JPH0891899A - Production of water reducing agent - Google Patents
Production of water reducing agentInfo
- Publication number
- JPH0891899A JPH0891899A JP6235142A JP23514294A JPH0891899A JP H0891899 A JPH0891899 A JP H0891899A JP 6235142 A JP6235142 A JP 6235142A JP 23514294 A JP23514294 A JP 23514294A JP H0891899 A JPH0891899 A JP H0891899A
- Authority
- JP
- Japan
- Prior art keywords
- reducing agent
- water reducing
- aqueous solution
- calcium
- raw material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/02—Treatment
- C04B20/023—Chemical treatment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/30—Condensation polymers of aldehydes or ketones
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
- C04B2111/1025—Alkali-free or very low alkali-content materials
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、アルカリ分であるナト
リウムとカリウムを全く含まないか著しく少くした減水
剤の製造方法に関する。本発明で得られた減水剤は、セ
メント、石膏などの水性ペースト、モルタル、コンクリ
ートなどの用途、特にアルカリ分の混入を極力抑制する
用途に好適に利用される。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a water reducing agent which contains no or significantly reduced amounts of sodium and potassium which are alkaline components. The water reducing agent obtained by the present invention is suitably used for applications such as cement, gypsum and other aqueous pastes, mortar, concrete, etc., especially for the purpose of suppressing the inclusion of alkali components as much as possible.
【０００２】[0002]
【従来の技術】近年、所謂アルカリ骨材反応によるコン
クリートの早期劣化が問題となっている。この対策のひ
とつとして、コンクリート中のアルカリ分としてナトリ
ウムとカリウムの量をNa20換算にて３．０ｋｇ／ｍ3 以
下に抑えるように規制されている。そのためには、原料
セメントおよび骨材に由来するアルカリ分を抑制するこ
とが何よりも優先して重要であるが、コンクリート混和
剤である減水剤もアルカリ分の少ない方がより好ましい
と考えられる。特に、単位セメント量を５００ｋｇ／ｍ
3 以上も使用する高強度コンクリートや高性能減水剤を
より多く使用する高流動化コンクリートの場面では、ア
ルカリ分を全く含まないかまたは著しく少なくした減水
剤がより好ましいことになる。2. Description of the Related Art In recent years, early deterioration of concrete due to so-called alkaline aggregate reaction has become a problem. As one of the measures against this, the amount of sodium and potassium as an alkali content in concrete is regulated to be 3.0 kg / m 3 or less in terms of Na 20 conversion. For that purpose, it is important to suppress the alkali content derived from the raw material cement and the aggregate, and it is considered that the water-reducing agent which is a concrete admixture preferably has a small alkali content. Especially, the unit cement amount is 500 kg / m
In the case of high-strength concrete that uses 3 or more or high-fluidity concrete that uses a large amount of high-performance water reducing agent, a water reducing agent that contains no or significantly reduced alkali content is more preferable.
【０００３】上述した背景に対応して、カルシウム塩型
の減水剤の各種の製造方法が提案されている。例えば、
カルシウム塩型のメラミン系減水剤の製造方法として
は、特公平１−４０８５０号公報には、メラミン、ホル
ムアルデヒドおよび亜硫酸カルシウムを１：３．５〜
６：０．５〜１の一定モル比でスルホン化メチロールメ
ラミンを一旦生成させた後、酸性にて縮合反応をさせ、
次いで水酸化カルシウムなどにて中和する方法が開示さ
れている。特開平３−２８５８５１号公報には、メラミ
ン、ホルムアルデヒドおよびアミドスルホン酸カルシウ
ムを１：３．３〜６．０：０．３〜１．５の一定モル比
で混合し、ｐＨ６．５〜８．０と６０〜９５℃で加熱す
る方法が開示されている。また、特公昭４１−１１７３
７号公報には、ナフタレンを濃硫酸にてスルホン化した
後、ホルムアルデヒドにて縮合し、次いで水酸化カルシ
ウムまたは酸化カルシウムにて中和してカルシウム塩型
のナフタレン系減水剤を得る方法が開示されている。In response to the above background, various methods for producing calcium salt type water reducing agents have been proposed. For example,
As a method for producing a calcium salt-type melamine-based water reducing agent, Japanese Patent Publication No. 1-40850 discloses that melamine, formaldehyde and calcium sulfite are added at a ratio of 1: 3.5-.
After once producing sulfonated methylolmelamine at a constant molar ratio of 6: 0.5 to 1, a condensation reaction is carried out under acidic conditions,
Then, a method of neutralizing with calcium hydroxide or the like is disclosed. JP-A-3-285851 discloses that melamine, formaldehyde, and calcium amidosulfonate are mixed at a constant molar ratio of 1: 3.3 to 6.0: 0.3 to 1.5, and the pH is 6.5 to 8. A method of heating at 0 and 60 to 95 ° C is disclosed. In addition, Japanese Examined Japanese Patent Publication 41-1173
Japanese Unexamined Patent Publication (Kokai) No. 7 discloses a method in which naphthalene is sulfonated with concentrated sulfuric acid, condensed with formaldehyde, and then neutralized with calcium hydroxide or calcium oxide to obtain a calcium salt-type naphthalene-based water reducing agent. ing.
【０００４】[0004]
【発明が解決しようとする課題】特公平１−４０８５０
号公報の方法では、実際には亜硫酸カルシウムを利用で
きないので、同公報の例３に記載されているように酸化
カルシウム存在下にて二酸化硫黄ガスを導入してスルホ
ン化反応を行う方法となり、製造自体が効率的とはいえ
ない。特開平３−２８５８５１号公報の方法では、反応
条件に制約があるために得られたカルシウム塩型のメラ
ミン系減水剤は、従来のナトリウム塩メラミン系減水剤
と比べ、減水性能および長期安定性が不十分である。ま
た、カルシウム塩型のナフタレン系減水剤の製造方法
は、中和工程にて生成した、濾過が困難な大量の硫酸カ
ルシウムを除去する必要があるので効率的でなく、しか
もその性能は、従来のナトリウム塩ナフタレン系減水剤
のそれより不十分であるという問題がある。そこで、本
発明者らは、カルシウム塩型の減水剤の製造方法を鋭意
検討した結果、既存の減水剤を出発原料として、減水性
能と長期安定性を損なうことなくカルシウム塩型の減水
剤が効率的かつ簡便に製造できる方法を見出し本発明を
完成した。[Patent Document 1] Japanese Patent Publication No. 1-40850
In the method of the publication, since calcium sulfite cannot be actually used, as described in Example 3 of the publication, a method of introducing a sulfur dioxide gas in the presence of calcium oxide to carry out a sulfonation reaction is produced. It is not efficient in itself. In the method of JP-A-3-285851, the calcium salt-type melamine-based water reducing agent obtained due to the restriction of the reaction conditions is superior in water-reducing performance and long-term stability to the conventional sodium salt melamine-based water reducing agent. Is insufficient. Further, the method for producing a calcium salt-type naphthalene-based water reducing agent is not efficient because it is necessary to remove a large amount of calcium sulfate which is generated in the neutralization step and which is difficult to filter. There is a problem that it is insufficient than that of the sodium salt naphthalene type water reducing agent. Therefore, as a result of intensive studies on the method for producing a calcium salt-type water reducing agent, the present inventors have found that an existing water reducing agent can be used as a starting material and a calcium salt-type water reducing agent can be efficiently used without impairing the water reducing performance and long-term stability. The present invention has been completed by finding a method that can be produced simply and simply.
【０００５】[0005]
【課題を解決するための手段】すなわち、本発明は、カ
ルシウム型カチオン交換樹脂を充填したカラムにナトリ
ウムおよび／またはカリウムを含む原料減水剤水溶液を
通液することにより、該水溶液に含まれるナトリウムお
よび／またはカリウムを該交換樹脂のカルシウムとイオ
ン交換させることを特徴とする減水剤水溶液の製造方法
である。That is, according to the present invention, a raw material water reducing agent aqueous solution containing sodium and / or potassium is passed through a column packed with a calcium-type cation exchange resin to obtain sodium and sodium contained in the aqueous solution. And / or potassium is ion-exchanged with calcium of the exchange resin, which is a method for producing an aqueous solution of a water reducing agent.
【０００６】以下、本発明を詳細に説明する。本発明に
使用される原料減水剤水溶液は、アルカリ分としてナト
リウムおよび／またはカリウムを含むところの、ナフタ
レン系減水剤であるナフタレンホルムアルデヒド縮合物
のスルホン酸塩水溶液、メラミン系減水剤であるメラミ
ンホルムアルデヒド縮合物のスルホン酸塩水溶液、リグ
ニンスルホン酸塩水溶液、オキシカルボン酸塩水溶液、
ポリカルボン酸塩および芳香族アミノスルホン酸塩ポリ
マー水溶液から選ばれる。これらの減水剤水溶液を２〜
３種混合して原料減水剤水溶液とすることもできる。特
に、高性能減水剤として広く利用されているナフタレン
ホルムアルデヒド縮合物のスルホン酸塩水溶液すなわち
ナフタレン系減水剤、メラミンホルムアルデヒド縮合物
のスルホン酸塩水溶液すなわちメラミン系減水剤および
これらの混合物が、本発明の原料減水剤水溶液として好
ましい。最も好ましくはメラミンホルムアルデヒド縮合
物のスルホン酸塩水溶液であるメラミン系減水剤であ
る。カルシウム型カチオン交換樹脂を充填したカラムに
通液するときのこれらの減水剤水溶液は、１．０〜６．
０重量％、好ましくは２．０〜５．０重量％のナトリウ
ムおよび／またはカリウムを含み、かつ２〜８００ｍＰ
ａ・ｓ、望ましくは３〜２００ｍＰａ・ｓの粘度を有す
る。場合によっては、濃縮または水希釈もしくは加熱し
て粘度を調整した原料減水剤水溶液を該カラムに通液す
る。The present invention will be described in detail below. The raw material water-reducing agent aqueous solution used in the present invention is a naphthalene-type water-reducing agent, a naphthalene-formaldehyde condensate sulfonate solution containing sodium and / or potassium as an alkaline component, and a melamine-type water-reducing agent, melamine formaldehyde condensation. Sulfonate aqueous solution, lignin sulfonate aqueous solution, oxycarboxylate aqueous solution,
It is selected from aqueous solutions of polycarboxylates and aromatic aminosulfonate polymers. 2 to 2 of these water reducing agent aqueous solutions
It is also possible to mix three kinds to obtain a raw material water reducing agent aqueous solution. Particularly, a sulfonate aqueous solution of a naphthalene formaldehyde condensate, that is, a naphthalene-based water reducing agent, a sulfonate aqueous solution of a melamine-formaldehyde condensate, that is, a melamine-based water reducing agent and a mixture thereof, which are widely used as a high-performance water reducing agent, are used in the present invention. Preferred as a raw material water reducing agent aqueous solution. Most preferred is a melamine-type water reducing agent which is an aqueous sulfonate solution of a melamine formaldehyde condensate. These water-reducing agent aqueous solutions when they are passed through a column packed with a calcium type cation exchange resin are 1.0 to 6.
0% by weight, preferably 2.0-5.0% by weight sodium and / or potassium, and 2-800 mP
It has a viscosity of a · s, preferably 3 to 200 mPa · s. Depending on the case, the raw material water reducing agent aqueous solution whose viscosity is adjusted by concentration or dilution with water or heating is passed through the column.
【０００７】本発明で使用するカチオン交換樹脂は、カ
ルシウム型カチオン交換樹脂であるが、スルホン酸基ま
たはカルボン酸基を有する、スチレン系、アクリル系、
メタクリル系などの通常の市販のカチオン交換樹脂から
出発してカルシウム型カチオン交換樹脂へ調製する。例
えば、カルシウム型カチオン交換樹脂は、次のように調
製される。ナトリウム型カチオン交換樹脂をカラムに充
填し、イオン交換容量を越える量の過剰の酸、例えば、
塩酸を通液して水素型カチオン交換樹脂に換えた後、流
出水のｐＨが中性になるまで純水を通液・洗浄する。そ
の後、イオン交換容量を越える充分な量のカルシウム塩
の水溶液を通液する。水酸化カルシウムにて飽和したカ
ルシウム塩の水溶液を通液する方がイオン交換を促進す
るので都合がよい。該カルシウム塩としては、水への溶
解度の大きな塩化カルシウム、硝酸カルシウム、アミド
スルホン酸カルシウムなどの水溶液が挙げられる。次い
で、流出水のｐＨがアルカリ性を示さなくなるまで純水
で洗浄すると、カルシウム型カチオン交換樹脂となる。The cation exchange resin used in the present invention is a calcium type cation exchange resin, which has sulfonic acid group or carboxylic acid group, styrene type, acrylic type,
A calcium type cation exchange resin is prepared by starting from an ordinary commercially available cation exchange resin such as methacrylic resin. For example, a calcium type cation exchange resin is prepared as follows. Sodium type cation exchange resin was packed in a column and an excess amount of acid exceeding the ion exchange capacity, for example,
After passing through hydrochloric acid to change to a hydrogen-type cation exchange resin, pure water is passed through and washed until the pH of the outflow water becomes neutral. Then, a sufficient amount of an aqueous solution of calcium salt exceeding the ion exchange capacity is passed. It is convenient to pass an aqueous solution of a calcium salt saturated with calcium hydroxide because it promotes ion exchange. Examples of the calcium salt include aqueous solutions of calcium chloride, calcium nitrate, calcium amidosulfonate, etc., which have high solubility in water. Then, the calcium-type cation exchange resin is obtained by washing with pure water until the pH of the outflow water does not show alkalinity.
【０００８】上記のように得られたカルシウム型カチオ
ン交換樹脂カラムに、上記の原料減水剤水溶液を空間速
度 1〜5 で通液すると、該水溶液中のナトリウムおよび
／またはカリウムイオンのアルカリ分の大部分は、カル
シウムイオンと置換され、本発明のカルシウム塩型の減
水剤水溶液が得られる。この場合、該水溶液に含まれる
カチオンをイオン交換するに充分なイオン交換容量をも
ったカルシウム型カチオン交換樹脂を使用することが重
要であることは勿論である。また、該原料水溶液の粘度
が大きい場合には、原料水溶液を加熱または水希釈し
て、逆に粘度が小さい場合には濃縮して、粘度を調節し
て該カラムに供給することも可能である。このようにし
て、一回のイオン交換の操作により、該水溶液のアルカ
リ分が５０％以上、通常８０％以上の交換率にてカルシ
ウムイオンにイオン交換された減水剤水溶液が得られ
る。また、得られたカルシウム塩塩型の減水剤水溶液
を、さらに別のカルシウム型カチオン交換樹脂カラムに
通液してイオン交換率をさらに増加させることも可能で
ある。なお、イオン交換操作を経たカラムは、ナトリウ
ム型および／またはカリウム型カチオン交換樹脂となっ
ているので、上述した方法によりカルシウム型カチオン
交換樹脂に再生すれば繰り返し再使用ができる。When the above raw material water reducing agent aqueous solution is passed through the calcium type cation exchange resin column obtained as described above at a space velocity of 1 to 5, a large amount of alkali content of sodium and / or potassium ions in the aqueous solution is obtained. A part is replaced with calcium ion, and the calcium salt type water reducing agent aqueous solution of the present invention is obtained. In this case, it is of course important to use a calcium type cation exchange resin having an ion exchange capacity sufficient to ion exchange the cations contained in the aqueous solution. Further, when the viscosity of the raw material aqueous solution is high, the raw material aqueous solution can be heated or diluted with water, and conversely, when the viscosity is low, the raw material aqueous solution can be concentrated to adjust the viscosity and then supplied to the column. . In this way, a single ion exchange operation gives an aqueous solution of the water reducing agent ion-exchanged with calcium ions at an exchange rate of 50% or more, usually 80% or more, of the aqueous solution. It is also possible to pass the obtained calcium salt salt type water reducing agent aqueous solution through another calcium type cation exchange resin column to further increase the ion exchange rate. Since the column that has undergone the ion exchange operation is a sodium type and / or potassium type cation exchange resin, it can be reused repeatedly by regenerating it into a calcium type cation exchange resin by the method described above.
【０００９】[0009]
【作用】カルシウム型カチオン交換樹脂を充填したカラ
ムに原料減水剤水溶液を通液する操作のみで、該水溶液
中のナトリウムおよび／またはカリウムのアルカリ分の
大部分が、カラム中の該樹脂のカルシウムとイオン交換
し、カルシウム塩型の減水剤水溶液が容易に得られる。[Function] Most of the alkali content of sodium and / or potassium in the aqueous solution of the raw water-reducing agent is passed through the column filled with the calcium-type cation exchange resin and the calcium content of the resin in the column A calcium salt type water reducing agent aqueous solution can be easily obtained by ion exchange.
【００１０】原料減水剤水溶液に含まれるナトリウムお
よび／またはカリウムの量が１．０重量％未満では、イ
オン交換率が急激に低下するので効率的でない。ナトリ
ウムおよび／またはカリウムの量が６．０重量％を越す
原料減水剤水溶液にも、原理上、本発明の方法を適用で
きるが、原料減水剤水溶液自体の性能が劣る場合が多く
実用的でない。When the amount of sodium and / or potassium contained in the raw material water-reducing agent aqueous solution is less than 1.0% by weight, the ion exchange rate is drastically reduced, which is not efficient. In principle, the method of the present invention can be applied to a raw material water reducing agent aqueous solution in which the amount of sodium and / or potassium exceeds 6.0% by weight, but the raw material water reducing agent aqueous solution itself is often inferior in performance, which is not practical.
【００１１】原料減水剤水溶液の粘度が８００ｍＰａ・
ｓを越す場合、イオン交換率が低下する。原料減水剤水
溶液の粘度が２ｍＰａ・ｓ未満では、原料減水剤水溶液
の固形分が小さすぎるかまたはその性能に問題があるの
で実用性に乏しい。The viscosity of the raw water reducing agent aqueous solution is 800 mPa.
If it exceeds s, the ion exchange rate decreases. When the viscosity of the raw material water-reducing agent aqueous solution is less than 2 mPa · s, the solid content of the raw material water-reducing agent aqueous solution is too small or the performance thereof is poor, so that it is not practical.
【００１２】[0012]
【実施例】以下に実施例を示し、本発明をより具体的に
説明する。 実施例１ 内径２０ｃｍで高さ７０ｃｍのイオン交換塔にナトリウ
ム型カチオン交換樹脂（オルガノ株式会社の商品名 ア
ンバーライトＩＲ−１２０Ｂ）１９リットルを湿潤状態
で充填した。このカラムに交換容量以上の１０重量％塩
酸を通液・水洗して水素型カチオン交換樹脂とした。次
に、このカラムに、水酸化カルシウムを飽和させた１０
重量％塩化カルシウム水溶液を交換容量以上に通液し
た。水洗してカルシウム型カチオン交換樹脂カラムを得
た。一方、特公平２−４３７６３号公報の実施例２に準
じて、固形分４２．０重量％、粘度１５０ｍＰａ・ｓ
（２０℃）およびナトリウム４．２重量％である原料減
水剤水溶液を調製した。この原料減水剤水溶液２０．８
０ｋｇを空間速度１．０と温度２０℃の通液条件にて上
記カラムに通液してイオン交換を行ったところ、固形分
３５．０重量％でナトリウム０．３２重量％を含むカル
シウム塩型の減水剤水溶液を得た。このときのイオン交
換率は、９１％であった。EXAMPLES The present invention will be described more concretely with reference to the following examples. Example 1 An ion exchange column having an inner diameter of 20 cm and a height of 70 cm was filled with 19 liters of sodium type cation exchange resin (trade name: Amberlite IR-120B, manufactured by Organo Corporation) in a wet state. A hydrogen-type cation exchange resin was obtained by passing 10% by weight of hydrochloric acid having an exchange capacity or more through this column and washing with water. The column was then saturated with calcium hydroxide 10
A weight% calcium chloride aqueous solution was passed over the exchange volume. It was washed with water to obtain a calcium type cation exchange resin column. On the other hand, according to Example 2 of JP-B-2-43763, the solid content is 42.0% by weight and the viscosity is 150 mPa · s.
(20 ° C.) and a raw water reducing agent aqueous solution containing 4.2% by weight of sodium were prepared. This raw water reducing agent aqueous solution 20.8
When 0 kg was passed through the column under the passing conditions of a space velocity of 1.0 and a temperature of 20 ° C. for ion exchange, a calcium salt type containing 35.0% by weight of solids and 0.32% by weight of sodium A water reducing agent aqueous solution was obtained. The ion exchange rate at this time was 91%.
【００１３】実施例２ 実施例１と同様にカルシウム型カチオン交換樹脂１９リ
ットルを充填したカラムを使用した。原料減水剤水溶液
であるメラミン系減水剤は、実施例１と同様に特公平２
−４３７６３号公報の実施例２に準じて調製した。ただ
し、縮合時間を短縮して、より低粘度とした。固形分４
２．０重量％で粘度５０ｍＰａ・ｓ（２０℃）であり、
ナトリウム４．２重量％を含む原料減水剤水溶液を実施
例１と同一条件にて上記カラムに通液してイオン交換を
行い、固形分３５．０重量％でナトリウム０．３５重量
％のカルシウム塩型の減水剤水溶液を得た。このときの
イオン交換率は、９０％であった。Example 2 A column packed with 19 liters of calcium type cation exchange resin was used as in Example 1. The melamine-based water reducing agent, which is an aqueous solution of the raw material water reducing agent, was prepared in the same manner as in Example 1
It was prepared according to Example 2 of JP-A-43763. However, the condensation time was shortened to lower the viscosity. Solid content 4
It has a viscosity of 50 mPa · s (20 ° C.) at 2.0 wt%,
A raw material water reducing agent aqueous solution containing 4.2% by weight of sodium was passed through the column under the same conditions as in Example 1 to perform ion exchange, and a calcium salt of solid content 35.0% by weight and sodium 0.35% by weight. A water reducing agent aqueous solution of the type was obtained. The ion exchange rate at this time was 90%.
【００１４】実施例３ 実施例１と同様にカルシウム型カチオン交換樹脂１９リ
ットルを充填したカラムを調製し使用した。原料減水剤
水溶液であるメラミン系減水剤は、実施例１と同様に特
公平２−４３７６３号公報の実施例２に準じて調製し
た。ただし、縮合時間を延長して、より高粘度とした。
固形分４２．０重量％で粘度７５０ｍＰａ・ｓ（２０
℃）であり、ナトリウム４．２重量％を含む原料減水剤
水溶液を実施例１と同一条件にて上記カラムに通液して
イオン交換を行い、固形分３５．０重量％でナトリウム
１．６８重量％を含むカルシウム塩型の減水剤水溶液を
得た。このときのイオン交換率は、５２％であった。Example 3 A column packed with 19 liters of calcium type cation exchange resin was prepared and used in the same manner as in Example 1. A melamine-based water reducing agent, which is an aqueous raw material water reducing agent solution, was prepared in the same manner as in Example 1 according to Example 2 of JP-B-2-43763. However, the condensation time was extended to obtain a higher viscosity.
The solid content is 42.0% by weight and the viscosity is 750 mPa · s (20
C.), and a raw material water reducing agent aqueous solution containing 4.2% by weight of sodium was passed through the column under the same conditions as in Example 1 to perform ion exchange, so that the solid content was 35.0% by weight and sodium was 1.68. An aqueous calcium salt-type water reducing agent solution containing 50% by weight was obtained. The ion exchange rate at this time was 52%.
【００１５】実施例４ 実施例３で調製した原料減水剤水溶液を５０℃に加熱し
て、その粘度を７４ｍＰａ・ｓ（５０℃）として実施例
１と同様な方法にて調製したカルシウム型カチオン交換
樹脂１９リットルを充填したカラムに供給した。また、
カラム温度を５０℃とした以外は、実施例３と同様にカ
チオン交換操作を行った。固形分３５．０重量％でナト
リウム０．３４重量％のカルシウム塩型の減水剤水溶液
を得た。このときのイオン交換率は、９０％であった。Example 4 Calcium-type cation exchange prepared in the same manner as in Example 1 by heating the raw water-reducing agent aqueous solution prepared in Example 3 to 50 ° C. and adjusting the viscosity to 74 mPa · s (50 ° C.). The column was filled with 19 liters of resin. Also,
A cation exchange operation was performed in the same manner as in Example 3 except that the column temperature was 50 ° C. An aqueous calcium salt type water reducing agent solution having a solid content of 35.0% by weight and a sodium content of 0.34% by weight was obtained. The ion exchange rate at this time was 90%.
【００１６】実施例５ 実施例１で調製した原料減水剤水溶液を純水で希釈し
て、固形分１０．０重量％、粘度７ｍＰａ・ｓ（２０
℃）およびナトリウム１．００重量％の原料減水剤水溶
液を調製した。この原料減水剤水溶液８７．３６ｋｇ
を、実施例１と同様な方法にて調製したカルシウム型カ
チオン交換樹脂１９リットルを充填したカラムに空間速
度１．０、温度２０℃の通液条件にてイオン交換を行っ
たところ、固形分９.0重量％でナトリウム０．２6 重量
％を含んだカルシウム塩型の減水剤水溶液を得た。この
ときのイオン交換率は、７1 ％であった。Example 5 The raw material water reducing agent aqueous solution prepared in Example 1 was diluted with pure water to obtain a solid content of 10.0% by weight and a viscosity of 7 mPa · s (20
C.) and sodium 1.00 wt% raw material water reducing agent aqueous solution was prepared. 87.36 kg of this raw material water reducing agent aqueous solution
Was subjected to ion exchange in a column filled with 19 liters of calcium-type cation exchange resin prepared by the same method as in Example 1 under the passing conditions of a space velocity of 1.0 and a temperature of 20 ° C., to obtain a solid content of 9 A calcium salt type water reducing agent aqueous solution containing 0.06% by weight of sodium and 0.26% by weight of sodium was obtained. The ion exchange rate at this time was 71%.
【００１７】実施例６ 実施例１で調製した原料減水剤水溶液を純水で希釈し
て、固形分２０．０重量％、粘度１０ｍＰａ・ｓ（２０
℃）およびナトリウム２．０重量％の原料減水剤水溶液
を調製した。この原料減水剤水溶液４３．６８ｋｇを、
実施例１と同様な方法にて調製したカルシウム型カチオ
ン交換樹脂１９リットルを充填したカラムに空間速度
１．０で温度２０℃の通液条件にてイオン交換を行った
ところ、固形分１８．０重量％でナトリウム０．２１重
量％を含んだカルシウム塩型の減水剤水溶液を得た。こ
のときのイオン交換率は、８８％であった。Example 6 The raw material water reducing agent aqueous solution prepared in Example 1 was diluted with pure water to obtain a solid content of 20.0% by weight and a viscosity of 10 mPa · s (20
C.) and sodium 2.0% by weight as raw material water reducing agent aqueous solution was prepared. 43.68 kg of this raw material water reducing agent aqueous solution,
A column packed with 19 liters of a calcium-type cation exchange resin prepared by the same method as in Example 1 was subjected to ion exchange under the passing conditions of a space velocity of 1.0 and a temperature of 20 ° C. to obtain a solid content of 18.0. An aqueous calcium salt type water reducing agent solution containing 0.21% by weight of sodium was obtained. The ion exchange rate at this time was 88%.
【００１８】実施例７ 実施例１と同様にカルシウム型カチオン交換樹脂１９リ
ットルを充填したカラムを使用した。実施例１に使用し
た原料減水剤水溶液１３．８７ｋｇを空間速度１．０で
温度２０℃の通液条件にてイオン交換を行ったところ、
固形分３５．０重量％でナトリウム０．０１重量％以下
を含むカルシウム塩型の減水剤水溶液を得た。このとき
のイオン交換率は、ほぼ１００％であった。Example 7 As in Example 1, a column packed with 19 liters of calcium type cation exchange resin was used. When 13.87 kg of the raw material water-reducing agent aqueous solution used in Example 1 was subjected to ion exchange under the passing conditions of a space velocity of 1.0 and a temperature of 20 ° C.,
An aqueous calcium salt type water reducing agent solution having a solid content of 35.0% by weight and containing 0.01% by weight or less of sodium was obtained. The ion exchange rate at this time was almost 100%.
【００１９】実施例８ 実施例１と同様な方法にてカルシウム型カチオン交換樹
脂１９リットルを調製し、これを充填カラムとした。実
施例１に使用した原料減水剤水溶液２０．８０ｋｇを空
間速度５．０で温度２０℃の通液条件にてイオン交換を
行ったところ、固形分３５．０重量％でナトリウム０．
５1 重量％を含むカルシウム塩型の減水剤水溶液を得
た。このときのイオン交換率は、８6 ％であった。Example 8 In the same manner as in Example 1, 19 liters of calcium type cation exchange resin was prepared and used as a packed column. When 20.80 kg of the raw material water-reducing agent aqueous solution used in Example 1 was subjected to ion exchange under the passing conditions of a space velocity of 5.0 and a temperature of 20 ° C., the solid content was 35.0 wt% and the sodium content was 0.
A calcium salt type water reducing agent aqueous solution containing 51% by weight was obtained. The ion exchange rate at this time was 86%.
【００２０】実施例９ 実施例１と同様な方法にてカルシウム型カチオン交換樹
脂１９リットルを調製し、これを充填カラムとした。固
形分２２重量％でナトリウム２．３重量％を含む市販の
メラミン系減水剤３７．９８ｋｇを、空間速度１．０で
温度２０℃の通液条件にてカラムに通液した。その結
果、固形分２０重量％でナトリウム０．１３重量％を含
むカルシウム塩型の減水剤水溶液を得た。このときのイ
オン交換率は、９４％であった。Example 9 19 liters of calcium type cation exchange resin was prepared in the same manner as in Example 1 and used as a packed column. 37.98 kg of a commercially available melamine-type water reducing agent containing 22% by weight of solids and 2.3% by weight of sodium was passed through the column under the passing conditions of a space velocity of 1.0 and a temperature of 20 ° C. As a result, a calcium salt type water reducing agent aqueous solution containing 20% by weight of solids and 0.13% by weight of sodium was obtained. The ion exchange rate at this time was 94%.
【００２１】実施例１０ 実施例１と同様な方法にてカルシウム型カチオン交換樹
脂１９リットルを調製し、これを充填カラムとした。固
形分３５．０重量％で粘度３０ｍＰａ・ｓ（２０℃）お
よびナトリウム３．６重量％を含む市販のメラミン系減
水剤２４．２７ｋｇを、空間速度１．０で温度２０℃の
通液条件にてカラムに通液した。その結果、固形分３
０．０重量％でナトリウム０．３１重量％を含むカルシ
ウム塩型の減水剤水溶液を得た。このときのイオン交換
率は、９０％であった。Example 10 In the same manner as in Example 1, 19 liters of calcium type cation exchange resin was prepared and used as a packed column. 24.27 kg of a commercially available melamine-based water reducing agent containing a solid content of 35.0% by weight and a viscosity of 30 mPa · s (20 ° C.) and sodium of 3.6% by weight was subjected to a liquid passing condition of a space velocity of 1.0 and a temperature of 20 ° C. And passed through the column. As a result, solid content 3
A calcium salt type water reducing agent aqueous solution containing 0.01% by weight of sodium and 0.31% by weight of sodium was obtained. The ion exchange rate at this time was 90%.
【００２２】実施例１１ 実施例１と同様な方法にてカルシウム型カチオン交換樹
脂１９リットルを調製し、これを充填カラムとした。固
形分４０重量％、粘度５０ｍＰａ・ｓ（２０℃）および
ナトリウム２．７重量％である市販のナフタレン系減水
剤３２．３６ｋｇを、空間速度１．０で温度２０℃の条
件にてカラムに通液した。その結果、固形分３４重量％
でナトリウム０．２８重量％を含むカルシウム塩型の減
水剤水溶液を得た。このときのイオン交換率は、８８％
であった。Example 11 19 liters of calcium type cation exchange resin was prepared in the same manner as in Example 1 and used as a packed column. 32.36 kg of a commercially available naphthalene-based water reducing agent having a solid content of 40% by weight, a viscosity of 50 mPa · s (20 ° C) and sodium of 2.7% by weight was passed through the column at a space velocity of 1.0 and a temperature of 20 ° C. Liquor As a result, solid content 34% by weight
A calcium salt type water reducing agent aqueous solution containing 0.28% by weight of sodium was obtained. The ion exchange rate at this time is 88%
Met.
【００２３】参考例１ 本発明で得られた減水剤の性能を調べるため、第１表に
示すコンクリート配合の全材料を５０リットル傾胴型ミ
キサーに投入して３分間混練した。練り上がり後、直ち
に、JIS A 1101に従いスランプ値、JIS A 1128に従い空
気量をそれぞれ測定した。その結果の一部を第２表に示
した。第２表にて、比較例１、２および３の減水剤は、
それぞれ、実施例１、９および１０におけるイオン交換
に使用した原料減水剤水溶液である。なお、実施例１〜
１１で得られたカルシウム塩型の減水剤水溶液は、いず
れも減水性能と長期安定性に関して、原料減水剤水溶液
とほぼ同等であることを確認された。Reference Example 1 In order to investigate the performance of the water reducing agent obtained in the present invention, all the materials having the concrete composition shown in Table 1 were put into a 50 liter tilt type mixer and kneaded for 3 minutes. Immediately after kneading, the slump value according to JIS A 1101 and the air amount according to JIS A 1128 were measured. Some of the results are shown in Table 2. In Table 2, the water reducing agents of Comparative Examples 1, 2 and 3 are
These are the raw material water reducing agent aqueous solutions used for ion exchange in Examples 1, 9 and 10, respectively. In addition, Example 1
It was confirmed that each of the calcium salt-type water reducing agent aqueous solutions obtained in No. 11 had almost the same water reducing performance and long-term stability as the raw material water reducing agent aqueous solution.
【００２４】[0024]
【表１】 [Table 1]
【００２５】[0025]
【表２】 [Table 2]
【００２６】[0026]
【発明の効果】本発明の減水剤の製造方法により、原料
減水剤のアルカリ分の大部分を容易かつ効率的にカルシ
ウムと置換することができ、ほとんどアルカリ分を含ま
ないか、従来の減水剤水溶液のアルカリ分の２０％程度
しか含まないカルシウム塩型の減水剤水溶液が得られ
る。しかも従来の減水剤水溶液と同等の安定性と性能を
有する。従って、アルカリ分の混入を極力抑制する用
途、例えば、高強度コンクリートや高流動化コンクリー
トに好適に利用することができる。EFFECTS OF THE INVENTION According to the method for producing a water reducing agent of the present invention, most of the alkali content of the raw water reducing agent can be easily and efficiently replaced with calcium, and the water reducing agent containing almost no alkali content or the conventional water reducing agent can be used. A calcium salt type water reducing agent aqueous solution containing only about 20% of the alkali content of the aqueous solution is obtained. Moreover, it has the same stability and performance as the conventional water reducing agent aqueous solution. Therefore, it can be suitably used for applications in which the mixing of alkali components is suppressed as much as possible, for example, high-strength concrete and highly fluidized concrete.
Claims (3)
たカラムにナトリウムおよび／またはカリウムを含む原
料減水剤水溶液を通液することにより、該水溶液に含ま
れるナトリウムおよび／またはカリウムを該交換樹脂の
カルシウムとイオン交換させることを特徴とする減水剤
水溶液の製造方法。1. A sodium- and / or potassium-containing raw material water-reducing agent aqueous solution is passed through a column packed with a calcium-type cation-exchange resin to convert sodium and / or potassium contained in the aqueous solution into calcium of the exchange resin. A method for producing an aqueous solution of a water reducing agent, which comprises performing ion exchange.
％のナトリウムおよび／またはカリウムを含みかつ２〜
８００ｍＰａ・ｓの粘度である請求項１の製造方法。2. The raw material water reducing agent aqueous solution contains 1.0 to 6.0% by weight of sodium and / or potassium, and 2 to
The method of claim 1, wherein the viscosity is 800 mPa · s.
よび／またはナフタレン系減水剤である請求項１または
２記載の製造方法。3. The method according to claim 1, wherein the raw material water reducing agent aqueous solution is a melamine water reducing agent and / or a naphthalene water reducing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23514294A JP3477840B2 (en) | 1994-09-29 | 1994-09-29 | Manufacturing method of water reducing agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23514294A JP3477840B2 (en) | 1994-09-29 | 1994-09-29 | Manufacturing method of water reducing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0891899A true JPH0891899A (en) | 1996-04-09 |
| JP3477840B2 JP3477840B2 (en) | 2003-12-10 |
Family
ID=16981681
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23514294A Expired - Fee Related JP3477840B2 (en) | 1994-09-29 | 1994-09-29 | Manufacturing method of water reducing agent |
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| Country | Link |
|---|---|
| JP (1) | JP3477840B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119023A (en) * | 2014-06-25 | 2014-10-29 | 芜湖市三兴混凝土外加剂有限公司 | High-efficiency delayed coagulation water reducing agent |
-
1994
- 1994-09-29 JP JP23514294A patent/JP3477840B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104119023A (en) * | 2014-06-25 | 2014-10-29 | 芜湖市三兴混凝土外加剂有限公司 | High-efficiency delayed coagulation water reducing agent |
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| Publication number | Publication date |
|---|---|
| JP3477840B2 (en) | 2003-12-10 |
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