JPS6257617A - High molecular flocculant composition - Google Patents
High molecular flocculant compositionInfo
- Publication number
- JPS6257617A JPS6257617A JP9653985A JP9653985A JPS6257617A JP S6257617 A JPS6257617 A JP S6257617A JP 9653985 A JP9653985 A JP 9653985A JP 9653985 A JP9653985 A JP 9653985A JP S6257617 A JPS6257617 A JP S6257617A
- Authority
- JP
- Japan
- Prior art keywords
- polyacrylamide
- high molecular
- mannich
- modified
- molecular flocculant
- 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
Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、長期安定性に浸れた高分子凝集剤組成物に
関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application This invention relates to polymeric flocculant compositions endowed with long-term stability.
工場廃水、上下水および化学工業における各種の工程よ
り排出される懸濁液の処理や、その結果発生する汚泥の
濃縮、脱水、Ｍ紙工業及びパルブ工業の抄紙工程や洗浄
工程などから排出される白水の回収など′１に目的とし
て、各棟の高分子凝集剤を使用する方法か提案され、実
用化されている。なかでも、ポリアクリルアミド系マン
ニッヒ変性物はカブオン性が強く、負に帯電した懸濁物
質の電荷′ｆ：谷易に中和して優れた凝集効果を示すた
め、実用化研究が精力的に進められている。Processing of suspensions discharged from various processes in factory wastewater, water and sewage, and chemical industries, concentration and dewatering of the resulting sludge, discharged from paper making and cleaning processes of M Paper Industries and Pulp Industries, etc. A method of using polymer flocculants in each building has been proposed and put into practical use for purposes such as recovering white water. Among these, polyacrylamide-based Mannich-modified products have strong cabonic properties, easily neutralize the charge 'f of negatively charged suspended solids, and exhibit excellent aggregation effects, so research into practical application is being actively pursued. It is being
ポリアクリルアミド系マンニッヒ変性物は。Mannich modified polyacrylamide.
アクリルアミド系ポリマーのカルバモイル基ｌモルアｆ
ｃす、ホルムアルデヒド０１〜２．０−Ｅ−ル及びジア
ルキルアミン０．２〜４．０モルヲ作用させて得られる
アクリルアミド系ポリマーのアミノアルキル化物であっ
て、高分子鎖中には一搬に、−Ｃｎ、−ｃＨ−
弾
Ｃ０ＮＨＣＨ，ＯＨ
の３種類の構造単位が含まれている。Carbamoyl group l mole f of acrylamide polymer
C. An aminoalkylated acrylamide polymer obtained by the action of 0.1 to 2.0 moles of formaldehyde and 0.2 to 4.0 moles of dialkylamine, and the polymer chain contains, at once, It contains three types of structural units: -Cn, -cH-, C0NHCH,OH.
従って、マンニッヒ変性物は加水分解を受けやすく、そ
の結果、カチオン密度の低下を起こしやすい。また、Ｎ
−メチロール基は極めて反応性が高く、溶液状態で貯蔵
すると、とのＮ−メチロール基が分子間あるいは分子内
で架橋反応や、特に酸性下では復員環生成反応を起こし
てゲル化（不溶物の生成）し、商品価値を著しく低下さ
せてしまう。Therefore, Mannich modifications are susceptible to hydrolysis and, as a result, a decrease in cation density. Also, N
- Methylol groups are extremely reactive, and when stored in a solution state, the N-methylol groups of and cause cross-linking reactions between or within molecules, and especially under acidic conditions, cleavage formation reactions occur, resulting in gelation (insoluble matter). (formation), which significantly reduces the product value.
このため、従来、貯蔵安定性を高めるために各種の方法
が提案（例えば特開昭５７−３１９０４、發公昭４９−
１５９５２、特公昭４９−１５９５３、特公昭５７−８
８０１）されている。For this reason, various methods have been proposed to improve storage stability (e.g., Japanese Patent Application Laid-Open No. 57-31904, Publication No. 49-1999).
15952, Special Publication No. 49-15953, Special Publication No. 57-8
801) has been done.
一般に高分子凝集剤の貯蔵は高濃度（５％以上）のもの
ほど、好ましく、かつ、ｌＩＬ場には４０℃程度の高温
下にさらされることが多く、貯蔵期間も若干の余裕をみ
て、製造から少くとも１ケ月間程度は必要である。従っ
て、これらの条件を全て満足するような貯蔵安定性に優
れたマンニッヒ変性物か要求されている。しかし、上述
の従来方法では上記の諸条件を全て満足させることはで
きなかった。In general, the higher the concentration (5% or more) of polymer flocculants is, the better it is, and since they are often exposed to high temperatures of around 40°C in the IL field, it is better to store them with some leeway in the storage period. It is necessary for at least one month. Therefore, there is a need for a Mannich modified product that satisfies all of these conditions and has excellent storage stability. However, the conventional method described above could not satisfy all of the above conditions.
〔問題点を解決するための手段」
この発明は、上記の貯蔵安定性に関する諸要件を満足す
るポリアクリルアミド系マンニッヒ変性物を含む高分子
凝集剤組成物の開発を目的として成されたものであって
、ポリアクリルアミド系マンニッヒ変性物と、１式で表
わされる化合物とを含むことを特徴とする高分子凝集剤
組成物である。[Means for Solving the Problems] The present invention was made for the purpose of developing a polymer flocculant composition containing a polyacrylamide-based Mannich modified product that satisfies the above requirements regarding storage stability. This is a polymer flocculant composition characterized by containing a polyacrylamide-based Mannich modified product and a compound represented by formula 1.
式中Ｒ’ 、 Ｒ”は炭素数１〜３のアルキル基を、Ｒ
３は炭素数１〜３のγルキレン基をそれぞれ表わす。In the formula, R' and R'' represent an alkyl group having 1 to 3 carbon atoms;
3 represents a γ-alkylene group having 1 to 3 carbon atoms.
この発明においてポリアクリルアミド系とは、アクリル
アミド又はメタクリルアミドのホモ重合体またはこれら
のいずれかの七ツマ−と共重合可能な他のビニル系モノ
マーとの共重合体を意味する。In the present invention, polyacrylamide refers to a homopolymer of acrylamide or methacrylamide, or a copolymer of any of these heptamers with another vinyl monomer copolymerizable.
ポリアクリルアミド系マンニッヒ変性物は、前記重合体
を常法によって、ホルムアルデヒド及びジアルキルアミ
ンとを反応させて得られた変性物でもよいし、アクリル
アミド又はメタクリルアミドモノマーを予め常法によっ
てマンニッヒ変性しておき、こうして得られたマンニッ
ヒ変性上ツマ−を、必要に応じて他の共重合可能なビニ
ル系モノマーとともに重合させて得られる変性物重合体
でもよい。The polyacrylamide-based Mannich-modified product may be a modified product obtained by reacting the above polymer with formaldehyde and dialkylamine in a conventional manner, or a Mannich-modified polyacrylamide or methacrylamide monomer may be previously Mannich-modified in a conventional manner. A modified polymer obtained by polymerizing the thus-obtained Mannich-modified supermer with other copolymerizable vinyl monomers may also be used.
このポリアクリルアミド系マンニッヒ変性物の貯蔵安定
性を高めるために、この発＼セは上記１式で表される化
合物を配合する。In order to enhance the storage stability of this Mannich-modified polyacrylamide-based product, this product contains a compound represented by the above formula 1.
１式で表わされる化合物は、具体的にはＮ、Ｎ−ジメチ
ルメタノールアミン、Ｎ、Ｎ−ジメチルエタノールアミ
ン、Ｎ、Ｎ−ジエチルエタノールアミンＳＮ、Ｎ−ジエ
チルプロパノールアミン、Ｎ。Specifically, the compound represented by Formula 1 is N,N-dimethylmethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine SN, N-diethylpropanolamine, N.
Ｎ−ジプロピルエタノールアミンなどが該当する。N-dipropylethanolamine and the like fall under this category.
これらＮ、Ｎ−ジアルキルアルカノールアミンの配合割
合は、ポリアクリルアミド系マンニッヒ変性物に対して
１〜３０重量％、好ましくは５〜１５重量％とする。ｔ
た、配合方法としてＬ、ポリアクリルアミド系マンニッ
ヒ変性物を含む水溶液に、Ｎ、Ｎ−ジアルキルアルカノ
ールアミンを所定量添加してもよいし、マンニッヒ変性
前にポリアクリルアミド系重合体に予めＮ。The blending ratio of these N,N-dialkylalkanolamines is 1 to 30% by weight, preferably 5 to 15% by weight, based on the Mannich-modified polyacrylamide product. t
In addition, as a blending method, a predetermined amount of N,N-dialkylalkanolamine may be added to an aqueous solution containing the L, polyacrylamide-based Mannich-modified product, or N may be added to the polyacrylamide-based polymer in advance before Mannich modification.
Ｎ−ジアルキルアルカノールアミンｌＴｒ定量添加して
おき、この水溶液にホルムアルデヒドとジメチルアミン
を添加して常法に従ってマンニッヒ変性してもよい、さ
らに、マンニッヒ変性七ツマ−から重合体を製造する場
合には、このマンニッヒ変性モノマーに所定量のＮ、Ｎ
−シフルキルアルカノールアミンを添加後、重合させれ
ばよい。N-dialkylalkanolamine lTr may be added in a fixed amount, and formaldehyde and dimethylamine may be added to this aqueous solution to Mannich modification according to a conventional method.Furthermore, when producing a polymer from Mannich-modified heptamine, A predetermined amount of N, N is added to this Mannich modified monomer.
- Polymerization may be carried out after adding cyfurkyl alkanolamine.
かくして得られたポリアクリルアミド系マンニッヒ変性
物を含む高分子凝集剤組成物は懸濁物質の沈降促進剤、
汚泥の濃縮脱水促進剤および白水の歩留り向上剤として
、さらには紙力増強剤としても効果的に使用することが
できる。The polymer flocculant composition containing the polyacrylamide-based Mannich modified product obtained in this way can be used as a sedimentation accelerator for suspended solids,
It can be effectively used as a sludge concentration and dehydration accelerator, a white water retention improver, and a paper strength enhancer.
この発明の作用は明らかではないが、１式で表わされる
Ｎ、Ｎ−ジアルキルアルカノールアミンがポリアクリル
アミド系マンニッヒ変性物中のＮ−メチロール基に対し
て何らかの関与あるいは反応を行なって、Ｎ−メチロー
ル基の加架反応に基くゲル化を防止するものと推定され
る。Although the effect of this invention is not clear, the N,N-dialkylalkanolamine represented by formula 1 participates or reacts with the N-methylol group in the polyacrylamide-based Mannich modified product, and the N-methylol group It is presumed that this prevents gelation caused by cross-linking reaction.
実施例１
アクリルアミドモノマーを水に２．０モル／ｌ溶解し、
開始剤としてメタ過ヨウ素酸ナトリウムをモノマーに対
しＯ，ＯＳ、％使用し％ ４５℃で８時間重合させてポ
リアクリルアミド水溶液を５、９ （ｄｌ／Ｗ−）であ
った。Example 1 Acrylamide monomer was dissolved in water at 2.0 mol/l,
Sodium metaperiodate was used as an initiator in % O, OS, based on the monomer, and polymerization was carried out at 45 DEG C. for 8 hours to give a polyacrylamide aqueous solution of 5.9 (dl/W-).
次にこの重合体水溶液に３７％ポルマリンと５０％、ジ
メチルアミン水溶液の混ｔＬ（ホルマリンとしてポリア
クリルアミドに対し等モル、ジメチルアミンとしてポリ
アクリルアミドに対し１．４倍モル）ｆｔ加え、４０℃
で４時間反応させ、ポリアクリルアミドのマンニッヒ変
性物水溶液３０℃
を得た。この重合体の固有粘度”〕ｌＮ−Ｎａ１ｌは６
．４ （ｄｌ／）） 、コロイド当量値はｐ）ｌ ４で
６．６（ｍｅ（！／？）、ｐＨ１０で−０，０（ｍｅ
ｑ／ｉ）でｈった。Next, to this polymer aqueous solution was added tL of a mixture of 37% Polmarine, 50%, and a dimethylamine aqueous solution (equal mole as formalin to polyacrylamide, 1.4 times mole as dimethylamine to polyacrylamide) ft, and heated to 40°C.
The mixture was reacted for 4 hours to obtain an aqueous Mannich-modified polyacrylamide solution at 30°C. The intrinsic viscosity of this polymer is 6
．． 4 (dl/)), the colloidal equivalent value is 6.6(me(!/?)) at p)l4, -0.0(me
q/i).
このポリアクリルアミドのマンニッヒ変性物水溶液を水
で希釈して１０重蓋に水溶液とし、これに前記重合体に
対し５１［４１％のＮ、Ｎ−ジメチルエタノールアミン
を添加し、４０℃で経時変化を見た。結果を表に示す。This Mannich modified aqueous solution of polyacrylamide was diluted with water to make an aqueous solution in a 10-layer lid, and 51[41% N,N-dimethylethanolamine was added to the polymer, and the change over time was observed at 40°C. saw. The results are shown in the table.
実施例２
実施例１においてＮ、Ｎ−ジメチルエタノールアミンを
１０重量％添加した以外は実施例１と全く同様の操作を
行なって経時変化を見た。結果を表に示す。Example 2 The same operation as in Example 1 was performed except that 10% by weight of N,N-dimethylethanolamine was added, and the changes over time were observed. The results are shown in the table.
実施例３
実施例１において％Ｎ、Ｎ−ジメチルエタノールアミン
５重量％にかえて、 Ｎ、Ｎ−ジメチルプロパノールア
ミ２１０重量％とした以外は実施例１と全く同様の操作
を行なって経時変化を見た。結果を表に示す。Example 3 The same operation as in Example 1 was performed except that 5% by weight of N,N-dimethylethanolamine in Example 1 was changed to 210% by weight of N,N-dimethylpropanolamine, and changes over time were observed. saw. The results are shown in the table.
実施例４
実施例１においてＮ、Ｎ−ジメチルエタノールアミンｔ
−１！量％添加した以外は実施例１と全く同様の操作を
行なって経時変化を見た。結果を表に示す。Example 4 In Example 1, N,N-dimethylethanolamine t
-1! The same operation as in Example 1 was performed except that the amount of % was added, and the changes over time were observed. The results are shown in the table.
実施例５
実施例１においてＮ、Ｎ−ジメチルエタノールアミンを
３０重量％添加した以外は実施例１と全く同様の操作を
行なって経時変化を見た。結果を表に示す。Example 5 The same procedure as in Example 1 was performed except that 30% by weight of N,N-dimethylethanolamine was added, and the changes over time were observed. The results are shown in the table.
比較例１
実施例１で得られたｌＯ重ｆ％のポリアクリルアミドの
マンニッヒ変性物水溶ｇを、その１１４０℃に放置して
経時変化を見た。結果を表に示す。Comparative Example 1 An aqueous solution of the Mannich-modified polyacrylamide containing 1O w/f% obtained in Example 1 (g) was left at 1140° C. to observe changes over time. The results are shown in the table.
比較例２
実施例１で得しれたｉｏ重ｔ％のポリアクリルアミドの
マンニッヒ変性物水浴液にｌＮ塩酸を添加してｐＨｆ
３に調整した後、 ４０℃に放置して経時変化を見た。Comparative Example 2 1N hydrochloric acid was added to the Mannich modified water bath solution of polyacrylamide of io weight % obtained in Example 1 to adjust the pH
After adjusting the temperature to 3, it was left at 40°C to observe changes over time.
結果全表に示す。The results are shown in the full table.
比較例３
実施例１で得られた１０重′ｊｔ％のポリアクリルアミ
ドのマンニッヒ変性物水浴液に対し、１Ｏｉｔ％の塩酸
ヒドロキシルアミンを加え、次に塩酸でｐＨ’ｉ ３に
調整した後、４０℃に放置して経時変化を見た。結果を
表に示す。Comparative Example 3 1 Oit% of hydroxylamine hydrochloride was added to the 10wt% Mannich modified polyacrylamide water bath solution obtained in Example 1, and then the pH was adjusted to 3 with hydrochloric acid. It was left at ℃ and observed changes over time. The results are shown in the table.
この表から、Ｎ、Ｎ−ジアルキルアルカノールアミンの
添加量がマンニッヒ変性物に対して、１〜３．ｏｉ証シ
の範囲で良好であり、３０日を経過した時点でも固有粘
度、コロイド当量値においてほとんど変化かないことか
わかる。とりわけ、５〜１５重量うの範囲においては極
めて良好であることがわかる。From this table, it can be seen that the amount of N,N-dialkylalkanolamine added is 1 to 3. It can be seen that the results are good within the Oi test range, and that there is almost no change in the intrinsic viscosity or colloid equivalent value even after 30 days. In particular, it can be seen that the weight range of 5 to 15 weight is extremely good.
一方、従来方法を示す 比較例１においては。On the other hand, in Comparative Example 1 showing the conventional method.
いずれも固有粘度の上昇、ｐＨ４における正のコロイド
当量値の低下、ｐＨＩ Ｏにおける負のコロイド当ｆｆ
１ｌＩの増加か認められ、３０日後には一部水に不ｆ＆
なグル化物が生成した。また、比較例２．３においては
、それぞれ２．５日後には水に全く溶解せず、明らかに
ゲル化物を生成した。Both increase the intrinsic viscosity, decrease the positive colloid equivalent value at pH 4, and negative colloid equivalent value at pHI Off.
An increase in 1lI was observed, and after 30 days, some of the water contained
Glycide was produced. In addition, in Comparative Examples 2 and 3, after 2.5 days, they were not dissolved at all in water and clearly formed a gelled product.
〔発明の効果」
この発明の高分子凝集剤組成物はｌＯ％程度の高濃度水
溶液状態で、４０℃の高温下、１力月間貯蔵しても製品
の品質にほとんど変化か認められず、極めて良好な貯蔵
安定性を示す。従って、従来のように冷蔵保管する必要
がない。[Effects of the Invention] The polymer flocculant composition of the present invention, in the form of a highly concentrated aqueous solution of about 10%, shows almost no change in product quality even when stored for one month at a high temperature of 40°C, and is extremely stable. Shows good storage stability. Therefore, there is no need for refrigerated storage as in the past.
Claims (1)
表わされる化合物とを含むことを特徴とする高分子凝集
剤組成物。 ▲数式、化学式、表等があります▼〔１〕 式中Ｒ＾１、Ｒ＾２は炭素数１〜３のアルキル基を、Ｒ
＾３は炭素数１〜３のアルキレン基をそれぞれ表わす。 ２、ポリアクリルアミド系がポリアクリルアミドまたは
ポリメタクリルアミドである特許請求の範囲第１項記載
の組成物。 ３、１式で表わされる化合物がＮ，Ｎ−ジエチルエタノ
ールアミン又はＮ，Ｎ−ジメチルプロパノールアミンで
ある特許請求の範囲第１項又は第２項記載の組成物。[Scope of Claims] 1. A polymer flocculant composition comprising a polyacrylamide Mannich-modified product and a compound represented by formula 1. ▲There are mathematical formulas, chemical formulas, tables, etc.▼[1] In the formula, R^1 and R^2 are alkyl groups having 1 to 3 carbon atoms, and R
^3 represents an alkylene group having 1 to 3 carbon atoms, respectively. 2. The composition according to claim 1, wherein the polyacrylamide system is polyacrylamide or polymethacrylamide. 3. The composition according to claim 1 or 2, wherein the compound represented by formula 1 is N,N-diethylethanolamine or N,N-dimethylpropanolamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9653985A JPS6257617A (en) | 1985-05-07 | 1985-05-07 | High molecular flocculant composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9653985A JPS6257617A (en) | 1985-05-07 | 1985-05-07 | High molecular flocculant composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6257617A true JPS6257617A (en) | 1987-03-13 |
| JPH0446162B2 JPH0446162B2 (en) | 1992-07-29 |
Family
ID=14167912
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9653985A Granted JPS6257617A (en) | 1985-05-07 | 1985-05-07 | High molecular flocculant composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6257617A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013518718A (en) * | 2010-02-10 | 2013-05-23 | クィーンズ ユニバーシティー アット キングストン | Water with switchable ionic strength |
| US10377647B2 (en) | 2010-12-15 | 2019-08-13 | Queen's University at Kingson | Systems and methods for use of water with switchable ionic strength |
-
1985
- 1985-05-07 JP JP9653985A patent/JPS6257617A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013518718A (en) * | 2010-02-10 | 2013-05-23 | クィーンズ ユニバーシティー アット キングストン | Water with switchable ionic strength |
| US11498853B2 (en) | 2010-02-10 | 2022-11-15 | Queen's University At Kingston | Water with switchable ionic strength |
| US10377647B2 (en) | 2010-12-15 | 2019-08-13 | Queen's University at Kingson | Systems and methods for use of water with switchable ionic strength |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0446162B2 (en) | 1992-07-29 |
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