CN1523349A - 液相色谱用填充剂、其制造方法及用途 - Google Patents
液相色谱用填充剂、其制造方法及用途 Download PDFInfo
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- CN1523349A CN1523349A CNA2004100046088A CN200410004608A CN1523349A CN 1523349 A CN1523349 A CN 1523349A CN A2004100046088 A CNA2004100046088 A CN A2004100046088A CN 200410004608 A CN200410004608 A CN 200410004608A CN 1523349 A CN1523349 A CN 1523349A
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- phase chromatography
- filling agent
- alkyl
- integer
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- 239000012071 phase Substances 0.000 claims abstract description 52
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- 125000005372 silanol group Chemical group 0.000 claims abstract description 26
- 239000000741 silica gel Substances 0.000 claims abstract description 24
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- 239000000126 substance Substances 0.000 claims abstract description 18
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
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- FKPRNUYMAWSSLI-UHFFFAOYSA-N CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC[Si](C)(Cl)Cl Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC[Si](C)(Cl)Cl FKPRNUYMAWSSLI-UHFFFAOYSA-N 0.000 description 1
- TZBJWVGVTBVMJO-UHFFFAOYSA-N C[Si](Cl)(Cl)Cl.C[Si](OC)(OC)OC Chemical compound C[Si](Cl)(Cl)Cl.C[Si](OC)(OC)OC TZBJWVGVTBVMJO-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47G—HOUSEHOLD OR TABLE EQUIPMENT
- A47G7/00—Flower holders or the like
- A47G7/02—Devices for supporting flower-pots or cut flowers
- A47G7/03—Needle cushions or needle plates for supporting flowers in pots or vases
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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- B01J20/3246—Non-macromolecular compounds having a well defined chemical structure
- B01J20/3257—Non-macromolecular compounds having a well defined chemical structure the functional group or the linking, spacer or anchoring group as a whole comprising at least one of the heteroatoms nitrogen, oxygen or sulfur together with at least one silicon atom, these atoms not being part of the carrier as such
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
- B01J2220/54—Sorbents specially adapted for analytical or investigative chromatography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/50—Aspects relating to the use of sorbent or filter aid materials
- B01J2220/58—Use in a single column
Abstract
本发明提供了一种残留硅烷醇基极少、显著抑制了碱性化合物的拖尾现象的高效液相色谱用填充剂。在液相或气相条件下,使下述通式(II)表示的封端剂与经过化学修饰剂表面修饰的硅胶发生反应,使封端剂化学键合在硅胶表面的残留硅烷醇基上。式中R3及R4可以相同,也可以不同,表示碳原子数1~4的烷基;n为形成环的单元系数,为2~10的整数。
Description
技术领域
本发明涉及液相色谱用填充剂的新型制造方法。
液相色谱作为医药品或食品、天然化合物等领域内的重要分析分离手段而被广泛使用。常用的液相色谱用填充剂是表面经过烷基等修饰的多孔硅胶。作为表面修饰硅胶,最常见的是通过硅原子在表面的羟基(OH)上导入了十八烷基的十八烷基硅烷(ODS),导入基团已知有辛基、丁基、甲基等。另外,烷基末端也可以具有苯基或氨基、氰基等官能团。
但是,即使利用烷基化对硅胶进行表面修饰,在二氧化硅表面仍残留有硅烷醇基(Si-OH)。残留的硅烷醇基在以碱性化合物为分析或制备性分离对象时,存在因与该化合物间较强的相互作用而使其无法溶出,或峰拖尾等问题。为了避免上述问题出现,有必要在表面修饰后,利用二次甲硅烷基化对残留的硅烷醇基进行封端,使二氧化硅表面进一步惰化。
背景技术
作为现有的封端法,特开平4-212058号公报中公开了如下方法:使作为封端剂的特定的环硅氧烷、氢硅氧烷、烷氧基硅烷或硅氧烷在经过化学修饰剂表面修饰的硅胶或多孔玻璃上发生气相反应,使封端剂化学键合在硅胶表面残留的硅烷醇基上;特开平8-304371号公报中公开了使特定的聚二甲基硅氧烷、聚苯基甲基硅氧烷、聚二苯基二甲基硅氧烷、聚氰基丙基甲基二甲基硅氧烷、聚氰基丙基甲基苯基甲基硅氧烷等与硅胶反应的方法;特开平10-73579号公报中公开了如下方法:在180~240℃下,使特定的硅氮烷、二硅氮烷、硅氧烷、聚硅氧烷等末端加成剂中的至少2种与经过化学修饰剂表面修饰的硅胶发生气相反应。
但是,在这些方法中,除了反应必须在高温下进行之外,也无法充分减少二氧化硅表面上残留的硅烷醇基。因此,利用这些方法获得的填充剂无法防止碱性化合物的拖尾现象。
发明内容
基于上述现状,本发明的目的为提供一种将残留的硅烷醇基减至极低水平、并显著抑制了碱性化合物的拖尾现象的高效液相色谱用填充剂。
本发明者为了解决上述问题,进行了各种研究,结果发现了使用特定化合物、在特定条件下进行封端反应的液相色谱用填充剂制造方法。
即,本发明的液相色谱用填充剂制造方法的特征在于,在液相或气相条件下,使下述通式(II)表示的封端剂与经过化学修饰剂表面修饰的硅胶发生反应,使封端剂化学键合在硅胶表面的残留硅烷醇基上。
式中R3及R4可以相同,也可以不同,表示碳原子数1~4的烷基;n为形成环的单元系数,为2~10的整数。
上述化学修饰剂优选为下述通式(I)表示的烷基硅烷。但是化学修饰剂并不限定于此。
式中,X1为氢原子、卤素原子或碳原子数1~4的烷氧基;R0、R1及R2可以相同,也可以不同,分别表示烷基或芳基;a为R0的系数,是0~3的整数;b为R1的系数,是0~3的整数;c为R2的系数,是0~3的整数;d为X1的系数,是1~3的整数;a+b+c+d=4。
在本说明书及权利要求的范围内,烷基可以为直链状、支链状或脂环状烷基。
通式(I)中的R0、R1及R2表示的烷基优选具有1~50个碳原子,更优选具有1~30个碳原子。此烷基可以在末端具有芳基、氨基或氰基;也可以在非末端具有酰胺基(-NH-C(O)-)、氨基甲酸酯基(-O-C(O)-NH-)或脲基(-NH-C(O)-NH-)、酯基(-O-C(O)-)或碳酸酯基(-O-C(O)-O-)。
通式(I)中的R0、R1及R2表示的芳基可以为苯基、甲苯基、萘基等。
对于利用上述方法制成的液相色谱用填充剂而言,用29Si固相NMR求出的硅烷醇基残留量极小(优选为5%或5%以下)。填充了此液相色谱用填充剂的液相色谱柱特别适用于反相液相色谱法,在化合物、尤其是碱性化合物的分析及制备性分离方面有用。
原料硅胶是具备下述特性的多孔硅胶:粒径通常为1~1000μm、优选为2~200μm,细孔径通常为10~10000埃、优选为50~3000埃,表面积通常为1~1000m2/g、优选为5~600m2/g。分析柱用填充剂的原料硅胶优选为高纯度的球形物。
通式(I)表示的化学修饰剂为单官能、双官能或三官能的、具有氢原子、卤素原子或烷氧基的烷基硅烷或芳基硅烷。化学修饰剂的具体例如表1所示。
表1
R1(简记) | 单官能烷基化剂 | 双官能烷基化剂 | 三官能烷基化剂 |
C30 | 三十烷基二甲基氯硅烷三十烷基二甲基甲氧基硅烷 | 三十烷基甲基二氯硅烷三十烷基甲基二甲氧基硅烷 | 三十烷基三氯硅烷三十烷基三甲氧基硅烷 |
C22 | 二十二烷基二甲基氯硅烷二十二烷基二甲基甲氧基硅烷 | 二十二烷基甲基二氯硅烷二十二烷基甲基二甲氧基硅烷 | 二十二烷基三氯硅烷二十二烷基三甲氧基硅烷 |
C18 | 十八烷基二甲基氯硅烷十八烷基二甲基甲氧基硅烷 | 十八烷基甲基二氯硅烷十八烷基甲基二甲氧基硅烷 | 十八烷基三氯硅烷十八烷基三甲氧基硅烷 |
C8 | 辛基二甲基氯硅烷辛基二甲基甲氧基硅烷 | 辛基甲基二氯硅烷辛基甲基二甲氧基硅烷 | 辛基三氯硅烷辛基三甲氧基硅烷 |
C4 | 丁基二甲基氯硅烷丁基二甲基甲氧基硅烷 | 丁基甲基二氯硅烷丁基甲基二甲氧基硅烷 | 丁基三氯硅烷丁基三甲氧基硅烷 |
CI | 三甲基氯硅烷三甲基甲氧基硅烷 | 二甲基二氯硅烷二甲基二甲氧基硅烷 | 甲基三氯硅烷甲基三甲氧基硅烷 |
Ph | 苯基二甲基氯硅烷苯基二甲基甲氧基硅烷 | 苯基甲基二氯硅烷苯基甲基二甲氧基硅烷 | 苯基三氯硅烷苯基三甲氧基硅烷 |
NH2 | 3-氨基丙基二甲基甲氧基硅烷3-氨基丙基二甲基乙氧基硅烷 | 3-氨基丙基甲基二甲氧基硅烷3-氨基丙基甲基二乙氧基硅烷 | 3-氨基丙基三甲氧基硅烷3-氨基丙基三乙氧基硅烷 |
CN | 3-氰基丙基二甲基氯硅烷3-氰基丙基二甲基甲氧基硅烷 | 3-氰基丙基甲基二氯硅烷3-氰基丙基甲基二甲氧基硅烷 | 3-氰基丙基三氯硅烷3-氰基丙基三甲氧基硅烷 |
使用通式(I)表示的物质作为化学修饰剂时,通常在60~200℃、优选100~160℃的条件下,优选在液相中进行硅胶的表面修饰反应。作为溶剂,只要是不与硅胶和化学修饰剂反应,且在上述反应温度下稳定的溶剂即可,优选苯、甲苯、二甲苯、均三甲苯等芳香族烃,二氯苯等取代芳香族化合物。反应压力通常为常压,但是,也可以在1.5~5.0kg/cm2的加压条件下进行反应。反应时间通常为0.5~20小时,优选为3~10小时。优选添加吡啶、咪唑之类碱性化合物。
表面修饰反应后的反应液可以直接用于随后的封端反应,也可以将固形成分从表面修饰反应液中取出,将其洗涤干燥后用于封端反应。
通式(II)表示的封端剂为双官能环状硅氮烷,例如有1,1,3,3,5,5-六甲基环丙硅氮烷、1,1,3,3,5,5,7,7-八甲基环丁硅氮烷、1,1,3,3,5,5,7,7,9,9-十甲基环戊硅氮烷、1,1,3,3,5,5,7,7,9,9,11,11-十二甲基环己硅氮烷、1,1,3,3,5,5-六乙基环丙硅氮烷、1,1,3,3,5,5,7,7-八乙基环丁硅氮烷、1,1,3,3,5,5,7,7,9,9-十乙基环戊硅氮烷、1,1,3,3,5,5,7,7,9,9,11,11-十二乙基环己硅氮烷等。这些物质可以单独使用,也可以使用其中2种或2种以上的混合物。封端剂(II)也可以与通式(III)表示的双官能硅烷(例如二甲基二氯硅烷、二甲基二甲氧基硅烷等)混合使用。
式中,X2及X3可以相同也可以不同,表示氢原子、卤素原子或碳原子数1~4的烷氧基;R5及R6可以相同也可以不同,分别表示碳原子数1~4的烷基或芳基。
作为封端剂的双官能环状硅氮烷具有如下优点:与三甲基氯硅烷或六甲基二硅氮烷等单官能物质相比,能够反应的位点多,活性更高;与甲基三氯硅烷等三官能物质相比,副反应少。双官能环状硅氮烷的沸点高于类似结构的环状硅氧烷约50℃,适于液相反应。另外,与硅氧烷反应中副生成水相反,在使用硅氮烷的液相反应中,氨气逸出至气相,有利于反应进行,而且能够将未反应的硅氮烷回收再利用。
封端剂的使用量以封端剂/表面修饰硅胶的重量比计,通常为0.1~20,优选为0.2~2。
封端剂可以直接用于反应,也可以经过有机溶剂稀释后使用,能够降低此时的成本。用于稀释的有机溶剂只要不与封端剂反应、并且在反应温度下稳定即可,优选苯、甲苯、二甲苯、均三甲苯等芳香族烃,二氯苯等取代芳香族化合物。稀释倍率以溶剂/封端剂的重量比计,通常为0.1~200,优选为1~20。
封端反应可以在气相中进行,但是,如果在液相中进行,则不仅反应设备可以为简易装置,而且能够增加每批的处理量。
封端反应的反应温度优选为100~200℃,更优选为140~180℃。虽然反应温度越高,越能够获得促进封端反应进行的效果,但是设备的负担也越大。
封端反应可以在常压下进行,优选在1.5~5.0kg/cm2的加压条件下进行。另外,通过选择使用沸点在反应温度附近的有机溶剂,能够将反应时的压力抑制在较低水平,缓和了对反应设备耐压性的要求。
封端反应的反应时间通常为0.5~20小时,优选为3~10小时。
封端反应后,能够利用固液分离回收未反应的封端剂,进行再利用。用甲醇洗涤分离后的固形成分,干燥后得到液相色谱用填充剂。
根据本发明,能够在200℃或200℃以下较温和的温度下,使用较简易的反应设备,以较低的成本制造高效液相色谱用填充剂。
本发明的液相色谱用填充剂是硅烷醇基残留量极少(利用29Si固相NMR求出的硅烷醇基残留量优选为5%或5%以下)、显著抑制了碱性化合物的拖尾现象、且大幅度改善了峰对称性的高性能物质,特别适用于反相液相色谱,并且在碱性化合物的分析及制备性分离方面有用。
附图说明
图1是实施例1中得到的液相色谱用填充剂的29Si-NMR图。
图2是使用实施例1中得到的液相色谱用填充剂的阿米替林(amitriptyline)液相色谱图。
图3是实施例2中得到的液相色谱用填充剂的29Si-NMR图。
图4是使用实施例2中得到的液相色谱用填充剂的阿米替林液相色谱图。
图5是实施例3中得到的液相色谱用填充剂的29Si-NMR图。
图6是使用实施例3中得到的液相色谱用填充剂的阿米替林液相色谱图。
图7是比较例1中得到的液相色谱用填充剂的29Si-NMR图。
图8是使用比较例1中得到的液相色谱用填充剂的阿米替林液相色谱图。
图9是比较例2中得到的液相色谱用填充剂的29Si-NMR图。
图10是使用比较例2中得到的液相色谱用填充剂的阿米替林液相色谱图。
图11是使用比较例3的G社制ODS柱I的阿米替林液相色谱图。
图12是使用比较例4的Y社制ODS柱P的阿米替林液相色谱图。
图13是使用比较例5的N社制ODS柱M的阿米替林液相色谱图。
图14是使用比较例6的S社制ODS柱C的阿米替林液相色谱图。
具体实施方式
下面列举几个本发明的实施例,具体地说明本发明。但是,本发明并不限定于这些实施例。为了对比,举出使用现有封端剂的实施例。另外,也使用市售的代表性ODS柱进行了对比试验。
实施例1
在200ml甲苯中,将作为硅胶的Daisogel SP-100-5P(球形高纯度硅胶,平均粒径5μm,细孔径100埃,表面积450m2/g)15g进行共沸脱水后,加入作为化学修饰剂的十八烷基二甲基氯硅烷4.7g和吡啶1.3g,加热此混合物,回流5小时,将反应混合物冷却、过滤后,用甲醇多次洗涤得到的固形成分,干燥后得到表面修饰硅胶19g。
将得到的表面修饰硅胶19g、作为封端剂的1,1,3,3,5,5-六甲基环丙硅氮烷20g和二甲苯200g加入到高压釜中,在液相中温度160℃、压力1.5~3.0kg/cm2的条件下,进行5小时封端反应,将反应混合物冷却、过滤后,用甲醇多次洗涤得到的固形成分,干燥后得到液相色谱用填充剂20g。
实施例2
使用十八烷基甲基二氯硅烷5.0g作为化学修饰剂,将吡啶的添加量改为2.6g,除此之外与实施例1同样地操作,得到液相色谱用填充剂20g。
实施例3
使用十八烷基三氯硅烷5.3g作为化学修饰剂,将吡啶的添加量改为3.9g,除此之外与实施例1同样地操作,得到液相色谱用填充剂20g。
比较例1
将使用与实施例1相同的化学修饰剂、进行相同操作得到的表面修饰硅胶19g加入到作为封端剂的三甲基氯硅烷20g和甲苯200g中,在液相温度110℃、常压条件下,进行5小时封端反应,与实施例1同样地处理得到的反应混合物,得到液相色谱用填充剂20g。
比较例2
将使用与实施例1相同的化学修饰剂、进行相同操作得到的表面修饰硅胶19g、六甲基二硅氮烷20g和甲苯200g加入到高压釜中,在液相中温度140℃、压力1.5~3.0kg/cm2的条件下,进行5小时封端反应,与实施例1同样地处理得到的反应混合物,得到液相色谱用填充剂20g。
比较例3
准备G社制ODS柱I(内径4.6mm,长150mm)。
比较例4
准备Y社制ODS柱P(内径4.6mm,长150mm)。
比较例5
准备N社制ODS柱M(内径4.6mm,长150mm)。
比较例6
准备S社制ODS柱C(内径4.6mm,长150mm)。
评价试验
1)硅烷醇基残留量的定量
针对实施例及比较例中得到的液相色谱用填充剂即经过封端处理的硅胶,使用高分解能500MHz 29Si固相NMR(日本电子社制“JeolECP-500”),按照单脉冲幻角自旋法,在下述条件下,进行Si种类的NMR测定,利用下式由得到的NMR光谱计算硅烷醇基残留量。
硅烷醇基残留量=[Q3/(Q3+Q4)]×100%
Q3:在-100ppm附近属于具有硅烷醇基的Si的峰积分值
Q4:在-110ppm附近属于不具有硅烷醇基的Si的峰积分值
当然,硅烷醇基残留量越低越好,优选为5%或5%以下。29Si-NMR测定条件:
旋转数:5000Hz
磁场强度:11.7T
振动频率:99.36MHz
脉冲长:2.8μs
测定周期:25s
扫描次数:2500
实施例1~3及比较例1~2中得到的液相色谱用填充剂的29Si-NMR图分别如图1、图3、图5、图7及图9所示。由图可知,在实施例1~3的液相色谱用填充剂中未检出残留硅烷醇基(-100ppm附近的峰(Q3))。
由实施例1~3及比较例1~2的液相色谱用填充剂求出的硅烷醇基残留量如表2所示。由表2可知,实施例1~3的液相色谱用填充剂的硅烷醇基残留量为0%,是理想的结果。比较例1~2的液相色谱用填充剂的硅烷醇基残留量多,不是理想的结果。
2)液相色谱法评价
将实施例及比较例中得到的液相色谱用填充剂填充在不锈钢柱(内径4.6mm,长150mm)内,使用阿米替林(amitriptyline)作为标准样品,进行液相色谱法评价试验。阿米替林是具有抗抑郁作用的强碱性化合物(pKa=9.4),是在液相色谱法中拖尾剧烈、难以进行分析的代表性化合物。使用最容易受残留硅烷醇基影响的物质(pH7.0,温度20℃)作为构成移动相的缓冲液,在下述操作条件下进行液相色谱法评价试验。实施例1~3及比较例1~6的液相色谱用填充剂的阿米替林液相色谱图分别如图2、图4、图6、图8、图10、图11、图12、图13及图14所示。
如下述式所示,以10%峰高为基准计算实施例1~3及比较例1~6的液相色谱用填充剂的非对称系数(As)。得到的值如表2及表3所示。非对称系数优选为3.0或3.0以下,更理想的为1.0,数值越低表示峰对称性越优良,拖尾越小。由表可知,使用实施例1~3的液相色谱用填充剂时,非对称系数为3.0或3.0以下,是较理想的结果。使用比较例1~6的液相色谱用填充剂时,非对称系数远远超出3.0,不是理想的结果。
As=b/a
a:10%峰高处的峰前半部分的峰宽
b:10%峰高处的峰后半部分的峰宽
液相色谱的操作条件
移动相:20mM K2HPO4-KH2PO4缓冲液(pH=7.0)/甲醇
=35/65(体积比)
流速:1.4ml/分
柱温:20℃
检测器:UV240nm
样品:阿米替林(0.75mg/ml、10μl)
表2
化学修饰剂 | 封端剂 | 硅烷醇基残留量(%) | 非对称系数(As) | |
实施例1 | 十八烷基二甲基氯硅烷 | 1,1,3,3,5,5-六甲基环丙硅氮烷 | 0 | 1.7 |
实施例2 | 十八烷基甲基二氯硅烷 | 1,1,3,3,5,5-六甲基环丙硅氮烷 | 0 | 2.5 |
实施例3 | 十八烷基三氯硅烷 | 1,1,3,3,5,5-六甲基环丙硅氮烷 | 0 | 2.9 |
比较例1 | 十八烷基二甲基氯硅烷 | 三甲基氯硅烷 | 13.1 | 6.2 |
比较例2 | 十八烷基二甲基氯硅烷 | 六甲基二硅氮烷 | 12.2 | 5.6 |
表3
市售柱 | 非对称系数(As) | |
比较例3 | G社制ODS柱I | 4.9 |
比较例4 | Y社制ODS柱P | 7.4 |
比较例5 | N社制ODS柱M | 7.4 |
比较例6 | S社制ODS柱C | 4.2 |
Claims (7)
1、一种液相色谱用填充剂制造方法,其特征在于,在液相或气相条件下,使下述通式II表示的封端剂与经过化学修饰剂表面修饰的硅胶发生反应,使封端剂化学键合在硅胶表面的残留硅烷醇基上;
式中R3及R4可以相同,也可以不同,表示碳原子数1~4的烷基;n为形成环的单元系数,为2~10的整数。
2、如权利要求1所述的液相色谱用填充剂制造方法,其中,化学修饰剂为下述通式I表示的烷基硅烷;
式中,X1为氢原子、卤素原子或碳原子数1~4的烷基;R0、R1及R2可以相同,也可以不同,分别表示烷基或芳基;a为R0的系数,是0~3的整数;b为R1的系数,是0~3的整数;c为R2的系数,是0~3的整数;d为X1的系数,是1~3的整数;a+b+c+d=4。
3、如权利要求2所述的液相色谱用填充剂制造方法,其中,通式I中的R0、R1及R2表示的烷基在末端具有芳基、氨基或氰基,或在非末端具有酰胺基、氨基甲酸酯基或脲基、酯基或碳酸酯基。
4、一种液相色谱用填充剂,是利用权利要求1~3所述的方法制造的液相色谱用填充剂。
5、如权利要求4所述的液相色谱用填充剂,其中,由29Si固相NMR求出的硅烷醇基残留量为5%或5%以下。
6、一种液相色谱用柱,是填充了权利要求4所述的液相色谱用填充剂的液相色谱用柱。
7、一种化合物分析方法或制备性分离方法,是使用权利要求6所述的液相色谱用柱的化合物分析方法或制备性分离方法。
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CN101785991B (zh) * | 2009-12-12 | 2012-08-29 | 鲁东大学 | 一种硅胶键载氨基甘油吸附剂的制备方法 |
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CN107441770A (zh) * | 2017-09-13 | 2017-12-08 | 江易扬 | 黄酮化合物的萃取方法以及苯基键合硅胶固相萃取柱 |
CN107970900A (zh) * | 2017-11-28 | 2018-05-01 | 中国科学院青岛生物能源与过程研究所 | 一种mt-pdms键合硅胶反相高效液相色谱固定相及其制备和应用 |
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US7537703B2 (en) * | 2004-06-23 | 2009-05-26 | Daiso Co., Ltd. | High-endurance packing material for liquid chromatography |
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CN103736471A (zh) * | 2013-12-23 | 2014-04-23 | 北京迪马欧泰科技发展中心 | 一种高效液相色谱固定相封端方法 |
CN103736471B (zh) * | 2013-12-23 | 2018-05-15 | 北京迪马欧泰科技发展中心 | 一种高效液相色谱固定相封端方法 |
CN107441770A (zh) * | 2017-09-13 | 2017-12-08 | 江易扬 | 黄酮化合物的萃取方法以及苯基键合硅胶固相萃取柱 |
CN107970900A (zh) * | 2017-11-28 | 2018-05-01 | 中国科学院青岛生物能源与过程研究所 | 一种mt-pdms键合硅胶反相高效液相色谱固定相及其制备和应用 |
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