JP2010155956A - Sulfonic acid group-containing amphoteric aqueous water-soluble polymer solution and method for producing the same - Google Patents
Sulfonic acid group-containing amphoteric aqueous water-soluble polymer solution and method for producing the same Download PDFInfo
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本発明は、スルホン酸基を含有した両性水溶性高分子が水に溶解したスルホン酸基含有両性水溶性高分子水溶液およびその製造方法に関する。 The present invention relates to a sulfonic acid group-containing amphoteric water-soluble polymer aqueous solution in which an amphoteric water-soluble polymer containing a sulfonic acid group is dissolved in water, and a method for producing the same.
近年、水溶性高分子は、廃水処理、製紙・紙加工、化粧品・トイレタリー、あるいは塗料・インキなどの幅広い分野に利用されている。特に、水溶性高分子の中でも、分子鎖中にカチオン基とアニオン基の両方を有する、いわゆる両性高分子は、帯電防止剤、ヘアセット剤、あるいは汚泥脱水剤などの用途に利用されている。
一般に、両性水溶性高分子は水に溶解した状態で用いられるため、アニオン基を、酸性物質の存在下でその解離を抑制できるカルボキシ基等の弱酸にすることが多いが、用途によっては、スルホン酸基にすることもある。しかしながら、スルホン酸基などの強酸にすると、酸性物質の存在下においてもその解離を抑制することが困難になる。そのため、同一の分子内あるいは異なる分子同士でアニオン基とカチオン基とのイオンコンプレックスを生じて、両性水溶性高分子が水に溶解しにくくなることがあった。
In recent years, water-soluble polymers have been used in a wide range of fields such as wastewater treatment, papermaking / paper processing, cosmetics / toiletries, and paints / inks. In particular, among water-soluble polymers, so-called amphoteric polymers having both a cation group and an anion group in the molecular chain are used for applications such as antistatic agents, hair set agents, sludge dehydrating agents and the like.
In general, since amphoteric water-soluble polymers are used in a state of being dissolved in water, the anionic group is often a weak acid such as a carboxy group that can suppress dissociation in the presence of an acidic substance. It may be an acid group. However, when a strong acid such as a sulfonic acid group is used, it is difficult to suppress the dissociation even in the presence of an acidic substance. For this reason, an ionic complex of an anion group and a cation group is generated in the same molecule or between different molecules, and the amphoteric water-soluble polymer may be difficult to dissolve in water.
そこで、特許文献１では、スルホン酸基を導入した両性水溶性高分子をエマルジョン化し、水に分散させて、高分子凝集脱水剤として利用することが提案されている。 Therefore, Patent Document 1 proposes emulsifying an amphoteric water-soluble polymer into which a sulfonic acid group has been introduced, dispersing it in water, and using it as a polymer coagulation dehydrating agent.
しかしながら、特許文献１に記載の両性水溶性高分子では、スルホン酸基の導入量が０．１〜３モル％と少ない上に、形態がエマルジョンであるため、用途が限定されるという問題を有していた。
本発明は、上記事情を鑑みてなされたもので、スルホン酸基の量が多いスルホン酸基含有両性水溶性高分子が水に溶解されている両性水溶性高分子水溶液およびその製造方法を提供することを目的とする。
However, the amphoteric water-soluble polymer described in Patent Document 1 has a problem that the amount of sulfonic acid group introduced is as small as 0.1 to 3 mol% and the form is an emulsion, so that the application is limited. Was.
The present invention has been made in view of the above circumstances, and provides an amphoteric water-soluble polymer aqueous solution in which a sulfonic acid group-containing amphoteric water-soluble polymer having a large amount of sulfonic acid groups is dissolved in water, and a method for producing the same. For the purpose.
［１］ スルホン酸基含有両性水溶性高分子および無機塩が水に溶解された両性水溶性高分子水溶液であって、
スルホン酸基含有両性水溶性高分子は、下記一般式（１）で表される水溶性カチオン性単量体単位５〜９０モル％と、スルホン酸基含有水溶性アニオン性単量体単位５〜５０モル％と、水溶性カチオン単量体単位およびスルホン酸基含有水溶性アニオン性単量体単位以外の他の単量体単位５〜７０モル％とを有する共重合体であることを特徴とする両性水溶性高分子水溶液。
（一般式（１）中、Ｘは酸素原子またはＮＨであり、ＹはＣｌ，Ｂｒまたは１／２ＳＯ４であり、Ｒ１は水素原子またはメチル基であり、Ｒ２およびＲ３は各々独立して水素原子、メチル基またはエチル基であり、Ｒ４は水素原子、メチル基、エチル基またはベンジル基であり、ｎは１〜３のいずれかの整数である。）
[1] An amphoteric water-soluble polymer aqueous solution in which a sulfonic acid group-containing amphoteric water-soluble polymer and an inorganic salt are dissolved in water,
The sulfonic acid group-containing amphoteric water-soluble polymer is composed of 5 to 90 mol% of a water-soluble cationic monomer unit represented by the following general formula (1) and 5 to 90% of a sulfonic acid group-containing water-soluble anionic monomer unit. It is a copolymer having 50 mol% and 5 to 70 mol% of monomer units other than the water-soluble cationic monomer unit and the sulfonic acid group-containing water-soluble anionic monomer unit. Amphoteric water-soluble polymer aqueous solution.
(In the general formula (1), X is an oxygen atom or NH, Y is Cl, Br or 1 / 2SO 4 , R 1 is a hydrogen atom or a methyl group, and R 2 and R 3 are each independently Te hydrogen atom, a methyl group or an ethyl group, R 4 is a hydrogen atom, a methyl group, an ethyl group or a benzyl radical, n is any integer of 1-3.)
［２］ スルホン酸基含有両性水溶性高分子を、無機塩存在下で水に溶解するスルホン酸基含有両性水溶性高分子水溶液の製造方法であって、
スルホン酸基含有両性水溶性高分子として、上記一般式（１）で表される水溶性カチオン性単量体５〜９０モル％と、スルホン酸基含有水溶性アニオン性単量体５〜５０モル％と、水溶性カチオン単量体およびスルホン酸基含有水溶性アニオン性単量体以外の他の単量体５〜７０モル％とを共重合させた共重合体を用いることを特徴とするスルホン酸基含有両性水溶性高分子水溶液の製造方法。
（一般式（１）中、Ｘは酸素原子またはＮＨであり、ＹはＣｌ，Ｂｒまたは１／２ＳＯ４であり、Ｒ１は水素原子またはメチル基であり、Ｒ２およびＲ３は各々独立して水素原子、メチル基またはエチル基であり、Ｒ４は水素原子、メチル基、エチル基またはベンジル基であり、ｎは１〜３のいずれかの整数である。）
［３］ 無機塩の添加量が、スルホン酸基含有両性水溶性高分子に対して０．１〜１００質量倍であることを特徴とする［２］に記載のスルホン酸基含有両性水溶性高分子水溶液の製造方法。
［４］ スルホン酸基含有両性水溶性高分子が粉末状であることを特徴とする［２］または［３］に記載のスルホン酸基含有両性水溶性高分子水溶液の製造方法。
[2] A method for producing a sulfonic acid group-containing amphoteric water-soluble polymer aqueous solution in which a sulfonic acid group-containing amphoteric water-soluble polymer is dissolved in water in the presence of an inorganic salt,
As the sulfonic acid group-containing amphoteric water-soluble polymer, 5 to 90 mol% of the water-soluble cationic monomer represented by the general formula (1), and 5 to 50 mol of the sulfonic acid group-containing water-soluble anionic monomer. % And a copolymer obtained by copolymerizing a water-soluble cationic monomer and 5 to 70 mol% of a monomer other than the sulfonic acid group-containing water-soluble anionic monomer. A method for producing an acid group-containing amphoteric water-soluble polymer aqueous solution.
(In the general formula (1), X is an oxygen atom or NH, Y is Cl, Br or 1 / 2SO 4 , R 1 is a hydrogen atom or a methyl group, and R 2 and R 3 are each independently A hydrogen atom, a methyl group or an ethyl group, R 4 is a hydrogen atom, a methyl group, an ethyl group or a benzyl group, and n is an integer of 1 to 3.)
[3] The sulfonic acid group-containing amphoteric water-soluble high composition according to [2], wherein the inorganic salt is added in an amount of 0.1 to 100 times by mass with respect to the sulfonic acid group-containing amphoteric water-soluble polymer. Manufacturing method of molecular aqueous solution.
[4] The process for producing a sulfonic acid group-containing amphoteric water-soluble polymer aqueous solution according to [2] or [3], wherein the sulfonic acid group-containing amphoteric water-soluble polymer is in a powder form.
本発明の両性水溶性高分子水溶液は、スルホン酸基の量が多いスルホン酸基含有両性水溶性高分子が水に溶解されている。
本発明の両性水溶性高分子水溶液の製造方法によれば、スルホン酸基の量が多いスルホン酸基含有両性水溶性高分子を容易に水に溶解させることができる。
In the amphoteric water-soluble polymer aqueous solution of the present invention, a sulfonic acid group-containing amphoteric water-soluble polymer having a large amount of sulfonic acid groups is dissolved in water.
According to the method for producing an amphoteric water-soluble polymer aqueous solution of the present invention, a sulfonic acid group-containing amphoteric water-soluble polymer having a large amount of sulfonic acid groups can be easily dissolved in water.
以下、本発明を詳細に説明する。
（スルホン酸基含有両性水溶性高分子水溶液）
本発明のスルホン酸基含有両性水溶性高分子水溶液は、スルホン酸基含有両性水溶性高分子および無機塩が水に溶解されたものである。
Hereinafter, the present invention will be described in detail.
(Sulphonic acid group-containing amphoteric water-soluble polymer aqueous solution)
The sulfonic acid group-containing amphoteric water-soluble polymer aqueous solution of the present invention is obtained by dissolving a sulfonic acid group-containing amphoteric water-soluble polymer and an inorganic salt in water.
［スルホン酸基含有両性水溶性高分子］
スルホン酸基含有両性水溶性高分子は、上記一般式（１）で表される水溶性カチオン性単量体単位と、スルホン酸基含有水溶性アニオン性単量体単位と、水溶性カチオン単量体単位およびスルホン酸基含有水溶性アニオン性単量体単位以外の他の単量体単位（以下、他の単量体単位と略す。）とを有する共重合体である。
[Amphoteric water-soluble polymer containing sulfonic acid groups]
The sulfonic acid group-containing amphoteric water-soluble polymer comprises a water-soluble cationic monomer unit represented by the general formula (1), a sulfonic acid group-containing water-soluble anionic monomer unit, and a water-soluble cationic monomer. And a monomer unit other than the water-soluble anionic monomer unit containing a sulfonic acid group (hereinafter abbreviated as another monomer unit).
水溶性カチオン性単量体を表す一般式（１）におけるＸは、酸素原子またはＮＨである。
Ｙは、Ｃｌ，Ｂｒまたは１／２ＳＯ４である。
Ｒ１は、水素原子またはメチル基である。
Ｒ２およびＲ３は、各々独立して、水素原子、メチル基またはエチル基である。
Ｒ４は、水素原子、メチル基、エチル基またはベンジル基である。
ｎは１〜３のいずれかの整数である。
X in the general formula (1) representing the water-soluble cationic monomer is an oxygen atom or NH.
Y is Cl, Br or 1 / 2SO 4 .
R 1 is a hydrogen atom or a methyl group.
R 2 and R 3 are each independently a hydrogen atom, a methyl group or an ethyl group.
R 4 is a hydrogen atom, a methyl group, an ethyl group or a benzyl group.
n is an integer of 1 to 3.
このような水溶性カチオン性単量体としては、例えば、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、ジエチルアミノ−２−ヒドロキシプロピル（メタ）アクリレート等のジアルキルアミノアルキル（メタ）アクリレートの塩酸塩などの３級塩や、ジアルキルアミノアルキル（メタ）アクリレートの塩化メチル付加物などのハロゲン化アルキル付加物、塩化ベンジル付加物などのハロゲン化アリール付加物などの４級塩；ジメチルアミノプロピル（メタ）アクリルアミドなどのジアルキルアミノアルキル（メタ）アクリルアミドの塩酸塩などの３級塩や、ジアルキルアミノアルキル（メタ）アクリルアミドの塩化メチル付加物などのハロゲン化アルキル付加物、塩化ベンジル付加物などのハロゲン化アリール付加物などの４級塩などが挙げられる。これらの中でも、汎用性が高く、比較的安価であることから、ジメチルアミノエチル（メタ）アクリレートの塩化メチル４級塩が好ましい。これら水溶性カチオン性単量体は、１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of such water-soluble cationic monomers include dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and diethylamino-2-hydroxypropyl (meth) acrylate. Quaternary salts such as tertiary salt such as hydrochloride, alkyl halide adduct such as methyl chloride adduct of dialkylaminoalkyl (meth) acrylate, aryl halide adduct such as benzyl chloride adduct; dimethylaminopropyl ( Tertiary salts such as dialkylaminoalkyl (meth) acrylamide hydrochloride such as meth) acrylamide, halogenated alkyl adduct such as methyl chloride adduct of dialkylaminoalkyl (meth) acrylamide, halogen such as benzyl chloride adduct Such quaternary salts such as aryl adducts. Of these, methyl chloride quaternary salt of dimethylaminoethyl (meth) acrylate is preferred because of its high versatility and relatively low cost. These water-soluble cationic monomers may be used alone or in combination of two or more.
スルホン酸基含有両性水溶性高分子における水溶性カチオン性単量体単位の含有量は、スルホン酸基含有両性水溶性高分子を１００モル％とした際の５〜９０モル％であり、４０〜７０モル％であることが好ましい。水溶性カチオン性単量体単位の含有量が５モル％未満であると、水溶性カチオン性単量体単位を有することによる効果が発揮されにくくなって、用途が限定される。水溶性カチオン性単量体単位の含有量が９５モル％を超えると、スルホン酸基含有水溶性アニオン性単量体単位の含有量が５モル％未満になるため、スルホン酸基含有水溶性アニオン性単量体単位を有することによる効果が発揮されにくくなる。 The content of the water-soluble cationic monomer unit in the sulfonic acid group-containing amphoteric water-soluble polymer is 5 to 90 mol% with respect to 100 mol% of the sulfonic acid group-containing amphoteric water-soluble polymer. It is preferable that it is 70 mol%. When the content of the water-soluble cationic monomer unit is less than 5 mol%, the effect of having the water-soluble cationic monomer unit is hardly exhibited, and the use is limited. When the content of the water-soluble cationic monomer unit exceeds 95 mol%, the content of the sulfonic acid group-containing water-soluble anionic monomer unit becomes less than 5 mol%. The effect due to having a monomeric monomer unit is hardly exhibited.
スルホン酸基含有水溶性アニオン性単量体としては、例えば、アクリルアミド−２−メチルプロパンスルホン酸単量体および／またはその塩、ビニルスルホン酸および／またはその塩、スチレンスルホン酸および／またはその塩などが挙げられる。これらの中でも、汎用性が高く、比較的安価であることから、アクリルアミド−２−メチルプロパンスルホン酸単量体および／またはその塩が好ましい。これらスルホン酸基含有水溶性アニオン性単量体は、１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of the sulfonic acid group-containing water-soluble anionic monomer include acrylamide-2-methylpropane sulfonic acid monomer and / or salt thereof, vinyl sulfonic acid and / or salt thereof, styrene sulfonic acid and / or salt thereof. Etc. Among these, an acrylamide-2-methylpropanesulfonic acid monomer and / or a salt thereof is preferable because it is highly versatile and relatively inexpensive. These sulfonic acid group-containing water-soluble anionic monomers may be used alone or in combination of two or more.
スルホン酸基含有両性水溶性高分子におけるスルホン酸基含有水溶性アニオン性単量体単位の含有量は、スルホン酸基含有両性水溶性高分子を１００モル％とした際の５〜５０モル％であり、１０〜４０モル％であることが好ましい。スルホン酸基含有水溶性アニオン性単量体単位の含有量が５モル％未満であると、スルホン酸基含有水溶性アニオン性単量体単位の含有量が５モル％未満になるため、スルホン酸基含有水溶性アニオン性単量体単位を有することによる効果が発揮されにくくなる。スルホン酸基含有水溶性アニオン性単量体単位の含有量が５０モル％を超えると、水溶性カチオン性単量体のカチオン基とイオンコンプレックスを形成するため、スルホン酸基含有両性水溶性高分子が溶解されにくくなる。 The content of the sulfonic acid group-containing water-soluble anionic monomer unit in the sulfonic acid group-containing amphoteric water-soluble polymer is 5 to 50 mol% when the sulfonic acid group-containing amphoteric water-soluble polymer is 100 mol%. Yes, and preferably 10 to 40 mol%. When the content of the sulfonic acid group-containing water-soluble anionic monomer unit is less than 5 mol%, the content of the sulfonic acid group-containing water-soluble anionic monomer unit is less than 5 mol%. The effect of having a group-containing water-soluble anionic monomer unit is hardly exhibited. When the content of the sulfonic acid group-containing water-soluble anionic monomer unit exceeds 50 mol%, an ionic group is formed with the cation group of the water-soluble cationic monomer. Becomes difficult to dissolve.
他の単量体としては、水に溶解する成分であれば特に限定されないが、用途がより広がることから、水溶性非イオン性単量体である（メタ）アクリルアミド単量体、スルホン酸基含有水溶性アニオン性単量体以外の水溶性アニオン性単量体である（メタ）アクリル酸単量体および／またはその塩が好ましい。これら他の単量体は、１種を単独で用いてもよく、２種以上を併用してもよい。 The other monomer is not particularly limited as long as it is a component that dissolves in water. However, since the use is further expanded, a (meth) acrylamide monomer that is a water-soluble nonionic monomer, containing a sulfonic acid group A (meth) acrylic acid monomer and / or a salt thereof, which is a water-soluble anionic monomer other than the water-soluble anionic monomer, is preferred. These other monomers may be used individually by 1 type, and may use 2 or more types together.
他の単量体単位の含有量は、スルホン酸基含有両性水溶性高分子を１００モル％とした際の５〜７０モル％であり、１０〜５０モル％であることが好ましい。他の単量体単位の含有量が５モル％未満であると、スルホン酸基含有両性水溶性高分子の分子量が低くなり、特に高分子量を要する高分子凝集剤用途で充分な凝集脱水性能が得られないことがある。他の単量体単位の含有量が７０モル％を超えると、水溶性カチオン性単量体およびスルホン酸基含有水溶性アニオン性単量体の含有量が少なくなるため、両性水溶性高分子の用途が限定される。 The content of other monomer units is 5 to 70 mol%, preferably 10 to 50 mol%, based on 100 mol% of the sulfonic acid group-containing amphoteric water-soluble polymer. When the content of other monomer units is less than 5 mol%, the molecular weight of the sulfonic acid group-containing amphoteric water-soluble polymer is low, and sufficient agglomeration and dewatering performance can be obtained particularly for polymer flocculant applications that require a high molecular weight. It may not be obtained. When the content of other monomer units exceeds 70 mol%, the content of the water-soluble cationic monomer and the sulfonic acid group-containing water-soluble anionic monomer is reduced. Applications are limited.
［スルホン酸基含有両性水溶性高分子の製造方法］
上記スルホン酸基含有両性水溶性高分子は、水溶性カチオン性単量体とスルホン酸基含有水溶性アニオン性単量体と他の単量体とを共重合させることにより得られる。
共重合の方法としては、例えば、共重合させる単量体を含む単量体反応液を調製し、レドックス開始剤およびアゾ系開始剤などの熱によりラジカルを発生させる開始剤を用いて、単量体反応液を共重合する水溶液断熱重合方法が挙げられる。また、重合開始前の単量体反応液を均一にシート状にし、光開始剤を用いて可視光あるいは紫外光を照射して共重合を行う水溶液光重合方法が挙げられる。これらの中でも、水溶液光重合方法が好ましい。水溶液光重合方法では、通常、共重合が終了すると、含水ゲル状の共重合体（すなわち、スルホン酸基含有両性水溶性高分子化合物の含水物）が得られる。
[Method for producing amphoteric water-soluble polymer containing sulfonic acid group]
The sulfonic acid group-containing amphoteric water-soluble polymer can be obtained by copolymerizing a water-soluble cationic monomer, a sulfonic acid group-containing water-soluble anionic monomer, and another monomer.
As a copolymerization method, for example, a monomer reaction solution containing a monomer to be copolymerized is prepared, and an initiator that generates radicals by heat such as a redox initiator and an azo-based initiator is used. An aqueous solution adiabatic polymerization method in which a body reaction solution is copolymerized. Moreover, the aqueous solution photopolymerization method which makes a monomer reaction liquid before superposition | polymerization a uniform sheet form, irradiates visible light or ultraviolet light using a photoinitiator, and performs copolymerization is mentioned. Among these, the aqueous solution photopolymerization method is preferable. In the aqueous solution photopolymerization method, a water-containing gel-like copolymer (that is, a water-containing sulfonic acid group-containing amphoteric water-soluble polymer compound) is usually obtained when the copolymerization is completed.
光開始剤としては、例えば、２−ヒドロキシ−２−メチル−１−フェニル−１−プロパノン（チバ（Ｃｉｂａ）社製、ダロキュア（ＤＡＲＯＣＵＲ）１１７３）などが挙げられる。
光開始剤の添加量は、単量体反応液１００質量部に対して０．００１〜０．１質量部であることが好ましい。光開始剤の添加量が０．００１質量部以上であれば、充分な共重合速度および共重合率を確保でき、生産性および品質を向上させることができる。また、光開始剤の添加量が０．１質量部以下であれば、共重合反応の暴走および共重合体の品質低下を防止できる。
Examples of the photoinitiator include 2-hydroxy-2-methyl-1-phenyl-1-propanone (manufactured by Ciba, DAROCUR 1173).
It is preferable that the addition amount of a photoinitiator is 0.001-0.1 mass part with respect to 100 mass parts of monomer reaction liquid. If the addition amount of the photoinitiator is 0.001 part by mass or more, a sufficient copolymerization rate and copolymerization rate can be secured, and productivity and quality can be improved. Moreover, if the addition amount of a photoinitiator is 0.1 mass part or less, runaway of a copolymerization reaction and deterioration of the quality of a copolymer can be prevented.
また、共重合を行う際には、必要に応じて連鎖移動剤を添加してもよい。連鎖移動剤としては、例えば、次亜リン酸、ホスホン酸などが挙げられる。これらの中でも、連鎖移動させやすいことから、ホスホン酸が好ましい。連鎖移動剤の添加量は、単量体反応液１００質量部に対して、０．００１〜１質量部が好ましい。連鎖移動剤の添加量が０．００１質量部以上であれば、スルホン酸基含有両性水溶性高分子を水に溶かした際に水に不溶性の架橋した共重合体の発生を抑制できる。また、連鎖移動剤の添加量が１質量部以下であれば、充分な分子量を確保できるため、特に高分子量を必要とする高分子凝集剤用途において充分な凝集脱水性が得られる。
なお、水に不溶性の架橋した共重合体の発生量は、スルホン酸基含有両性水溶性高分子水溶液を、例えば、直径２０ｃｍ、８０メッシュの篩で濾過し、篩の上に残った不溶解分を定量することにより求めることができる。
Moreover, when performing copolymerization, you may add a chain transfer agent as needed. Examples of the chain transfer agent include hypophosphorous acid and phosphonic acid. Among these, phosphonic acid is preferable because it is easily chain-transferred. The addition amount of the chain transfer agent is preferably 0.001 to 1 part by mass with respect to 100 parts by mass of the monomer reaction solution. When the addition amount of the chain transfer agent is 0.001 part by mass or more, generation of a water-insoluble crosslinked copolymer can be suppressed when the sulfonic acid group-containing amphoteric water-soluble polymer is dissolved in water. In addition, when the amount of the chain transfer agent added is 1 part by mass or less, a sufficient molecular weight can be ensured, so that sufficient aggregation and dehydrating properties can be obtained particularly in the use of a polymer flocculant requiring a high molecular weight.
The amount of the crosslinked copolymer insoluble in water is determined by the amount of insoluble matter remaining on the sieve after the sulfonic acid group-containing amphoteric water-soluble polymer aqueous solution is filtered through, for example, a sieve having a diameter of 20 cm and 80 mesh. Can be determined by quantifying
［無機塩］
無機塩は、水溶性の無機塩であり、炭素を含まない酸と塩基の中和反応によって生じる化合物、および、炭酸塩、シアン酸塩、チオシアン酸塩のような炭素を含んだ単純構造の炭素化合物である。
具体的な無機塩としては、塩化ナトリウム、塩化カリウム、塩化マグネシウム、塩化カルシウム、塩化アルミニウムなどの典型金属元素塩、塩化第一鉄、塩化第二鉄、塩化亜鉛などの遷移金属元素塩、塩化アンモニウムなどのアンモニウム塩を含む塩酸塩；硫酸ナトリウム、硫酸カリウム、硫酸マグネシウム、硫酸カルシウム、硫酸アルミニウムなどの典型金属元素塩、硫酸第一鉄、硫酸亜鉛などの遷移金属元素塩、硫酸アンモニウムなどのアンモニウム塩を含む硫酸塩；硝酸ナトリウム、硝酸カリウム、硝酸マグネシウム、硝酸カルシウム、硝酸アルミニウムなどの典型金属元素塩、硝酸第一鉄、硝酸第二鉄、硝酸亜鉛などの遷移金属元素塩、硝酸アンモニウムなどのアンモニウム塩を含む硝酸塩；リン酸ナトリウム、リン酸カリウム、リン酸マグネシウム、リン酸カルシウム、リン酸アルミニウムなどの典型金属元素塩、リン酸第一鉄、リン酸第二鉄などの遷移金属元素塩、リン酸アンモニウムなどのアンモニウム塩を含むリン酸塩；炭酸ナトリウム、炭酸カリウム、炭酸マグネシウム、炭酸カルシウム、炭酸アルミニウムなどの典型金属元素塩、炭酸第一鉄などの遷移金属元素塩、炭酸アンモニウムなどのアンモニウム塩を含む炭酸塩などが挙げられる。これらの中でも、少量添加かつ比較的安価である塩化ナトリウムが好ましい。これら無機塩は、１種を単独で用いてもよいし、２種以上を併用してもよい。
[Inorganic salt]
Inorganic salts are water-soluble inorganic salts, compounds produced by neutralization reactions of carbon-free acids and bases, and carbons with a simple structure including carbon such as carbonates, cyanates, and thiocyanates. A compound.
Specific inorganic salts include typical metal element salts such as sodium chloride, potassium chloride, magnesium chloride, calcium chloride and aluminum chloride, transition metal element salts such as ferrous chloride, ferric chloride and zinc chloride, ammonium chloride Hydrochloric acid salts containing ammonium salts such as: Sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate, aluminum sulfate and other typical metal element salts, ferrous sulfate, zinc sulfate and other transition metal element salts, ammonium sulfate and other ammonium salts Contains sulfate salts; including typical metal element salts such as sodium nitrate, potassium nitrate, magnesium nitrate, calcium nitrate, and aluminum nitrate; transition metal element salts such as ferrous nitrate, ferric nitrate, and zinc nitrate; and ammonium salts such as ammonium nitrate Nitrate; sodium phosphate, potassium phosphate, lithium Phosphate including typical metal element salts such as magnesium phosphate, calcium phosphate and aluminum phosphate, transition metal element salts such as ferrous phosphate and ferric phosphate, ammonium salts such as ammonium phosphate; sodium carbonate, carbonate Examples include typical metal element salts such as potassium, magnesium carbonate, calcium carbonate, and aluminum carbonate, transition metal element salts such as ferrous carbonate, and carbonates including ammonium salts such as ammonium carbonate. Among these, sodium chloride which is added in a small amount and is relatively inexpensive is preferable. These inorganic salts may be used alone or in combination of two or more.
スルホン酸基含有両性水溶性高分子水溶液には、ｐＨが２〜１３の範囲になるように、ｐＨコントロール剤として、スルファミン酸などの酸性物質あるいは水酸化ナトリウムなどのアルカリ性物質が含まれてもよい。 The sulfonic acid group-containing amphoteric water-soluble polymer aqueous solution may contain an acidic substance such as sulfamic acid or an alkaline substance such as sodium hydroxide as a pH control agent so that the pH is in the range of 2 to 13. .
スルホン酸基含有両性水溶性高分子は、濃度０．５質量％で水中に溶解した水溶液（以下、スルホン酸基含有両性水溶性高分子の水溶液を「ポリマー水溶液」という。）とした際の塩粘度で、通常、５〜２００ｍＰａ・ｓ、好ましくは１０〜１００ｍＰａ・ｓである。０．５質量％ポリマー水溶液とした際の塩粘度が５ｍＰａ・ｓ以上であれば、特に高粘度を必要とする高分子凝集剤用途において充分な凝集性が得られる。また、０．５質量％ポリマー水溶液とした際の塩粘度が２００ｍＰａ・ｓ以下であれば、スルホン酸基含有両性水溶性高分子を水に溶かした際の水に不溶性の架橋した共重合体の発生を抑制できる。
ここで、塩粘度とは、スルホン酸基含有両性水溶性高分子を、スルホン酸基含有両性水溶性高分子に対して０．１〜１００質量倍の無機塩を含む水溶液に溶解させて０．５質量％ポリマー水溶液とした際の、Ｂ型粘度計にて測定した、２５℃における粘度のことである。なお、スルホン酸基含有両性水溶性高分子および無機塩を水に溶解する順番に特に制限はなく、スルホン酸基含有両性水溶性高分子を先に水に溶解してもよいし、無機塩を先に水に溶解してもよい。あるいは、スルホン酸基含有両性水溶性高分子および無機塩を同時に水に溶解してもよい。さらに、簡便性からスルホン酸基含有両性水溶性高分子が粉末状の場合は、あらかじめ無機塩と粉体同士で混合し、水に溶解してもよい。
The sulfonic acid group-containing amphoteric water-soluble polymer is a salt when an aqueous solution dissolved in water at a concentration of 0.5% by mass (hereinafter, the aqueous solution of the sulfonic acid group-containing amphoteric water-soluble polymer is referred to as “polymer aqueous solution”). The viscosity is usually 5 to 200 mPa · s, preferably 10 to 100 mPa · s. If the salt viscosity is 0.5 mPa · s or more when a 0.5% by mass polymer aqueous solution is used, sufficient cohesiveness can be obtained particularly in a polymer flocculant application requiring high viscosity. In addition, if the salt viscosity when the 0.5 mass% polymer aqueous solution is 200 mPa · s or less, the water-insoluble crosslinked copolymer when the sulfonic acid group-containing amphoteric water-soluble polymer is dissolved in water is used. Generation can be suppressed.
Here, the salt viscosity is a value obtained by dissolving a sulfonic acid group-containing amphoteric water-soluble polymer in an aqueous solution containing 0.1 to 100 times by mass inorganic salt with respect to the sulfonic acid group-containing amphoteric water-soluble polymer. It is the viscosity at 25 ° C. measured with a B-type viscometer when a 5% by mass polymer aqueous solution is obtained. The order of dissolving the sulfonic acid group-containing amphoteric water-soluble polymer and the inorganic salt in water is not particularly limited, and the sulfonic acid group-containing amphoteric water-soluble polymer may be dissolved in water first, You may melt | dissolve in water previously. Alternatively, the sulfonic acid group-containing amphoteric water-soluble polymer and the inorganic salt may be simultaneously dissolved in water. Furthermore, for convenience, when the sulfonic acid group-containing amphoteric water-soluble polymer is in a powder form, it may be mixed in advance with an inorganic salt and powder and dissolved in water.
スルホン酸基含有両性水溶性高分子の塩粘度は、スルホン酸基含有両性水溶性高分子の分子量、イオン性の割合、分子量分布、製造方法、組成分布、親水性・疎水性度合いなどの調整によって制御できる。
例えば、分子量を高くする程、イオン性の割合を低くする程、塩粘度の値が増加する傾向にある。一方、分子量を低くする程、イオン性の割合を高くする程、塩粘度の値が減少する傾向にある。
The salt viscosity of the sulfonic acid group-containing amphoteric water-soluble polymer is adjusted by adjusting the molecular weight, ionic ratio, molecular weight distribution, production method, composition distribution, hydrophilicity / hydrophobicity degree, etc. of the sulfonic acid group-containing amphoteric water-soluble polymer. Can be controlled.
For example, the value of salt viscosity tends to increase as the molecular weight increases or the ionic ratio decreases. On the other hand, the lower the molecular weight, the higher the ionic ratio, the lower the value of salt viscosity.
（スルホン酸基含有両性水溶性高分子水溶液の製造方法）
本発明のスルホン酸基含有両性水溶性高分子水溶液の製造方法は、スルホン酸基含有両性水溶性高分子を、無機塩存在下で水に溶解する方法である。
その際に使用するスルホン酸基含有両性水溶性高分子は、水への溶解性が向上することから、粉末状であることが好ましい。
(Method for producing sulfonic acid group-containing amphoteric water-soluble polymer aqueous solution)
The method for producing a sulfonic acid group-containing amphoteric water-soluble polymer aqueous solution of the present invention is a method of dissolving a sulfonic acid group-containing amphoteric water-soluble polymer in water in the presence of an inorganic salt.
The sulfonic acid group-containing amphoteric water-soluble polymer used at that time is preferably in the form of a powder because solubility in water is improved.
無機塩の添加量は、スルホン酸基含有両性水溶性高分子に対して０．１〜１００質量倍であり、１〜５０質量倍であることが好ましい。無機塩の添加量が０．１質量倍以上であれば、スルホン酸基含有両性水溶性高分子が水により溶解しやすくなり、１００質量倍以下であれば、スルホン酸基含有両性水溶性高分子の水溶液の塩粘度が適度なものとなる。 The addition amount of the inorganic salt is 0.1 to 100 times by mass and preferably 1 to 50 times by mass with respect to the sulfonic acid group-containing amphoteric water-soluble polymer. If the addition amount of the inorganic salt is 0.1 mass times or more, the sulfonic acid group-containing amphoteric water-soluble polymer is easily dissolved in water, and if it is 100 mass times or less, the sulfonic acid group-containing amphoteric water-soluble polymer. The salt viscosity of the aqueous solution is moderate.
本発明では、スルホン酸基含有両性水溶性高分子のスルホン酸基の量が５モル％以上と多いにもかかわらず、無機塩が存在することによって、スルホン酸基含有両性水溶性高分子が水に容易に溶解するようになっている。
このようなスルホン酸基含有両性水溶性高分子は、廃水処理、製紙・紙加工、化粧品・トイレタリー、あるいは塗料・インキなどの分野に好適に利用できる。中でも、より高い分子量が要求される汚泥の凝集脱水処理剤として特に適している。
In the present invention, although the amount of sulfonic acid group of the sulfonic acid group-containing amphoteric water-soluble polymer is as large as 5 mol% or more, the presence of the inorganic salt makes the sulfonic acid group-containing amphoteric water-soluble polymer water. It is designed to dissolve easily.
Such sulfonic acid group-containing amphoteric water-soluble polymers can be suitably used in the fields of wastewater treatment, papermaking / paper processing, cosmetics / toiletries, paints / inks, and the like. Among these, it is particularly suitable as an aggregating and dehydrating agent for sludge that requires a higher molecular weight.
以下、本発明を実施例により具体的に説明するが、本発明はこれらに限定されるものではない。なお、また、例中の「％」は、特に断らない限り、質量％を示す。また、得られるスルホン酸基含有両性水溶性高分子を「水溶性高分子」と略す場合がある。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. In addition, “%” in the examples indicates mass% unless otherwise specified. In addition, the resulting sulfonic acid group-containing amphoteric water-soluble polymer may be abbreviated as “water-soluble polymer”.
以下の実施例および比較例において、下記に示す０．５％塩粘度、および０．５％不溶解分量の測定には、スルホン酸基含有両性水溶性高分子が粉末状のものを用いた。 In the following examples and comparative examples, the sulfonic acid group-containing amphoteric water-soluble polymer in powder form was used for the measurement of 0.5% salt viscosity and 0.5% insoluble content shown below.
（０．５％塩粘度の測定）
試料２．３８ｇをスルホン酸基含有両性水溶性高分子に対して４．２〜４２．０質量倍の無機塩を含む水溶液に溶解し、０．５％ポリマー水溶液５００ｇを調製した。そして、Ｂ型粘度計（東機産業社製）を用い、温度２５℃、回転速度６０ｒｐｍの条件で、５分後のポリマー水溶液の塩粘度を測定した。
(Measurement of 0.5% salt viscosity)
2.38 g of the sample was dissolved in an aqueous solution containing an inorganic salt 4.2 to 22.0 times by mass with respect to the sulfonic acid group-containing amphoteric water-soluble polymer to prepare 500 g of a 0.5% aqueous polymer solution. Then, using a B-type viscometer (manufactured by Toki Sangyo Co., Ltd.), the salt viscosity of the aqueous polymer solution after 5 minutes was measured under the conditions of a temperature of 25 ° C. and a rotation speed of 60 rpm.
（０．５％不溶解分量の測定）
上記の方法により得られた０．５％ポリマー水溶液の全量（５００ｇ）を、直径２０ｃｍ、８０メッシュの篩で濾過し、篩上の残留物（不溶解分）の水分を拭き取り、その質量を測定した。
(Measurement of 0.5% insoluble content)
The whole amount (500 g) of the 0.5% polymer aqueous solution obtained by the above method is filtered through a sieve having a diameter of 20 cm and 80 mesh, and the residue (insoluble matter) on the sieve is wiped off and its mass is measured. did.
＜製造例１＞
水溶性カチオン性単量体としてジメチルアミノエチルメタクリレート塩化メチル４級塩（以下、「ＤＭＣ」と略す。）（大阪有機化学工業社製、純度８０％）２８８．８ｇおよびジメチルアミノエチルアクリレート塩化メチル４級塩（以下、「ＤＭＥ」と略す。）（大阪有機化学工業社製、純度８０％）２８８．８ｇ、スルホン酸基含有水溶性アニオン性単量体としてアクリルアミド−２−メチルプロパンスルホン酸（以下、「ＡＭＰＳ」と略す。）（東亞合成社製、純度５０％）２６４．０ｇ、他の単量体としてアクリルアミド（以下、「ＡＡＭ」と略す。）（ダイヤニトリックス社製、純度５０％）１３２．０ｇを、２０００ｍＬ褐色耐熱瓶に投入し、全単量体濃度５５％、総質量１２００ｇになるように蒸留水を加え、ｐＨが４．５になるように１ｍｏｌ／Ｌ硫酸で調整し、単量体反応液（ＤＭＣ：ＤＭＥ：ＡＭＰＳ：ＡＡＭ＝２８．８：３０．８：１６．４：２４．０（モル％））を調製した。
さらに、光開始剤としてＤＡＲＯＣＵＲ １１７３（以下、「Ｄ−１１７３」と略す。）（Ｃｉｂａ社製）および連鎖移動剤としてホスホン酸（以下、「ＰＡ」と略す。）（関東化学社製）を、単量体反応液の総質量に対して、それぞれ２００ｐｐｍおよび１５００ｐｐｍとなるように投入し、これに窒素ガスを３０分間吹き込みながら溶液温度を１６℃に調節した。その後、単量体反応液をステンレス反応容器に移し、容器の下方から１７℃の水を噴霧しながら、表面温度計が３０℃になるまでケミカルランプを５Ｗ／ｍ２の照射強度で照射した。表面温度計が３０℃に到達した後は、２Ｗ／ｍ２の照射強度で４５分間照射した。さらに単量体の残存量を低減させるために照射強度を５０Ｗ／ｍ２にして１０分間照射して、共重合を行った。これにより、含水ゲル状の共重合体を得た。
この含水ゲル状の共重合体を容器から取り出し、小型ミートチョッパーを使用して解砕した。これを温度６０℃で１６時間乾燥後、粉砕して粉末状の水溶性高分子（Ａ−１）を得た。
<Production Example 1>
As a water-soluble cationic monomer, dimethylaminoethyl methacrylate methyl chloride quaternary salt (hereinafter abbreviated as “DMC”) (manufactured by Osaka Organic Chemical Industry Co., Ltd., purity 80%) 288.8 g and dimethylaminoethyl acrylate methyl chloride 4 288.8 g of grade salt (hereinafter abbreviated as “DME”) (manufactured by Osaka Organic Chemical Industry Co., Ltd., purity 80%), acrylamide-2-methylpropanesulfonic acid (hereinafter referred to as sulfonic acid group-containing water-soluble anionic monomer) , (AMPS).) (Toagosei Co., Ltd., purity 50%) 264.0 g, acrylamide as another monomer (hereinafter abbreviated as “AAM”) (Daanitrix, Inc., purity 50%) 132. 0 g is put into a 2000 mL brown heat-resistant bottle, and distilled water is added so that the total monomer concentration is 55% and the total mass is 1200 g. Adjusted with 1 mol / L sulfuric acid so that the monomer reaction solution (DMC: DME: AMPS: AAM = 28.8: 30.8:: 16.4 24.0 (mol%)) was prepared.
Furthermore, DAROCUR 1173 (hereinafter abbreviated as “D-1173”) (manufactured by Ciba) as a photoinitiator and phosphonic acid (hereinafter abbreviated as “PA”) (manufactured by Kanto Chemical Co., Ltd.) as a chain transfer agent, The total mass of the monomer reaction solution was charged to 200 ppm and 1500 ppm, respectively, and the solution temperature was adjusted to 16 ° C. while blowing nitrogen gas for 30 minutes. Thereafter, the monomer reaction solution was transferred to a stainless steel reaction vessel, while spraying 17 ° C. water from the lower container, a chemical lamp until the surface thermometer is 30 ° C. was irradiated at an irradiation intensity of 5W / m 2. After the surface thermometer reached 30 ° C., irradiation was performed for 45 minutes at an irradiation intensity of 2 W / m 2 . Furthermore, in order to reduce the residual amount of monomer, the irradiation intensity was 50 W / m 2 and irradiation was carried out for 10 minutes to carry out copolymerization. As a result, a hydrogel copolymer was obtained.
The hydrogel copolymer was taken out of the container and crushed using a small meat chopper. This was dried at a temperature of 60 ° C. for 16 hours and then pulverized to obtain a powdery water-soluble polymer (A-1).
＜製造例２＞
ＤＭＣ２８８．８ｇ、ＤＭＥ２８８．８ｇ、ＡＭＰＳ１３２．０ｇ、ＡＡＭ２６４．０ｇを、２０００ｍＬ褐色耐熱瓶に投入し、全単量体濃度５５％、総質量１２００ｇになるように蒸留水を加え、ｐＨが４．５になるように１ｍｏｌ／Ｌ硫酸で調整し、単量体反応液（ＤＭＣ：ＤＭＥ：ＡＭＰＳ：ＡＡＭ＝２４．８：２６．６：７．１：４１．５（モル％））を調製した。
さらに、Ｄ−１１７３およびＰＡを、単量体反応液の総質量に対して、それぞれ１５０ｐｐｍおよび１２００ｐｐｍとなるように投入した。以下、製造例１と同様の操作を行い、水溶性高分子（Ａ−２）を得た。
<Production Example 2>
DMC288.8g, DME288.8g, AMPS132.0g, AAM264.0g are put into a 2000mL brown heat-resistant bottle, and distilled water is added so that the total monomer concentration is 55% and the total mass is 1200g. In this way, a monomer reaction solution (DMC: DME: AMPS: AAM = 24.8: 26.6: 7.1: 41.5 (mol%)) was prepared using 1 mol / L sulfuric acid.
Furthermore, D-1173 and PA were added so as to be 150 ppm and 1200 ppm, respectively, with respect to the total mass of the monomer reaction solution. Thereafter, the same operation as in Production Example 1 was performed to obtain a water-soluble polymer (A-2).
＜製造例３＞
ＤＭＣ１６５．０ｇ、ＤＭＥ２０６．３ｇ、ＡＭＰＳ６６０．０ｇ、ＡＡＭ６６．０ｇを、２０００ｍＬ褐色耐熱瓶に投入し、全単量体濃度５５％、総質量１２００ｇになるように蒸留水を加え、ｐＨが４．５になるように１ｍｏｌ／Ｌ硫酸で調整し、単量体反応液（ＤＭＣ：ＤＭＥ：ＡＭＰＳ：ＡＡＭ＝１７．９：２４．０：４５．０：１３．１（モル％））を調製した。
さらに、Ｄ−１１７３およびＰＡを、単量体反応液の総質量に対して、それぞれ２５０ｐｐｍおよび２０００ｐｐｍとなるように投入した。以下、製造例１と同様の操作を行い、水溶性高分子（Ａ−３）を得た。
<Production Example 3>
DMC 165.0 g, DME 206.3 g, AMPS 660.0 g, and AAM 66.0 g were put into a 2000 mL brown heat-resistant bottle, and distilled water was added so that the total monomer concentration was 55% and the total mass was 1200 g. The monomer reaction solution (DMC: DME: AMPS: AAM = 17.9: 24.0: 45.0: 13.1 (mol%)) was prepared.
Furthermore, D-1173 and PA were added so as to be 250 ppm and 2000 ppm, respectively, with respect to the total mass of the monomer reaction solution. Thereafter, the same operation as in Production Example 1 was performed to obtain a water-soluble polymer (A-3).
＜製造例４＞
ＤＭＣ２８８．８ｇ、ＤＭＥ２８８．８ｇ、ＡＭＰＳ２６４．０ｇ、ＡＡＭ６６．０ｇ、およびその他単量体としてアクリル酸（以下、「ＡＡ」と略す。）（三菱化学社製、純度５０％）６６．０ｇを、２０００ｍＬ褐色耐熱瓶に投入し、全単量体濃度５５％、総質量１２００ｇになるように蒸留水を加え、ｐＨが２．６になるように１ｍｏｌ／Ｌ硫酸で調整し、単量体反応液（ＤＭＣ：ＤＭＥ：ＡＭＰＳ：ＡＡＭ：ＡＡ＝２８．８：３０．９：１６．５：１２．０：１１．８（モル％））を調製した。
さらに、Ｄ−１１７３およびＰＡを、単量体反応液の総質量に対して、それぞれ２５０ｐｐｍおよび２０００ｐｐｍとなるように投入した。以下、製造例１と同様の操作を行い、水溶性高分子（Ａ−４）を得た。
<Production Example 4>
2000 mL of DMC288.8 g, DME288.8 g, AMPS264.0 g, AAM66.0 g, and 66.0 g of acrylic acid (hereinafter abbreviated as “AA”) as other monomer (Mitsubishi Chemical Corporation, purity 50%) Put in a brown heat-resistant bottle, add distilled water so that the total monomer concentration is 55%, and the total mass is 1200 g, and adjust with 1 mol / L sulfuric acid so that the pH is 2.6. DMC: DME: AMPS: AAM: AA = 28.8: 30.9: 16.5: 12.0: 11.8 (mol%)) was prepared.
Furthermore, D-1173 and PA were added so as to be 250 ppm and 2000 ppm, respectively, with respect to the total mass of the monomer reaction solution. Thereafter, the same operation as in Production Example 1 was performed to obtain a water-soluble polymer (A-4).
＜製造例５＞
ＤＭＣ２８８．８ｇ、ＤＭＥ２８８．８ｇ、ＡＭＰＳ１３２．０ｇ、ＡＡＭ１９８．０ｇ、ＡＡ６６．０ｇを、２０００ｍＬ褐色耐熱瓶に投入し、全単量体濃度５５％、総質量１２００ｇになるように蒸留水を加え、ｐＨが２．６になるように１ｍｏｌ／Ｌ硫酸で調整し、単量体反応液（ＤＭＣ：ＤＭＥ：ＡＭＰＳ：ＡＡＭ：ＡＡ＝２４．９：２６．７：７．１：３１．１：１０．２（モル％））を調製した。
さらに、Ｄ−１１７３およびＰＡを、単量体反応液の総質量に対して、それぞれ１５０ｐｐｍおよび１２００ｐｐｍとなるように投入した。以下、製造例１と同様の操作を行い、水溶性高分子（Ａ−５）を得た。
<Production Example 5>
DMC288.8g, DME288.8g, AMPS132.0g, AAM198.0g, AA66.0g are put into a 2000mL brown heat-resistant bottle, and distilled water is added so that the total monomer concentration is 55% and the total mass is 1200g, and pH is adjusted. Was adjusted with 1 mol / L sulfuric acid so as to be 2.6, and the monomer reaction solution (DMC: DME: AMPS: AAM: AA = 24.9: 26.7: 7.1: 31.1: 10. 2 (mol%)) was prepared.
Furthermore, D-1173 and PA were added so as to be 150 ppm and 1200 ppm, respectively, with respect to the total mass of the monomer reaction solution. Thereafter, the same operation as in Production Example 1 was performed to obtain a water-soluble polymer (A-5).
＜製造例６＞
ＤＭＣ１６５．０ｇ、ＤＭＥ１６５．０ｇ、ＡＭＰＳ６６０．０ｇ、ＡＡＭ６６．０ｇ、ＡＡ６６．０ｇを、２０００ｍＬ褐色耐熱瓶に投入し、全単量体濃度５５％、総質量１２００ｇになるように蒸留水を加え、ｐＨが２．６になるように１ｍｏｌ／Ｌ硫酸で調整し、単量体反応液（ＤＭＣ：ＤＭＥ：ＡＭＰＳ：ＡＡＭ：ＡＡ＝１６．６：１７．８：４１．５：１２．１：１２．０（モル％））を調製した。
さらに、Ｄ−１１７３およびＰＡを、単量体反応液の総質量に対して、それぞれ２５０ｐｐｍおよび２０００ｐｐｍとなるように投入した。以下、製造例１と同様の操作を行い、水溶性高分子（Ａ−６）を得た。
<Production Example 6>
DMC 165.0 g, DME 165.0 g, AMPS 660.0 g, AAM 66.0 g, AA 66.0 g are put into a 2000 mL brown heat-resistant bottle, and distilled water is added so that the total monomer concentration is 55% and the total mass is 1200 g. Was adjusted with 1 mol / L sulfuric acid so as to be 2.6, and the monomer reaction solution (DMC: DME: AMPS: AAM: AA = 16.6: 17.8: 41.5: 12.1: 1.12. 0 (mol%) was prepared.
Furthermore, D-1173 and PA were added so as to be 250 ppm and 2000 ppm, respectively, with respect to the total mass of the monomer reaction solution. Thereafter, the same operation as in Production Example 1 was performed to obtain a water-soluble polymer (A-6).
＜比較製造例１＞
ＤＭＣ１２３．８ｇ、ＤＭＥ１２３．８ｇ、ＡＭＰＳ８５８．０ｇ、ＡＡＭ６６．０ｇを、２０００ｍＬ褐色耐熱瓶に投入し、全単量体濃度５５％、総質量１２００ｇになるように蒸留水を加え、ｐＨが４．５になるように１ｍｏｌ／Ｌ硫酸で調整し、単量体反応液（ＤＭＣ：ＤＭＥ：ＡＭＰＳ：ＡＡＭ＝１３．５：１４．５：５８．８：１３．２（モル％））を調製した。
さらに、Ｄ−１１７３およびＰＡを、単量体反応液の総質量に対して、それぞれ２５０ｐｐｍおよび２０００ｐｐｍとなるように投入した。以下、製造例１と同様の操作を行い、水溶性高分子（Ｂ−１）を得た。
<Comparative Production Example 1>
DMC 123.8 g, DME 123.8 g, AMPS 858.0 g, and AAM 66.0 g were put into a 2000 mL brown heat-resistant bottle, and distilled water was added so that the total monomer concentration was 55% and the total mass was 1200 g. The monomer reaction solution (DMC: DME: AMPS: AAM = 13.5: 14.5: 58.8: 13.2 (mol%)) was prepared.
Furthermore, D-1173 and PA were added so as to be 250 ppm and 2000 ppm, respectively, with respect to the total mass of the monomer reaction solution. Thereafter, the same operation as in Production Example 1 was performed to obtain a water-soluble polymer (B-1).
＜比較製造例２＞
ＤＭＣ１２３．８ｇ、ＤＭＥ１２３．８ｇ、ＡＭＰＳ８５８．０ｇ、ＡＡＭ２６．４ｇ、ＡＡ３９．６ｇを、２０００ｍＬ褐色耐熱瓶に投入し、全単量体濃度５５％、総質量１２００ｇになるように蒸留水を加え、ｐＨが２．６になるように１ｍｏｌ／Ｌ硫酸で調整し、単量体反応液（ＤＭＣ：ＤＭＥ：ＡＭＰＳ：ＡＡＭ：ＡＡ＝１３．５：１４．５：５８．９：５．３：７．８（モル％））を調製した。
さらに、Ｄ−１１７３およびＰＡを、単量体反応液の総質量に対して、それぞれ２５０ｐｐｍおよび２０００ｐｐｍとなるように投入した。以下、製造例１と同様の操作を行い、水溶性高分子（Ｂ−２）を得た。
<Comparative Production Example 2>
DMC123.8g, DME123.8g, AMPS858.0g, AAM26.4g, AA39.6g are put into a 2000mL brown heat-resistant bottle, and distilled water is added so that the total monomer concentration is 55% and the total mass is 1200g. Is adjusted with 1 mol / L sulfuric acid so as to be 2.6, and monomer reaction solution (DMC: DME: AMPS: AAM: AA = 13.5: 14.5: 58.9: 5.3: 7. 8 (mol%)) was prepared.
Furthermore, D-1173 and PA were added so as to be 250 ppm and 2000 ppm, respectively, with respect to the total mass of the monomer reaction solution. Thereafter, the same operation as in Production Example 1 was performed to obtain a water-soluble polymer (B-2).
＜実施例１〜５、比較例１，２＞
製造例１〜６、比較製造例１〜２で得られた水溶性高分子を、各々、水に溶解し、さらに無機塩（塩化ナトリウム［実施例１］、硝酸ナトリウム［実施例２］、硫酸ナトリウム［実施例３］、炭酸ナトリウム［実施例４］、およびリン酸ナトリウム［実施例５］のいずれか）を所定量添加して、スルホン酸基含有両性水溶性高分子水溶液を得た。
得られたスルホン酸基含有両性水溶性高分子水溶液について、０．５％塩粘度および０．５％不溶解分量を測定した。塩粘度の測定結果については表１〜表５に、不溶解分量については表６〜１０に示す。
なお、無機塩添加後でもポリマー水溶液が未溶解の場合は、未測定とした。なお、未溶解とは、０．５％不溶解分量で１００ｇ以上の量のことである。
<Examples 1 to 5, Comparative Examples 1 and 2>
The water-soluble polymers obtained in Production Examples 1 to 6 and Comparative Production Examples 1 and 2 were each dissolved in water, and further inorganic salts (sodium chloride [Example 1], sodium nitrate [Example 2], sulfuric acid) A predetermined amount of sodium [Example 3], sodium carbonate [Example 4] and sodium phosphate [Example 5] was added to obtain a sulfonic acid group-containing amphoteric water-soluble polymer aqueous solution.
About the obtained sulfonic acid group-containing amphoteric water-soluble polymer aqueous solution, 0.5% salt viscosity and 0.5% insoluble content were measured. The measurement results of the salt viscosity are shown in Tables 1 to 5, and the insoluble amounts are shown in Tables 6 to 10.
In addition, it was set as the unmeasurement when the polymer aqueous solution was not melt | dissolved even after inorganic salt addition. In addition, undissolved means the amount of 100 g or more with a 0.5% insoluble content.
請求項１に規定した組成のスルホン酸基含有両性水溶性高分子および無機塩が水に溶解された実施例の水溶性高分子水溶液では、塩粘度が適度なものとなり、不溶解分量が少なかった。
これに対し、スルホン酸基含有水溶性アニオン性単量体単位が５０モル％を超えていた比較例１，２では、無機塩存在下で水溶性高分子が全く溶解しないか、溶解量が少なかった。すなわち、不溶解量が多かった。
In the water-soluble polymer aqueous solution of the example in which the sulfonic acid group-containing amphoteric water-soluble polymer having the composition defined in claim 1 and the inorganic salt were dissolved in water, the salt viscosity was appropriate and the insoluble content was small. .
On the other hand, in Comparative Examples 1 and 2 in which the sulfonic acid group-containing water-soluble anionic monomer unit exceeded 50 mol%, the water-soluble polymer was not dissolved at all in the presence of the inorganic salt, or the amount dissolved was small. It was. That is, the insoluble amount was large.
さらには、表６〜表１０より、無機塩量により各水溶性高分子の０．５％塩粘度値は異なり、その添加量が多いほどその値は小さくなる傾向にあることが分かった。また、無機塩の種類によらず、添加量が同じであれば、０．５％塩粘度の値はほぼ同じであった。
表６〜表１０より、無機塩量により各水溶性高分子の０．５％不溶解分量は異なり、その添加量が多いほどその量は小さくなる傾向にあることが分かった。また、無機塩の種類によって０．５％不溶解分量は異なり、塩化ナトリウムを用いたときに不溶解分量が最も少ないことが分かった。
Furthermore, from Tables 6 to 10, it was found that the 0.5% salt viscosity value of each water-soluble polymer differs depending on the amount of inorganic salt, and the value tends to decrease as the amount added increases. In addition, regardless of the kind of inorganic salt, if the addition amount was the same, the value of 0.5% salt viscosity was almost the same.
From Table 6 to Table 10, it was found that the amount of 0.5% insoluble matter of each water-soluble polymer varies depending on the amount of inorganic salt, and the amount tends to decrease as the amount added increases. In addition, the amount of 0.5% insoluble matter differs depending on the type of inorganic salt, and it was found that the amount of insoluble matter was the smallest when sodium chloride was used.
Claims (4)
スルホン酸基含有両性水溶性高分子は、下記一般式（１）で表される水溶性カチオン性単量体単位５〜９０モル％と、スルホン酸基含有水溶性アニオン性単量体単位５〜５０モル％と、水溶性カチオン単量体単位およびスルホン酸基含有水溶性アニオン性単量体単位以外の他の単量体単位５〜７０モル％とを有する共重合体であることを特徴とする両性水溶性高分子水溶液。
The sulfonic acid group-containing amphoteric water-soluble polymer is composed of 5 to 90 mol% of a water-soluble cationic monomer unit represented by the following general formula (1) and 5 to 90% of a sulfonic acid group-containing water-soluble anionic monomer unit. It is a copolymer having 50 mol% and 5 to 70 mol% of monomer units other than the water-soluble cationic monomer unit and the sulfonic acid group-containing water-soluble anionic monomer unit. Amphoteric water-soluble polymer aqueous solution.
スルホン酸基含有両性水溶性高分子として、下記一般式（１）で表される水溶性カチオン性単量体５〜９０モル％と、スルホン酸基含有水溶性アニオン性単量体５〜５０モル％と、水溶性カチオン単量体およびスルホン酸基含有水溶性アニオン性単量体以外の他の単量体５〜７０モル％とを共重合させた共重合体を用いることを特徴とするスルホン酸基含有両性水溶性高分子水溶液の製造方法。
As the sulfonic acid group-containing amphoteric water-soluble polymer, 5 to 90 mol% of a water-soluble cationic monomer represented by the following general formula (1) and 5 to 50 mol of a sulfonic acid group-containing water-soluble anionic monomer % And a copolymer obtained by copolymerizing a water-soluble cationic monomer and 5 to 70 mol% of a monomer other than the sulfonic acid group-containing water-soluble anionic monomer. A method for producing an acid group-containing amphoteric water-soluble polymer aqueous solution.
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| JPS59182881A (en) * | 1983-03-25 | 1984-10-17 | エクソン・リサ−チ・アンド・エンジニアリング・カンパニ− | Excavation mud water |
| JPS60108409A (en) * | 1983-10-19 | 1985-06-13 | ソシエテ・フランセーズ・ヘキスト | Cationic amphoteric quaternary polymer and cosmetic composition |
| JPH11512752A (en) * | 1996-05-13 | 1999-11-02 | ロレアル | Composition for treating keratin materials containing a combination of amphoteric polyelectrolyte polymer and non-volatile water-insoluble organopolysiloxane |
| JP2001508826A (en) * | 1997-01-20 | 2001-07-03 | チバ スペシャルティ ケミカルズ ウォーター トリートメント リミテッド | Polymer compositions and their production and use |
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| JPS59182881A (en) * | 1983-03-25 | 1984-10-17 | エクソン・リサ−チ・アンド・エンジニアリング・カンパニ− | Excavation mud water |
| JPS60108409A (en) * | 1983-10-19 | 1985-06-13 | ソシエテ・フランセーズ・ヘキスト | Cationic amphoteric quaternary polymer and cosmetic composition |
| JPH11512752A (en) * | 1996-05-13 | 1999-11-02 | ロレアル | Composition for treating keratin materials containing a combination of amphoteric polyelectrolyte polymer and non-volatile water-insoluble organopolysiloxane |
| JP2001508826A (en) * | 1997-01-20 | 2001-07-03 | チバ スペシャルティ ケミカルズ ウォーター トリートメント リミテッド | Polymer compositions and their production and use |
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| JP2011167656A (en) * | 2010-02-22 | 2011-09-01 | Daiyanitorikkusu Kk | Treatment method of inorganic material-suspended waste water |
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