JPH025701B2 - - Google Patents
Info
- Publication number
- JPH025701B2 JPH025701B2 JP17032685A JP17032685A JPH025701B2 JP H025701 B2 JPH025701 B2 JP H025701B2 JP 17032685 A JP17032685 A JP 17032685A JP 17032685 A JP17032685 A JP 17032685A JP H025701 B2 JPH025701 B2 JP H025701B2
- Authority
- JP
- Japan
- Prior art keywords
- cement
- formula
- unit represented
- vinyl polymer
- structural unit
- 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
Links
- 239000004568 cement Substances 0.000 claims description 28
- 229920002554 vinyl polymer Polymers 0.000 claims description 26
- 239000002270 dispersing agent Substances 0.000 claims description 22
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 230000000694 effects Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000002209 hydrophobic effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- -1 gravel Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- ZZTCCAPMZLDHFM-UHFFFAOYSA-N ammonium thioglycolate Chemical compound [NH4+].[O-]C(=O)CS ZZTCCAPMZLDHFM-UHFFFAOYSA-N 0.000 description 1
- 229940075861 ammonium thioglycolate Drugs 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- BRXCDHOLJPJLLT-UHFFFAOYSA-N butane-2-sulfonic acid Chemical compound CCC(C)S(O)(=O)=O BRXCDHOLJPJLLT-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- CSTSNBRPNUBCLM-UHFFFAOYSA-N ethanesulfonic acid;2-methylprop-2-enamide Chemical compound CCS(O)(=O)=O.CC(=C)C(N)=O CSTSNBRPNUBCLM-UHFFFAOYSA-N 0.000 description 1
- DHUSXRNOMZWNNA-UHFFFAOYSA-N ethanesulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CCS(O)(=O)=O DHUSXRNOMZWNNA-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- VFIXVALRCZHRKN-UHFFFAOYSA-N methanesulfonic acid;2-methylprop-2-enamide Chemical compound CS(O)(=O)=O.CC(=C)C(N)=O VFIXVALRCZHRKN-UHFFFAOYSA-N 0.000 description 1
- BFOQBMCQGCJJTA-UHFFFAOYSA-N methanesulfonic acid;prop-2-enamide Chemical compound CS(O)(=O)=O.NC(=O)C=C BFOQBMCQGCJJTA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- AAYRWMCIKCRHIN-UHFFFAOYSA-N propane-1-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CCCS(O)(=O)=O AAYRWMCIKCRHIN-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- FWFUWXVFYKCSQA-UHFFFAOYSA-M sodium;2-methyl-2-(prop-2-enoylamino)propane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(C)(C)NC(=O)C=C FWFUWXVFYKCSQA-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
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
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
Description
＜産業上の利用分野＞
本発明はセメント用混和剤としての分散剤に関
する。
コンクリートは、セメント、砂利、砂等を水と
共に練り、セメントの水和反応によつて硬化させ
るものであるが、このとき補助剤として分散剤が
多くの場合で使用される。分散剤は、水系におけ
るセメント粒子の分散をよくすることにより、作
業性を向上させ、セメントの水和反応を助長し、
減水効果をもたらすものであり、結果としてコン
クリート等の強度を向上するものである。したが
つて、セメント用分散剤には、(1)セメント粒子の
分散性が大きいこと、(2)該分散性の経時変化が少
ないこと（スランプロスが少ないこと）、(3)硬化
体の強度低下につながる過大なエントレンドエア
ーを起こさないこと、(4)経済性がよいこと等、以
上の諸特性が要求される。
本発明は総じてかかる要求に応える改良された
セメント用分散剤に関するものである。
＜従来の技術、その問題点＞
従来、セメント用分散剤として、リグニンスル
ホン酸塩、オキシカルボン酸塩、ナフタリンスル
ホン酸ホルマリン縮合物、多環芳香族スルホン酸
塩、メラミンスルホン酸ホルマリン縮合物塩等、
多くの提案がある。これらにはそれぞれ、相応の
特長がある反面で相応の問題点もあることは周知
の通りである。
一方、例えば鎖状オレフイン−エチレン性不飽
和ジカルボン酸共重合物の水溶性塩のように、ビ
ニル重合体をセメント用分散剤に応用しようとす
る各種の提案がある（特開昭59−162160、特開昭
59−162164、特開昭59−195565、特開昭59−
203745、特開昭60−16852、特開昭60−27636、特
開昭60−54957）。しかし、これらの従来提案に
は、部分的に有効なものもあるが、セメント用分
散剤に対する前述したような要求を全て充足する
ものはなく、実用に供するには未だ不充分という
問題点がある。尚、ビニル重合体については、こ
れをセメント用分散剤ではなく、水中コンクリー
ト用混和剤として使用する提案もある（特開昭60
−42264）。この提案は、ビニル重合体に増粘剤と
しての効果を期待して、該ビニル重合体を水中へ
のセメント逸散防止のために使用するものであ
り、該ビニル重合体にセメント用分散剤のような
例えば経時的変化の少ない分散効果を求めるもの
ではない。実際、この提案中で良好な結果が得ら
れるとされているビニル重合体をセメント用分散
剤として使用してみても、よい結果は得難い。
＜発明が解決しようとする問題点、その解決手段
＞
本発明は、叙上の如き従来の問題点、特にビニ
ル重合体に関する問題点を解決して、前述したよ
うな要求を全て充足する改良されたセメント用分
散剤を提供するものである。
しかして本発明者らは、以上の実情に鑑みて、
良好なセメント用分散剤を得るべく鋭意研究した
結果、分子内に特定の親水性構成単位と特定の疎
水性構成単位を有する特定構造のビニル重合体が
セメント用分散剤として他のビニル重合体にはみ
られない優れた諸特性を持つことを見出し、本発
明を完成するに到つた。
すなわち本発明は、
下記式（）で示される親水性の構成単位及び
下記式（）で示される親水性の構成単位並びに
下記式（）で示される疎水性の構成単位を有す
る水溶性或いは水分散性のビニル重合体であつ
て、式（）で示される構成単位／式（）で示
される構成単位／式（）で示される構成単位＝
５〜40／90〜40／５〜40（各重量％）であるビニ
ル重合体を含有することを特徴とするセメント用
分散剤に係る。
〔但し、R1、R3、R4はＨ又はCH3。R2は炭素数
１〜５のアルキレン基。M1、M2はＨ、アルカリ
金属又はアルカリ土類金属。ＸはCOOR5（R5は炭
素数１〜８のアルキル基）、CN、C6H5又は
OCOCH3。〕
本発明のビニル重合体において、式（）で示
される親水性の構成単位を形成するモノマー成分
としては、アクリルアミドメタンスルホン酸、ア
クリルアミドエタンスルホン酸、アクリルアミド
プロパンスルホン酸、２−アクリルアミド−２−
メチルプロパンスルホン酸、メタアクリルアミド
メタンスルホン酸、メタアクリルアミドエタンス
ルホン酸、及びこれらの塩等がある。また、式
（）で示される親水性の構成単位を形成するモ
ノマー成分としては、アクリル酸、メタクリル
酸、及びこれらの塩等がある。更に、式（）で
示される疎水性の構成単位を形成するモノマー成
分としては、アクリル酸メチル、メタクリル酸メ
チル、アクリル酸エチル、メタクリル酸エチル、
アクリル酸プロピル、メタクリル酸プロピル、ア
クリル酸ブチル、メタクリル酸ブチルの如きアク
リル酸或いはメタクリル酸の低級アルキルエステ
ル、スチレン、アクリロニトリル、及び酢酸ビニ
ル等がある。
上記のようなモノマー成分から形成される各構
成単位の相互割合は、式（）で示される構成単
位／式（）で示される構成単位／式（）で示
される構成単位＝５〜40／90〜40／５〜40（各重
量％）とする。該相互割合の範囲から外れると、
当該ビニル重合体をセメント用分散剤として使用
した場合に、効果の経時変化が起きやすくなつた
り、分散力が不足気味となつたり、空気量が過大
になりやすかつたりする。特に、式（）で示さ
れる疎水性の構成単位は重要である。式（）や
式（）で示される親水性の構成単位だけからな
る共重合体では、分散性を示すものの該分散性の
経時変化が大きく、実用上大きな問題となるのに
対し、これらに式（）で示される疎水性の構成
単位が含まれる共重合体すなわち本発明のビニル
重合体はそのような経時変化が少ない良好な結果
を与えるからである。分散性の経時変化に関する
本発明の上記のような特長的効果は、式（）や
式（）で示される親水性の構成単位に対する式
（）で示される疎水性の構成単位それ自体の本
質的特性及び当該共重合体の化学構造並びに当該
共重合体において取りうるその豊富な組合せや数
によるものと考えられる。そして、本発明のビニ
ル重合体の分子量は数平均分子量500〜20000
（GPC法、ポリエチレンゴリコール換算）にする
のが好ましく、これより高すぎると当該ビニル重
合体をセメント用分散剤として使用した場合に分
散性が不足気味となり、逆にこれより低すぎると
経時変化が起き易くなる傾向を示す。
本発明のビニル重合体の製造方法は、本発明で
特に限定するものではなく、従来公知の方法がい
ずれも適用できるが、操作の簡便さ等から、水系
或いは水／水溶性有機溶媒の混合系で溶液重合す
るのがよい。
本発明に係るセメント用分散剤は、以上説明し
たビニル重合体のみから成つていても、或いは本
発明の効果を損なわない範囲において、ある特定
の特性を強化するため、又は他の目的のため、他
の成分を含有していてもよい。このような他の成
分としては例えば、AE剤、凝結遅延剤、防腐剤、
防黴剤等がある。
以下、本発明の構成及び効果をより具体的にす
るため、本発明のビニル重合体の合成例、実施例
等を挙げるが、本発明はこれらの各例に限定され
るものではない。
＜合成例＞
２−アクリルアミド−２−メチルプロパンスル
ホン酸ナトリウム塩10部（重量部、以下同じ）、
アクリル酸80部及びメチルアクリレート10部を、
温度計、滴下ロート、撹拌機、窒素導入管を付け
た四つ口フラスコに、水250部及びイソプロパノ
ール100部で溶解し、雰囲気を窒素置換した。次
いで、連鎖移動剤として50％チオグリコール酸ア
ンモニウム液5.5部を加えて溶解し、60℃に加温
した後、重合開始剤として２％過硫酸アンモニウ
ム水溶液50部を加え、６時間撹拌し、重合を完結
させた（実施例１のビニル重合体）。
以下、第１表及び第２表中のビニル重合体（実
施例２〜14、比較例１〜17、比較例21〜23）はほ
ぼ同様にして重合した。
＜試験方法＞
得られたビニル重合体等を各々使用し、次の条
件及び方法下にコンクリート試験を行なつて、ス
ランプと空気量、それらの経時変化（直後→60分
後）及び圧縮強度を測定した。
●条件；セメント（小野田社製普通ポルトランド
セメント）を320Kg／m3、細骨材（大井川砂、
比重2.62）を880Kg／m3、粗骨材（鉢地山砕石、
比重2.65）を932Kg／m3、水（蒲郡市水）を182
Kg／m3。また、ビニル重合体等（分散剤）を
0.15重量％（対セメント）。この使用量はビニ
ル重合体を使用する各実施例の目標スランプを
21cmとする量である。したがつて、ビニル重合
体を使用しない比較例18〜20については、各分
散剤を同じ目標スランプとする適量（対セメン
トでそれぞれ、0.3重量％、0.25重量％、0.06重
量％）で使用した。更に、AE剤（併用剤、竹
本油脂社製、チユーポールＣ、アルキルサルフ
エートその他を含む）を適量使用した（第１表
及び第２表に記載）。この使用量は直後の空気
量を４〜６％とする量である。したがつて、分
散剤のみで直後の空気量が６％を超えるものは
AE剤を無添加とした。尚、実施例３は遅延剤
（併用剤、竹本油脂社製、チユーポールNR、
オキシカルボン酸誘導体を含む）を対セメント
で0.03重量％使用した。
●方法；全材料を、第１表及び第２表に記載の通
りで傾胴ミキサーに投入後、３分間撹拌して均
一状態とした直後にサンプリングした。引き続
き、低速（4r.p.m.）で60分間撹拌してサンプ
リングした。そして、各サンプルについてスラ
ンプ及び空気量を測定した。また、直後のサン
プルについて、１週及び４週後の圧縮強度を測
定した。
実施例 １〜14
第１表に記載の実施例１〜14を各々調整し、前
述の試験方法にしたがつて各サンプルを測定し
た。結果を同表に示した。
<Industrial Application Field> The present invention relates to a dispersant as an admixture for cement. Concrete is made by mixing cement, gravel, sand, etc. with water and hardening it by the hydration reaction of the cement. At this time, a dispersant is often used as an auxiliary agent. Dispersants improve workability by improving the dispersion of cement particles in an aqueous system, promoting the hydration reaction of cement,
It brings about a water reduction effect, and as a result improves the strength of concrete, etc. Therefore, dispersants for cement have the following properties: (1) high dispersibility of cement particles, (2) little change in dispersibility over time (low slump loss), and (3) strength of the cured product. The above-mentioned characteristics are required, such as not causing excessive entrended air that would lead to deterioration, and (4) good economic efficiency. The present invention generally relates to an improved cement dispersant that meets these needs. <Conventional technology and its problems> Conventionally, dispersants for cement include lignin sulfonate, oxycarboxylate, naphthalene sulfonic acid formalin condensate, polycyclic aromatic sulfonate, melamine sulfonic acid formalin condensate, etc. ,
There are many suggestions. It is well known that each of these has its own merits, but also has its own problems. On the other hand, there are various proposals for applying vinyl polymers as dispersants for cement, such as water-soluble salts of linear olefin-ethylenically unsaturated dicarboxylic acid copolymers (Japanese Patent Application Laid-open No. 162-160-1989, Tokukai Akira
59-162164, JP-A-59-195565, JP-A-59-
203745, JP 60-16852, JP 60-27636, JP 60-54957). However, although some of these conventional proposals are partially effective, none satisfy all of the above-mentioned requirements for cement dispersants, and they are still insufficient for practical use. . Regarding vinyl polymers, there is also a proposal to use them as admixtures for underwater concrete, rather than as dispersants for cement (Japanese Patent Application Laid-Open No. 1983-1999).
−42264). This proposal is to use a vinyl polymer to prevent cement from escaping into water, expecting the effect of a vinyl polymer as a thickener, and to add a cement dispersant to the vinyl polymer. For example, it is not intended to seek a dispersion effect with little change over time. In fact, even if the vinyl polymer, which is said to give good results in this proposal, is used as a dispersant for cement, it is difficult to obtain good results. <Problems to be Solved by the Invention and Means for Solving the Problems> The present invention solves the conventional problems as described above, particularly those related to vinyl polymers, and provides an improved product that satisfies all of the above-mentioned requirements. The present invention provides a dispersant for cement. However, in view of the above circumstances, the present inventors
As a result of intensive research to obtain a good dispersant for cement, a vinyl polymer with a specific structure that has a specific hydrophilic constitutional unit and a specific hydrophobic constitutional unit in the molecule was used as a dispersant for cement in conjunction with other vinyl polymers. The present inventors have discovered that they have various excellent properties not found in other plants, and have completed the present invention. That is, the present invention provides a water-soluble or water-dispersed product having a hydrophilic constitutional unit represented by the following formula (), a hydrophilic constitutional unit represented by the following formula (), and a hydrophobic constitutional unit represented by the following formula (). is a vinyl polymer of the same type, and the structural unit represented by the formula () / the structural unit represented by the formula () / the structural unit represented by the formula () =
The present invention relates to a dispersant for cement characterized by containing a vinyl polymer of 5 to 40/90 to 40/5 to 40 (each weight %). [However, R 1 , R 3 and R 4 are H or CH 3 . R 2 is an alkylene group having 1 to 5 carbon atoms. M 1 and M 2 are H, an alkali metal or an alkaline earth metal. X is COOR 5 (R 5 is an alkyl group having 1 to 8 carbon atoms), CN, C 6 H 5 or
OCOCH 3 . ] In the vinyl polymer of the present invention, monomer components forming the hydrophilic structural unit represented by the formula () include acrylamide methanesulfonic acid, acrylamide ethanesulfonic acid, acrylamide propanesulfonic acid, 2-acrylamide-2-
Examples include methylpropanesulfonic acid, methacrylamide methanesulfonic acid, methacrylamide ethanesulfonic acid, and salts thereof. Furthermore, monomer components forming the hydrophilic structural unit represented by formula () include acrylic acid, methacrylic acid, salts thereof, and the like. Furthermore, as monomer components forming the hydrophobic structural unit represented by formula (), methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate,
Examples include lower alkyl esters of acrylic acid or methacrylic acid such as propyl acrylate, propyl methacrylate, butyl acrylate, and butyl methacrylate, styrene, acrylonitrile, and vinyl acetate. The mutual ratio of each structural unit formed from the above monomer components is structural unit represented by formula () / structural unit represented by formula () / structural unit represented by formula () = 5 to 40/90 ~40/5~40 (each weight%). If it falls outside the mutual ratio range,
When the vinyl polymer is used as a dispersant for cement, the effect tends to change over time, the dispersing power tends to be insufficient, and the amount of air tends to be excessive. In particular, the hydrophobic structural unit represented by formula () is important. Copolymers consisting only of hydrophilic structural units represented by formula () or formula () exhibit dispersibility, but the dispersibility changes significantly over time, which poses a major problem in practice. This is because the copolymer containing the hydrophobic structural unit represented by (), that is, the vinyl polymer of the present invention, gives good results with little such change over time. The above-mentioned characteristic effect of the present invention regarding the change in dispersibility over time is due to the essential effect of the hydrophobic constituent unit represented by formula () relative to the hydrophilic constituent unit represented by formula () or formula (). This is thought to be due to the characteristics, the chemical structure of the copolymer, and the rich combinations and numbers that can be formed in the copolymer. The molecular weight of the vinyl polymer of the present invention is a number average molecular weight of 500 to 20,000.
(GPC method, polyethylene golicol equivalent). If it is higher than this, the vinyl polymer will have insufficient dispersibility when used as a dispersant for cement, and if it is lower than this, it will deteriorate over time. This shows a tendency for this to occur more easily. The method for producing the vinyl polymer of the present invention is not particularly limited in the present invention, and any conventionally known method can be applied. However, for ease of operation, a water-based method or a mixed method of water/water-soluble organic solvent is used. Solution polymerization is recommended. The dispersant for cement according to the present invention may be composed only of the vinyl polymer described above, or may be used for enhancing certain characteristics or for other purposes as long as the effects of the present invention are not impaired. , may contain other components. Examples of such other ingredients include AE agents, setting retarders, preservatives,
There are antifungal agents, etc. Hereinafter, in order to make the structure and effects of the present invention more specific, synthesis examples and examples of the vinyl polymer of the present invention will be given, but the present invention is not limited to these examples. <Synthesis example> 10 parts of 2-acrylamido-2-methylpropanesulfonic acid sodium salt (parts by weight, same below),
80 parts of acrylic acid and 10 parts of methyl acrylate,
The mixture was dissolved in 250 parts of water and 100 parts of isopropanol in a four-necked flask equipped with a thermometer, dropping funnel, stirrer, and nitrogen inlet tube, and the atmosphere was replaced with nitrogen. Next, 5.5 parts of a 50% ammonium thioglycolate solution as a chain transfer agent was added and dissolved, and the mixture was heated to 60°C. Then, 50 parts of a 2% ammonium persulfate aqueous solution was added as a polymerization initiator, and the mixture was stirred for 6 hours to induce polymerization. (vinyl polymer of Example 1). Below, the vinyl polymers (Examples 2 to 14, Comparative Examples 1 to 17, and Comparative Examples 21 to 23) in Tables 1 and 2 were polymerized in substantially the same manner. <Test method> Using each of the vinyl polymers obtained, concrete tests were conducted under the following conditions and methods to determine slump and air content, their changes over time (immediately → 60 minutes later), and compressive strength. It was measured. ●Conditions: 320Kg/ m3 of cement (ordinary Portland cement made by Onoda Corporation), fine aggregate (Oigawa sand,
specific gravity 2.62) and 880Kg/ m3 , coarse aggregate (Hachiyama crushed stone,
Specific gravity 2.65) is 932Kg/ m3 , water (Gamagori city water) is 182
Kg/ m3 . In addition, vinyl polymers, etc. (dispersants)
0.15% by weight (based on cement). This usage amount corresponds to the target slump of each example using vinyl polymer.
The amount is 21cm. Therefore, for Comparative Examples 18 to 20 in which no vinyl polymer was used, each dispersant was used in an appropriate amount (0.3% by weight, 0.25% by weight, and 0.06% by weight, respectively, based on cement) to achieve the same target slump. Furthermore, an appropriate amount of an AE agent (concomitant agent, manufactured by Takemoto Yushi Co., Ltd., including Tyupol C, alkyl sulfate, and others) was used (listed in Tables 1 and 2). This usage amount is such that the amount of air immediately after is 4 to 6%. Therefore, if the amount of air immediately after using only a dispersant exceeds 6%,
No AE agent was added. In addition, Example 3 is a retardant (combined agent, manufactured by Takemoto Yushi Co., Ltd., Tyupol NR,
(including oxycarboxylic acid derivatives) was used at 0.03% by weight based on cement. ●Method: All the materials were put into a tilting mixer as described in Tables 1 and 2, and immediately after stirring for 3 minutes to obtain a homogeneous state, samples were taken. Subsequently, the sample was stirred at low speed (4 r.pm) for 60 minutes. Then, the slump and air amount were measured for each sample. Moreover, the compressive strength of the sample immediately after one week and four weeks was measured. Examples 1 to 14 Examples 1 to 14 listed in Table 1 were each prepared, and each sample was measured according to the test method described above. The results are shown in the same table.
【表】【table】
【表】
比較例 １〜23
第２表に記載の比較例１〜23を各々調整し、前
述の試験方法にしたがつて各サンプルを測定し
た。結果を同表に示した。[Table] Comparative Examples 1 to 23 Comparative Examples 1 to 23 listed in Table 2 were each prepared, and each sample was measured according to the test method described above. The results are shown in the same table.
【表】【table】
【表】
＜発明の効果＞
第２表に対する第１表の結果からも明らかなよ
うに、本発明には、セメント粒子の分散性が大き
く、該分散性の経時変化が少なく、適正な空気量
を保持して硬化体の強度に優れ、経済性もよいと
いう効果がある。[Table] <Effects of the Invention> As is clear from the results in Table 1 relative to Table 2, the present invention has high dispersibility of cement particles, little change in dispersibility over time, and an appropriate amount of air. The cured product has excellent strength and economical efficiency.
Claims (1)
び下記式（）で示される親水性の構成単位並び
に下記式（）で示される疎水性の構成単位を有
する水溶性或いは水分散性のビニル重合体であつ
て、式（）で示される構成単位／式（）で示
される構成単位／式（）で示される構成単位＝
５〜40／90〜40／５〜40（各重量％）であるビニ
ル重合体を含有することを特徴とするセメント用
分散剤。 〔但し、R1、R3、R4はＨ又はCH3。R2は炭素数
１〜５のアルキレン基。M1、M2はＨ、アルカリ
金属又はアルカリ土類金属。ＸはCOOR5（R5は炭
素数１〜８のアルキル基）、CN、C6H5又は
OCOCH3。[Claims] 1. A water-soluble or Water-dispersible vinyl polymer, structural unit represented by formula () / structural unit represented by formula () / structural unit represented by formula () =
5-40/90-40/5-40 (each weight %) of a dispersant for cement. [However, R 1 , R 3 and R 4 are H or CH 3 . R 2 is an alkylene group having 1 to 5 carbon atoms. M 1 and M 2 are H, an alkali metal or an alkaline earth metal. X is COOR 5 (R 5 is an alkyl group having 1 to 8 carbon atoms), CN, C 6 H 5 or
OCOCH 3 .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60170326A JPS6230648A (en) | 1985-07-31 | 1985-07-31 | Dispersant for cement |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60170326A JPS6230648A (en) | 1985-07-31 | 1985-07-31 | Dispersant for cement |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6230648A JPS6230648A (en) | 1987-02-09 |
| JPH025701B2 true JPH025701B2 (en) | 1990-02-05 |
Family
ID=15902874
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60170326A Granted JPS6230648A (en) | 1985-07-31 | 1985-07-31 | Dispersant for cement |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6230648A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01226757A (en) * | 1988-03-04 | 1989-09-11 | Takemoto Oil & Fat Co Ltd | Dispersing agent for cement |
| EP0448717B1 (en) * | 1989-07-25 | 1995-11-29 | Nippon Shokubai Co., Ltd. | Cement admixture, production thereof, and cement composition |
| JPH04363159A (en) * | 1991-06-10 | 1992-12-16 | Daikin Ind Ltd | Ceiling embedded air cleaner |
| DE69208976T2 (en) * | 1991-08-23 | 1997-04-17 | Nippon Catalytic Chem Ind | Biodegradable, hydrophilic, cross-linked polymer, process for its preparation and its use |
| DE4320220A1 (en) * | 1993-06-18 | 1994-12-22 | Basf Ag | Use of polymers I which contain copolymerized special monoethylenically unsaturated sulfonic acids as auxiliaries in the spray drying of aqueous dispersions of polymers II |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56109774A (en) * | 1980-02-05 | 1981-08-31 | Seiko Epson Corp | Printer |
| JPS56150583A (en) * | 1980-04-24 | 1981-11-21 | Tokyo Electric Co Ltd | Printer |
| JPS58187382A (en) * | 1982-04-26 | 1983-11-01 | Matsushita Electric Ind Co Ltd | Printer |
| JPS5935055U (en) * | 1982-08-27 | 1984-03-05 | 日立工機株式会社 | printing device |
| JPS6014946U (en) * | 1983-07-08 | 1985-01-31 | 富士通株式会社 | Bookkeeping machine |
-
1985
- 1985-07-31 JP JP60170326A patent/JPS6230648A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6230648A (en) | 1987-02-09 |
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