JP3235002B2 - Cement dispersant - Google Patents
Cement dispersantInfo
- Publication number
- JP3235002B2 JP3235002B2 JP20377493A JP20377493A JP3235002B2 JP 3235002 B2 JP3235002 B2 JP 3235002B2 JP 20377493 A JP20377493 A JP 20377493A JP 20377493 A JP20377493 A JP 20377493A JP 3235002 B2 JP3235002 B2 JP 3235002B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- mol
- acid
- polyalkylene polyamine
- meth
- 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.)
- Expired - Lifetime
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
- C04B24/2652—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles
-
- 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
- C04B24/2641—Polyacrylates; Polymethacrylates
-
- 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
- C04B2103/0045—Polymers chosen for their physico-chemical characteristics
- C04B2103/0053—Water-soluble polymers
-
- 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
- C04B2103/40—Surface-active agents, dispersants
- C04B2103/408—Dispersants
Description
【０００１】[0001]
【産業上の利用分野】本発明はセメント混和剤用の分散
剤、更に詳しくは効果の持続性に優れかつ低起泡性で分
散力に優れたセメント分散剤に関するものである。The present invention relates to a dispersion for cement admixtures.
Agents, more particularly to a cement dispersant excellent in dispersing power with excellent and TeiOkoshi foaming the sustainability of effects.
【０００２】[0002]
【従来の技術と課題】従来セメント分散剤としてはポリ
ナフタリンスルホネ−ト、ポリメラミンスルホネ−ト、
リグニンスルホネ−トなどが使用されて来たが、これら
の化合物は分散効果が不十分であるばかりでなく、効果
の持続性即ちスランプロスに問題があり、業界の大きな
問題となって来た。BACKGROUND OF THE INVENTION Conventional cement dispersants include polynaphthalene sulfonate, polymelamine sulfonate,
Lignin sulfonate and the like have been used, but these compounds not only have insufficient dispersing effect, but also have a problem in sustainability of the effect, that is, slump loss, which has become a major problem in the industry. .
【０００３】このような問題点を解決するためにポリカ
ルボン酸系の分散剤が提案されるようになり、たとえ
ば、特公昭５８−３８３８０の如くポリエチレングリコ
−ルモノアリルエ−テルとポリオキシエチレンポリオキ
シプロピレングリコ−ルマレイン酸エステル、又はマレ
イン酸のアルカリ金属塩、及び(メタ)アクリル酸のアル
コ−ルエステルなどの共重合体、特開昭６２−２１６９
５０の如く(メタ)アクリル酸のポリエチレン(プロピレ
ン)グリコ−ルエステル、(メタ)アクリル(アルキレン又
はヒドロキシアルキレン)スルホン酸塩、(メタ)アクリ
ル酸塩などの共重合体、特開平１−２２６７５７の如く
(メタ)アクリル酸塩、(メタ)アクリルスルホン酸塩、ポ
リエチレングリコ−ル(アルキルエ−テル)又はポリプロ
ピレングリコ−ル(アルキルエ−テル)の共重合体、特公
平２−４０６２３の如く(メタ)アクリル酸アミド、(メ
タ)アクリル酸塩、アクリロニトリル又はアクリル酸エ
ステル又はスチレンの共重合体、特開昭６２−３０６４
８の如く(メタ)アクリル酸アミドアルキルスルホネ−
ト、(メタ)アクリル酸塩、アクリロニトリル又はアクリ
ル酸エステル又はスチレンの共重合体、特開昭６２−２
１２２５３及び特開昭６２−２１２２５２の如く(メタ)
アクリル酸アルキル(ヒドロキシアルキル)スルホネ−
ト、(メタ)アクリル酸塩、アクリロニトリル又はアクリ
ル酸エステル又はスチレンの共重合体、特開昭５９−１
６２１５７の如く(メチル又はフェニル)アクリル酸のポ
リオキシエチレン又はポリオキシプロピレングリコ−ル
のエステル、(メタ)アクリル酸塩又はそのエステルの共
重合体、特開昭５９−１９５５６５の如く(メチル)アク
リル酸又はアミドのポリオキシエチレン又はポリオキシ
プロピレングリコ−ルのエステル(エ−テル)、(メタ)ア
クリル酸塩の共重合体などがあるが、いずれも製品の安
定性、分散性能、低起泡性、経済性などを全て満足する
ものはなく、業界の大きな課題となってきている。本発
明者らはかかる従来のセメント分散剤の問題点を解決す
べく鋭意研究の結果、本発明に到達したものである。In order to solve such problems, polycarboxylic acid-based dispersants have been proposed. For example, as disclosed in JP-B-58-38380, polyethylene glycol monoallyl ether and polyoxyethylene polyoxypropylene are used. Copolymers such as glycol maleate or alkali metal salt of maleic acid and alcohol ester of (meth) acrylic acid, JP-A-62-2169.
Copolymers such as polyethylene (propylene) glycol ester of (meth) acrylic acid, (meth) acrylic (alkylene or hydroxyalkylene) sulfonate, (meth) acrylate as in JP-A-50, and JP-A-1-226557.
(Meth) acrylate, (meth) acrylsulfonate, copolymer of polyethylene glycol (alkyl ether) or polypropylene glycol (alkyl ether), (meth) acrylic Acid amide, (meth) acrylate, acrylonitrile or acrylate or styrene copolymer, JP-A-62-3064
8 (meth) acrylamide amide alkyl sulfone
(Meth) acrylate, acrylonitrile or acrylate or styrene copolymer, JP-A-62-2
12253 and JP-A-62-212252 (meth)
Alkyl (hydroxyalkyl) sulfone acrylate
G, (meth) acrylate, acrylonitrile or acrylate or styrene copolymer, JP-A-59-1
62157, such as polyoxyethylene or polyoxypropylene glycol ester of (methyl or phenyl) acrylic acid, (meth) acrylate or a copolymer of the ester, and (methyl) acrylic as disclosed in JP-A-59-195565. Acid or amide polyoxyethylene or polyoxypropylene glycol ester (ether), (meth) acrylate copolymer, etc., all of which have product stability, dispersion performance, and low foaming There is no one that satisfies all aspects such as economy and economy, and this is becoming a major issue for the industry. The present inventors have intensively studied to solve the problems of the conventional cement dispersant, and have reached the present invention.
【０００４】[0004]
【課題を解決するための手段】即ち、本発明は新規なセ
メント分散剤として、（化合物I） 一般式(１)にて示される化合物 (但しＲは水素原子、又はメチル基、Ｍは一価のアルカ
リ金属、アンモニウム、アルカノ−ルアンモニウム) 及び（化合物II） 一般式(２)にて示される化合物 (但しＲは水素原子、又はメチル基、Ｒ1はエチレン又は
／及びプロピレン基、ブチレン基、Ｒ2は水素又はメチ
ル基、ｘは５〜３０の整数) 及び（化合物III） 下記にて表される化合物(３) ポリアルキレンポリアミン１モルに、二塩基酸０.５〜
０.９モル、アクリル酸又はメタクリル酸０.２〜１.０
モルを反応せしめたポリアルキレンポリアミンのアマイ
ドにエチレンオキサイド又は／及びプロピレンオキサイ
ドを、原料ポリアルキレンポリアミンのアミノ基残基１
個当り０〜４モル付加せしめた化合物。 ・・・ (３)とを重量部で（化合物I）１０〜４０：(化合物II）５０
〜８０：(化合物III）１０〜４０（但し合計が１００と
なる） の割合で共重合した水溶性共重合体を主成分とす
るセメント分散剤を提案するものである。That is, the present invention provides a novel method.C
Mentor dispersantAs(Compound I) Compound represented by general formula (1)(Where R is a hydrogen atom or a methyl group, M is a monovalent alka
Metal, ammonium, alkanolammonium) and(Compound II) Compound represented by general formula (2)(Where R is a hydrogen atom or a methyl group, R1IsethyleneOr
/as well asPropylene group,Butylene group, RTwoIs hydrogen or methyl
And x is an integer of 5 to 30); and(Compound III) Compound (3) represented by the following: 1 mol of polyalkylene polyamine is added with
0.9 mol, acrylic acid or methacrylic acid 0.2-1.0
Amy of polyalkylene polyamine reacted with mole
Ethylene oxide and / or propylene oxide
To the amino group residue 1 of the raw material polyalkylene polyamine.
A compound added in an amount of 0 to 4 mol per unit. ... (3)And in parts by weight of (Compound I) 10 to 40: (Compound II) 50
To 80: (Compound III) 10 to 40 (provided that the total is 100
Become) Water-soluble copolymer copolymerized at a ratio of
ToCement dispersantIs proposed.
【０００５】本発明において使用される一般式(１)に示
される化合物はアクリル酸、メタアクリル酸のナトリウ
ム、カリウム、アンモニウム、モノ又はジ又はトリエタ
ノールアミン塩を挙げることができるが性能及び経済性
の面からはナトリウム及びトリエタノ−ルアミンが好ま
しい。The compounds represented by the general formula (1) used in the present invention include sodium, potassium, ammonium, mono- or di- or triethanolamine salts of acrylic acid and methacrylic acid. In view of the above, sodium and triethanolamine are preferred.
【０００６】本発明において使用される一般式(２)に示
される化合物は式に示される如く、公知の方法によって
得られる物で、ポリエチレングリコ−ルモノ(メタ)アク
リレ−ト、メトキシポリエチレングリコ−ルモノ(メタ)
アクリレ−トを挙げることが出来、アクリル酸又はメタ
クリル酸にエチレンオキサイド又は／及びプロピレンオ
キサイド、ブチレンオキサイドを５〜３０モル付加する
ことによって、あるいはメタノ−ルにエチレンオキサイ
ド又は／及びプロピレンオキサイド、ブチレンオキサイ
ドを５〜３０モル付加した後アクリル酸又はメタクリル
酸とエステル化することによって得られるが、性能上エ
チレンオキサイドを８〜１５モル付加させたポリエチレ
ングリコ−ルモノ(メタ)アクリレ−ト、メトキシポリエ
チレングリコ−ルモノ(メタ)アクリレ−トが好ましい。The compound represented by the general formula (2) used in the present invention can be obtained by a known method as shown in the formula, and includes polyethylene glycol mono (meth) acrylate, methoxypolyethylene glycol mono. (Meta)
Acrylates may be mentioned, for example, by adding 5 to 30 mol of ethylene oxide or / and propylene oxide and butylene oxide to acrylic acid or methacrylic acid, or by adding ethylene oxide or / and / or propylene oxide and butylene oxide to methanol. Is added and then esterified with acrylic acid or methacrylic acid. From the viewpoint of performance, polyethylene glycol mono (meth) acrylate and methoxypolyethylene glycol to which ethylene oxide is added in an amount of 8 to 15 mol are added. Lumono (meth) acrylate is preferred.
【０００７】化合物(３)に示されるポリアルキレンポリ
アミンの例としては、ジエチレントリアミン、トリエチ
レンテトラミン、テトラエチレンペンタミン、ペンタエ
チレンヘキサミン、ジプロピレントリアミン、トリプロ
ピレンテトラミン、テトラプロピレンペンタミン類及び
これらの混合物であり、二塩基酸としてはマロン酸、コ
ハク酸、フマル酸、マレイン酸、グルタル酸、アジピン
酸、ピメリン酸、アゼライン酸、セバチン酸、及びこれ
らの混合物である。本化合物は従来公知の技術を応用す
ることで得られるが性能面よりポリアルキレンポリアミ
ンはジエチレントリアミン又はトリエチレンテトラミン
が良く、二塩基酸としてはアジピン酸が好ましい。Examples of the polyalkylenepolyamine represented by the compound (3) include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, dipropylenetriamine, tripropylenetetramine, tetrapropylenepentamines, and mixtures thereof. And the dibasic acids include malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, and mixtures thereof. This compound can be obtained by applying a conventionally known technique, but from the viewpoint of performance, the polyalkylenepolyamine is preferably diethylenetriamine or triethylenetetramine, and the dibasic acid is preferably adipic acid.
【０００８】二塩基酸とアクリル酸又はメタクリル酸の
合計１モル(但し、二塩基酸１モルに対しアクリル酸又
はメタクリル酸は１／２モルに相当するものとして)に
対しポリアルキレンポリアミンの割合は０.０３〜０.１
モル過剰が好ましい範囲である。これはポリアマイドポ
リアミンのゲル体の生成を抑えるために有効である。二
塩基酸とアクリル酸又はメタクリル酸の割合は二塩基酸
０.５〜０.９モルに対してアクリル酸又はメタクリル酸
０.２〜１.０モルの割合である。エチレンオキサイド、
プロピレンオキサイドの付加モル数は原料ポリアルキレ
ンポリアミンのアミノ基残基に対して０〜４モルであ
り、好ましくはエチレンオキサイド１〜２モルである。
一般式(１)及び一般式(２)及び化合物(３)で表される化
合物を使用して水溶性共重合体を得る方法については従
来公知の技術を応用することで容易に得ることができる
ものである。The ratio of the polyalkylene polyamine to the total of 1 mol of dibasic acid and acrylic acid or methacrylic acid (provided that acrylic acid or methacrylic acid corresponds to 1/2 mol per mol of dibasic acid) 0.03-0.1
A molar excess is a preferred range . This is effective for suppressing the formation of a gel of polyamide polyamine. The ratio of dibasic acid to acrylic acid or methacrylic acid is from 0.5 to 0.9 mol of dibasic acid to 0.2 to 1.0 mol of acrylic acid or methacrylic acid. Ethylene oxide,
The addition mole number of propylene oxide is 0 to 4 moles, preferably 1 to 2 moles of ethylene oxide, based on the amino group residue of the raw material polyalkylene polyamine.
A method for obtaining a water-soluble copolymer using the compounds represented by the general formulas (1), (2) and (3) can be easily obtained by applying a conventionally known technique. Things.
【０００９】かくして得られた本発明のセメント分散剤
は安定した水溶液で、分散性に優れ、スランプロスが少
なく、製造の上でも反応が単純で原料も比較的安価であ
る。また低起泡性であるので泡の持ち込みは少ないが、
場合によってはエ−テル系、エステル系、シリコ−ン系
等の一般に知られている消泡剤等を加えても良い。更に
本発明のセメント分散剤は他の一般に知られているセメ
ント分散剤との併用もしくは混合使用も可能である。The thus obtained cement dispersant of the present invention is a stable aqueous solution, has excellent dispersibility, has little slump loss, has a simple reaction in production, and is relatively inexpensive in raw materials. In addition, since it is low foaming, the carry-in of foam is small,
In some cases, generally known antifoaming agents such as ether type, ester type and silicone type may be added. Further, the cement dispersant of the present invention can be used in combination with or mixed with other generally known cement dispersants.
【００１０】本発明のセメント分散剤はセメントに対し
通常０.０５〜２％使用される。使用する方法は普通一
般に行われているセメント分散剤の場合と同じであり、
セメント混練時に原液添加するか、予め混練水に希釈し
て添加する。あるいはコンクリ−ト又はモルタルを練り
混ぜた後に添加し再度均一に混練しても良い。[0010] The cement dispersant of the present invention is usually used in an amount of 0.05 to 2% based on cement. The method used is the same as that for cement dispersants that are commonly used,
The stock solution is added at the time of kneading the cement, or it is diluted with kneading water in advance and added. Alternatively, it may be added after kneading and mixing concrete or mortar, and kneaded again uniformly.
【００１１】[0011]
ジエチレントリアミン１０７.３ｇ(１.０４モル)、アジ
ピン酸８７.７ｇ(０.６モル)、メタクリル酸６８.８ｇ
(０.８モル)、及び重合禁止剤としてハイドロキノンメ
チルエ−テル０.５ｇを撹拌機、温度計、コンデンサ−
付きトラップを付けたフラスコに仕込み、窒素ガスを吹
きこみながら１５０〜１７０℃に加熱し、約４時間反応
させ酸価２０.５を示したときに反応を停止した。溜出
物３６ｇと共に反応生成物として常温で黄褐色半固体の
生成物２２８ｇを得た。この生成物１７９ｇ(０.７８モ
ル)を１リットルの撹拌器付き実験用オ−トクレ−ブ中
に仕込み、水３９３ｇで溶解した。窒素ガスで空気を置
換した後５０〜８０℃でエチレンオキサイド８３ｇ(原
料ポリアルキレンポリアミンのアミノ基残基に対し１．
８モル)を逐次導入し付加反応を行った。反応終了後３
５℃に冷却し、黄褐色粘稠液体６５５ｇ(固形分４０％)
の化合物Ａを得た。本品については実施例１の合成に使
用する。以下同様にして表１の化合物Ｂ〜Ｆを合成し、
実施例２〜９の合成に使用した。107.3 g (1.04 mol) of diethylenetriamine, 87.7 g (0.6 mol) of adipic acid, 68.8 g of methacrylic acid
(0.8 mol), and 0.5 g of hydroquinone methyl ether as a polymerization inhibitor, a stirrer, a thermometer, and a condenser.
The mixture was heated to 150 to 170 ° C. while blowing nitrogen gas into the flask, and reacted for about 4 hours. When the acid value reached 20.5 , the reaction was stopped. 228 g of a tan semi-solid product was obtained at room temperature as a reaction product together with 36 g of the distillate. 179 g (0.78 mol) of this product were charged into a 1 liter laboratory autoclave with stirrer and dissolved with 393 g of water. After replacing the air with nitrogen gas, 83 g of ethylene oxide at 50 to 80 ° C. ( 1 to the amino group residue of the starting polyalkylene polyamine) .
(8 mol) were successively introduced to carry out an addition reaction. After reaction 3
Cool to 5 ° C, 655 g of yellowish brown viscous liquid (solid content 40%)
Was obtained. This product is used in the synthesis of Example 1. Hereinafter, compounds BF of Table 1 were synthesized in the same manner,
Used for the synthesis of Examples 2-9.
【００１２】[0012]
【表１】 [Table 1]
【００１３】 ＊１：ジエチレントリアミン ＊２：トリエチレンテトラミン ＊３：エチレンオキサイド ＊４：プロピレンオキサイド[0013] * 1: Diethylenetriamine * 2: triethylenetetramine * 3: Ethylene oxide * 4: profile propylene oxide
【００１４】〔実施例１の合成〕 温度計、撹拌機、滴下ロ−ト、窒素導入管、及び還流冷
却器付き四つ口フラスコに、水１４８ｇを仕込み撹拌し
ながらフラスコ内を窒素置換し、窒素雰囲気中で９０℃
まで加熱した。次いで化合物Ａ５０ｇ、ポリエチレング
リコ−ルモノメタクリレ−ト(エチレンオキサイド付加
モル数、８モル)６０ｇ、メタクリル酸１６ｇの混合物
とチオグリコ−ル酸アンモニュウム５０％水溶液４ｇ、
過硫酸アンモニュウム５％液４０ｇを９５℃にて１２０
分かけて添加した。更に同温で４時間撹拌重合を行い、
反応を終了させた後６０℃に冷却して２５％苛性ソ−ダ
２９ｇで中和し、本発明の実施例１の共重合物３４７ｇ
を得た。 以下同様にして表２記載の実施例２〜９の共
重合物を得た。[Synthesis of Example 1] A four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen inlet tube, and a reflux condenser was charged with 148 g of water, and the flask was purged with nitrogen while stirring. 90 ° C in nitrogen atmosphere
Until heated. Next, 50 g of compound A, 60 g of polyethylene glycol monomethacrylate (mol number of ethylene oxide added, 8 mol), 4 g of a mixture of 16 g of methacrylic acid and 50% aqueous solution of ammonium thioglycolate,
40 g of a 5% solution of ammonium persulfate at 95 ° C. for 120
Added over minutes. Stirring polymerization was further performed at the same temperature for 4 hours.
After the reaction was completed, the mixture was cooled to 60 ° C., neutralized with 29 g of 25% sodium hydroxide, and 347 g of the copolymer of Example 1 of the present invention.
I got Thereafter, copolymers of Examples 2 to 9 shown in Table 2 were obtained in the same manner.
【００１５】[0015]
【表２】 [Table 2]
【００１６】 ＊１：アクリル酸Ｎａ塩 ＊２：メタクリル酸Ｎａ塩 ＊３：メタクリル酸トリエタノールアミン塩 ＊４：ポリエチレングリコールメタクリレート 数字は酸化エチレン付加モル数 ＊５：メトキシポリエチレングリコールメタクリレート 数字は酸化エチレン付加モル数* 1: Na acrylate * 2: Na methacrylate * 3: Triethanolamine methacrylate * 4: Polyethylene glycol methacrylate Number is ethylene oxide added mole number * 5: Methoxy polyethylene glycol methacrylate Number is ethylene oxide Number of moles added
【００１７】〔比較例〕 化合物（３）を含まない比較共重合物として、実施例１
と同様な合成方法により表３記載の比較例１〜３を得
た。 [0017](Comparative example) Example 1 was used as a comparative copolymer containing no compound (3).
Comparative Examples 1 to 3 shown in Table 3 were obtained by the same synthesis method as described above.
Was.
【表３】 表３中の数字は選択した化合物の重量％を表す。 [Table 3] The numbers in Table 3 represent the weight percent of the selected compound.
【００１８】〔セメント分散試験〕 セメント 普通ポルトランドセメント(比重３.１７) ３２０ Kg／m3 細骨剤 川砂 (比重２.５６) ８６７ Kg／m3 粗骨剤 川砂利 (比重２.５８) ９４７ Kg／m3 水 １７６ Kg／m3 の配合割合でコンクリ−トを調整した場合のスランプが
１８ｃｍとなるように共重合物合成例で得た１〜９の共
重合物の添加量を求め、その時の空気量、スランプ、圧
縮強度、及びその強度変化について測定した。なお、空
気量はＪＩＳ Ａ１１１６、スランプはＪＩＳ Ａ１１
０１、圧縮強度はＪＩＳ Ａ１１０８の方法に準じて測
定した。表４に実施例の結果と比較例の結果を示した。 [Cement dispersion test] Cement Ordinary Portland cement (specific gravity 3.17) 320 Kg / m 3 Fine aggregate Kawasuna (specific gravity 2.56) 867 Kg / m 3 Coarse aggregate River gravel (specific gravity 2.58) 947 Kg / m 3 The amount of the copolymers 1 to 9 obtained in the copolymer synthesis example was determined so that the slump was 18 cm when the concrete was adjusted at a mixing ratio of 176 Kg / m 3 of water, and the air volume at that time was determined. , Slump, compressive strength, and changes in strength. The air volume is JIS A1116, and the slump is JIS A11.
01, the compressive strength was measured according to the method of JIS A1108. Table 4 shows the results of the examples and the comparative examples.
【００１９】[0019]
【表４】 [Table 4]
【００２０】比較例１〜３は、分散性は良好であるが、
経過時間によって空気量が増える傾向にあり、又比較例
２は浮き水が顕著であった。表４から明らかなように本
発明品は初期流動性に優れており、更に経時安定性即ち
スランプロスが著しく小さい、極めて優れたセメント用
分散剤といえる。Comparative Examples 1 to 3 have good dispersibility,
The amount of air tended to increase with the lapse of time, and in Comparative Example 2, floating water was remarkable. As is clear from Table 4, the product of the present invention is excellent in initial fluidity, and furthermore, it can be said that it is a very excellent cement dispersant, which has a stability with time, that is, extremely small slump loss.
【００２１】[0021]
【発明の効果】本発明に係わる化合物I、II、IIIを規定The compounds I, II and III according to the present invention are defined.
の割合で共重合し得られる本発明セメント分散剤は、コThe cement dispersant of the present invention obtained by copolymerization at a ratio of
ンクリート混練時に添加することにより初期流動性に優Excellent initial fluidity by adding during concrete kneading
れ、経時安定性即ちスランプロスが著しく小さい、極めAging stability, slump loss is extremely small,
て優れた効果を示す。It shows excellent effect.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C04B 24/26 B01F 17/00 C08F 290/06 C04B 103:40 ──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int. Cl. 7 , DB name) C04B 24/26 B01F 17/00 C08F 290/06 C04B 103: 40
Claims (1)
リ金属、アンモニウム、アルカノ−ルアンモニウム)（化合物II） 一般式(２)にて示される化合物 (但しＲは水素原子、又はメチル基、Ｒ1はエチレン又は
／及びプロピレン基、ブチレン基、Ｒ2は水素又はメチ
ル基、ｘは５〜３０の整数)（化合物III） 下記にて表される化合物 ポリアルキレンポリアミン１モルに、二塩基酸０.５〜
０.９モル、アクリル酸又はメタクリル酸０.２〜１.０
モルを反応せしめたポリアルキレンポリアミンのアマイ
ドにエチレンオキサイド又は／及びプロピレンオキサイ
ドを、原料ポリアルキレンポリアミンのアミノ基残基１
個当り０〜４モル付加せしめた化合物 ・・・・ (３)とを重量部で（化合物I）１０〜４０：(化合物II）５０
〜８０：(化合物III）１０〜４０（但し合計が１００と
なる） の割合で共重合した水溶性共重合体を主成分とす
るセメント分散剤。(1)(Compound I) Compound represented by general formula (1)(Where R is a hydrogen atom or a methyl group, M is a monovalent alka
(Metal, ammonium, alkanol ammonium)(Compound II) Compound represented by general formula (2)(Where R is a hydrogen atom or a methyl group, R1IsethyleneOr
/as well asPropylene group,Butylene group, RTwoIs hydrogen or methyl
Group, x is an integer of 5 to 30)(Compound III) Compounds represented by 1 mol of polyalkylene polyamine, 0.5 mol of dibasic acid
0.9 mol, acrylic acid or methacrylic acid 0.2-1.0
Amy of polyalkylene polyamine reacted with mole
Ethylene oxide and / or propylene oxide
To the amino group residue 1 of the raw material polyalkylene polyamine.
Compound added with 0 to 4 moles per unit ... (3)And in parts by weight of (Compound I) 10 to 40: (Compound II) 50
To 80: (Compound III) 10 to 40 (provided that the total is 100
Become) Water-soluble copolymer copolymerized at a ratio of
ToCement dispersant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20377493A JP3235002B2 (en) | 1993-07-27 | 1993-07-27 | Cement dispersant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20377493A JP3235002B2 (en) | 1993-07-27 | 1993-07-27 | Cement dispersant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0733496A JPH0733496A (en) | 1995-02-03 |
| JP3235002B2 true JP3235002B2 (en) | 2001-12-04 |
Family
ID=16479576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20377493A Expired - Lifetime JP3235002B2 (en) | 1993-07-27 | 1993-07-27 | Cement dispersant |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3235002B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006059723A1 (en) | 2004-12-02 | 2006-06-08 | Sika Ltd. | Powdery polycarboxylic-acid cement dispersant and dispersant composition containing the dispersant |
| WO2008032798A1 (en) | 2006-09-13 | 2008-03-20 | Toho Chemical Industry Co., Ltd. | Cement dispersant |
| US7393886B2 (en) | 2004-06-25 | 2008-07-01 | Sika Ltd. | Cement dispersant and concrete composition containing the dispersant |
| US7662884B2 (en) | 2002-04-25 | 2010-02-16 | Nippon Shokubai Co., Ltd. | Cement admixture and production method thereof |
| WO2018147378A1 (en) | 2017-02-08 | 2018-08-16 | シーカ・テクノロジー・アーゲー | Hydraulic composition admixture |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3336456B2 (en) | 1998-12-25 | 2002-10-21 | 日本シーカ株式会社 | Cement dispersant and concrete composition containing the dispersant |
| EP1061089B1 (en) * | 1999-06-15 | 2004-03-03 | Sika Schweiz AG | Multipurpose, cement dispersing polymers for high flow and high strength concrete |
| JP4514426B2 (en) * | 2003-10-02 | 2010-07-28 | ミヨシ油脂株式会社 | Cement admixture and method for producing the same |
| WO2005072685A1 (en) * | 2004-01-30 | 2005-08-11 | Toho Chemical Industry Co., Ltd. | Dispersant for cosmetic and cosmetic composition containing the dispersant |
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1993
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7662884B2 (en) | 2002-04-25 | 2010-02-16 | Nippon Shokubai Co., Ltd. | Cement admixture and production method thereof |
| US7393886B2 (en) | 2004-06-25 | 2008-07-01 | Sika Ltd. | Cement dispersant and concrete composition containing the dispersant |
| WO2006059723A1 (en) | 2004-12-02 | 2006-06-08 | Sika Ltd. | Powdery polycarboxylic-acid cement dispersant and dispersant composition containing the dispersant |
| JPWO2006059723A1 (en) * | 2004-12-02 | 2008-06-05 | 日本シーカ株式会社 | Powdered polycarboxylic acid cement dispersant and dispersant composition containing the dispersant |
| WO2008032798A1 (en) | 2006-09-13 | 2008-03-20 | Toho Chemical Industry Co., Ltd. | Cement dispersant |
| WO2018147378A1 (en) | 2017-02-08 | 2018-08-16 | シーカ・テクノロジー・アーゲー | Hydraulic composition admixture |
| US11091400B2 (en) | 2017-02-08 | 2021-08-17 | Sika Technology Ag | Admixture for hydraulic composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0733496A (en) | 1995-02-03 |
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