JP4738576B2 - Dispersant for hydraulic composition - Google Patents
Dispersant for hydraulic composition Download PDFInfo
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- JP4738576B2 JP4738576B2 JP2000247368A JP2000247368A JP4738576B2 JP 4738576 B2 JP4738576 B2 JP 4738576B2 JP 2000247368 A JP2000247368 A JP 2000247368A JP 2000247368 A JP2000247368 A JP 2000247368A JP 4738576 B2 JP4738576 B2 JP 4738576B2
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- 239000002270 dispersing agent Substances 0.000 title claims description 36
- 239000000203 mixture Substances 0.000 title claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 43
- 150000003077 polyols Chemical group 0.000 claims description 40
- 125000004432 carbon atom Chemical group C* 0.000 claims description 38
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 30
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 20
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 20
- 125000000129 anionic group Chemical group 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 18
- 125000000524 functional group Chemical group 0.000 claims description 16
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 13
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 claims description 6
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 24
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 21
- 239000004568 cement Substances 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 18
- 229920005862 polyol Polymers 0.000 description 17
- 239000002904 solvent Substances 0.000 description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 14
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 14
- -1 oxyethylene, oxypropylene Chemical group 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000002253 acid Substances 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 229920000388 Polyphosphate Polymers 0.000 description 8
- 150000001408 amides Chemical class 0.000 description 8
- 238000002523 gelfiltration Methods 0.000 description 8
- 239000001205 polyphosphate Substances 0.000 description 8
- 235000011176 polyphosphates Nutrition 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 7
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 125000006353 oxyethylene group Chemical group 0.000 description 6
- 230000000865 phosphorylative effect Effects 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 239000007790 solid phase Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 239000011398 Portland cement Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 230000000274 adsorptive effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920001515 polyalkylene glycol Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000001384 succinic acid Substances 0.000 description 3
- 125000000542 sulfonic acid group Chemical group 0.000 description 3
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- 235000012241 calcium silicate Nutrition 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
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- 239000005017 polysaccharide Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 101000969688 Homo sapiens Macrophage-expressed gene 1 protein Proteins 0.000 description 1
- 102100021285 Macrophage-expressed gene 1 protein Human genes 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229930182478 glucoside Natural products 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000003340 retarding agent Substances 0.000 description 1
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- 239000008107 starch Substances 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Polyethers (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、セメント、モルタル、コンクリート等の水硬性組成物用分散剤に関する。
【０００２】
【従来の技術】
近年、ポルトランドセメント等の水硬性組成物の分散剤として、複数のポリエーテル鎖とカルボキシレートを側鎖に有するラジカル共重合体（ポリカルボン酸系分散剤）が多用されている。一般に、水中に存在する粒子には、静電引力やファンデルワールス力が作用し、機械的に分散させても再凝集する性質があるが、該分散剤は、カルボキシル基を介して固相表面に吸着するとともに、ポリエーテル鎖による立体障害効果によって粒子間引力を弱め、固体粒子の凝集を防ぐことにより固相を水中に分散安定化させる機能を有する。
【０００３】
従来、このような分散剤は、ω−メトキシオリゴ（オキシエチレン）メタクリレートや、ω−ヒドロキシオリゴ（オキシエチレン）アリルエーテル等のポリエーテル鎖を含むマクロモノマーと、メタクリル酸、アクリル酸、無水マレイン酸等をラジカル共重合させ、櫛形高分子として製造されていた。
【０００４】
しかし、該分散剤はカルボキシル基を介して固相表面に吸着するが、カルボキシル基の近傍（主にγ位）に存在するポリエーテル鎖が立体的な障害となって、吸着に関与し得るカルボキシル基の数が減少して分散剤自体の吸着力が低下し、未吸着のカルボキシル基や未吸着の分散剤が液相に多数存在する。そして、この未吸着のカルボキシル基や分散剤は、セメントの遅延剤として作用するほか、スラリーの粘性を高める作用を有することが知られている。特に、低い水粉体比のスラリーでは、所定の流動性を得るために分散剤を過剰に添加する必要があるが、この過剰添加により、更に多量の分散剤が液相中にも存在することになる。このため、従来のポリカルボン酸系分散剤は、分散性の発現に実質的に関与する割合が少なく、非効率的であるほか、セメントの凝結が著しく遅延する等の問題があった。
【０００５】
【発明が解決しようとする課題】
従って、本発明の目的は、高い分散能を有し、水硬性組成物の凝結に対する影響が小さい分散剤を提供することにある。
【０００６】
【課題を解決するための手段】
そこで、本発明者らは、鋭意研究を行った結果、ポリオキシアルキレン基と片末端に必要十分な量のアニオン性官能基を有する化合物を用いれば、セメントへの吸着力が向上して少量の添加量で高い分散能を示し、水硬性組成物の凝結への影響が小さい分散剤が得られることを見出し、本発明を完成した。
【０００７】
すなわち、本発明は、１個のポリオキシアルキレン基と片末端に２〜２０個のアニオン性官能基を有する化合物を含有する水硬性組成物用分散剤を提供するものである。
【０００８】
【発明の実施の形態】
本発明の分散剤に用いられる化合物は、１個のポリオキシアルキレン基と、片末端に２〜２０個のアニオン性官能基を有するものであり、ポリオキシアルキレン基部分は立体障害効果により分散性を高め、アニオン性官能基は固相表面への吸着官能基として作用するものである。この様な構造を有する化合物は、分子が個々独立して固相表面に強固に吸着できるとともに、粉末の分散性に寄与するポリオキシアルキレン基の立体障害効果を最大限に発揮することができる。
オキシアルキレン基としては、オキシエチレン、オキシプロピレン、オキシブチレン等の炭素数２〜４のオキシアルキレン基が挙げられ、これらの平均付加モル数は３〜３００、特に９〜１５０が好ましい。平均付加モル数がこの範囲内であると、十分な立体障害効果と固相表面への吸着力が得られ好ましい。
このようなポリオキシアルキレン基は、化合物中に１個のみ存在する。複数個存在すると、セメントへの吸着力が悪く、また水硬性組成物の凝結が遅延する。
【０００９】
また、アニオン性官能基としては、例えばリン酸基、カルボキシル基（カルボキシル基、メチレンカルボキシル基等）、硫酸基、スルホン酸基（スルホン酸基、メチレンスルホン酸基等）、ホスホン酸基（ホスホン酸基、メチレンホスホン酸基等）、これらの塩等が挙げられ、塩としては、アルカリ金属塩、アルカリ土類金属塩、アンモニウム塩等が挙げられる。これらのうち、特にリン酸基、カルボキシル基及びこれらの塩が、固相表面への吸着力に優れるので好ましい。
アニオン性官能基は１種又は２種以上が結合していてもよく、その総数は２〜２０個、好ましくは３〜１５個である。２個未満ではポリオキシアルキレン基を固相表面に留める効果が不十分になり、２０個を超えると分散性よりもセメントの遅延性が大きくなり好ましくない。
アニオン性官能基がリン酸基の場合は２〜１０個、特に３〜６個が好ましく、カルボキシル基の場合には３〜２０個、特に５〜１５個が好ましい。
【００１０】
本発明で用いる化合物は、アニオン性官能基を有する片末端と反対の末端に水酸基又はアルコキシ基、特に炭素数１〜４のアルコキシ基を有するのが好ましい。アルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基等が挙げられ、特にメトキシ基が好ましい。
【００１１】
このような化合物としては、例えば次の一般式（１）〜（７）で表わされるものが挙げられる。
【００１２】
Ｒ1−（ＯＡ）l−Ｏ−Ｂ（ＯＨ）m（ＯＸ）n （１）
（式中、Ｒ1は水素原子又は炭素数１〜４のアルキル基を示し、ＯＡは炭素数２〜４のオキシアルキレン基を示し、Ｂはポリオール残基を示し、ＯＸはポリオール残基にエーテル結合したメチレンカルボキシル基及び／又はエステル結合したリン酸基、又はこれらの塩を示し、ｌは平均付加モル数で３〜３００の数を示し、ｎは２〜２０の数を示し、ｍ＋ｎはＢの水酸基の数を示す）
【００１３】
Ｒ1−（ＯＡ）l−ＮＨ−ＣＯ−Ｒ2−ＣＯ−ＮＨ−Ｂ（ＯＨ）m（ＯＸ）n （２）
（式中、Ｒ1は水素原子又は炭素数１〜４のアルキル基を示し、ＯＡは炭素数２〜４のオキシアルキレン基を示し、Ｒ2は炭素数１〜４のアルキレン基、ビニレン基又はフェニレン基を示し、Ｂはポリオール残基を示し、ＯＸはポリオール残基にエーテル結合したメチレンカルボキシル基及び／又はエステル結合したリン酸基、又はこれらの塩を示し、ｌは平均付加モル数で３〜３００の数を示し、ｎは２〜２０の数を示し、ｍ＋ｎはＢの水酸基の数を示す）
【００１４】
Ｒ1−（ＯＡ）l−Ｏ−ＣＯ−Ｒ3（−ＣＯＯＭ）n （３）
（式中、Ｒ1は水素原子又は炭素数１〜４のアルキル基を示し、ＯＡは炭素数２〜４のオキシアルキレン基を示し、Ｒ3は炭素数２〜６０の炭化水素基を示し、ＣＯＯＭはカルボキシル基及び／又はその塩を示し、ｌは平均付加モル数で３〜３００の数を示し、ｎは２〜２０の数を示す）
【００１５】
Ｒ1−（ＯＡ）l−ＣＯＯ−Ｂ（ＯＨ）m（ＯＸ）n （４）
（式中、Ｒ1は水素原子又は炭素数１〜４のアルキル基を示し、ＯＡは炭素数２〜４のオキシアルキレン基を示し、Ｂはポリオール残基を示し、ＯＸはポリオール残基にエーテル結合したメチレンカルボキシル基及び／又はエステル結合したリン酸基、又はこれらの塩を示し、ｌは平均付加モル数で３〜３００の数を示し、ｎは２〜２０の数を示し、ｍ＋ｎはＢの水酸基の数を示す）
【００１６】
Ｒ1−（ＯＡ）l−ＣＯ−ＮＨ−Ｂ（ＯＨ）m（ＯＸ）n （５）
（式中、Ｒ1は水素原子又は炭素数１〜４のアルキル基を示し、ＯＡは炭素数２〜４のオキシアルキレン基を示し、Ｂはポリオール残基を示し、ＯＸはポリオール残基にエーテル結合したメチレンカルボキシル基及び／又はエステル結合したリン酸基、又はこれらの塩を示し、ｌは平均付加モル数で３〜３００の数を示し、ｎは２〜２０の数を示し、ｍ＋ｎはＢの水酸基の数を示す）
【００１７】
Ｒ1−（ＯＡ）l−Ｏ−ＣＯ−Ｒ2−ＣＯ−ＮＨ−Ｂ（ＯＨ）m（ＯＸ）n （６）
（式中、Ｒ1は水素原子又は炭素数１〜４のアルキル基を示し、ＯＡは炭素数２〜４のオキシアルキレン基を示し、Ｒ2は炭素数１〜４のアルキレン基、ビニレン基又はフェニレン基を示し、Ｂはポリオール残基を示し、ＯＸはポリオール残基にエーテル結合したメチレンカルボキシル基及び／又はエステル結合したリン酸基、又はこれらの塩を示し、ｌは平均付加モル数で３〜３００の数を示し、ｎは２〜２０の数を示し、ｍ＋ｎはＢの水酸基の数を示す）
【００１８】
Ｒ1−（ＯＡ）l−Ｏ−ＣＯ−Ｒ2−ＣＯ−Ｏ−Ｂ（ＯＨ）m（ＯＸ）n （７）
（式中、Ｒ1は水素原子又は炭素数１〜４のアルキル基を示し、ＯＡは炭素数２〜４のオキシアルキレン基を示し、Ｒ2は炭素数１〜４のアルキレン基、ビニレン基又はフェニレン基を示し、Ｂはポリオール残基を示し、ＯＸはポリオール残基にエーテル結合したメチレンカルボキシル基及び／又はエステル結合したリン酸基、又はこれらの塩を示し、ｌは平均付加モル数で３〜３００の数を示し、ｎは２〜２０の数を示し、ｍ＋ｎはＢの水酸基の数を示す）
【００１９】
前記一般式（１）の化合物は、ポリオキシアルキレンの一方の末端水酸基とポリオールを１個のエーテル結合を介して結合させ、該ポリオールの２個以上の水酸基に、メチレンカルボキシル基、リン酸基等のアニオン性官能基を結合させたものである。
このような化合物のうち、アニオン性基がリン酸基であるものは、例えば多糖等のポリオールとポリオキシアルキレングリコールを酸性触媒とともに加熱することによりポリオキシアルキレングリコールグルコシドポリオールとした後、これらとオキシ塩化リン等のリン酸化剤を反応させることにより、製造することができる。酸性触媒としては、例えば塩化水素、酢酸等を用いることができる。
【００２０】
また、一般式（２）の化合物は、ポリオキシアルキレンアミンの末端アミノ基とモノアミノポリオールを、２価カルボン酸を用いて酸アミド結合を介して結合させ、該ポリオールの２個以上の水酸基に、メチレンカルボキシル基、リン酸基等のアニオン性官能基を結合させたものである。
一般式（２）で表わされる化合物のうち、アニオン性基がリン酸基であるものは、例えばジメチルスルホキシド等の溶媒の存在下、モノアミノポリオールと２価カルボン酸を反応させて、これらのハーフアミドを得、これとポリオキシアルキレンアミン又はアルコキシポリオキシアルキレンアミンを、ジメチルホルムアミド等の溶媒中、縮合剤の存在下に反応させてアミドとし、更にこれとオキシ塩化リン等のリン酸化剤を反応させることにより、製造することができる。縮合剤としては、前記と同様のものを用いることができる。
【００２１】
一般式（３）の化合物は、ポリオキシアルキレンの一方の末端水酸基とオリゴカルボン酸を１個のエステル結合を介して結合させたものである。
このような化合物は、例えばオリゴカルボン酸とポリアルキレングリコール又はアルコキシポリアルキレングリコールを、ジメチルホルムアミド等の溶媒中、縮合剤の存在下に反応させることにより、オリゴカルボン酸の末端カルボン酸とポリアルキレングリコールが縮合したエステルを製造することができる。縮合剤としては、前記と同様のものを用いることができる。
【００２２】
一般式（４）の化合物は、ポリオキシアルキレンカルボン酸の末端カルボン酸とポリオールをエステル結合を介して結合させ、該ポリオールの２個以上の水酸基に、メチレンカルボキシル基、リン酸基等のアニオン性官能基を結合させたものである。
このような化合物のうち、アニオン性基がリン酸基であるものは、例えばポリオキシアルキレンカルボン酸とポリオールを、ジメチルホルムアミド等の溶媒中、縮合剤の存在下に反応させることにより、ポリオキシアルキレンカルボン酸の末端カルボン酸とポリオールが縮合したエステルとし、更にこれとオキシ塩化リン等のリン酸化剤を反応させることにより、製造することができる。縮合剤としては、前記と同様のものを用いることができる。
【００２３】
一般式（５）の化合物は、ポリオキシアルキレンカルボン酸の末端カルボン酸とモノアミノポリオールを、酸アミドを介して結合させ、該ポリオールの２個以上の水酸基に、メチレンカルボキシル基、リン酸基等のアニオン性官能基を結合させたものである。
このような化合物は、例えばポリオキシアルキレンカルボン酸とモノアミノポリオールを、ジメチルスルホキシド等の溶媒の存在下に反応させてアミドを得、更にこれとオキシ塩化リン等のリン酸化剤を反応させることにより、製造することができる。
【００２４】
一般式（６）の化合物は、例えばメトキシポリエチレングリコールコハク酸ハーフエステル等のポリオキシアルキレンジカルボン酸エステルの末端カルボン酸とモノアミノポリオールを酸アミドを介して結合させ、該ポリオールの２個以上の水酸基に、メチレンカルボキシル基、リン酸基等のアニオン性官能基を結合させたものである。
このような化合物は、例えばメトキシポリオキシアルキレンジカルボン酸エステルとモノアミノポリオールを、ジメチルスルホキシド等の溶媒の存在下に反応させてアミドを得、更にこれとオキシ塩化リン等のリン酸化剤を反応させることにより、製造することができる。
【００２５】
一般式（７）で表わされる化合物のうち、アニオン性基がメチレンカルボキシル基である化合物は、例えばジメチルスルホキシド等の溶媒の存在下、カルボキシメチルセルロースと２価カルボン酸を縮合剤の存在下に反応させて、これらのハーフエステルを得、これとポリオキシアルキレングリコール又はアルコキシポリオキシアルキレングリコールを、ジメチルスルホキシド等の溶媒中、縮合剤の存在下に反応させることにより、製造することができる。縮合剤としては、前記と同様のものを用いることができる。
【００２６】
なお、前記一般式中、ポリオールとしては、例えばグリセリン、糖アルコール、多糖類、ポリビニルアルコール等が挙げられ；モノアミノポリオールとしては、例えばグルカミン等が挙げられ；２価カルボン酸としては、例えばマレイン酸、マロン酸、コハク酸、グルタル酸、オルトフタル酸、メタフタル酸、パラフタル酸等が挙げられ；オリゴカルボン酸としては、例えばクエン酸、オリゴアクリル酸、オリゴメタクリル酸等が挙げられる。
【００２７】
本発明の分散剤は、前記のような化合物を含有するものであり、それ以外に、例えば消泡剤、抑泡剤、ＡＥ剤、遅延剤、凝結促進剤、収縮低減剤、膨張剤、その他の分散剤等を含有していてもよい。
本発明の分散剤は、セメント、モルタル、コンクリート等の水硬性組成物に用いられ、これらを混練する際、混練水に溶解して使用するほか、セメント等に予めドライブレンドして使用することもできる。
【００２８】
【実施例】
次に、実施例を挙げて本発明を更に詳細に説明するが、本発明はこれらにより何ら制限されるものではない。なお、以下の合成例において、得られた化合物の同定は、ＮＭＲ分析及びＴＯＦ−ＭＳ分析により行った。また、得られた各化合物において、リン酸基の置換位置は式で示されたものに限定されず、他の配位も含まれる。
【００２９】
合成例１（ポリリン酸化合物（Ａ）及び（Ｂ）の合成）
グルカミン１(eq)をジメチルスルホキシド（ＤＭＳＯ）に溶解し、無水コハク酸１(eq)とジイソプロピルエチルアミン（ＤＩＥＡ）２(eq)を加えて室温で２時間攪拌した後、溶媒を留去してグルカミンとコハク酸のハーフアミド（Ａ”）を得た。
次に、（Ａ”）の１(eq)とオキシエチレンの付加モル数１００のメトキシポリオキシエチレンアミン（ＭＰＯＥＡ）１(eq)をジメチルホルムアミドに溶解し、ベンゾトリアゾール−１−イル−オキシ−トリス（ジメチルアミノ）ホスホニウム ヘキサフルオロホスフェート（縮合剤、ＢＯＰ）２．５(eq)とＤＩＥＡ５(eq)を加えて室温で一晩攪拌した後、溶媒を留去し、ゲル濾過により精製し、グルカミンとＭＰＯＥＡとコハク酸のアミド（Ａ’）を得た。
次に、（Ａ’）１(eq)に水１(eq)とＤＩＥＡ６(eq)を加え、０℃に冷却してオキシ塩化リン１００(eq)を徐々に添加し、室温で一晩攪拌した。再度０℃に冷却した後、水を滴下して未反応のオキシ塩化リンを分解し、更にＤＩＥＡを加えて中和した後、溶媒を留去し、ゲル濾過により精製して、ポリリン酸化合物（Ａ）のアミン塩を得た。
また、リン酸化剤として亜リン酸化剤（オルトキシリレン−Ｎ，Ｎ−ジエチルフォスホロアミダイト）を用い、ポリリン酸化合物（Ｂ）を同様にして製造した。
導入されたリン酸基の数はＩＣＰ分析により定量した。
【００３０】
【化１】
合成例２（ポリリン酸化合物（Ｃ）の合成）
マルトース１(eq)とオキシエチレンの付加モル数１００のメトキシポリオキシエチレングリコール−コハク酸エステル（ＭＰＯＥＧＳ）１(eq)をジメチルホルミアミドに溶解し、ＢＯＰ１．２５(eq)とＤＩＥＡ１．２５(eq)を加え、室温で一晩攪拌した後、溶媒を留去し、ゲル濾過により精製し、マルトースとＭＰＯＥＧＳのエステル（Ｃ’）を得た。
次に、（Ｃ’）１(eq)に水１(eq)とＤＩＥＡ６(eq)を加え、０℃に冷却してオキシ塩化リン１００(eq)を徐々に添加し、室温で一晩攪拌した。再度０℃に冷却した後、水を滴下して未反応のオキシ塩化リンを分解し、更にＤＩＥＡを加えて中和した後、溶媒を留去し、ゲル濾過により精製して、ポリリン酸化合物（Ｃ）のアミン塩を得た。
【００３２】
【化２】
合成例３（ポリリン酸化合物（Ｄ）の合成）
でんぷん（グルコース単位で３(eq)）をオキシエチレンの付加モル数１００のメトキシポリオキシエチレングリコール（ＭＰＥＧ）１(eq)と混合し、酸触媒（塩化水素）の存在下、１３０℃で４５分間加熱し、メトキシポリオキシエチレンと三糖がアセタール結合した化合物（Ｄ’）を得た。
次に、（Ｄ’）１(eq)に水１(eq)とＤＩＥＡ６(eq)を加え、０℃に冷却してオキシ塩化リン１００(eq)を徐々に添加し、室温で一晩攪拌した。再度０℃に冷却した後、水を滴下して未反応のオキシ塩化リンを分解し、更にＤＩＥＡを加えて中和した後、溶媒を留去し、ゲル濾過により精製して、ポリリン酸化合物（Ｄ）を得た。
【００３４】
【化３】
合成例４（ポリカルボン酸化合物（Ｅ）、（Ｆ）及び（Ｇ）の合成）
オリゴメタアクリル酸（重合度５、９又は１５；各々（Ｅ’）、（Ｆ’）、（Ｇ’）に対応）１(eq)とＭＰＥＧ１(eq)をジメチルホルムアミドに溶解し、ＢＯＰ１．２５(eq)とＤＩＥＡ１．２５(eq)を加えて室温で一晩攪拌した後、溶媒を留去し、ゲル濾過により精製し、オリゴメタアクリル酸とＭＰＥＧのエステル（Ｅ）、（Ｆ）及び（Ｇ）を得た。
【００３６】
【化４】
合成例５（ポリリン酸化合物（Ｈ）の合成）
グルカミン１(eq)とオキシエチレンの付加モル数１０のメトキシポリオキシエチレングリコール−コハク酸エステル（ＭＰＯＥＧＳ（Ｈ”））１(eq)をジメチルホルムアミドに溶解し、ＢＯＰ１．２５(eq)とＤＩＥＡ１．２５(eq)を加えて室温で一晩攪拌した後、溶媒を留去し、ゲル濾過により精製し、グルカミンとＭＰＯＥＧＳのアミド（Ｈ’）を得た。
次に、（Ｈ’）１(eq)に水１(eq)とＤＩＥＡ６(eq)を加え、０℃に冷却してオキシ塩化リン１００(eq)を徐々に添加し、室温で一晩攪拌した。再度０℃に冷却した後、水を滴下して未反応のオキシ塩化リンを分解し、更にＤＩＥＡを加えて中和した後、溶媒を留去し、ゲル濾過により精製して、ポリリン酸化合物（Ｈ）のアミン塩を得た。
【００３８】
【化５】
実施例１
表１に示す分散剤の所定量を混練水に溶解し、普通ポルトランドセメント（ＮＰＣ）又は高ビーライト型低熱ポルトランドセメント（ＬＨＣ）に加えて３分間混練し、水セメント比３０％の普通ポルトランドセメントペースト、又は水セメント比１８％の高ビーライト型低熱ポルトランドセメントペーストを調製した。混練直後のペーストのフロー値、分散剤のセメントへの吸着率及びセメントの凝結時間を測定した。
フロー値は、内径２５mm、高さ２０mmの円筒リング内にペーストを充填し、リングを引き抜いた後のペーストの広がりを、直行する２方向について測定し、その平均値をフロー値とした。分散剤のセメントへの吸着率は、遠心分離したセメントペースト液相中の分散剤量を全有機炭素計で測定し、それと当初添加した分散剤量との差から、分散剤のセメントへの吸着率を求めた。また、セメントの凝結時間は、フロー値を測定した後のペーストを用いて自動凝結試験機（マルトー製作所社製）により終結時間を測定した。これらの結果を表２に示す。
【００４０】
【表１】
【表２】
表２の結果より、本発明の分散剤はいずれも、セメントへの吸着率が高く、分散能に優れるとともに、セメントの凝結への影響が小さいものであった。
【００４３】
【発明の効果】
本発明の分散剤は、少量の添加量で高い分散性能を有し、セメントの凝結に対する影響が小さいものである。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a dispersant for hydraulic compositions such as cement, mortar and concrete.
[0002]
[Prior art]
In recent years, radical copolymers (polycarboxylic acid-based dispersants) having a plurality of polyether chains and carboxylates in side chains have been frequently used as dispersants for hydraulic compositions such as Portland cement. In general, electrostatic attraction and van der Waals forces act on particles present in water and have the property of reaggregating even when mechanically dispersed. And has a function of stabilizing the dispersion of the solid phase in water by weakening the attractive force between the particles by the steric hindrance effect due to the polyether chain and preventing the aggregation of the solid particles.
[0003]
Conventionally, such dispersants include macromonomers containing polyether chains such as ω-methoxy oligo (oxyethylene) methacrylate and ω-hydroxy oligo (oxyethylene) allyl ether, methacrylic acid, acrylic acid, and maleic anhydride. Etc. were radically copolymerized to produce a comb polymer.
[0004]
However, the dispersant adsorbs to the solid phase surface via the carboxyl group, but the polyether chain present in the vicinity of the carboxyl group (mainly the γ position) becomes a steric hindrance and can participate in the adsorption. The number of groups decreases and the adsorptive power of the dispersant itself decreases, and a large number of unadsorbed carboxyl groups and unadsorbed dispersant exist in the liquid phase. And it is known that this unadsorbed carboxyl group or dispersant acts as a cement retarder and has an action of increasing the viscosity of the slurry. In particular, in a slurry having a low water powder ratio, it is necessary to add an excessive amount of a dispersant in order to obtain a predetermined fluidity. By this excessive addition, a larger amount of the dispersant is also present in the liquid phase. become. For this reason, the conventional polycarboxylic acid-based dispersant has a problem that the ratio of the substantial participation in the expression of dispersibility is small and inefficient, and the setting of the cement is significantly delayed.
[0005]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide a dispersant having a high dispersibility and a small influence on the setting of the hydraulic composition.
[0006]
[Means for Solving the Problems]
Therefore, as a result of intensive studies, the present inventors have improved the adsorptive power to cement by using a compound having a polyoxyalkylene group and a necessary and sufficient amount of an anionic functional group at one end, and a small amount of it. The present inventors have found that a dispersant can be obtained that exhibits high dispersibility by the addition amount and has a small influence on the setting of the hydraulic composition.
[0007]
That is, this invention provides the dispersing agent for hydraulic compositions containing the compound which has one polyoxyalkylene group and 2-20 anionic functional groups in one terminal.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The compound used in the dispersant of the present invention has one polyoxyalkylene group and 2 to 20 anionic functional groups at one end, and the polyoxyalkylene group portion is dispersible due to steric hindrance effect. The anionic functional group acts as an adsorption functional group on the solid surface. The compound having such a structure can exhibit the steric hindrance effect of the polyoxyalkylene group contributing to the dispersibility of the powder to the maximum while the molecules can be firmly adsorbed to the solid phase surface independently.
Examples of the oxyalkylene group include oxyalkylene groups having 2 to 4 carbon atoms such as oxyethylene, oxypropylene, and oxybutylene, and the average added mole number thereof is preferably 3 to 300, particularly preferably 9 to 150. When the average added mole number is within this range, a sufficient steric hindrance effect and adsorption force to the solid surface are obtained.
There is only one such polyoxyalkylene group in the compound. When there are a plurality, the adsorptive power to cement is poor, and the setting of the hydraulic composition is delayed.
[0009]
Examples of anionic functional groups include phosphoric acid groups, carboxyl groups (carboxyl groups, methylene carboxyl groups, etc.), sulfuric acid groups, sulfonic acid groups (sulfonic acid groups, methylene sulfonic acid groups, etc.), phosphonic acid groups (phosphonic acid groups). Groups, methylenephosphonic acid groups, etc.), salts thereof, and the like. Examples of the salts include alkali metal salts, alkaline earth metal salts, ammonium salts, and the like. Among these, a phosphate group, a carboxyl group, and salts thereof are particularly preferable because of their excellent adsorption power to the solid phase surface.
One type or two or more types of anionic functional groups may be bonded, and the total number thereof is 2 to 20, preferably 3 to 15. If the number is less than 2, the effect of retaining the polyoxyalkylene group on the solid phase surface becomes insufficient. If the number exceeds 20, the cement retardance becomes larger than the dispersibility, which is not preferable.
When the anionic functional group is a phosphate group, 2 to 10, particularly 3 to 6 are preferable, and when it is a carboxyl group, 3 to 20, particularly 5 to 15 are preferable.
[0010]
The compound used in the present invention preferably has a hydroxyl group or an alkoxy group, particularly an alkoxy group having 1 to 4 carbon atoms, at a terminal opposite to one terminal having an anionic functional group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and a methoxy group is particularly preferable.
[0011]
Examples of such compounds include those represented by the following general formulas (1) to (7).
[0012]
R 1 — (OA) 1 —O—B (OH) m (OX) n (1)
(In the formula, R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, OA represents an oxyalkylene group having 2 to 4 carbon atoms, B represents a polyol residue, and OX represents an ether in the polyol residue. A bonded methylene carboxyl group and / or an ester-bonded phosphate group, or a salt thereof, l represents an average added mole number of 3 to 300, n represents a number of 2 to 20, and m + n represents B Indicates the number of hydroxyl groups)
[0013]
R 1 — (OA) 1 —NH—CO—R 2 —CO—NH—B (OH) m (OX) n (2)
(Wherein R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, OA represents an oxyalkylene group having 2 to 4 carbon atoms, and R 2 represents an alkylene group having 1 to 4 carbon atoms, a vinylene group or Represents a phenylene group, B represents a polyol residue, OX represents a methylene carboxyl group ether-bonded to the polyol residue and / or an ester-bonded phosphate group, or a salt thereof, and l represents an average addition mole number of 3 ) Represents a number of ˜300, n represents a number of 2 to 20, and m + n represents the number of hydroxyl groups of B)
[0014]
R 1 — (OA) 1 —O—CO—R 3 (—COOM) n (3)
(In the formula, R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, OA represents an oxyalkylene group having 2 to 4 carbon atoms, R 3 represents a hydrocarbon group having 2 to 60 carbon atoms, COOM represents a carboxyl group and / or a salt thereof, l represents an average added mole number of 3 to 300, and n represents a number of 2 to 20)
[0015]
R 1 — (OA) 1 —COO—B (OH) m (OX) n (4)
(In the formula, R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, OA represents an oxyalkylene group having 2 to 4 carbon atoms, B represents a polyol residue, and OX represents an ether in the polyol residue. A bonded methylene carboxyl group and / or an ester-bonded phosphate group, or a salt thereof, l represents an average added mole number of 3 to 300, n represents a number of 2 to 20, and m + n represents B Indicates the number of hydroxyl groups)
[0016]
R 1 — (OA) 1 —CO—NH—B (OH) m (OX) n (5)
(In the formula, R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, OA represents an oxyalkylene group having 2 to 4 carbon atoms, B represents a polyol residue, and OX represents an ether in the polyol residue. A bonded methylene carboxyl group and / or an ester-bonded phosphate group, or a salt thereof, l represents an average added mole number of 3 to 300, n represents a number of 2 to 20, and m + n represents B Indicates the number of hydroxyl groups)
[0017]
R 1 — (OA) 1 —O—CO—R 2 —CO—NH—B (OH) m (OX) n (6)
(Wherein R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, OA represents an oxyalkylene group having 2 to 4 carbon atoms, and R 2 represents an alkylene group having 1 to 4 carbon atoms, a vinylene group or Represents a phenylene group, B represents a polyol residue, OX represents a methylene carboxyl group ether-bonded to the polyol residue and / or an ester-bonded phosphate group, or a salt thereof, and l represents an average addition mole number of 3 ) Represents a number of ˜300, n represents a number of 2 to 20, and m + n represents the number of hydroxyl groups of B)
[0018]
R 1 — (OA) 1 —O—CO—R 2 —CO—O—B (OH) m (OX) n (7)
(Wherein R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, OA represents an oxyalkylene group having 2 to 4 carbon atoms, and R 2 represents an alkylene group having 1 to 4 carbon atoms, a vinylene group or Represents a phenylene group, B represents a polyol residue, OX represents a methylene carboxyl group ether-bonded to the polyol residue and / or an ester-bonded phosphate group, or a salt thereof, and l represents an average addition mole number of 3 ) Represents a number of ˜300, n represents a number of 2 to 20, and m + n represents the number of hydroxyl groups of B)
[0019]
In the compound of the general formula (1), one terminal hydroxyl group of polyoxyalkylene and a polyol are bonded through one ether bond, and a methylene carboxyl group, a phosphate group, or the like is bonded to two or more hydroxyl groups of the polyol. These anionic functional groups are bonded.
Among such compounds, those in which the anionic group is a phosphoric acid group are obtained by, for example, heating a polyol such as polysaccharide and polyoxyalkylene glycol together with an acidic catalyst to form a polyoxyalkylene glycol glucoside polyol, It can be produced by reacting a phosphorylating agent such as phosphorus chloride. As the acidic catalyst, for example, hydrogen chloride, acetic acid and the like can be used.
[0020]
In addition, the compound of the general formula (2) is obtained by bonding a terminal amino group of polyoxyalkyleneamine and a monoaminopolyol through an acid amide bond using a divalent carboxylic acid, to two or more hydroxyl groups of the polyol. , An anionic functional group such as a methylene carboxyl group and a phosphate group.
Among the compounds represented by the general formula (2), those in which the anionic group is a phosphoric acid group are obtained by reacting a monoaminopolyol with a divalent carboxylic acid in the presence of a solvent such as dimethyl sulfoxide. An amide is obtained, and this is reacted with polyoxyalkyleneamine or alkoxypolyoxyalkyleneamine in a solvent such as dimethylformamide in the presence of a condensing agent, and further reacted with a phosphorylating agent such as phosphorus oxychloride. By making it, it can manufacture. As the condensing agent, the same ones as described above can be used.
[0021]
The compound of the general formula (3) is obtained by bonding one terminal hydroxyl group of polyoxyalkylene and an oligocarboxylic acid via one ester bond.
Such a compound is obtained by reacting, for example, an oligocarboxylic acid and a polyalkylene glycol or an alkoxy polyalkylene glycol in a solvent such as dimethylformamide in the presence of a condensing agent, thereby causing the terminal carboxylic acid of the oligocarboxylic acid and the polyalkylene glycol to react. Can be produced. As the condensing agent, the same ones as described above can be used.
[0022]
In the compound of the general formula (4), a terminal carboxylic acid of a polyoxyalkylene carboxylic acid and a polyol are bonded via an ester bond, and an anionic property such as a methylene carboxyl group or a phosphate group is bonded to two or more hydroxyl groups of the polyol. A functional group is bonded.
Among such compounds, those in which the anionic group is a phosphoric acid group are obtained by reacting, for example, a polyoxyalkylene carboxylic acid and a polyol in a solvent such as dimethylformamide in the presence of a condensing agent. The ester can be produced by condensing a terminal carboxylic acid of a carboxylic acid with a polyol and further reacting this with a phosphorylating agent such as phosphorus oxychloride. As the condensing agent, the same ones as described above can be used.
[0023]
In the compound of the general formula (5), a terminal carboxylic acid of a polyoxyalkylene carboxylic acid and a monoamino polyol are bonded via an acid amide, and a methylene carboxyl group, a phosphate group, or the like is bonded to two or more hydroxyl groups of the polyol. These anionic functional groups are bonded.
Such a compound is obtained, for example, by reacting a polyoxyalkylene carboxylic acid and a monoamino polyol in the presence of a solvent such as dimethyl sulfoxide to obtain an amide, and further reacting this with a phosphorylating agent such as phosphorus oxychloride. Can be manufactured.
[0024]
The compound of the general formula (6) is obtained by, for example, bonding a terminal carboxylic acid of a polyoxyalkylene dicarboxylic acid ester such as methoxypolyethyleneglycol succinic acid half ester and a monoamino polyol via an acid amide, and two or more hydroxyl groups of the polyol And an anionic functional group such as a methylene carboxyl group and a phosphate group.
Such a compound is obtained by reacting, for example, a methoxypolyoxyalkylene dicarboxylic acid ester and a monoamino polyol in the presence of a solvent such as dimethyl sulfoxide to obtain an amide, which is further reacted with a phosphorylating agent such as phosphorus oxychloride. Can be manufactured.
[0025]
Among the compounds represented by the general formula (7), a compound in which the anionic group is a methylene carboxyl group is obtained by reacting carboxymethyl cellulose and a divalent carboxylic acid in the presence of a condensing agent in the presence of a solvent such as dimethyl sulfoxide. Thus, these half esters can be obtained and can be produced by reacting this with a polyoxyalkylene glycol or alkoxy polyoxyalkylene glycol in a solvent such as dimethyl sulfoxide in the presence of a condensing agent. As the condensing agent, the same ones as described above can be used.
[0026]
In the above general formula, examples of the polyol include glycerin, sugar alcohol, polysaccharide, and polyvinyl alcohol; examples of the monoamino polyol include glucamine; and examples of the divalent carboxylic acid include maleic acid. , Malonic acid, succinic acid, glutaric acid, orthophthalic acid, metaphthalic acid, paraphthalic acid and the like; examples of the oligocarboxylic acid include citric acid, oligoacrylic acid and oligomethacrylic acid.
[0027]
The dispersant of the present invention contains the compound as described above. Besides, for example, an antifoaming agent, an antifoaming agent, an AE agent, a retarding agent, a setting accelerator, a shrinkage reducing agent, an expanding agent, and the like. The dispersant may be contained.
The dispersant of the present invention is used in hydraulic compositions such as cement, mortar, concrete and the like, and when these are kneaded, in addition to being used by dissolving in kneaded water, it can also be used by dry blending in cement or the like in advance. it can.
[0028]
【Example】
EXAMPLES Next, although an Example is given and this invention is demonstrated still in detail, this invention is not restrict | limited at all by these. In the following synthesis examples, the obtained compounds were identified by NMR analysis and TOF-MS analysis. Further, in each of the obtained compounds, the substitution position of the phosphate group is not limited to that shown in the formula, and other coordination is also included.
[0029]
Synthesis Example 1 (Synthesis of polyphosphate compounds (A) and (B))
Glucamine 1 (eq) is dissolved in dimethyl sulfoxide (DMSO), succinic anhydride 1 (eq) and diisopropylethylamine (DIEA) 2 (eq) are added and stirred at room temperature for 2 hours, and then the solvent is distilled off to remove glucamine. And a succinic acid half amide (A ″).
Next, 1 (eq) of (A ″) and methoxypolyoxyethyleneamine (MPOEA) 1 (eq) having an addition mole number of oxyethylene of 100 are dissolved in dimethylformamide, and benzotriazol-1-yl-oxy-tris is dissolved. (Dimethylamino) phosphonium hexafluorophosphate (condensing agent, BOP) 2.5 (eq) and DIEA5 (eq) were added and stirred overnight at room temperature, and then the solvent was distilled off and purified by gel filtration to obtain glucamine and An amide (A ′) of MPOEA and succinic acid was obtained.
Next, water (1eq) and DIEA6 (eq) were added to (A ') 1 (eq), cooled to 0 ° C, and phosphorus oxychloride 100 (eq) was gradually added, followed by stirring at room temperature overnight. . After cooling again to 0 ° C., water was added dropwise to decompose unreacted phosphorus oxychloride, and further neutralized by adding DIEA. Then, the solvent was distilled off and purified by gel filtration to obtain a polyphosphate compound ( The amine salt of A) was obtained.
In addition, a polyphosphoric acid compound (B) was produced in the same manner using a phosphite (orthoxylylene-N, N-diethylphosphoroamidite) as a phosphorylating agent.
The number of phosphate groups introduced was quantified by ICP analysis.
[0030]
[Chemical 1]
Synthesis Example 2 (Synthesis of polyphosphate compound (C))
Methoxypolyoxyethylene glycol-succinic acid ester (MPOEGS) 1 (eq) having an addition mole number of maltose 1 (eq) and oxyethylene is dissolved in dimethylformamide, and BOP1.25 (eq) and DIEA 1.25 ( eq) was added, and the mixture was stirred overnight at room temperature. Then, the solvent was distilled off, and the residue was purified by gel filtration to obtain an ester (C ′) of maltose and MPOEGS.
Next, water 1 (eq) and DIEA 6 (eq) were added to (C ′) 1 (eq), cooled to 0 ° C., 100 eq of phosphorus oxychloride was gradually added, and the mixture was stirred overnight at room temperature. . After cooling again to 0 ° C., water was added dropwise to decompose unreacted phosphorus oxychloride, and further neutralized by adding DIEA. Then, the solvent was distilled off and purified by gel filtration to obtain a polyphosphate compound ( The amine salt of C) was obtained.
[0032]
[Chemical 2]
Synthesis Example 3 (Synthesis of polyphosphate compound (D))
Starch (3 (eq) in glucose units) is mixed with methoxypolyoxyethylene glycol (MPEG) 1 (eq) having an addition mole number of oxyethylene of 100 and 45 minutes at 130 ° C. in the presence of an acid catalyst (hydrogen chloride). By heating, a compound (D ′) in which methoxypolyoxyethylene and trisaccharide were acetal-bonded was obtained.
Next, water 1 (eq) and DIEA 6 (eq) were added to (D ′) 1 (eq), cooled to 0 ° C., 100 eq of phosphorus oxychloride was gradually added, and the mixture was stirred overnight at room temperature. . After cooling again to 0 ° C., water was added dropwise to decompose unreacted phosphorus oxychloride, and further neutralized by adding DIEA. Then, the solvent was distilled off and purified by gel filtration to obtain a polyphosphate compound ( D) was obtained.
[0034]
[Chemical 3]
Synthesis Example 4 (Synthesis of polycarboxylic acid compounds (E), (F) and (G))
Oligomethacrylic acid (degree of polymerization 5, 9 or 15; corresponding to (E ′), (F ′), (G ′) respectively) 1 (eq) and MPEG1 (eq) are dissolved in dimethylformamide and BOP 1.25 (eq) and DIEA 1.25 (eq) were added and stirred overnight at room temperature, then the solvent was distilled off and purified by gel filtration to obtain oligomethacrylic acid and MPEG esters (E), (F) and ( G) was obtained.
[0036]
[Formula 4]
Synthesis Example 5 (Synthesis of polyphosphate compound (H))
Glucamine 1 (eq) and oxyethylene addition mole 10 methoxypolyoxyethylene glycol-succinic acid ester (MPOEGS (H ")) 1 (eq) is dissolved in dimethylformamide, and BOP1.25 (eq) and DIEA1. After adding 25 (eq) and stirring at room temperature overnight, the solvent was distilled off and the residue was purified by gel filtration to obtain glucamine and MPOEGS amide (H ′).
Next, water 1 (eq) and DIEA 6 (eq) were added to (H ′) 1 (eq), cooled to 0 ° C., 100 eq of phosphorus oxychloride was gradually added, and the mixture was stirred overnight at room temperature. . After cooling again to 0 ° C., water was added dropwise to decompose unreacted phosphorus oxychloride, and further neutralized by adding DIEA. Then, the solvent was distilled off and purified by gel filtration to obtain a polyphosphate compound ( The amine salt of H) was obtained.
[0038]
[Chemical formula 5]
Example 1
A predetermined amount of the dispersant shown in Table 1 is dissolved in kneaded water, added to ordinary Portland cement (NPC) or high belite type low heat Portland cement (LHC), and kneaded for 3 minutes. A high belite type low heat Portland cement paste having a paste or water cement ratio of 18% was prepared. The paste flow value immediately after kneading, the adsorption rate of the dispersant to the cement, and the setting time of the cement were measured.
The flow value was measured by measuring the spread of the paste after pulling out the ring in a cylindrical ring having an inner diameter of 25 mm and a height of 20 mm in two orthogonal directions, and taking the average value as the flow value. The adsorption rate of the dispersant to the cement is determined by measuring the amount of dispersant in the centrifuged cement paste liquid phase with a total organic carbon meter, and the difference between the amount of dispersant added initially and the amount of dispersant added to the cement. The rate was determined. Moreover, the setting time of the cement was measured by an automatic setting tester (manufactured by Maruto Co., Ltd.) using the paste after measuring the flow value. These results are shown in Table 2.
[0040]
[Table 1]
[Table 2]
From the results shown in Table 2, all of the dispersants of the present invention had a high adsorption rate to cement, excellent dispersibility, and a small influence on cement setting.
[0043]
【The invention's effect】
The dispersant of the present invention has high dispersion performance with a small amount of addition, and has little influence on cement setting.
Claims (9)
Ｒ1−（ＯＡ）l−Ｏ−Ｂ（ＯＨ）m（ＯＸ）n （１）
（式中、Ｒ1は水素原子又は炭素数１〜４のアルキル基を示し、ＯＡは炭素数２〜４のオキシアルキレン基を示し、Ｂはポリオール残基を示し、ＯＸはポリオール残基にエーテル結合したメチレンカルボキシル基及び／又はエステル結合したリン酸基、又はこれらの塩を示し、ｌは平均付加モル数で３〜３００の数を示し、ｎは２〜２０の数を示し、ｍ＋ｎはＢの水酸基の数を示す）
で表わされるものである請求項１又は２記載の水硬性組成物用分散剤。The compound is represented by the general formula (1)
R 1 — (OA) 1 —O—B (OH) m (OX) n (1)
(In the formula, R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, OA represents an oxyalkylene group having 2 to 4 carbon atoms, B represents a polyol residue, and OX represents an ether in the polyol residue. A bonded methylene carboxyl group and / or an ester-bonded phosphate group, or a salt thereof, l represents an average added mole number of 3 to 300, n represents a number of 2 to 20, and m + n represents B Indicates the number of hydroxyl groups)
The dispersant for a hydraulic composition according to claim 1 or 2, which is represented by the formula:
Ｒ1−（ＯＡ）l−ＮＨ−ＣＯ−Ｒ2−ＣＯ−ＮＨ−Ｂ（ＯＨ）m（ＯＸ）n （２）（式中、Ｒ1は水素原子又は炭素数１〜４のアルキル基を示し、ＯＡは炭素数２〜４のオキシアルキレン基を示し、Ｒ2は炭素数１〜４のアルキレン基、ビニレン基又はフェニレン基を示し、Ｂはポリオール残基を示し、ＯＸはポリオール残基にエーテル結合したメチレンカルボキシル基及び／又はエステル結合したリン酸基、又はこれらの塩を示し、ｌは平均付加モル数で３〜３００の数を示し、ｎは２〜２０の数を示し、ｍ＋ｎはＢの水酸基の数を示す）
で表わされるものである請求項１又は２記載の水硬性組成物用分散剤。The compound is represented by the general formula (2)
R 1 — (OA) 1 —NH—CO—R 2 —CO—NH—B (OH) m (OX) n (2) (wherein R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). OA represents an oxyalkylene group having 2 to 4 carbon atoms, R 2 represents an alkylene group having 1 to 4 carbon atoms, a vinylene group or a phenylene group, B represents a polyol residue, and OX represents a polyol residue. An ether-bonded methylene carboxyl group and / or an ester-bonded phosphate group, or a salt thereof, l represents an average added mole number of 3 to 300, n represents a number of 2 to 20, and m + n represents Indicates the number of hydroxyl groups in B)
The dispersant for a hydraulic composition according to claim 1 or 2, which is represented by the formula:
Ｒ1−（ＯＡ）l−Ｏ−ＣＯ−Ｒ3（−ＣＯＯＭ）n （３）
（式中、Ｒ1は水素原子又は炭素数１〜４のアルキル基を示し、ＯＡは炭素数２〜４のオキシアルキレン基を示し、Ｒ3は炭素数２〜６０の炭化水素基を示し、ＣＯＯＭはカルボキシル基及び／又はその塩を示し、ｌは平均付加モル数で３〜３００の数を示し、ｎは２〜２０の数を示す）
で表わされるものである請求項１又は２記載の水硬性組成物用分散剤。The compound has the general formula (3)
R 1 — (OA) 1 —O—CO—R 3 (—COOM) n (3)
(In the formula, R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, OA represents an oxyalkylene group having 2 to 4 carbon atoms, R 3 represents a hydrocarbon group having 2 to 60 carbon atoms, COOM represents a carboxyl group and / or a salt thereof, l represents an average added mole number of 3 to 300, and n represents a number of 2 to 20)
The dispersant for a hydraulic composition according to claim 1 or 2, which is represented by the formula:
Ｒ1−（ＯＡ）l−ＣＯＯ−Ｂ（ＯＨ）m（ＯＸ）n （４）
（式中、Ｒ1は水素原子又は炭素数１〜４のアルキル基を示し、ＯＡは炭素数２〜４のオキシアルキレン基を示し、Ｂはポリオール残基を示し、ＯＸはポリオール残基にエーテル結合したメチレンカルボキシル基及び／又はエステル結合したリン酸基、又はこれらの塩を示し、ｌは平均付加モル数で３〜３００の数を示し、ｎは２〜２０の数を示し、ｍ＋ｎはＢの水酸基の数を示す）
で表わされるものである請求項１又は２記載の水硬性組成物用分散剤。The compound has the general formula (4)
R 1 — (OA) 1 —COO—B (OH) m (OX) n (4)
(In the formula, R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, OA represents an oxyalkylene group having 2 to 4 carbon atoms, B represents a polyol residue, and OX represents an ether in the polyol residue. A bonded methylene carboxyl group and / or an ester-bonded phosphate group, or a salt thereof, l represents an average added mole number of 3 to 300, n represents a number of 2 to 20, and m + n represents B Indicates the number of hydroxyl groups)
The dispersant for a hydraulic composition according to claim 1 or 2, which is represented by the formula:
Ｒ1−（ＯＡ）l−ＣＯ−ＮＨ−Ｂ（ＯＨ）m（ＯＸ）n （５）
（式中、Ｒ1は水素原子又は炭素数１〜４のアルキル基を示し、ＯＡは炭素数２〜４のオキシアルキレン基を示し、Ｂはポリオール残基を示し、ＯＸはポリオール残基にエーテル結合したメチレンカルボキシル基及び／又はエステル結合したリン酸基、又はこれらの塩を示し、ｌは平均付加モル数で３〜３００の数を示し、ｎは２〜２０の数を示し、ｍ＋ｎはＢの水酸基の数を示す）
で表わされるものである請求項１又は２記載の水硬性組成物用分散剤。The compound has the general formula (5)
R 1 — (OA) 1 —CO—NH—B (OH) m (OX) n (5)
(In the formula, R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, OA represents an oxyalkylene group having 2 to 4 carbon atoms, B represents a polyol residue, and OX represents an ether in the polyol residue. A bonded methylene carboxyl group and / or an ester-bonded phosphate group, or a salt thereof, l represents an average added mole number of 3 to 300, n represents a number of 2 to 20, and m + n represents B Indicates the number of hydroxyl groups)
The dispersant for a hydraulic composition according to claim 1 or 2, which is represented by the formula:
Ｒ1−（ＯＡ）l−Ｏ−ＣＯ−Ｒ2−ＣＯ−ＮＨ−Ｂ（ＯＨ）m（ＯＸ）n （６）
（式中、Ｒ1は水素原子又は炭素数１〜４のアルキル基を示し、ＯＡは炭素数２〜４のオキシアルキレン基を示し、Ｒ2は炭素数１〜４のアルキレン基、ビニレン基又はフェニレン基を示し、Ｂはポリオール残基を示し、ＯＸはポリオール残基にエーテル結合したメチレンカルボキシル基及び／又はエステル結合したリン酸基、又はこれらの塩を示し、ｌは平均付加モル数で３〜３００の数を示し、ｎは２〜２０の数を示し、ｍ＋ｎはＢの水酸基の数を示す）
で表わされるものである請求項１又は２記載の水硬性組成物用分散剤。The compound has the general formula (6)
R 1 — (OA) 1 —O—CO—R 2 —CO—NH—B (OH) m (OX) n (6)
(Wherein R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, OA represents an oxyalkylene group having 2 to 4 carbon atoms, and R 2 represents an alkylene group having 1 to 4 carbon atoms, a vinylene group or Represents a phenylene group, B represents a polyol residue, OX represents a methylene carboxyl group ether-bonded to the polyol residue and / or an ester-bonded phosphate group, or a salt thereof, and l represents an average addition mole number of 3 ) Represents a number of ˜300, n represents a number of 2 to 20, and m + n represents the number of hydroxyl groups of B)
The dispersant for a hydraulic composition according to claim 1 or 2, which is represented by the formula:
Ｒ1−（ＯＡ）l−Ｏ−ＣＯ−Ｒ2−ＣＯ−Ｏ−Ｂ（ＯＨ）m（ＯＸ）n （７）
（式中、Ｒ1は水素原子又は炭素数１〜４のアルキル基を示し、ＯＡは炭素数２〜４のオキシアルキレン基を示し、Ｒ2は炭素数１〜４のアルキレン基、ビニレン基又はフェニレン基を示し、Ｂはポリオール残基を示し、ＯＸはポリオール残基にエーテル結合したメチレンカルボキシル基及び／又はエステル結合したリン酸基、又はこれらの塩を示し、ｌは平均付加モル数で３〜３００の数を示し、ｎは２〜２０の数を示し、ｍ＋ｎはＢの水酸基の数を示す）
で表わされるものである請求項１又は２記載の水硬性組成物用分散剤。The compound has the general formula (7)
R 1 — (OA) 1 —O—CO—R 2 —CO—O—B (OH) m (OX) n (7)
(Wherein R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, OA represents an oxyalkylene group having 2 to 4 carbon atoms, and R 2 represents an alkylene group having 1 to 4 carbon atoms, a vinylene group or Represents a phenylene group, B represents a polyol residue, OX represents a methylene carboxyl group ether-bonded to the polyol residue and / or an ester-bonded phosphate group, or a salt thereof, and l represents an average addition mole number of 3 ) Represents a number of ˜300, n represents a number of 2 to 20, and m + n represents the number of hydroxyl groups of B)
The dispersant for a hydraulic composition according to claim 1 or 2, which is represented by the formula:
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| JP2000247368A JP4738576B2 (en) | 2000-08-17 | 2000-08-17 | Dispersant for hydraulic composition |
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| JP4738576B2 true JP4738576B2 (en) | 2011-08-03 |
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| JP3109145B2 (en) * | 1991-06-17 | 2000-11-13 | 新日本理化株式会社 | Novel hexacarboxylic acid and method for producing the same |
| JP2754322B2 (en) * | 1993-10-01 | 1998-05-20 | 竹本油脂株式会社 | Method for imparting fluidity to polymer mortar or polymer concrete |
| JP3588782B2 (en) * | 1993-12-06 | 2004-11-17 | 日本油脂株式会社 | Additive for cement |
| JP3618795B2 (en) * | 1994-10-07 | 2005-02-09 | 花王株式会社 | Admixture composition for concrete products |
| JPH1179816A (en) * | 1997-08-29 | 1999-03-23 | Denki Kagaku Kogyo Kk | Cement admixture for grout and cement composition |
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