JPH06298555A - Admixture for cement - Google Patents
Admixture for cementInfo
- Publication number
- JPH06298555A JPH06298555A JP5108902A JP10890293A JPH06298555A JP H06298555 A JPH06298555 A JP H06298555A JP 5108902 A JP5108902 A JP 5108902A JP 10890293 A JP10890293 A JP 10890293A JP H06298555 A JPH06298555 A JP H06298555A
- Authority
- JP
- Japan
- Prior art keywords
- group
- component
- maleic anhydride
- general formula
- copolymer
- 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2664—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers
- C04B24/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of ethylenically unsaturated dicarboxylic acid polymers, e.g. maleic anhydride copolymers containing polyether side chains
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/308—Slump-loss preventing agents
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はセメント用添加剤に関す
る。FIELD OF THE INVENTION The present invention relates to an additive for cement.
【０００２】[0002]
【従来の技術】従来、コンクリート等、セメント配合物
の添加剤として、ナフタレンスルホン酸ホルムアルデヒ
ド縮合物塩、メラミンスルホン酸ホルムアルデヒド縮合
物塩、リグニンスルホン酸塩等が減水剤として用いられ
ている。近年、コンクリートには高強度の要求が高ま
り、コンクリート組成物中の水の量を少なくする必要性
が出てきた。上記添加剤はコンクリート組成物中の水の
量を少なくする効果はあるが、経時的に起こるコンクリ
ート組成物の流動性の低下、すなわち、スランプロスを
避けることはできなかった。このスランプロスを防止す
るために、種々の提案がなされている。特開昭６０−１
６８５１号公報には、粉体状のオレフィン・無水マレイ
ン酸共重合物とナフタリンスルホン酸ホルマリン縮合物
等の減水剤との配合物が提案されているが、分離が起き
やすく、不均一となる問題点がある。特開昭５９−１６
２１６２号公報には、ナフタリンスルホン酸ホルマリン
縮合物塩またはメラミンスルホン酸ホルマリン縮合物塩
とアリルアルコールアルキレンオキシド付加物−不飽和
ジカルボン酸共重合物との併用がスランプロスの防止に
有効であることが開示されているが、必ずしも十分では
ない。特開昭６３−２８５１４０号公報には、ポリオキ
シアルキレン不飽和エーテルと無水マレイン酸との共重
合体、その加水分解物またはその加水分解物の塩が提案
されているが、この場合もスランプロスの防止の面で必
ずしも十分でない。特開平２−１６３１０８号公報に
は、ポリオキシアルキレン不飽和エーテルとマレイン酸
エステルとの共重合物が提案されている。しかしながら
エステルを形成するアルコールが、２官能以上の場合は
水に不溶あるいは難溶で使いにくく、１官能の場合は凝
結時間が長くなるといった問題点がある。2. Description of the Related Art Conventionally, as additives for cement compounds such as concrete, naphthalene sulfonic acid formaldehyde condensate salt, melamine sulfonic acid formaldehyde condensate salt, lignin sulfonate and the like have been used as water reducing agents. In recent years, the demand for high strength in concrete has increased, and it has become necessary to reduce the amount of water in concrete compositions. Although the above-mentioned additives have the effect of reducing the amount of water in the concrete composition, it was not possible to avoid a decrease in fluidity of the concrete composition over time, that is, slump loss. Various proposals have been made to prevent this slump loss. JP 60-1
6851 proposes a blend of a powdery olefin / maleic anhydride copolymer and a water-reducing agent such as a naphthalenesulfonic acid formalin condensate, but the problem that separation easily occurs and becomes non-uniform There is a point. Japanese Patent Laid-Open No. 59-16
No. 2162 discloses that the combined use of a naphthalene sulfonic acid formalin condensate salt or a melamine sulfonic acid formalin condensate salt and an allyl alcohol alkylene oxide adduct-unsaturated dicarboxylic acid copolymer is effective in preventing slump loss. Although disclosed, it is not always sufficient. JP-A-63-285140 proposes a copolymer of a polyoxyalkylene unsaturated ether and maleic anhydride, a hydrolyzate thereof or a salt of the hydrolyzate, and in this case also, slump loss It is not always sufficient in terms of prevention. JP-A-2-163108 proposes a copolymer of a polyoxyalkylene unsaturated ether and a maleic acid ester. However, when the alcohol forming the ester is bifunctional or more, it is insoluble or sparingly soluble in water and is difficult to use, and when it is monofunctional, there is a problem that the setting time becomes long.
【０００３】[0003]
【発明が解決しようとする課題】上記のスランプロスの
防止は、コンクリート業界の大きな関心事であり、早期
の解決が望まれていた。本発明の目的はスランプロス防
止効果に優れ、減水性が大きく、かつ使用に際し作業性
の良いセメント用の添加剤を提供することにある。The prevention of the above-mentioned slump loss is of great concern to the concrete industry, and an early solution has been desired. An object of the present invention is to provide an additive for cement, which has an excellent slump loss prevention effect, a large water reduction property, and a good workability in use.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、上記の好
ましい性質を有するセメント用添加剤を開発すべく鋭意
研究を重ねた結果、特定の成分を特定の割合で反応させ
たエステル化反応物が本発明の目的に適合し得るもので
あることを見いだし、この知見に基づき本発明を完成す
るに至った。すなわち、本発明は、（Ａ）成分（イ）一
般式［１］ ＣＨ2＝ＣＨＣＨ2Ｏ(ＡＯ)nＲ …［１］ （ただし、ＡＯは炭素数２〜４のオキシアルキレン基で
その５０〜１００モル％はオキシエチレン基、Ｒは炭素
数１〜４のアルキル基、ｎ＝４〜１５０である）で示さ
れるポリオキシアルキレン誘導体と（ロ）無水マレイン
酸とを必須単量体とする共重合物と（Ｂ）成分一般式
［２］ Ｚ[Ｏ(Ａ2Ｏ)mＨ)]K …［２］ （ただし、Ｚは２〜８個の水酸基含有化合物の残基、Ａ
2Ｏは炭素数２〜４のオキシアルキレン基、ｍは０〜３
００、ｋは２〜８である）で示されるポリオキシアルキ
レン誘導体とを、（Ａ）成分の無水マレイン酸由来の酸
無水物基１当量に対して（Ｂ）成分の水酸基０.０１〜
０.３当量となるような比率で結合している反応物を有
効成分とするセメント用添加剤を提供するものである。Means for Solving the Problems As a result of intensive studies to develop a cement additive having the above-mentioned preferable properties, the present inventors have found that an esterification reaction in which a specific component is reacted in a specific ratio. It was found that the product is suitable for the purpose of the present invention, and the present invention has been completed based on this finding. That is, the present invention provides the component (A): the general formula [1] CH 2 ═CHCH 2 O (AO) n R ... [1] (where AO is an oxyalkylene group having 2 to 4 carbon atoms; To 100 mol% is an oxyethylene group, R is an alkyl group having 1 to 4 carbon atoms, and n = 4 to 150), and (b) maleic anhydride is an essential monomer. Copolymer and Component (B) General Formula [2] Z [O (A 2 O) m H)] K ... [2] (where Z is a residue of 2 to 8 hydroxyl group-containing compounds, A
2 O is an oxyalkylene group having 2 to 4 carbon atoms, m is 0 to 3
00, k is 2 to 8) and a hydroxyl group of component (B) of 0.01 to 1 equivalent of an acid anhydride group derived from maleic anhydride of component (A).
The present invention provides an additive for cement, which contains as an active ingredient a reaction product bound in a ratio of 0.3 equivalent.
【０００５】以下に本発明を詳細に説明する。本発明セ
メント用添加剤は、上記（Ａ）成分共重合体と（Ｂ）成
分の特殊ポリオキシルアルキレン誘導体を特定の割合で
反応させたものである。本発明（Ａ）成分の一般式
［１］のＡＯで示される炭素数２〜４のオキシアルキレ
ン基としては、オキシエチレン基、オキシプロピレン
基、オキシブチレン基、オキシテトラメチレン基があげ
られ、その５０〜１００モル％はオキシエチレン基であ
る。オキシエチレン基が５０モル％未満の場合は、水溶
性が不十分のため高い減水性を得ることができない。一
般式［１］のＲで示される炭素数１〜４のアルキル基と
しては、メチル基、エチル基、プロピル基、イソプロピ
ル基、ブチル基、イソブチル基、第三ブチル基があげら
れる。一般式［１］のｎは４〜１５０であり、４未満の
場合は凝結が遅くなり、１５０より大きいと粘度が高く
なるために、製造が困難となる。The present invention will be described in detail below. The cement additive of the present invention is obtained by reacting the component (A) copolymer and the component (B) special polyoxylalkylene derivative in a specific ratio. Examples of the C2-4 oxyalkylene group represented by AO of the general formula [1] of the component (A) of the present invention include an oxyethylene group, an oxypropylene group, an oxybutylene group, and an oxytetramethylene group. 50 to 100 mol% is an oxyethylene group. When the oxyethylene group content is less than 50 mol%, high water-reducing property cannot be obtained due to insufficient water solubility. Examples of the alkyl group having 1 to 4 carbon atoms represented by R in the general formula [1] include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tert-butyl group. In the general formula [1], n is 4 to 150. When it is less than 4, coagulation becomes slow, and when it is more than 150, the viscosity becomes high, which makes production difficult.
【０００６】本発明（Ｂ）成分の一般式［２］のＺを残
基とする２〜８個の水酸基をもつ化合物としては、カテ
コール、レゾルシン、ヒドロキノンなどの多価フェノー
ル、エチレングリコール、プロピレングリコール、ブチ
レングリコール、ドデシレングリコール、オクタデシレ
ングリコール、ネオペンチルグリコール、グリセリン、
ジグリセリン、ポリグリセリン、トリメチルロールプロ
パン、ペンタエリスリトール、ジペンタエリトール、ソ
ルビトール、ソルビタンなどの多価アルコール、キシロ
ール、グリコース、フルクトース、ガラクトース、マル
トース、シュクロースなどの糖類、さらにそれらの部分
エーテル化物や部分エステル化物等があげられる。一般
式［２］のＡ2Ｏで示される炭素数２〜４のオキシアル
キレン基としては、オキシエチレン基、オキシプロピレ
ン基、オキシブチレン基、オキシテトラメチレン基があ
げられる。一般式［１］の化合物と無水マレイン酸との
共重合物は、一般式［１］の化合物と無水マレイン酸と
を過酸化物系重合開始剤あるいはアゾ系ラジカル開始剤
を用いて共重合させることにより、容易に得ることがで
きる。その際、スチレン、α−オレフィン、酢酸ビニル
等の他のラジカル共重合可能な成分を混合して共重合さ
せても良い。一般式［１］の化合物と無水マレイン酸と
の比率はモル比で１：０.５〜１：２であるが、より好
ましくは１：０.９〜１：１.２である。本発明に用いる
（Ａ）成分の一般式［１］の化合物と無水マレイン酸と
の共重合物と（Ｂ）成分の一般式［２］の化合物との比
率は共重合物の無水マレイン酸由来の酸無水物基１当量
に対し一般式［２］の化合物の水酸基０.０１〜０.３当
量となるような比率である。一般式［２］の化合物の比
率が０.３当量より大きいと水溶性が失われ、０.０１当
量より小さいと添加剤としてスランプロス防止効果が小
さく好ましくない。一般式［１］の化合物と無水マレイ
ン酸との共重合物と一般式［２］の化合物との反応物は
部分的なエステル化物であり、水酸化カリウム、水酸化
ナトリウム、ナトリウムメチラート等のアルカリ類ある
いはアミン類、パラトルエンスルホン酸などの酸類等を
触媒として反応させることにより、容易に製造すること
ができる。また、無触媒で加熱することによっても得る
ことができる。Examples of the compound having 2 to 8 hydroxyl groups having Z as a residue in the general formula [2] of the component (B) of the present invention include polyphenols such as catechol, resorcin, hydroquinone, ethylene glycol and propylene glycol. , Butylene glycol, dodecylene glycol, octadecylene glycol, neopentyl glycol, glycerin,
Diglycerin, polyglycerin, trimethylol propane, pentaerythritol, dipentaerythritol, sorbitol, polyhydric alcohols such as sorbitan, xylol, glycose, fructose, galactose, maltose, sucrose, and their partial etherified products and Examples include partially esterified products. The oxyalkylene group having 2 to 4 carbon atoms represented by A 2 O in the general formula [2], an oxyethylene group, oxypropylene group, oxybutylene group, oxytetramethylene group. The copolymer of the compound of the general formula [1] and maleic anhydride is obtained by copolymerizing the compound of the general formula [1] and maleic anhydride using a peroxide polymerization initiator or an azo radical initiator. Therefore, it can be easily obtained. At that time, other radically copolymerizable components such as styrene, α-olefin and vinyl acetate may be mixed and copolymerized. The molar ratio of the compound of the general formula [1] to maleic anhydride is 1: 0.5 to 1: 2, and more preferably 1: 0.9 to 1: 1.2. The ratio of the copolymer of the general formula [1] of the component (A) and the maleic anhydride used in the present invention to the compound of the general formula [2] of the component (B) is derived from the maleic anhydride of the copolymer. The ratio is 0.01 to 0.3 equivalent of the hydroxyl group of the compound of the general formula [2] with respect to 1 equivalent of the acid anhydride group. If the ratio of the compound of the general formula [2] is more than 0.3 equivalent, water solubility is lost, and if it is less than 0.01 equivalent, the effect of preventing slump loss as an additive is small, which is not preferable. The reaction product of the copolymer of the compound of the general formula [1] with maleic anhydride and the compound of the general formula [2] is a partial esterified product such as potassium hydroxide, sodium hydroxide and sodium methylate. It can be easily produced by reacting an alkali, an amine, an acid such as paratoluenesulfonic acid, or the like as a catalyst. It can also be obtained by heating without a catalyst.
【０００７】本発明の添加剤は、上記製造方法に代え
て、（Ａ）成分の共重合反応とエステル化反応を同時に
行う方法、例えば、一般式［１］の化合物と一般式
［２］の化合物のマレイン酸エステル及び無水マレイ
ン酸、マレイン酸の１種または２種との反応によっても
得ることができる。この場合は、共重合反応及びエステ
ル交換反応が同時に進行して、本発明の添加剤を前記製
造方法と同様に製造することができる。本発明の添加剤
の使用量はセメントに対して０.０１〜３重量％、好ま
しくは０.０４〜１重量％である。本発明の添加剤は、
ナフタレンスルホン酸ホルマリン縮合物塩、メラミンス
ルホン酸ホルムアルデヒド縮合物塩、ポリカルボン酸系
化合物等の添加剤、あるいは消泡剤、空気連行剤、防錆
剤、凝結促進剤、凝結遅延剤等と併用しても良い。ポリ
カルボン酸系化合物としては、一般式［１］の化合物と
無水マレイン酸との共重合物、ポリオキシエチレンモノ
メチルエーテルのメタクリル酸エステルとメタクリル酸
塩との共重合物、スチレンと無水マレイン酸との共重合
物の塩、オレフィンと無水マレイン酸との共重合物の
塩、ポリアクリル酸塩、ポリメタクリル酸塩等がある。
本発明の添加剤は、水酸化カリウム、水酸化ナトリウ
ム、水酸化カルシウム等のアルカリ類、アミン類等を添
加しても良い。The additive of the present invention can be produced by a method of carrying out the copolymerization reaction and the esterification reaction of the component (A) at the same time in place of the above-mentioned production method, for example, the compound of the general formula [1] and the general formula [2] It can also be obtained by reacting a maleic acid ester of a compound with one or two of maleic anhydride and maleic acid. In this case, the copolymerization reaction and the transesterification reaction proceed simultaneously, and the additive of the present invention can be produced in the same manner as in the above-mentioned production method. The use amount of the additive of the present invention is 0.01 to 3% by weight, preferably 0.04 to 1% by weight, based on the cement. The additive of the present invention is
Used in combination with additives such as naphthalene sulfonic acid formalin condensate salt, melamine sulfonic acid formaldehyde condensate salt, polycarboxylic acid compounds, or antifoaming agents, air entraining agents, rust preventives, setting accelerators, setting retarders, etc. May be. Examples of the polycarboxylic acid compound include a copolymer of the compound of the general formula [1] and maleic anhydride, a copolymer of a methacrylic acid ester of polyoxyethylene monomethyl ether and a methacrylic acid salt, and styrene and maleic anhydride. There are salts of copolymers of the above, salts of copolymers of olefin and maleic anhydride, polyacrylic acid salts, polymethacrylic acid salts and the like.
As the additive of the present invention, alkalis such as potassium hydroxide, sodium hydroxide and calcium hydroxide, amines and the like may be added.
【０００８】[0008]
製造例１〜１３ 第１表に本発明（Ａ）成分の一般式［１］の化合物と無
水マレイン酸との共重合物を示す。その共重合物と第２
表に示した一般式［２］の化合物とを、第２表に示した
重量％の比率で、撹拌装置、窒素吹き込み管、温度計、
還流管の付いた四つ口フラスコに仕込んだ。さらに共重
合物の０.１重量％のナトリウムメチラートを加え１０
０℃、３時間反応させた。得られた反応物の重量平均分
子量を第２表に示す。Production Examples 1 to 13 Table 1 shows copolymers of the compound of the general formula [1] of the component (A) of the present invention and maleic anhydride. The copolymer and the second
The compound of the general formula [2] shown in the table was mixed at a weight% ratio shown in Table 2 with a stirrer, a nitrogen blowing tube, a thermometer,
A four-necked flask equipped with a reflux tube was charged. Furthermore, 0.1% by weight of sodium methylate of the copolymer was added and
The reaction was carried out at 0 ° C for 3 hours. The weight average molecular weight of the obtained reaction product is shown in Table 2.
【０００９】[0009]
【表１】 [Table 1]
【００１０】注１）｛ ｝内がランダム状付加体である
ことを示す。 ２）Ｃ4Ｈ8Ｏはオキシテトラメチレン基を示す。Note 1) The inside of {} indicates that it is a random adduct. 2) C 4 H 8 O represents an oxytetramethylene group.
【００１１】[0011]
【表２】 [Table 2]
【００１２】注１）｛ ｝内がランダム状付加体である
ことを示す。 ２）Ｃ4Ｈ8Ｏはオキシテトラメチレン基を示す。 ３）［ ］内は共重合物の無水マレイン酸残基１当量に
対する一般式［２］の化合物の水酸基当量を示す。 製造例１４〜１７ 製造例２で示した反応物と第３表に示す他の添加剤とを
第３表で示す比率で混合し、混合物を得た。Note 1) The inside of {} indicates that it is a random adduct. 2) C 4 H 8 O represents an oxytetramethylene group. 3) The value in [] indicates the hydroxyl group equivalent of the compound of the general formula [2] with respect to 1 equivalent of the maleic anhydride residue of the copolymer. Production Examples 14 to 17 The reaction product shown in Production Example 2 and the other additives shown in Table 3 were mixed at the ratios shown in Table 3 to obtain a mixture.
【００１３】[0013]
【表３】 [Table 3]
【００１４】実施例１〜１４及び比較例１ 製造例１〜６、９〜１７および比較例１に示した反応物
および混合物を用いてコンクリートによる試験を実施し
た。配合組成、試験条件を次に示す。 配合組成（kg／ｍ3） 水 １６６ セメント ４５０ 砂 ６８１ 砕石 １０３２ 添加剤 第４表に示す。 水／セメント比 ３６.９％ 細骨材料 ３９.９％ 上記の各成分を強制練りミキサーにとり、２分間練り混
ぜたのち取り出し、混練直後のスランプおよび空気量を
測定した。さらに可倒式ミキサーに移し、毎分２回転で
混合し、３０分後、６０分後、９０分後のスランプおよ
び空気量を測定して、この数値との比較によってスラン
プロスを評価した。また凝結時間、圧縮強度についても
測定を行い、これらの結果を第４表に示した。Examples 1 to 14 and Comparative Example 1 Concrete tests were carried out using the reactants and mixtures shown in Production Examples 1 to 6, 9 to 17 and Comparative Example 1. The composition and test conditions are shown below. Composition (kg / m 3 ) Water 166 Cement 450 Sand 681 Crushed stone 1032 Additives Table 4 shows. Water / cement ratio 36.9% Fine bone material 39.9% The above components were placed in a forced kneading mixer, kneaded for 2 minutes and then taken out, and the slump and the amount of air immediately after kneading were measured. Furthermore, the slump and the amount of air were measured after 30 minutes, 60 minutes, and 90 minutes after transferring to a tilting mixer and mixing at 2 revolutions per minute, and the slump loss was evaluated by comparison with this value. The setting time and compressive strength were also measured, and the results are shown in Table 4.
【００１５】[0015]
【表４】 [Table 4]
【００１６】[0016]
【表５】 [Table 5]
【００１７】比較例２〜６ 次に示す化合物を比較例として、実施例１〜１４と同様
の試験を行った。その結果を第４表に示す。 比較例２ ナフタレンスルホン酸ホルマリン縮合物ナト
リウム塩 比較例３ ポリエチレングリコールモノアリルエーテル
マレイン酸共重合物ナトリウム塩 比較例４ 比較例１の化合物７５％、比較例２の化合物
２５％の混合物 比較例５ 第１表の共重合物名Ａで使用した一般式
［１］の化合物とマレイン酸のポリオキシエチレンモノ
メチルエーテルによるモノエステル化物との共重合物Comparative Examples 2 to 6 Using the compounds shown below as comparative examples, the same tests as in Examples 1 to 14 were conducted. The results are shown in Table 4. Comparative Example 2 Naphthalenesulfonic acid formalin condensate sodium salt Comparative Example 3 Polyethylene glycol monoallyl ether maleic acid copolymer sodium salt Comparative Example 4 Mixture of 75% of the compound of Comparative Example 1 and 25% of the compound of Comparative Example 2 Comparative Example 5th Copolymer of the compound of the general formula [1] used as the copolymer name A in Table 1 and a monoester of maleic acid with polyoxyethylene monomethyl ether
【００１８】比較例６ 添加剤なし 比較例６は水の量を多くしないとセメント混合物の混練
ができないので、配合組成は次のように変更した。 配合組成（kg／ｍ3） 水 １９５ セメント ４５０ 砂 ６５２ 砕石 ９８５ 水／セメント比 ４３.３ 細骨材料 ４０.０ 比較例７ 第２表の製造例７で示したように、第１表の共重合物Ａ
で示した一般式［１］の化合物と無水マレイン酸との共
重合物４５.６重量％、第２表の製造例１で示した一般
式［２］の化合物５４.４重量％の比率で仕込んだ他は
製造例１〜１３と同様の反応を行った。得られた反応物
は水に不溶の固体であり、通常の方法でのコンクリート
による試験を行うことができなかった。 比較例８ 第２表の製造例８で示したように、第１表の共重合物Ａ
で示した一般式［１］の化合物と無水マレイン酸との共
重合物２９.６重量％、第２表の製造例１で示した一般
式［２］の化合物７０.４重量％の比率で仕込んだ他は
製造例１〜１３と同様の反応を行った。得られた反応物
は水に不溶の固体であり、通常の方法でのコンクリート
による試験を行うことができなかった。比較例１、３、
４および６は経時的にスランプ値が小さくなり、流動性
が少なくなるのに対し、実施例１〜１４は経時的にスラ
ンプ値が小さくならず、流動性が保持されている。比較
例２、５は凝結時間が長くなっている。また添加剤なし
の場合は、水の量を多くしないと一定のスランプ値を得
ることができず、圧縮強度が小さいのに比べ、本発明の
添加剤を使用すると水の量を少なくして一定のスランプ
値を得ることができるため、圧縮強度が大きくなってい
る。Comparative Example 6 No Additive In Comparative Example 6, the cement mixture could not be kneaded unless the amount of water was increased, so the composition was changed as follows. Composition (kg / m 3 ) Water 195 Cement 450 Sand 652 Crushed stone 985 Water / cement ratio 43.3 Fine bone material 40.0 Comparative Example 7 As shown in Production Example 7 in Table 2, Polymer A
At a ratio of 45.6% by weight of a copolymer of the compound of the general formula [1] shown in Table 1 and maleic anhydride and 54.4% by weight of the compound of the general formula [2] shown in Production Example 1 of Table 2. The same reactions as in Production Examples 1 to 13 were carried out except for charging. The reaction product obtained was a water-insoluble solid and could not be tested in the usual way on concrete. Comparative Example 8 As shown in Production Example 8 in Table 2, the copolymer A in Table 1 was used.
At a ratio of 29.6% by weight of a copolymer of the compound of the general formula [1] shown with and maleic anhydride and 70.4% by weight of the compound of the general formula [2] shown in Production Example 1 of Table 2. The same reactions as in Production Examples 1 to 13 were carried out except for charging. The reaction product obtained was a water-insoluble solid and could not be tested in the usual way on concrete. Comparative Examples 1, 3,
In Nos. 4 and 6, the slump value decreases with time and the fluidity decreases, whereas in Examples 1 to 14, the slump value does not decrease with time and the fluidity is maintained. In Comparative Examples 2 and 5, the setting time is long. Further, in the case of using no additive, a constant slump value cannot be obtained unless the amount of water is increased, and the compressive strength is small. Since the slump value can be obtained, the compressive strength is increased.
【００１９】[0019]
【発明の効果】本発明の添加剤は共重合性のポリオキシ
アルキレン誘導体と無水マレイン酸との共重合物と２個
以上の水酸基を持つポリオキシアルキレン誘導体との部
分エステル化物を有効成分とすることにより、高いスラ
ンプロス防止性、高い減水性を有し、かつ優れた作業性
を有する物である。The additive of the present invention comprises, as an active ingredient, a partial esterified product of a copolymerizable polyoxyalkylene derivative and a maleic anhydride copolymer and a polyoxyalkylene derivative having two or more hydroxyl groups. As a result, the product has high slump loss prevention property, high water reduction property, and excellent workability.
Claims (1)
その５０〜１００モル％はオキシエチレン基、Ｒは炭素
数１〜４のアルキル基、ｎ＝４〜１５０である）で示さ
れるポリオキシアルキレン誘導体と（ロ）無水マレイン
酸とを必須単量体とする共重合物と（Ｂ）成分一般式
［２］ Ｚ[Ｏ(Ａ2Ｏ)mＨ)]K …［２］ （ただし、Ｚは２〜８個の水酸基含有化合物の残基、Ａ
2Ｏは炭素数２〜４のオキシアルキレン基、ｍは０〜３
００、ｋは２〜８である）で示されるポリオキシアルキ
レン誘導体とを、（Ａ）成分の無水マレイン酸由来の酸
無水物基１当量に対して（Ｂ）成分の水酸基０.０１〜
０.３当量となるような比率で結合している反応物を有
効成分とするセメント用添加剤。1. Component (A) (a) General formula [1] CH 2 ═CHCH 2 O (AO) n R ... [1] (where AO is an oxyalkylene group having 2 to 4 carbon atoms; 100 mol% is an oxyethylene group, R is an alkyl group having 1 to 4 carbon atoms, and n = 4 to 150) and a polyoxyalkylene derivative (b) maleic anhydride as an essential monomer. Polymer and Component (B) General Formula [2] Z [O (A 2 O) m H)] K [2] (where Z is a residue of 2 to 8 hydroxyl group-containing compounds, A
2 O is an oxyalkylene group having 2 to 4 carbon atoms, m is 0 to 3
00, k is 2 to 8) and a hydroxyl group of component (B) of 0.01 to 1 equivalent of an acid anhydride group derived from maleic anhydride of component (A).
An additive for cement, which contains as an active ingredient a reaction product bound in a ratio of 0.3 equivalent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10890293A JP3293230B2 (en) | 1993-04-12 | 1993-04-12 | Additive for cement |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10890293A JP3293230B2 (en) | 1993-04-12 | 1993-04-12 | Additive for cement |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06298555A true JPH06298555A (en) | 1994-10-25 |
| JP3293230B2 JP3293230B2 (en) | 2002-06-17 |
Family
ID=14496531
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10890293A Expired - Fee Related JP3293230B2 (en) | 1993-04-12 | 1993-04-12 | Additive for cement |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3293230B2 (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5925184A (en) * | 1996-02-22 | 1999-07-20 | Nippon Shokubai Co., Ltd. | Cement composition |
| JP2003327459A (en) * | 2002-05-10 | 2003-11-19 | Nippon Shokubai Co Ltd | Cement admixture |
| EP2003154A2 (en) | 2000-12-27 | 2008-12-17 | Nippon Shokubai Co., Ltd. | Polycarboxylic acid type copolymer, method for producing the same, cement additive and cement composition |
| WO2010013744A1 (en) | 2008-07-31 | 2010-02-04 | 株式会社日本触媒 | Shrinkage-reducing agent for hydraulic material and shrinkage –reducing agent composition for hydraulic material |
| US7662884B2 (en) | 2002-04-25 | 2010-02-16 | Nippon Shokubai Co., Ltd. | Cement admixture and production method thereof |
| US7691982B2 (en) | 2004-09-24 | 2010-04-06 | Nippon Shokubai Co., Ltd. | Dispersant using kraft lignin and novel lignin derivative |
| WO2012043395A1 (en) | 2010-09-30 | 2012-04-05 | 株式会社日本触媒 | Monomer composition containing unsaturated polyalkylene glycol ether-based monomer, method for producing composition, polymer obtained using composition, and method for producing polymer |
| JP2014177385A (en) * | 2013-03-15 | 2014-09-25 | Nippon Shokubai Co Ltd | Glycerol-containing polymer and method of producing the same |
| CN108047396A (en) * | 2018-01-24 | 2018-05-18 | 武汉优城科技有限公司 | A kind of anti-chamotte mould polycarboxylate water-reducer of polycation and preparation method thereof |
| WO2019039609A1 (en) | 2017-08-24 | 2019-02-28 | 日本製紙株式会社 | Lignin derivative compound and use thereof |
| WO2020032216A1 (en) | 2018-08-09 | 2020-02-13 | 日本製紙株式会社 | Composition, method for producing same, and dispersant |
-
1993
- 1993-04-12 JP JP10890293A patent/JP3293230B2/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5925184A (en) * | 1996-02-22 | 1999-07-20 | Nippon Shokubai Co., Ltd. | Cement composition |
| EP2003154A2 (en) | 2000-12-27 | 2008-12-17 | Nippon Shokubai Co., Ltd. | Polycarboxylic acid type copolymer, method for producing the same, cement additive and cement composition |
| US7662884B2 (en) | 2002-04-25 | 2010-02-16 | Nippon Shokubai Co., Ltd. | Cement admixture and production method thereof |
| JP2003327459A (en) * | 2002-05-10 | 2003-11-19 | Nippon Shokubai Co Ltd | Cement admixture |
| US7691982B2 (en) | 2004-09-24 | 2010-04-06 | Nippon Shokubai Co., Ltd. | Dispersant using kraft lignin and novel lignin derivative |
| WO2010013744A1 (en) | 2008-07-31 | 2010-02-04 | 株式会社日本触媒 | Shrinkage-reducing agent for hydraulic material and shrinkage –reducing agent composition for hydraulic material |
| WO2012043395A1 (en) | 2010-09-30 | 2012-04-05 | 株式会社日本触媒 | Monomer composition containing unsaturated polyalkylene glycol ether-based monomer, method for producing composition, polymer obtained using composition, and method for producing polymer |
| JP2014177385A (en) * | 2013-03-15 | 2014-09-25 | Nippon Shokubai Co Ltd | Glycerol-containing polymer and method of producing the same |
| WO2019039609A1 (en) | 2017-08-24 | 2019-02-28 | 日本製紙株式会社 | Lignin derivative compound and use thereof |
| CN108047396A (en) * | 2018-01-24 | 2018-05-18 | 武汉优城科技有限公司 | A kind of anti-chamotte mould polycarboxylate water-reducer of polycation and preparation method thereof |
| CN108047396B (en) * | 2018-01-24 | 2020-06-23 | 武汉优城科技有限公司 | Multi-cation mud-resistant polycarboxylate superplasticizer and preparation method thereof |
| WO2020032216A1 (en) | 2018-08-09 | 2020-02-13 | 日本製紙株式会社 | Composition, method for producing same, and dispersant |
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|---|---|
| JP3293230B2 (en) | 2002-06-17 |
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