JPH06157668A - Water-in-oil cationic emulsion, its preparation and its use as polymeric flocculant - Google Patents
Water-in-oil cationic emulsion, its preparation and its use as polymeric flocculantInfo
- Publication number
- JPH06157668A JPH06157668A JP33950292A JP33950292A JPH06157668A JP H06157668 A JPH06157668 A JP H06157668A JP 33950292 A JP33950292 A JP 33950292A JP 33950292 A JP33950292 A JP 33950292A JP H06157668 A JPH06157668 A JP H06157668A
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- JP
- Japan
- Prior art keywords
- water
- emulsion
- polymer
- group
- carbon atoms
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、油中水型カチオン性エ
マルジョン、その製法および高分子凝集剤としての用途
に関するものであり、さらに詳しくは水溶性、分散安定
性、保存安定性が良好であり、かつ有姿粘度の低い油中
水型カチオン性エマルジョン、およびその製法、さらに
製紙用歩留まり向上剤および濾水性向上剤、産業廃水用
および下水し尿処理用の凝集剤および脱水剤などの用途
に対し、高い性能を示す上記油中水型カチオン性エマル
ジョンを主成分とする新規な高分子凝集剤に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-in-oil type cationic emulsion, a method for producing the same, and its use as a polymer flocculant. More specifically, it has good water solubility, dispersion stability and storage stability. Water-in-oil type cationic emulsion with low viscosity and its production method, and its applications such as retention and drainage improving agents for papermaking, coagulants and dehydrating agents for industrial wastewater and sewage and urine treatment On the other hand, the present invention relates to a novel polymer flocculant containing the above water-in-oil type cationic emulsion, which exhibits high performance, as a main component.
【0002】[0002]
【従来の技術】従来、製紙用歩留まり向上剤および濾水
性向上剤、産業廃水用および下水し尿処理用の凝集剤お
よび脱水剤などの用途に対し、カチオン性高分子凝集剤
が広く用いられてきた。これらカチオン性高分子凝集剤
は、カチオン性ビニル単量体の単独重合体またはこれと
他の水溶性ビニル単量体との共重合体が一般的であり、
その製品形態は粉末状ポリマーが主流であった。一方、
近年、その取扱性の良さから、製品形態として油中水型
ポリマーエマルジョンタイプの高分子凝集剤が数多く提
案されている。例えば、特公昭54−37986号公報
には、単量体水溶液30〜70重量%と疎水性液体70
〜30重量%を界面活性剤を用いて乳化分散させ、油中
水型ポリマーエマルジョンを得る方法が提案されてお
り、特開昭63−90510号公報には、水溶性ビニル
モノマーと架橋剤を含む水溶液と、HLB値が3〜6で
ある疎水性界面活性剤を含む有機分散媒とを混合した
後、ラジカル重合触媒の存在下、温度30〜80℃で重
合させ油中水型エマルジョンポリマーを製造する方法な
どが提案されており、また、特公昭51−47156号
公報には、水溶性かつエチレン性不飽和単量体水溶液3
0〜70重量%、疎水性液体、濃度0.1ないし10重
量%の油中水型乳化剤、フリーラジカル開始剤からなる
油中水型乳濁液を作り、それを加熱して、フリーラジカ
ルを生成させて該単量体を重合させて重合体ラッテクス
とし、これを下水、産業用廃液から固形分を濃縮脱水す
るのに用いる方法が提案されている。2. Description of the Related Art Conventionally, cationic polymer flocculants have been widely used for applications such as retention aids for papermaking and drainage improvers, flocculants for industrial wastewater and sewage treatment, and dehydrating agents. . These cationic polymer flocculants are generally homopolymers of cationic vinyl monomers or copolymers of these with other water-soluble vinyl monomers,
The product form was mainly a powdered polymer. on the other hand,
In recent years, a large number of water-in-oil type polymer emulsion type polymer flocculants have been proposed as product forms because of their easy handling. For example, Japanese Patent Publication No. 54-37986 discloses a monomer aqueous solution of 30 to 70% by weight and a hydrophobic liquid 70.
A method for obtaining a water-in-oil polymer emulsion by emulsifying and dispersing 30 to 30% by weight of a surfactant has been proposed. JP-A-63-90510 includes a water-soluble vinyl monomer and a crosslinking agent. An aqueous solution and an organic dispersion medium containing a hydrophobic surfactant having an HLB value of 3 to 6 are mixed and then polymerized at a temperature of 30 to 80 ° C. in the presence of a radical polymerization catalyst to produce a water-in-oil emulsion polymer. And the like, and JP-B-51-47156 discloses a water-soluble and ethylenically unsaturated monomer aqueous solution 3
A water-in-oil emulsion consisting of 0 to 70% by weight of a hydrophobic liquid, a water-in-oil emulsifier with a concentration of 0.1 to 10% by weight, and a free radical initiator is prepared and heated to generate free radicals. There has been proposed a method of producing and polymerizing the monomer to obtain a polymer latex, which is used for concentrating and dewatering solids from sewage and industrial waste liquid.
【0003】しかし、油中水型ポリマーエマルジョンを
例えば高分子凝集剤として使用する際の基本的要求性能
は、製紙工程、廃水処理工程などにおいて対象懸濁粒子
を凝集させることであり、この目的を達成するためには
ポリマーをいかに高分子量化するかが大きな課題であ
る。しかし、従来の油中水型ポリマーエマルジョンで
は、高分子量化するための重合条件を選択すれば保存安
定性が悪化し、保管時においてポリマー粒子の沈降、再
凝集、増粘などが生じ、経時により性能および水溶解性
が低下するという大きな問題点が存在し、性能と保存安
定性の両者を充分に満足させることは困難であった。However, the basic performance required when using a water-in-oil type polymer emulsion as, for example, a polymer flocculant is to flocculate the target suspended particles in a papermaking process, a wastewater treatment process, etc. To achieve this, how to increase the polymer molecular weight is a major issue. However, in the conventional water-in-oil type polymer emulsion, if the polymerization conditions for increasing the molecular weight are selected, the storage stability deteriorates, and sedimentation, re-aggregation, thickening, etc. of the polymer particles occur during storage, and There is a big problem that performance and water solubility are lowered, and it is difficult to sufficiently satisfy both performance and storage stability.
【0004】[0004]
【発明が解決しようとする課題】上記の従来の油中水型
ポリマーエマルジョンは、モノマー組成、界面活性剤組
成などについて種々の改良がなされたものの、上記問題
は未解決であり、性能と保存安定性などをバランスよく
有する油中水型ポリマーエマルジョンおよびその製造方
法、さらにそれを用いた高分子凝集剤が強く求められて
いる。本発明は、水溶性、分散安定性、保存安定性が良
好であり、かつ有姿粘度の低い油中水型カチオン性ポリ
マーエマルジョン、およびその製法、さらに製紙用歩留
まり向上剤および濾水性向上剤、産業廃水用および下水
し尿処理用の凝集剤および脱水剤などの用途に対し、高
い性能を示す油中水型カチオン性ポリマーエマルジョン
タイプの新規な高分子凝集剤を提供することを目的とす
る。The above-mentioned conventional water-in-oil type polymer emulsion has various improvements in the monomer composition, the surfactant composition, etc., but the above problems have not been solved yet, and the performance and the storage stability are stable. There is a strong demand for a water-in-oil type polymer emulsion having a good balance of properties, a method for producing the same, and a polymer flocculant using the same. The present invention is water-soluble, dispersion stability, good storage stability, and a low water-in-oil type cationic polymer emulsion having a low viscosity, a method for producing the same, and a retention aid and drainage improver for papermaking, An object of the present invention is to provide a novel polymer flocculant of water-in-oil type cationic polymer emulsion type showing high performance for applications such as flocculants and dehydrators for industrial wastewater and sewage treatment.
【0005】[0005]
【課題を解決するための手段】本発明者等は従来の問題
点を解決するために鋭意検討を重ねた結果、従来の油中
水型ポリマーエマルジョンにおいてはエマルジョン粒子
の重量平均粒子径を微細化することに着目した改良は見
当たらず、しかも従来の油中水型ポリマーエマルジョン
のエマルジョン粒子は、重量平均粒子径が1.0μm以
上のものがほとんどであり、0.3μm以下のものは製
造されていないこと、および、従来にない超微粒子径の
エマルジョン粒子を有する油中水型カチオン性ポリマー
エマルジョンを用いれば上記課題を解決し得ることを見
い出し、本発明を完成するに到った。Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the conventional problems, and as a result, in the conventional water-in-oil type polymer emulsion, the weight average particle diameter of emulsion particles was reduced. However, most of the emulsion particles of the conventional water-in-oil type polymer emulsion have a weight average particle diameter of 1.0 μm or more, and those having a weight average particle diameter of 0.3 μm or less are not produced. It has been found that the above problems can be solved by using a water-in-oil type cationic polymer emulsion having emulsion particles having an ultrafine particle diameter, which has not been found in the past, and completed the present invention.
【0006】本発明の請求項1の発明は、下記一般式
(化3)で表わされるカチオン性ビニル単量体を水、疎
水性有機液体、非イオン性界面活性剤の存在下で単独重
合、またはこれと他の水溶性ビニル単量体と共重合させ
て得られる油中水型ポリマーエマルジョンであって、
(A)ポリマーの濃度が、20〜70重量%であり、
(B)疎水性有機液体の濃度が、10〜50重量%であ
り、(C)非イオン性界面活性剤の濃度が、8重量%以
下であり、そして(D)ポリマーエマルジョンの重量平
均粒子径が、0.3μm以下であることを特徴とする油
中水型カチオン性エマルジョンである。According to the first aspect of the present invention, a cationic vinyl monomer represented by the following general formula (Formula 3) is homopolymerized in the presence of water, a hydrophobic organic liquid and a nonionic surfactant, Or a water-in-oil polymer emulsion obtained by copolymerizing this with another water-soluble vinyl monomer,
(A) the concentration of the polymer is 20 to 70% by weight,
(B) the concentration of the hydrophobic organic liquid is 10 to 50% by weight, (C) the concentration of the nonionic surfactant is 8% by weight or less, and (D) the weight average particle diameter of the polymer emulsion. Is 0.3 μm or less, which is a water-in-oil type cationic emulsion.
【0007】[0007]
【化3】 [Chemical 3]
【0008】(式中、Aは酸素原子またはNH;Zは炭
素数1〜4のアルキレン基または炭素数2〜4のヒドロ
キシアルキレン基;R1 は水素またはメチル基;R2 は
炭素数1〜4のアルキル基、炭素数2〜4のヒドロキシ
アルキル基またはベンジル基;R3 、R4 はそれぞれ独
立に炭素数1〜4のアルキル基または炭素数2〜4のヒ
ドロキシアルキル基;X- は塩を形成する陰イオンを表
わす。)(In the formula, A is an oxygen atom or NH; Z is an alkylene group having 1 to 4 carbon atoms or a hydroxyalkylene group having 2 to 4 carbon atoms; R 1 is hydrogen or a methyl group; R 2 is 1 to 1 carbon atoms. 4 alkyl group, a hydroxyalkyl group or a benzyl group having 2 to 4 carbon atoms; hydroxyalkyl group R 3, R 4 2-4 alkyl group carbon atoms or 1 to 4 carbon atoms are each independently; X - salt Represents the anion that forms.)
【0009】本発明の請求項2の発明は、下記一般式
(化4)で表わされるカチオン性ビニル単量体を水、疎
水性有機液体、非イオン性界面活性剤の存在下で単独重
合、またはこれと他の水溶性ビニル単量体と共重合さ
せ、油中水型ポリマーエマルジョンを製造する時、重合
開始前に重量平均粒子径0.3μm以下の安定な油中水
型のモノマーエマルジョンを形成させた後、重合を開始
することを特徴とする油中水型カチオン性ポリマーエマ
ルジョンの製造方法である。According to the second aspect of the present invention, a cationic vinyl monomer represented by the following general formula (Formula 4) is homopolymerized in the presence of water, a hydrophobic organic liquid and a nonionic surfactant, Alternatively, when a water-in-oil type polymer emulsion is copolymerized with this and another water-soluble vinyl monomer, a stable water-in-oil type monomer emulsion having a weight average particle size of 0.3 μm or less is prepared before the initiation of polymerization. A method for producing a water-in-oil type cationic polymer emulsion, which comprises initiating polymerization after formation.
【0010】[0010]
【化4】 [Chemical 4]
【0011】(式中、Aは酸素原子またはNH;Zは炭
素数1〜4のアルキレン基または炭素数2〜4のヒドロ
キシアルキレン基;R1 は水素またはメチル基;R2 は
炭素数1〜4のアルキル基、炭素数2〜4のヒドロキシ
アルキル基またはベンジル基;R3 、R4 はそれぞれ独
立に炭素数1〜4のアルキル基または炭素数2〜4のヒ
ドロキシアルキル基;X- は塩を形成する陰イオンを表
わす。)(In the formula, A is an oxygen atom or NH; Z is an alkylene group having 1 to 4 carbon atoms or a hydroxyalkylene group having 2 to 4 carbon atoms; R 1 is hydrogen or a methyl group; R 2 is 1 to 1 carbon atoms. 4 alkyl group, a hydroxyalkyl group or a benzyl group having 2 to 4 carbon atoms; hydroxyalkyl group R 3, R 4 2-4 alkyl group carbon atoms or 1 to 4 carbon atoms are each independently; X - salt Represents the anion that forms.)
【0012】本発明の請求項3の発明は、請求項1記載
の油中水型ポリマーエマルジョンを主成分とする高分子
凝集剤である。A third aspect of the present invention is a polymer flocculant containing the water-in-oil polymer emulsion according to the first aspect as a main component.
【0013】本発明で用いる一般式(1)、(2)で示
されるカチオン性ビニル単量体としては、ジメチルア
ミノエチル(メタ)アクリレート、ジエチルアミノエチ
ル(メタ)アクリレート、ジメチルアミノヒドロキシプ
ロピル(メタ)アクリレートなどのようなジアルキルア
ミノ(ヒドロキシ)アルキル(メタ)アクリレートの中
和塩または4級化物、ジメチルアミノエチル(メタ)
アクリルアミド、ジメチルアミノプロピル(メタ)アク
リルアミド、ジメチルアミノヒドロキシプロピル(メ
タ)アクリルアミドなどのようなジアルキルアミノ(ヒ
ドロキシ)アルキル(メタ)アクリルアミドの中和塩ま
たは4級化物などが挙げられる。The cationic vinyl monomers represented by the general formulas (1) and (2) used in the present invention include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and dimethylaminohydroxypropyl (meth). Neutralized salts or quaternary compounds of dialkylamino (hydroxy) alkyl (meth) acrylates such as acrylate, dimethylaminoethyl (meth)
Examples thereof include neutralized salts or quaternary compounds of dialkylamino (hydroxy) alkyl (meth) acrylamides such as acrylamide, dimethylaminopropyl (meth) acrylamide, dimethylaminohydroxypropyl (meth) acrylamide and the like.
【0014】本発明で用いる他の水溶性ビニル単量体と
しては、(メタ)アクリルアミド、N,N′−ジメチ
ル(メタ)アクリルアミド、アクリロニトリル、メチル
メタクリレート、ヒドロキシプロピル(メタ)アクリレ
ートなどのノニオン性ビニル単量体、ビニルピリジ
ン、ビニルイミダゾリンなどのカチオン性ビニル単量
体、アクリル酸、メタクリル酸、アクリル酸ナトリウ
ム、アクリルアミドプロパンスルホン酸などのアニオン
性ビニル単量体などが挙げられる。Other water-soluble vinyl monomers used in the present invention include (meth) acrylamide, N, N'-dimethyl (meth) acrylamide, acrylonitrile, methyl methacrylate, and nonionic vinyl such as hydroxypropyl (meth) acrylate. Examples include monomers, cationic vinyl monomers such as vinyl pyridine and vinyl imidazoline, and anionic vinyl monomers such as acrylic acid, methacrylic acid, sodium acrylate, and acrylamidopropanesulfonic acid.
【0015】本発明で用いる疎水性有機液体としては、
灯油、軽油、ヘキサン、イソパラフィン、ベンゼン、ト
ルエン、キシレンなどの脂肪族炭化水素または芳香族炭
化水素などが挙げられる。As the hydrophobic organic liquid used in the present invention,
Examples thereof include kerosene, light oil, hexane, isoparaffin, benzene, toluene, xylene and other aliphatic hydrocarbons or aromatic hydrocarbons.
【0016】本発明で用いる非イオン界面活性剤として
は、ポリオキシエチレンソルビタンモノオレエート、ポ
リオキシエチレンソルビタントリステアレート、ポリオ
キシエチレンラウリルエーテル、ポリエチレングリコー
ルモノオレエート、ソルビタンモノラウレートなどが挙
げられる。Examples of the nonionic surfactant used in the present invention include polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan tristearate, polyoxyethylene lauryl ether, polyethylene glycol monooleate and sorbitan monolaurate. To be
【0017】本発明においては、ビニル単量体を重合さ
せるための重合開始剤は、一般的に用いられるラジカル
重合開始剤でよく、過硫酸アンモニウム、過酸化水素な
どの過酸化物、またはそれらと亜硫酸ナトリウムなどの
還元剤を組み合わせたレドックス系重合開始剤、アゾビ
スイソブチロニトリルなどのアゾ化合物などが挙げられ
る。さらに、これらの重合開始剤を用いずに紫外線、放
射線などを用いてラジカル重合を開始させる方法もあ
る。In the present invention, the polymerization initiator for polymerizing the vinyl monomer may be a generally used radical polymerization initiator, such as a peroxide such as ammonium persulfate and hydrogen peroxide, or a peroxide thereof and sulfurous acid. Examples thereof include redox polymerization initiators in combination with reducing agents such as sodium, azo compounds such as azobisisobutyronitrile, and the like. Further, there is also a method of initiating radical polymerization by using ultraviolet rays, radiation or the like without using these polymerization initiators.
【0018】本発明においては、重合前に重量平均粒子
径0.3μm以下の安定な油中水型のモノマーエマルジ
ョンを形成させることが肝要である。一般的に、重合前
のモノマーエマルジョンを微細化することにより重合後
のポリマーエマルジョンも均一かつ超微細なエマルジョ
ン粒子とすることができる。従って、重合後のポリマー
エマルジョンは、分子量が高く、保存安定性が良好とな
り、さらに水への溶解性が向上する。モノマーエマルジ
ョンの重量平均粒子径が0.3μmを越えると、高分子
量かつ保存安定性良好なポリマーエマルジョンを得るこ
とは難しい。In the present invention, it is essential to form a stable water-in-oil type monomer emulsion having a weight average particle diameter of 0.3 μm or less before polymerization. Generally, by making the monomer emulsion before polymerization fine, the polymer emulsion after polymerization can also be made into uniform and ultrafine emulsion particles. Therefore, the polymer emulsion after polymerization has a high molecular weight, has good storage stability, and further has improved solubility in water. When the weight average particle diameter of the monomer emulsion exceeds 0.3 μm, it is difficult to obtain a polymer emulsion having a high molecular weight and good storage stability.
【0019】モノマーエマルジョンの重量平均粒子径を
0.3μm以下にする方法としては、モノマー、水、疎
水性有機液体、非イオン界面活性剤の組成比率および疎
水性有機液体、非イオン界面活性剤の種類の選定などを
充分に検討することはもちろんであるが、これら混合液
に対して、極めて強力な剪断力を与えることが必要とな
る。剪断力を与える手段としては、ホモジナイザー、イ
ンラインホモミキサーなどの機器を用いて、充分な平均
循環数(液が羽根と外壁の間を通過する回数の平均値)
を保つことが重要である。As a method for adjusting the weight average particle diameter of the monomer emulsion to 0.3 μm or less, the composition ratio of the monomer, water, the hydrophobic organic liquid and the nonionic surfactant and the hydrophobic organic liquid and the nonionic surfactant are used. It is needless to say that the selection of the type should be thoroughly examined, but it is necessary to apply an extremely strong shearing force to these mixed liquids. A device such as a homogenizer or an in-line homomixer is used as a means for giving a shearing force, and a sufficient average circulation number (the average number of times the liquid passes between the blade and the outer wall).
It is important to keep
【0020】モノマーエマルジョンの重量平均粒子径を
測定する方法としては、光散乱法・遠心沈降光透過法・
レーザー回折法・電気的検知帯法などの種々の測定方法
があり、各々の方法に対応した測定機器が考案されてい
るが、測定範囲と精度から考えると、光散乱法が好まし
い。As a method for measuring the weight average particle size of the monomer emulsion, a light scattering method, a centrifugal sedimentation light transmission method,
There are various measuring methods such as a laser diffraction method and an electric detection zone method, and a measuring instrument corresponding to each method has been devised, but the light scattering method is preferable from the viewpoint of measuring range and accuracy.
【0021】本発明のポリマーエマルジョンのエマルジ
ョン粒子の重量平均粒子径は、0.3μm以下である。
0.3μmを越えるとポリマーエマルジョンの安定化と
ポリマーの高分子量化を充分に図ることは困難となる。
本発明のポリマーエマルジョンにおけるポリマー濃度
は、通常20〜70重量%、好ましくは30〜50重量
%である。70重量%を越える濃度の場合、エマルジョ
ン粒子の重量平均粒子径を0.3μm以下とすること
は、非常に困難となる。また、20重量%を下回る濃度
の場合、ポリマーを充分に高分子量化することが困難と
なる。本発明のポリマーエマルジョンにおける非イオン
性界面活性剤の濃度は、通常8重量%以下、好ましくは
2〜6重量%である。本発明のポリマーエマルジョンに
おける疎水性有機液体の濃度は、通常10〜50重量
%、好ましくは25〜40重量%である。10重量%を
下回る濃度の場合、エマルジョン粒子の重量平均粒子径
を0.3μm以下とすることは非常に困難となる。ま
た、50重量%を超える濃度の場合も、保存安定性が良
好なポリマーエマルジョンを得ることが困難となる。The weight average particle diameter of the emulsion particles of the polymer emulsion of the present invention is 0.3 μm or less.
When it exceeds 0.3 μm, it is difficult to sufficiently stabilize the polymer emulsion and increase the polymer molecular weight.
The polymer concentration in the polymer emulsion of the present invention is usually 20 to 70% by weight, preferably 30 to 50% by weight. When the concentration exceeds 70% by weight, it becomes very difficult to set the weight average particle diameter of the emulsion particles to 0.3 μm or less. Further, if the concentration is less than 20% by weight, it becomes difficult to sufficiently increase the molecular weight of the polymer. The concentration of the nonionic surfactant in the polymer emulsion of the present invention is usually 8% by weight or less, preferably 2 to 6% by weight. The concentration of the hydrophobic organic liquid in the polymer emulsion of the present invention is usually 10 to 50% by weight, preferably 25 to 40% by weight. When the concentration is less than 10% by weight, it becomes very difficult to set the weight average particle diameter of the emulsion particles to 0.3 μm or less. Further, even when the concentration exceeds 50% by weight, it becomes difficult to obtain a polymer emulsion having good storage stability.
【0022】本発明のポリマーエマルジョンのエマルジ
ョン粒子の重量平均粒子径を測定する方法としては、上
記のモノマーエマルジョンの重量平均粒子径を測定する
方法と同様に光散乱法・遠心沈降光透過法・レーザー回
折法・電気的検知帯法などの種々の測定方法があり、各
々の方法に対応した測定機器が考案されているが、測定
範囲と精度から考えると、光散乱法が最も適しているも
のと思われる。The method for measuring the weight average particle diameter of the emulsion particles of the polymer emulsion of the present invention is the same as the method for measuring the weight average particle diameter of the above-mentioned monomer emulsion, such as a light scattering method, a centrifugal sedimentation light transmission method and a laser. There are various measurement methods such as the diffraction method and the electrical detection zone method, and measuring instruments corresponding to each method have been devised, but considering the measurement range and accuracy, the light scattering method is the most suitable. Seem.
【0023】重合開始前に超微粒子径のモノマーエマル
ジョンを形成させた後、重合を開始させることにより得
られる本発明の油中水型カチオン性ポリマーエマルジョ
ンは、均一かつ微細な粒子となるため、分子量が高く、
低い有姿粘度を有し、保管時におけるエマルジョン粒子
の沈澱や再凝集などがなく、分散安定性、保存安定性に
優れたものとなる。The water-in-oil type cationic polymer emulsion of the present invention obtained by forming a monomer emulsion having an ultrafine particle size before the initiation of polymerization and then initiating the polymerization has uniform and fine particles, and therefore has a molecular weight of Is high,
It has low physical viscosity, does not cause precipitation or re-aggregation of emulsion particles during storage, and has excellent dispersion stability and storage stability.
【0024】本発明の高分子凝集剤は本発明の油中水型
カチオン性ポリマーエマルジョンを主成分とするもので
あって、従来の高分子凝集剤に比べ、性能が著しく改良
されており、保管時におけるエマルジョン粒子の沈澱や
再凝集などがなく、保存安定性、水溶解性に優れ、かつ
充分に高分子量化されたものであるので、製紙用歩留ま
り向上剤および濾水性向上剤、産業廃水用および下水し
尿処理用の凝集剤および脱水剤などの用途に好適であ
る。The polymer flocculant of the present invention comprises the water-in-oil type cationic polymer emulsion of the present invention as a main component, and the performance is remarkably improved as compared with the conventional polymer flocculant, and the polymer flocculant is stored. Emulsion particles do not precipitate or re-aggregate during storage, have excellent storage stability and water solubility, and have a sufficiently high molecular weight. Therefore, they are retention aids for papermaking and drainage improvers, for industrial wastewater. It is also suitable for use as a flocculant and a dehydrating agent for treating sewage and urine.
【0025】[0025]
【実施例】以下実施例を挙げて本発明を具体的に説明す
るが、本発明は、その主旨を越えない限り、以下の実施
例に限定されるものではない。 (実施例1)2リットルビーカーにて疎水性有機液体と
してn−ヘキサン640gおよび非イオン性界面活性剤
としてポリオキシエチレンステアリルエーテル80gを
混合し、オイル液を作製した。別に1リットルビーカー
にてジメチルアミノエチルメタアクリレート塩酸塩36
0g(80%水溶液)およびアクリルアミド192gを
イオン交換水316gに溶解し、単量体水溶液を作製し
た。オイル液に対してホモジナイザーを用い、8000
rpm にて攪拌しながら単量体水溶液を徐々に加えた。添
加終了後、180分間乳化分散を継続し(平均循環数:
3000パス)、モノマーエマルジョンを作製した。攪
拌機、温度計および窒素導入管を接続した2リットルの
3つ口セパラブルフラスコに作製したモノマーエマルジ
ョンを全量仕込み、窒素ガスを1.5リットル/分の流
量で120分間バブリングし、モノマーエマルジョンを
脱気した。次に、このモノマーエマルジョンの温度を3
5℃の一定温度に保持した後、重合開始剤として0.1
%塩化第一鉄水溶液28gおよび0.1%過硫酸アンモ
ニウム14gを順次添加して重合を開始した。約4時間
後に重合は終了し、重量平均粒子径が0.21μm(光
散乱法にて測定)の油中水型カチオン性ポリマーエマル
ジョンを得た。EXAMPLES The present invention will be specifically described with reference to the following examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. (Example 1) 640 g of n-hexane as a hydrophobic organic liquid and 80 g of polyoxyethylene stearyl ether as a nonionic surfactant were mixed in a 2 liter beaker to prepare an oil liquid. Separately, in a 1 liter beaker, dimethylaminoethyl methacrylate hydrochloride 36
0 g (80% aqueous solution) and 192 g of acrylamide were dissolved in 316 g of ion-exchanged water to prepare a monomer aqueous solution. 8000 using a homogenizer for the oil liquid
The monomer aqueous solution was gradually added while stirring at rpm. After the addition was completed, the emulsion dispersion was continued for 180 minutes (average circulation number:
3000 passes) to prepare a monomer emulsion. A 2-liter 3-neck separable flask connected with a stirrer, a thermometer and a nitrogen inlet tube was charged with the whole amount of the monomer emulsion prepared, and nitrogen gas was bubbled at a flow rate of 1.5 liter / min for 120 minutes to remove the monomer emulsion. I noticed. Next, the temperature of this monomer emulsion is set to 3
After maintaining at a constant temperature of 5 ° C., 0.1 as a polymerization initiator
% Of an aqueous ferrous chloride solution and 14 g of 0.1% ammonium persulfate were sequentially added to initiate polymerization. Polymerization was completed after about 4 hours, and a water-in-oil type cationic polymer emulsion having a weight average particle diameter of 0.21 μm (measured by a light scattering method) was obtained.
【0026】(実施例2〜5)また、同様の方法で疎水
性有機液体、非イオン性界面活性剤、単量体などの組成
と重合開始剤を変更して重合を行うことによって油中水
型カチオン性ポリマーエマルジョンを得た。それらの組
成、重合開始剤、モノマーエマルジョンの重量平均粒子
径および重合後のポリマーエマルジョンの重量平均粒子
径を併せて表1に示す。(Examples 2 to 5) Further, by changing the composition of the hydrophobic organic liquid, the nonionic surfactant, the monomer and the like and the polymerization initiator in the same manner, polymerization is carried out to give water in oil. A type cationic polymer emulsion was obtained. Table 1 also shows their composition, polymerization initiator, weight average particle diameter of the monomer emulsion and weight average particle diameter of the polymer emulsion after polymerization.
【0027】[0027]
【表1】 [Table 1]
【0028】(比較例1)実施例1の重合条件と同様の
方法で、ホモジナイザーの回転数と乳化時間を変更し、
モノマーエマルジョンの重量平均粒子径および重合後の
ポリマーエマルジョンの重量平均粒子径を本発明の範囲
外としたポリマーエマルジョンを得た。 (比較例2)実施例3の重合条件と同様の方法で、ホモ
ジナイザーの回転数と乳化時間を変更し、モノマーエマ
ルジョンの重量平均粒子径および重合後のポリマーエマ
ルジョンの重量平均粒子径を本発明の範囲外としたポリ
マーエマルジョンを得た。 (比較例3)実施例5の重合条件と同様の方法で、ホモ
ジナイザーの回転数と乳化時間を変更し、モノマーエマ
ルジョンの重量平均粒子径および重合後のポリマーエマ
ルジョンの重量平均粒子径を本発明の範囲外としたポリ
マーエマルジョンを得た。 (比較例4)実施例1の重合条件と同様の方法で、ホモ
ジナイザーの回転数と乳化時間・界面活性剤とイオン交
換水の組成を変更し、モノマーエマルジョンの重量平均
粒子径および重合後のポリマーエマルジョンの重量平均
粒子径を本発明の範囲外としたポリマーエマルジョンを
得た。 (比較例5)実施例1の重合条件と同様の方法で、ホモ
ジナイザーの回転数と乳化時間・界面活性剤とイオン交
換水の組成を変更し、モノマーエマルジョンの重量平均
粒子径および重合後のポリマーエマルジョンの重量平均
粒子径を本発明の範囲外としたポリマーエマルジョンを
得た。 表2に比較例1〜5の乳化条件・組成条件・モノマーエ
マルジョンの重量平均粒子径およびポリマーエマルジョ
ンの重量平均粒子径を示す。(Comparative Example 1) In the same manner as the polymerization conditions of Example 1, the number of revolutions of the homogenizer and the emulsification time were changed,
A polymer emulsion was obtained in which the weight average particle size of the monomer emulsion and the weight average particle size of the polymer emulsion after polymerization were out of the range of the present invention. (Comparative Example 2) In the same manner as in the polymerization conditions of Example 3, the number of revolutions of the homogenizer and the emulsification time were changed, and the weight average particle diameter of the monomer emulsion and the weight average particle diameter of the polymer emulsion after polymerization were determined according to the present invention. A polymer emulsion out of range was obtained. (Comparative Example 3) By changing the number of revolutions of the homogenizer and the emulsification time in the same manner as in the polymerization conditions of Example 5, the weight average particle diameter of the monomer emulsion and the weight average particle diameter of the polymer emulsion after polymerization were determined according to the present invention. A polymer emulsion out of range was obtained. (Comparative Example 4) In the same manner as in the polymerization conditions of Example 1, the number of revolutions of the homogenizer, the emulsification time, the composition of the surfactant and the ion-exchanged water were changed, and the weight average particle diameter of the monomer emulsion and the polymer after polymerization were changed. A polymer emulsion having a weight average particle size of the emulsion outside the range of the present invention was obtained. (Comparative Example 5) In the same manner as in the polymerization conditions of Example 1, the number of revolutions of the homogenizer, the emulsification time, the composition of the surfactant and the ion-exchanged water were changed, and the weight average particle diameter of the monomer emulsion and the polymer after polymerization were changed. A polymer emulsion having a weight average particle size of the emulsion outside the range of the present invention was obtained. Table 2 shows the emulsification conditions / composition conditions, the weight average particle size of the monomer emulsion and the weight average particle size of the polymer emulsion of Comparative Examples 1 to 5.
【0029】[0029]
【表2】 [Table 2]
【0030】実施例1〜5、比較例1〜5によって得ら
れた各ポリマーエマルジョンの重合収率、有姿粘度、
0.2%水溶液粘度、重量平均分子量(Mw)、エマル
ジョン状態を表3に示した。重合収率は、液体クロマト
グラフィーにて測定し、有姿粘度および0.2%水溶液
粘度は、B型回転粘度計(ローターNo.3,30rp
m)にて30℃で測定し、重量平均分子量は、GPCに
て測定した。また、エマルジョン状態は、目視によりエ
マルジョンの分散性と均一性を評価した。Polymerization yields, physical viscosities of the polymer emulsions obtained in Examples 1 to 5 and Comparative Examples 1 to 5,
Table 3 shows the viscosity of 0.2% aqueous solution, weight average molecular weight (Mw), and emulsion state. The polymerization yield was measured by liquid chromatography. The physical viscosity and 0.2% aqueous solution viscosity were measured using a B-type rotational viscometer (rotor No. 3, 30 rp).
m) at 30 ° C., and the weight average molecular weight was measured by GPC. As for the emulsion state, the dispersibility and uniformity of the emulsion were visually evaluated.
【0031】[0031]
【表3】 [Table 3]
【0032】次に、実施例1〜5、比較例1〜5によっ
て得られた各ポリマーエマルジョンの保存安定性を調べ
るために、各ポリマーエマルジョンを製造直後から60
日間40℃の恒温槽中に保管し、有姿粘度とエマルジョ
ン状態を経時的に測定した。これら保存安定性の測定結
果を表4に示す。Next, in order to examine the storage stability of each polymer emulsion obtained in Examples 1 to 5 and Comparative Examples 1 to 5, each polymer emulsion was prepared from 60 immediately after its production.
It was stored in a constant temperature bath at 40 ° C for a day, and the apparent viscosity and emulsion state were measured with time. Table 4 shows the results of these storage stability measurements.
【0033】[0033]
【表4】 [Table 4]
【0034】表3〜表4に示すように、本発明の製造方
法に従って作られた実施例1〜5の油中水型ポリマーエ
マルジョンは、比較例1〜5の油中水型ポリマーエマル
ジョンに比して高分子量でかつエマルジョンの分散性、
均一性、保存安定性に優れ、有姿粘度が低いものである
ことがわかる。As shown in Tables 3 to 4, the water-in-oil type polymer emulsions of Examples 1 to 5 prepared according to the production method of the present invention were compared with the water-in-oil type polymer emulsions of Comparative Examples 1 to 5. Has high molecular weight and dispersibility of emulsion,
It can be seen that it has excellent uniformity and storage stability, and has a low physical viscosity.
【0035】(実施例6)パルプスラリー(NBKP,
濃度:0.5%,CSF:210ml)に、填料として対
パルプ固形分当り10%の酸化チタンを添加してスラリ
ーを調整した。このスラリー1500mlを硫酸にてpH
4.5に調整した後、実施例1〜5、比較例1〜5で得
られたポリマーエマルジョンからなる高分子凝集剤の
0.1%水溶液を添加し、プロペラ羽根付き攪拌機を用
いて500rpm で60秒間攪拌し、フロックを形成させ
た。DDJテスター(TAPPIスタンダード,100
メッシュ金網)を用いて、凝集したスラリーを500rp
m で30秒間攪拌した後濾過し、濾液のSS濃度を測定
した。結果を表5に示す。Example 6 Pulp slurry (NBKP,
A slurry was prepared by adding 10% titanium oxide to the pulp solids as a filler to a concentration of 0.5% and CSF of 210 ml. The pH of 1500 ml of this slurry was adjusted with sulfuric acid.
After adjusting to 4.5, a 0.1% aqueous solution of a polymer flocculant consisting of the polymer emulsions obtained in Examples 1 to 5 and Comparative Examples 1 to 5 was added, and the mixture was stirred at 500 rpm using a stirrer with a propeller blade. Stir for 60 seconds to allow flock formation. DDJ tester (TAPPI standard, 100
(500 mesh) using a mesh wire mesh)
The mixture was stirred at m 3 for 30 seconds and then filtered, and the SS concentration of the filtrate was measured. The results are shown in Table 5.
【0036】[0036]
【表5】 [Table 5]
【0037】(実施例7)パルプスラリー(NBKP,
濃度:1.0%,CSF:440ml)に、填料として対
パルプ固形分当り20%の重炭酸ナトリウムを添加して
スラリーを調整した。このスラリー1000mlに対し
て、実施例1〜5、比較例1〜5で得られたポリマーエ
マルジョンからなる高分子凝集剤の0.1%水溶液を添
加し、プロペラ羽根付き攪拌機を用いて500rpm で6
0秒間攪拌し、フロックを形成させた。カナディアンス
タンダードフリーネステスターを用いて、凝集したスラ
リーの濾水度を測定した。結果を表6に示す。Example 7 Pulp slurry (NBKP,
Concentration: 1.0%, CSF: 440 ml), a slurry was prepared by adding 20% of sodium bicarbonate to the pulp solid content as a filler. To 1000 ml of this slurry, a 0.1% aqueous solution of a polymer flocculant consisting of the polymer emulsions obtained in Examples 1 to 5 and Comparative Examples 1 to 5 was added, and the mixture was stirred at 500 rpm using a stirrer with a propeller blade.
Stir for 0 seconds to allow flock formation. The freeness of the agglomerated slurry was measured using a Canadian Standard Freeness Tester. The results are shown in Table 6.
【0038】[0038]
【表6】 [Table 6]
【0039】(実施例8)紙パルプ排水の生物処理によ
り発生した余剰汚泥(pH5.8,SS濃度:2.0
%)の200mlに対して、実施例1〜5、比較例1〜5
で得られたポリマーエマルジョンからなる高分子凝集剤
の0.1%水溶液を添加し、プロペラ羽根付き攪拌機を
用いて500rpm で90秒間攪拌し、フロックを形成さ
せた。凝集したスラリーに対して、ヌッチェテスト(1
00メッシュナイロン濾布)を行い、30秒後の濾液量
を測定した。さらに、得られたフロックを遠心脱水し
(100メッシュナイロン濾布,3000rpm ,1
分)、フロックの含水率を測定した。結果を表7に示
す。(Example 8) Excess sludge (pH 5.8, SS concentration: 2.0) generated by biological treatment of paper pulp wastewater
%) Of 200 ml, Examples 1-5, Comparative Examples 1-5
A 0.1% aqueous solution of a polymer flocculant consisting of the polymer emulsion obtained in 1. was added, and the mixture was stirred for 90 seconds at 500 rpm using a stirrer with a propeller blade to form flocs. The Nutsche test (1
00 mesh nylon filter cloth) and the amount of filtrate after 30 seconds was measured. Further, the resulting flocs were centrifugally dehydrated (100 mesh nylon filter cloth, 3000 rpm, 1
Min), and the water content of the floc was measured. The results are shown in Table 7.
【0040】[0040]
【表7】 [Table 7]
【0041】表5〜表7に示すように、本発明による油
中水型ポリマーエマルジョンタイプの高分子凝集剤は、
比較例のポリマーエマルジョンからなる高分子凝集剤に
比して製紙用歩留まり向上剤および濾水性向上剤、産業
廃水用の脱水剤などの用途に対し、優れた性能を示すこ
とがわかる。As shown in Tables 5 to 7, the water-in-oil type polymer emulsion type polymer flocculants according to the present invention are
It can be seen that, as compared with the polymer flocculant composed of the polymer emulsion of Comparative Example, it exhibits excellent performance for applications such as a retention improver for papermaking and a drainage improver, and a dehydrating agent for industrial wastewater.
【0042】[0042]
【発明の効果】本発明の油中水型カチオン性エマルジョ
ンは、カチオン性ビニル単量体を水、疎水性有機液体、
非イオン性界面活性剤の存在下で単独重合、またはこれ
と他の水溶性ビニル単量体と共重合させて得られる、特
定の(A)ポリマーの濃度、(B)疎水性有機液体の濃
度、(C)非イオン性界面活性剤の濃度を有し、かつ
(D)ポリマーエマルジョンの重量平均粒子径が、0.
3μm以下である油中水型カチオン性エマルジョンであ
って、水溶性、分散安定性、保存安定性が良好であり、
かつ有姿粘度が低いものである。重合開始前に重量平均
粒子径0.3μm以下の安定な油中水型のモノマーエマ
ルジョンを形成させた後、重合を開始することにより本
発明の油中水型カチオン性エマルジョンを容易に製造す
ることができる。本発明の油中水型カチオン性エマルジ
ョンを主成分とする高分子凝集剤は、従来にない超微粒
子径のエマルジョン粒子を有し、保存安定性、水溶解性
に優れており、かつ充分に高分子量化されたものであり
製紙用歩留まり向上剤および濾水性向上剤、産業廃水用
および下水し尿処理用の凝集剤および脱水剤などの用途
に対して、従来の高分子凝集剤に比べ、高い性能を示
す。本発明においては、高分子量化するための重合条件
を選択すれば保存安定性が悪化するという従来の油中水
型ポリマーエマルジョンにおける大きな問題を解決し、
性能と保存安定性の両者を充分に満足させることができ
るので、その産業上の利用価値は大きい。The water-in-oil type cationic emulsion of the present invention comprises a cationic vinyl monomer, water, a hydrophobic organic liquid,
Specific (A) polymer concentration, (B) concentration of hydrophobic organic liquid obtained by homopolymerization in the presence of a nonionic surfactant or by copolymerization thereof with another water-soluble vinyl monomer , (C) a nonionic surfactant concentration, and (D) the polymer emulsion has a weight average particle size of 0.
A water-in-oil type cationic emulsion having a particle size of 3 μm or less, which has good water solubility, dispersion stability, and storage stability,
It also has a low physical viscosity. To easily produce the water-in-oil type cationic emulsion of the present invention by forming a stable water-in-oil type monomer emulsion having a weight average particle size of 0.3 μm or less before starting the polymerization and then initiating the polymerization. You can The polymer flocculant containing the water-in-oil type cationic emulsion of the present invention as a main component has emulsion particles having an ultrafine particle diameter which has never been used, is excellent in storage stability and water solubility, and is sufficiently high. Higher performance than conventional polymer flocculants for applications such as retention aids and drainage improvers for papermaking, flocculants for industrial wastewater and sewage and sewage treatment, and dehydrating agents. Indicates. In the present invention, solving the big problem in the conventional water-in-oil polymer emulsion that the storage stability is deteriorated by selecting the polymerization conditions for increasing the molecular weight,
Since both performance and storage stability can be fully satisfied, its industrial utility value is great.
フロントページの続き (72)発明者 橋本 忠義 神奈川県川崎市川崎区扇町5−1 昭和電 工株式会社化学品研究所内Continued Front Page (72) Inventor Tadayoshi Hashimoto 5-1 Ogimachi, Kawasaki-ku, Kawasaki-shi, Kanagawa Showa Denko K.K.
Claims (3)
ン性ビニル単量体を水、疎水性有機液体、非イオン性界
面活性剤の存在下で単独重合、またはこれと他の水溶性
ビニル単量体と共重合させて得られる油中水型ポリマー
エマルジョンであって、 (A)ポリマーの濃度が、20〜70重量%であり、 (B)疎水性有機液体の濃度が、10〜50重量%であ
り、 (C)非イオン性界面活性剤の濃度が、8重量%以下で
あり、そして (D)ポリマーエマルジョンの重量平均粒子径が、0.
3μm以下であることを特徴とする油中水型カチオン性
エマルジョン。 【化1】 (式中、Aは酸素原子またはNH;Zは炭素数1〜4の
アルキレン基または炭素数2〜4のヒドロキシアルキレ
ン基;R1 は水素またはメチル基;R2 は炭素数1〜4
のアルキル基、炭素数2〜4のヒドロキシアルキル基ま
たはベンジル基;R3 、R4 はそれぞれ独立に炭素数1
〜4のアルキル基または炭素数2〜4のヒドロキシアル
キル基;X- は塩を形成する陰イオンを表わす。)1. A cationic vinyl monomer represented by the following general formula (Formula 1) is homopolymerized in the presence of water, a hydrophobic organic liquid, or a nonionic surfactant, or a water-soluble vinyl thereof and another water-soluble vinyl monomer. A water-in-oil polymer emulsion obtained by copolymerizing with a monomer, wherein the concentration of (A) polymer is 20 to 70% by weight, and the concentration of (B) hydrophobic organic liquid is 10 to 50%. % By weight, (C) the concentration of the nonionic surfactant is 8% by weight or less, and (D) the weight average particle size of the polymer emulsion is 0.
A water-in-oil type cationic emulsion characterized by having a size of 3 μm or less. [Chemical 1] (In the formula, A is an oxygen atom or NH; Z is an alkylene group having 1 to 4 carbon atoms or a hydroxyalkylene group having 2 to 4 carbon atoms; R 1 is hydrogen or a methyl group; R 2 is 1 to 4 carbon atoms.
Alkyl group, a C2-C4 hydroxyalkyl group or a benzyl group; R 3 and R 4 are each independently C 1
To 4 alkyl or hydroxyalkyl group having 2 to 4 carbon atoms; X - represents an anion which forms a salt. )
ン性ビニル単量体を水、疎水性有機液体、非イオン性界
面活性剤の存在下で単独重合、またはこれと他の水溶性
ビニル単量体と共重合させ、油中水型ポリマーエマルジ
ョンを製造する時、重合開始前に重量平均粒子径0.3
μm以下の安定な油中水型のモノマーエマルジョンを形
成させた後、重合を開始することを特徴とする油中水型
カチオン性ポリマーエマルジョンの製造方法。 【化2】 (式中、Aは酸素原子またはNH;Zは炭素数1〜4の
アルキレン基または炭素数2〜4のヒドロキシアルキレ
ン基;R1 は水素またはメチル基;R2 は炭素数1〜4
のアルキル基、炭素数2〜4のヒドロキシアルキル基ま
たはベンジル基;R3 、R4 はそれぞれ独立に炭素数1
〜4のアルキル基または炭素数2〜4のヒドロキシアル
キル基;X- は塩を形成する陰イオンを表わす。)2. A homopolymerization of a cationic vinyl monomer represented by the following general formula (Formula 2) in the presence of water, a hydrophobic organic liquid or a nonionic surfactant, or a water-soluble vinyl thereof and another water-soluble vinyl monomer. When a water-in-oil type polymer emulsion is produced by copolymerizing with a monomer, the weight average particle size is 0.3 before starting the polymerization.
A method for producing a water-in-oil type cationic polymer emulsion, which comprises forming a stable water-in-oil type monomer emulsion having a size of not more than μm and then initiating the polymerization. [Chemical 2] (In the formula, A is an oxygen atom or NH; Z is an alkylene group having 1 to 4 carbon atoms or a hydroxyalkylene group having 2 to 4 carbon atoms; R 1 is hydrogen or a methyl group; R 2 is 1 to 4 carbon atoms.
Alkyl group, a C2-C4 hydroxyalkyl group or a benzyl group; R 3 and R 4 are each independently C 1
To 4 alkyl or hydroxyalkyl group having 2 to 4 carbon atoms; X - represents an anion which forms a salt. )
ジョンを主成分とする高分子凝集剤。3. A polymer flocculant containing the water-in-oil polymer emulsion according to claim 1 as a main component.
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JP4339502A JP2671249B2 (en) | 1992-11-27 | 1992-11-27 | Water-in-oil type cationic emulsion, its production method and use as a polymer flocculant |
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---|---|---|---|
JP4339502A JP2671249B2 (en) | 1992-11-27 | 1992-11-27 | Water-in-oil type cationic emulsion, its production method and use as a polymer flocculant |
Publications (2)
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JPH06157668A true JPH06157668A (en) | 1994-06-07 |
JP2671249B2 JP2671249B2 (en) | 1997-10-29 |
Family
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JPH09225499A (en) * | 1995-12-21 | 1997-09-02 | Hymo Corp | Organic sludge dehydrator, treatment of organic and production of organic sludge dehydrator |
JPH09276605A (en) * | 1996-04-16 | 1997-10-28 | Kurita Water Ind Ltd | Flocculant in water-in-oil type emulsion state |
JPH1133600A (en) * | 1997-05-21 | 1999-02-09 | Hymo Corp | Method for dewatering construction aggregate washing sludge |
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JP2002114810A (en) * | 2000-08-03 | 2002-04-16 | Hymo Corp | Method for producing water-in-oil type polymer emulsion and method for using the same |
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