JPH05247221A - Method of solubilizing water-swellable crosslinked polymer - Google Patents
Method of solubilizing water-swellable crosslinked polymerInfo
- Publication number
- JPH05247221A JPH05247221A JP4578792A JP4578792A JPH05247221A JP H05247221 A JPH05247221 A JP H05247221A JP 4578792 A JP4578792 A JP 4578792A JP 4578792 A JP4578792 A JP 4578792A JP H05247221 A JPH05247221 A JP H05247221A
- Authority
- JP
- Japan
- Prior art keywords
- water
- ascorbic acid
- polymer
- crosslinked polymer
- swellable crosslinked
- 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
- 229920006037 cross link polymer Polymers 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims description 20
- 230000003381 solubilizing effect Effects 0.000 title claims description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 69
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 22
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 22
- 230000007928 solubilization Effects 0.000 abstract description 18
- 238000005063 solubilization Methods 0.000 abstract description 18
- 229920000642 polymer Polymers 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract 2
- 239000006185 dispersion Substances 0.000 abstract 1
- 230000029219 regulation of pH Effects 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 13
- 239000002211 L-ascorbic acid Substances 0.000 description 12
- 235000000069 L-ascorbic acid Nutrition 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000000499 gel Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 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
- 229940048053 acrylate Drugs 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 210000002700 urine Anatomy 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-DUZGATOHSA-N D-isoascorbic acid Chemical compound OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 235000010350 erythorbic acid Nutrition 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 229940026239 isoascorbic acid Drugs 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229940047670 sodium acrylate Drugs 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】この発明は、水膨潤性架橋重合体
の可溶化方法に関するものである。詳しくは、通常、粉
末あるいは水膨潤ゲル状の水膨潤性架橋重合体を水系媒
体に可溶化する方法に関するものである。FIELD OF THE INVENTION The present invention relates to a method for solubilizing a water-swellable crosslinked polymer. More specifically, the present invention relates to a method of solubilizing a water-swellable crosslinked polymer, which is usually in the form of powder or water-swelling gel, in an aqueous medium.
【０００２】[0002]
【従来の技術およびその課題】従来、水膨潤性架橋重合
体の可溶化は、水膨潤ゲルに紫外線を照射し分解する方
法（特開平１−２３１９８３）や水膨潤ゲルをアルカリ
物質・酸化剤により液状化する方法（特公昭５３−１３
４９５、特公昭５３−１３６７８、特開平１−２８４５
０７）などが知られている。しかし、前者による方法
は、紫外線を照射するための装置が必要であり必ずしも
簡便な方法とは言えない。また後者は、多量のアルカリ
物質あるいは酸化剤添加による比較的簡便な方法である
が、一般的に多量のアルカリ物質や酸化剤は取り扱いに
注意を要し危険を伴う。この様な背景から、前記の諸問
題が解決された水膨潤性架橋重合体の可溶化方法が望ま
れていた。2. Description of the Related Art Conventionally, the solubilization of a water-swellable crosslinked polymer has been carried out by irradiating a water-swelling gel with ultraviolet rays to decompose the water-swelling gel (Japanese Patent Laid-Open No. 1-231983) or by using an alkaline substance and an oxidizing agent for the water-swelling gel. Liquefaction method (Japanese Patent Publication No. 53-13
495, Japanese Patent Publication No. 53-13678, Japanese Patent Laid-Open No. 1-2845.
07) and the like are known. However, the former method is not necessarily a simple method because it requires an apparatus for irradiating ultraviolet rays. The latter is a relatively simple method by adding a large amount of an alkaline substance or an oxidizing agent, but generally, a large amount of an alkaline substance or an oxidizing agent requires careful handling and is dangerous. From such a background, a method for solubilizing a water-swellable crosslinked polymer, which solves the above problems, has been desired.
【０００３】[0003]
【課題を解決するための手段】本発明者らは、上記課題
を解決するために鋭意検討を重ねた結果、水膨潤性架橋
重合体を、比較的入手が容易で且つ安全性の高い試薬で
あるアスコルビン酸を用いて、その可溶化系のｐＨを特
定の範囲に制御することにより、容易に水膨潤性架橋重
合体を水系溶媒に可溶化できることを見いだし本発明に
到達した。すなわち本発明は、水膨潤性架橋重合体に水
およびアスコルビン酸を添加し、その際のｐＨを４から
７．５の範囲に制御することを特徴とする水膨潤性架橋
重合体の可溶化方法を提供する。Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a water-swellable crosslinked polymer can be used as a reagent that is relatively easily available and highly safe. The inventors have found that the water-swellable cross-linked polymer can be easily solubilized in an aqueous solvent by controlling the pH of the solubilized system within a specific range using a certain ascorbic acid, and arrived at the present invention. That is, the present invention is a method for solubilizing a water-swellable cross-linked polymer, which comprises adding water and ascorbic acid to the water-swellable cross-linked polymer and controlling the pH in the range of 4 to 7.5. I will provide a.
【０００４】この発明により可溶化される水膨潤性架橋
重合体とは、自重の１０から１０００倍の水を吸収し膨
潤する能力を有する架橋重合体であり、たとえば、（メ
タ）アクリル酸塩架橋重合体、（メタ）アクリル酸エス
テル−酢酸ビニル共重合体のケン化物架橋体、デンプン
−アクリル酸塩グラフト重合体の架橋物等を挙げること
ができる。中でも、吸水能力の高いアクリル酸塩架橋重
合体に対して本発明の方法が特に有効である。このよう
な水膨潤性架橋重合体は、それ自体、当業者間によく知
られており、例えば米国特許第４，２８６，０８２号、
第３，６６１，８１５号、第４，０７６，６６３号、第
４，６８３，２７４号、特開昭５２−１４６８９号およ
び特公昭５３−１５９５９号等に開示されている。これ
ら先行技術に開示された製造方法において製造装置内に
付着した水膨潤性架橋重合体は、この発明の方法により
可溶化し、除去することも可能である。The water-swellable crosslinked polymer to be solubilized according to the present invention is a crosslinked polymer having an ability to absorb and swell 10 to 1000 times its own weight of water, and for example, (meth) acrylate crosslinked. Examples include polymers, crosslinked saponified products of (meth) acrylic acid ester-vinyl acetate copolymers, crosslinked products of starch-acrylic acid salt graft polymers, and the like. Among them, the method of the present invention is particularly effective for an acrylate cross-linked polymer having a high water absorption capacity. Such water-swellable crosslinked polymers are themselves well known to those skilled in the art and are described, for example, in US Pat. No. 4,286,082,
No. 3,661,815, 4,076,663, 4,683,274, JP-A-52-14689 and JP-B-53-15959. The water-swellable crosslinked polymer deposited in the manufacturing apparatus in the manufacturing methods disclosed in these prior arts can be solubilized and removed by the method of the present invention.
【０００５】この発明において処理剤として用いるアス
コルビン酸は、たとえば、Ｌ−アスコルビン酸、イソア
スコルビン酸などである。中でも最も一般的であるＬ−
アスコルビン酸が入手が容易で、且つ可溶化の効果も大
きいので好ましい。また、アスコルビン酸の使用形態
は、粉末状あるいは水溶液として用いることが好まし
い。アスコルビン酸の使用量は広い範囲とすることが出
来るが、通常水膨潤性架橋重合体１重量部に対して０．
０００１重量部以上５重量部以下、特に０．０１重量部
以上１重量部以下とするのが好適である。アスコルビン
酸の使用量が多すぎても、使用量に見合った効果の向上
は認められず、むしろその使用量に起因するｐＨの過大
低下を招き、ｐＨの調整に多量の塩基性物質の添加を要
して、経済的な不利益を招く場合がある。The ascorbic acid used as a treating agent in the present invention is, for example, L-ascorbic acid or isoascorbic acid. The most common of these is L-
Ascorbic acid is preferable because it is easily available and has a large solubilizing effect. The ascorbic acid is preferably used in the form of powder or an aqueous solution. Although the amount of ascorbic acid used can be in a wide range, it is usually 0.1% by weight with respect to 1 part by weight of the water-swellable crosslinked polymer.
The amount is preferably 0001 parts by weight or more and 5 parts by weight or less, particularly 0.01 parts by weight or more and 1 part by weight or less. Even if the amount of ascorbic acid used is too large, the improvement in the effect commensurate with the amount used is not observed, but rather the pH is excessively lowered due to the amount used, and the addition of a large amount of basic substance is necessary for adjusting the pH. In short, there may be an economic disadvantage.
【０００６】この発明において可溶化系のｐＨは４以上
７．５以下の範囲に制御されることが重要である。この
範囲を逸脱するとアスコルビン酸の使用量に起因して、
可溶化の効率が低下し、時には可溶化が起こらない。こ
の発明において可溶化系のｐＨを調製するに際し、ｐＨ
調製剤を併用することも可能である。この場合ｐＨ調製
剤は、一般的な酸・塩基でその役割を十分に果たし、た
とえば、硫酸・塩酸・水酸化ナトリウム（水溶液）・水
酸化カリウム（水溶液）などが挙げられる。In the present invention, it is important that the pH of the solubilizing system is controlled within the range of 4 or more and 7.5 or less. If you deviate from this range, due to the amount of ascorbic acid used,
Solubilization efficiency is reduced and sometimes solubilization does not occur. In adjusting the pH of the solubilization system in this invention,
It is also possible to use a preparation together. In this case, the pH adjusting agent sufficiently plays the role of a general acid / base, and examples thereof include sulfuric acid / hydrochloric acid / sodium hydroxide (aqueous solution) / potassium hydroxide (aqueous solution).
【０００７】本発明においては、処理中のｐＨを前記範
囲に制御することが重要で、水膨潤性架橋重合体を前記
規定量のアスコルビン酸で可溶化処理する手順は、特に
制限されない。典型的な実施態様は、たとえばアスコル
ビン酸を溶解させた水溶液を水膨潤性架橋重合体に吸収
させる処理法、吸水膨潤した水膨潤性架橋重合体にアス
コルビン酸（水溶液）を加える処理法、水膨潤性架橋重
合体とアスコルビン酸の混合物に水を加えての処理法な
どである。In the present invention, it is important to control the pH during the treatment within the above range, and the procedure for solubilizing the water-swellable crosslinked polymer with the specified amount of ascorbic acid is not particularly limited. Typical embodiments include, for example, a treatment method in which an aqueous solution in which ascorbic acid is dissolved is absorbed in a water-swellable crosslinked polymer, a treatment method in which ascorbic acid (aqueous solution) is added to the water-swelled water-swellable crosslinked polymer, and water swelling. A treatment method in which water is added to a mixture of the crosslinkable polymer and ascorbic acid.
【０００８】この発明では、可溶化処理中の水膨潤性架
橋重合体の形態は、たとえば、水膨潤ゲル状態、水分散
状態などが挙げられる。水の使用量は、通常水膨潤性架
橋重合体１重量部に対して０．０１重量部以上１０,０
００,０００重量部以下であるが、１重量部以上１,００
０,０００重量部以下が特に好ましい。また、処理され
る水膨潤性架橋重合体が尿などの種々の成分を含有して
いる水を吸収しているとき、この様な水中の固形分量は
一般的に無視できるほどに少量なので、水の重量比は、
たとえば、尿の量と添加した水の量の和を水膨潤性架橋
重合体の重量で割ることにより求められる。水膨潤性架
橋重合体に吸収される水は、通常、水であるが一部メタ
ノール・エタノール等の親水性有機溶剤を含有する水溶
液でもよい。In the present invention, the form of the water-swellable crosslinked polymer during the solubilization treatment includes, for example, a water-swelling gel state and a water-dispersed state. The amount of water used is usually 0.01 parts by weight or more and 10.0 parts by weight per 1 part by weight of the water-swellable crosslinked polymer.
000 parts by weight or less, but 1 part by weight or more and 1.00
Particularly preferably, it is not more than 000 parts by weight. Further, when the water-swellable crosslinked polymer to be treated absorbs water containing various components such as urine, the solid content in such water is generally so small that it can be ignored. The weight ratio of
For example, it is determined by dividing the sum of the amount of urine and the amount of added water by the weight of the water-swellable crosslinked polymer. The water absorbed by the water-swellable crosslinked polymer is usually water, but may be an aqueous solution containing a hydrophilic organic solvent such as methanol and ethanol.
【０００９】この発明での可溶化温度は、アスコルビン
酸が１５０度を越える高温で分解されるので１５０度以
下、好ましくは１００度以下がよい。また、上記含水組
成物が凍結しない程度の温度が必要である。詳しくは、
０度以上、好ましくは１５度以上がよい。また、経済的
な見地からみると、特別な装置を必要としない１５℃か
ら３０℃の範囲である室温による処理が最も効率的であ
り、室温処理はこの発明の効果を十分に発揮する。ま
た、上記範囲内の高温は可溶化を促進すると考えられ
る。系内に第３の成分、たとえば、金属イオン、たとえ
ば、銅イオンなどの影響により、ラジカルの発生が活発
化されて可溶化が促進されることもある。また、そのほ
かの活性化法として可溶化系の撹拌などが挙げられる。The solubilization temperature in the present invention is 150 ° C. or less, preferably 100 ° C. or less because ascorbic acid is decomposed at a high temperature exceeding 150 ° C. Further, the temperature is required to such an extent that the water-containing composition does not freeze. For more information,
It is 0 degree or more, preferably 15 degrees or more. From an economical point of view, the treatment at room temperature in the range of 15 ° C. to 30 ° C., which does not require a special device, is the most efficient, and the room temperature treatment sufficiently exerts the effect of the present invention. Further, it is considered that a high temperature within the above range promotes solubilization. Occurrence of radicals may be activated and solubilization may be promoted by the influence of a third component, such as a metal ion, for example, a copper ion, in the system. Other activation methods include stirring of the solubilization system.
【００１０】[0010]
【作用】水膨潤性架橋重合体は、通常は粉体あるいは水
膨潤ゲル状である。この発明によれば、水膨潤性架橋重
合体の可溶化は、水膨潤性架橋重合体、水およびアスコ
ルビン酸が前記条件下に混在していれば達成されるので
あって、この条件を著しく変化させない範囲において、
その他の付加的条件が加わることは、一向に差し支えな
い。例えば、水膨潤性架橋重合体は、前記のように単独
で用いる必要はなく、水膨潤性架橋重合体が繊維と混合
又は複合化されて用いられる紙おむつや生理用品などの
衛生用品や、建設土木分野での掘削工法において止水・
吸水の目的で使用された水膨潤性架橋重合体を均一混合
の状態で含有する土砂のように水膨潤性架橋重合体を単
独の状態に分離することが困難な状態の物品中は、その
まま本発明の方法に用いることにより、水膨潤性架橋重
合体を可溶化し、分離することができる。The water-swellable crosslinked polymer is usually in the form of powder or water-swelling gel. According to the present invention, the solubilization of the water-swellable cross-linked polymer is achieved if the water-swellable cross-linked polymer, water and ascorbic acid are mixed under the above conditions. In the range not to
There is no problem in adding other additional conditions. For example, the water-swellable cross-linked polymer does not need to be used alone as described above, and the water-swellable cross-linked polymer is used as a mixture or a composite with a fiber, such as a sanitary article such as a paper diaper or a sanitary article, and construction civil engineering. In the field excavation method
In articles in a state where it is difficult to separate the water-swellable cross-linked polymer into a single state such as earth and sand containing the water-swellable cross-linked polymer used for the purpose of absorbing water in a uniformly mixed state, the product is used as it is. By using the method of the invention, the water-swellable crosslinked polymer can be solubilized and separated.
【００１１】上記のように処理することにより、水膨潤
性架橋重合体を可溶化することができる。この可溶化は
水膨潤性架橋重合体の低分子量化によると思われるが、
処理条件を適宜設定することにより、その分子量を制御
することも可能である。分子量を制御された重合体は、
目的に応じた用途に供しても良い。The water-swellable crosslinked polymer can be solubilized by the treatment as described above. This solubilization is considered to be due to the lower molecular weight of the water-swellable crosslinked polymer,
The molecular weight can be controlled by appropriately setting the processing conditions. The polymer whose molecular weight is controlled is
It may be used for any purpose.
【００１２】[0012]
【実施例】以下に、この発明の具体的な実施例および比
較例を示すが、この発明は下記の実施例に限定されな
い。尚、実施例に記載の水膨潤性架橋重合体の可溶化度
は下記の試験方法に従って測定した値で示す。また、部
は重量部を示す。EXAMPLES Specific examples and comparative examples of the present invention will be shown below, but the present invention is not limited to the following examples. The solubilization degree of the water-swellable crosslinked polymer described in Examples is shown by a value measured according to the following test method. Moreover, a part shows a weight part.
【００１３】（１）水可溶分 水膨潤性架橋重合体０．５ｇを１０００ｇの脱イオン水
中に分散し、所定の時間後、濾紙で濾過し、濾液中の固
形分量を滴定により測定して次式に従って水可溶分を求
めた。(1) Water-Soluble Content 0.5 g of the water-swellable cross-linked polymer was dispersed in 1000 g of deionized water, and after a predetermined time, filtered with filter paper, and the solid content in the filtrate was measured by titration. The water-soluble content was determined according to the following formula.
【００１４】[0014]
【数１】 [Equation 1]
【００１５】（２）水可溶分の分子量 分子量が既知の種々のポリアクリル酸ナトリウムを標準
にして、ゲルパーミエーションクロマトグラフィーによ
って、（１）の方法でサンプリングした水可溶分の分子
量を求めた。(2) Molecular Weight of Water-Soluble Component The molecular weight of the water-soluble component sampled by the method (1) was determined by gel permeation chromatography using various sodium polyacrylates having known molecular weight as standards. It was
【００１６】−水膨潤性架橋重合体の合成例− アクリル酸ナトリウム７４．９５モル％、アクリル酸２
５モル％およびトリメチロールプロパントリアクリレー
ト０．０５モル％からなるアクリル酸塩系単量体の３７
％水溶液４０００部を過硫酸アンモニウム２．０部およ
びＬ−アスコルビン酸０．０８部を用いて窒素雰囲気中
３０ー８０℃で重合を行い、ゲル状含水架橋重合体を得
た。得られた含水ゲル状架橋重合体を１５０℃の熱風乾
燥機で乾燥後、ハンマーミルで粉砕し、２０メッシュ
（タイラーの標準ふるい。）金網でふるい分けして、２
０メッシュ通過物を得た。これを水膨潤性架橋重合体
（ａ）と言う。-Synthesis Example of Water-Swellable Cross-Linked Polymer- Sodium acrylate 74.95 mol%, acrylic acid 2
37% of acrylate type monomer consisting of 5 mol% and 0.05 mol% of trimethylolpropane triacrylate
% Aqueous solution of 4000 parts and 2.0 parts of ammonium persulfate and 0.08 part of L-ascorbic acid were polymerized at 30-80 ° C. in a nitrogen atmosphere to obtain a gel-like water-containing crosslinked polymer. The resulting hydrogel crosslinked polymer was dried with a hot air dryer at 150 ° C., crushed with a hammer mill, and sieved with a 20 mesh (Tyler standard sieve) wire mesh to obtain 2
A 0 mesh pass product was obtained. This is called a water-swellable crosslinked polymer (a).
【００１７】−実施例１− 脱イオン水１０００ｇにＬ−アスコルビン酸（片山化学
工業株式会社製、特級試薬）０．２５ｇを撹拌溶解させ
た。このように調製されたアスコルビン酸水溶液に水膨
潤性架橋重合体（ａ）を０．５ｇ添加して、表１に示す
条件でｐＨを５．９に制御して可溶化処理した。２４時
間処理後には水可溶分量は９８％であり、その平均分子
量は３０,０００であった。Example 1 In 1000 g of deionized water, 0.25 g of L-ascorbic acid (special grade reagent manufactured by Katayama Chemical Co., Ltd.) was dissolved with stirring. 0.5 g of the water-swellable crosslinked polymer (a) was added to the thus-prepared ascorbic acid aqueous solution, and the pH was controlled to 5.9 under the conditions shown in Table 1 for solubilization treatment. After the treatment for 24 hours, the water-soluble content was 98% and the average molecular weight was 30,000.
【００１８】−実施例２− 脱イオン水９８５ｇに０．１規定水酸化ナトリウム水溶
液１５ｇ、Ｌ−アスコルビン酸０．２５ｇを撹拌溶解さ
せた。以後は実施例１と同様にし、ｐＨを７．０に制御
して処理した。-Example 2- 15 g of 0.1N sodium hydroxide aqueous solution and 0.25 g of L-ascorbic acid were dissolved in 985 g of deionized water with stirring. Thereafter, the treatment was carried out in the same manner as in Example 1 while controlling the pH to 7.0.
【００１９】−実施例３− 脱イオン水９７５ｇに０．１規定塩酸２５ｇ、Ｌ−アス
コルビン酸０．２５ｇを撹拌溶解させた。以後は実施例
１と同様にし、ｐＨを４．４に制御して処理した。Example 3 In 975 g of deionized water, 25 g of 0.1N hydrochloric acid and 0.25 g of L-ascorbic acid were dissolved with stirring. After that, the same treatment as in Example 1 was performed while controlling the pH to 4.4.
【００２０】−実施例４− 実施例１と同様に処理した。但し、湯浴で加温した。-Example 4-Processing was carried out in the same manner as in Example 1. However, it was heated in a hot water bath.
【００２１】−実施例５− 脱イオン水１０００ｇにＬ−アスコルビン酸０．２５ｇ
を撹拌溶解させた。この様に調整されたアスコルビン酸
水溶液に水膨潤性架橋重合体（三洋化成工業株式会社製
「ＩＭ１０００」）を０．５ｇ添加して、表１に示す条
件でｐＨを５．７に制御して可溶化処理した。Example 5-0.25 g of L-ascorbic acid in 1000 g of deionized water
Was dissolved by stirring. 0.5 g of a water-swellable crosslinked polymer (“IM1000” manufactured by Sanyo Kasei Co., Ltd.) was added to the thus-prepared ascorbic acid aqueous solution, and the pH was controlled to 5.7 under the conditions shown in Table 1. Solubilized.
【００２２】−実施例６− ０．９％塩化ナトリウム水溶液４９．５ｇとＬ−アスコ
ルビン酸０．５ｇからなる水溶液に水酸化ナトリウムの
粒を２粒を加えて撹拌溶解させた。このように調製され
たアスコルビン酸水溶液に水膨潤性架橋重合体（三洋化
成工業株式会社製「ＩＭ１０００」）を２ｇ添加して、
表１に示す条件で、ｐＨを６．４に制御して可溶化処理
した。Example 6 Two particles of sodium hydroxide were added to an aqueous solution containing 49.5 g of 0.9% sodium chloride aqueous solution and 0.5 g of L-ascorbic acid, and dissolved by stirring. 2 g of a water-swellable crosslinked polymer (“IM1000” manufactured by Sanyo Kasei Co., Ltd.) was added to the thus-prepared ascorbic acid aqueous solution,
Under the conditions shown in Table 1, the solubilization treatment was performed while controlling the pH to 6.4.
【００２３】−比較例１− 脱イオン水９５０ｇに０．１規定水酸化ナトリウム水溶
液５０ｇ、Ｌ−アスコルビン酸０．２５ｇを撹拌溶解さ
せた。以後は実施例１と同様にし、ｐＨを８．０に制御
して処理した。Comparative Example 1 50 g of a 0.1N aqueous sodium hydroxide solution and 0.25 g of L-ascorbic acid were dissolved in 950 g of deionized water with stirring. After that, the same treatment as in Example 1 was performed while controlling the pH to 8.0.
【００２４】−比較例２− 脱イオン水９５０ｇに０．１規定塩酸５０ｇ、Ｌ−アス
コルビン酸０．２５ｇを撹拌溶解させた。以後は実施例
１と同様にし、ｐＨを３．７に制御して処理した。Comparative Example 2 In 950 g of deionized water, 50 g of 0.1N hydrochloric acid and 0.25 g of L-ascorbic acid were dissolved with stirring. Thereafter, the treatment was carried out in the same manner as in Example 1 while controlling the pH to 3.7.
【００２５】−比較例３− 脱イオン水１０００ｇに水膨潤性架橋重合体（ａ）を
０．５ｇ添加して、表１に示す条件で可溶化処理した。
なお、表１には、水膨潤性架橋重合体１重量部に対する
Ｌ−アスコルビン酸の重量部、水膨潤性架橋重合体１重
量部に対する水の重量部、可溶化系の温度（℃）、処理
時間（ｈ）、可溶化系のｐＨ、水可溶分（％）を示し
た。Comparative Example 3 0.5 g of the water-swellable crosslinked polymer (a) was added to 1000 g of deionized water, and solubilization treatment was carried out under the conditions shown in Table 1.
In addition, in Table 1, 1 part by weight of the water-swellable crosslinked polymer, 1 part by weight of L-ascorbic acid, 1 part by weight of the water-swellable crosslinked polymer, 1 part by weight of water, the temperature (° C.) of the solubilization system, and the treatment The time (h), pH of the solubilized system, and water-soluble content (%) are shown.
【００２６】表１にみられるように、Ｌ−アスコルビン
酸を添加しない（比較例３）場合は可溶化は進まない。
また、実施例１から５は効率よく可溶化されており、ｐ
Ｈの範囲は４以上７．５以下である。As can be seen from Table 1, solubilization does not proceed when L-ascorbic acid is not added (Comparative Example 3).
Further, Examples 1 to 5 were efficiently solubilized, and p
The range of H is 4 or more and 7.5 or less.
【００２７】[0027]
【表１】 [Table 1]
【００２８】[0028]
【発明の効果】この発明によれば、取り扱い易い試薬Ｌ
−アスコルビン酸を用いてｐＨを中性付近に制御するこ
とにより、水膨潤性架橋重合体を水可溶化することがで
きる。According to the present invention, the reagent L that is easy to handle
-By controlling the pH to near neutral with ascorbic acid, the water-swellable crosslinked polymer can be solubilized in water.
【００２９】[0029]
フロントページの続き (72)発明者 下村 忠生 大阪府吹田市西御旅町５番８号 株式会社 日本触媒中央研究所内Front page continuation (72) Inventor Tadao Shimomura 5-8 Nishiomitabicho Suita City, Osaka Prefecture Central Research Institute of Nippon Shokubai Co., Ltd.
Claims (1)
ビン酸を添加し、その際のｐＨを４から７．５の範囲に
制御することを特徴とする水膨潤性架橋重合体の可溶化
方法。1. A method for solubilizing a water-swellable cross-linked polymer, which comprises adding water and ascorbic acid to the water-swellable cross-linked polymer and controlling the pH in the range of 4 to 7.5. ..
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04578792A JP3149251B2 (en) | 1992-03-03 | 1992-03-03 | Method for solubilizing water-swellable crosslinked polymer and solubilizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04578792A JP3149251B2 (en) | 1992-03-03 | 1992-03-03 | Method for solubilizing water-swellable crosslinked polymer and solubilizer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05247221A true JPH05247221A (en) | 1993-09-24 |
| JP3149251B2 JP3149251B2 (en) | 2001-03-26 |
Family
ID=12728996
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|---|---|---|---|
| JP04578792A Expired - Fee Related JP3149251B2 (en) | 1992-03-03 | 1992-03-03 | Method for solubilizing water-swellable crosslinked polymer and solubilizer |
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| Country | Link |
|---|---|
| JP (1) | JP3149251B2 (en) |
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| WO2024101349A1 (en) | 2022-11-07 | 2024-05-16 | 株式会社日本触媒 | Method for producing solubilizing polymer and method for producing water absorbent resin |
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1992
- 1992-03-03 JP JP04578792A patent/JP3149251B2/en not_active Expired - Fee Related
Cited By (9)
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| WO2017017964A1 (en) * | 2015-07-29 | 2017-02-02 | 株式会社日本触媒 | Novel acrylic acid crosslinked polymer and use thereof |
| US10696895B2 (en) | 2015-07-29 | 2020-06-30 | Nippon Shokubai Co., Ltd. | Acrylic acid crosslinked polymer and use thereof |
| JP2020116569A (en) * | 2019-01-21 | 2020-08-06 | 三洋化成工業株式会社 | Sanitary article processing method |
| WO2020213298A1 (en) | 2019-04-16 | 2020-10-22 | 三洋化成工業株式会社 | Method for producing water-absorbing resin particles |
| JPWO2020213298A1 (en) * | 2019-04-16 | 2020-10-22 | ||
| WO2024101349A1 (en) | 2022-11-07 | 2024-05-16 | 株式会社日本触媒 | Method for producing solubilizing polymer and method for producing water absorbent resin |
| EP4617301A1 (en) | 2022-11-07 | 2025-09-17 | Nippon Shokubai Co., Ltd. | Method for producing solubilizing polymer and method for producing water absorbent resin |
| WO2025028083A1 (en) | 2023-07-31 | 2025-02-06 | 株式会社日本触媒 | Manufacturing method for solubilized polymer |
| WO2025032998A1 (en) | 2023-08-09 | 2025-02-13 | 株式会社日本触媒 | Water-absorbing resin and method for producing same |
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| Publication number | Publication date |
|---|---|
| JP3149251B2 (en) | 2001-03-26 |
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