JPH0258292B2 - - Google Patents
Info
- Publication number
- JPH0258292B2 JPH0258292B2 JP56045011A JP4501181A JPH0258292B2 JP H0258292 B2 JPH0258292 B2 JP H0258292B2 JP 56045011 A JP56045011 A JP 56045011A JP 4501181 A JP4501181 A JP 4501181A JP H0258292 B2 JPH0258292 B2 JP H0258292B2
- Authority
- JP
- Japan
- Prior art keywords
- cellulose
- weight
- formaldehyde
- dmso
- cellulose material
- 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.)
- Expired - Lifetime
Links
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 43
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 33
- 229920002678 cellulose Polymers 0.000 claims description 26
- 239000001913 cellulose Substances 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 17
- 230000008961 swelling Effects 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 229930040373 Paraformaldehyde Natural products 0.000 description 4
- 230000007717 exclusion Effects 0.000 description 4
- 229920002866 paraformaldehyde Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000002523 gelfiltration Methods 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- 229920002284 Cellulose triacetate Polymers 0.000 description 2
- PTHCMJGKKRQCBF-UHFFFAOYSA-N Cellulose, microcrystalline Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC)C(CO)O1 PTHCMJGKKRQCBF-UHFFFAOYSA-N 0.000 description 2
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 2
- 239000007863 gel particle Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000004627 regenerated cellulose Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Description
【発明の詳細な説明】
本発明はセルロース材料を処理して多孔性セル
ロースを製造する方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of processing cellulosic materials to produce porous cellulose.
ゲル濾過法あるいは分子篩クロマトグラフイー
は対象物質を変質させることなく分離精製できる
特長を有し、蛋白質など不安定な物質の分離法と
して生化学分野で特に重用されている。この分離
法のための濾剤として多孔性セルロースが使用さ
れている。本発明は多孔性セルロースの新しい製
法を提供しようとするものである。 Gel filtration or molecular sieve chromatography has the advantage of being able to separate and purify target substances without altering them, and is particularly important in the biochemical field as a separation method for unstable substances such as proteins. Porous cellulose is used as a filter medium for this separation method. The present invention aims to provide a new method for producing porous cellulose.
本発明はジメチルスルホキシド（以下DMSO
と略記する）とホルムアルデヒドの混合物に一定
の形状を有するセルロース材料を浸漬し加熱して
膨潤させ必要に応じてホルムアルデヒドを除去精
製することにより多孔性セルロース材料を製造す
るものである。 The present invention uses dimethyl sulfoxide (hereinafter referred to as DMSO).
A porous cellulose material is produced by immersing a cellulose material having a certain shape in a mixture of (hereinafter referred to as "porous cellulose material") and formaldehyde, heating it to swell it, and removing formaldehyde as necessary for purification.
原料の一定の形状を有するセルロース材料とし
てはパルプ、木綿リンター、セルロース粉末、結
晶セルロース、木綿繊維、木綿布、セルロースフ
イルム、粒状セルロースなどを使用できる。特に
再生セルロース粒、例えば特公昭55−39565号等
に記されているような三酢酸セルロースをアルカ
リけん化して得られるセルロース球状粒子材料を
用いるのが良い。 As the cellulose material having a certain shape as a raw material, pulp, cotton linter, cellulose powder, crystalline cellulose, cotton fiber, cotton cloth, cellulose film, granular cellulose, etc. can be used. In particular, it is preferable to use regenerated cellulose particles, such as cellulose spherical particles obtained by saponifying cellulose triacetate with an alkali as described in Japanese Patent Publication No. 55-39565.
本発明において、DMSOの含水量がセルロー
スの膨潤に影響する（含水量が多いと膨潤力が低
下する）が、市販の試薬をそのまま使用できる。
必要があればモレキユラーシーブス等を加えて乾
燥する。DMSOはセルロース材料１重量部に対
し15ないし50重量部用いるのがよい。15重量部よ
り少ないときは膨潤が充分にできなくなるおそれ
があり、50重量部より多くしても不経済になるば
かりだからである。 In the present invention, the water content of DMSO affects the swelling of cellulose (if the water content is high, the swelling power decreases), but commercially available reagents can be used as they are.
If necessary, add molecular sieves and dry. DMSO is preferably used in an amount of 15 to 50 parts by weight per part by weight of cellulosic material. This is because if it is less than 15 parts by weight, sufficient swelling may not be achieved, and if it is more than 50 parts by weight, it will only become uneconomical.
前記ホルムアルデヒドの最も容易な入手源は通
常パラホルムアルデヒドである。 The most readily available source of formaldehyde is usually paraformaldehyde.
本発明においてホルムアルデヒドは一概には言
えないが通常セルロース材料１重量部当り約0.1
ないし1.3重量部使用するのがよい。多量に使用
すれば高い膨潤度が得られ過剰に用いればセルロ
ースが溶解する。パルプ等の天然セルロースに対
しては５重量部以上を要する場合もある。また
DMSOがセルロース材料１重量部に対して50重
量部近くも多量に使用される場合は、ホルムアル
デヒドは通常約1.3重量部まで使用しえ、DMSO
が15重量部近くの比較的少ない使用量の場合は、
ホルムアルデヒドは通常約0.8重量部まで使用し
うる。ホルムアルデヒドの使用上限は前述のよう
に、使用する原料セルロース材料の種類によつ
て、またDMSOの種類によつて異なるが、要す
るにセルロース材料を溶解せず膨潤させる限度と
いうことになる。パラホルムアルデヒドとジメチ
ルスルホキシドを混合し、これにセルロース材料
を浸漬し必要に応じて撹拌しつつ80ないし130℃
に加熱するとよい。こうすると５分から30分程度
で膨潤する。80℃より温度が低いとセルロース材
料の膨潤が因難となり、130℃より高いとセルロ
ース材料の好ましくない反応が生じ変質するおそ
れがある。セルロース材料を膨潤させた後、これ
を濾過しジメチルスルホキシドとイソプロピルア
ルコール等の低級アルコール、水又はこれらの混
合物とで順次洗浄あるいは熱抽出してホルムアル
デヒドを除去し精製するとよい。 In the present invention, formaldehyde is usually about 0.1 part by weight per 1 part by weight of cellulose material, although it cannot be said in general terms.
It is preferable to use between 1 and 1.3 parts by weight. If used in a large amount, a high degree of swelling will be obtained, and if used in excess, cellulose will dissolve. For natural cellulose such as pulp, 5 parts by weight or more may be required. Also
If DMSO is used in large amounts, approaching 50 parts by weight per part by weight of cellulosic material, formaldehyde can typically be used up to about 1.3 parts by weight, and DMSO
When using a relatively small amount of nearly 15 parts by weight,
Formaldehyde can typically be used up to about 0.8 parts by weight. As mentioned above, the upper limit for the use of formaldehyde varies depending on the type of raw cellulose material used and the type of DMSO, but in short, it is the limit that will swell the cellulose material without dissolving it. Mix paraformaldehyde and dimethyl sulfoxide, immerse the cellulose material in this, and heat to 80 to 130°C while stirring as necessary.
It is best to heat it to This will allow it to swell in about 5 to 30 minutes. If the temperature is lower than 80°C, swelling of the cellulose material may be a problem, and if it is higher than 130°C, there is a risk that undesirable reactions of the cellulose material may occur, leading to deterioration. After the cellulose material is swollen, it is preferably purified by filtering it and sequentially washing with dimethyl sulfoxide, a lower alcohol such as isopropyl alcohol, water, or a mixture thereof, or by thermal extraction to remove formaldehyde.
本発明の方法によれば高分子量物質の分離に適
する排除限界分子量（limMW）（ゲルクロマト
グラフイー法による測定）の高いセルロースゲル
濾過剤が得られる。またDMSOとホルムアルデ
ヒドの使用量を調節することにより容易に
limMWを調節することができる。ゲル濾過に用
いる機器に適した種々の形態の濾剤、特に球状粒
子のものを容易に製造することができる。 According to the method of the present invention, a cellulose gel filtration agent with a high exclusion limit molecular weight (limMW) (measured by gel chromatography) suitable for separating high molecular weight substances can be obtained. Also, by adjusting the amount of DMSO and formaldehyde used,
limMW can be adjusted. Various forms of filter media suitable for equipment used in gel filtration, particularly those with spherical particles, can be readily produced.
実施例 １
三酢酸セルロースをメチレンクロライドに溶解
し、分散安定剤含有水中に滴下して分散させメチ
レンクロライドを蒸発させて球状粒子を得、この
粒子を水酸化カリウムのメタノール溶液でけん化
する方法によつて得た再生セルロース粒子を原料
として使用する。この原料粒子は、1700の排除限
界分子量及び2.5ml／ｇ（乾燥重量）の膨潤度を
持つ。乾燥した原料粒子20ｇと、パラホルムアル
デヒド6.5ｇ、ジメチルスルホキシド350mlを撹拌
機付三口500mlフラスコに入れて混合し115℃で１
時間加熱撹拌し膨潤させた。冷却後ジメチルスル
ホキシド350mlを混合して濾過し、濾紙上で膨潤
ゲル粒子をジメチルスルホキシドとイソプロピル
アルコールで順次洗浄し、イソプロピルアルコー
ル300ml中に分散させ80℃で１時間撹拌した。こ
れを濾過しイソプロピルアルコールと水で順次洗
浄し水400mlに分散させ80℃で１時間撹拌した。
これを濾過し水洗した。湿潤粒子収量：72ｇ、得
られた粒子の膨潤度：８ml／ｇ（乾燥重量）、同
排除限界分子量：３×104であつた。Example 1 Cellulose triacetate was dissolved in methylene chloride, dispersed by dropping it into water containing a dispersion stabilizer, evaporated methylene chloride to obtain spherical particles, and the particles were saponified with a methanol solution of potassium hydroxide. The regenerated cellulose particles obtained are used as a raw material. The raw particles have an exclusion limit molecular weight of 1700 and a degree of swelling of 2.5 ml/g (dry weight). 20 g of dried raw material particles, 6.5 g of paraformaldehyde, and 350 ml of dimethyl sulfoxide were mixed in a three-necked 500 ml flask with a stirrer and heated at 115°C.
The mixture was heated and stirred for hours to swell. After cooling, 350 ml of dimethyl sulfoxide was mixed and filtered, and the swollen gel particles were sequentially washed with dimethyl sulfoxide and isopropyl alcohol on a filter paper, dispersed in 300 ml of isopropyl alcohol, and stirred at 80° C. for 1 hour. This was filtered, washed sequentially with isopropyl alcohol and water, dispersed in 400 ml of water, and stirred at 80°C for 1 hour.
This was filtered and washed with water. Wet particle yield: 72 g, degree of swelling of the obtained particles: 8 ml/g (dry weight), exclusion limit molecular weight: 3 x 104 .
実施例 ２
実施例１と同じ原料粒子15ｇとパラホルムアル
デヒド17ｇ、ジメチルスルホキシド670mlを容量
１のフラスコに入れて混合し、135℃で２時間
撹拌し膨潤させた。これを実施例１と同様に濾過
洗浄、熱抽出して球状セルロースゲル膨潤粒子を
得た。湿潤粒子収量：99ｇ、得られた粒子の膨潤
度：13ml／ｇ（乾燥重量）、同排除限界分子量：
７×104であつた。Example 2 15 g of the same raw material particles as in Example 1, 17 g of paraformaldehyde, and 670 ml of dimethyl sulfoxide were mixed in a flask with a capacity of 1, and the mixture was stirred at 135° C. for 2 hours to swell. This was filtered, washed, and heat extracted in the same manner as in Example 1 to obtain spherical swollen cellulose gel particles. Wet particle yield: 99 g, degree of swelling of the obtained particles: 13 ml/g (dry weight), exclusion limit molecular weight:
It was 7×10 4 .
Claims (1)
チルスルホキシド（以下DMSOと略記する）と
ホルムアルデヒドの混合物に浸漬し加熱して膨潤
させホルムアルデヒドを除去精製することを特徴
とする多孔性セルロースの製造方法。 ２ 第１項の方法において、前記DMSOを前記
セルロース材料の１重量部に対して、15〜50重量
部使用することを特徴とする前記方法。 ３ 第１項又は第２項の方法において、前記ホル
ムアルデヒドを、前記セルロース材料の１重量部
に対して、0.1重量部以上使用することを特徴と
する前記方法。 ４ 第１ないし３項のいずれかに記載の方法にお
いて、前記膨潤のための加熱温度を80〜130℃と
することを特徴とする前記方法。 ５ 第１ないし４項のいずれかに記載の方法にお
いて、前記ホルムアルデヒドの除去精製を前記膨
潤させたセルロースを低級アルコール、水又はこ
れらの混合物での洗浄又は熱抽出により行なうこ
とを特徴とする前記方法。[Claims] 1. A porous cellulose characterized in that a cellulose material having a certain shape is immersed in a mixture of dimethyl sulfoxide (hereinafter abbreviated as DMSO) and formaldehyde, heated to swell, and purified by removing formaldehyde. manufacturing method. 2. The method according to item 1, wherein 15 to 50 parts by weight of the DMSO is used per 1 part by weight of the cellulose material. 3. The method according to item 1 or 2, wherein the formaldehyde is used in an amount of 0.1 part by weight or more per 1 part by weight of the cellulose material. 4. The method according to any one of items 1 to 3, characterized in that the heating temperature for the swelling is 80 to 130°C. 5. The method according to any one of items 1 to 4, wherein the formaldehyde removal and purification is carried out by washing the swollen cellulose with a lower alcohol, water, or a mixture thereof, or by thermal extraction. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4501181A JPS57159802A (en) | 1981-03-27 | 1981-03-27 | Production of porous cellulose material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4501181A JPS57159802A (en) | 1981-03-27 | 1981-03-27 | Production of porous cellulose material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57159802A JPS57159802A (en) | 1982-10-02 |
| JPH0258292B2 true JPH0258292B2 (en) | 1990-12-07 |
Family
ID=12707414
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4501181A Granted JPS57159802A (en) | 1981-03-27 | 1981-03-27 | Production of porous cellulose material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57159802A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2794439B2 (en) * | 1989-02-23 | 1998-09-03 | チッソ株式会社 | Method for controlling micropore size of cellulosic material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55117915A (en) * | 1979-03-07 | 1980-09-10 | Toray Ind Inc | Production of cellulose system hollow yarn film |
-
1981
- 1981-03-27 JP JP4501181A patent/JPS57159802A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55117915A (en) * | 1979-03-07 | 1980-09-10 | Toray Ind Inc | Production of cellulose system hollow yarn film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57159802A (en) | 1982-10-02 |
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