JPH0113721B2 - - Google Patents
Info
- Publication number
- JPH0113721B2 JPH0113721B2 JP24424383A JP24424383A JPH0113721B2 JP H0113721 B2 JPH0113721 B2 JP H0113721B2 JP 24424383 A JP24424383 A JP 24424383A JP 24424383 A JP24424383 A JP 24424383A JP H0113721 B2 JPH0113721 B2 JP H0113721B2
- Authority
- JP
- Japan
- Prior art keywords
- dialdehyde starch
- starch
- reaction
- acid
- dialdehyde
- 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
- 229920002085 Dialdehyde starch Polymers 0.000 claims description 49
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 229920002472 Starch Polymers 0.000 claims description 15
- 239000008107 starch Substances 0.000 claims description 15
- 235000019698 starch Nutrition 0.000 claims description 15
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000012429 reaction media Substances 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 20
- JQWHASGSAFIOCM-UHFFFAOYSA-M sodium periodate Chemical compound [Na+].[O-]I(=O)(=O)=O JQWHASGSAFIOCM-UHFFFAOYSA-M 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 12
- 239000004202 carbamide Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000003463 adsorbent Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 210000003298 dental enamel Anatomy 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000012567 medical material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- NALMPLUMOWIVJC-UHFFFAOYSA-N n,n,4-trimethylbenzeneamine oxide Chemical compound CC1=CC=C([N+](C)(C)[O-])C=C1 NALMPLUMOWIVJC-UHFFFAOYSA-N 0.000 description 4
- 239000011697 sodium iodate Substances 0.000 description 4
- 235000015281 sodium iodate Nutrition 0.000 description 4
- 229940032753 sodium iodate Drugs 0.000 description 4
- 102000009027 Albumins Human genes 0.000 description 3
- 108010088751 Albumins Proteins 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 241000234314 Zingiber Species 0.000 description 3
- 235000006886 Zingiber officinale Nutrition 0.000 description 3
- PNNCWTXUWKENPE-UHFFFAOYSA-N [N].NC(N)=O Chemical compound [N].NC(N)=O PNNCWTXUWKENPE-UHFFFAOYSA-N 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 235000008397 ginger Nutrition 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- MLIWQXBKMZNZNF-KUHOPJCQSA-N (2e)-2,6-bis[(4-azidophenyl)methylidene]-4-methylcyclohexan-1-one Chemical compound O=C1\C(=C\C=2C=CC(=CC=2)N=[N+]=[N-])CC(C)CC1=CC1=CC=C(N=[N+]=[N-])C=C1 MLIWQXBKMZNZNF-KUHOPJCQSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 235000015165 citric acid Nutrition 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 208000001647 Renal Insufficiency Diseases 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- 229940099112 cornstarch Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 201000006370 kidney failure Diseases 0.000 description 1
- 208000019423 liver disease Diseases 0.000 description 1
- 230000005976 liver dysfunction Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- JLKDVMWYMMLWTI-UHFFFAOYSA-M potassium iodate Chemical compound [K+].[O-]I(=O)=O JLKDVMWYMMLWTI-UHFFFAOYSA-M 0.000 description 1
- 239000001230 potassium iodate Substances 0.000 description 1
- 235000006666 potassium iodate Nutrition 0.000 description 1
- 229940093930 potassium iodate Drugs 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Landscapes
- External Artificial Organs (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Description
本発明は医用材料として使用できる高純度のジ
アルデヒド澱粉の製造法に関するものである。
腎不全、尿素症、肝機能障害などの患者の治療
法の１つとして、生体内の有毒物質を除去するこ
とを目的としてジアルデヒド澱粉を主体とする吸
着剤を経口投与する方法が知られている。この種
の吸着剤として例えば特公昭57−29449号に記載
のごとくジアルデヒド澱粉の表面を生体適合性の
ある高分子物質で処理したものは尿素およびアン
モニアの吸着剤として有用であることが知られて
いる。しかし特に医用材料として好適なジアルデ
ヒド澱粉の製造法および精製法は知られておら
ず、通常の方法で製造したジアルデヒド澱粉は人
体に有害な重金属や反応副生成物を含んでいるた
め、このまま医用材料として使用できない。
本発明の目的は医用材料として使用できる高純
度のかつ尿素およびアンモニアに対して吸着能の
大きいジアルデヒド澱粉の製造法を提供すること
にある。
すなわち本発明は、反応媒体中の澱粉スラリー
濃度を５ないし40重量％とし、該反応媒体のPHを
1.5ないし４とし、過よう素酸および又はその塩
を理論反応量の１ないし1.1倍添加し、反応温度
５℃ないし50℃にて反応した後、残留している過
よう素酸またはよう素酸またはそれらの塩を除去
するために生成したジアルデヒド澱粉をPH１ない
し３に調節した酸性水溶液で洗浄することを特徴
とするジアルデヒド澱粉の製造法である。
本発明の方法に用いる過よう素酸またはその塩
類は過よう素酸、過よう素酸ナトリウム、過よう
素酸カリウムを一般に用い、またそれらの混合物
でも良い。
本発明の方法における澱粉スラリー濃度は一般
に５ないし40重量％を用いる。好ましくは５ない
し20重量％を用いる。５重量％未満では特に反応
の進行に問題はないが、反応器が大きくなり経済
的には不利となり、一方40重量％を越えると澱粉
粒子が均一に分散しなくなり、反応が不均一とな
り、カルボン酸などの不純物を生ずる。
本発明の方法における反応媒体のPHは1.5ない
し４を用いる。1.5未満では得られるジアルデヒ
ド澱粉が収縮し、表面積が小さくなりその結果尿
素およびアンモニアの吸着剤としての用途に供し
た場合吸着能が低下する。一方４を越えるとジア
ルデヒド澱粉が糊化し、ロ過が困難となり工業的
に不利になる。またジアルデヒド澱粉粒子の溶解
が起こり収率が悪くなる。
本発明の方法における過よう素酸またはその塩
の添加量は(1)式により示される反応理論量の１な
いし1.1倍とする。
（式中ＭはＨ又はNa，Ｋを表わす。）
本発明の方法における反応温度は５℃ないし50
℃とする。５℃より低いと反応の進行が著しく遅
くなり工業的に不利である。一方50℃を越えると
糊化し、ロ過が困難となる。
本発明で使用する洗浄用の酸性水溶液は塩酸、
硫酸、リン酸等の鉱酸の水溶液および酢酸、ギ
酸、修酸、リンゴ酸、クエン酸等の有機酸の水溶
液が一般に用いられる。酸性水溶液のPHは１ない
し３が好ましい。PHが１より小さいとジアルデヒ
ド澱粉の収縮が起こるためこれを原料として吸着
剤としても尿素およびアンモニアの吸着能が低下
する。一方３より大きいとジアルデヒド澱粉に残
留している未反応の過よう素酸または(1)式により
生成したよう素酸またはそれらの塩および重金属
の除去効率が低下する。
本発明者らはジアルデヒド澱粉は、澱粉中のグ
ルコース単位が一般式
The present invention relates to a method for producing highly pure dialdehyde starch that can be used as a medical material. As one of the treatment methods for patients with renal failure, ureaemia, liver dysfunction, etc., it is known that an adsorbent mainly composed of dialdehyde starch is orally administered for the purpose of removing toxic substances in the body. There is. This kind of adsorbent is known to be useful as an adsorbent for urea and ammonia, for example, one in which the surface of dialdehyde starch is treated with a biocompatible polymeric substance as described in Japanese Patent Publication No. 57-29449. ing. However, there are no known production or purification methods for dialdehyde starch that is particularly suitable as a medical material, and dialdehyde starch produced by conventional methods contains heavy metals and reaction by-products that are harmful to the human body, so it cannot be used as is. Cannot be used as a medical material. An object of the present invention is to provide a method for producing dialdehyde starch of high purity and high adsorption capacity for urea and ammonia, which can be used as a medical material. That is, in the present invention, the starch slurry concentration in the reaction medium is 5 to 40% by weight, and the PH of the reaction medium is
1.5 to 4, add 1 to 1.1 times the theoretical reaction amount of periodic acid and/or its salt, and react at a reaction temperature of 5°C to 50°C, and then remove the remaining periodic acid or iodic acid. A method for producing dialdehyde starch is characterized in that the dialdehyde starch produced is washed with an acidic aqueous solution adjusted to pH 1 to 3 in order to remove salts thereof. Periodic acid or its salts used in the method of the present invention generally include periodic acid, sodium periodate, and potassium periodate, and may also be mixtures thereof. The starch slurry concentration in the method of the present invention is generally 5 to 40% by weight. Preferably 5 to 20% by weight is used. If it is less than 5% by weight, there will be no particular problem in the progress of the reaction, but the reactor will become large and it will be economically disadvantageous.On the other hand, if it exceeds 40% by weight, the starch particles will not be uniformly dispersed, the reaction will be non-uniform, and the carbon Produces impurities such as acids. The pH of the reaction medium used in the method of the present invention is 1.5 to 4. If it is less than 1.5, the resulting dialdehyde starch will shrink and its surface area will become smaller, resulting in a lower adsorption capacity when used as an adsorbent for urea and ammonia. On the other hand, if it exceeds 4, the dialdehyde starch will gelatinize, making filtration difficult and industrially disadvantageous. Furthermore, the dialdehyde starch particles are dissolved, resulting in poor yield. The amount of periodic acid or its salt added in the method of the present invention is 1 to 1.1 times the theoretical reaction amount shown by formula (1). (In the formula, M represents H, Na, or K.) The reaction temperature in the method of the present invention is 5°C to 50°C.
℃. If the temperature is lower than 5°C, the progress of the reaction will be extremely slow, which is industrially disadvantageous. On the other hand, if the temperature exceeds 50°C, it will gelatinize and become difficult to filter. The acidic aqueous solution for cleaning used in the present invention is hydrochloric acid,
Aqueous solutions of mineral acids such as sulfuric acid and phosphoric acid and aqueous solutions of organic acids such as acetic acid, formic acid, oxalic acid, malic acid and citric acid are generally used. The pH of the acidic aqueous solution is preferably 1 to 3. If the pH is less than 1, shrinkage of dialdehyde starch occurs, so even if this starch is used as a raw material as an adsorbent, its ability to adsorb urea and ammonia will decrease. On the other hand, if it is larger than 3, the removal efficiency of unreacted periodic acid remaining in the dialdehyde starch or iodic acid or salts thereof and heavy metals generated by the formula (1) will decrease. The present inventors have discovered that dialdehyde starch has a structure in which the glucose units in the starch have the general formula
【式】
で表わされる単位で置換された割合（以下酸化度
と呼ぶ）が60〜95％のものが医用に好適であるこ
とを見い出した。すなわち酸化度のみで判断する
と酸化度が95％を越えると澱粉主鎖の切断が起こ
り、溶解がしやすくなり、分解生成物が生成し、
また60％未満では、これを原料として吸着剤とし
ても尿素およびアンモニアの単位重量当りの吸着
量が低くなる。本発明では前記の反応条件を採用
することにより酸化度60〜95％のジアルデヒド澱
粉を製造することができるようにしたものであ
る。本発明の方法によれば、医用として使用でき
る不純物の少ない、かつ工業的に安定したジアル
デヒド澱粉の製造が可能となり、この方法により
生成したジアルデヒド澱粉を原料として吸着剤と
すれば尿素およびアンモニアの単位重量当りの吸
着能が高いものが得られる。
以下、実施例により本発明の実施態様を示す
が、これに限定されるものではない。
実施例 １
撹拌機を付した10のホーロー反応槽にあらか
じめ５℃に冷却したPH1.5、濃度0.569mol／の
過よう素酸溶液6.9を入れ、撹拌しながらジヤ
ガイモデンプン（水分16.7％）1.2Kgを加え澱粉
スラリー濃度を11.2％とした。３分後に液温は17
℃まで上昇したが、冷却して10℃で90分間撹拌し
た。過よう素酸の反応率は95％に達した。次に遠
心分離機で生成したジアルデヒド澱粉を分離し、
ジアルデヒド澱粉粒子に付着しているよう素酸
は、あらかじめ塩酸でPH1.2に調節された水260
により洗浄した。次にエタノールで洗浄後減圧下
で乾燥して酸化度60.5％のジアルデヒド澱粉996
ｇを得た。水分は７％であつた。
酸化度の測定法は水素化ホウ素ナトリウム法に
よつた。又、生成物中の残留よう素酸の分析結果
は検出限界の1ppm以下であつた。
実施例 ２
撹拌機を付した30のホーロー反応槽に、あら
かじめPH3.8に調節した過よう素酸ナトリウムの
0.525mol／溶液19.4を入れ、撹拌しながら水
分18.1％のタピオカデンプン1.9Kgを加え澱粉ス
ラリー濃度38.6％とした。５分後に液温は47℃ま
で上昇したが、自然放冷で120分間撹拌した。過
よう素酸の反応率は88.7％に達した。次に遠心分
離機で生成したジアルデヒド澱粉を分離した。ジ
アルデヒド澱粉粒子に付着しているよう素酸ナト
リウムは、酢酸であらかじめPH2.5とした水450
で洗浄することによつて除去した。次にエタノー
ルで十分洗浄後乾燥して酸化度94.1％のジアルデ
ヒド澱粉1.5Kg（水分９％）を得た。生成物中の
残留よう素酸の分析結果は検出限界の1ppm以下
であつた。
実施例 ３
撹拌機を付した30のホーロー反応槽に、あら
かじめPH3.8にセツトした過よう素酸カリウムの
0.379mol／溶液16.6を入れ、撹拌しながら水
分15.2％のコーンスターチ1.2Kgを加え澱粉スラ
リー濃度を5.4％とした。３分後に液温は46℃ま
で上昇したが、自然放冷で60分撹拌した。過よう
素酸の反応率は81％に達した。次に遠心分離機で
生成したジアルデヒド澱粉を分離し、ジアルデヒ
ド澱粉粒子に付着しているよう素酸カリウムは、
硫酸であらかじめ塩酸でPH2.0とした水260で洗
浄することによつて除去した。次にエタノールで
十分洗浄後乾燥して酸化度80.3％のジアルデヒド
澱粉1.1Kg（水分10.1％）を得た。生成物中の残
留よう素酸の分析結果は検出限界の1ppm以下で
あつた。
実施例 ４
クエン酸でPH2.0に調節した水260により洗浄
する以外は、実施例１と全く同様の方法により、
酸化度60.7％のジアルデヒド澱粉994ｇを得た。
水分は７％であつた。又、ジアルデヒド澱粉中の
残留よう素酸の分析結果は検出限界の1ppm以下
であつた。
実施例 ５
リンゴ酸でPH2.5に調節した水260により洗浄
する以外は、実施例１と全く同様の方法により、
酸化度60.6％のジアルデヒド澱粉995ｇを得た。
水分は８％であつた。又、ジアルデヒド澱粉中の
残留よう素酸の分析結果は検出限界の1ppm以下
であつた。
比較例 １
PH1.0、濃度0.522mol／の過よう素酸溶液7.5
を用いる以外は実施例１と全く同様の操作によ
り、酸化度61.0％のジアルデヒド澱粉990ｇを得
た。水分は7.5％であつた。ジアルデヒド澱粉は
第１表に示す様に尿素吸着能が低かつた。
比較例 ２
PH5.0、濃度0.491mol／の過よう素酸ナトリ
ウム溶液20.7を用いる以外は実施例２と全く同
様の操作により120分間反応したところ、遠心分
離機にかけたが糊化が激しく洗浄不可能であり、
ジアルデヒド澱粉中の残留よう素酸ナトリウムの
分析結果は1200ppmであつた。
比較例 ３
撹拌機を付した10のホーロー反応槽にあらか
じめ３℃に冷却したPH3.5、濃度0.308mol／の
過よう素酸ナトリウム溶液10を入れ、撹拌しな
がらジヤガイモデンプン（水分16.7％）1.2Kgを
加え澱粉スラリー濃度を9.7％とした。３分後に
液温は15℃まで上昇したが、冷却して３℃で90分
間撹拌したが、過よう素酸ナトリウムの反応率は
30％と低かつた。さらに３℃で反応を継続した
が、過よう素酸ナトリウムの反応率が90％に達す
るにはさらに18時間を要した。次に遠心分離機で
ジアルデヒド澱粉を分離したところ、ロ布上には
ジアルデヒド澱粉にまじつてよう素酸ナトリウム
の結果が多量に析出していた。
比較例 ４
撹拌機を付した10のホーロー反応槽に、あら
かじめ30℃に加温したPH3.5、濃度0.567mol／
の過よう素酸ナトリウム溶液6.9を入れ、撹拌
しながらジヤガイモデンプン（水分16.7％）1.2
Kgを加えスラリー濃度を11.8％とした。３分後に
液温は54℃まで上昇したが、60℃にセツトして30
分間撹拌した。過よう素酸ナトリウムの反応率は
98％に達した。次に遠心分離機でジアルデヒド澱
粉を分離ようとしたが、ジアルデヒド澱粉の糊化
が激しく、洗浄も不可能であり、得られたジアル
デヒド澱粉中によう素酸ナトリウムが1300ppm混
入していた。
比較例 ５
あらかじめ硫酸でPH0.5に調節した水を用いて
洗浄する他は、実施例１と全く同様の方法で行
い、酸化度60.8％のジアルデヒド澱粉1002ｇを得
た。水分は7.4％であつた。ジアルデヒド澱粉は
第１表に示す様に尿素吸着能が低かつた。
比較例 ６
あらかじめ酢酸によつてPH4.0に調節した水を
用いて洗浄する他は、実施例１と全く同様の方法
で行つたところ、洗浄水量を650としたがジア
ルデヒド澱粉中のよう素酸は200ppmであつた。
又、洗浄後のジアルデヒド澱粉は糊化していた。
参考例
実施例１〜５、比較例１および５で得たジアル
デヒド澱粉10ｇを各々10％濃度で水に分散させ、
撹拌下に50℃で３時間膨潤させた後室温まで冷却
し、１％アルブミン水溶液10ｇを滴下し１時間反
応させた後、80℃に昇温し30分撹拌して再び室温
まで冷却した後遠心分離し、凍結乾燥して白色粉
末状のアルブミン処理ジアルデヒドデンプンを得
た。得られたジアルデヒドデンプンの0.5ｇを尿
素窒素濃度117mg／dlの透析液（TM−ソリタ、
武田薬品工業製）５mlを入れたＬ字型培養管に入
れ、37℃で５時間振とうした後アルブミン処理ジ
アルデヒドデンプンを除去し、尿素窒素テストワ
コー（商品名、和光純薬工業製）を用いてフエア
ロン（Fearon）反応させ被処理液の残存尿素窒
素濃度を調べ、ジアルデヒド澱粉単位重量当りの
尿素吸着量を求めた。その結果を第１表に示す。
第１表により、本発明の方法により得られるジ
アルデヒド澱粉を使用したものは尿素の吸着能が
優れていることがわかる。It has been found that those having a substitution ratio of 60 to 95% with units represented by the formula (hereinafter referred to as oxidation degree) are suitable for medical use. In other words, if the degree of oxidation exceeds 95%, judging only by the degree of oxidation, the starch main chain will break, making it easier to dissolve, and decomposition products will be generated.
If it is less than 60%, the amount of adsorption of urea and ammonia per unit weight will be low even if this is used as a raw material as an adsorbent. In the present invention, dialdehyde starch having an oxidation degree of 60 to 95% can be produced by employing the above reaction conditions. According to the method of the present invention, it is possible to produce dialdehyde starch that can be used for medical purposes, has few impurities, and is industrially stable.If the dialdehyde starch produced by this method is used as a raw material as an adsorbent, it can absorb urea and ammonia. A product with high adsorption capacity per unit weight can be obtained. Hereinafter, embodiments of the present invention will be illustrated by examples, but the present invention is not limited thereto. Example 1 A periodic acid solution of pH 1.5 and a concentration of 0.569 mol/6.9 kg, which had been cooled to 5°C in advance, was placed in 10 enamel reaction vessels equipped with a stirrer, and 1.2 kg of ginger starch (water content 16.7%) was added while stirring. was added to make the starch slurry concentration 11.2%. After 3 minutes, the liquid temperature is 17
℃, but was cooled and stirred at 10℃ for 90 minutes. The reaction rate of periodic acid reached 95%. Next, the dialdehyde starch produced is separated using a centrifuge.
The iodic acid attached to the dialdehyde starch particles is dissolved in water 260 which has been adjusted to pH 1.2 with hydrochloric acid in advance.
Washed with Next, after washing with ethanol and drying under reduced pressure, dialdehyde starch 996 with an oxidation degree of 60.5% is obtained.
I got g. The moisture content was 7%. The degree of oxidation was measured by the sodium borohydride method. In addition, the analysis result of residual iodic acid in the product was below the detection limit of 1 ppm. Example 2 Sodium periodate, which had been adjusted to pH 3.8, was placed in 30 enamel reactors equipped with a stirrer.
0.525 mol/solution 19.4 was added, and while stirring, 1.9 kg of tapioca starch with a moisture content of 18.1% was added to make the starch slurry concentration 38.6%. After 5 minutes, the liquid temperature rose to 47°C, but the mixture was allowed to cool naturally and was stirred for 120 minutes. The reaction rate of periodic acid reached 88.7%. Next, the dialdehyde starch produced was separated using a centrifuge. Sodium iodate attached to dialdehyde starch particles is dissolved in water whose pH has been adjusted to pH 2.5 with acetic acid at 450°C.
It was removed by washing with. Next, the mixture was thoroughly washed with ethanol and dried to obtain 1.5 kg of dialdehyde starch (water content: 9%) with an oxidation degree of 94.1%. The analysis result of residual iodic acid in the product was below the detection limit of 1 ppm. Example 3 Potassium periodate, which had been set at pH 3.8, was placed in 30 enamel reactors equipped with a stirrer.
0.379 mol/solution 16.6 was added, and while stirring, 1.2 kg of cornstarch with a moisture content of 15.2% was added to make the starch slurry concentration 5.4%. After 3 minutes, the liquid temperature rose to 46°C, but the mixture was allowed to cool naturally and was stirred for 60 minutes. The reaction rate of periodic acid reached 81%. Next, the dialdehyde starch produced is separated using a centrifuge, and the potassium iodate attached to the dialdehyde starch particles is removed.
It was removed by washing with water 260, which had been adjusted to pH 2.0 with hydrochloric acid and sulfuric acid. Next, it was thoroughly washed with ethanol and dried to obtain 1.1 kg of dialdehyde starch (moisture 10.1%) with an oxidation degree of 80.3%. The analysis result of residual iodic acid in the product was below the detection limit of 1 ppm. Example 4 In exactly the same manner as in Example 1, except for washing with water 260 adjusted to pH 2.0 with citric acid,
994 g of dialdehyde starch with an oxidation degree of 60.7% was obtained.
The moisture content was 7%. In addition, the analysis results of residual iodic acid in dialdehyde starch were below the detection limit of 1 ppm. Example 5 In exactly the same manner as in Example 1, except for washing with water 260 adjusted to pH 2.5 with malic acid,
995 g of dialdehyde starch with an oxidation degree of 60.6% was obtained.
The moisture content was 8%. In addition, the analysis results of residual iodic acid in dialdehyde starch were below the detection limit of 1 ppm. Comparative example 1 Periodic acid solution with pH 1.0 and concentration 0.522 mol/7.5
990 g of dialdehyde starch with an oxidation degree of 61.0% was obtained by the same operation as in Example 1 except that . The moisture content was 7.5%. As shown in Table 1, dialdehyde starch had a low urea adsorption capacity. Comparative Example 2 A reaction was carried out for 120 minutes in exactly the same manner as in Example 2, except that a sodium periodate solution of pH 5.0 and a concentration of 0.491 mol/20.7 was used. Although the reaction was applied to a centrifuge, gelatinization was severe and washing was impossible. It is possible and
The analysis result of residual sodium iodate in dialdehyde starch was 1200 ppm. Comparative Example 3 Into 10 enamel reaction vessels equipped with a stirrer, 10 liters of sodium periodate solution with a pH of 3.5 and a concentration of 0.308 mol/cooled to 3°C was placed, and while stirring, 1.2 liters of ginger starch (moisture 16.7%) was added. Kg was added to make the starch slurry concentration 9.7%. After 3 minutes, the liquid temperature rose to 15℃, but after cooling and stirring at 3℃ for 90 minutes, the reaction rate of sodium periodate was
It was as low as 30%. The reaction was further continued at 3°C, but it took another 18 hours for the reaction rate of sodium periodate to reach 90%. Next, when the dialdehyde starch was separated using a centrifuge, a large amount of sodium iodate was precipitated on the cloth mixed with the dialdehyde starch. Comparative Example 4 10 enamel reaction vessels equipped with a stirrer were heated to 30°C in advance with a pH of 3.5 and a concentration of 0.567 mol/min.
Add 6.9 liters of sodium periodate solution and add 1.2 ounces of ginger starch (moisture 16.7%) while stirring.
Kg was added to make the slurry concentration 11.8%. After 3 minutes, the liquid temperature rose to 54℃, but after setting it to 60℃,
Stir for a minute. The reaction rate of sodium periodate is
It reached 98%. Next, an attempt was made to separate the dialdehyde starch using a centrifuge, but the gelatinization of the dialdehyde starch was so severe that washing was impossible, and the resulting dialdehyde starch contained 1300 ppm of sodium iodate. . Comparative Example 5 1002 g of dialdehyde starch with an oxidation degree of 60.8% was obtained in the same manner as in Example 1, except for washing with water that had been adjusted to pH 0.5 with sulfuric acid. The moisture content was 7.4%. As shown in Table 1, dialdehyde starch had a low urea adsorption capacity. Comparative Example 6 The same method as in Example 1 was carried out except that the washing was carried out using water that had been adjusted to pH 4.0 with acetic acid. The acid was 200 ppm.
In addition, the dialdehyde starch after washing was gelatinized. Reference Example 10 g of dialdehyde starch obtained in Examples 1 to 5 and Comparative Examples 1 and 5 were each dispersed in water at a concentration of 10%,
After swelling at 50℃ for 3 hours with stirring, cooling to room temperature, adding 10g of 1% albumin aqueous solution dropwise and reacting for 1 hour, heating to 80℃, stirring for 30 minutes, cooling to room temperature again, and centrifuging. It was separated and lyophilized to obtain albumin-treated dialdehyde starch in the form of a white powder. 0.5 g of the obtained dialdehyde starch was added to a dialysate with a urea nitrogen concentration of 117 mg/dl (TM-Sorita,
After shaking at 37℃ for 5 hours, the albumin-treated dialdehyde starch was removed, and urea nitrogen test Wako (trade name, manufactured by Wako Pure Chemical Industries, Ltd.) was added to an L-shaped culture tube containing 5 ml of Takeda Pharmaceutical Co., Ltd. The residual urea nitrogen concentration of the treated solution was investigated using a Fearon method, and the amount of urea adsorbed per unit weight of dialdehyde starch was determined. The results are shown in Table 1. Table 1 shows that the products using dialdehyde starch obtained by the method of the present invention have excellent urea adsorption ability.
Claims (1)
重量パーセントとし、該反応媒体のPHを1.5ない
し４とし、過よう素酸および又は過よう素酸塩を
理論反応量の１ないし1.1倍添加し、反応温度５
℃ないし50℃にて反応せしめた後、生成したジア
ルデヒド澱粉をPH１ないし３に調節した酸性水溶
液で洗浄することを特徴とするジアルデヒド澱粉
の製造法。1 Starch slurry concentration in reaction medium from 5 to 40
weight percent, the pH of the reaction medium is 1.5 to 4, periodic acid and/or periodate salt is added 1 to 1.1 times the theoretical reaction amount, and the reaction temperature is 5.
1. A method for producing dialdehyde starch, which comprises carrying out a reaction at a temperature of .degree. C. to 50.degree. C., and then washing the resulting dialdehyde starch with an acidic aqueous solution adjusted to pH 1 to 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24424383A JPS60137902A (en) | 1983-12-26 | 1983-12-26 | Production of dialdehyde starch |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24424383A JPS60137902A (en) | 1983-12-26 | 1983-12-26 | Production of dialdehyde starch |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60137902A JPS60137902A (en) | 1985-07-22 |
| JPH0113721B2 true JPH0113721B2 (en) | 1989-03-08 |
Family
ID=17115860
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24424383A Granted JPS60137902A (en) | 1983-12-26 | 1983-12-26 | Production of dialdehyde starch |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60137902A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2023160131A (en) * | 2022-04-21 | 2023-11-02 | カーリットホールディングス株式会社 | Polyaldehyde compound-containing composition and method for producing the same |
-
1983
- 1983-12-26 JP JP24424383A patent/JPS60137902A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60137902A (en) | 1985-07-22 |
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