-3-甲基环己基)甲烷等。
制孔剂是指能够溶解环氧化合物及固化剂,且在它们进行聚合之后,可以使其发生反应诱发相分离的溶剂。作为制孔剂,例如可以举出甲基溶纤剂、乙基溶纤剂等溶纤剂类,乙二醇-甲醚乙酸酯、丙二醇-甲醚乙酸酯等酯类,或聚乙二醇、聚亚丙基二醇等二醇类。其中,优选分子量为600以下的聚乙二醇,特别优选分子量为300以下的聚乙二醇等。
在本发明的制造方法中,在作为环氧化合物使用2,2,2-三-(2,3-环氧丙基)-异氰尿酸酯的情况下,用摩尔比表示胺相对环氧化合物的原料组成,环氧化合物∶胺=1∶1~1∶3的范围为适当的值。
另外,制孔剂的添加量相对环氧化合物、胺及制孔剂的总重量,1~99重量%为适当的值。
本发明的整体柱分离介质由于其骨架相具有超微到微米尺寸的平均直径,具有不是粒子凝集型的共连续结构,由来自二官能性以上的环氧化合物与二官能性以上的胺化合物的加聚物构成,富含有机物质,而且不含有来源于芳香族的碳原子,因此,可以用作赋予过去完全未见的高性能的液相色谱用固定相。那么,可以用于从毛细管色谱柱到常用尺寸的柱。
由该分离介质构成的分离用柱是对应每1米柱长具有50000塔板以上的理论塔板数的柱。
在环氧化合物及胺化合物均使用旋光物而成为整体柱分离介质的情况下,可以利用该分离介质彼此分离光学对映体的S体和R体。
本发明的制造方法是在制孔剂中加热环氧化合物和胺化合物从而使其聚合的极简单的方法,所以可以有效地在从毛细管色谱柱到具有较大直径的柱中利用。
附图说明
图1是表示利用一个实施例制造而成的有机聚合物整体式毛细管柱的扫描型电子显微镜的图。
图2是利用同一实施例的毛细管柱的尿嘧啶和烷基苯的分离色谱。
图3是根据利用其他实施例制造的有机聚合物整体式毛细管柱的光学对映体的分离色谱。
图4是根据利用比较例制造的有机聚合物整体式毛细管色谱柱的尿嘧啶和苯的分离色谱。
具体实施方式
形成为非粒子凝集型且高性能的聚合物整体柱而成的本发明的分离介质利用在原料中使用的环氧化合物与固化剂的特定的组合形成。具体而言,优选环氧化合物为二官能性以上的非芳香族环氧化合物,固化剂为非芳香族胺化合物。
在这些组合中,作为非芳香族环氧化合物,优选2,2,2-三-(2,3-环氧丙基)-异氰尿酸酯(例如TEPIC:日产化学公司的商品名),在向其组合二官能性以上的胺化合物的情况下,可以得到为非粒子凝集型且具有三维分支结构的高性能聚合物整体柱分离介质,所以优选。
以下对可以在本发明中使用的环氧化合物及固化剂进行例示。
例示的环氧化合物为2,2,2-三-(2,3-环氧丙基)-异氰尿酸酯,可以为消旋物或旋光物。
实施例
接着,对分离介质的实施例和适于有效地制造该分离介质的制造方法的实施例进行说明。
(实施例1)
[试剂及溶剂]
作为环氧化合物,使用作为旋光物的SSS体的2,2,2-三-(2,3-环氧丙基)-异氰尿酸酯(TEPIC-S),作为胺化合物,使用双(4-氨基环己基)甲烷(bis(4-aminocyclohexyl)methane:BACM),作为制孔剂,使用分子量为200的聚乙二醇(PEG200:Nacalai Tesque公司的商品名)。
TEPIC和BACM的化学结构式如下所示。
[聚合物整体柱的制作]
相对1.6g的TEPIC-S,配合为BACM成为0.37g、PEG200成为7.00g,用热搅拌器加热、搅拌,成为已溶解的状态,然后填充于熔融石英玻璃毛细管中,用80℃的干燥机加热20小时,使其聚合。
然后,用水和甲醇清洗后进行真空干燥。
制造条件
TEPIC-S……1.6g
BACM……0.37g
PEG200……7.00g
温度……80℃
所述的利用聚合制造的有机聚合物整体式毛细管柱的扫描电子显微镜如图1所示。可知,该整体柱的骨架相具有超微尺寸的平均直径,具有不是粒子凝集型的共连续结构,利用该骨架相形成的细孔呈三维网状。
使用在所述中制造的本发明的有机聚合物整体式毛细管柱(内径100μm,长度21.5cm)进行的尿嘧啶和烷基苯的分离色谱如图2所示。烷基苯包括取代基的碳原子数为0的苯到6的己基苯。移动相为60%的乙腈水溶液(利用20mM磷酸缓冲液,pH7.0),柱温度为室温,利用在210nm下的紫外线吸收进行检测。
图2中的N为理论塔板数,从上面开始,为尿嘧啶、苯和烷基苯,越是下面的塔板,烷基苯的取代基的碳原子数越多。
理论塔板数利用半幅值法,由下式计算。
N=5.54(tr/W0.5h)2
在此,tr为保持时间,W0.5h为半幅值。
如果利用该结果,则可知,相对所有的溶质,以21.5cm的柱可以得到30000塔板以上的理论塔板数(N)。就是说,换算成每米,成为约14万塔板。
(实施例2)
通过环氧化合物和胺化合物均使用旋光物,来制造手性的有机聚合物整体式毛细管柱。
作为环氧化合物,使用作为旋光物的SSS体的2,2,2-三-(2,3-环氧丙基)-异氰尿酸酯(TEPIC-S)0.40g,作为胺化合物,使用其也为旋光物的(1S,2S)-(+)-1,2-环己烷二胺((1S,2S)-(+)-1,2-cyclohexanediamine)0.63g,向其中配合分子量为300的聚乙二醇(PEG300)10g,加热、搅拌,成为已溶解的状态,然后填充于熔融石英玻璃毛细管中,用120℃的烘箱加热聚合4小时。
然后,用水和甲醇进行清洗,然后进行真空干燥。
制造条件
TEPIC-S……0.40g
(1S,2S)-(+)-1,2-环己烷二胺……0.63g
PEG300……12.64g
温度……120℃
所述的利用聚合制造的实施例2的有机聚合物整体柱也为与实施例1同样的骨架相。
使用在所述中制造的本发明的有机聚合物整体式毛细管柱(内径100μm,长度17.5cm)进行的光学对映体(R,S)-1,1’-双-2-萘酚的分离色谱如图3所示。移动相为60%的乙腈水溶液(利用20mM磷酸缓冲液,pH7.0),柱温度为28℃,移动相的流量为0.6μL/分(L为升),线速度为0.86mm/秒,压力为112kg/cm2,样本浓度为1mg/mL,注入1μL,在距离柱9cm的位置,利用在210nm下的紫外线吸收进行检测。
如果利用图3的结果,则可知,-1,1’-双-2-萘酚的R体和S体已被分离。
(比较例)
作为环氧化合物,使用作为芳香族化合物的2-[(4-(1-甲基-1-[4-(2环氧乙烷基甲氧基)苯基]乙基)苯氧基)甲基]环氧乙烷(2-[(4-(1-甲基-1-[4-(2oxiranylmethoxy)phenyl]ethyl)phenoxy)methyl]oxirane:BADE),胺化合物和制孔剂与实施例1相同,作为胺化合物,使用BACM,作为制孔剂,使用PEG200。
将0.52g的BACM加热溶解于7.20g的PEG200,然后加入2.33g的BADE,混合并搅拌。将该溶液填充于熔融石英玻璃毛细管中,用120℃的烘箱加热聚合1小时。
然后,用水和甲醇进行清洗,然后进行真空干燥。
制造条件
BADE……2.33g
BACM……0.52g
PEG200……7.20g
温度……120℃
使用在所述中制造的比较例的有机聚合物整体式毛细管柱(内径100μm,长度20cm)进行的尿嘧啶和苯的分离色谱如图4所示。移动相为60%的乙腈水溶液(利用20mM磷酸缓冲液,pH7.0),柱温度为室温,移动相的流量为0.15mL/分,线速度为1.01mm/秒,压力为50kg/cm2,用配置在距离柱9cm的位置的内径为50μm的毛细管,利用在210nm下的紫外线吸收进行检测。
在图4中,前面的峰为尿嘧啶,后面的峰为苯。利用半幅值法求得的理论塔板数成为尿嘧啶3085、苯378,与实施例1的本发明的理论塔板数相比,为1/10以下。
这可能是因为,由于使用芳香族化合物作为环氧化合物,所以形成的骨架相包括来源于芳香族的碳原子。
产业上的可利用性
本发明的整体柱分离介质可以作为液相色谱用固定相,利用于从毛细管柱到常用尺寸的柱中。
Claims (12)
1.一种有机高分子凝胶状色谱用整体柱分离介质,其中,
具备:骨架相,和
利用所述骨架相形成的以三维网状连续的细孔,和
存在于所述骨架相的表面且可以导入新的官能团的官能团,
所述骨架相由来自二官能性以上的环氧化合物与二官能性以上的胺化合物的加聚物构成,并且所述环氧化合物为2,2,2-三-(2,3-环氧丙基)-异氰尿酸酯,所述胺化合物为脂肪族胺类、脂环式聚胺类或由聚胺类与二聚酸构成的脂肪族聚酰胺胺类,以摩尔比表示相对于所述环氧化合物的胺的原料组成,为环氧化合物∶胺=1∶1~1∶3的范围,所述骨架相具有超微到微米尺寸的平均直径,具备具有三维网状连续的细孔的结构,富含有机物质,而且不含有来源于芳香族的碳原子。
2.根据权利要求1所述的整体柱分离介质,其中,
所述胺化合物为双(4-氨基环己基)甲烷。
3.根据权利要求1或2所述的整体柱分离介质,其中,
由该分离介质构成的高速液相色谱用分离柱中,对应每1米柱长具有50000塔板以上的理论塔板数。
4.根据权利要求1所述的整体柱分离介质,其中,
所述环氧化合物及所述胺化合物均为旋光物,该分离介质对光学对映体具有分离能力。
5.根据权利要求4所述的整体柱分离介质,其中,
所述胺化合物为(1S,2S)-(+)-1,2-环己烷二胺。
6.一种整体柱分离介质的制造方法,其是制造权利要求1所述的整体柱分离介质的方法,其中,
包括:
(A)在制孔剂中,在60℃~200℃的范围内加热二官能性以上的环氧化合物和二官能性以上的胺化合物,使其聚合,得到凝胶状体的工序,
(B)然后,用溶剂清洗该凝胶状体,除去制孔剂,从而残留骨架相的工序,以及
(C)然后,进行干燥的工序,
其中所述环氧化合物为2,2,2-三-(2,3-环氧丙基)-异氰尿酸酯,
所述胺化合物为脂肪族胺类、脂环式聚胺类或由聚胺类与二聚酸构成的脂肪族聚酰胺胺类,
所述制孔剂为溶纤剂类、酯类或二醇类,
以摩尔比表示相对于所述环氧化合物的胺的原料组成,为环氧化合物∶胺=1∶1~1∶3的范围,
制孔剂的添加量相对环氧化合物、胺及制孔剂的总重量,为1~99重量%。
7.根据权利要求6所述的整体柱分离介质的制造方法,其中,
所述脂肪族胺类为乙二胺、二亚乙基三胺、三亚乙基四胺、三缩四乙二胺、亚氨基双丙胺、双(六亚甲基)三胺、1,3,6-三氨基甲基己烷、聚亚甲基二胺、三甲基六亚甲基二胺或聚醚二胺,
所述脂环式聚胺类为异佛尔酮二胺、薄荷烷二胺、N-氨基乙基哌嗪、3,9-双(3-氨丙基)2,4,8,10-四氧螺环、双(4-氨基环己基)甲烷、环己烷二胺或它们的改性物。
8.根据权利要求6所述的整体柱分离介质的制造方法,其中,
所述环氧化合物为2,2,2-三-(2,3-环氧丙基)-异氰尿酸酯,所述胺化合物为双(4-氨基环己基)甲烷。
9.根据权利要求6所述的整体柱分离介质的制造方法,其中,
作为所述环氧化合物及所述胺化合物,均使用旋光物。
10.根据权利要求9所述的整体柱分离介质的制造方法,其中,
所述环氧化合物为2,2,2-三-(2,3-环氧丙基)-异氰尿酸酯,所述胺化合物为(1S,2S)-(+)-1,2-环己烷二胺。
11.根据权利要求6所述的整体柱分离介质的制造方法,其中,
所述溶纤剂类为甲基溶纤剂或乙基溶纤剂,
所述酯类为乙二醇一甲醚乙酸酯或丙二醇一甲醚乙酸酯,
所述二醇类为聚乙二醇或聚丙二醇。
12.根据权利要求6所述的整体柱分离介质的制造方法,其中,
所述制孔剂为聚乙二醇。
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