KR100971939B1 - 실리카 기초 물질 - Google Patents
실리카 기초 물질 Download PDFInfo
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- KR100971939B1 KR100971939B1 KR1020087014553A KR20087014553A KR100971939B1 KR 100971939 B1 KR100971939 B1 KR 100971939B1 KR 1020087014553 A KR1020087014553 A KR 1020087014553A KR 20087014553 A KR20087014553 A KR 20087014553A KR 100971939 B1 KR100971939 B1 KR 100971939B1
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Abstract
Description
실시예 |
유기실란 |
오토클레베이션 |
유기-개질된 물질에서의 탄소 함량[%] |
작용기화 |
6 | 메틸트리메톡시-실란 | 아니오 | 2.9 | C18 |
7 | 메틸트리메톡시-실란 | 예 | 3.1 | C18 |
8 | 에틸트리메톡시-실란 | 아니오 | 6.9 | - |
9 | 에틸트리메톡시-실란 | 아니오 | 6.9 | C18 |
10 | 에틸트리메톡시-실란 | 예 | 7.2 | - |
11 | 에틸트리메톡시-실란 | 예 | 7.2 | C18 |
12 | 비스(트리에톡시실릴) 에탄 | 예 | 2.6 | - |
13 | 비스(트리에톡시실릴) 에탄 | 예 | 2.6 | C18 |
14 | 프로필트리메톡시-실란 | 예 | 6.4 | C18 |
시간(h) |
k' 톨루엔 |
△k'/△t |
k' 노르트리프틸린 |
△k'/△t |
k' 이미프라민 |
△k'/△t |
k' 아미트리프틸린 |
△k'/△t |
0 | 7.62 | - | 12.15 | - | 19.55 | - | 24.58 | - |
40 | 7.74 | 0.003 | 13.76 | 0.040 | 20.96 | 0.035 | 26.33 | 0.044 |
80 | 7.68 | -0.0015 | 14.09 | 0.0082 | 21.16 | 0.0050 | 26.56 | 0.0058 |
120 | 7.66 | -0.0005 | 14.26 | 0.0042 | 21.25 | 0.0022 | 26.68 | 0.0030 |
시간(h) |
k' 톨루엔 |
△k'/△t |
k' 노르트리프틸린 |
△k'/△t |
k' 이미프라민 |
△k'/△t |
k' 아미트리프틸린 |
△k'/△t |
0 | 7.22 | - | 11.41 | - | 18.92 | - | 23.73 | - |
40 | 7.37 | -0.0038 | 13.42 | 0.050 | 20.90 | 0.050 | 26.21 | 0.062 |
80 | 7.36 | -0.0002 | 13.78 | 0.0090 | 21.13 | 0.025 | 26.55 | 0.0085 |
120 | 7.33 | -0.0008 | 14.00 | 0.0055 | 21.31 | 0.0045 | 26.77 | 0.0055 |
시간(h) |
k' 톨루엔 |
△k'/△t |
k' 노르트리프틸린 |
△k'/△t |
k' 이미프라민 |
△k'/△t |
k' 아미트리프틸린 |
△k'/△t |
0 | 8.45 | - | 15.22 | - | 25.18 | - | 32.67 | - |
40 | 8.61 | 0.0040 | 19.94 | 0.12 | 27.76 | 0.064 | 35.89 | 0.080 |
80 | 8.61 | 0 | 21.69 | 0.044 | 28.49 | 0.018 | 36.69 | 0.020 |
120 | 8.62 | 0.0002 | 22.88 | 0.030 | 29.07 | 0.014 | 37.37 | 0.017 |
상 | 노르트리프틸린 | 아미트리프틸린 | ||||
k' 전 | k' 후 | % 변화 | k' 전 | k' 후 | % 변화 | |
상용의 C18 상 | 1.08 | 5.73 | +433 | 4.46 | 10.89 | +144 |
본원 발명(실시예 7) | 0.91 | 4.46 | +392 | 3.77 | 6.57 | +74 |
본원 발명(실시예 8) | 0.89 | 1.74 | +95 | 3.37 | 3.92 | +16 |
본원 발명(실시예 9) | 0.84 | 3.30 | +292 | 3.57 | 5.79 | +62 |
본원 발명(실시예 11) | 0.77 | 1.27 | +64 | 3.06 | 3.37 | +10 |
본원 발명(실시예 12) | 1.33 | 3.46 | +160 | 5.08 | 6.62 | +30 |
본원 발명(실시예 13) | 0.91 | 1.96 | +115 | 3.75 | 4.70 | +25 |
컬럼 함량 | NaOH 용액의 농도 [mM] | |
10 | 100 | |
본원 발명에 따른 물질 배치 1 |
0.016 [ppm Si/㎡/g] | 0.098 [ppm Si/㎡/g] |
본원 발명에 따른 물질 배치 2 |
0.015 [ppm Si/㎡/g] | 0.13 [ppm Si/㎡/g] |
본원 발명에 따른 물질 배치 3 |
0.016 [ppm Si/㎡/g] | 0.13 [ppm Si/㎡/g] |
상용의 C18-물질 | 0.039 [ppm Si/㎡/g] | 0.21 [ppm Si/㎡/g] |
압력 증가(%) | ||
피스톤 압력 | 본원 발명의 물질(실시예 3) | 상용의 C4-상(Kromasil C4) |
40 | 0 | 0 |
60 | 3.3 | 8.3 |
80 | 9.9 | 13.9 |
100 | 16.5 | 22.2 |
120 | 19.8 | 30.6 |
150 | 27.5 | 38.9 |
200 | 40.7 | 44.4 |
250 | 54.9 | 69.4 |
300 | 65.9 | 108.3 |
Claims (35)
- 유기-개질된(organo-modified) 실리카 기초 물질의 제조 방법에 있어서, 25 내지 100 중량% 물을 포함하는 수용성 매질(medium)에서 실리카 기초 물질(S)과 하나 이상의 유기실란 화합물(A)을 혼합하여 반응 혼합물을 제공하는 단계와 혼합물을 반응시키는 단계를 포함하고, 하나 이상의 유기실란 화합물(A)은- 일반식 (R1)3-n(X)nSiR3인 화합물이고, 여기서 R1은 C1-C4 알킬, C2-C4 알켄일, 또는 C2-C4 알킨일이고, R3는 C1-C8 알킬, C2-C8 알켄일, 또는 C2-C8 알킨일이며, X는 이탈기이고, n=2 또는 3이거나- 일반식 (R4)3-n(X)nSiR6Si(R5)3-m(Y)m인 화합물이고, 여기서 R4 및 R5는 서로 독립적으로 C1-C4 알킬, C2-C4 알켄일 또는 C2-C4 알킨일이고, R6는 C1-C8 알킬렌, C2-C8 알켄일렌 또는 C2-C8 알킨일렌이며, X 및 Y는 이탈기이고, n=2 또는 3, m=2 또는 3이고실리카 기초 물질(S)는 10 내지 3000 Å의 메조세공 크기를 가지는 모노리스 물질의 형태 또는 다공성 입자의 형태인 것을 특징으로 하는, 유기-개질된 실리카 기초 물질의 제조 방법.
- 제 1 항에 있어서, 하나 이상의 유기실란 화합물(A)가 다음의 화합물인 것을 특징으로 하는, 유기-개질된 실리카 기초 물질의 제조 방법:- 일반식 (R1)3-n(X)nSiR3인 화합물, 여기서 R1은 C1-C2 알킬이고, R3는 C1-C2 알킬이며, X는 이탈기이고, n=2 또는 3이거나- 일반식 (R4)3-n(X)nSiR6Si(R5)3-m(Y)m인 화합물, 여기서 R4 및 R5는 서로 독립적으로 C1-C2 알킬이고, R6는 C1-C3 알킬렌 또는 C2-C3 알켄일렌이며, X 및 Y는 이탈기이고, n=2 또는 3, m=2 또는 3임.
- 제 1 항에 있어서, 반응 혼합물이 다음을 임의의 순서로 수행하여 제공되는 것을 특징으로 하는, 유기-개질된 실리카 기초 물질의 제조 방법,(i) 25 내지 100 중량% 물을 포함하는 수용성 매질에 하나 이상의 유기실란 화합물(A)을 첨가하고 적어도 부분적으로 용해시킴 및(ii) 실리카 기초 물질(S)을 첨가.
- 제 1 항 내지 3 항 중의 어느 한 항에 있어서, 반응 혼합물의 온도가 40 내지 300℃임을 특징으로 하는, 유기-개질된 실리카 기초 물질의 제조 방법.
- 제 1 항 내지 3 항 중의 어느 한 항에 있어서, 반응 혼합물의 온도가 75 내지 175℃임을 특징으로 하는, 유기-개질된 실리카 기초 물질의 제조 방법.
- 제 1 항 내지 3 항 중의 어느 한 항에 있어서, 실리카 기초 물질(S)과 하나 이상의 유기실란 화합물(A)의 반응 혼합물이 온도 TEMP1에서 반응되는 첫 번째 단계 및 첫 번째 단계에서 생성된 반응 실리카 기초 물질이 온도 TEMP2를 거치는 것을 포함하는 두 번째 단계를 포함하고, 여기서 TEMP2>TEMP1임을 특징으로 하는, 유기-개질된 실리카 기초 물질의 제조 방법.
- 제 6 항에 있어서, 온도 TEMP1이 75 내지 100℃의 범위 내에 있고, 온도 TEMP2가 100 내지 175℃의 범위 내에 있는 것을 특징으로 하는, 유기-개질된 실리카 기초 물질의 제조 방법.
- 제 1 항 내지 3 항 중의 어느 한 항에 따른 방법으로 수득된 유기-개질된 실리카 기초 물질.
- 개질되지 않은 실리카 부분 및-OSi≡기에 포함된 실리콘 원자에 결합된 알킬기, 알켄일기 또는 알킨일기, 또는, -OSi≡기에 각각 포함된 두 개의 실리콘 원자에 결합된 알킬렌기, 알켄일렌기 또는 알킨일렌기를 포함하는 부분을 포함하고,10 내지 3000 Å의 메조세공 크기를 가지는 모노리스 물질의 형태이거나 다공성 입자의 형태인 것을 특징으로 하는, 유기-개질된 실리카 기초 물질.
- 제 9 항에 있어서, 알킬기가 C1-C4 알킬기이고, 알켄일기가 C2-C4 알켄일기이며, 알킨일기가 C2-C4 알킨일기인 것을 특징으로 하는, 유기-개질된 실리카 기초 물질.
- 제 9 항에 있어서, 알킬렌기가 C1-C8 알킬렌기이고, 알켄일렌기가 C2-C8 알켄일렌기이며, 알킨일렌기가 C2-C8 알킨일렌기인 것을 특징으로 하는, 유기-개질된 실리카 기초 물질.
- 제 10 항에 있어서, 알킬기가 C1-C2 알킬기이고, 알켄일기가 C2-C3 알켄일기이며, 알킨일기가 C2-C3 알킨일기인 것을 특징으로 하는, 유기-개질된 실리카 기초 물질.
- 제 11 항에 있어서, 알킬렌기가 C1-C3 알킬렌기이고, 알켄일렌기가 C2-C3 알켄일렌기이며, 알킨일렌기가 C2-C3 알킨일렌기인 것을 특징으로 하는, 유기-개질된 실리카 기초 물질.
- 제 9 항에 있어서, -OSi≡기에 포함된 실리콘 원자에 결합된 C1-C4 알킬기를 포함하는 부분을 포함하는 것을 특징으로 하는, 유기-개질된 실리카 기초 물질.
- 제 9 항 내지 14 항 중의 어느 한 항에 있어서, 고체 상태 NMR 분광법으로 결정되는 바와 같이, T2 구조를 가지는 실리콘 원자의 양 대 T3 구조를 가지는 실리콘 원자의 양의 비율이 1 이하인 것을 특징으로 하는, 유기-개질된 실리카 기초 물질.
- 제 9 항 내지 14 항 중의 어느 한 항에 있어서, 고체 상태 NMR 분광법으로 결정되는 바와 같이, T3의 양 대 (T1+T2+T3) 모두의 양의 비율이 0.60과 같거나 그 이상인 것을 특징으로 하는, 유기-개질된 실리카 기초 물질.
- 제 9 항 내지 14 항 중의 어느 한 항에 있어서, 25℃의 온도에서, 에탄올과 1:1 부피 관계로 혼합한 41.5 ㎖의 10 mM NaOH를 2.5 g의 유기-개질된 실리카 기초 물질로 충전된 길이 215 ㎜, 내경 4.6 ㎜의 컬럼을 통하여 1 ㎖/min로 주입하는 절차의 용출액에서 비표면적당 ppm 실리콘(BET 방법)[ppm Si/㎡/g]으로서 결정되는 알칼리 안정성이 0.035 [ppm Si/㎡/g] 이하인 것을 특징으로 하는, 유기-개질된 실리카 기초 물질.
- 제 9 항 내지 14 항 중의 어느 한 항에 있어서, 25℃의 온도에서, 에탄올과 1:1 부피 관계로 혼합한 41.5 ㎖의 100 mM NaOH를 2.5 g의 유기-개질된 실리카 기초 물질로 충전된 길이 215 ㎜, 내경 4.6 ㎜의 컬럼을 통하여 1 ㎖/min로 주입하는 절차의 용출액에서 비표면적당 ppm 실리콘(BET 방법)[ppm Si/㎡/g]으로서 결정되는 알칼리 안정성이 0.2 [ppm Si/㎡/g] 이하인 것을 특징으로 하는, 유기-개질된 실리카 기초 물질.
- 제 9 항 내지 14 항 중의 어느 한 항에 있어서, 표면에서부터 실리카 기초 물질까지 점차 감소하는 농도로 분포된 유기기(organic group)를 포함하는 것을 특징으로 하는, 유기-개질된 실리카 기초 물질.
- 제 9 항 내지 14 항 중의 어느 한 항에 있어서, 크로마토그래피를 위한 정지상 분리 물질로서 사용되는, 유기-개질된 실리카 기초 물질.
- 제 9 항 내지 14 항 중의 어느 한 항에 있어서, 크로마토그래피를 위한 정지상 분리 물질을 제조할 때 더욱 작용기화하기 위한 염기로서 사용되는, 유기-개질된 실리카 기초 물질.
- 제 9 항 내지 14 항 중의 어느 한 항에 따른 유기-개질된 실리카 기초 물질을 포함하는 정지상 분리 물질.
- 제 22 항에 있어서, 하나 이상의 작용기 형태로 표면-작용기화를 더욱 포함하는 것을 특징으로 하는, 정지상 분리 물질.
- 제 23 항에 있어서, 하나 이상의 작용기가 디올-치환된 알킬, 아미노-치환된 알킬, 시아노알킬, 플루오로알킬, 페닐, 플루오로페닐, 페닐알킬 또는 C1-C30 알킬의 그룹에 속하는 것을 특징으로 하는, 정지상 분리 물질.
- 제 22 항에 있어서, 고체 상태 NMR 분광법으로 결정되는 바와 같이, T3의 양 대 (T1+T2+T3) 모두의 양의 비율이 0.70과 같거나 그 이상인 것을 특징으로 하는, 정지상 분리 물질.
- 제 22 항에 있어서, 25℃의 온도에서, 에탄올과 1:1 부피 관계로 혼합한 41.5 ㎖의 10 mM NaOH를 2.5 g의 유기-개질된 실리카 기초 물질로 충전된 길이 215 ㎜, 내경 4.6 ㎜의 컬럼을 통하여 1 ㎖/min로 주입하는 절차의 용출액에서 비표면적당 ppm 실리콘(BET 방법)[ppm Si/㎡/g]으로서 결정되는 알칼리 안정성이 0.035 [ppm Si/㎡/g] 이하인 것을 특징으로 하는, 정지상 분리 물질.
- 제 22 항에 있어서, 25℃의 온도에서, 에탄올과 1:1 부피 관계로 혼합한 41.5 ㎖의 100 mM NaOH를 2.5 g의 유기-개질된 실리카 기초 물질로 충전된 길이 215 ㎜, 내경 4.6 ㎜의 컬럼을 통하여 1 ㎖/min로 주입하는 절차의 용출액에서 비표면적당 ppm 실리콘(BET 방법)[ppm Si/㎡/g]으로서 결정되는 알칼리 안정성이 0.2 [ppm Si/㎡/g] 이하인 것을 특징으로 하는, 정지상 분리 물질.
- 제 9 항 내지 14 항 중의 어느 한 항에 따른 유기-개질 실리카 기초 물질을 작용기를 포함하는 작용기화제와 반응시키는 것을 포함하는 정지상 분리 물질의 제조 방법.
- 제 28 항에 있어서, 작용기가 디올-치환된 알킬, 아미노-치환된 알킬, 시아노알킬, 플루오로알킬, 페닐, 플루오로페닐, 페닐알킬 또는 C1-C30 알킬인 것을 특징으로 하는, 정지상 분리 물질의 제조 방법.
- 제 28 항에 있어서, 작용기화제가 유기실란인 것을 특징으로 하는, 정지상 분리 물질의 제조 방법.
- 제 9 항 내지 14 항 중의 어느 한 항에 있어서, 크로마토그래피 분리 방법에 사용되는 유기-개질된 실리카 기초 물질.
- 제 22 항에 따른 정지상 분리 물질을 포함하는 크로마토그래피를 위한 분리 컬럼.
- 제 22 항에 있어서, 크로마토그래피 분리 방법에 사용되는 정지상 분리 물질.
- 삭제
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JP4615848B2 (ja) * | 2003-11-26 | 2011-01-19 | Agcエスアイテック株式会社 | 耐アルカリ性化学修飾型シリカゲル及びその製造方法 |
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2006
- 2006-12-11 UA UAA200808105A patent/UA88413C2/ru unknown
- 2006-12-11 DK DK06824629.7T patent/DK1960099T3/da active
- 2006-12-11 CN CN2006800474779A patent/CN101356003B/zh not_active Expired - Fee Related
- 2006-12-11 ES ES06824629T patent/ES2757566T3/es active Active
- 2006-12-11 WO PCT/SE2006/050570 patent/WO2007070001A2/en active Application Filing
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US4775520A (en) | 1985-09-25 | 1988-10-04 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Spherical SiO2 particles |
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Also Published As
Publication number | Publication date |
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ES2757566T3 (es) | 2020-04-29 |
IL191909A0 (en) | 2009-08-03 |
EP1960099B1 (en) | 2019-10-23 |
KR20080077627A (ko) | 2008-08-25 |
JP4999861B2 (ja) | 2012-08-15 |
CN101356003B (zh) | 2011-05-11 |
AR062446A1 (es) | 2008-11-12 |
RU2401694C2 (ru) | 2010-10-20 |
UA88413C2 (ru) | 2009-10-12 |
HRP20080266A2 (en) | 2008-09-30 |
JP2009519201A (ja) | 2009-05-14 |
IL191909A (en) | 2013-03-24 |
EP1960099A2 (en) | 2008-08-27 |
BRPI0619969A2 (pt) | 2011-10-25 |
DK1960099T3 (da) | 2020-01-27 |
EG26120A (en) | 2013-03-05 |
RU2008129104A (ru) | 2010-01-27 |
CA2633444A1 (en) | 2007-06-21 |
CN101356003A (zh) | 2009-01-28 |
CA2633444C (en) | 2012-07-17 |
WO2007070001A2 (en) | 2007-06-21 |
BRPI0619969B1 (pt) | 2016-05-24 |
WO2007070001A3 (en) | 2007-09-07 |
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