JPS5849704A - Preparation of water-soluble cationic high polymer having high polymerization degree - Google Patents
Preparation of water-soluble cationic high polymer having high polymerization degreeInfo
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- JPS5849704A JPS5849704A JP14723381A JP14723381A JPS5849704A JP S5849704 A JPS5849704 A JP S5849704A JP 14723381 A JP14723381 A JP 14723381A JP 14723381 A JP14723381 A JP 14723381A JP S5849704 A JPS5849704 A JP S5849704A
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- water
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- Polysaccharides And Polysaccharide Derivatives (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
水浴性陽イオン性高分子物質は凝集剤、！Ｊ！紙工場に
おける歩留り向上剤、抄速増進剤、増粘剤、また 高粘
度水溶液を圧入する方法による石油回収用の流動性調整
剤等として広く利用されている。このような目的に用い
られる水溶性陽イオン性高分子物質は一般に重合度が高
い程有効であることが知られており、重合度のより高い
高分子物質を得るために水溶液重合、乳化重合、懸濁重
合、塊状重合等の重合法や重縮合法の改良が研究されて
いる。。[Detailed Description of the Invention] The water-bathable cationic polymeric substance is a flocculant! J! It is widely used as a retention improver, paper speed enhancer, and thickener in paper mills, as well as a fluidity regulator for oil recovery by press-injecting a high-viscosity aqueous solution. It is generally known that water-soluble cationic polymeric substances used for such purposes are more effective as the degree of polymerization increases, and in order to obtain polymeric substances with a higher degree of polymerization, aqueous solution polymerization, emulsion polymerization, Improvements in polymerization methods such as suspension polymerization and bulk polymerization and polycondensation methods are being studied. .
高重合度の水溶性陽イオン性高分子物質を得る条件は反
応形態により異なるが、一般に重合法では重合開始方法
、原料モノマーの種類とその品質１！！、また重縮合法
では原料単位の種類とその品質、触媒、温度、加熱時間
等であり、現状で得られる水溶性陽イオン性高分子物質
の分子量はこれらの最適な条件下でもＳＯＯ万程度が限
界である。The conditions for obtaining a water-soluble cationic polymer substance with a high degree of polymerization vary depending on the reaction type, but in general, polymerization methods include the polymerization initiation method, the type of raw material monomer, and its quality. ! In addition, in the polycondensation method, the type of raw material unit, its quality, catalyst, temperature, heating time, etc. are determined, and the molecular weight of the water-soluble cationic polymer substance obtained at present is about SOO 10,000 even under these optimal conditions. This is the limit.
それゆえ、水溶性陽イオン性高分子物質を各使用目的に
おいて一層高い効果を発揮させるためＫ、従来より高い
重合度をもつ水溶性陽イオン性高分子物質の出現が望ま
れていた。Therefore, in order to make water-soluble cationic polymeric substances more effective for various purposes, it has been desired to develop water-soluble cationic polymeric substances with a higher degree of polymerization than before.
本発明者等は、従来より高い重合度の水溶性陽イオン性
高分子物質を得る方法について研究をした結果、本発明
を完成した。The present inventors completed the present invention as a result of research on a method for obtaining a water-soluble cationic polymer substance with a higher degree of polymerization than conventional ones.
すなわち、本発明は、分子内に第一アミノ基または第ニ
アミノ基の１種または２８［以上を有する水溶性高分子
物質に式０ＨＯ−Ｒ−ＣｔｌｉＯ（式中。That is, the present invention provides a water-soluble polymer substance having the formula 0HO-R-CtliO (in the formula:
Ｒはアルキレン基またはアルケニレン基を示す。）で表
わされる脂肪族ジアルデヒド類の１梱または２種以上を
加え【反応させ、生成する陽イオン性高分子物質が水溶
性を保つ範囲内で原料の高分子物質を相互に結合させる
ことを特像とする高重合度の水溶性陽イオン性高分子物
質の製法であり、本発明により得られる水溶性陽イオン
性高分子物質は従来にない高重合度のものである。R represents an alkylene group or an alkenylene group. ) is added to the aliphatic dialdehydes represented by one or more of the following: This is a method for producing a water-soluble cationic polymeric substance with a high degree of polymerization, and the water-soluble cationic polymeric substance obtained by the present invention has an unprecedentedly high degree of polymerization.
本発明により得られる高重合度の水溶性陽イオン性高分
子物質は用水・廃水処理、上水・下水処理および各種生
産工程における懸濁液の処理に使用する凝集剤、製紙工
程における歩留り向上剤および抄速増進剤、増粘剤、採
油業における高粘度水の圧入のための増粘剤等の各目的
に用いられ効果的である。The water-soluble cationic polymer substance with a high degree of polymerization obtained by the present invention is a flocculant used in water/waste water treatment, water/sewage treatment, and treatment of suspensions in various production processes, and a retention improver in paper manufacturing processes. It is also effectively used for various purposes such as a papermaking speed enhancer, a thickener, and a thickener for the injection of high-viscosity water in the oil extraction industry.
本発明で使用する原料の第一アミノ基または第ニアミノ
基を有する水溶性高分子物質は高分子の主鎖または＠鎗
に第一アミノ基および／または第ニアミノ基を有する高
分子物質であれば特に限定はなく、例えばキトサン、ア
ミノデンプンなどの天然高分子物質またはその変性物。The water-soluble polymeric substance having a primary amino group or a secondary amino group as a raw material used in the present invention is a polymeric substance having a primary amino group and/or a secondary amino group in the main chain of the polymer. There are no particular limitations, and examples include natural polymeric substances such as chitosan and aminostarch, or modified products thereof.
ポリエチレンイミン、ポリビニルイミダシリン、ポリア
クリルアミドまたはポリメタクリルアミドのホ７７ン反
応生成物またはマンニッヒ反応生成物などの重合体また
はその変性物、ビニルイミダシリンと他の共重合可能な
モノマーとの共重合体などである。共重合可能なモノマ
ーとし【は、好ましくはビニルピロリドン、ビニルピリ
ジン等を使用することができる。共重合体の場合は重合
体中に含まれる第一アミノ基または第ニアミノ基を有す
るモノマ一単位が重合前のモノマー換算で１０モル−以
上であることが望ましい。Polymers or modifications thereof such as polyethyleneimine, polyvinylimidacilline, polyacrylamide or polymethacrylamide or Mannich reaction products, co-existences of vinylimidacillin with other copolymerizable monomers. Polymers, etc. As the copolymerizable monomer, vinylpyrrolidone, vinylpyridine, etc. can be preferably used. In the case of a copolymer, it is desirable that one monomer unit having a primary amino group or a secondary amino group contained in the polymer is 10 moles or more in terms of the monomer before polymerization.
本発明で使用する式０１０−Ｒ−Ｃ！ＨＯ（式中Ｒは前
記と同義である。）で表わされる脂肪族ジアルデヒド類
としては、例えばマロンアルデヒド、スクシンアルデヒ
ド、グルタルアルデヒド、アセトアルデヒドなどのアル
キレンジアルデヒドやマレインジアルデヒド、フマルジ
アルデヒドなどのアルケニレンジアルデヒドを使用する
ことができ、単独で用いるかまたは併用する。これらの
脂肪族ジアルデヒド類は水溶液またはメタノール、エタ
ノール、アセトンなどの有機溶媒の溶液あるいはガス状
として使用する。また、ホルムアルデヒド、アセトアル
デヒド、グリオキザールなどと併用することもできる。Formula 010-R-C used in the present invention! Examples of aliphatic dialdehydes represented by HO (wherein R has the same meaning as above) include alkylene dialdehydes such as malonaldehyde, succinaldehyde, glutaraldehyde, and acetaldehyde, maleic dialdehyde, and fumardialdehyde. Alkenylene dialdehydes can be used, either alone or in combination. These aliphatic dialdehydes are used in the form of an aqueous solution, a solution in an organic solvent such as methanol, ethanol, acetone, or the like, or in the form of a gas. It can also be used in combination with formaldehyde, acetaldehyde, glyoxal, etc.
本発明にかかる高重合度の水溶性陽イオン性高分子物質
の製法は、原料の分子内に第一アミノ基または第ニアミ
ノ基を有する水湿性高分子物質の粉末または溶液をガス
状または溶液状の脂肪族ジアルデヒド類とタンク類の中
で、あるいはパイプ、とい等により輸送中に混合すると
とＫより実施できる。The method for producing a water-soluble cationic polymer substance with a high degree of polymerization according to the present invention is to prepare a powder or solution of a water-wet polymer substance having a primary amino group or a secondary amino group in the molecule of the raw material in a gaseous or solution form. It can be carried out by mixing with the aliphatic dialdehyde in a tank or during transportation using a pipe, gutter, etc.
原料の水浴性高分子物質を水溶液として反応させる場合
、その溶液の濃度は原料の高分子物質の種類や分子量な
どＫより異なるが、一般にはａＳ〜３０ ％が望ましい
。濃度がａｓ％以下では反応が遅くなり、十分な重合−
変化が行なわれなくなる。また、３０チ以上では溶液が
高粘度となるため脂肪族ジアルデヒド類との混合が悪く
なり、適度な高重合度化を図るための反応の調整が困難
となるか、あるいは反応中に水に不溶性の高分子物質が
生成する。When reacting a water-bathable polymer material as a raw material in the form of an aqueous solution, the concentration of the solution differs from K, such as the type and molecular weight of the raw material polymer material, but is generally desirably aS to 30%. If the concentration is below as%, the reaction will be slow and sufficient polymerization will not occur.
Changes will not take place. In addition, if the solution exceeds 30%, the viscosity of the solution becomes high, making it difficult to mix with the aliphatic dialdehyde, making it difficult to adjust the reaction to achieve an appropriately high degree of polymerization, or causing water to leak during the reaction. An insoluble polymeric substance is produced.
原料の水溶性高分子物質を水溶液として反応させる場合
の反応液のｐａは酸性でもアルカリ性でもよいが、アル
カリ性の方が反応が速いので、ｐＨ１１以上であること
が望ましい。When reacting the water-soluble polymer material as a raw material in the form of an aqueous solution, the pa of the reaction solution may be acidic or alkaline, but the pH is preferably 11 or higher because the reaction is faster in alkaline solutions.
水溶液での反応は氷点以上沸点以下の温度で実施できる
が、低温では反応が遅いので２０〜１００℃のより高い
温度が好ましい。The reaction in an aqueous solution can be carried out at a temperature above the freezing point and below the boiling point, but a higher temperature of 20 to 100°C is preferred since the reaction is slow at low temperatures.
原料の水溶性高分子物質に対する脂肪族ジアルデヒドの
使用量は、原料の高分子物質の種類や分子ｉｔ％その温
液の濃度や液性、反応温度等により異なるが、一般には
原料の高分子物質の第一７５ノ基の１／２個または第ニ
アミノ基の１個に対し、脂肪族ジアルデヒドのアルデヒ
ド基が１〜１／１０００８程度である。脂肪族ジアルデ
ヒドを過剰に使うと反応が短時間で急速に進むため、適
度な高重合度化を図るための反応のｍ整が困難となると
共に、生成する高分子物質が水圧不°溶性となる。脂肪
族ジアルデヒドの使用量が少ないと、十分に高重合度化
され水溶性高分子物質が得られない。The amount of aliphatic dialdehyde to be used in relation to the water-soluble polymer material used as a raw material varies depending on the type of polymer material used as the raw material, the molecule it%, the concentration and liquid properties of the hot liquid, the reaction temperature, etc. The number of aldehyde groups of the aliphatic dialdehyde is about 1 to 1/10,008 to 1/2 of the first 75 groups or one of the second amino groups of the substance. If too much aliphatic dialdehyde is used, the reaction will proceed rapidly in a short period of time, making it difficult to control the reaction temperature to achieve an appropriately high degree of polymerization, and the resulting polymeric substance may become insoluble under water pressure. Become. If the amount of aliphatic dialdehyde used is small, the degree of polymerization will be sufficiently high and a water-soluble polymeric substance will not be obtained.
本発明の方法による高重合度化の機作は、原料の高分子
物質の第一アミノ基または第ニアミノ基が脂肪族ジアル
デヒドのアルデヒド基と付加反応、縮合反応、ｉａ合反
応を起すことにより、さらに高重合度の線状または線状
に近い高分子物質に変化するのである。The mechanism of increasing the degree of polymerization by the method of the present invention is that the primary amino group or the ni-amino group of the raw material polymer substance undergoes an addition reaction, condensation reaction, or ia synthesis reaction with the aldehyde group of the aliphatic dialdehyde. , it changes into a linear or nearly linear polymer substance with a higher degree of polymerization.
原料の水溶性高分子物質と脂肪族ジアルデヒドとの反応
を水溶液で行なう場合、反応液の粘度を測定するととＫ
より反応の進行度が明らかとなる。この反応により生成
する高重合度の水溶性陽イオン性高分子物質がその水溶
性を保つためｔｉｃｋ−１，１反応液の粘度が適度に向
上したところで反応を中止するか、あるいは十分に遅延
させるよ５に反応系を安定化すればよい。反応系を安定
化するには反応液を希釈する１反応液のｐＨを中性にす
る１反応源度を急激に低下する、などの方法があるが１
反応液をＱ、ＳＳ以下、好ましくは０．１〜０．２ ％
濃度Ｋまで水で希釈すると、その希釈液が−そのまま各
利用目的に使用で５きるので一般に都合がよい。When the reaction between the raw material water-soluble polymer substance and the aliphatic dialdehyde is carried out in an aqueous solution, the viscosity of the reaction solution is measured and the K
The progress of the reaction becomes clearer. In order to maintain the water solubility of the water-soluble cationic polymer substance with a high degree of polymerization produced by this reaction, the reaction is stopped when the viscosity of the tick-1, 1 reaction solution increases appropriately, or the reaction is delayed sufficiently. Step 5 is to stabilize the reaction system. There are several methods to stabilize the reaction system, such as diluting the reaction solution, making the pH of the reaction solution neutral, and rapidly reducing the reaction source.
The reaction solution is Q, SS or less, preferably 0.1 to 0.2%.
Dilution with water to a concentration of K is generally convenient since the diluted solution can be used as is for various purposes.
原料の水溶性高分子物質を粉末状で反応させる場合には
、脂肪族ジアルデヒドを前記の使用量でメタノール、エ
タノール、アセトンなどの有機溶媒に溶解した溶液にそ
の粉末を懸濁するか、あるいはこの溶液を粉末に噴霧し
混合すればよい。When reacting the water-soluble polymer material as a raw material in powder form, the powder is suspended in a solution of an aliphatic dialdehyde dissolved in an organic solvent such as methanol, ethanol, or acetone in the amount used above, or This solution may be sprayed onto the powder and mixed.
本発明で使用する脂肪族ジアルデヒド類の原料の水溶性
高分子物質に対する反応性をホルムアルデヒド、アセト
アルデヒドおよびグリオキザールと比較した場合、ホル
ムアルデヒドやアセトアルデヒドでは脂肪族ジアルデヒ
ドに比して反応性が小さく、とくにアセトアルデヒドに
よる高重合度化は困難であった。またグリオキザールは
広い範囲のｐＨでかなりの反応性を示したが、脂１ｉｌ
ｋジアルデヒドに比して生成した高重合度の高分子物質
の性質が劣ることがわかった。これは本発明で使用する
脂肪族ジアルデヒドがグリオキザールと異なり１分子中
の２個のアルデヒド基間にアルキレン基またはアルケニ
レン基が存在するため、２個のアルデヒド基が相互作用
することなく、原料の水溶性高分子物質を二量化または
多量化し易くするからであり、これＫより線状−または
線状に近い高重合度の水溶性陽イオン性高分子物質が生
成するからであると思われる。When comparing the reactivity of raw materials of aliphatic dialdehydes used in the present invention with water-soluble polymeric substances with formaldehyde, acetaldehyde, and glyoxal, formaldehyde and acetaldehyde have lower reactivity than aliphatic dialdehydes; It was difficult to increase the degree of polymerization using acetaldehyde. Glyoxal also showed considerable reactivity over a wide range of pH;
It was found that the properties of the produced polymeric substance with a high degree of polymerization were inferior to that of k-dialdehyde. This is because the aliphatic dialdehyde used in the present invention, unlike glyoxal, has an alkylene group or alkenylene group between two aldehyde groups in one molecule, so the two aldehyde groups do not interact and the raw material This is thought to be because it facilitates dimerization or multimerization of the water-soluble polymeric substance, and this is because a water-soluble cationic polymeric substance with a higher polymerization degree that is linear or nearly linear than K is produced.
本発明の方法によれば、キトサン、アミノデンプンなど
の天然高分子物質またはその変性物、ポリエチレンイミ
ン、ポリメタクリル酸アミノメチルエステル、ポリメタ
クリル酸モノアミノメチルエステル、ポリビニルイミダ
シリン、ポリアクリルアンドまたはポリメタクリルアミ
ドのホフマン反応生成物またはマンニッヒ反応生成物な
どの重合体またはその変性物、ビニルイミダシリンと他
の共重合可能なモノマー、例えばビニルピロリドン、ビ
ニルピリジン等との共重合体など各種の水溶性陽イオン
性高分子物質の高重合度化が可能である。According to the method of the present invention, natural polymeric substances such as chitosan, aminostarch or modified products thereof, polyethyleneimine, polymethacrylic acid aminomethyl ester, polymethacrylic acid monoaminomethyl ester, polyvinylimidacillin, polyacrylate or Polymers such as Hofmann reaction products or Mannich reaction products of polymethacrylamide or modified products thereof, copolymers of vinylimidacillin with other copolymerizable monomers such as vinylpyrrolidone, vinylpyridine, etc. It is possible to increase the degree of polymerization of water-soluble cationic polymer substances.
本発明の方法により水溶液反応で製造された高重合度の
水溶性陽イオン性高分子物質は１反応液を水で希釈する
ことにより水溶液のまま各利用目的に使用することがで
きるが、反応液を減圧濃縮や凍結乾燥することＫより濃
縮液や粉末にすることもできる。The water-soluble cationic polymer substance with a high degree of polymerization produced by an aqueous reaction by the method of the present invention can be used for various purposes as an aqueous solution by diluting one reaction solution with water. It can also be made into a concentrated liquid or powder by concentrating it under reduced pressure or freeze-drying it.
本発明の方法により製造された水溶性陽イオン性高分子
物質は従来にない高重合度をもつ新規物質であり、凝集
剤や増粘剤として少蓋使用するだけで顕著な効果を示し
、例えば凝集剤として汚泥の脱水に使用するときは、脱
水ケーキの含水率低下による脱水ケーキの燃焼効率の改
善に効果が認められ、懸濁液の清澄・濃縮処理−に用い
る場合は懸濁液処理ｍ設の能力向上を図ることができ、
石油回収に用いると゛きは散性、塩類濃度が高い場合、
に用いても粘度低下がほとんどなく、また抄紙工程にお
いては抄速増進、１水性向上、歩留り向上Ｋｆｉ著な効
果を示すなど、本発明の工業的価値は非常に大きい。The water-soluble cationic polymeric substance produced by the method of the present invention is a new substance with an unprecedentedly high degree of polymerization, and shows remarkable effects even when used in a small amount as a flocculant or thickener. When used as a flocculant for dewatering sludge, it is effective in improving the combustion efficiency of the dehydrated cake by reducing the water content of the dehydrated cake. It is possible to improve the capacity of the facility.
When used for oil recovery, it is dispersive and has a high salt concentration.
The industrial value of the present invention is extremely large, as there is almost no decrease in viscosity even when used in papermaking processes, and in the papermaking process, it exhibits remarkable effects in increasing papermaking speed, improving water resistance, and improving yield Kfi.
以下に実施例を示しで本発明をさらに詳しく説明するが
１本発明はこれらによって限定されるものではない。The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto.
実施例１
ポリビニルイミダシリンの２１水溶液ｓｓｙを５０％硫
酸水溶液でｐＨ１０に調整後、グルタルアルデヒドのｓ
ｌ水溶液？、 ５ 、ｆを加えて４０℃で５０分間反応
させ、反゛応液の粘度を４０’ＣでＢ型回転粘度計によ
りＩｌ、定した。この反応液に水２００ ｍを加えて希
釈し、ｓｌ希硫酸でｐＨ６に調整後、再び水を加えて０
５％濃度（原料のポリビニルイミダシリン換算）の希釈
液とし、・この液の粘度を２ｓ℃で前記と同様に測定し
た。Example 1 After adjusting 21 aqueous solution ssy of polyvinylimidacillin to pH 10 with 50% sulfuric acid aqueous solution, ssy of glutaraldehyde
l Aqueous solution? . This reaction solution was diluted with 200 m of water, adjusted to pH 6 with sl diluted sulfuric acid, and water was added again to make it 0.
A diluted solution with a concentration of 5% (based on raw material polyvinylimidacillin) was prepared, and the viscosity of this solution was measured at 2 s° C. in the same manner as above.
比較のため、前記の反応なグルタルアルデヒドの代りに
グリオキザールのＳ−水溶液４４１を加えて３０分間行
ない、またグリオキザールの代りにホルムアルデヒドの
５５６水溶液龜ｏｌを加えて３５分間行ない、各反応液
の粘度を前記と同様Ｋ Ｉｌｊ定した。さらに各反応液
を前記と同様に希釈・中和してａ、Ｓチ濃度となし、各
希釈液の粘度も同様に測定した。For comparison, the reaction was carried out for 30 minutes by adding S-aqueous solution 441 of glyoxal in place of the above-mentioned reactive glutaraldehyde, and for 35 minutes by adding 556 aqueous solution of formaldehyde in place of glyoxal. K Ilj was determined in the same manner as above. Furthermore, each reaction solution was diluted and neutralized in the same manner as described above to obtain the concentrations of a and S, and the viscosity of each diluted solution was also measured in the same manner.
各反応による反応液と（Ｌ５＊Ｊ１度の希釈液の各粘度
を表１に示す。Table 1 shows the viscosity of the reaction solution for each reaction and the diluted solution of (L5*J1 degree).
表 １
表１から明らかなように、本発明により原料のポリビニ
ルイミダシリンにグルタルアルデヒドを反応させて得た
反応液の結反はポリビニルイミダシリンの２％水浴液（
ｐＨ１０）より約１０倍も高く、グルタルアルデヒドの
代りにホルムアルデヒドやグリオキザールを反応させた
各反応液とほば同じであったが、各反応液をａｓｈ濃度
に希釈した各希釈液の粘度は、本発明によりグルタルア
ルデヒドを反応させて得た水浴性高分子物質が、原料の
ポリビニルイミダシリンやこれにホルマリンまたはグリ
オキザールを反応させて得た水溶性高分子物質よりも２
〜３倍も高く、グルタルアルデヒドがホルマリンやグリ
オキザールよりもポリビニルイミダシリンの高重合度化
に高い効果を示すことがわかる。Table 1 As is clear from Table 1, the reaction solution obtained by reacting raw material polyvinylimidacillin with glutaraldehyde according to the present invention has a 2% water bath solution of polyvinylimidacillin (
The pH was approximately 10 times higher than that of the ash concentration (pH 10), and was almost the same as each reaction solution in which formaldehyde or glyoxal was reacted instead of glutaraldehyde. According to the invention, the water-bathable polymer obtained by reacting glutaraldehyde is 2 times higher than the raw material polyvinylimidacillin and the water-soluble polymer obtained by reacting it with formalin or glyoxal.
It is found that glutaraldehyde is more effective than formalin or glyoxal in increasing the degree of polymerization of polyvinylimidacillin.
それゆえ、本発明によりポリビニルイミダシリンにグル
タルアルデヒドを反応させて得た水溶性高分子物質は増
粘剤とし【使用する場合、少量で十分な増粘効果を示す
ことがわかる。Therefore, it can be seen that when the water-soluble polymeric substance obtained by reacting polyvinylimidacillin with glutaraldehyde according to the present invention is used as a thickener, it exhibits a sufficient thickening effect with a small amount.
：実施例２
実施例１でポリビニルイミダシリンにグルタルアルデヒ
ドを反応させて得た水浴性高分子物質のａｓｈ希釈液を
カオリン懸濁液に加え、生成した凝集物の沈降速度を測
定した。: Example 2 An ash diluted solution of the water bathable polymer substance obtained by reacting polyvinylimidacillin with glutaraldehyde in Example 1 was added to a kaolin suspension, and the sedimentation rate of the resulting aggregate was measured.
沈降速度は、１００−メスシリンダー中の３チ。The sedimentation rate is 3 inches in a 100-graduated cylinder.
カオリン懸濁液１０（１−に前記の希釈液１．８．９を
加え、メスシリンダーを転倒してよく振り、静置後凝集
したカオリン粒子が沈降する速度として側楚した。The above-mentioned diluent 1.8.9 was added to Kaolin Suspension 10 (1-), the measuring cylinder was shaken well by inverting it, and after being allowed to stand still, the flocculated kaolin particles were set at a rate at which they would settle, and the mixture was shaken on the side.
比較のため、実施例１でグルタルアルデヒドの代りにホ
ルマリンまたはグリオキザールを反応させて得た各水溶
性高分子物質のａｓｈ希釈液による沈降速度も同様に測
定した。For comparison, the sedimentation rate of each water-soluble polymer substance obtained by reacting formalin or glyoxal instead of glutaraldehyde in Example 1 with the ash diluted solution was also measured in the same manner.
各水溶性高分子物質の希釈液による沈降速度を表２に示
す。−
表 ２
表２から明らかなように、一本発明により原料のポリビ
ニルイミダシリンにグルタルア−ルデヒドを反応させて
得た水溶性高分子物ＷＫよるカオリンの沈降速度は、ポ
リビニルイミダシリンとこれにホルムアルデヒドまたは
グリオキザールを反応させて得た各水溶性高分子物質よ
りもはるかに速く、それゆえグルタルアルデヒドで高重
合度化した水溶性高分子物質の凝集性能はホルマリンや
グリオキザールで高重合度−化したものよりも著しく向
上していることがわかる。Table 2 shows the sedimentation rate of each water-soluble polymer substance depending on the diluted solution. - Table 2 As is clear from Table 2, the sedimentation rate of kaolin by the water-soluble polymer WK obtained by reacting raw material polyvinylimidacillin with glutaraldehyde according to the present invention is different from that of polyvinylimidacillin. The flocculation performance of water-soluble polymer substances obtained by reacting formaldehyde or glyoxal with glutaraldehyde is much faster than that of water-soluble polymer substances obtained by reacting formaldehyde or glyoxal with formalin or glyoxal. It can be seen that this is a marked improvement over the previous one.
実施例３
希硫酸でｐＨ１ｏに調整したポリエチレンイミンの１０
チ水溶液（ＳＯＣでの粘度は１６ ｃｐ ）１００１１
にマレインジアルデヒドのｓｌ水浴液９．６９を加えて
、５０℃で３０分間反応した。反応液の粘度は９１ ｃ
ｐであった。この反応液に水を加支てＱ、５％濃度に希
釈して安定化した。この希釈液の粘度は２５℃で５Ｊｃ
ｐであった。Example 3 Polyethyleneimine 10 adjusted to pH 1o with dilute sulfuric acid
Aqueous solution (viscosity at SOC is 16 cp) 10011
9.69 sl water bath solution of maleic dialdehyde was added to the mixture, and the mixture was reacted at 50°C for 30 minutes. The viscosity of the reaction solution is 91 c
It was p. This reaction solution was stabilized by adding water to dilute it to a concentration of 5%. The viscosity of this diluted solution is 5 Jc at 25°C.
It was p.
一方、ポリエチレンイミンの前記の１０１水溶液を水で
Ｏ，Ｓチ濃度に希釈した希釈液の粘度は２５℃でＬ２ｏ
ｐであり、ポリエチレンイミンにマレインジアルデヒド
を反応させて得た反応液の粘度は希釈してもなお十分な
粘度の上昇が認められた。On the other hand, the viscosity of a diluted solution obtained by diluting the above 101 aqueous solution of polyethyleneimine with water to a concentration of O, S is at 25°C.
p, and the viscosity of the reaction solution obtained by reacting polyethyleneimine with maleic dialdehyde was found to be sufficiently increased even after dilution.
実施例４
希硫酸でｐａｔｏ＆ｃｒａ整したポリアクリルアミドの
ホフマン反応生成物の１チ水溶液（アミド基のアミノ化
率３ｓチ、ＳＯＣでの粘度２７０Ｃｐ）２００．９にア
ジプアルデヒドの１チ水溶液１．２ｊＦを加え、Ｓｅｃ
で２０分間反応した。反応液の粘度は１２００ｃｐであ
った。この反応液に水を加えて希釈し、５チ希硫酸でｐ
Ｈ９ｉに調整後、さらに水を加えて０．２９６濃度の希
釈液とした。この希釈液の粘度は２５℃で１１ ｃｐで
あった。Example 4 A 100.9% aqueous solution of a Hofmann reaction product of polyacrylamide prepared by pato & cra with dilute sulfuric acid (amination rate of amide group 3s, viscosity at SOC 270Cp) was mixed with a 100.9% aqueous solution of adipaldehyde 1.2jF. Add Sec
The reaction was carried out for 20 minutes. The viscosity of the reaction solution was 1200 cp. This reaction solution was diluted with water, and diluted with 5-dilute sulfuric acid.
After adjusting to H9i, water was further added to make a diluted solution with a concentration of 0.296. The viscosity of this diluted solution was 11 cp at 25°C.
一方、ポリアクリルアミドのホフマン、反応生成物の前
記の１チ水浴液を５チ希硫酸でｐＨ６Ｋ調整し、水で希
釈した０、２チ濃度の希釈液の粘度は２５℃で３３ ｃ
ｐであり、ポリアクリルアミドのホフマン反応生成物に
アジプアルデヒドを反応させて得た反応液の粘度は希釈
してもなお十分な粘度の上昇が認められた。On the other hand, the viscosity of diluted solution of polyacrylamide Hofmann, 0 and 2 concentration diluted solution prepared by adjusting the pH of the 1T water bath solution of the reaction product with 5T diluted sulfuric acid to 6K and diluting it with water is 33C at 25℃.
p, and the viscosity of the reaction solution obtained by reacting the Hofmann reaction product of polyacrylamide with adipaldehyde was found to be sufficiently increased even after dilution.
実施例５
実施例１のポリビニルイミダシリンおよびこれにグルタ
ルアルデヒドを反応させて得た水浴性高分子物質を含む
反応液の各０．５チ濃度の希釈液、および実施例４のポ
リアクリルアミドのホフマン反応生成物およびこれにア
ジプアルデヒドを反応させて得た水溶性高分子物質を含
む反応液の各０２％濃度の希釈液をそれぞれ下水処理場
の余剰汚泥に添加し、余剰汚泥を同一液分離する際の凝
集性能を比較した。その結果を表３に示す。 、
表 ３
余剰汚泥の懸濁物濃度は２．０５ ％ 、 ｐＨは１．
５であった。 、
最適添加量ｊ％、汚泥に対する希釈液中の水溶性高分子
物質の最適添加量とし、トリトン社製１３１型装置を使
用して測定した０８Ｔ （キャピラリーサクションタイ
ム）から求めた。Example 5 Diluted solutions of the polyvinylimidacillin of Example 1 and the reaction solution containing the water-bathable polymer substance obtained by reacting the polyvinylimidacillin with glutaraldehyde, each having a concentration of 0.5%, and the polyacrylamide of Example 4. A diluted solution containing a Hofmann reaction product and a water-soluble polymer substance obtained by reacting it with adipaldehyde at a concentration of 0.2% was added to excess sludge at a sewage treatment plant, and the excess sludge was added to the same solution. The flocculation performance during separation was compared. The results are shown in Table 3. , Table 3 The suspended solids concentration of surplus sludge is 2.05%, and the pH is 1.
It was 5. , the optimum addition amount j%, which is the optimum addition amount of the water-soluble polymer substance in the diluent to the sludge, was determined from 08T (capillary suction time) measured using a Triton Model 131 device.
また汚泥ケーキ含水率は、最適添加量で処理した汚泥を
１２０メツシユのナイロンＨｆｉ布を用いて４．００Ｏ
ｒｐｍで６０秒間遠心分離し、ｒ布上に分離された汚泥
ケーキの含水率として測定した。In addition, the water content of the sludge cake was 4.00O
It was centrifuged at rpm for 60 seconds and measured as the water content of the sludge cake separated on r cloth.
表３から明らかなよ５に、本発明の方法により得られた
水湿性高分子物質は少ない使用量で汚泥ケーキ含水率の
低下を図ることができ、汚泥などの固−液分離に極めて
有効であることがわかる。As is clear from Table 3, the water-wet polymeric substance obtained by the method of the present invention can reduce the water content of sludge cake with a small amount of use, and is extremely effective for solid-liquid separation of sludge and the like. I understand that there is something.
出願人 三共化成工業株式会社
代理人 弁理士 樫 出 庄 治
手続補正書（自発）
昭和５７年９月１日
昭和５６年特許願籐１４７２３３号
２、 発明の名称
高重合度の水溶性陽イオン性高分子物質の製法
３、補正をする者
居所 東京部品川区広町１丁目２番５８号三共株式会社
内
７、 補正の内容
（１） 明細書第２頁２行め「歩留り向上剤、秒速増
進剤」を「歩留ｐ向上剤および秒速増進剤」と訂正する
。Applicant Sankyo Kasei Kogyo Co., Ltd. Agent Patent Attorney Izusho Kashi Procedural Amendment (spontaneous) September 1, 1980 Patent Application No. 147233 No. 147233 of 1988 Title of Invention Water-soluble cationic compound with high degree of polymerization Process for producing polymeric substances 3. Address of the person making the amendment: 7 Sankyo Co., Ltd., 1-2-58 Hiromachi, Honbunagawa-ku, Tokyo. Details of the amendment (1) Page 2, line 2 of the specification: ``Retention improver, speed per second''"enhancingagent" is corrected to "retention p-enhancing agent and speed per second enhancing agent."
（２） 同第２頁１２行の「反応形態により異なるが
、」を［反応形態によシ異なる。」と訂正する。(2) On page 2, line 12 of the same page, ``It varies depending on the reaction type'' was replaced with ``It depends on the reaction type.'' ” he corrected.
（３） 同第２頁１５行の「加熱時間勢であり、」を
［加熱時間等で異な〕、］と訂正する。(3) On page 2, line 15, ``The heating time is different'' is corrected to ``It varies depending on the heating time, etc.''.
（４） 同第４頁３行の「圧入のための増粘剤等」を
「圧入のための流動性調整剤尋」と訂正する。(4) On page 4, line 3, "Thickeners, etc. for press fitting" is corrected to "Fluidity modifier for press fitting."
（５） 同第６頁下から３行乃至２行の「２０〜１０
０℃のより高い温度」を「２０〜１００℃の温度」と訂
正する。(5) “20-10
"Temperatures higher than 0°C" are corrected to "temperatures between 20 and 100°C."
（６） 同第７頁１１行の「十伊に高重合度化され」
□ を［十分に高重合度化され九」と訂正する。(6) “The degree of polymerization was increased in 10th century” on page 7, line 11.
□ is corrected to ``The degree of polymerization is sufficiently high.''
（７） 同第１０頁１行乃至２行の「メチルエステル
、ｌリメタクリル酸モノアミノメチルエステル」ヲ「エ
チルエステル、ポリメタクリル酸モノメチルアミノエチ
ルエステル」と訂正する。(7) On page 10, lines 1 and 2, "methyl ester, l-methacrylic acid monoaminomethyl ester" is corrected to "ethyl ester, polymethacrylic acid monomethylaminoethyl ester."
（８） 同第１０頁１行行と１６行との間に次の文章
を挿入する。(8) Insert the following sentence between lines 1 and 16 on page 10.
「本発明にかかる水溶性高分子物質を凝集剤または増粘
剤として使用する場合には、使用直前に製造し、その１
１使用することが好ましい、」
（９）同第１２頁１１１上欄の「種アルデヒド」を「ア
ルデヒド」と訂正する。"When using the water-soluble polymeric substance according to the present invention as a flocculant or thickener, it must be prepared immediately before use, and
(9) "Seed aldehyde" in the upper column of page 111, page 12, is corrected to "aldehyde."
以上that's all
Claims (2)
または２種以上を有する水溶性高分子物質に式 ０ＨＯ
−Ｒ−（３ＨＯ（式中、Ｒはアルキレ。 ン基またはアルケニレン基を示す）で表わされｉ脂肪族
ジアルデヒド類り１種または２種以上を加えて反応させ
、生成する高分子物質が水溶性を保つ範囲内で原料の高
分子物質を相互に結合させることを特徴とする高重合度
の水溶性陽イオン性高分子物質の製法。(1) Water-soluble polymeric substances having one or more types of primary amino groups or secondary amino groups in the molecule with the formula 0HO
-R- (represented by 3HO (in the formula, R represents an alkylene group or an alkenylene group), and one or more aliphatic dialdehydes are added and reacted, and the resulting polymer substance is A method for producing a water-soluble cationic polymer substance with a high degree of polymerization, which is characterized by bonding raw polymer substances to each other within a range that maintains water solubility.
ルデヒドであ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。(2) The aliphatic dialdehyde is malonaldehyde. Succinaldehyde, malonaldehyde. 7. The method according to claim 1, characterized in that it is maldialdehyde, beta rutaraldehyde, adipaldehyde.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14723381A JPS5849704A (en) | 1981-09-18 | 1981-09-18 | Preparation of water-soluble cationic high polymer having high polymerization degree |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14723381A JPS5849704A (en) | 1981-09-18 | 1981-09-18 | Preparation of water-soluble cationic high polymer having high polymerization degree |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5849704A true JPS5849704A (en) | 1983-03-24 |
| JPS6411047B2 JPS6411047B2 (en) | 1989-02-23 |
Family
ID=15425577
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14723381A Granted JPS5849704A (en) | 1981-09-18 | 1981-09-18 | Preparation of water-soluble cationic high polymer having high polymerization degree |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5849704A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6151006A (en) * | 1984-08-20 | 1986-03-13 | Mitsubishi Chem Ind Ltd | Production of crosslinked spherical particle of polyvinylamine |
| CN103663646A (en) * | 2013-12-09 | 2014-03-26 | 山东华亚环保科技有限公司 | Flocculant for treating papermaking wastewater |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49129783A (en) * | 1973-03-28 | 1974-12-12 | ||
| JPS56124977A (en) * | 1980-03-07 | 1981-09-30 | Sanyo Electric Co Ltd | Printing control system |
-
1981
- 1981-09-18 JP JP14723381A patent/JPS5849704A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49129783A (en) * | 1973-03-28 | 1974-12-12 | ||
| JPS56124977A (en) * | 1980-03-07 | 1981-09-30 | Sanyo Electric Co Ltd | Printing control system |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6151006A (en) * | 1984-08-20 | 1986-03-13 | Mitsubishi Chem Ind Ltd | Production of crosslinked spherical particle of polyvinylamine |
| CN103663646A (en) * | 2013-12-09 | 2014-03-26 | 山东华亚环保科技有限公司 | Flocculant for treating papermaking wastewater |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6411047B2 (en) | 1989-02-23 |
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