JPS5910691B2 - Manufacturing method of porous hydrophilic structure - Google Patents
Manufacturing method of porous hydrophilic structureInfo
- Publication number
- JPS5910691B2 JPS5910691B2 JP52120886A JP12088677A JPS5910691B2 JP S5910691 B2 JPS5910691 B2 JP S5910691B2 JP 52120886 A JP52120886 A JP 52120886A JP 12088677 A JP12088677 A JP 12088677A JP S5910691 B2 JPS5910691 B2 JP S5910691B2
- Authority
- JP
- Japan
- Prior art keywords
- cellulose
- molecular weight
- water
- saponification
- porous
- 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
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 42
- 239000001913 cellulose Substances 0.000 claims description 37
- 150000001875 compounds Chemical class 0.000 claims description 23
- 238000007127 saponification reaction Methods 0.000 claims description 19
- -1 monosaccharide ester Chemical class 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 150000004676 glycans Chemical class 0.000 claims description 3
- 239000005076 polymer ester Substances 0.000 claims description 3
- 229920001282 polysaccharide Polymers 0.000 claims description 3
- 239000005017 polysaccharide Substances 0.000 claims description 3
- 229920001059 synthetic polymer Polymers 0.000 claims description 3
- 235000010980 cellulose Nutrition 0.000 description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 14
- 239000012798 spherical particle Substances 0.000 description 14
- 239000002131 composite material Substances 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 239000000499 gel Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229920000936 Agarose Polymers 0.000 description 8
- 229920002472 Starch Polymers 0.000 description 8
- 150000002148 esters Chemical class 0.000 description 8
- 239000012510 hollow fiber Substances 0.000 description 8
- 239000008107 starch Substances 0.000 description 8
- 235000019698 starch Nutrition 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 229920002284 Cellulose triacetate Polymers 0.000 description 5
- 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 5
- 239000012466 permeate Substances 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 4
- 238000000502 dialysis Methods 0.000 description 4
- 239000008103 glucose Chemical class 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 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 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical class OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 229920002689 polyvinyl acetate Polymers 0.000 description 3
- 239000011118 polyvinyl acetate Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229920002545 silicone oil Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 3
- 229920001747 Cellulose diacetate Polymers 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002772 monosaccharides Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Chemical class OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 244000099147 Ananas comosus Species 0.000 description 1
- 235000007119 Ananas comosus Nutrition 0.000 description 1
- DQEFEBPAPFSJLV-UHFFFAOYSA-N Cellulose propionate Chemical compound CCC(=O)OCC1OC(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C1OC1C(OC(=O)CC)C(OC(=O)CC)C(OC(=O)CC)C(COC(=O)CC)O1 DQEFEBPAPFSJLV-UHFFFAOYSA-N 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 229930091371 Fructose Chemical class 0.000 description 1
- 239000005715 Fructose Chemical class 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical class OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 108010093096 Immobilized Enzymes Proteins 0.000 description 1
- 229920001202 Inulin Polymers 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Chemical class O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical class O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- UGZICOVULPINFH-UHFFFAOYSA-N acetic acid;butanoic acid Chemical compound CC(O)=O.CCCC(O)=O UGZICOVULPINFH-UHFFFAOYSA-N 0.000 description 1
- AVMNFQHJOOYCAP-UHFFFAOYSA-N acetic acid;propanoic acid Chemical compound CC(O)=O.CCC(O)=O AVMNFQHJOOYCAP-UHFFFAOYSA-N 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical class OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical class OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229920006218 cellulose propionate Polymers 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 108010025899 gelatin film Proteins 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- JYJIGFIDKWBXDU-MNNPPOADSA-N inulin Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@]1(OC[C@]2(OC[C@]3(OC[C@]4(OC[C@]5(OC[C@]6(OC[C@]7(OC[C@]8(OC[C@]9(OC[C@]%10(OC[C@]%11(OC[C@]%12(OC[C@]%13(OC[C@]%14(OC[C@]%15(OC[C@]%16(OC[C@]%17(OC[C@]%18(OC[C@]%19(OC[C@]%20(OC[C@]%21(OC[C@]%22(OC[C@]%23(OC[C@]%24(OC[C@]%25(OC[C@]%26(OC[C@]%27(OC[C@]%28(OC[C@]%29(OC[C@]%30(OC[C@]%31(OC[C@]%32(OC[C@]%33(OC[C@]%34(OC[C@]%35(OC[C@]%36(O[C@@H]%37[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O%37)O)[C@H]([C@H](O)[C@@H](CO)O%36)O)[C@H]([C@H](O)[C@@H](CO)O%35)O)[C@H]([C@H](O)[C@@H](CO)O%34)O)[C@H]([C@H](O)[C@@H](CO)O%33)O)[C@H]([C@H](O)[C@@H](CO)O%32)O)[C@H]([C@H](O)[C@@H](CO)O%31)O)[C@H]([C@H](O)[C@@H](CO)O%30)O)[C@H]([C@H](O)[C@@H](CO)O%29)O)[C@H]([C@H](O)[C@@H](CO)O%28)O)[C@H]([C@H](O)[C@@H](CO)O%27)O)[C@H]([C@H](O)[C@@H](CO)O%26)O)[C@H]([C@H](O)[C@@H](CO)O%25)O)[C@H]([C@H](O)[C@@H](CO)O%24)O)[C@H]([C@H](O)[C@@H](CO)O%23)O)[C@H]([C@H](O)[C@@H](CO)O%22)O)[C@H]([C@H](O)[C@@H](CO)O%21)O)[C@H]([C@H](O)[C@@H](CO)O%20)O)[C@H]([C@H](O)[C@@H](CO)O%19)O)[C@H]([C@H](O)[C@@H](CO)O%18)O)[C@H]([C@H](O)[C@@H](CO)O%17)O)[C@H]([C@H](O)[C@@H](CO)O%16)O)[C@H]([C@H](O)[C@@H](CO)O%15)O)[C@H]([C@H](O)[C@@H](CO)O%14)O)[C@H]([C@H](O)[C@@H](CO)O%13)O)[C@H]([C@H](O)[C@@H](CO)O%12)O)[C@H]([C@H](O)[C@@H](CO)O%11)O)[C@H]([C@H](O)[C@@H](CO)O%10)O)[C@H]([C@H](O)[C@@H](CO)O9)O)[C@H]([C@H](O)[C@@H](CO)O8)O)[C@H]([C@H](O)[C@@H](CO)O7)O)[C@H]([C@H](O)[C@@H](CO)O6)O)[C@H]([C@H](O)[C@@H](CO)O5)O)[C@H]([C@H](O)[C@@H](CO)O4)O)[C@H]([C@H](O)[C@@H](CO)O3)O)[C@H]([C@H](O)[C@@H](CO)O2)O)[C@@H](O)[C@H](O)[C@@H](CO)O1 JYJIGFIDKWBXDU-MNNPPOADSA-N 0.000 description 1
- 229940029339 inulin Drugs 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical group 0.000 description 1
- 229920000120 polyethyl acrylate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Description
【発明の詳細な説明】 本発明は多孔質親水性構造物の製法に関する。[Detailed description of the invention] The present invention relates to a method for producing porous hydrophilic structures.
従来セルロースは板状、シート状、フィルム状、繊維状
、中空繊維状、球状粒子状、フレーク状、粉末状等の形
態で利用されているが、セルロースの分子構造上その構
造物の内部に浸透できるものは、分子量５０００以下の
水溶性化合物だけである。従つてＧＰＣ充填剤、イオン
交換体等の球状粒子の中間原料として利用される場合は
、分子量約５０００以上の化合物はその粒子内に浸透す
ることができないので、その用途範囲が大きく制限され
ている。またセルロースのフィルム又は中空繊維を透析
の目的で利用する場合も、同じ理由で分子量約５０００
以上の化合物はこれらの透析膜を通過することができな
い。本発明者はこれらの欠点を除くため研究した結果、
セルロースエステル及び他のエステルから成る構造物を
けん化することにより、分子量５０００以上の水溶性化
合物を浸透しうるセルロース含有多孔質構造物が得られ
ることを見出して本発明を完成した。Conventionally, cellulose has been used in the form of plates, sheets, films, fibers, hollow fibers, spherical particles, flakes, powders, etc. However, due to the molecular structure of cellulose, it cannot penetrate into the structure. Only water-soluble compounds with a molecular weight of 5000 or less can be used. Therefore, when used as an intermediate raw material for spherical particles such as GPC fillers and ion exchangers, compounds with a molecular weight of about 5,000 or more cannot penetrate into the particles, so the range of use is greatly limited. . Furthermore, when cellulose films or hollow fibers are used for dialysis purposes, the molecular weight is approximately 5000 for the same reason.
The above compounds cannot pass through these dialysis membranes. As a result of research to eliminate these drawbacks, the present inventor found that
The present invention was completed based on the discovery that a cellulose-containing porous structure that is permeable to a water-soluble compound having a molecular weight of 5,000 or more can be obtained by saponifying a structure made of cellulose ester and other esters.
本発明は、セルロースエステル（Ａ）及び多糖類もしく
は単糖類のエステル又は合成高分子エステル（Ｂ）を溶
融し又は溶剤に溶解し、この溶融物又は溶液から構造物
を形成し、そしてけん化することにより分子量５０００
〜１００００００の水溶性化合物が浸透できるセルロー
ス含有多孔質構造物とすることを特徴とする、多孔質親
水性構造物の製法である。The present invention involves melting or dissolving a cellulose ester (A) and an ester of a polysaccharide or a monosaccharide or a synthetic polymer ester (B) in a solvent, forming a structure from this melt or solution, and saponifying it. molecular weight 5000
This is a method for producing a porous hydrophilic structure, characterized in that it is a cellulose-containing porous structure that can be penetrated by a water-soluble compound of up to 1,000,000.
本方法においてけん化したのちセルロース以外の成分を
除去することは特に好ましい。本発明においてセルロー
スエステル（にとしては、たとえば次のものが用いられ
る。三酢酸セルロース、三プロピオン酸セルロース、三
硝酸セルロース、三酪酸セルロース等、セルロースの混
合エステルたとえば酢酸一酪酸セルロース、酢酸−プロ
ピオン酸セルロース、プロピオン酸一酪酸セルロース等
、ならびにセルロースの部分エステルたとえば二酢酸セ
ルロース、二硝酸セルロース、ニプロピオン酸セルロー
ス、二酪酸セルロース、一酢酸セルロース、一硝酸セル
ロース等及びこれらの中間エステル化合物。これらのセ
ルロースエステＩ ルは単独で又は２種以上混合して用
いられる。セルロース以外のエステル面としては、その
けん化物が水溶性の高分子化合物であることが好ましい
が、低分子化合物でもよく、たとえば次のものが用いら
れる。セルロース以外の多糖類もしくｊ は単糖類たと
えば寒天、アガロース、殿粉、可溶性殿粉、デキストラ
ン、イヌリン、マツアン、蔗糖、麦芽糖、ブドウ糖、果
糖等のエステル、ならびに合成高分子エステルたとえば
ポリ酢酸ビニル、ポリ蟻酸ビニル、ポリプロピオン酸ビ
ニル、ポリメタクリル酸メチル、ポリアクリル酸メチル
、ポリメタクリル酸エチル、ポリアクリル酸エチル等。In this method, it is particularly preferable to remove components other than cellulose after saponification. In the present invention, the following cellulose esters (for example, cellulose triacetate, cellulose tripropionate, cellulose trinitrate, cellulose tributyrate, etc.), mixed esters of cellulose such as cellulose acetate monobutyrate, acetic acid-propionate, etc. Cellulose, cellulose propionate monobutyrate, etc., partial esters of cellulose such as cellulose diacetate, cellulose dinitrate, cellulose nipropionate, cellulose dibutyrate, cellulose monoacetate, cellulose mononitrate, etc., and intermediate ester compounds thereof.These celluloses. Ester I may be used alone or in combination of two or more.As for esters other than cellulose, it is preferable that the saponified product is a water-soluble polymer compound, but it may also be a low molecular compound, such as the following: Polysaccharides other than cellulose or j include monosaccharides such as agar, agarose, starch, soluble starch, dextran, inulin, pineapple, sucrose, maltose, glucose, fructose, and other esters, as well as synthetic polymer esters. For example, polyvinyl acetate, polyvinyl formate, polyvinyl propionate, polymethyl methacrylate, polymethyl acrylate, polyethyl methacrylate, polyethyl acrylate, etc.
これらのエステルも単独で又は２種以上混合して用いる
ことができる。本発明方法を実施するに際しては、まず
成分Ａ及び成分Ｂを溶融し又は溶剤に溶解する。These esters can be used alone or in combination of two or more. In carrying out the method of the present invention, component A and component B are first melted or dissolved in a solvent.
溶融の際には普通の可塑剤たとえばスルホラン等を存在
させることが好ましい。溶剤としては、たとえば塩化メ
チレン、クロロホルム、アセトン、メチルエチルケトン
、ニトロメタン、スルホン等が単独で又は混合して用い
られる。これらの溶剤にさらにメタノール、エタノール
、酢酸メチル、酢酸エチル等を加えることもできる。次
いで成分Ａ及び成分Ｂの溶融物又は溶液から構造物を製
造する。Preferably, common plasticizers such as sulfolane are present during melting. As the solvent, for example, methylene chloride, chloroform, acetone, methyl ethyl ketone, nitromethane, sulfone, etc. can be used alone or in combination. Methanol, ethanol, methyl acetate, ethyl acetate, etc. can also be added to these solvents. A structure is then produced from the melt or solution of component A and component B.
本発明において構造物とは、たとえば板状、棒状、シー
ト状、フイルム状、繊維状、中空繊維状、粒状、球状、
顆粒状、フレーク状、粉末状その他の形態のものを意味
する。これらの構造物は種々の手段により形成すること
が可能である。溶融物からはたとえば紡糸、成形、造粒
などにより、また溶液からはたとえば流延、媒体中で沈
殿又は懸濁させ、生成した沈殿又は懸濁粒子を分離する
方法などにより、構造物を得ることができる。球状粒子
は、好ましくは次のようにして得られる。In the present invention, structures include, for example, plate-like, rod-like, sheet-like, film-like, fibrous, hollow fiber-like, granular, spherical,
It means granules, flakes, powders and other forms. These structures can be formed by various means. A structure can be obtained from a melt by, for example, spinning, molding, granulation, etc., and from a solution by, for example, casting, precipitation or suspension in a medium, and separation of the generated precipitated or suspended particles. I can do it. Spherical particles are preferably obtained as follows.
成分Ａ及び成分Ｂを溶剤に溶解し、常法により乾式紡糸
したのち、フイラメントをその直径の約１〜２倍の長さ
に切断してチツプとなす。直球状粒子を製造するために
は、チツプの長さはフイラメント直径とできるだけ等し
いことが好ましい。次いでチツプを適宜な媒体中で加熱
溶融して球状粒子となし、冷却して分離する。溶融温度
は一般に２５０〜３５０℃、好ましくは２８０〜３００
℃であり、溶融媒体としてはシリコーン油のほか、ポリ
塩化ビフエニル好ましくはヘキサ−又はオクタ塩化ビフ
エニル等を用いてもよい。次いでこれらの構造物中のエ
ステルをけん化すると、セルロースを含有する多孔質複
合構造物が得られる。Component A and component B are dissolved in a solvent and dry spun by a conventional method, and then the filament is cut into a length about 1 to 2 times its diameter to form chips. In order to produce straight spherical particles, the length of the tip is preferably as equal as possible to the filament diameter. The chips are then heated and melted in a suitable medium to form spherical particles, which are cooled and separated. The melting temperature is generally 250-350°C, preferably 280-300°C.
As the melting medium, in addition to silicone oil, polychlorinated biphenyl, preferably hexa- or octachlorinated biphenyl, etc. may be used. The esters in these structures are then saponified to yield cellulose-containing porous composite structures.
けん化は常法により、たとえば苛性アルカリ及びアルコ
ールを用いて、好ましくは低温たとえば２〜１０℃で行
なうことができる。苛性アルカリとしてはたとえば水酸
化ナトリウム、水酸化カリウム等の水溶液、アルコール
としては低級アルコール、一般にメタノール、エタノー
ル等を用いることが好ましい。通常は５Ｎ−ＮａＯＨ溶
液にその約２０〜３０％のメタノールを加えた溶液中に
構造物を２〜１０゜Ｃで放置すると、約１２時間でけん
化は終了する。こうして得られたけん化生成物は、セル
ロースを含有する多孔質の複合ゲルであり、普通のセル
ロースゲル中には分子量５０００以下の化合物しか浸透
できないのに対し、分子量１００万以下の水溶性化合物
が浸透可能である。Saponification can be carried out by conventional methods, for example using caustic alkali and alcohol, preferably at low temperatures, for example from 2 to 10°C. As the caustic alkali, it is preferable to use an aqueous solution such as sodium hydroxide or potassium hydroxide, and as the alcohol, lower alcohols such as methanol and ethanol are preferably used. Usually, when the structure is left in a solution of 5N NaOH and about 20 to 30% methanol added thereto at 2 to 10°C, saponification is completed in about 12 hours. The saponification product obtained in this way is a porous composite gel containing cellulose, and while only compounds with a molecular weight of 5000 or less can penetrate into ordinary cellulose gel, water-soluble compounds with a molecular weight of 1 million or less can penetrate. It is possible.
たとえば三酢酸セルロース（Ａ）２部及び酢酸化アガロ
ース（Ｂ）１部から出発して得られたセルロースーアガ
ロース複合ゲルは、分子量１６万以下の水溶性化合物を
その中に浸透することができる。こうして得られたセル
ロース含有多孔質複合ゲルからセルロース以外の成分を
除去すると、さらに高分子量の化合物をも浸透可能にな
るので特に好ましい。For example, a cellulose-agarose composite gel obtained starting from 2 parts of cellulose triacetate (A) and 1 part of acetated agarose (B) is capable of penetrating into it a water-soluble compound having a molecular weight of 160,000 or less. It is particularly preferable to remove components other than cellulose from the cellulose-containing porous composite gel thus obtained, since this allows even higher molecular weight compounds to penetrate.
セルロース以外の成分を除去するには、用いた成分Ｂの
種類にもよるが、一般に約８０℃の熱湯中で約１時間処
理することにより溶出除去できる。たとえば前記のセル
ロースーアガロース複合ゲルからアガロースを除去する
と、得られた多孔質のセルロースゲルはその中に分子量
２５万以下の化合物を浸透することができる。本発明方
法により製造された多孔質のセルロース複合構造物及び
セルロース構造物のうち、球状粒子、フレーク、粉末、
顆粒等は、カラム充填用固定化酵素の担体、液体クロマ
トグラフイ用充填剤、セルロースイオン交換体の製造原
料などとして、またフイルム及び中空繊維は透析用材料
、特に人工腎臓用部品として工業上有用である。Components other than cellulose can generally be removed by elution by treatment in hot water at about 80° C. for about 1 hour, although it depends on the type of component B used. For example, when agarose is removed from the cellulose-agarose composite gel, the resulting porous cellulose gel can allow compounds with a molecular weight of 250,000 or less to penetrate therein. Among the porous cellulose composite structures and cellulose structures produced by the method of the present invention, spherical particles, flakes, powders,
Granules are industrially useful as carriers for immobilized enzymes for column filling, packing materials for liquid chromatography, raw materials for manufacturing cellulose ion exchangers, etc., and films and hollow fibers are industrially useful as dialysis materials, especially parts for artificial kidneys. It is.
実施例 １三酢酸セルロース３０９、三酢酸可溶性殿粉
１０９及びスルホラン１０９の混合物を、２８０〜３０
０℃で常法により溶融紡糸して直径約３００μのフイラ
メントを製造し、冷却後にフイラメントを２００〜４０
０μの長さに切断してチツプにする。Example 1 A mixture of cellulose triacetate 309, triacetic acid soluble starch 109 and sulfolane 109 was mixed with 280-30
A filament with a diameter of approximately 300μ is produced by melt spinning at 0°C using a conventional method, and after cooling, the filament is
Cut into chips with a length of 0μ.
このチツプを２７０〜３００℃に加熱したシリコーン油
中に投入すると、溶融して球状粒子となる。冷却してシ
リコーン油から分離した球状粒子をけん化浴中で２０℃
において１２時間けん化する。けん化浴としては、Ｎａ
，ＳＯ４２Ｏ％を溶解した３Ｎ−ＮａＯＨ中にその２５
容量％のメタノールを加えた溶液を用いる。こうして得
られたけん化生成物は、セルロース可溶性殿粉複合ゲル
の球状粒子で、このゲル中に分子量８万以下の水溶性化
合物が浸透することができる。実施例 ２
実施例１の生成物を８０℃で２時間熱湯中で処理すると
、可溶性殿粉が溶出して多孔性のセルロースゲル球状粒
子が得られる。When this chip is put into silicone oil heated to 270-300°C, it melts into spherical particles. The spherical particles separated from the silicone oil by cooling were heated at 20°C in a saponification bath.
Saponify for 12 hours. As a saponification bath, Na
, 25% of SO4 in 3N-NaOH dissolved in 20%
A solution containing % by volume of methanol is used. The saponification product thus obtained is a spherical particle of a cellulose-soluble starch composite gel, into which a water-soluble compound having a molecular weight of 80,000 or less can penetrate. Example 2 The product of Example 1 is treated in hot water at 80° C. for 2 hours, resulting in the elution of soluble starch and porous cellulose gel spherical particles.
このゲル中に分子量１３万以下の水溶性化合物が浸透す
ることができる。実施例 ３
三酢酸セルロース３０ｆ１酢酸化アガロース１０ｇ及び
スルホラン１０ｆ！の混合物を、２８０〜３０『Ｃで常
法により溶融紡糸して、内径２５０μ及び外径３００μ
の中空繊維を製造する。A water-soluble compound having a molecular weight of 130,000 or less can permeate into this gel. Example 3 Cellulose triacetate 30f1 acetated agarose 10g and sulfolane 10f! The mixture was melt-spun by a conventional method at 280 to 30°C to obtain an inner diameter of 250μ and an outer diameter of 300μ.
manufactures hollow fibers.
次いでこの中空繊維をけん化浴中で２〜５℃において１
２時間けん化する。けん化浴としては、２Ｎ−ＮａＯＨ
中にその２５容量？のメタノールを加えた溶液を用いる
。得られたけん化生成物は、多孔質のセルロースーアガ
ロース複合中空繊維で、分子量５０万以下の水＠性化合
物がその中空繊維壁を通して浸透することができる。実
施例 ４
実施例３の生成物を８０℃で１時間熱湯中で処理すると
、アガロースが溶出して多孔性のセルロース中空繊維が
得られる。The hollow fibers were then heated in a saponification bath at 2-5°C for 1
Saponify for 2 hours. As a saponification bath, 2N-NaOH
That 25 capacity inside? Use a solution to which methanol has been added. The resulting saponified product is a porous cellulose-agarose composite hollow fiber, through which a water-based compound having a molecular weight of 500,000 or less can penetrate. Example 4 The product of Example 3 is treated in hot water at 80° C. for 1 hour, resulting in elution of agarose and porous cellulose hollow fibers.
この中空繊維の壁を通して分子量８０万以下の水溶性化
合物が浸透することができる。実施例 ５
二酢酸セルロース１０ｙ及びポリ酢酸ビニル３ｙを塩化
メチレン１３６ｍ１及びエタノール１４ｍ１からの混合
溶媒に溶解する。Water-soluble compounds with a molecular weight of 800,000 or less can permeate through the walls of these hollow fibers. Example 5 10y of cellulose diacetate and 3y of polyvinyl acetate are dissolved in a mixed solvent of 136ml of methylene chloride and 14ml of ethanol.
この溶液を、ゼラチン３％を含有する水溶液中に２『Ｃ
で攪拌下に滴下すると懸濁液が生成する。攪拌を続けな
がら徐徐に温度を上げ、懸濁液を４『Ｃで５時間加熱す
ると、塩化メチレンの大部分が蒸発除去される。次いで
温度を７５゜Ｃに上げて３時間攪拌したのち、更に温度
を８０℃に上げてｌ時間攪拌する。ゼラチン水溶液から
懸濁物を涙別して水洗すると、直径５０〜５００μの二
酢酸セルロース−ポリ酢酸ビニル複合球状粒子が得られ
る。この複合粒子をけん化浴中で２０℃において１２時
間けん化する。けん化浴としては、３Ｎ−ＮａＯＨ中に
その２５容量？のメタノールを加えた溶液を用いる。得
らノタ
θ
れたけん化生成物（ま、セルロース−ポリビニルアルコ
ール複合ゲルの球状粒子で、このゲル中に分子量１万以
下の水溶性化合物が浸透することができる。This solution was added to an aqueous solution containing 3% gelatin at 2'C.
When added dropwise while stirring, a suspension is formed. The temperature is gradually increased while stirring is continued, and the suspension is heated at 4'C for 5 hours, during which most of the methylene chloride is evaporated off. Next, the temperature was raised to 75°C and stirred for 3 hours, and then the temperature was further raised to 80°C and stirred for 1 hour. When the suspension is separated from the aqueous gelatin solution and washed with water, cellulose diacetate-polyvinyl acetate composite spherical particles having a diameter of 50 to 500 μm are obtained. The composite particles are saponified in a saponification bath at 20° C. for 12 hours. As a saponification bath, 25 volumes in 3N-NaOH? Use a solution to which methanol has been added. The resulting saponified product (well, spherical particles of cellulose-polyvinyl alcohol composite gel) allows water-soluble compounds with a molecular weight of 10,000 or less to penetrate into this gel.
実施例 ６
実施例５の生成物を８０℃で１時間熱湯中で処理すると
、ポリビニルアルコールが溶出して多孔質のセルロース
球状粒子が得られる。Example 6 The product of Example 5 is treated in hot water at 80° C. for 1 hour to elute the polyvinyl alcohol and obtain porous cellulose spherical particles.
このセルロース球状粒子中に分子量３万以下の水溶性化
合物が浸透することができる。実施例 ７
三酢酸セルロース１０ｆ及び酢酸化グルコース３ｆ！を
塩化メチレン１５０ｍ１＆Ｃ溶解し、流延したのち乾燥
して厚さ５０μのフイルムを製造する。A water-soluble compound having a molecular weight of 30,000 or less can permeate into the cellulose spherical particles. Example 7 Cellulose triacetate 10f and acetated glucose 3f! was dissolved in 150ml of methylene chloride, cast and dried to produce a film with a thickness of 50μ.
このフイルムをけん化浴中で２゜Ｃにおいて１２時間け
ん化する。けん化溶としては、３Ｎ−ＮａＯＨ中にその
２５容量？のメタノールを加えた溶液を用いる。けん化
後にセルロース−グルコース複合ゲルのフイルムが得ら
れ、このフイルムを通して分子量５５００以下の水溶性
化合物が浸透できる。実施例 ８実施例７により得られ
た複合ゲルのフイルムを８０℃の熱湯中でｌ時間処理す
ると、グルコースが溶出して多孔質のセルロースフイル
ムが得られる。The film is saponified in a saponification bath at 2°C for 12 hours. As a saponification solution, 25 volumes in 3N-NaOH? Use a solution to which methanol has been added. After saponification, a film of cellulose-glucose composite gel is obtained, through which a water-soluble compound having a molecular weight of 5500 or less can permeate. Example 8 When the composite gel film obtained in Example 7 is treated in hot water at 80° C. for 1 hour, glucose is eluted and a porous cellulose film is obtained.
この多孔質フイルムを通して分子量６０００以下の水溶
性化合物が浸透することができ、これらの化合物を透析
によつて除去することができる。実施例 ９二硝酸セル
ロース１０ｙ及び二硝酸可溶性殿粉３ｙをアセトン１５
０ｄに溶解し、攪拌下に水中に投入すると、フレーク状
の沈殿が生成する。Water-soluble compounds having a molecular weight of 6,000 or less can permeate through this porous film, and these compounds can be removed by dialysis. Example 9 10 y of cellulose dinitrate and 3 y of dinitrate-soluble starch were mixed with 15 y of acetone.
When dissolved in 0d and poured into water with stirring, a flaky precipitate is formed.
この沈殿をけん化浴中で３０℃において５時間けん化す
る。けん化浴としては、２Ｎ−ＮａＯＨ中にその２５容
量？のメタノールを加えた溶液を用いる。得られたけん
化生成物は多孔質のセルロース殿粉複合ゲルのフレーク
状物で、このゲル中に分子量１２万以下の水溶性化合物
が浸透できる。実施例 １０実施例９の生成物を８０゜
Ｃ（′ｌ時間熱湯中で処理すると、可溶性殿粉が溶出し
て多孔質セルロースのフレーク状物が得られる。This precipitate is saponified in a saponification bath at 30° C. for 5 hours. As a saponification bath, 25? Use a solution to which methanol has been added. The saponification product obtained is a flake-like porous cellulose starch composite gel, into which a water-soluble compound having a molecular weight of 120,000 or less can penetrate. EXAMPLE 10 The product of Example 9 is treated in boiling water at 80 DEG C. ('l hour) to dissolve the soluble starch and give flakes of porous cellulose.
Claims (1)
類のエステル又は合成高分子エステル（Ｂ）を溶融し又
は溶剤に溶解し、この溶融物又は溶液から構造物を形成
し、そしてけん化することにより、分子量５０００〜１
００００００の水溶性化合物が浸透できるセルロース含
有多孔質構造物とすることを特徴とする、多孔質親水性
構造物の製法。 ２ けん化したのちセルロース以外の成分を除去するこ
とを特徴とする、特許請求の範囲第１項に記載の方法。[Claims] 1. A cellulose ester (A) and a polysaccharide or monosaccharide ester or a synthetic polymer ester (B) are melted or dissolved in a solvent, a structure is formed from this melt or solution, and By saponification, the molecular weight is 5000-1
1. A method for producing a porous hydrophilic structure, characterized in that the cellulose-containing porous structure is permeable to a water-soluble compound of 0.000000. 2. The method according to claim 1, which comprises removing components other than cellulose after saponification.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP52120886A JPS5910691B2 (en) | 1977-10-11 | 1977-10-11 | Manufacturing method of porous hydrophilic structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP52120886A JPS5910691B2 (en) | 1977-10-11 | 1977-10-11 | Manufacturing method of porous hydrophilic structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5455055A JPS5455055A (en) | 1979-05-01 |
| JPS5910691B2 true JPS5910691B2 (en) | 1984-03-10 |
Family
ID=14797402
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP52120886A Expired JPS5910691B2 (en) | 1977-10-11 | 1977-10-11 | Manufacturing method of porous hydrophilic structure |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5910691B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62159797U (en) * | 1986-03-31 | 1987-10-09 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61106168A (en) * | 1984-10-30 | 1986-05-24 | 帝人株式会社 | Permselective hollow yarn membrane, its production and serum component separator using the same |
| JPS61293469A (en) * | 1985-06-21 | 1986-12-24 | 帝人株式会社 | Permselective hollow yarn membrane and serum component separator using the same |
-
1977
- 1977-10-11 JP JP52120886A patent/JPS5910691B2/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62159797U (en) * | 1986-03-31 | 1987-10-09 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5455055A (en) | 1979-05-01 |
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