JP5101982B2 - Dispersant for hydraulic composition - Google Patents
Dispersant for hydraulic composition Download PDFInfo
- Publication number
- JP5101982B2 JP5101982B2 JP2007270060A JP2007270060A JP5101982B2 JP 5101982 B2 JP5101982 B2 JP 5101982B2 JP 2007270060 A JP2007270060 A JP 2007270060A JP 2007270060 A JP2007270060 A JP 2007270060A JP 5101982 B2 JP5101982 B2 JP 5101982B2
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- group
- weight
- dispersant
- hydraulic composition
- 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.)
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- 239000000203 mixture Substances 0.000 title claims description 53
- 239000002270 dispersing agent Substances 0.000 title claims description 39
- 239000000178 monomer Substances 0.000 claims description 163
- 229920001577 copolymer Polymers 0.000 claims description 45
- 239000000843 powder Substances 0.000 claims description 33
- 239000004568 cement Substances 0.000 claims description 31
- -1 alcohol compound Chemical class 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 11
- 239000000470 constituent Substances 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 239000002893 slag Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 239000011398 Portland cement Substances 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 3
- 238000005227 gel permeation chromatography Methods 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- 238000004581 coalescence Methods 0.000 claims 1
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 239000007788 liquid Substances 0.000 description 36
- 230000014759 maintenance of location Effects 0.000 description 31
- 229920000642 polymer Polymers 0.000 description 29
- 239000004567 concrete Substances 0.000 description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 229920001515 polyalkylene glycol Polymers 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 230000007062 hydrolysis Effects 0.000 description 9
- 238000006460 hydrolysis reaction Methods 0.000 description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000003505 polymerization initiator Substances 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- 150000002148 esters Chemical group 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- 230000003472 neutralizing effect Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000012986 chain transfer agent Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 125000002843 carboxylic acid group Chemical group 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000010881 fly ash Substances 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 229910021487 silica fume Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000003573 thiols Chemical group 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical compound CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MOYAFQVGZZPNRA-UHFFFAOYSA-N Terpinolene Chemical compound CC(C)=C1CCC(C)=CC1 MOYAFQVGZZPNRA-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000011400 blast furnace cement Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- 150000008282 halocarbons Chemical group 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000006353 oxyethylene group Chemical group 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- YHQGMYUVUMAZJR-UHFFFAOYSA-N α-terpinene Chemical compound CC(C)C1=CC=C(C)CC1 YHQGMYUVUMAZJR-UHFFFAOYSA-N 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- YKFLAYDHMOASIY-UHFFFAOYSA-N γ-terpinene Chemical compound CC(C)C1=CCC(C)=CC1 YKFLAYDHMOASIY-UHFFFAOYSA-N 0.000 description 2
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OALMZWNBNXQUAL-UHFFFAOYSA-N 2-[(1-amino-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanamide Chemical compound NC(=O)C(C)(C)N=NC(C)(C)C(N)=O OALMZWNBNXQUAL-UHFFFAOYSA-N 0.000 description 1
- BKMMTJMQCTUHRP-UHFFFAOYSA-N 2-aminopropan-1-ol Chemical compound CC(N)CO BKMMTJMQCTUHRP-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- ZRIMDWRLVGDUBW-UHFFFAOYSA-N 5-hydroxy-2-methylpent-2-enoic acid phosphoric acid Chemical compound P(=O)(O)(O)O.OCCC=C(C(=O)O)C ZRIMDWRLVGDUBW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- WSTYNZDAOAEEKG-UHFFFAOYSA-N Mayol Natural products CC1=C(O)C(=O)C=C2C(CCC3(C4CC(C(CC4(CCC33C)C)=O)C)C)(C)C3=CC=C21 WSTYNZDAOAEEKG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- JHLNERQLKQQLRZ-UHFFFAOYSA-N calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005886 esterification reaction Methods 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
- 238000006266 etherification reaction Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- MADOXCFISYCULS-UHFFFAOYSA-N octyl 2-sulfanylacetate Chemical compound CCCCCCCCOC(=O)CS MADOXCFISYCULS-UHFFFAOYSA-N 0.000 description 1
- LWNSNYBMYBWJDN-UHFFFAOYSA-N octyl 3-sulfanylpropanoate Chemical compound CCCCCCCCOC(=O)CCS LWNSNYBMYBWJDN-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- FBKBIOOBMXQNBA-UHFFFAOYSA-N propane-2-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CC(C)S(O)(=O)=O FBKBIOOBMXQNBA-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229940035024 thioglycerol Drugs 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 239000008096 xylene 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
- C04B24/24—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
- C04B2103/40—Surface-active agents, dispersants
- C04B2103/408—Dispersants
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、水硬性組成物用分散剤に関する。 The present invention relates to a dispersant for a hydraulic composition.
コンクリート等の水硬性組成物に対して、流動性を付与するためにナフタレン系、メラミン系、アミノスルホン酸系、ポリカルボン酸系等の混和剤（高性能減水剤等）が用いられている。減水剤等の混和剤については、水硬性組成物に対する流動性の付与、流動性の保持性（流動保持性）、硬化遅延の防止など、種々の性能が求められ、ポリカルボン酸系混和剤についてもこうした観点から改善が提案されている。 In order to impart fluidity to hydraulic compositions such as concrete, admixtures such as naphthalene-based, melamine-based, aminosulfonic acid-based, and polycarboxylic acid-based materials (high performance water reducing agents) are used. For admixtures such as water reducing agents, various performances are required such as imparting fluidity to hydraulic compositions, fluidity retention (flow retention), prevention of cure delay, etc. Improvements are also proposed from this perspective.
特許文献１には、特定のエチレン性不飽和単量体単位とエチレン性不飽和カルボン酸エステル単位とを構造単位として有する共重合体からなるコンクリート混和剤を、高性能減水剤と併用することが開示されている。また、特許文献２には、ポリオキシアルキレン基を有するエチレン系単量体、不飽和有機酸系単量体及びアルカリ性水溶液中において加水分解されうる単量体の３元共重合体からなるセメント混和剤、特許文献３にはポリアルキレングリコールモノ（メタ）アクリル酸エステル系単量体、モノ（メタ）アクリル酸エステル系単量体、及び不飽和結合を有するカルボン酸系単量体の共重合体からなるセメント混和剤がスランプ保持性の向上や作業性の改善に優れる事が開示されている。
特許文献１〜３には、水硬性組成物の流動性や粘性を維持する技術が開示されているが、セメントの種類によって、その初期流動性や流動保持性能が変動してしまい、同様の添加量で期待の性能が得られない事がある。水硬性組成物に用いられる水硬性粉末（セメント等）の種類によらず、同様な添加量で同様な流動性の維持効果と粘性の維持効果が発現する水硬性組成物用分散剤が望まれる。 Patent Documents 1 to 3 disclose a technique for maintaining the fluidity and viscosity of a hydraulic composition, but depending on the type of cement, the initial fluidity and fluidity retention performance fluctuate. Expected performance may not be obtained in quantity. Regardless of the type of hydraulic powder (cement, etc.) used in the hydraulic composition, a dispersant for a hydraulic composition that exhibits the same fluidity maintaining effect and viscosity maintaining effect with the same addition amount is desired. .
本発明の課題は、水硬性粉末の種類によらず安定した初期流動性と流動保持性を発揮する水硬性組成物用の分散剤を提供することである。 An object of the present invention is to provide a dispersant for a hydraulic composition that exhibits stable initial fluidity and fluidity retention regardless of the type of hydraulic powder.
特許文献１及び２では、初期流動性と流動保持性の両立を目指しているが、その流動性や流動保持性はセメント種によって敏感に変動してしまう傾向がある。これは、比較的大きい平均付加モル数ｎのオキシアルキレン基を構造に導入しているためと考えられる。 Patent Documents 1 and 2 aim to achieve both initial fluidity and fluidity, but the fluidity and fluidity tend to vary sensitively depending on the cement type. This is probably because a relatively large average addition mole number n of oxyalkylene groups was introduced into the structure.
また特許文献３では、初期流動性を示すものの流動保持性が不十分である。これは、初期流動性への寄与が大きいカルボン酸ユニットの導入量が多く、流動保持性への寄与が大きいエステル系ユニットが少ないためと考えられる。また、初期流動性もセメント種によって敏感に変動してしまう傾向がある。 Moreover, in patent document 3, although the initial fluidity | liquidity is shown, the fluid retainability is inadequate. This is presumably because the introduction amount of the carboxylic acid unit having a large contribution to the initial fluidity is large and the ester unit having a large contribution to the fluidity retention is small. Also, the initial fluidity tends to vary sensitively depending on the cement type.
水硬性粉体の種類が異なるとその鉱物組成が異なる。その結果、水硬性粉体と水とを混練した際に、水和速度や水相に溶出してくる硫酸イオン等の濃度が、水硬性粉体の種類により異なってくるので流動性が変動する。この理由として、ポリカルボン酸系の重合体が水相中の塩濃度によって重合体の立体構造が変化し分散性能が変わること、水硬性粉体表面に吸着した重合体が水和物に取り込まれる速度が異なることにより、流動性や保持性が水硬性粉体の種類により異なると考えられる。 Different types of hydraulic powders have different mineral compositions. As a result, when the hydraulic powder and water are kneaded, the fluidity varies because the hydration rate and the concentration of sulfate ions eluted in the aqueous phase vary depending on the type of hydraulic powder. . This is because the polycarboxylic acid polymer has a three-dimensional structure that changes depending on the salt concentration in the aqueous phase and the dispersion performance changes, and the polymer adsorbed on the surface of the hydraulic powder is taken into the hydrate. It is considered that the flowability and the holding property differ depending on the kind of hydraulic powder due to the difference in speed.
従来は、ポリカルボン酸系重合体のＡＯ平均付加モル数がある程度大きくないと立体反発による流動性の寄与がなく、加水分解による吸着基の増加では、経時での流動性保持効果が小さいと考えられていた（特許文献２、段落００１０）。しかし、本発明者らは、ポリカルボン酸系の重合体において、水相の塩濃度によって分散性の変化を小さくする為のオキシアルキレン基（立体反発ユニット）の平均付加モル数と、それの吸着基とのバランス、更に経時において吸着基となり得る特定のユニット（加水分解ユニット）及び初期の吸着ユニット（カルボン酸ユニット）のバランスを調整することで、初期流動性と流動保持性に優れ、しかも水硬性粉体の種類に対する汎用性の高い分散剤を完成した。 Conventionally, if the AO average addition mole number of the polycarboxylic acid polymer is not large to some extent, there is no contribution of fluidity due to steric repulsion, and the increase in adsorbing groups due to hydrolysis is considered to have a small fluidity retention effect over time. (Patent Document 2, paragraph 0010). However, the present inventors have found that in polycarboxylic acid polymers, the average number of added moles of oxyalkylene groups (steric repulsion units) for reducing the change in dispersibility depending on the salt concentration of the aqueous phase and the adsorption thereof. By adjusting the balance between the specific unit (hydrolysis unit) and the initial adsorbing unit (carboxylic acid unit) that can become an adsorbing group over time, the initial fluidity and fluid retention are excellent, and water A highly versatile dispersant for hard powder types has been completed.
すなわち、本発明は、一般式（１）で表される単量体１と一般式（２）で表される単量体２と一般式（３）で表される単量体３とを重合して得られる共重合体を含有する水硬性組成物用分散剤であって、
該共重合体の構成単量体中、単量体１の比率が２５〜８５重量％であり、単量体２の比率が１０〜７０重量％であり、単量体３の比率が５〜２０重量％である水硬性組成物用分散剤に関する。
That is, the present invention polymerizes the monomer 1 represented by the general formula (1), the monomer 2 represented by the general formula (2), and the monomer 3 represented by the general formula (3). A dispersant for a hydraulic composition containing a copolymer obtained by:
Among the constituent monomers of the copolymer, the ratio of monomer 1 is 25 to 85% by weight, the ratio of monomer 2 is 10 to 70% by weight, and the ratio of monomer 3 is 5 to 5%. It is related with the dispersing agent for hydraulic compositions which is 20 weight%.
〔式中、Ｒ1〜Ｒ3は、それぞれ水素原子又はメチル基を表し、ＡＯは炭素数２〜４のオキシアルキレン基を表し、ｎはＡＯの平均付加モル数であり、５〜２０の数を表し、Ｒ4は水素原子又は炭素数１〜４のアルキル基、ｑは０〜２の整数、ｐは０又は１を表す。〕 [Wherein, R 1 to R 3 each represent a hydrogen atom or a methyl group, AO represents an oxyalkylene group having 2 to 4 carbon atoms, n represents an average added mole number of AO, and a number of 5 to 20 R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, q represents an integer of 0 to 2, and p represents 0 or 1. ]
〔式中、Ｒ5は、炭素数１〜４のヘテロ原子を含んでよい炭化水素基である。〕 [Wherein R 5 is a hydrocarbon group which may contain a hetero atom having 1 to 4 carbon atoms. ]
〔式中、Ｒ6〜Ｒ8は、それぞれ水素原子、メチル基又は(ＣＨ2)sＣＯＯＭ2であり、(ＣＨ2)sＣＯＯＭ2はＣＯＯＭ1又は他の(ＣＨ2)sＣＯＯＭ2と無水物を形成していてもよく、その場合、それらの基のＭ1、Ｍ2は存在しない。ｓは０〜２の整数を表す。Ｍ1、Ｍ2は、それぞれ水素原子、アルカリ金属、アルカリ土類金属、アンモニウム基、アルキルアンモニウム基、置換アルキルアンモニウム基、アルキル基、ヒドロキシアルキル基、又はアルケニル基を表す。〕 Wherein, R 6 to R 8 are each a hydrogen atom, a methyl group or (CH 2) s COOM 2, (CH 2) s COOM 2 is COOM 1 or another (CH 2) s COOM 2 and anhydrous In this case, M 1 and M 2 of those groups are not present. s represents the integer of 0-2. M 1 and M 2 each represent a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an alkyl ammonium group, a substituted alkyl ammonium group, an alkyl group, a hydroxyalkyl group, or an alkenyl group. ]
本発明によれば、水硬性粉末の種類によらず初期の流動性と流動保持性に優れた水硬性組成物用の分散剤が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the dispersing agent for hydraulic compositions excellent in the initial fluidity | liquidity and fluid holding | maintenance property is provided irrespective of the kind of hydraulic powder.
＜単量体１＞
単量体１は、ポリアルキレングリコールモノエステル系単量体及びポリアルキレングリコールアルキルエーテル系単量体等の不飽和ポリアルキレングリコール系単量体であり、単量体１において、一般式（１）中のＡＯは炭素数２〜４のオキシアルキレン基を表し、オキシエチレン基、オキシプロピレン基、オキシブチレン基からなる群より選ばれる少なくとも１種以上が挙げられ、中でもオキシエチレン基が好ましい。ｎはＡＯの平均付加モル数であり、５〜２０の数を表し、初期分散性・流動保持性の汎用性の観点から、好ましくは６〜２０、より好ましくは７〜１９、更に好ましくは８〜１８、更により好ましくは９〜１７である。ｎが２０を超えると水硬性粉末の種類による初期流動性や流動保持性の変動が大きくなる。Ｒ4は水素原子又は炭素数１〜４のアルキル基であり、流動保持性の観点から好ましくは水素原子又はメチル基であり、より好ましくはメチル基である。
<Monomer 1>
The monomer 1 is an unsaturated polyalkylene glycol monomer such as a polyalkylene glycol monoester monomer and a polyalkylene glycol alkyl ether monomer, and in the monomer 1, the general formula (1) AO in it represents an oxyalkylene group having 2 to 4 carbon atoms and includes at least one selected from the group consisting of an oxyethylene group, an oxypropylene group, and an oxybutylene group, and among them, an oxyethylene group is preferable. n is the average number of added moles of AO and represents a number of 5 to 20, preferably 6 to 20, more preferably 7 to 19, and still more preferably 8 from the viewpoint of versatility of initial dispersibility and fluidity retention. -18, and even more preferably 9-17. When n exceeds 20, fluctuations in initial fluidity and fluidity due to the type of hydraulic powder increase. R 4 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom or a methyl group, more preferably a methyl group, from the viewpoint of fluidity retention.
単量体１としては、メトキシポリエチレングリコール、メトキシポリエチレンポリプロピレングリコール、エトキシポリエチレングリコール、エトキシポリエチレンポリプロピレングリコール、プロポキシポリエチレングリコール、プロポキシポリエチレンポリプロピレングリコール等の片末端アルキル封鎖ポリアルキレングリコールとアクリル酸又はメタクリル酸とのエステル化物や、アクリル酸又はメタクリル酸へのエチレンオキシド又はプロピレンオキシドの付加物、前記片末端アルキル封鎖ポリアルキレングリコールと（メタ）アルケニルアルコールとのエーテル化物、及びアルケニルアルコールへの炭素数２〜４のアルキレンオキシドの付加物等を用いることができる。具体的には、ω−メトキシポリエチレングリコールモノメタクリレート、ω−メトキシポリエチレングリコールモノアクリレート、ポリオキシエチレンモノアリルエーテル、ω−メトキシポリエチレングリコールモノアリルエーテル、３−メチル−３−ブテン−１−オールのポリオキシエチレンモノアリルエーテル等を挙げることができる。流動保持性の観点から、片末端アルキル封鎖ポリアルキレングリコールとアクリル酸又はメタクリル酸とのエステル化物が好ましく、好ましくはω−メトキシポリエチレングリコールモノメタクリレート、ω−メトキシポリエチレングリコールモノアクリレートが挙げられ、ω−メトキシポリエチレングリコールモノメタクリレートがより好ましい。 As monomer 1, methoxypolyethylene glycol, methoxypolyethylenepolypropylene glycol, ethoxypolyethyleneglycol, ethoxypolyethylenepolypropyleneglycol, propoxypolyethyleneglycol, propoxypolyethylenepolypropyleneglycol, etc., one-end alkyl-capped polyalkyleneglycol and acrylic acid or methacrylic acid Esterified products, addition products of ethylene oxide or propylene oxide to acrylic acid or methacrylic acid, etherification products of the above-mentioned one-end alkyl-blocked polyalkylene glycol and (meth) alkenyl alcohol, and alkylene having 2 to 4 carbon atoms to alkenyl alcohol An oxide adduct or the like can be used. Specifically, ω-methoxypolyethylene glycol monomethacrylate, ω-methoxypolyethyleneglycol monoacrylate, polyoxyethylene monoallyl ether, ω-methoxypolyethyleneglycol monoallyl ether, poly (3-methyl-3-buten-1-ol) Examples include oxyethylene monoallyl ether. From the viewpoint of fluidity retention, esterified products of one-end alkyl-blocked polyalkylene glycol and acrylic acid or methacrylic acid are preferred, preferably ω-methoxypolyethylene glycol monomethacrylate, ω-methoxypolyethyleneglycol monoacrylate, ω- Methoxy polyethylene glycol monomethacrylate is more preferred.
＜単量体２＞
単量体２は、アクリル酸エステル系単量体であり、構造上、アクリル酸とＲ5−ＯＨで表されるアルコール化合物のエステルとして捉えることができ、Ｒ5は、炭素数１〜４、好ましくは２〜３のヘテロ原子を含んでよい炭化水素基である。ヘテロ原子は酸素原子、窒素原子が挙げられる。
<Monomer 2>
The monomer 2 is an acrylate monomer and can be regarded as an ester of an alcohol compound represented by acrylic acid and R 5 —OH in terms of structure. R 5 has 1 to 4 carbon atoms, Preferably it is a hydrocarbon group which may contain 2 to 3 heteroatoms. Examples of the hetero atom include an oxygen atom and a nitrogen atom.
本発明では、単量体２の少なくとも一部として、一般式（２）で表される単量体のうち特定の単量体が用いられる事が好ましい。すなわち、単量体２の少なくとも一部として、一般式（２）中のＲ5が、一般式（２）中のＲ5に対応するＲ5−ＯＨのｌｏｇＰ値と、単量体２の分子量Ｍｗとが、［Ｒ5−ＯＨのｌｏｇＰ値／単量体２の分子量Mw］＜−０．００９となる化合物（以下、単量体２−１という）が用いられることが好ましい。また、単量体２−１以外、即ち単量体２のうち［Ｒ5−ＯＨのｌｏｇＰ値／単量体２の分子量Mw］≧−０．００９となる化合物を、単量体２−２という。このような関係を満たすＲ5−ＯＨとしてエチレングリコール（ｌｏｇＰ値：−１．３６９）、グリセリン（ｌｏｇＰ値：−１．５３８）等が挙げられる。単量体２に占める単量体２−１の割合は、水硬性粉末の種類に対する汎用性、更には流動保持性及び粘性の観点から、単量体２中で３０モル％以上が好ましく、５０モル％以上がより好ましく、７０モル％以上がより好ましく、９０モル％以上が更に好ましく、実質１００モル％が更により好ましい。 In the present invention, it is preferable that a specific monomer among the monomers represented by the general formula (2) is used as at least a part of the monomer 2. That is, as at least part of the monomer 2, the general formula (2) R 5 in a logP value of R 5 -OH corresponding to R 5 in the general formula (2), the molecular weight of the monomer 2 It is preferable to use a compound (hereinafter referred to as monomer 2-1) in which Mw is [log P value of R 5 —OH / molecular weight Mw of monomer 2] <− 0.009. Further, in addition to the monomer 2-1, that is, in the monomer 2, a compound having [R 5 —OH logP value / monomer 2 molecular weight Mw] ≧ −0.009 is obtained. That's it. Examples of R 5 —OH satisfying such a relationship include ethylene glycol (log P value: −1.369), glycerin (log P value: −1.538), and the like. The proportion of the monomer 2-1 in the monomer 2 is preferably 30 mol% or more in the monomer 2 from the viewpoints of versatility with respect to the type of hydraulic powder, and also flow retention and viscosity. More preferably, mol% or more is more preferable, 70 mol% or more is more preferable, 90 mol% or more is further more preferable, and substantially 100 mol% is still more preferable.
単量体２−１としては、流動性保持の観点から２−ヒドロキシエチルアクリレートが好ましい。また、単量体２−２としては、メチルアクリレート、ヒドロキシブチルアクリレート、メトキシエチルアクリレート等が挙げられる。単量体２−１及び単量体２−２は、それぞれ二種以上の単量体を用いてもよい。 As the monomer 2-1, 2-hydroxyethyl acrylate is preferable from the viewpoint of maintaining fluidity. Examples of the monomer 2-2 include methyl acrylate, hydroxybutyl acrylate, methoxyethyl acrylate, and the like. Two or more types of monomers may be used for each of the monomer 2-1 and the monomer 2-2.
本発明の分散剤となる共重合体においては、単量体２を導入することで、水硬性組成物への添加初期から経時に渡り水硬性組成物の流動性を維持できる。これは、水硬性組成物への添加前には単量体２はアクリル酸のエステル構造を有するため、添加後に経時的にエステル結合の加水分解が進行し、カルボン酸型又はカルボン酸塩型になり、前記共重合体が水硬性粉体表面に徐々に吸着し、水硬性粉体の分散を維持することにより、水硬性粉体の水和による粘度上昇を相殺していると推察される。また、水硬性組成物のイオン強度等の因子により加水分解速度が変化することが水硬性粉末の種類によらず同様の流動保持性を発現するものと推察される。類似する構造であっても、アクリル酸より加水分解しにくいメタクリル酸のエステルやそのアルキレンオキサイド付加物では単量体２のような効果は得られない。 In the copolymer serving as the dispersant of the present invention, by introducing the monomer 2, the fluidity of the hydraulic composition can be maintained from the initial stage of addition to the hydraulic composition over time. This is because, since monomer 2 has an acrylic ester structure before addition to the hydraulic composition, hydrolysis of the ester bond progresses over time after addition, resulting in a carboxylic acid type or a carboxylate type. Thus, it is presumed that the copolymer gradually adsorbs on the surface of the hydraulic powder and maintains the dispersion of the hydraulic powder to offset the increase in viscosity due to the hydration of the hydraulic powder. Further, it is speculated that the change in hydrolysis rate due to factors such as the ionic strength of the hydraulic composition exhibits the same fluidity retention regardless of the type of hydraulic powder. Even if it has a similar structure, the effect of the monomer 2 cannot be obtained with an ester of methacrylic acid or its alkylene oxide adduct, which is harder to hydrolyze than acrylic acid.
また、単量体２−１については、単量体２−１の分子量及び単量体２−１の置換基Ｒ5と水酸基ＯＨにより構成されるＲ5−ＯＨで表される化合物のｌｏｇＰ（水／オクタノール分配係数）（以下、ｌｏｇＰは特記しない限り当該化合物のｌｏｇＰをいう）と、水硬性粉体の分散性の発現速度とに、相関があることを見出した。すなわち、アクリル酸のエステル置換基によって加水分解性が異なり、加水分解性は、水分子のエステルへの求核とアルコールの脱離のステップがあり、それぞれ立体障害の大きさとアルコールの脱離のしやすさが寄与すると考えられた。単量体の分子量が大きい（立体障害が大きい）ほど加水分解率が小さくなり、エステルを構成するアルコール化合物の加水分解基の親水性（ｌｏｇＰ）の値が小さいほど加水分解率が大きくなる。そこで、ｌｏｇＰをアクリル酸エステルの分子量Ｍｗで規格化し、導入した基の効率性（カルボキシル基の生成率）の指標とした。したがって、ｌｏｇＰ／分子量Mwの値が小さいほど、単量体２−１の加水分解性が大きい。本発明ではこの値が−０．００９以下であり、−０．０１０以下がより好ましく、−０．０１１以下が更に好ましい。ｌｏｇＰは、CS Chem Draw Ultra（Ver.8.0）（頒布元 ケンブリッジソフト）のソフトウエアを用いてClogP値として得ることができ、例えばWindows（登録商標） XPの稼動するパーソナルコンピュータで前記ソフトウエアを実行できる。 In addition, as for the monomer 2-1, the molecular weight of the monomer 2-1 and the log P of the compound represented by R 5 —OH composed of the substituent R 5 and the hydroxyl group OH of the monomer 2-1 ( It was found that there is a correlation between the water / octanol distribution coefficient (hereinafter logP refers to logP of the compound unless otherwise specified) and the speed of expression of the dispersibility of the hydraulic powder. That is, the hydrolyzability varies depending on the ester substituent of acrylic acid, and hydrolyzation has steps of nucleophilicity of water molecule to ester and elimination of alcohol. It was thought that ease contributed. The hydrolysis rate decreases as the molecular weight of the monomer increases (the steric hindrance increases), and the hydrolysis rate increases as the hydrophilicity (log P) value of the hydrolysis group of the alcohol compound constituting the ester decreases. Therefore, logP was normalized by the molecular weight Mw of the acrylate ester, and used as an index of the efficiency of the introduced group (carboxyl group production rate). Therefore, the smaller the value of logP / molecular weight Mw, the greater the hydrolyzability of monomer 2-1. In the present invention, this value is −0.009 or less, more preferably −0.010 or less, and even more preferably −0.011 or less. logP can be obtained as a ClogP value using the software of CS Chem Draw Ultra (Ver. 8.0) (distributed Cambridge Software). it can.
［単量体３］
単量体３は、一般式（３）において、Ｒ6〜Ｒ8は、それぞれ水素原子、メチル基又は(ＣＨ2)sＣＯＯＭ2であり、(ＣＨ2)sＣＯＯＭ2はＣＯＯＭ1又は他の(ＣＨ2)sＣＯＯＭ2と無水物を形成していてもよい。その場合、それらの基のＭ1、Ｍ2は存在しない。ｓは０〜２の整数を表す。Ｒ1は水素原子が好ましく、Ｒ2はメチル基が好ましい。Ｒ3は水素原子又は(ＣＨ2)sＣＯＯM7が好ましい。
[Monomer 3]
Monomer 3 are the compounds of formula (3), R 6 ~R 8 are each a hydrogen atom, a methyl group or (CH 2) s COOM 2, (CH 2) s COOM 2 is COOM 1 or other (CH 2 ) s COOM 2 and an anhydride may be formed. In that case, M 1 and M 2 of those groups do not exist. s represents the integer of 0-2. R 1 is preferably a hydrogen atom, and R 2 is preferably a methyl group. R 3 is preferably a hydrogen atom or (CH 2 ) s COOM 7 .
Ｍ1、Ｍ2は、それぞれ水素原子、アルカリ金属、アルカリ土類金属、アンモニウム基、アルキルアンモニウム基、置換アルキルアンモニウム基、アルキル基、ヒドロキシアルキル基、又はアルケニル基である。Ｍ1、Ｍ2は、それぞれ水素原子、アルカリ金属が好ましい。 M 1 and M 2 are each a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an alkylammonium group, a substituted alkylammonium group, an alkyl group, a hydroxyalkyl group, or an alkenyl group. M 1 and M 2 are each preferably a hydrogen atom or an alkali metal.
具体的には、（メタ）アクリル酸、クロトン酸等のモノカルボン酸系単量体、マレイン酸、イタコン酸、フマル酸等のジカルボン酸系単量体、又はこれらの無水物もしくは塩（例えばアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、水酸基が置換されていてもよいモノ、ジ、トリアルキル（炭素数２〜８）アンモニウム塩）もしくはエステルが挙げられ、好ましくは（メタ）アクリル酸、マレイン酸、無水マレイン酸、更に好ましくは（メタ）アクリル酸又はこれらのアルカリ金属塩である。なお、（メタ）アクリル酸は、アクリル酸及び／又はメタクリル酸の意味である（以下同様）。 Specifically, monocarboxylic acid monomers such as (meth) acrylic acid and crotonic acid, dicarboxylic acid monomers such as maleic acid, itaconic acid and fumaric acid, or anhydrides or salts thereof (for example, alkalis) Metal salt, alkaline earth metal salt, ammonium salt, mono-, di-, trialkyl (carbon number 2 to 8) ammonium salt optionally substituted with hydroxyl group) or ester, preferably (meth) acrylic acid, Maleic acid, maleic anhydride, more preferably (meth) acrylic acid or an alkali metal salt thereof. In addition, (meth) acrylic acid means acrylic acid and / or methacrylic acid (hereinafter the same).
本発明の分散剤となる共重合体においては、単量体２と共に、単量体３を導入する事で、初期に所定の吸着量を示し、初期流動性を示す事ができる。その際、単量体３の含有量（重量％）と単量体２の含有量（重量％）の量的関係は流動保持性に影響するため、後述の特定の関係であることが好ましい。 In the copolymer serving as the dispersant of the present invention, by introducing the monomer 3 together with the monomer 2, a predetermined adsorption amount can be initially shown and initial fluidity can be shown. At that time, since the quantitative relationship between the content (% by weight) of the monomer 3 and the content (% by weight) of the monomer 2 affects the fluidity retention, it is preferably a specific relationship described later.
＜共重合体＞
本発明の共重合体は、該共重合体の構成単量体中、単量体１の比率が２５〜８５重量％であり、単量体２の比率が１０〜７０重量％であり、単量体３の比率が５〜２０重量％である。また、共重合体の構成単量体中の比率において、単量体２／単量体３（重量比）が１超であることが好ましい。更に、共重合体の構成単量体中、単量体１、単量体２及び単量体３の比率が合計で９０重量％以上が好ましい。この比率は、単量体の仕込み時の比率であってもよい。単量体１の比率が２５重量％未満では初期流動性及び流動保持性が低下し、８５重量％を超えても吸着性が低くなる為，初期流動性・流動保持性が低下する。単量体２の比率が１０重量％未満又は単量体３の比率が２０重量％を超えると流動保持性が低下する。
<Copolymer>
The copolymer of the present invention has a monomer 1 ratio of 25 to 85% by weight and a monomer 2 ratio of 10 to 70% by weight. The ratio of the monomer 3 is 5 to 20% by weight. Moreover, it is preferable that monomer 2 / monomer 3 (weight ratio) exceeds 1 in the ratio in the constituent monomer of the copolymer. Furthermore, the ratio of monomer 1, monomer 2 and monomer 3 in the constituent monomers of the copolymer is preferably 90% by weight or more in total. This ratio may be the ratio when the monomer is charged. If the ratio of the monomer 1 is less than 25% by weight, the initial fluidity and the fluidity retention are lowered, and if it exceeds 85% by weight, the adsorptivity is lowered, so that the initial fluidity and fluidity retention are lowered. When the ratio of the monomer 2 is less than 10% by weight or the ratio of the monomer 3 exceeds 20% by weight, the fluidity retention is lowered.
単量体１の比率は初期流動性及び流動保持性を向上させ、水硬性粉末の種類による影響を抑える観点から、より好ましくは３５〜７０重量％、更に好ましくは４０〜７０である。また、単量体２の比率は初期流動性及び流動保持性の観点から共重合体の重合の際に用いる全単量体中、好ましくは１５〜６０重量％であり、より好ましくは１７〜５０重量％、更に好ましくは２０〜４０重量％である。また、単量体３の比率は初期流動性及び流動保持性の観点から共重合体の重合の際に用いる全単量体中、好ましくは５〜１５重量％であり、より好ましくは８〜１５重量％、更に好ましくは１０〜１５重量％である。 The ratio of the monomer 1 is preferably 35 to 70% by weight, more preferably 40 to 70, from the viewpoint of improving the initial fluidity and fluidity retention and suppressing the influence of the kind of hydraulic powder. Further, the ratio of the monomer 2 is preferably 15 to 60% by weight, more preferably 17 to 50% in the total monomers used in the polymerization of the copolymer from the viewpoint of initial fluidity and fluidity retention. % By weight, more preferably 20-40% by weight. Further, the ratio of the monomer 3 is preferably 5 to 15% by weight, more preferably 8 to 15% in the total monomers used in the polymerization of the copolymer from the viewpoint of initial fluidity and fluidity retention. % By weight, more preferably 10 to 15% by weight.
本発明の共重合体は、ｎの異なる単量体１を２種以上併用することができる。その際は上記単量体１の比率は、ｎの異なる単量体１の平均値（モル分率による）をｎとする（以下同様）。 In the copolymer of the present invention, two or more monomers 1 having different n can be used in combination. In that case, the ratio of the monomer 1 is n (the same applies hereinafter) for the average value (depending on the molar fraction) of the monomers 1 having different n.
共重合体の全構成単量体中の単量体１と単量体２と単量体３の合計は、初期流動性と流動保持性の観点から共重合体の重合の際に用いる全単量体中、９０重量％以上が好ましく、更に９５重量％以上、より更に９８重量％以上が好ましい。 The total of monomer 1, monomer 2 and monomer 3 in all the constituent monomers of the copolymer is the total amount used in the polymerization of the copolymer from the viewpoint of initial fluidity and fluidity retention. In the polymer, 90% by weight or more is preferable, more preferably 95% by weight or more, and still more preferably 98% by weight or more.
また、構成単量体中の単量体２と単量体３の合計比率は、初期流動性と流動保持性の観点から共重合体の重合の際に用いる全単量体中、好ましくは１５〜７５重量％、より好ましくは２２〜７２重量％であり、更に好ましくは３０〜６５重量％である。 Further, the total ratio of the monomer 2 and the monomer 3 in the constituent monomers is preferably 15 in the total monomers used in the polymerization of the copolymer from the viewpoint of initial fluidity and fluidity retention. It is -75 weight%, More preferably, it is 22-72 weight%, More preferably, it is 30-65 weight%.
また流動保持性と水硬性粉末の種類による影響が小さい観点から、構成単量体中の単量体２と単量体３の重量比は、単量体２／単量体３で１超であることが好ましく、より好ましくは１．２以上、更に好ましくは１．５以上である。 Further, from the viewpoint of little influence by the kind of the fluid retaining property and the hydraulic powder, the weight ratio of the monomer 2 to the monomer 3 in the constituent monomers is more than 1 for the monomer 2 / monomer 3. Preferably, it is 1.2 or more, more preferably 1.5 or more.
単量体１、単量体２及び単量体３の重量比（単量体１／単量体２／単量体３）は流動保持性の観点から、２５〜８５／１０〜７０／５〜２０、好ましくは２８〜７８／１５〜６０／５〜１５、より好ましくは３５〜７５／１７〜５０／８〜１５、更に好ましくは４０〜７０／２０〜４０／１０〜１５である。 The weight ratio of monomer 1, monomer 2 and monomer 3 (monomer 1 / monomer 2 / monomer 3) is 25 to 85/10 to 70/5 from the viewpoint of fluidity retention. -20, preferably 28-78 / 15-60 / 5-15, more preferably 35-75 / 17-50 / 8-15, still more preferably 40-70 / 20-40 / 10-15.
また本発明の共重合体は、単量体１〜３と共重合可能な単量体４を共重合しても良い。単量体４は、初期流動性や流動保持性能を抑制する観点から、共重合体の全構成単量体中好ましくは５重量％以下であり、より好ましくは２．５重量％以下、更に好ましくは１．０重量％以下である。 Moreover, the copolymer of this invention may copolymerize the monomer 4 copolymerizable with the monomers 1-3. The monomer 4 is preferably 5% by weight or less, more preferably 2.5% by weight or less, and still more preferably from all the constituent monomers of the copolymer from the viewpoint of suppressing initial fluidity and fluid retention performance. Is 1.0% by weight or less.
単量体４としては、リン酸ジ−〔（２−ヒドロキシエチル）メタクリル酸〕エステル、リン酸ジ−〔（２−ヒドロキシエチル）アクリル酸〕エステル、リン酸モノ（２−ヒドロキシエチル）メタクリル酸エステル、リン酸モノ（２−ヒドロキシエチル）アクリル酸エステル、ポリアルキレレングリコールモノ（メタ）アクリレートアシッドリン酸エステル、を挙げることができ、またこれらの何れか１種以上のアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、アミン塩や無水マレイン酸などの酸無水物であっても良い。 As the monomer 4, phosphoric acid di-[(2-hydroxyethyl) methacrylic acid] ester, phosphoric acid di-[(2-hydroxyethyl) acrylic acid] ester, phosphoric acid mono (2-hydroxyethyl) methacrylic acid Ester, mono (2-hydroxyethyl) acrylate ester, polyalkylene glycol mono (meth) acrylate acid phosphate ester, and any one or more alkali metal salts, alkali Acid anhydrides such as earth metal salts, ammonium salts, amine salts and maleic anhydride may be used.
その他の単量体４として、アリルスルホン酸、メタリルスルホン酸、これら何れかのアルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、又はアミン塩や、（メタ）アクリルアミド、Ｎ−メチル（メタ）アクリルアミド、Ｎ、Ｎ−ジメチル（メタ）アクリルアミド、２−（メタ）アクリルアミド−２−メタスルホン酸、２−（メタ）アクリルアミド−２−エタンスルホン酸、２−（メタ）アクリルアミド−２−プロパンスルホン酸、スチレン、スチレンスルホン酸などの強酸の酸基又はそれらの中和基を有する単量体が挙げられる。これらの単量体を例えば共重合体の分子量の調整等のために共重合してもよい。これらの強酸の酸基は水硬性組成物中で安定な塩として存在しセメント等の水硬性粉体への吸着基としては機能しない。 Other monomers 4 include allyl sulfonic acid, methallyl sulfonic acid, any of these alkali metal salts, alkaline earth metal salts, ammonium salts, or amine salts, (meth) acrylamide, N-methyl (meth) Acrylamide, N, N-dimethyl (meth) acrylamide, 2- (meth) acrylamide-2-metasulfonic acid, 2- (meth) acrylamide-2-ethanesulfonic acid, 2- (meth) acrylamide-2-propanesulfonic acid, Examples thereof include monomers having acid groups of strong acids such as styrene and styrenesulfonic acid or neutralizing groups thereof. These monomers may be copolymerized for adjusting the molecular weight of the copolymer, for example. The acid groups of these strong acids exist as stable salts in the hydraulic composition and do not function as adsorbing groups to hydraulic powders such as cement.
本発明における共重合体は公知の方法で製造することができる。例えば、特開昭６２−１１９１４７号公報、特開昭６２−７８１３７号公報等に記載された溶液重合法が挙げられる。即ち、適当な溶媒中で、上記単量体１、単量体２及び単量体３を上記の割合で組み合わせて重合させることにより製造される。すなわち、共重合体の重合の際に用いる全単量体中、単量体１の比率を２５〜８５重量％、単量体２の比率を１０〜７０重量％、単量体３の比率を５〜２０重量％として重合させる。 The copolymer in the present invention can be produced by a known method. Examples thereof include solution polymerization methods described in JP-A-62-1119147 and JP-A-62-78137. That is, it is produced by polymerizing the monomer 1, the monomer 2 and the monomer 3 in combination in the above ratio in an appropriate solvent. That is, in all monomers used for copolymerization, the ratio of monomer 1 is 25 to 85% by weight, the ratio of monomer 2 is 10 to 70% by weight, and the ratio of monomer 3 is Polymerize as 5-20% by weight.
溶液重合法において用いる溶剤としては、水、メチルアルコール、エチルアルコール、イソプロピルアルコール、ベンゼン、トルエン、キシレン、シクロヘキサン、ｎ−ヘキサン、酢酸エチル、アセトン、メチルエチルケトン等が挙げられる。取り扱いと反応設備から考慮すると、水及びメチルアルコール、エチルアルコール、イソプロピルアルコールが好ましい。 Examples of the solvent used in the solution polymerization method include water, methyl alcohol, ethyl alcohol, isopropyl alcohol, benzene, toluene, xylene, cyclohexane, n-hexane, ethyl acetate, acetone, and methyl ethyl ketone. In consideration of handling and reaction equipment, water and methyl alcohol, ethyl alcohol, and isopropyl alcohol are preferable.
水系の重合開始剤としては、過硫酸のアンモニウム塩又はアルカリ金属塩あるいは過酸化水素、２、２’−アゾビス（２−アミジノプロパン）ジヒドロクロライド、２、２’−アゾビス（２−メチルプロピオンアミド）ジハイドレート等の水溶性アゾ化合物が使用される。水系以外の溶剤を用いる溶液重合にはベンゾイルパーオキシド、ラウロイルパーオキシド等のパーオキシド、アゾビスイソブチロニトリル等の脂肪族アゾ化合物等が用いられる。 As an aqueous polymerization initiator, persulfuric acid ammonium salt or alkali metal salt or hydrogen peroxide, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis (2-methylpropionamide) Water-soluble azo compounds such as dihydrate are used. For solution polymerization using a non-aqueous solvent, peroxides such as benzoyl peroxide and lauroyl peroxide, aliphatic azo compounds such as azobisisobutyronitrile, and the like are used.
連鎖移動剤としては、チオール系連鎖移動剤、ハロゲン化炭化水素系連鎖移動剤等が挙げられ、チオール系連鎖移動剤が好ましい。 Examples of chain transfer agents include thiol chain transfer agents and halogenated hydrocarbon chain transfer agents, and thiol chain transfer agents are preferred.
チオール系連鎖移動剤としては、−ＳＨ基を有するものが好ましく、特に一般式ＨＳ−Ｒ−Ｅｇ（ただし、式中Ｒは炭素原子数１〜４の炭化水素由来の基を表し、Ｅは−ＯＨ、−ＣＯＯＭ、−ＣＯＯＲ’または−ＳＯ3Ｍ基を表し、Ｍは水素原子、一価金属、二価金属、アンモニウム基または有機アミン基を表し、Ｒ’は炭素原子数１〜１０のアルキル基を表わし、ｇは１〜２の整数を表す。）で表されるものが好ましく、例えば、メルカプトエタノール、チオグリセロール、チオグリコール酸、２−メルカプトプロピオン酸、３−メルカプトプロピオン酸、チオリンゴ酸、チオグリコール酸オクチル、３−メルカプトプロピオン酸オクチル等が挙げられ、単量体１〜３を含む共重合反応での連鎖移動効果の観点から、メルカプトプロピオン酸、メルカプトエタノールが好ましく、メルカプトプロピオン酸が更に好ましい。これらの１種または２種以上を用いることができる。 As the thiol chain transfer agent, those having a —SH group are preferable, and in particular, the general formula HS—R—Eg (wherein R represents a hydrocarbon-derived group having 1 to 4 carbon atoms, and E is − OH, —COOM, —COOR ′ or —SO 3 M group, M represents a hydrogen atom, monovalent metal, divalent metal, ammonium group or organic amine group, and R ′ represents an alkyl having 1 to 10 carbon atoms. In which g represents an integer of 1 to 2, for example, mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiomalic acid, Examples include octyl thioglycolate, octyl 3-mercaptopropionate, and the like from the viewpoint of chain transfer effect in a copolymerization reaction including monomers 1 to 3. Mercaptoethanol are preferable, more preferably mercaptopropionic acid. These 1 type (s) or 2 or more types can be used.
ハロゲン化炭化水素系連鎖移動剤としては、四塩化炭素、四臭化炭素などが挙げられる。 Examples of the halogenated hydrocarbon chain transfer agent include carbon tetrachloride and carbon tetrabromide.
その他の連鎖移動剤としては、α−メチルスチレンダイマー、ターピノーレン、α−テルピネン、γ−テルピネン、ジペンテン、２−アミノプロパン−１−オールなどを挙げることができる。連鎖移動剤は、１種又は２種以上を用いることができる。 Examples of other chain transfer agents include α-methylstyrene dimer, terpinolene, α-terpinene, γ-terpinene, dipentene, 2-aminopropan-1-ol and the like. A chain transfer agent can use 1 type (s) or 2 or more types.
本発明に係る共重合体の製造方法の一例を示す。反応容器に所定量の水を仕込み、窒素等の不活性気体で雰囲気を置換し昇温する。予め単量体１、単量体２、単量体３、連鎖移動剤を水に混合溶解したものと、重合開始剤を水に溶解したものとを用意し、０．５〜５時間かけて反応容器に滴下する。その際、各単量体、連鎖移動剤及び重合開始剤を別々に滴下してもよく、また、単量体の混合溶液を予め反応容器に仕込み、重合開始剤のみを滴下することも可能である。すなわち、連鎖移動剤、重合開始剤、その他の添加剤は、単量体溶液とは別に添加剤溶液として添加しても良いし、単量体溶液に配合して添加してもよいが、重合の安定性の観点からは、単量体溶液とは別に添加剤溶液として反応系に供給することが好ましい。また、好ましくは所定時間の熟成を行う。なお、重合開始剤は、全量を単量体と同時に滴下しても良いし、分割して添加しても良いが、分割して添加することが未反応単量体の低減の点では好ましい。例えば、最終的に使用する重合開始剤の全量中、１／２〜２／３の重合開始剤を単量体と同時に添加し、残部を単量体滴下終了後１〜２時間熟成した後、添加することが好ましい。必要に応じ、熟成終了後に更にアルカリ剤（水酸化ナトリウム等）で中和し、本発明に係る共重合体を得る。 An example of the manufacturing method of the copolymer which concerns on this invention is shown. A predetermined amount of water is charged into a reaction vessel, the atmosphere is replaced with an inert gas such as nitrogen, and the temperature is raised. Prepare monomer 1, monomer 2, monomer 3, chain transfer agent mixed and dissolved in water, and polymerization initiator dissolved in water, and take 0.5 to 5 hours. Drip into the reaction vessel. At that time, each monomer, chain transfer agent and polymerization initiator may be dropped separately, or a mixed solution of monomers can be charged in a reaction vessel in advance and only the polymerization initiator can be dropped. is there. That is, the chain transfer agent, the polymerization initiator, and other additives may be added as an additive solution separately from the monomer solution, or may be added to the monomer solution after being added. From the viewpoint of stability, it is preferable to supply the reaction system as an additive solution separately from the monomer solution. Further, aging is preferably performed for a predetermined time. The polymerization initiator may be added dropwise at the same time as the monomer, or may be added in portions, but it is preferable to add in portions in terms of reducing unreacted monomers. For example, in the total amount of the polymerization initiator to be finally used, 1/2 to 2/3 polymerization initiator is added simultaneously with the monomer, and the remainder is aged for 1 to 2 hours after the completion of the monomer dropping, It is preferable to add. If necessary, the copolymer according to the present invention is obtained by further neutralizing with an alkali agent (such as sodium hydroxide) after completion of aging.
また、本発明に係る共重合体は、単量体１を含有する液Ａと、単量体２を含有する液Ｂ及び単量体３を含有する液Ｃとを反応系に導入して共重合反応に用いることもでき、液Ａ，液Ｂ及び液Ｃはそれぞれ別々に反応系に導入することができる。また、反応系に導入される液Ａ，液Ｂ及び液Ｃの全量のそれぞれ９０重量％以上を並行して反応系に導入することが好ましい。液Ａ，液Ｂ及び液Ｃの反応系への導入方法として、具体的には滴下及び噴霧が挙げられ、液Ａ，液Ｂ及び液Ｃの粘度の観点から滴下が好ましい。液Ａは凝固点の観点から水を含む溶媒とすることが好ましく、液Ｂは加水分解の観点から水を含まない溶媒とすることが好ましい。液Ａのノズル（導入口）と液Ｂのノズル（導入口）及び液Ｃのノズル（導入口）の距離は任意に設定できる。また、滴下は気中及び液中いずれも可能であるが、液を全て導入する観点から気中滴下が好ましい。ノズル径は液滴の表面積を大きくする点及び溶解性の点から小さい方が好ましい。このように液Ａと液Ｂとを別々に反応系に導入することで、単量体２の水との接触機会を少なくし加水分解が抑制される。また、反応系に導入される液Ａ，液Ｂ及び液Ｃの全量のそれぞれ９０重量％以上を並行して反応系に導入することで、各単量体がランダムに導入された共重合体が得られる。液Ａと液Ｂ及び液Ｃの合計量の９０重量％以上とは、言い換えると、反応系に単独で導入される液Ａ，液Ｂ及び液Ｃの量が、反応系に導入される液Ａ，液Ｂ及び液Ｃの全量のそれぞれ１０重量％以下であることである。 Further, the copolymer according to the present invention is obtained by introducing a liquid A containing monomer 1, a liquid B containing monomer 2 and a liquid C containing monomer 3 into a reaction system. It can also be used for the polymerization reaction, and liquid A, liquid B, and liquid C can be separately introduced into the reaction system. Moreover, it is preferable to introduce 90% by weight or more of each of the total amount of liquid A, liquid B and liquid C introduced into the reaction system in parallel. Specific examples of the method of introducing the liquid A, the liquid B, and the liquid C into the reaction system include dropping and spraying, and the dropping is preferable from the viewpoint of the viscosity of the liquid A, the liquid B, and the liquid C. The liquid A is preferably a solvent containing water from the viewpoint of the freezing point, and the liquid B is preferably a solvent not containing water from the viewpoint of hydrolysis. The distance between the nozzle for liquid A (introduction port), the nozzle for liquid B (introduction port), and the nozzle for liquid C (introduction port) can be set arbitrarily. Moreover, although dripping can be carried out in air or in liquid, air dripping is preferred from the viewpoint of introducing all of the liquid. The nozzle diameter is preferably smaller from the viewpoint of increasing the surface area of the droplet and the solubility. Thus, by introducing the liquid A and the liquid B separately into the reaction system, the opportunity of contact of the monomer 2 with water is reduced and hydrolysis is suppressed. Moreover, by introducing 90% by weight or more of each of the total amount of liquid A, liquid B and liquid C introduced into the reaction system in parallel into the reaction system, a copolymer in which each monomer is randomly introduced is obtained. can get. In other words, 90% by weight or more of the total amount of the liquid A, the liquid B, and the liquid C means that the amount of the liquid A, the liquid B, and the liquid C that are independently introduced into the reaction system is the liquid A that is introduced into the reaction system. , Liquid B and liquid C are each 10% by weight or less of the total amount.
また、本発明に係る共重合体の製造にあたっては、材料、温度及び配合に対する汎用性の観点から、重合中に単量体１，単量体２，単量体３の共重合モル比を一回以上変化させて、重合させることが好ましい。 Further, in the production of the copolymer according to the present invention, from the viewpoint of versatility with respect to materials, temperature, and blending, the copolymerization molar ratio of monomer 1, monomer 2 and monomer 3 is set to a constant during polymerization. It is preferable to polymerize by changing it more than once.
本発明における共重合体の重量平均分子量（ゲルパーミエーションクロマトグラフィー法／ポリエチレングリコール換算）は、流動保持性の観点から、５０００〜２０００００の範囲が好ましく、１００００〜１５００００がより好ましく、１５０００〜１０００００が更に好ましく、２００００〜８００００が好ましく、２５０００〜６００００がより更に好ましく、３００００〜５００００がより更に好ましい。 The weight average molecular weight (gel permeation chromatography method / polyethylene glycol equivalent) of the copolymer in the present invention is preferably from 5,000 to 200,000, more preferably from 10,000 to 150,000, and more preferably from 15,000 to 100,000 from the viewpoint of fluidity retention. More preferably, 20000-80000 are preferable, 25000-60000 are still more preferable, and 30000-50000 are still more preferable.
本発明の水硬性組成物用分散剤は、該共重合体を含有する水溶液として用いることができる。 The dispersant for hydraulic composition of the present invention can be used as an aqueous solution containing the copolymer.
＜水硬性組成物用分散剤＞
本発明に係る水硬性組成物用分散剤は、上記本発明の共重合体を単独で用いる事も出来るが、カルボン酸基、リン酸基、スルホン酸基及びそれらの中和基から選ばれる少なくとも１種を有する重合体Ａ（以下、重合体Ａという）を含有しても良い。一般に、重合体Ａは水硬性組成物用の混和剤（分散剤等）として知られている重合体である。本発明の水硬性組成物用分散剤は、本発明の共重合体と重合体Ａとを含有する水溶液として用いることができる。
<Dispersant for hydraulic composition>
As the dispersant for a hydraulic composition according to the present invention, the copolymer of the present invention can be used alone, but at least selected from carboxylic acid groups, phosphoric acid groups, sulfonic acid groups, and neutralizing groups thereof. You may contain the polymer A which has 1 type (henceforth the polymer A). In general, the polymer A is a polymer known as an admixture (dispersant or the like) for a hydraulic composition. The dispersant for hydraulic composition of the present invention can be used as an aqueous solution containing the copolymer of the present invention and the polymer A.
重合体Ａのうち、カルボン酸基又はその中和基を有するものとしては、オキシアルキレン基またはポリオキシアルキレン基とカルボン酸を有する重合体である。例えば、特開平７−２２３８５２号公報に示される炭素数２〜３のオキシアルキレン基１１０〜３００モルを導入したポリアルキレングリコールモノエステル系単量体とアクリル酸系重合体、特表２００４−５１９４０６号公報の重合体Ａ、Ｂに示されるような重合体や、特開２００４−２１０５８７号公報や特開２００４−２１０５８９号公報に記載されているアミド系マクロモノマーを含むような重合体、特開２００３−１２８７３８号公報や特開２００６−５２５２１９号公報に記載されているポリエチレンイミンを含有する重合体が挙げられる。 Among the polymers A, those having a carboxylic acid group or a neutralizing group thereof are polymers having an oxyalkylene group or a polyoxyalkylene group and a carboxylic acid. For example, a polyalkylene glycol monoester monomer and an acrylic acid polymer into which 110 to 300 moles of an oxyalkylene group having 2 to 3 carbon atoms shown in JP-A-7-223852 are introduced, JP-A-2004-519406. Japanese Patent Application Laid-Open No. 2004-210587, Japanese Patent Application Laid-Open No. 2004-210589, and an amide macromonomer described in Japanese Patent Application Laid-Open No. 2004-210589 -1288738 gazette and JP, 2006-525219, A polymer containing polyethyleneimine is mentioned.
カルボン酸基又はその中和基を有する重合体Ａの市販品としては、（１）BASFポゾリス（株）のレオビルドSP8LS/8LSR、SP8LS、SP8LSR、SP8N、SP8S、SP8R、SP8SE/8RE、SP8SE、SP8RE、SP8SBシリーズ（Sタイプ、Mタイプ、Lタイプ、LLタイプ）、SP8HE、SP8HR、SP8SV/8RV、SP8RV、SP8HU、SP9N、SP9R、SP9HS、レオビルド８０００シリーズ、（２）日本シーカ（株）のシーカメント1100NT、シーカメント1100NTR、シーカメント2300、（３）（株）フローリックのフローリックSF500S（500SB）、フローリックSF500H、フローリックSF500R（500RB）、（４）竹本油脂（株）のチューポールHP-8、HP-11、HP-8R、HP-11R、SSP-104、NV-G1、NV-G5、（５）（株）日本触媒のアクアロックFC600S、アクアロックFC900、（６）日本油脂（株）のマリアリムAKM、マリアリムEKMなどが挙げられるが、この限りではない。 Examples of commercially available polymers A having a carboxylic acid group or a neutralizing group thereof include (1) BASF Pozzolith Co., Ltd. Leo Build SP8LS / 8LSR, SP8LS, SP8LSR, SP8N, SP8S, SP8R, SP8SE / 8RE, SP8SE, SP8RE , SP8SB series (S type, M type, L type, LL type), SP8HE, SP8HR, SP8SV / 8RV, SP8RV, SP8HU, SP9N, SP9R, SP9HS, Leo build 8000 series, (2) Nihon Sika Co., Ltd. SeaCament 1100NT , Sea Kament 1100NTR, Sea Kament 2300, (3) Floric's Floric SF500S (500SB), Floric SF500H, Floric SF500R (500RB), (4) Tulip HP-8, HP -11, HP-8R, HP-11R, SSP-104, NV-G1, NV-G5, (5) Nippon Catalyst's Aqualock FC600S, Aqualock FC900, (6) Maria Lim, Nippon Oil & Fats Co., Ltd. AKM, Mariarim EKM, etc. are mentioned, but not limited to this.
また、重合体Ａのうち、リン酸基又はその中和基を有するものとしては、ポリオキシアルキレン基とリン酸基を有する重合体である。例えば、特開２００６−０５２３８１号公報記載の重合体が挙げられる。具体的には、炭素数２〜３のオキシアルキレン基を平均３〜２００モル導入したポリアルキレングリコールモノエステル系単量体と、リン酸ジ−〔（２−ヒドロキシエチル）メタクリル酸〕エステルと、リン酸モノ（２−ヒドロキシエチル）メタクリル酸エステルとの共重合体等が挙げられる。 The polymer A having a phosphate group or a neutralizing group thereof is a polymer having a polyoxyalkylene group and a phosphate group. For example, the polymer of Unexamined-Japanese-Patent No. 2006-052381 is mentioned. Specifically, a polyalkylene glycol monoester monomer introduced with an average of 3 to 200 moles of an oxyalkylene group having 2 to 3 carbon atoms, di-[(2-hydroxyethyl) methacrylic acid] ester phosphate, And a copolymer with mono (2-hydroxyethyl) methacrylate ester.
重合体Ａのうち、スルホン酸基又はその中和基を有するものとしては、ナフタレン系重合体（例えばマイテイ１５０：花王（株）製）、メラミン系重合体（例えばマイテイ１５０Ｖ−２：花王（株）製）、アミノスルホン酸系重合体（例えばパリックＦＰ：藤沢化学（株）製）が挙げられる。 Among the polymers A, those having a sulfonic acid group or a neutralizing group thereof include naphthalene polymers (for example, Mighty 150: manufactured by Kao Corporation), melamine polymers (for example, Mighty 150V-2: Kao Corporation) ) And aminosulfonic acid polymers (for example, PARIC FP: manufactured by Fujisawa Chemical Co., Ltd.).
本発明に係る水硬性組成物用分散剤において、本発明の共重合体の含有量（固形分換算）は１〜９９重量％、更に２〜８０重量％、特に５〜７０重量％が好ましい。また、重合体Ａの含有量（固形分換算）は１〜９９重量％、更に２０〜９８重量％、特に３０〜９５重量％が好ましい。また分散剤は二種以上用いることもできるが、合計含有量が上記範囲であることが好ましい。重合体Ａは二種以上を用いる事が出来るが、合計含有量が上記範囲であることが好ましい。水硬性組成物用分散剤中の本発明の共重合体と重合体Ａの重量比率（本発明の共重合体／重合体Ａ（固形分換算））は、流動性と流動保持性の観点から５／９５〜９５／５が好ましく、１０／９０〜９０／１０がより好ましく、１５／８５〜８５／１５が更に好ましく、２０／８０〜８０／２０がより更に好ましい。 In the dispersant for a hydraulic composition according to the present invention, the content (in terms of solid content) of the copolymer of the present invention is preferably 1 to 99% by weight, more preferably 2 to 80% by weight, and particularly preferably 5 to 70% by weight. Further, the content of the polymer A (in terms of solid content) is 1 to 99% by weight, more preferably 20 to 98% by weight, and particularly preferably 30 to 95% by weight. Two or more dispersants can be used, but the total content is preferably in the above range. Two or more types of polymers A can be used, but the total content is preferably in the above range. The weight ratio of the copolymer of the present invention to the polymer A in the dispersant for hydraulic composition (copolymer of the present invention / polymer A (solid content conversion)) is from the viewpoint of fluidity and fluidity retention. 5 / 95-95 / 5 are preferable, 10 / 90-90 / 10 are more preferable, 15 / 85-85 / 15 are still more preferable, and 20 / 80-80 / 20 are still more preferable.
また、本発明に係る水硬性組成物用分散剤は、本発明の共重合体及び重合体Ａ以外に、例えば高性能減水剤、ＡＥ剤、ＡＥ減水剤、流動化剤、遅延剤、早強剤、促進剤、起泡剤、発泡剤、消泡剤、増粘剤、防水剤、防泡剤や珪砂、高炉スラグ、フライアッシュ、シリカヒューム等の公知の添加剤（材）と併用することができる。 In addition to the copolymer and polymer A of the present invention, the dispersant for hydraulic composition according to the present invention includes, for example, a high-performance water reducing agent, AE agent, AE water reducing agent, fluidizing agent, retarder, early strength. In combination with known additives (materials) such as agents, accelerators, foaming agents, foaming agents, antifoaming agents, thickeners, waterproofing agents, antifoaming agents, silica sand, blast furnace slag, fly ash, silica fume, etc. Can do.
＜水硬性組成物＞
本発明の水硬性組成物は、上記本発明の水硬性組成物用分散剤と、水硬性粉体と、水とを含有する。更に上記重合体Ａを含有してもよい。本発明の水硬性組成物を得る際には、本発明の共重合体と重合体Ａは、予め混合して用いても良いし、別々に用いても良い。
<Hydraulic composition>
The hydraulic composition of the present invention contains the above-described dispersant for hydraulic composition of the present invention, hydraulic powder, and water. Further, the polymer A may be contained. When the hydraulic composition of the present invention is obtained, the copolymer of the present invention and the polymer A may be mixed in advance or used separately.
本発明の水硬性組成物に使用される水硬性粉体とは、水和反応により硬化する物性を有する粉体のことであり、セメント、石膏等が挙げられる。好ましくは普通ポルトランドセメント、ビーライトセメント、中庸熱セメント、早強セメント、超早強セメント、耐硫酸セメント等のセメントであり、またこれらに高炉スラグ、フライアッシュ、シリカフューム、石粉（炭酸カルシウム粉末）等が添加された高炉スラグセメント、フライアッシュセメント、シリカフュームセメント等でもよい。なお、これらの粉体に骨材として、砂、砂及び砂利が添加されて最終的に得られる水硬性組成物が、一般にそれぞれモルタル、コンクリートなどと呼ばれている。本発明の水硬性組成物は、生コンクリート、コンクリート振動製品分野の外、セルフレベリング用、耐火物用、プラスター用、石膏スラリー用、軽量又は重量コンクリート用、ＡＥ用、補修用、プレパックド用、トレーミー用、グラウト用、地盤改良用、寒中用等の種々のコンクリートの何れの分野においても有用である。 The hydraulic powder used in the hydraulic composition of the present invention is a powder having physical properties that are cured by a hydration reaction, and examples thereof include cement and gypsum. Preferred are ordinary Portland cement, Belite cement, moderate heat cement, early strong cement, super early strong cement, sulfuric acid resistant cement, etc., and blast furnace slag, fly ash, silica fume, stone powder (calcium carbonate powder), etc. Blast furnace slag cement, fly ash cement, silica fume cement or the like to which is added may be used. In addition, the hydraulic composition finally obtained by adding sand, sand and gravel as aggregates to these powders is generally called mortar, concrete, etc., respectively. The hydraulic composition of the present invention is used in the field of ready-mixed concrete, concrete vibration products, self-leveling, refractory, plaster, gypsum slurry, lightweight or heavy concrete, AE, repair, pre-packed, tray It is useful in any field of various concrete such as for grouting, for ground improvement, for cold weather.
特に、生コンクリートの製造現場においては、普通ポルトランドセメント・中庸熱ポルトランドセメント・高炉スラグセメントを用いたコンクリートを通常に併産しており、更には水／粉体比の異なる種々の配合のコンクリートを製造することが日常となっている。このような状況において、セメントの品質によって流動性や流動保持性の変動が少ないことは意義あることである。最近では、普通ポルトランドセメントのロットによっても、流動保持性の変動が確認されることもあり、汎用的な流動保持性を提供することは意義あることである。 In particular, in the production site of ready-mixed concrete, concrete using ordinary Portland cement, medium-heated Portland cement, and blast furnace slag cement is usually co-produced, and concrete of various blends with different water / powder ratios is also produced. Manufacturing has become a daily routine. In such a situation, it is significant that there is little fluctuation in fluidity and fluidity retention depending on the quality of cement. Recently, fluctuations in fluid retention may be confirmed depending on the lot of ordinary Portland cement, and it is meaningful to provide general fluid retention.
本発明の水硬性組成物は、水／水硬性粉体比〔スラリー中の水と水硬性粉体の重量百分率（重量％）、通常Ｗ／Ｐと略記されるが、粉体がセメントの場合、Ｗ／Ｃと略記されることがある。〕が好ましくは６０重量％以下、より好ましくは５８〜１５重量％、好ましくは５７〜１８重量％、更に好ましくは５６〜２０重量％、より更に好ましくは５５〜２３重量％であることができる。 The hydraulic composition of the present invention has a water / hydraulic powder ratio [weight percentage (% by weight) of water and hydraulic powder in the slurry, usually abbreviated as W / P. , W / C may be abbreviated. ] Is preferably 60% by weight or less, more preferably 58-15% by weight, preferably 57-18% by weight, more preferably 56-20% by weight, and still more preferably 55-23% by weight.
本発明の水硬性組成物において、本発明の水硬性組成物用分散剤は、水硬性粉体１００重量部に対して０．０２〜１０重量部、更に０．０２〜５重量部、更に０．０５〜２重量部の比率（固形分換算）で添加されることが好ましい。また、本発明の共重合体は、水硬性粉体１００重量部に対して０．００２〜５重量部、更に０．０１〜４重量部、更に０．０２〜２重量部の比率（固形分換算）で添加されることが好ましい。重合体Ａは、水硬性粉体１００重量部に対して０．０１〜８重量部、更に０．０２〜４重量部の比率（固形分換算）で添加されることが好ましい。 In the hydraulic composition of the present invention, the dispersant for the hydraulic composition of the present invention is 0.02 to 10 parts by weight, further 0.02 to 5 parts by weight, and further 0 to 100 parts by weight of the hydraulic powder. It is preferably added at a ratio of 0.05 to 2 parts by weight (in terms of solid content). Further, the copolymer of the present invention has a ratio (solid content of 0.002 to 5 parts by weight, further 0.01 to 4 parts by weight, and further 0.02 to 2 parts by weight with respect to 100 parts by weight of the hydraulic powder. It is preferable to add by conversion. The polymer A is preferably added in a ratio (converted to solid content) of 0.01 to 8 parts by weight and further 0.02 to 4 parts by weight with respect to 100 parts by weight of the hydraulic powder.
＜製造例＞
攪拌機付きガラス製反応容器（四つ口フラスコ）に水１１５．３ｇを仕込み、撹拌しながら窒素置換をし、窒素雰囲気中で８０℃まで昇温した。ω−メトキシポリエチレングリコールモノメタクリレート（エチレンオキサイドの平均付加モル数１７、水分９．８％）７７．５ｇとメタクリル酸（表中ＭＡＡと表記する）１２．５ｇと３−メルカプトプロピオン酸（シグマ アルドリッチ ジャパン株式会社、試薬）１．５８ｇとを混合溶解した単量体溶液と２−ヒドロキシエチルアクリレート（表中ＨＥＡと表記する）４２．６ｇ、過硫酸アンモニウム水溶液（Ｉ）〔過硫酸アンモニウム（和光純薬工業株式会社、試薬）２．４５ｇを水４５ｇに溶解したもの〕の３者を、同時に滴下を開始し、それぞれ１．５時間かけて滴下した後、過硫酸アンモニウム水溶液（ＩＩ）〔過硫酸アンモニウム０．４１ｇを水１５ｇに溶解したもの〕を０．５時間かけて滴下した。その後、８０℃で１時間熟成した。熟成終了後に２０％水酸化ナトリウム水溶液で中和し、表１の本発明品７の共重合体（分散剤）を得た。なお、２−ヒドロキシエチルアクリレートは、一般式（２）で、Ｒ5がヒドロキシエチル基の化合物（分子量１１６．１）であり、Ｒ5−ＯＨで表される化合物のｌｏｇＰ値は−１．３６９の化合物である。よって、２−ヒドロキシエチルアクリレートは、［ｌｏｇＰ値／単量体２の分子量Mw］は−１．３６９／１１６．１＝−０．０１１８である。
<Production example>
A glass reaction vessel (four-necked flask) with a stirrer was charged with 115.3 g of water, purged with nitrogen while stirring, and heated to 80 ° C. in a nitrogen atmosphere. 77.5 g of ω-methoxypolyethylene glycol monomethacrylate (average added mole number of ethylene oxide 17, moisture 9.8%), 12.5 g of methacrylic acid (indicated as MAA in the table) and 3-mercaptopropionic acid (Sigma Aldrich Japan) Co., Ltd. Reagents) 1.58 g of mixed monomer solution and 2-hydroxyethyl acrylate (referred to as HEA in the table) 42.6 g, ammonium persulfate aqueous solution (I) [ammonium persulfate (Wako Pure Chemical Industries Ltd. The company, reagent) 2.45 g dissolved in 45 g of water] started to be added at the same time, and each was added dropwise over 1.5 hours, then ammonium persulfate aqueous solution (II) [ammonium persulfate 0.41 g was added. Water dissolved in 15 g] was added dropwise over 0.5 hours. Thereafter, aging was performed at 80 ° C. for 1 hour. After completion of aging, the mixture was neutralized with a 20% aqueous sodium hydroxide solution to obtain a copolymer (dispersant) of the product 7 of the present invention shown in Table 1. Incidentally, 2-hydroxyethyl acrylate, in the general formula (2) is a compound of R 5 is a hydroxyethyl group (molecular weight 116.1), logP value of the compound represented by R 5 -OH is -1.369 It is a compound of this. Therefore, 2-hydroxyethyl acrylate has [log P value / molecular weight Mw of monomer 2] of −1.369 / 116.1 = −0.0118.
なお、ω−メトキシポリエチレングリコールモノメタクリレートは、特許第3874917号記載の方法に準じて、エステル化反応により合成し、未反応物として残留するメタクリル酸を留去により、１重量%未満にしたものを用いた。 Incidentally, ω-methoxypolyethylene glycol monomethacrylate was synthesized by esterification reaction according to the method described in Japanese Patent No. 3879917, and methacrylic acid remaining as an unreacted product was distilled off to less than 1% by weight. Using.
表１の単量体及び比率で、上記本発明品７の製造と同様に他の共重合体（分散剤）を製造した。得られた共重合体を以下の実施例及び比較例に用いた。 Other copolymers (dispersants) were produced in the same manner as in the production of the product 7 of the present invention with the monomers and ratios shown in Table 1. The obtained copolymer was used in the following Examples and Comparative Examples.
表中の記号は以下の意味である。なお、単量体の重量％は、共重合体の構成単量体中の重量％である、
・ＭＥ−ＰＥＧ：ω−メトキシポリエチレングリコールモノメタクリレート、カッコ内の数値は、エチレンオキサイドの平均付加モル数である。
・ＨＥＡ：２−ヒドロキシエチルアクリレート（エチレングリコールｌｏｇＰ：−１．３６９、ｌｏｇＰ／Ｍｗ：−１．３６９／１１６．１＝−０．０１１８、和光純薬工業株式会社、試薬）
・アクリル酸メチル（メタノールｌｏｇＰ：−０．７６４、ｌｏｇＰ／Ｍｗ：−０．７６４／８６．１＝−０．００８９、和光純薬工業株式会社、試薬）
The symbols in the table have the following meanings. The weight% of the monomer is the weight% in the constituent monomer of the copolymer.
ME-PEG: ω-methoxypolyethylene glycol monomethacrylate, the value in parentheses is the average number of moles of ethylene oxide added.
HEA: 2-hydroxyethyl acrylate (ethylene glycol log P: -1.369, log P / Mw: -1.369 / 116.1 = -0.0118, Wako Pure Chemical Industries, Reagent)
-Methyl acrylate (methanol log P: -0.764, log P / Mw: -0.764 / 86.1 = -0.0089, Wako Pure Chemical Industries, Ltd., reagent)
実施例１（ペースト試験）
＜ペースト配合＞
Example 1 (Paste test)
<Paste formulation>
Ｗ： 上水道水
Ｃ１： 普通ポルトランドセメント （太平洋セメント（株）製）
Ｃ２： 高炉スラグセメント（Ｂ種）（太平洋セメント（株）製）
Ｃ３： 中庸熱セメント（太平洋セメント（株）製）
W: Tap water C1: Ordinary Portland cement (manufactured by Taiheiyo Cement Co., Ltd.)
C2: Blast furnace slag cement (Type B) (manufactured by Taiheiyo Cement Co., Ltd.)
C3: Medium heat cement (manufactured by Taiheiyo Cement Co., Ltd.)
５００ｍｌ容器に、配合１に従い、セメント及び表１の分散剤（対セメント１００重量部に対し０．０８重量部）を含む水を投入し、ハンドミキサー（低速６３ｒｐｍ程度）で２分間混練し、ペーストを得た。以下の初期流動性及び流動保持性の評価には、配合１のＣをＣ１として調製したペーストを用いた。 In a 500 ml container, according to Formulation 1, water containing cement and the dispersant of Table 1 (0.08 parts by weight with respect to 100 parts by weight of cement) is added, kneaded for 2 minutes with a hand mixer (low speed of about 63 rpm), and paste Got. For the following evaluation of initial fluidity and fluidity retention, a paste prepared with C in Formulation 1 as C1 was used.
＜初期流動性及び流動保持性の評価＞
得られたペーストを円筒状コーン（φ５０ｍｍ×５１ｍｍ）に充填し、垂直に引き上げた時の広がり（最も長い直径の長さとそれと垂直方向の長さの平均値）をペーストフローとして測定した。測定は、混練終了直後（０分後）、混練終了１２０分後に行い、フロー値の経時変化を測定した。流動保持性の指標として、１２０分後のフロー値／０分後のフロー値×１００（％）を流動保持率として算出した。混練終了直後のフロー値を初期流動性とした。分散剤を添加しない場合の初期流動性は１００ｍｍであった。
<Evaluation of initial fluidity and fluidity>
The obtained paste was filled into a cylindrical cone (φ50 mm × 51 mm), and the spread (the longest diameter length and the average value in the vertical direction) when pulled up vertically was measured as a paste flow. The measurement was performed immediately after the end of kneading (after 0 minutes) and 120 minutes after the end of kneading, and the change in flow value with time was measured. As an index of fluid retention, the flow value after 120 minutes / the flow value after 0 minutes × 100 (%) was calculated as the fluid retention. The flow value immediately after completion of kneading was defined as initial fluidity. The initial fluidity when no dispersant was added was 100 mm.
この評価では、初期流動性は１２０ｍｍ以上、流動保持率は９０％以上であれば、水硬性組成物用分散剤として良好であると判断できる。ペーストがモルタル、コンクリートになると保持性は低下する傾向があるので、流動保持率は数値が大きい方が比較的好ましい。 In this evaluation, if the initial fluidity is 120 mm or more and the flow retention is 90% or more, it can be judged that the dispersant for a hydraulic composition is good. Since the retention tends to decrease when the paste becomes mortar or concrete, it is relatively preferable that the fluid retention rate is larger.
表３の結果から以下のような考察が得られる。
カルボン酸系単量体の含量が多くなるほど初期流動性が向上する傾向にある。カルボン酸系単量体（単量体３）の含量が０及び２．５重量％である比較例２及び４については初期流動性が１２０ｍｍ以下と劣る。一方、カルボン酸系単量体（単量体３）の含量が５重量％の本発明品２では初期流動性が１２０ｍｍを越え、１０重量％（本発明品３、７）、１５重量％（本発明品１、４）では更に初期流動性が高くなった。一方で、流動保持率は、単量体２の重量比率（重量％）の低下と共に低下する傾向にある。流動保持率は実用上９０％以上あることが好ましい。単量体２の含有量が５重量％の比較品１０では、初期流動性は１６５ｍｍであるが、流動保持率が６０％と劣る。
The following considerations can be obtained from the results in Table 3.
As the content of the carboxylic acid monomer increases, the initial fluidity tends to improve. In Comparative Examples 2 and 4 in which the content of the carboxylic acid monomer (monomer 3) is 0 and 2.5% by weight, the initial fluidity is inferior to 120 mm or less. On the other hand, in the product 2 of the present invention in which the content of the carboxylic acid monomer (monomer 3) is 5% by weight, the initial fluidity exceeds 120 mm, 10% by weight (present products 3, 7), 15% by weight ( In the inventive products 1, 4), the initial fluidity was further increased. On the other hand, the fluid retention rate tends to decrease with a decrease in the weight ratio (% by weight) of the monomer 2. The fluid retention is preferably 90% or more practically. In the comparative product 10 in which the content of the monomer 2 is 5% by weight, the initial fluidity is 165 mm, but the fluid retention is inferior at 60%.
＜汎用性の評価＞
表１の分散剤の一部を用いて、表２の配合１におけるＣをＣ1、Ｃ２又はＣ３にした配合に対する評価を行った。評価は、初期流動性、流動保持性について行った。流動保持性は前記流動保持率の評価と同様に行った。セメントとしてＣ１（表４中、「普通」と表記）、Ｃ２（表４中、「高炉スラグ」と表記）、Ｃ３（表４中、「中庸熱」と表記）を用いた場合の初期流動性と流動保持性の変動比率（標準偏差）を以下の式で算出し、汎用性の指標とした。結果を表４に示す。尚、標準偏差は小さいほどセメントの種類によらず同様の流動性を示すので汎用性に優れる。
<Evaluation of versatility>
Using some of the dispersants in Table 1, evaluations were made on formulations in which C in Formula 1 in Table 2 was C1, C2 or C3. Evaluation was performed about initial fluidity and fluidity retention. The fluid retention was performed in the same manner as the evaluation of the fluid retention. Initial fluidity when C1 (indicated as “normal” in Table 4), C2 (indicated as “blast furnace slag” in Table 4), C3 (indicated as “medium heat” in Table 4) as cements And the fluctuation ratio (standard deviation) of fluidity retention was calculated by the following formula, and used as an index of versatility. The results are shown in Table 4. The smaller the standard deviation, the better the versatility because the same fluidity is exhibited regardless of the type of cement.
この評価では、標準偏差が小さいほど汎用性に優れると判断できる。初期流動性については、標準偏差が好ましくは１６以下、より好ましくは１２以下、更に好ましくは８以下であれば、汎用性に優れる分散剤であると判断できる。流動保持性については、標準偏差が好ましくは１９以下、より好ましくは１７以下、更に好ましくは１５以下であれば、汎用性に優れる分散剤であると判断できる。 In this evaluation, it can be determined that the smaller the standard deviation, the more versatile. Regarding the initial fluidity, if the standard deviation is preferably 16 or less, more preferably 12 or less, and still more preferably 8 or less, it can be determined that the dispersant is excellent in versatility. Regarding the flow retention, if the standard deviation is preferably 19 or less, more preferably 17 or less, and even more preferably 15 or less, it can be judged that the dispersant is excellent in versatility.
この評価で用いたＣ１〜Ｃ３のセメントは、コンクリート製造において使用比率の特に高い代表的なものであり、これら三種のセメント汎用性に優れる事は、コンクリート製造業者にとってきわめて重要な事である。高炉セメントには、高炉スラグが配合されており、オキシアルキレン基の平均付加モル数ｎの大きい分散剤は、吸着性が高く、高い初期流動性を示すが、一方で流動保持性が低下する傾向がある。 The C1 to C3 cement used in this evaluation is a typical one with a particularly high use ratio in concrete production, and it is extremely important for a concrete manufacturer that these three kinds of cements have excellent versatility. Blast furnace cement is blended with blast furnace slag, and a dispersant having a large average addition mole number n of oxyalkylene groups has high adsorptivity and high initial fluidity, but on the other hand, fluid retention tends to decrease. There is.
即ち、比較品４は普通セメントに対して初期流動性及び流動保持率に優れていたが、高炉スラグセメントや中庸熱セメントに対する流動性の変化が大きく、標準偏差が大きくなった。オキシアルキレン基の平均付加モル数ｎが４５である比較品２については、ｎが２８の比較品４よりもさらに標準偏差が大きくなった。対して、オキシアルキレン基の平均付加モル数ｎが２０以下の本発明品５〜７（ｎが９〜１７）では標準偏差は相対的に小さく、汎用性が良好となった。 That is, the comparative product 4 was excellent in the initial fluidity and fluid retention rate with respect to the ordinary cement, but the change in fluidity with respect to the blast furnace slag cement and the medium heat cement was large, and the standard deviation was large. For the comparative product 2 in which the average added mole number n of oxyalkylene groups was 45, the standard deviation was larger than that of the comparative product 4 with n of 28. On the other hand, in the inventive products 5 to 7 (n is 9 to 17) in which the average addition mole number n of the oxyalkylene group is 20 or less (n is 9 to 17), the standard deviation is relatively small, and the versatility is good.
Claims (7)
該共重合体の構成単量体中、単量体１の比率が２５〜８５重量％であり、単量体２の比率が１０〜７０重量％であり、単量体３の比率が５〜１５重量％である水硬性組成物用分散剤。
〔式中、Ｒ1〜Ｒ3は、それぞれ水素原子又はメチル基を表し、ＡＯは炭素数２〜４のオキシアルキレン基を表し、ｎはＡＯの平均付加モル数であり、５〜２０の数を表し、Ｒ4は水素原子又は炭素数１〜４のアルキル基、ｑは０〜２の整数、ｐは０又は１を表す。〕
〔式中、Ｒ5は、炭素数１〜４のヘテロ原子を含んでよい炭化水素基である。〕
〔式中、Ｒ6〜Ｒ8は、それぞれ水素原子、メチル基又は(ＣＨ2)sＣＯＯＭ2であり、(ＣＨ2)sＣＯＯＭ2はＣＯＯＭ1又は他の(ＣＨ2)sＣＯＯＭ2と無水物を形成していてもよく、その場合、それらの基のＭ1、Ｍ2は存在しない。ｓは０〜２の整数を表す。Ｍ1、Ｍ2は、それぞれ水素原子、アルカリ金属、アルカリ土類金属、アンモニウム基、アルキルアンモニウム基、置換アルキルアンモニウム基、アルキル基、ヒドロキシアルキル基、又はアルケニル基を表す。〕 Copolymer obtained by polymerizing monomer 1 represented by general formula (1), monomer 2 represented by general formula (2), and monomer 3 represented by general formula (3) A dispersant for a hydraulic composition containing a coalescence,
Among the constituent monomers of the copolymer, the ratio of monomer 1 is 25 to 85% by weight, the ratio of monomer 2 is 10 to 70% by weight, and the ratio of monomer 3 is 5 to 5%. The dispersing agent for hydraulic compositions which is 15 weight%.
[Wherein, R 1 to R 3 each represent a hydrogen atom or a methyl group, AO represents an oxyalkylene group having 2 to 4 carbon atoms, n represents an average added mole number of AO, and a number of 5 to 20 R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, q represents an integer of 0 to 2, and p represents 0 or 1. ]
[Wherein R 5 is a hydrocarbon group which may contain a hetero atom having 1 to 4 carbon atoms. ]
Wherein, R 6 to R 8 are each a hydrogen atom, a methyl group or (CH 2) s COOM 2, (CH 2) s COOM 2 is COOM 1 or another (CH 2) s COOM 2 and anhydrous In this case, M 1 and M 2 of those groups are not present. s represents the integer of 0-2. M 1 and M 2 each represent a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an alkyl ammonium group, a substituted alkyl ammonium group, an alkyl group, a hydroxyalkyl group, or an alkenyl group. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| JP5027063B2 (en) * | 2008-06-23 | 2012-09-19 | 花王株式会社 | Dispersion retention agent for hydraulic composition |
| JP2011084459A (en) * | 2009-09-18 | 2011-04-28 | Nippon Shokubai Co Ltd | Cement admixture, cement composition, and polycarboxylic acid copolymer for cement admixture |
| JP5841834B2 (en) * | 2011-12-26 | 2016-01-13 | 花王株式会社 | Admixture for hydraulic composition |
| JP6074517B2 (en) * | 2012-12-05 | 2017-02-01 | 江蘇蘇博特新材料股▲ふん▼有限公司Ｓｏｂｕｔｅ Ｎｅｗ Ｍａｔｅｒｉａｌｓ Ｃｏ．，Ｌｔｄ． | Method for producing slump retention type polycarboxylate-based high performance fluidizing agent |
| JP6963540B2 (en) * | 2018-10-25 | 2021-11-10 | 花王株式会社 | Dispersant composition for water-hardening composition for centrifugal molding or vibration molding |
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| JPS59162161A (en) * | 1983-03-01 | 1984-09-13 | 三洋化成工業株式会社 | Cement dispersant |
| JP4151941B2 (en) * | 2002-03-27 | 2008-09-17 | 日本製紙株式会社 | Cement dispersion aid and cement dispersant, and cement composition containing them |
| JP2003286058A (en) * | 2002-03-27 | 2003-10-07 | Nippon Paper Industries Co Ltd | Cement dispersing agent and cement composition |
| JP2005330129A (en) * | 2004-05-18 | 2005-12-02 | Nippon Shokubai Co Ltd | Cement admixture |
| JP4425775B2 (en) * | 2004-12-24 | 2010-03-03 | 花王株式会社 | Hydraulic powder dispersion copolymer |
| JP5122370B2 (en) * | 2007-05-22 | 2013-01-16 | 花王株式会社 | Dispersion retention agent for hydraulic composition |
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