JP5311360B2 - Method for producing water-soluble polymer - Google Patents
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本発明は、水溶性重合体の製造方法に関し、詳しくは、残存モノマーの少ない水溶性重合体の製造方法に関する。 The present invention relates to a method for producing a water-soluble polymer, and in particular, relates to a method for producing a water-soluble polymer with little residual monomer.
アクリルアミド系モノマーおよび／またはアニオン性ビニルモノマーの水溶性単独重合体または水溶性共重合体（以下、これらをまとめて水溶性重合体と記す）は、優れた凝集作用を有し、上水道または廃水処理用高分子凝集剤などとして広く用いられている。 Water-soluble homopolymers or water-soluble copolymers of acrylamide monomers and / or anionic vinyl monomers (hereinafter collectively referred to as water-soluble polymers) have excellent aggregating action, and are used for water and wastewater treatment. Widely used as a polymer flocculant and the like.
このような水溶性重合体中には、未反応のモノマー（残存モノマー）が存在しないことが、環境および取扱い上の理由から必要とされている。特に、アクリルアミドは毒性を有しているので、水溶性重合体中の残存アクリルアミドの量は、できるだけ少なくすることが求められている。例えば、水溶性重合体を凝集剤として上水道に使用する場合は、残存アクリルアミドの量は５００ｐｐｍ以下、一般廃水処理に使用する場合は、残存アクリルアミドの量は２０００ｐｐｍ以下とされている。 In such a water-soluble polymer, it is necessary for environmental and handling reasons that no unreacted monomer (residual monomer) is present. In particular, since acrylamide is toxic, the amount of residual acrylamide in the water-soluble polymer is required to be as small as possible. For example, when a water-soluble polymer is used as a flocculant in waterworks, the amount of residual acrylamide is 500 ppm or less, and when it is used for general wastewater treatment, the amount of residual acrylamide is 2000 ppm or less.
また、水溶性重合体は、その分子量が高いほど凝集性能が優れている。そのため、水溶性重合体の分子量、粘度、組成等を変化させることなく、すなわち高分子凝集剤としての機能を低下させることなく、未反応のモノマーを低減することが求められている。 In addition, the water-soluble polymer has better aggregation performance as its molecular weight is higher. Therefore, it is required to reduce unreacted monomers without changing the molecular weight, viscosity, composition, etc. of the water-soluble polymer, that is, without reducing the function as a polymer flocculant.
水溶性重合体中の残存モノマーを減少させる方法が、これまでにいくつか提案されている。
特開昭５６−１０３２０７号公報には、水溶性重合体に亜硫酸水素アルカリ金属塩、亜硫酸アルカリ金属塩等を添加し、これらを混合した後、乾燥する方法が提案されている。しかしながら、この方法により水溶性重合体中の残存モノマーは減少するものの、水溶性重合体の粘度が著しく低下してしまい、高分子凝集剤としての性能が劣化してしまうという問題があった。Several methods have been proposed so far to reduce the residual monomer in the water-soluble polymer.
Japanese Patent Application Laid-Open No. 56-103207 proposes a method in which an alkali metal hydrogen sulfite or an alkali metal sulfite is added to a water-soluble polymer, and these are mixed and then dried. However, although the residual monomer in the water-soluble polymer is reduced by this method, there is a problem that the viscosity of the water-soluble polymer is remarkably lowered and the performance as a polymer flocculant is deteriorated.
特開平９−３０２０２２号公報には、アルカリ剤と、仕込みモノマーに対して２〜１５重量％の亜硫酸水素アルカリ金属塩、亜硫酸アルカリ金属塩等とを、含水状態の水溶性重合体に添加し、これらを混合した後、乾燥する方法が提案されている。しかしながら、この方法によって水溶性重合体中の残存モノマーは減少するものの、この方法は、水溶性重合体を加水分解させることを必須としているため、水溶性重合体の組成が変化し、高分子凝集剤の性能が変化もしくは低下してしまうという問題があった。 In JP-A-9-302022, an alkali agent and 2 to 15% by weight of an alkali metal hydrogen sulfite, an alkali metal sulfite or the like with respect to a charged monomer are added to a water-soluble polymer in a water-containing state, A method is proposed in which these are mixed and then dried. However, although the residual monomer in the water-soluble polymer is reduced by this method, this method requires hydrolysis of the water-soluble polymer. There was a problem that the performance of the agent changed or decreased.
よって、本発明の目的は、高分子凝集剤としての水溶性重合体の性能を劣化、変化させることなく、水溶性重合体中の残存モノマーが低減された水溶性重合体を得ることができる水溶性重合体の製造方法を提供することにある。 Therefore, an object of the present invention is to provide a water-soluble polymer in which the residual monomer in the water-soluble polymer is reduced without deteriorating or changing the performance of the water-soluble polymer as a polymer flocculant. It is in providing the manufacturing method of a conductive polymer.
【課題を解決するための手段】
本発明の水溶性重合体の製造方法は、少なくともアクリルアミド系モノマー、あるいは、少なくともアクリルアミド系モノマーおよびアニオン性ビニルモノマーを重合して得られた含水状態の水溶性重合体を乾燥するに際し、含水状態の水溶性重合体に、まず、仕込みモノマーに対して０．６質量％以上１．２質量％以下の亜硫酸アルカリ金属塩、亜硫酸水素アルカリ金属塩およびピロ亜硫酸アルカリ金属塩からなる群より選ばれた少なくとも１種を添加し、ついで、仕込みモノマーに対して０．５質量％以上１．０質量％以下のアルカリ剤を添加した後、含水状態の水溶性重合体を乾燥する水溶性重合体の製造方法であって、前記亜硫酸アルカリ金属塩、亜硫酸水素アルカリ金属塩およびピロ亜硫酸アルカリ金属塩からなる群より選ばれた少なくとも１種の添加量と前記アルカリ剤の添加量との比（亜硫酸塩の添加量／アルカリ剤の添加量）が、１．０以上１．２以下であることを特徴とする。
[Means for Solving the Problems]
The method for producing a water-soluble polymer according to the present invention comprises a step of drying a water-soluble polymer obtained by polymerizing at least an acrylamide monomer , or at least an acrylamide monomer and an anionic vinyl monomer. In the water-soluble polymer, first, at least selected from the group consisting of an alkali metal sulfite, an alkali metal bisulfite, and an alkali metal pyrosulfite with respect to the charged monomer in an amount of 0.6% by mass to 1.2% by mass. A method for producing a water-soluble polymer comprising adding one kind and then adding 0.5% by mass or more and 1.0% by mass or less of an alkaline agent to the charged monomer, and then drying the water-soluble water-soluble polymer And selected from the group consisting of alkali metal sulfites, alkali metal hydrogen sulfites and alkali metal pyrosulfites. The ratio of the amount of one additive amount of the alkali agent even without (the addition amount of the sulfite / added amount of the alkali agent), characterized in that 1.0 to 1.2.
また、前記アニオン性ビニルモノマーは、アクリル酸、アクリル酸の塩、メタアクリル酸、メタクリル酸の塩、ビニルスルホン酸およびビニルスルホン酸の塩からなる群から選ばれた少なくとも１種であることが望ましい。 The anionic vinyl monomer is preferably at least one selected from the group consisting of acrylic acid, acrylic acid salt, methacrylic acid, methacrylic acid salt, vinyl sulfonic acid and vinyl sulfonic acid salt. .
以下、本発明について説明する。
本発明における水溶性重合体は、アクリルアミド系モノマーおよび／またはアニオン性ビニルモノマーと、必要に応じて他のビニル系モノマーとを重合して得られる単独重合体または共重合体である。
前記アクリルアミド系モノマーとしては、アクリルアミド、メタクリルアミドおよびこれらの塩などが挙げられる。The present invention will be described below.
The water-soluble polymer in the present invention is a homopolymer or copolymer obtained by polymerizing an acrylamide monomer and / or an anionic vinyl monomer and, if necessary, another vinyl monomer.
Examples of the acrylamide monomers include acrylamide, methacrylamide, and salts thereof.
前記アニオン性ビニルモノマーとは、水溶液中でイオンに解離してアニオン（陰イオン）となるビニル系モノマーである。中でも、得られる重合体が水溶性、凝集性能等に優れることから、アクリル酸、メタアクリル酸、ビニルスルホン酸およびそれらの塩が好適に用いられる。ビニルスルホン酸としては、例えば、２−アクリルアミド−２−メチルプロパンスルホン酸などが挙げられる。 The anionic vinyl monomer is a vinyl monomer that dissociates into ions in an aqueous solution and becomes an anion (anion). Among them, acrylic acid, methacrylic acid, vinyl sulfonic acid, and salts thereof are preferably used because the resulting polymer is excellent in water solubility and aggregation performance. Examples of vinyl sulfonic acid include 2-acrylamido-2-methylpropane sulfonic acid.
これらアクリルアミド系モノマーおよび／またはアニオン性ビニルモノマーと共重合させる他のビニル系モノマーとしては、例えば、アクリル酸エステル、メタクリル酸エステル等のアクリル酸系モノマー、アクリロニトリル、Ｎ−ビニルアセトアミドなどが挙げられる。
他のビニル系モノマーの仕込量は、全仕込みモノマーに対して、好ましくは４０ｍｏｌ％以下、より好ましくは２０ｍｏｌ％以下とされる。他のビニル系モノマーの仕込量が４０ｍｏｌ％を超えると、凝集性能に優れた水溶性重合体が得られないおそれがある。Examples of other vinyl monomers copolymerized with these acrylamide monomers and / or anionic vinyl monomers include acrylic acid monomers such as acrylic acid esters and methacrylic acid esters, acrylonitrile, N-vinylacetamide, and the like.
The amount of other vinyl monomers charged is preferably 40 mol% or less, more preferably 20 mol% or less, based on the total amount of monomers charged. If the amount of other vinyl monomer charged exceeds 40 mol%, a water-soluble polymer having excellent aggregation performance may not be obtained.
本発明における水溶性重合体は、少なくともアクリルアミド系モノマーおよび／またはアニオン性ビニルモノマーを重合してゲル、スラリー、分散液等の含水状態の水溶性重合体を得て、これに、亜硫酸アルカリ金属塩、亜硫酸水素アルカリ金属塩およびピロ亜硫酸アルカリ金属塩からなる群より選ばれた少なくとも１種とアルカリ剤とをあらかじめ添加した後、含水状態の水溶性重合体を乾燥することによって製造される。 The water-soluble polymer in the present invention is obtained by polymerizing at least an acrylamide monomer and / or an anionic vinyl monomer to obtain a water-soluble water-soluble polymer such as a gel, a slurry, a dispersion, and the like. In addition, at least one selected from the group consisting of alkali metal bisulfite and alkali metal pyrosulfite and an alkali agent are added in advance, and then the water-soluble water-soluble polymer is dried.
重合方法は、ビニル系モノマーの重合に採用される方法であれば特に制限されい。重合方法としては、例えば、モノマーを水等の水性媒体中で重合する水溶液重合法が挙げられる。 The polymerization method is not particularly limited as long as it is a method employed for polymerization of vinyl monomers. Examples of the polymerization method include an aqueous solution polymerization method in which a monomer is polymerized in an aqueous medium such as water.
重合に際しては、通常使用される重合開始剤を用いることができる。これら重合開始剤として、例えば、ベンゾイルパーオキサイド、過硫酸塩などの過酸化物系開始剤、２，２’−アゾビス−（２−アミジノプロパン）ジハイドロクロライド、アゾビスイソブチロニトリルなどのアゾ系開始剤、酸化物と還元剤の組合せのようなレドックス触媒などが挙げられる。レドックス触媒の酸化剤としては、例えば、過硫酸アンモニウム、過硫酸カリウムなどの過硫酸塩が挙げられる。また、還元剤としては、例えば、亜硫酸水素ナトリウム、硫酸第１鉄、塩化第１鉄などが挙げられる。 In the polymerization, a commonly used polymerization initiator can be used. Examples of these polymerization initiators include peroxide initiators such as benzoyl peroxide and persulfate, azo such as 2,2′-azobis- (2-amidinopropane) dihydrochloride, azobisisobutyronitrile, and the like. Examples thereof include a redox catalyst such as a system initiator and a combination of an oxide and a reducing agent. Examples of the oxidizing agent for the redox catalyst include persulfates such as ammonium persulfate and potassium persulfate. Examples of the reducing agent include sodium bisulfite, ferrous sulfate, and ferrous chloride.
アゾ系開始剤の添加量は、仕込み調合液に対して、好ましくは１０〜４０００ｐｐｍ、より好ましくは５０〜８００ｐｐｍである。レドックス触媒の添加量は、通常、酸化剤、還元剤ともに、仕込み調合液に対して、好ましくは１〜１０００ｐｐｍ、より好ましくは５〜５００ｐｐｍである。酸化剤および還元剤は、それぞれ異なる量で使用することができるが、通常は、ほぼ等モル量で使用される。 The addition amount of the azo-based initiator is preferably 10 to 4000 ppm, more preferably 50 to 800 ppm with respect to the charged preparation liquid. The addition amount of the redox catalyst is preferably 1 to 1000 ppm, more preferably 5 to 500 ppm, based on the charged preparation liquid, for both the oxidizing agent and the reducing agent. The oxidizing agent and the reducing agent can be used in different amounts, but are usually used in approximately equimolar amounts.
水性媒体中におけるモノマー濃度は、通常、１５〜３５質量％、好ましくは２２〜３０質量％である。モノマー濃度が１５質量％未満では、重合後における乾燥工程に時間がかかりすぎる。モノマー濃度が３５質量％を超えると、重合反応系が高温となり、水溶性重合体の品質が低下しやすく、また、水溶性重合体の種類によっては高濃度ゲルとなり、取扱いが困難となる。
重合温度は、通常、−１０〜１００℃であり、重合開始温度は、−５〜２０℃である。重合時間は、特に限定されず、通常、０．５〜１０時間程度である。The monomer concentration in the aqueous medium is usually 15 to 35% by mass, preferably 22 to 30% by mass. If the monomer concentration is less than 15% by mass, the drying process after polymerization takes too much time. When the monomer concentration exceeds 35% by mass, the polymerization reaction system becomes high temperature, the quality of the water-soluble polymer is likely to be lowered, and depending on the type of the water-soluble polymer, a high-concentration gel is formed and handling becomes difficult.
The polymerization temperature is usually −10 to 100 ° C., and the polymerization start temperature is −5 to 20 ° C. The polymerization time is not particularly limited, and is usually about 0.5 to 10 hours.
含水状態の水溶性重合体に添加される、亜硫酸アルカリ金属塩、亜硫酸水素アルカリ金属塩およびピロ亜硫酸アルカリ金属塩（以下、これらを亜硫酸塩と記す）の中でも、残存モノマー削減効果の点で、亜硫酸アルカリ金属塩と亜硫酸水素アルカリ金属塩が好ましく、亜硫酸アルカリ金属塩が特に好ましい。アルカリ金属としては、水への溶解性の点で、ナトリウム、カリウムが好ましく、特に好ましくはナトリウムである。したがって、本発明においては、含水状態の水溶性重合体の乾燥は、亜硫酸ナトリウムおよび／または亜硫酸水素ナトリウムの存在下、特に亜硫酸ナトリウムの存在下で行われる。 Among alkali metal sulfites, alkali hydrogen sulfites and alkali metal pyrosulfites (hereinafter referred to as sulfites) added to water-soluble polymers containing water, sulfur dioxide is used in terms of the residual monomer reduction effect. Alkali metal salts and alkali metal hydrogen sulfites are preferred, and alkali metal sulfites are particularly preferred. As the alkali metal, sodium and potassium are preferable from the viewpoint of solubility in water, and sodium is particularly preferable. Therefore, in the present invention, the water-soluble polymer in the water-containing state is dried in the presence of sodium sulfite and / or sodium bisulfite, particularly in the presence of sodium sulfite.
これら亜硫酸塩の添加量は、仕込みモノマー質量に対して、０．１質量％以上２．０質量％未満、好ましくは０．３〜１．９質量％、より好ましくは０．５〜１．８質量％である。亜硫酸塩の添加量が０．１質量％未満では、未反応アクリルアミド等の残存モノマーが多くなる。亜硫酸塩の添加量が２．０質量％以上では、水溶性重合体の粘度が低下して、凝集性能が低下する。
これら亜硫酸塩は、含水状態の水溶性重合体に均一に接触させるために、水溶液として添加される。その濃度は、通常１０〜３０質量％である。The addition amount of these sulfites is 0.1% by weight or more and less than 2.0% by weight, preferably 0.3 to 1.9% by weight, more preferably 0.5 to 1.8%, based on the charged monomer weight. % By mass. When the amount of sulfite added is less than 0.1% by mass, the amount of residual monomers such as unreacted acrylamide increases. When the amount of sulfite added is 2.0% by mass or more, the viscosity of the water-soluble polymer is lowered and the aggregation performance is lowered.
These sulfites are added as an aqueous solution in order to uniformly contact the water-soluble water-soluble polymer. The concentration is usually 10 to 30% by mass.
また、亜硫酸塩の添加量は、アルカリ剤の添加量以上、すなわち亜硫酸塩の添加量とアルカリ剤の添加量の比率（亜硫酸塩の添加量／アルカリ剤添加量）は、1．０以上であることが望ましい。亜硫酸塩の添加量／アルカリ剤添加量が１．０未満では、水溶性重合体の加水分解により水溶性重合体の組成が変化するため凝集性能が変化する。 The amount of sulfite added is equal to or greater than the amount of alkali agent added, that is, the ratio of the amount of sulfite added to the amount of alkali agent (sulfite added amount / alkali agent added amount) is 1.0 or more. It is desirable. When the addition amount of sulfite / alkaline agent is less than 1.0, the composition of the water-soluble polymer changes due to hydrolysis of the water-soluble polymer, so that the aggregation performance changes.
アルカリ剤としては、アルカリ金属の水酸化物；無機酸、有機酸の塩等が挙げられる。具体的には、苛性ソーダ、苛性カリ、炭酸ソーダ、炭酸カリなど、ナトリウムやカリウム等の１価の塩類が挙げられる。 Examples of the alkali agent include alkali metal hydroxides; salts of inorganic acids and organic acids. Specific examples include monovalent salts such as sodium and potassium, such as caustic soda, caustic potash, sodium carbonate, potassium carbonate and the like.
アルカリ剤の添加量は、仕込みモノマーに対して、０．１質量％以上２．０質量％未満、好ましくは０．３〜１．８質量％、より好ましくは０．５〜１．５質量％である。アルカリ剤の添加量が０．１質量％未満では、水溶性重合体の粘度が著しく低下する。アルカリ剤の添加量が２．０質量％以上では、水溶性重合体の加水分解により水溶性重合体の組成が変化する。
アルカリ剤は、含水状態の水溶性重合体に均一に接触させるために、水溶液として添加される。その濃度は、通常２０〜５０質量％である。The addition amount of the alkaline agent is 0.1% by mass or more and less than 2.0% by mass, preferably 0.3 to 1.8% by mass, and more preferably 0.5 to 1.5% by mass with respect to the charged monomer. It is. When the addition amount of the alkaline agent is less than 0.1% by mass, the viscosity of the water-soluble polymer is remarkably lowered. When the addition amount of the alkaline agent is 2.0% by mass or more, the composition of the water-soluble polymer changes due to hydrolysis of the water-soluble polymer.
The alkaline agent is added as an aqueous solution in order to uniformly contact the water-containing water-soluble polymer. The density | concentration is 20-50 mass% normally.
亜硫酸塩およびアルカリ剤は、含水状態の水溶性重合体が乾燥される前に存在させてあればよく、その添加手段は制限されない。水溶性重合体がゲル状である場合、亜硫酸塩およびアルカリ剤との混合を充分に達成するために、ゲル状物を適宜、細断、粉砕することが好ましい。細断には、肉引き機（チョッパー）等が用いられる。ゲル状物は、通常、３〜１０ｍｍ程度のサイズに細断、粉砕される。 The sulfite and the alkali agent may be present before the water-soluble polymer in the water-containing state is dried, and the addition means is not limited. When the water-soluble polymer is in the form of a gel, it is preferable to appropriately chop and pulverize the gel-like product in order to sufficiently achieve mixing with the sulfite and the alkali agent. For shredding, a meat drawing machine (chopper) or the like is used. The gel-like material is usually shredded and pulverized to a size of about 3 to 10 mm.
また、亜硫酸塩およびアルカリ剤を含水状態の水溶性重合体に添加する際には、まず、亜硫酸塩水溶液を含水状態の水溶性重合体に添加し、これらを混合した後、これにアルカリ剤水溶液を添加、混合することが望ましい。アルカリ剤を亜硫酸塩よりも先に含水状態の水溶性重合体に添加した場合、水溶性重合体の加水分解および水溶性重合体の粘度低下が生じるおそれがある。 In addition, when adding a sulfite and an alkali agent to a water-soluble polymer in a water-containing state, first, an aqueous sulfite solution is added to the water-soluble polymer in a water-containing state, and after mixing these, It is desirable to add and mix. If the alkaline agent is added to the water-soluble water-soluble polymer prior to the sulfite, hydrolysis of the water-soluble polymer and viscosity reduction of the water-soluble polymer may occur.
亜硫酸ナトリウム等の亜硫酸塩およびアルカリ剤が添加された含水状態の水溶性重合体は、通常使用されている乾燥機、例えば、ドラムドライヤー、流動層乾燥機などによって乾燥される。
乾燥温度は、通常、４０〜１２０℃であり、乾燥時間は、通常、１〜１２時間である。乾燥温度をあまりに高温にすると、水溶性重合体のゲル化が進み、品質低下の原因となるので好ましくない。水溶性重合体の乾燥は、含水率が、好ましくは１０質量％以下、より好ましくは８質量％以下になるまで行われる。The water-soluble water-soluble polymer to which a sulfite such as sodium sulfite and an alkali agent are added is dried by a commonly used dryer such as a drum dryer or a fluidized bed dryer.
The drying temperature is usually 40 to 120 ° C., and the drying time is usually 1 to 12 hours. If the drying temperature is too high, gelation of the water-soluble polymer proceeds, which causes a decrease in quality, which is not preferable. The water-soluble polymer is dried until the water content is preferably 10% by mass or less, more preferably 8% by mass or less.
以下、実施例により本発明をさらに詳細に説明する。なお、本発明は、以下の例に限定されるものではない。
本実施例における、水溶性重合体のアニオン当量値（ＡＶ値）、０．１％粘度および残存アクリルアミドは、以下のようにして測定した。
［ＡＶ値］
０．１％ポリマー溶液５ｇを１００ｍｌビーカーに秤取し、純粋を加えて１００ｇとする。マグネチックスターラーで攪拌した後、Ｎ／２００メチルグリコールキトサン溶液５ｍｌを加え、更に攪拌した後、Ｎ／４００ポリビニル硫酸カリウム溶液（ファクター：ｆ、通常は１．０）で滴定し終点（Ｖ1 ）を求める。また別にブランクでの終点（Ｖ2 ）を求める。ｆ、Ｖ1 およびＶ2 を用いて次式によりＡＶ値を算出する。
ＡＶ（ｍｅｑ／ｇ）＝ｆ×（Ｖ2−Ｖ1）／２Hereinafter, the present invention will be described in more detail with reference to examples. In addition, this invention is not limited to the following examples.
In this example, the anion equivalent value (AV value), 0.1% viscosity and residual acrylamide of the water-soluble polymer were measured as follows.
[AV value]
Weigh 5 g of 0.1% polymer solution into a 100 ml beaker and add pure to 100 g. After stirring with a magnetic stirrer, 5 ml of N / 200 methyl glycol chitosan solution was added and further stirred, and then titrated with N / 400 potassium potassium sulfate solution (factor: f, usually 1.0) to end point (V 1 ). Ask for. Separately, a blank end point (V 2 ) is obtained. The AV value is calculated by the following equation using f, V 1 and V 2 .
AV (meq / g) = f × (V 2 −V 1 ) / 2
［０．１％粘度］
イオン交換水にポリマーを添加し、０．１％ポリマー溶液としたのち、ブルックフィールド型粘度計にて２５℃、ローターＮｏ１、６ｒｐｍの条件で測定した。
［残存アクリルアミド］
水溶性重合体２．５ｇを溶剤（メタノール：水＝８：２）２５ｍｌで２４ｈｒ浸透抽出した後、ガスクロマトグラフィーにて測定した。[0.1% viscosity]
A polymer was added to ion-exchanged water to make a 0.1% polymer solution, and then measured with a Brookfield viscometer under conditions of 25 ° C., rotor No. 1 and 6 rpm.
[Residual acrylamide]
The water-soluble polymer 2.5 g was subjected to osmotic extraction for 24 hours with 25 ml of a solvent (methanol: water = 8: 2), and then measured by gas chromatography.
［実施例１］
５リットルのジュワー瓶にアクリルアミド（以下ＡＡｍと記す）２５質量％を含有した水溶液３０００ｇを入れた。ジュワー瓶内部を窒素ガスで置換し、１０℃に調温した。重合開始剤として、２，２’−アゾビス（２−アミジノプロパン）ジハイドロクロライド２００ｐｐｍ、過硫酸アンモニウム１０ｐｐｍ、亜硫酸水素ナトリウム１００ｐｐｍを加え、ＡＡｍを断熱重合させた。
得られた水溶性重合体ゲルを肉挽き機にて細断した。これに、２０質量％亜硫酸ナトリウム水溶液を仕込みモノマーに対して表１中の割合になるように添加、混合し、さらに、２４質量％苛性ソーダ水溶液を添加、混合した後、６０℃で１２時間乾燥した。得られた乾燥ペレットを粉砕機で粉砕し、粉末の水溶性重合体を得た。評価結果を表１に示す。[Example 1]
3000 g of an aqueous solution containing 25% by mass of acrylamide (hereinafter referred to as AAm) was placed in a 5-liter dewar. The inside of the dewar was replaced with nitrogen gas, and the temperature was adjusted to 10 ° C. As a polymerization initiator, 2,2′-azobis (2-amidinopropane) dihydrochloride (200 ppm), ammonium persulfate (10 ppm), and sodium hydrogensulfite (100 ppm) were added, and AAm was subjected to adiabatic polymerization.
The obtained water-soluble polymer gel was chopped with a meat grinder. To this, a 20% by mass sodium sulfite aqueous solution was added and mixed so as to have the ratio shown in Table 1 with respect to the monomer. Further, a 24% by mass caustic soda aqueous solution was added and mixed, and then dried at 60 ° C. for 12 hours. . The obtained dry pellets were pulverized with a pulverizer to obtain a powdered water-soluble polymer. The evaluation results are shown in Table 1.
［比較例１］
実施例１と同様にして水溶性重合体ゲルを得て、これを肉挽き機にて細断し、亜硫酸ナトリウム水溶液および苛性ソーダ水溶液を添加せずに、６０℃で１２時間乾燥した。得られた乾燥ペレットを粉砕機で粉砕し、粉末の水溶性重合体を得た。評価結果を表１に示す。[Comparative Example 1]
A water-soluble polymer gel was obtained in the same manner as in Example 1, and this was chopped with a meat grinder and dried at 60 ° C. for 12 hours without adding an aqueous sodium sulfite solution and an aqueous caustic soda solution. The obtained dry pellets were pulverized with a pulverizer to obtain a powdered water-soluble polymer. The evaluation results are shown in Table 1.
［比較例２〜３］
実施例１と同様にして水溶性重合体ゲルを得て、これを肉挽き機にて細断した。これに、２０質量％亜硫酸ナトリウム水溶液を仕込みモノマーに対して表１中の割合になるように添加、混合し、さらに、２４質量％苛性ソーダ水溶液を添加、混合した後、６０℃で１２時間乾燥した。得られた乾燥ペレットを粉砕機で粉砕し、粉末の水溶性重合体を得た。評価結果を表１に示す。[Comparative Examples 2-3]
A water-soluble polymer gel was obtained in the same manner as in Example 1, and this was chopped with a meat grinder. To this, a 20% by mass sodium sulfite aqueous solution was added and mixed so as to have the ratio shown in Table 1 with respect to the monomer. Further, a 24% by mass caustic soda aqueous solution was added and mixed, and then dried at 60 ° C. for 12 hours. . The obtained dry pellets were pulverized with a pulverizer to obtain a powdered water-soluble polymer. The evaluation results are shown in Table 1.
［実施例２］
ＡＡｍ２２．５質量％、アクリル酸ソーダ（ＡＡＮａ）２．５質量％を含有した水溶液を用いた以外は、実施例１と同様にして水溶性重合体ゲルを得た。
得られた水溶性重合体ゲルを肉挽き機にて細断した。これに、２０質量％亜硫酸ナトリウム水溶液を仕込みモノマーに対して表１中の割合になるように添加、混合し、さらに、２４質量％苛性ソーダ水溶液を添加、混合した後、６０℃で１２時間乾燥した。得られた乾燥ペレットを粉砕機で粉砕し、粉末の水溶性重合体を得た。評価結果を表１に示す。[Example 2]
A water-soluble polymer gel was obtained in the same manner as in Example 1 except that an aqueous solution containing 22.5% by mass of AAm and 2.5% by mass of sodium acrylate (AANa) was used.
The obtained water-soluble polymer gel was chopped with a meat grinder. To this, a 20% by mass sodium sulfite aqueous solution was added and mixed so as to have the ratio shown in Table 1 with respect to the monomer. Further, a 24% by mass caustic soda aqueous solution was added and mixed, and then dried at 60 ° C. for 12 hours. . The obtained dry pellets were pulverized with a pulverizer to obtain a powdered water-soluble polymer. The evaluation results are shown in Table 1.
［比較例４］
実施例２と同様にして水溶性重合体ゲルを得て、これを肉挽き機にて細断した。これに、２０質量％亜硫酸ナトリウム水溶液を仕込みモノマーに対して表１中の割合になるように添加、混合した。さらに、２４質量％苛性ソーダ水溶液を添加、混合した後、６０℃で１２時間乾燥した。得られた乾燥ペレットを粉砕機で粉砕し、粉末の水溶性重合体を得た。評価結果を表１に示す。[Comparative Example 4]
A water-soluble polymer gel was obtained in the same manner as in Example 2, and this was chopped with a meat grinder. To this, a 20 mass% sodium sulfite aqueous solution was added and mixed so as to have the ratio shown in Table 1 with respect to the monomer. Further, a 24 mass% aqueous sodium hydroxide solution was added and mixed, and then dried at 60 ° C for 12 hours. The obtained dry pellets were pulverized with a pulverizer to obtain a powdered water-soluble polymer. The evaluation results are shown in Table 1.
［実施例３］
ＡＡｍ２０．５質量％、アクリル酸ソーダ（ＡＡＮａ）４．５質量％を含有した水溶液を用いた以外は、実施例１と同様にして水溶性重合体ゲルを得た。
得られた水溶性重合体ゲルを肉挽き機にて細断した。これに、２０質量％亜硫酸ナトリウム水溶液を仕込みモノマーに対して表１中の割合になるように添加、混合し、さらに、２４質量％苛性ソーダ水溶液を添加、混合した後、６０℃で１２時間乾燥した。得られた乾燥ペレットを粉砕機で粉砕し、粉末の水溶性重合体を得た。評価結果を表１に示す。[Example 3]
A water-soluble polymer gel was obtained in the same manner as in Example 1 except that an aqueous solution containing 20.5% by mass of AAm and 4.5% by mass of sodium acrylate (AANa) was used.
The obtained water-soluble polymer gel was chopped with a meat grinder. To this, a 20% by mass sodium sulfite aqueous solution was added and mixed so as to have the ratio shown in Table 1 with respect to the monomer. Further, a 24% by mass caustic soda aqueous solution was added and mixed, and then dried at 60 ° C. for 12 hours. . The obtained dry pellets were pulverized with a pulverizer to obtain a powdered water-soluble polymer. The evaluation results are shown in Table 1.
［比較例５］
実施例３と同様にして水溶性重合体ゲルを得て、これを肉挽き機にて細断し、亜硫酸ナトリウム水溶液および苛性ソーダ水溶液を添加せずに、６０℃で１２時間乾燥した。得られた乾燥ペレットを粉砕機で粉砕し、粉末の水溶性重合体を得た。評価結果を表１に示す。[Comparative Example 5]
A water-soluble polymer gel was obtained in the same manner as in Example 3, and this was chopped with a meat grinder and dried at 60 ° C. for 12 hours without adding an aqueous sodium sulfite solution and an aqueous caustic soda solution. The obtained dry pellets were pulverized with a pulverizer to obtain a powdered water-soluble polymer. The evaluation results are shown in Table 1.
［実施例４］
ＡＡｍ１８．０質量％、アクリル酸ソーダ（ＡＡＮａ）７．０質量％を含有した水溶液を用いた以外は、実施例１と同様にして水溶性重合体ゲルを得た。
得られた水溶性重合体ゲルを肉挽き機にて細断した。これに、２０質量％亜硫酸ナトリウム水溶液を仕込みモノマーに対して表１中の割合になるように添加、混合し、さらに、２４質量％苛性ソーダ水溶液を添加、混合した後、６０℃で１２時間乾燥した。得られた乾燥ペレットを粉砕機で粉砕し、粉末の水溶性重合体を得た。評価結果を表１に示す。[Example 4]
A water-soluble polymer gel was obtained in the same manner as in Example 1 except that an aqueous solution containing 18.0% by mass of AAm and 7.0% by mass of sodium acrylate (AANa) was used.
The obtained water-soluble polymer gel was chopped with a meat grinder. To this, a 20% by mass sodium sulfite aqueous solution was added and mixed so as to have the ratio shown in Table 1 with respect to the monomer. Further, a 24% by mass caustic soda aqueous solution was added and mixed, and then dried at 60 ° C. for 12 hours. . The obtained dry pellets were pulverized with a pulverizer to obtain a powdered water-soluble polymer. The evaluation results are shown in Table 1.
［比較例６］
実施例４と同様にして水溶性重合体ゲルを得て、これを肉挽き機にて細断し、亜硫酸ナトリウム水溶液および苛性ソーダ水溶液を添加せずに、６０℃で１２時間乾燥した。得られた乾燥ペレットを粉砕機で粉砕し、粉末の水溶性重合体を得た。評価結果を表１に示す。[Comparative Example 6]
A water-soluble polymer gel was obtained in the same manner as in Example 4, and this was chopped with a meat grinder and dried at 60 ° C. for 12 hours without adding an aqueous sodium sulfite solution and an aqueous caustic soda solution. The obtained dry pellets were pulverized with a pulverizer to obtain a powdered water-soluble polymer. The evaluation results are shown in Table 1.
［実施例５］
ＡＡｍ２０．０質量％、アクリル酸ソーダ（ＡＡＮａ）２．０質量％、２−アクリルアミド−２−メチルプロパンスルホン酸ナトリウム３．０質量％を含有した水溶液を用いた以外は、実施例１と同様にして水溶性重合体ゲルを得た。
得られた水溶性重合体ゲルを肉挽き機にて細断した。これに、２０質量％亜硫酸ナトリウム水溶液を仕込みモノマーに対して表１中の割合になるように添加、混合し、さらに、２４質量％苛性ソーダ水溶液を添加、混合した後、６０℃で１２時間乾燥した。得られた乾燥ペレットを粉砕機で粉砕し、粉末の水溶性重合体を得た。評価結果を表１に示す。[Example 5]
Example 1 was used except that an aqueous solution containing 20.0% by weight of AAm, 2.0% by weight of sodium acrylate (AANa), and 3.0% by weight of sodium 2-acrylamido-2-methylpropanesulfonate was used. Thus, a water-soluble polymer gel was obtained.
The obtained water-soluble polymer gel was chopped with a meat grinder. To this, a 20% by mass sodium sulfite aqueous solution was added and mixed so as to have the ratio shown in Table 1 with respect to the monomer. Further, a 24% by mass caustic soda aqueous solution was added and mixed, and then dried at 60 ° C. for 12 hours. . The obtained dry pellets were pulverized with a pulverizer to obtain a powdered water-soluble polymer. The evaluation results are shown in Table 1.
［比較例７］
実施例５と同様にして水溶性重合体ゲルを得て、これを肉挽き機にて細断し、亜硫酸ナトリウム水溶液および苛性ソーダ水溶液を添加せずに、６０℃で１２時間乾燥した。得られた乾燥ペレットを粉砕機で粉砕し、粉末の水溶性重合体を得た。評価結果を表１に示す。[Comparative Example 7]
A water-soluble polymer gel was obtained in the same manner as in Example 5, and this was chopped with a meat grinder and dried at 60 ° C. for 12 hours without adding an aqueous sodium sulfite solution and an aqueous caustic soda solution. The obtained dry pellets were pulverized with a pulverizer to obtain a powdered water-soluble polymer. The evaluation results are shown in Table 1.
比較例１、５、６および７の水溶性重合体は、乾燥時に亜硫酸ナトリウムおよび苛性ソーダを添加していないので、残存ＡＡｍが多く検出された。
比較例２の水溶性重合体は、亜硫酸ナトリウムおよび苛性ソーダの添加量が２．０質量％以上であったため、水溶性重合体の加水分解によりＡＶ値と粘度が上昇した。
比較例３の水溶性重合体は、苛性ソーダの添加量が２．０質量％以上であり、かつ亜硫酸ナトリウムの添加量よりも多いため、水溶性重合体の加水分解によりＡＶ値と粘度が上昇した。
比較例４の水溶性重合体は、亜硫酸ナトリウムおよび苛性ソーダの添加量が０．１質量％未満であったため、残存ＡＡｍが多く検出された。In the water-soluble polymers of Comparative Examples 1, 5, 6, and 7, a large amount of residual AAm was detected because sodium sulfite and caustic soda were not added during drying.
In the water-soluble polymer of Comparative Example 2, since the addition amount of sodium sulfite and caustic soda was 2.0% by mass or more, the AV value and the viscosity increased due to hydrolysis of the water-soluble polymer.
In the water-soluble polymer of Comparative Example 3, the addition amount of caustic soda was 2.0% by mass or more and more than the addition amount of sodium sulfite, so that the AV value and the viscosity increased due to hydrolysis of the water-soluble polymer. .
In the water-soluble polymer of Comparative Example 4, the amount of sodium sulfite and caustic soda added was less than 0.1% by mass, and thus a large amount of residual AAm was detected.
以上説明したように、本発明の製造方法は、少なくともアクリルアミド系モノマーおよび／またはアニオン性ビニルモノマーを重合して得られた含水状態の水溶性重合体を乾燥するに際し、含水状態の水溶性重合体に、仕込みモノマーに対して０．１質量％以上２．０質量％未満の亜硫酸アルカリ金属塩、亜硫酸水素アルカリ金属塩およびピロ亜硫酸アルカリ金属塩からなる群より選ばれた少なくとも１種と、仕込みモノマーに対して０．１質量％以上２．０質量％未満のアルカリ剤とをあらかじめ添加した後、含水状態の水溶性重合体を乾燥する方法であるので、高分子凝集剤としての水溶性重合体の性能を劣化、変化させることなく、水溶性重合体中の残存モノマーが低減された水溶性重合体を得ることができる。 As described above, the production method of the present invention is a method for drying a water-soluble water-soluble polymer obtained by polymerizing at least an acrylamide monomer and / or an anionic vinyl monomer. And at least one selected from the group consisting of an alkali metal sulfite, an alkali metal bisulfite, and an alkali metal pyrosulfite with a content of 0.1% by mass or more and less than 2.0% by mass with respect to the charged monomer, and the charged monomer The water-soluble polymer as a polymer flocculant is a method of drying a water-soluble water-soluble polymer after adding 0.1% by mass or more and less than 2.0% by mass of an alkali agent in advance. A water-soluble polymer in which the residual monomer in the water-soluble polymer is reduced can be obtained without degrading or changing the performance.
また、前記アニオン性ビニルモノマーは、アクリル酸、アクリル酸の塩、メタアクリル酸、メタクリル酸の塩、ビニルスルホン酸およびビニルスルホン酸の塩からなる群から選ばれた少なくとも１種であれば、水溶性、凝集性能等に優れる水溶性重合体を得ることができる。
また、前記亜硫酸アルカリ金属塩、亜硫酸水素アルカリ金属塩およびピロ亜硫酸アルカリ金属塩からなる群より選ばれた少なくとも１種の添加量は、前記アルカリ剤の添加量以上であれば、水溶性重合体の機能を低下させることなく、未反応のモノマーを低減することができる。The anionic vinyl monomer is water-soluble if it is at least one selected from the group consisting of acrylic acid, acrylic acid salt, methacrylic acid, methacrylic acid salt, vinyl sulfonic acid and vinyl sulfonic acid salt. Water-soluble polymer having excellent properties and agglomeration performance can be obtained.
In addition, if the addition amount of at least one selected from the group consisting of the alkali metal sulfite, alkali metal bisulfite and alkali metal pyrosulfite is equal to or greater than the addition amount of the alkali agent, the water-soluble polymer Unreacted monomers can be reduced without reducing the function.
Claims (2)
When drying a water-soluble water-soluble polymer obtained by polymerizing at least an acrylamide-based monomer , or at least an acrylamide-based monomer and an anionic vinyl monomer, At least one selected from the group consisting of an alkali metal sulfite, an alkali metal bisulfite, and an alkali metal bisulphite of 0.6 to 1.2% by mass, and then added to the charged monomer. A method for producing a water-soluble polymer in which a water-soluble water-soluble polymer is dried after adding 0.5% by mass or more and 1.0% by mass or less of an alkaline agent, the alkali metal sulfite, hydrogen sulfite An addition amount of at least one selected from the group consisting of alkali metal salts and alkali metal pyrosulfites, and Method for producing a water-soluble polymer, wherein the ratio of the amount of agent (amount of addition amount / alkali agent sulfite) is 1.0 to 1.2.
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| CN113429512B (en) * | 2021-06-02 | 2022-08-02 | 宁波锋成先进能源材料研究院有限公司 | Application of water-soluble polymer as curing agent in cement-based material |
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