JP2009114270A - 多孔質樹脂ビーズの製造方法 - Google Patents
多孔質樹脂ビーズの製造方法 Download PDFInfo
- Publication number
- JP2009114270A JP2009114270A JP2007286835A JP2007286835A JP2009114270A JP 2009114270 A JP2009114270 A JP 2009114270A JP 2007286835 A JP2007286835 A JP 2007286835A JP 2007286835 A JP2007286835 A JP 2007286835A JP 2009114270 A JP2009114270 A JP 2009114270A
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- Prior art keywords
- meth
- porous resin
- acrylate
- acyloxystyrene
- resin beads
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- 239000006185 dispersion Substances 0.000 claims abstract description 16
- 125000004423 acyloxy group Chemical group 0.000 claims abstract description 13
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 13
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 29
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 229910000281 calcium bentonite Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000002773 nucleotide Substances 0.000 description 1
- 125000003729 nucleotide group Chemical group 0.000 description 1
- XNTUJOTWIMFEQS-UHFFFAOYSA-N octadecanoyl octadecaneperoxoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCCCCCCCC XNTUJOTWIMFEQS-UHFFFAOYSA-N 0.000 description 1
- MMSLOZQEMPDGPI-UHFFFAOYSA-N p-Mentha-1,3,5,8-tetraene Chemical compound CC(=C)C1=CC=C(C)C=C1 MMSLOZQEMPDGPI-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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Abstract
【解決手段】芳香族ビニル化合物とアシルオキシスチレンとジ(メタ)アクリレート化合物からなる単量体混合物と重合開始剤を有機溶媒に溶解させ、これを分散安定剤の存在下に水中に懸濁させ、懸濁共重合させて、芳香族ビニル化合物−アシルオキシスチレン−ジ(メタ)アクリレート化合物共重合体を得、次に、この共重合体中のアシルオキシスチレン単量体成分の有するアシルオキシ基を加水分解して、芳香族ビニル化合物−ヒドロキシスチレン−ジ(メタ)アクリレート共重合体からなる多孔質樹脂ビーズを得る。
【選択図】なし
Description
(懸濁重合)
冷却機、攪拌機及び窒素導入管を備えた500mL容量のセパラブルフラスコを恒温水槽に設置し、これにポリビニルアルコール2.5g及び蒸留水250gを入れて、300rpmにて攪拌し、溶解させて、ポリビニルアルコール水溶液を調製した。
得られた共重合体を蒸留水及びアセトンを用いて濾過、洗浄し、全量約1Lになるようにアセトン中に分散させた。
得られた分散液を静置して、ビーズ状の共重合体が沈殿し、液を傾けても沈殿が乱れない程度になるまで放置した後、上澄のアセトンを廃棄した。この沈殿に再度、アセトンを加えて、全量約500mLにして、静置、アセトン廃棄の操作を10回以上繰返すことによって分級を行った。このようにして得られた分散液を濾過し、減圧乾燥して、スチレン−p−アセトキシスチレン−エチレングリコールジメタクリレート共重合体からなる多孔質樹脂ビーズを粉末として得た。
冷却機、攪拌機及び窒素導入管を備えた500mL容量のセパラブルフラスコを恒温水槽に漬け、これに上記スチレン−p−アセトキシスチレン−エチレングリコールジメタクリレート共重合体からなる多孔質樹脂ビーズの粉末20gとエタノール100gを仕込んで、攪拌、分散させた。次いで、これに水酸化ナトリウム1gを蒸留水50gに溶解させた水溶液を加えた後、75℃に昇温し、3時間、加水分解反応を行った。反応終了後、得られた反応混合物を塩酸で中和した後、蒸留水とアセトンを用いて濾過、洗浄を行った。最後に得られた分散液を濾過し、減圧乾燥して、スチレン−p−ヒドロキシスチレン−エチレングリコールジメタクリレート共重合体からなる多孔質樹脂ビーズを粉末として得た。
得られた多孔質樹脂ビーズについて以下の分析を行った。
レーザー回折/散乱法((株)堀場製作所製レーザー回折/散乱式粒度分布装置LA−920)にて測定した。
水銀圧入法(Quantachrome製 水銀ポロシメータ PoreMaster 60GT)を用いて測定した。
JIS K 0070に基づいて、滴定法により測定した。即ち、測定対象の多孔質樹脂ビーズのヒドロキシ基を既知量のアセチル化試薬(無水酢酸/ピリジン)によってアセチル化し、上記アセチル化において消費されなかった無水酢酸量を水酸化カリウムによる滴定で求めることによって、試料のヒドロキシ基量を算出した。具体的には以下のとおりである。
(多孔質樹脂ビーズの作製)
実施例1において、スチレン40g、p−アセトキシスチレン3.5g(単量体混合物における割合369μmol/g)、トリエチレングリコールジメタクリレート15g(単量体混合物における割合897μmol/g)、1−ウンデカノール80g及び過酸化ベンゾイル(25%含水物)1gを用いた以外は、実施例1と同様にして、スチレン−p−ヒドロキシスチレン−トリエチレングリコールジメタクリレート共重合体からなる多孔質樹脂ビーズを粉末として得た。
上記多孔質樹脂ビーズ1g、DMT-dT-3'-succinate (Beijing OM Chemicals 製)0.18g、HBTU(Novabiochem 製) 0.09g、N,N−ジイソプロピルエチルアミン0.084mL及びアセトニトリル10mLを混合し、攪拌下、室温で12時間反応させ、アセトニトリルを用いて濾過、洗浄した後、乾燥させた。これにCapA (20%無水酢酸/80%アセトニトリル) 2.5mL、CapB (20%N−メチルイミダゾール/30%ピリジン/50%アセトニトリル) 2.5mL、4−ジメチルアミノピリジン0.025g及びアセトニトリル5mLを混合し、攪拌下、室温で12時間反応させ、アセトニトリルを用いて濾過、洗浄した後、減圧乾燥させ、DMT-dT-3'-succinate を結合した多孔質樹脂ビーズを得た。p−トルエンスルホン酸/アセトニトリル溶液を用いて脱保護したDMT基の吸光度測定 (412nm) から求めた DMT-dT-3'-succinate の結合量を表1に示す。
上記 DMT-dT-3'-succinate を結合した多孔質樹脂ビーズをカラムに詰め、Applied Biosystems 3400 DNA 合成機 (アプライドバイオシステムズ製) にセットして、合成スケール1μmol、DMT-off の条件にてオリゴヌクレオチド dT20 の合成を行った。合成後のカラムを乾燥させ、重量測定から得られたオリゴヌクレオチドの重量収量(mg/μmol) を表1に示す。
(多孔質樹脂ビーズの作製)
実施例1において、スチレン40g、p−アセトキシスチレン3.5g(単量体混合物における割合369μmol/g)、1,6−ヘキサンジオールジメタクリレート15g(単量体混合物における割合1008μmol/g) 、1−デカノール75g及び過酸化ベンゾイル (25%含水物) 1gを用いた以外は、実施例1と同様にして、スチレン−p−ヒドロキシスチレン−1,6−ヘキサンジオールジメタクリレート共重合体からなる多孔質樹脂ビーズを粉末として得た。
(多孔質樹脂ビーズの作製)
実施例1において、スチレン48g、p−アセトキシスチレン2.5g(単量体混合物における割合264μmol/g) 、1,9−ノナンジオールジアクリレート8g (単量体混合物における割合510μmol/g) 、1−ノナノール90g及び過酸化ベンゾイル (25%含水物) 1gを用いた以外は、実施例1と同様にして、スチレン−p−ヒドロキシスチレン−1,9−ノナンジオールアクリレート共重合体からなる多孔質樹脂ビーズを粉末として得た。
実施例2と同様にして、DMT-dT-3'-succinate を結合した多孔質樹脂ビーズの作製及びオリゴヌクレオチド dT20 の合成を行った。DMT-dT-3'-succinate の結合量、オリゴヌクレオチドの重量収量、オリゴヌクレオチドのOD収量及び dT20 (Full-length) の割合を表1に示す。
(多孔質樹脂ビーズの作製)
実施例1において、スチレン48g、p−アセトキシスチレン3.5g (単量体混合物における割合369μmol/g) 、ジビニルベンゼン(55%)7g (単量体混合物における割合506μmol/g) 、2−エチルヘキサノール52g、イソオクタン23g及び過酸化ベンゾイル(25%含水物)1gを用いた以外は、実施例1と同様にして、スチレン−p−ヒドロキシスチレン−ジビニルベンゼン共重合体からなる多孔質樹脂ビーズを粉末として得た。
実施例2と同様にして、DMT-dT-3'-succinate を結合した多孔質樹脂ビーズの作製及びオリゴヌクレオチド dT20 の合成を行った。DMT-dT-3'-succinate の結合量、オリゴヌクレオチドの重量収量、オリゴヌクレオチドのOD収量及び dT20 (Full-length) の割合を表1に示す。
(多孔質樹脂ビーズの作製)
実施例1において、スチレン48g、p−アセトキシスチレン3.5g (単量体混合物における割合369μmol/g) 、ジビニルベンゼン(55%)7g (単量体混合物における割合506μmol/g) 、1−デカノール75g及び過酸化ベンゾイル (25%含水物) 1gを用いた以外は、実施例1と同様にして、スチレン−p−ヒドロキシスチレン−ジビニルベンゼン共重合体からなる多孔質樹脂ビーズを粉末として得た。
実施例2と同様にして、DMT-dT-3'-succinate を結合した多孔質樹脂ビーズの作製及びオリゴヌクレオチド dT20 の合成を行った。DMT-dT-3'-succinate の結合量、オリゴヌクレオチドの重量収量、オリゴヌクレオチドのOD収量及び dT20 (Full-length) の割合を表1に示す。
Claims (4)
- 芳香族ビニル化合物とアシルオキシスチレンとジ (メタ) アクリレート化合物からなる単量体混合物と重合開始剤を有機溶媒に溶解させ、これを分散安定剤の存在下に水中に懸濁させ、懸濁共重合させて、芳香族ビニル化合物−アシルオキシスチレン−ジ(メタ) アクリレート化合物共重合体を得、次に、この共重合体におけるアシルオキシスチレン単量体成分の有するアシルオキシ基を加水分解することからなる芳香族ビニル化合物−ヒドロキシスチレン−ジ(メタ) アクリレート共重合体からなる多孔質樹脂ビーズの製造方法。
- ジ(メタ) アクリレートが(ポリ)エチレングリコールジ(メタ) アクリレート及びアルカンジオールジ(メタ) アクリレートから選ばれる少なくとも1種である請求項1に記載の多孔質樹脂ビーズの製造方法。
- 単量体混合物がアシルオキシスチレンを80〜800μmol/gの割合で含有し、ジ (メタ) アクリレート化合物を200〜2000μmol/gの割合で含有する請求項1に記載の多孔質樹脂ビーズの製造方法。
- 有機溶媒が炭化水素及びアルコールから選ばれる少なくとも1種であると共に、有機溶媒を単量体混合物に対する重量比0.5〜2.5にて用いる請求項1に記載の多孔質樹脂ビーズの製造方法。
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JP2007286835A JP5210597B2 (ja) | 2007-11-05 | 2007-11-05 | 多孔質樹脂ビーズの製造方法 |
AT08019288T ATE482237T1 (de) | 2007-11-05 | 2008-11-04 | Herstellungsverfahren für poröse harzperlen |
EP20080019288 EP2055724B1 (en) | 2007-11-05 | 2008-11-04 | Production method of porous resin bead |
DE200860002678 DE602008002678D1 (de) | 2007-11-05 | 2008-11-04 | Herstellungsverfahren für poröse Harzperlen |
CN2008101744314A CN101429261B (zh) | 2007-11-05 | 2008-11-05 | 多孔树脂珠的制备方法 |
US12/264,940 US20090118383A1 (en) | 2007-11-05 | 2008-11-05 | Production method of porous resin bead |
US13/235,869 US20120010396A1 (en) | 2007-11-05 | 2011-09-19 | Production method of porous resin bead |
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JP2009280544A (ja) * | 2008-05-26 | 2009-12-03 | Nitto Denko Corp | 核酸固相合成用担体 |
CN102817208B (zh) * | 2011-06-09 | 2017-03-01 | 塞罗斯有限公司 | 洗涤用固体颗粒及其洗涤方法 |
EP2666794A1 (en) | 2012-05-23 | 2013-11-27 | Nitto Denko Corporation | Solid-phase support for oligonucleotide synthesis and oligonucleotide synthesis method |
EP2886564B1 (en) * | 2013-12-04 | 2016-09-21 | Nitto Denko Corporation | Porous resin bead and production method of nucleic acid by using same |
CZ307994B6 (cs) * | 2014-06-09 | 2019-10-09 | Ústav Chemických Procesů Av Čr, V. V. I. | Styrenický polymer a způsob jeho přípravy |
EP3195846B1 (en) * | 2014-09-17 | 2020-01-01 | Kuraray Noritake Dental Inc. | Dental polymerizable composition |
EP3315516A1 (en) | 2016-10-31 | 2018-05-02 | University of Vienna | Macroporous beads |
CN108250372B (zh) * | 2018-01-12 | 2020-09-11 | 南京大学 | 一种亲水性磁性苯乙烯系强碱阴离子交换微球树脂及其制备方法 |
US11814450B2 (en) * | 2021-10-22 | 2023-11-14 | Hongene Biotech Corporation | Polymeric solid support for oligonucleotide synthesis |
Citations (3)
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JPH04248819A (ja) * | 1991-01-25 | 1992-09-04 | Mitsubishi Kasei Corp | 多孔性樹脂及びその製造方法 |
JPH0586132A (ja) * | 1991-09-30 | 1993-04-06 | Mitsubishi Kasei Corp | 多孔性樹脂及びその製造方法 |
JP2005097545A (ja) * | 2003-08-29 | 2005-04-14 | Nitto Denko Corp | 多孔質樹脂ビーズおよびその製造方法 |
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JPS5223193A (en) | 1975-08-15 | 1977-02-21 | Cosmo Co Ltd | Preparation of microporous resin |
JPS58210914A (ja) | 1982-06-02 | 1983-12-08 | Cosmo Co Ltd | マクロ多孔性樹脂の製造方法 |
EP0496405A1 (en) * | 1991-01-25 | 1992-07-29 | Mitsubishi Kasei Corporation | Porous resin and process for its production |
US5461017A (en) * | 1991-12-13 | 1995-10-24 | Mobil Oil Corporation | Olefin polymerization catalysts |
JP4799831B2 (ja) * | 2004-05-14 | 2011-10-26 | 日東電工株式会社 | 多孔質樹脂の製造方法 |
WO2006029023A2 (en) * | 2004-09-02 | 2006-03-16 | Isis Pharmaceuticals, Inc. | Polymeric beads for oligonucleotide synthesis |
CN1297579C (zh) * | 2005-02-28 | 2007-01-31 | 天津南开和成科技有限公司 | 新型交联聚苯乙烯凝胶与用途 |
JP2007286835A (ja) | 2006-04-14 | 2007-11-01 | Victor Co Of Japan Ltd | 音声コンテンツ配信システム及びコンテンツ受信再生端末 |
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JPH04248819A (ja) * | 1991-01-25 | 1992-09-04 | Mitsubishi Kasei Corp | 多孔性樹脂及びその製造方法 |
JPH0586132A (ja) * | 1991-09-30 | 1993-04-06 | Mitsubishi Kasei Corp | 多孔性樹脂及びその製造方法 |
JP2005097545A (ja) * | 2003-08-29 | 2005-04-14 | Nitto Denko Corp | 多孔質樹脂ビーズおよびその製造方法 |
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US20120010396A1 (en) | 2012-01-12 |
ATE482237T1 (de) | 2010-10-15 |
EP2055724A1 (en) | 2009-05-06 |
US20090118383A1 (en) | 2009-05-07 |
DE602008002678D1 (de) | 2010-11-04 |
CN101429261A (zh) | 2009-05-13 |
CN101429261B (zh) | 2011-12-07 |
JP5210597B2 (ja) | 2013-06-12 |
EP2055724B1 (en) | 2010-09-22 |
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