JP4911759B2 - Method for preparing concrete - Google Patents
Method for preparing concrete Download PDFInfo
- Publication number
- JP4911759B2 JP4911759B2 JP2006180993A JP2006180993A JP4911759B2 JP 4911759 B2 JP4911759 B2 JP 4911759B2 JP 2006180993 A JP2006180993 A JP 2006180993A JP 2006180993 A JP2006180993 A JP 2006180993A JP 4911759 B2 JP4911759 B2 JP 4911759B2
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- Prior art keywords
- chemical formula
- concrete
- mass
- group
- component
- 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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Links
- 238000000034 method Methods 0.000 title claims description 34
- 239000000126 substance Substances 0.000 claims description 43
- 229920000578 graft copolymer Polymers 0.000 claims description 34
- 239000010881 fly ash Substances 0.000 claims description 27
- 125000006353 oxyethylene group Chemical group 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 19
- -1 alkylene glycol Chemical compound 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 239000004568 cement Substances 0.000 claims description 17
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 16
- 125000001931 aliphatic group Chemical group 0.000 claims description 14
- 229920001577 copolymer Polymers 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 10
- 229920000570 polyether Polymers 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 4
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 150000007514 bases Chemical class 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- 239000004615 ingredient Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 11
- 239000003638 chemical reducing agent Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000010526 radical polymerization reaction Methods 0.000 description 7
- 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 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 239000003999 initiator Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- WRKCIHRWQZQBOL-UHFFFAOYSA-N octyl dihydrogen phosphate Chemical compound CCCCCCCCOP(O)(O)=O WRKCIHRWQZQBOL-UHFFFAOYSA-N 0.000 description 4
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000010883 coal ash Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000011398 Portland cement Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 238000010257 thawing Methods 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 239000004373 Pullulan Substances 0.000 description 1
- 229920001218 Pullulan Polymers 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000003493 decenyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- VVTGHWARMCSPKY-UHFFFAOYSA-N dodecan-1-amine;oxirane Chemical compound C1CO1.CCCCCCCCCCCCN VVTGHWARMCSPKY-UHFFFAOYSA-N 0.000 description 1
- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 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
- 235000019423 pullulan Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 0.000 description 1
- KRIXEEBVZRZHOS-UHFFFAOYSA-N tetradecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCOP(O)(O)=O KRIXEEBVZRZHOS-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004078 waterproofing Methods 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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
-
- 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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/29—Frost-thaw resistance
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明はコンクリートの調製方法に関し、特に未燃カーボンを８〜２５質量％の高濃度で含有するフライアッシュを用いるコンクリートの調製方法に関する。近年、フライアッシュの発生量、なかでも石炭火力発電所において石炭灰として発生するフライアッシュの発生量が増加している。石炭火力発電所において発生するかかるフライアッシュは未燃カーボンを８〜２５質量％の高濃度で含有しており、しかもそれが発生する発電所によって未燃カーボンの濃度のバラツキが大きいという特性を有する。本発明は、石炭火力発電所において発生するフライアッシュのような未燃カーボンを８〜２５質量％の高濃度で含有するフライアッシュを用いるコンクリートの調製方法に関する。 The present invention relates to a method for preparing concrete, and more particularly to a method for preparing concrete using fly ash containing unburned carbon at a high concentration of 8 to 25% by mass. In recent years, the amount of fly ash generated, especially the amount of fly ash generated as coal ash in coal-fired power plants, has increased. Such fly ash generated in a coal-fired power plant contains unburned carbon in a high concentration of 8 to 25% by mass, and has a characteristic that the variation in the concentration of unburned carbon varies depending on the power plant in which it is generated. . The present invention relates to a method for preparing concrete using fly ash containing unburned carbon such as fly ash generated in a coal-fired power plant at a high concentration of 8 to 25% by mass.
未燃カーボンを８〜２５質量％の高濃度で含有するフライアッシュを用いてコンクリートを調製すると、１）所要の流動性を得るための高性能減水剤乃至高性能ＡＥ減水剤の使用量が増大し、コストアップになる、２）流動性の経時的な低下（スランプロス）が大きくなる、３）所要の連行空気量を得るためのＡＥ剤の使用量が増大し、コストアップになる、４）得られる硬化体の凍結融解作用に対する抵抗性が低下する、５）得られる硬化体の強度が低下する等、様々な支障を生じる。 When concrete is prepared using fly ash containing unburned carbon at a high concentration of 8 to 25% by mass, 1) the amount of high-performance water reducing agent or high-performance AE water reducing agent used to obtain the required fluidity increases. 2) Increase in fluidity over time (slump loss) 3) Increase in the amount of AE agent used to obtain the required amount of entrained air, resulting in increased cost 4 Various problems occur such as :) the resistance of the obtained cured body to freeze-thaw action is lowered, and 5) the strength of the obtained cured body is lowered.
かかる様々な支障を改善するため、フライアッシュを用いてコンクリートを調製するとき、混和剤として、空気連行剤を用いる方法（例えば特許文献１〜２参照）、石炭灰用分散剤を用いる方法（例えば特許文献３〜５参照）、打ち肌面改良剤を用いる方法（例えば特許文献６〜７参照）等が知られている。ところが、これらの従来法には、これらを単独で行なう場合はいうまでもなく、これらを併用して行なう場合でも、フライアッシュとして未燃カーボンを８〜２５質量％の高濃度で含有するものを用いると、依然として前記したような様々な支障を生じるという問題がある。
本発明が解決しようとする課題は、コンクリートの調製に未燃カーボンを８〜２５質量％の高濃度で含有するフライアッシュを用いる場合であっても、１）所要の流動性を得るための高性能減水剤乃至高性能ＡＥ減水剤の使用量の増大を抑え、２）流動性の経時的な低下（スランプロス）を防止し、３）所要の連行空気量を得るためのＡＥ剤の使用量の増大を抑えて、４）得られる硬化体に凍結融解作用に対する強い抵抗性を与え、５）得られる硬化体に充分な強度を与えるという以上の１）〜５）の機能を同時に有するコンクリートを調製する方法を提供する処にある。 The problem to be solved by the present invention is that even when fly ash containing unburned carbon at a high concentration of 8 to 25% by mass is used for the preparation of concrete, 1) high to obtain the required fluidity Suppress the increase in the amount of performance water-reducing agent or high-performance AE water-reducing agent, 2) prevent the fluidity from decreasing over time (slump loss), and 3) the amount of AE agent used to obtain the required amount of entrained air 4) giving the hardened body obtained a strong resistance to freeze-thaw action and 5) giving the obtained hardened body a sufficient strength. It is in providing a method of preparation.
しかして本発明者らは、前記の課題を解決するべく研究した結果、未燃カーボンを８〜２５質量％の高濃度で含有するフライアッシュを用いてコンクリートを調製するときは、かかるフライアッシュを所定の単位量となるよう用い、また特定の３成分を所定割合で含有することとなる混和剤をセメントに対し所定量となるよう用いることが正しく好適であることを見出した。 Accordingly, as a result of researches to solve the above-mentioned problems, the present inventors have found that when preparing concrete using fly ash containing unburned carbon at a high concentration of 8 to 25% by mass, such fly ash is used. It has been found that it is correct and suitable to use a predetermined unit amount, and to use an admixture containing specific three components in a predetermined ratio with respect to the cement.
すなわち本発明は、未燃カーボンを８〜２５質量％の高濃度で含有するフライアッシュを用いてコンクリートを調製するに際し、かかるフライアッシュを単位量が４０〜１００ｋｇ／ｍ３となるよう用い、また下記のＡ成分を６２〜８９質量％、下記のＢ成分を１０〜３５質量％及び下記のＣ成分を０．３〜３質量％の割合で含有することとなり、且つこれらの３成分を合計で１００質量％となるよう含有することとなる混和剤を、セメント１００質量部当たり０．１〜３質量部の割合となるよう用いることを特徴とするコンクリートの調製方法に係る。 That is, in the present invention, when preparing concrete using fly ash containing unburned carbon at a high concentration of 8 to 25% by mass, the fly ash is used so that the unit amount is 40 to 100 kg / m 3. 62 to 89 mass% of the following A component, 10 to 35 mass% of the following B component, and 0.3 to 3 mass% of the following C component will be contained, and these three components in total The present invention relates to a method for preparing concrete, characterized in that the admixture to be contained in an amount of 100% by mass is used at a ratio of 0.1 to 3 parts by mass per 100 parts by mass of cement.
Ａ成分：１）下記の第１工程及び第２工程を経て得られるグラフト共重合体、２）更に下記の第３工程を経て得られるグラフト共重合体の塩、以上の１）及び２）から選ばれる一つ又は二つ以上。 Component A: 1) Graft copolymer obtained through the following first step and second step, 2) Graft copolymer salt obtained through the following third step, from the above 1) and 2) One or more selected.
第１工程：無水マレイン酸と下記の化１で示される単量体とを合計で９５モル％以上含有し且つ無水マレイン酸／該単量体＝５０／５０〜６５／３５（モル比）の割合で含有するラジカル重合性単量体混合物を溶剤の非存在下でラジカル重合して、質量平均分子量５０００〜７００００の共重合体を得る工程。 First step: maleic anhydride and monomers represented by the following chemical formula 1 are contained in a total of 95 mol% or more and maleic anhydride / the monomer = 50/50 to 65/35 (molar ratio). A step of radically polymerizing a radically polymerizable monomer mixture contained in a proportion in the absence of a solvent to obtain a copolymer having a mass average molecular weight of 5000 to 70000.
第２工程：第１工程で得た共重合体１００質量部当たり、下記の化２で示されるポリエーテル化合物を０．０５〜５．０質量部の割合でグラフト反応して、グラフト共重合体を得る工程。 Second step: The graft copolymer is obtained by graft-reacting the polyether compound represented by the following chemical formula 2 at a ratio of 0.05 to 5.0 parts by mass per 100 parts by mass of the copolymer obtained in the first step. Obtaining.
第３工程：第２工程で得たグラフト共重合体を、アルカリ金属水酸化物で部分中和又は完全中和処理して、グラフト共重合体の塩を得る工程。 Third step: A step of obtaining a graft copolymer salt by partially neutralizing or completely neutralizing the graft copolymer obtained in the second step with an alkali metal hydroxide.
化１及び化２において、
Ｒ１：メチル基又はアセチル基
Ｒ２：炭素数８〜２０の脂肪族炭化水素基
Ａ１：分子中に１〜１５０個のオキシエチレン単位のみ又は合計２〜１５０個のオキシエチレン単位とオキシプロピレン単位とで構成された（ポリ）オキシアルキレン基を有する（ポリ）アルキレングリコールから全ての水酸基を除いた残基
Ａ２：分子中に合計２３〜７０個のオキシエチレン単位とオキシプロピレン単位とで構成され且つ該オキシエチレン単位と該オキシプロピレン単位とがブロック状に結合したポリオキシアルキレン基を有するポリアルキレングリコールから全ての水酸基を除いた残基
In Chemical Formula 1 and Chemical Formula 2,
R 1 : Methyl group or acetyl group R 2 : Aliphatic hydrocarbon group having 8 to 20 carbon atoms A 1 : Only 1 to 150 oxyethylene units or 2 to 150 total oxyethylene units and oxypropylene in the molecule Residue obtained by removing all hydroxyl groups from a (poly) alkylene glycol having a (poly) oxyalkylene group composed of units A 2 : composed of a total of 23 to 70 oxyethylene units and oxypropylene units in the molecule And a residue obtained by removing all hydroxyl groups from a polyalkylene glycol having a polyoxyalkylene group in which the oxyethylene unit and the oxypropylene unit are bonded in a block form
Ｂ成分：下記の化３で示される有機アミンエチレンオキサイド付加物 Component B: Organic amine ethylene oxide adduct represented by the following chemical formula 3
化３において、
Ｒ３：炭素数８〜２０の脂肪族炭化水素基
ｎ，ｍ：１以上の整数であって、且つ４≦ｎ＋ｍ≦１２を満足する整数
In chemical formula 3,
R 3 : Aliphatic hydrocarbon group having 8 to 20 carbon atoms n, m: an integer of 1 or more and 4 ≦ n + m ≦ 12
Ｃ成分：下記の化４で示される有機リン酸エステル Component C: Organophosphate represented by the following chemical formula 4
化４において、
Ｒ４：炭素数８〜２０の脂肪族炭化水素基
Ｍ１，Ｍ２：水素原子、アルカリ金属、アルカリ土類金属、アンモニウム又は有機アミン
In chemical formula 4,
R 4 : Aliphatic hydrocarbon group having 8 to 20 carbon atoms M 1 , M 2 : Hydrogen atom, alkali metal, alkaline earth metal, ammonium or organic amine
本発明に係るコンクリートの調製方法（以下単に本発明の方法という）では、詳しくは後述するように、セメント、未燃カーボンを８〜２５質量％の高濃度で含有するフライアッシュ、細骨材、粗骨材及び水の他に、特定の混和剤を用いてコンクリートを調製する。本発明で用いる混和剤は、結果として、Ａ成分、Ｂ成分及びＣ成分の３成分で構成されることとなるものである。 In the concrete preparation method according to the present invention (hereinafter simply referred to as the method of the present invention), as will be described in detail later, fly ash, fine aggregate containing cement and unburned carbon at a high concentration of 8 to 25% by mass, In addition to coarse aggregate and water, concrete is prepared using specific admixtures. As a result, the admixture used in the present invention is composed of the three components of A component, B component and C component.
本発明の方法で用いる混和剤のＡ成分は、１）第１工程及び第２工程を経て得られる
グラフト共重合体、２）更に第３工程を経て得られるグラフト共重合体の塩、以上の１）及び２）から選ばれる一つ又は二つ以上である。したがってＡ成分には、１）グラフト共重合体から選ばれる一つ又は二つ以上、２）グラフト共重合体の塩から選ばれる一つ又は二つ以上、３）これらの混合物が含まれる。
The component A of the admixture used in the method of the present invention is 1) a graft copolymer obtained through the first step and the second step, 2) a salt of the graft copolymer obtained through the third step, One or more selected from 1) and 2). Therefore, the component A includes 1) one or more selected from graft copolymers, 2) one or more selected from salts of graft copolymers, and 3) mixtures thereof.
第１工程は、ラジカル重合性単量体混合物を溶剤の非存在下でラジカル重合して共重合体を得る工程である。ラジカル重合性単量体混合物としては、無水マレイン酸と化１で示される単量体とを合計で９５モル％以上含有し且つ無水マレイン酸／該単量体＝５０／５０〜６５／３５（モル比）の割合、好ましくは５２／４８〜６２／３８（モル比）の割合で含有するものを用いる。 The first step is a step of obtaining a copolymer by radical polymerization of a radical polymerizable monomer mixture in the absence of a solvent. As the radical polymerizable monomer mixture, maleic anhydride and the monomer represented by Chemical formula 1 are contained in a total of 95 mol% or more and maleic anhydride / the monomer = 50/50 to 65/35 ( (Molar ratio), preferably 52/48 to 62/38 (molar ratio).
化１で示される単量体において、化１中のＡ１としては、１）分子中にオキシエチレン単位のみで構成された（ポリ）オキシエチレン基を有する（ポリ）エチレングリコールから全ての水酸基を除いた残基、２）分子中にオキシエチレン単位とオキシプロピレン単位とで構成された（ポリ）オキシエチレン（ポリ）オキシプロピレン基を有する（ポリ）エチレン（ポリ）プロピレングリコールから全ての水酸基を除いた残基が挙げられ、２）の場合、オキシエチレン単位とオキシプロピレン単位との結合様式は、ランダム結合、ブロック結合のいずれでもよいが、１）の場合が好ましい。またＡ１を構成するオキシアルキレン単位の繰り返し数は１〜１５０とするが、１０〜９０とするのが好ましい。 In the monomer represented by Chemical formula 1, A 1 in Chemical formula 1 includes: 1) All hydroxyl groups from (poly) ethylene glycol having (poly) oxyethylene groups composed only of oxyethylene units in the molecule. Residues removed 2) Excluding all hydroxyl groups from (poly) ethylene (poly) propylene glycol having (poly) oxyethylene (poly) oxypropylene groups composed of oxyethylene units and oxypropylene units in the molecule In the case of 2), the bonding mode of the oxyethylene unit and the oxypropylene unit may be either a random bond or a block bond, but the case of 1) is preferred. The number of repeating oxyalkylene units constituting A 1 is 1 to 150, preferably 10 to 90.
以上説明した化１で示される単量体の具体例としては、１）α−アリル−ω−メチル−（ポリ）オキシエチレン、２）α−アリル−ω−メチル−（ポリ）オキシエチレン（ポリ）オキシプロピレン、３）α−アリル−ω−アセチル−（ポリ）オキシエチレン、４）α−アリル−ω−アセチル−（ポリ）オキシエチレン（ポリ）オキシプロピレン等が挙げられる。 Specific examples of the monomer represented by Chemical Formula 1 described above are: 1) α-allyl-ω-methyl- (poly) oxyethylene, 2) α-allyl-ω-methyl- (poly) oxyethylene (poly) ) Oxypropylene, 3) α-allyl-ω-acetyl- (poly) oxyethylene, 4) α-allyl-ω-acetyl- (poly) oxyethylene (poly) oxypropylene, and the like.
第１工程で用いるラジカル重合性単量体混合物は、無水マレイン酸と化１で示される単量体とを合計で９５モル％以上含有するものであり、言い換えれば、他のラジカル重合性単量体を５モル％以下の範囲内で含有することができるものである。かかる他のラジカル重合性単量体としては、スチレン、酢酸ビニル、アクリル酸、アクリル酸塩、アクリル酸アルキルエステル、メタクリル酸メチルエステル、（メタ）アリルスルホン酸、（メタ）アリルスルホン酸塩等が挙げられる。 The radical polymerizable monomer mixture used in the first step contains a total of 95 mol% or more of maleic anhydride and the monomer represented by Chemical Formula 1, in other words, other radical polymerizable monomer. The body can be contained within a range of 5 mol% or less. Such other radical polymerizable monomers include styrene, vinyl acetate, acrylic acid, acrylate, alkyl acrylate, methyl methacrylate, (meth) allyl sulfonic acid, (meth) allyl sulfonate, and the like. Can be mentioned.
第１工程では、以上説明したラジカル重合性単量体混合物にラジカル開始剤を加えてラジカル重合させ、質量平均分子量５０００〜７００００、好ましくは１００００〜５００００の共重合体を得る。本発明において、質量平均分子量は、ＧＰＣ法によるプルラン換算の質量平均分子量を意味する。前記のラジカル重合は、例えばラジカル重合性単量体混合物を反応缶に仕込み、窒素雰囲気下にてラジカル開始剤を加え、６０〜９０℃で５〜１０時間ラジカル重合反応させる方法である。ラジカル重合反応を制御して所望の共重合体を得るためには、ラジカル開始剤やラジカル連鎖移動剤の種類及び使用量、重合温度、重合時間等を適宜選択する。ラジカル開始剤としては、アゾビスイソブチロニトリル、２，２’−アゾビス（４−メトキシ２，４−ジメチルバレロニトリル）等のアゾ系開始剤、過酸化ベンゾイル、過酸化ラウロイル、クメンハイドロパーオキサイド等の非水系開始剤等が挙げられる。 In the first step, a radical initiator is added to the radical polymerizable monomer mixture described above for radical polymerization to obtain a copolymer having a mass average molecular weight of 5000 to 70000, preferably 10,000 to 50000. In the present invention, the weight average molecular weight means the weight average molecular weight in terms of pullulan according to the GPC method. The radical polymerization is a method in which, for example, a radical polymerizable monomer mixture is charged into a reaction vessel, a radical initiator is added in a nitrogen atmosphere, and a radical polymerization reaction is performed at 60 to 90 ° C. for 5 to 10 hours. In order to control the radical polymerization reaction to obtain a desired copolymer, the type and amount of radical initiator and radical chain transfer agent, polymerization temperature, polymerization time, etc. are appropriately selected. As radical initiators, azo initiators such as azobisisobutyronitrile, 2,2′-azobis (4-methoxy2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide And non-aqueous initiators.
第２工程は、第１工程で得た共重合体に、化２で示されるポリエーテル化合物をグラフト反応してグラフト共重合体を得る工程である。 The second step is a step of obtaining a graft copolymer by graft reaction of the polyether compound represented by Chemical Formula 2 to the copolymer obtained in the first step.
化２で示されるポリエーテル化合物において、化２中のＲ２としては、１）オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ペンタデシル基、ヘキサデシル基、オクタデシル基、イソアクタデシル基、ドゥオデシル基等の炭素数８〜２０の飽和脂肪族炭化水素基、２）デセニル基、テトラデセニル基、オクタデセニル基、エイコセニル基等の炭素数８〜２０の不飽和脂肪族炭化水素基が挙げられるが、なかでも炭素数１０〜２０の脂肪族炭化水素基が好ましく、炭素数１２〜１８の不飽和脂肪族炭化水素基がより好ましい。 In the polyether compound represented by Chemical formula 2, R 2 in Chemical formula 2 is as follows: 1) Octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, octadecyl group 8) a saturated aliphatic hydrocarbon group having 8 to 20 carbon atoms such as isoactadecyl group and doodecyl group, and 2) an unsaturated aliphatic hydrocarbon group having 8 to 20 carbon atoms such as decenyl group, tetradecenyl group, octadecenyl group and eicocenyl group. Among them, an aliphatic hydrocarbon group having 10 to 20 carbon atoms is preferable, and an unsaturated aliphatic hydrocarbon group having 12 to 18 carbon atoms is more preferable.
化２で示されるポリエーテル化合物において、化２中のＡ２は、分子中にオキシエチレン単位とオキシプロピレン単位とで構成され且つ該オキシエチレン単位と該オキシプロピレン単位とがブロック状に結合したポリオキシアルキレン基を有するポリアルキレングリコールから全ての水酸基を除いた残基である。Ａ２を構成するオキシエチレン単位及びオキシプロピレン単位の繰り返し数は合計で２３〜７０とするが、２５〜６０とするのが好ましい。以上説明した化２で示されるポリエーテル化合物は、炭素数８〜２０の脂肪族アルコール１モルに対してエチレンオキサイド及びプロピレンオキサイドを合計で２３〜７０モルの割合でブロック状に付加反応させる公知の方法で合成できる。 In the polyether compound represented by Chemical Formula 2, A 2 in Chemical Formula 2 is a polysiloxane composed of oxyethylene units and oxypropylene units in the molecule and having the oxyethylene units and the oxypropylene units bonded in a block form. A residue obtained by removing all hydroxyl groups from a polyalkylene glycol having an oxyalkylene group. The total number of repeating oxyethylene units and oxypropylene units constituting A 2 is 23 to 70, but is preferably 25 to 60. The polyether compound represented by the chemical formula 2 described above is a known compound that undergoes addition reaction of ethylene oxide and propylene oxide in a block form at a ratio of 23 to 70 mol in total with respect to 1 mol of an aliphatic alcohol having 8 to 20 carbon atoms. It can be synthesized by the method.
第２工程では、第１工程で得た共重合体１００質量部当たり、以上説明したような化２で示されるポリエーテル化合物を０．０５〜５質量部の割合、好ましくは０．２〜４質量部の割合でグラフト反応してグラフト共重合体を得る。かかるグラフト反応には、公知の方法を適用できる。例えば、第１工程で得た共重合体と、化２で示されるポリエーテル化合物と、塩基性触媒とを反応缶に仕込み、窒素雰囲気とした後、１００℃で４〜６時間グラフト反応させ、グラフト共重合体を得ることができる。ここで、塩基性触媒としては、酸無水物とアルコールとの開環エステル反応に用いる公知のものを使用できるが、なかでもアミン触媒が好ましく、低級アルキルアミンがより好ましい。 In the second step, the ratio of 0.05 to 5 parts by mass, preferably 0.2 to 4 parts, of the polyether compound represented by Chemical Formula 2 as described above per 100 parts by mass of the copolymer obtained in the first step. Graft reaction is carried out at a ratio of parts by mass to obtain a graft copolymer. A known method can be applied to the graft reaction. For example, the copolymer obtained in the first step, the polyether compound represented by Chemical Formula 2, and a basic catalyst are charged into a reaction can, and after a nitrogen atmosphere, the graft reaction is performed at 100 ° C. for 4 to 6 hours. A graft copolymer can be obtained. Here, as the basic catalyst, a known catalyst used in the ring-opening ester reaction between an acid anhydride and an alcohol can be used. Among them, an amine catalyst is preferable, and a lower alkylamine is more preferable.
第３工程は、第２工程で得たグラフト共重合体を、塩基性化合物で部分中和又は完全中和処理して、グラフト共重合体の塩を得る工程である。かかる塩基性化合物としては、１）水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物、２）水酸化カルシウム、水酸化マグネシウム等のアルカリ土類金属水酸化物、３）アンモニア、トリエタノールアミン等のアミン類が挙げられるが、アルカリ金属水酸化物が好ましい。 The third step is a step in which the graft copolymer obtained in the second step is partially or completely neutralized with a basic compound to obtain a graft copolymer salt. Examples of such basic compounds are 1) alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, 2) alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, 3) ammonia, triethanolamine. Amines such as alkali metal hydroxides are preferred.
本発明の方法で用いる混和剤のＢ成分は、化３で示される有機アミンエチレンオキサイド付加物である。化３で示される有機アミンエチレンオキサイド付加物は、炭素数８〜２０の一級アルキル又はアルケニルアミン１モルに対し、エチレンオキサイドを４〜１２モルの割合で付加したものである。 The B component of the admixture used in the method of the present invention is an organic amine ethylene oxide adduct represented by Chemical Formula 3. The organic amine ethylene oxide adduct represented by Chemical Formula 3 is obtained by adding ethylene oxide at a ratio of 4 to 12 moles with respect to 1 mole of primary alkyl or alkenylamine having 8 to 20 carbon atoms.
本発明の方法で用いる混和剤のＣ成分は、化４で示される有機リン酸エステルである。化４で示される有機リン酸エステルは炭素数８〜２０の脂肪族炭化水素基、好ましくは炭素数１０〜１６の脂肪族炭化水素基を有する有機リン酸エステルである。かかる有機リン酸エステルには、化４中のＭ１及びＭ２が水素原子である場合の有機リン酸モノエステル、該有機リン酸モノエステルのアルカリ金属塩、該有機リン酸モノエステルのアルカリ土類金属塩、該有機リン酸モノエステルのアンモニウム塩、該有機リン酸モノエステルの有機アミン塩が含まれるが、Ｃ成分の有機リン酸エステルとしては、前記のような有機リン酸モノエステルのアルカリ金属塩が好ましい。 The C component of the admixture used in the method of the present invention is an organic phosphate represented by Chemical Formula 4. The organic phosphate ester represented by Chemical Formula 4 is an organic phosphate ester having an aliphatic hydrocarbon group having 8 to 20 carbon atoms, preferably an aliphatic hydrocarbon group having 10 to 16 carbon atoms. Such organophosphates include organophosphate monoesters when M 1 and M 2 in Chemical Formula 4 are hydrogen atoms, alkali metal salts of the organophosphate monoesters, alkaline earths of the organophosphate monoesters Metal salt, ammonium salt of organic phosphoric acid monoester, organic amine salt of organic phosphoric acid monoester, and organic phosphoric acid ester of component C includes alkali of organic phosphoric acid monoester as described above Metal salts are preferred.
化４で示される有機リン酸エステルは公知の方法で合成できる。例えば、炭素数８〜２０の高級アルコールに無水リン酸を反応させた後、有機溶媒を用いて再結晶することにより、化４中のＭ１及びＭ２が水素である場合の有機リン酸モノエステルを合成でき、またこの有機リン酸モノエステルをアルカリ金属水酸化物で中和することにより、有機リン酸モノエステルアルカリ金属塩を合成できる。 The organophosphate ester represented by Chemical Formula 4 can be synthesized by a known method. For example, after reacting a higher alcohol having 8 to 20 carbon atoms with phosphoric anhydride and then recrystallizing with an organic solvent, the organic phosphoric acid mono-mono when M 1 and M 2 in Chemical Formula 4 are hydrogen. An ester can be synthesized, and an organic phosphoric acid monoester alkali metal salt can be synthesized by neutralizing the organic phosphoric acid monoester with an alkali metal hydroxide.
本発明の方法で用いる混和剤は、以上説明したようなＡ成分を６２〜８９質量％、Ｂ成分を１０〜３５質量％及びＣ成分を０．３〜３質量％含有することとなり、且つこれらの３成分を合計で１００質量％となるよう含有することとなるものである。各成分の含有割合がこれらの範囲から外れることになると、そのような混和剤を用いて調製したコンクリートは前記した所期の多機能を同時に備えるのが難しくなる。 The admixture used in the method of the present invention contains 62 to 89% by mass of the A component as described above, 10 to 35% by mass of the B component, and 0.3 to 3% by mass of the C component. These three components are contained so as to be 100% by mass in total. When the content ratio of each component deviates from these ranges, it becomes difficult for the concrete prepared using such an admixture to simultaneously have the desired multi-function described above.
本発明の方法では、セメント、未燃カーボンを８〜２５質量％の高濃度で含有するフライアッシュ、細骨材、粗骨材、水及び以上説明したような混和剤を練り混ぜ、コンクリートを調製するが、この際に混和剤は、セメント１００質量部当たり、０．１〜３質量部、好ましくは０．１５〜２質量部の割合となるよう用いる。混和剤の使用量がこれより少ないと、調製したコンクリートは流動性が悪く、また前記した所期の多機能を同時に備えるのが難しくなる。逆に混和剤の使用量をこれより多くしても、それに見合うだけの効果が得られない。 In the method of the present invention, cement, fly ash containing fine unburned carbon at a high concentration of 8 to 25% by mass, fine aggregate, coarse aggregate, water and an admixture as described above are mixed to prepare concrete. However, in this case, the admixture is used in an amount of 0.1 to 3 parts by mass, preferably 0.15 to 2 parts by mass, per 100 parts by mass of cement. When the amount of the admixture used is less than this, the prepared concrete has poor fluidity, and it becomes difficult to simultaneously provide the desired multi-function described above. On the contrary, even if the amount of the admixture used is larger than this, an effect commensurate with it cannot be obtained.
混和剤を添加する方法は特に制限されない。混和剤として、各成分の所定量を予め混合しておいたものを用いてもよいし、又は各成分の所定量を別々に用いてもよい。通常は、セメント、未燃カーボンを高濃度で含有するフライアッシュ、細骨材及び粗骨材をミキサーで空練りする一方で、別に各成分の所定量を予め混合しておいた混和剤を練り混ぜ水で希釈し、しかる後に双方を練り混ぜる方法が好ましい。 The method for adding the admixture is not particularly limited. As the admixture, a premixed predetermined amount of each component may be used, or a predetermined amount of each component may be used separately. Normally, cement, fly ash containing a high concentration of unburned carbon, fine aggregate, and coarse aggregate are kneaded with a mixer, while kneading a premixed mixture of each component in advance. A method of diluting with mixed water and then kneading both is preferable.
本発明の方法において、セメントとしては、普通セメント、早強セメント、中庸熱セメント、耐硫酸塩セメント等の各種ポルトランドセメントが挙げられるが、普通セメントが好ましい。またセメントの使用量は特に制限されないが、その単位量が２００〜４００kg／ｍ３となるよう用いるのが初期強度を充分に確保するうえで好ましい。 In the method of the present invention, examples of the cement include various portland cements such as ordinary cement, early-strength cement, intermediate heat cement, sulfate resistant cement, and ordinary cement is preferable. The amount of cement used is not particularly limited, but is preferably used so that the unit amount is 200 to 400 kg / m 3 in order to sufficiently secure the initial strength.
本発明の方法において、フライアッシュとしては、未燃カーボンを８〜２５質量％の高濃度で含有するもの、例えば前記したような石炭火力発電所から発生する石炭灰を用いる。本発明の効果は、特に未燃カーボンを８〜２５質量％の高濃度で含有するフライアッシュを用いてコンクリートを調製する場合に顕著に発揮される。かかるフライアッシュは、その単位量が４０〜１００kg／ｍ３となるように用いる。得られる硬化体の初期強度を充分に確保するためである。 In the method of the present invention, as fly ash, one containing unburned carbon at a high concentration of 8 to 25% by mass, for example, coal ash generated from a coal-fired power plant as described above is used. The effects of the present invention are particularly prominent when concrete is prepared using fly ash containing unburned carbon at a high concentration of 8 to 25% by mass. Such fly ash is used so that the unit amount is 40 to 100 kg / m 3 . This is for sufficiently securing the initial strength of the obtained cured product.
本発明の方法において、細骨材としては、川砂、山砂、海砂、砕砂等が挙げられ、また粗骨材としては、川砂利、砕石、軽量骨材等が挙げられる。 In the method of the present invention, examples of the fine aggregate include river sand, mountain sand, sea sand, and crushed sand, and examples of the coarse aggregate include river gravel, crushed stone, and lightweight aggregate.
本発明の方法において、得られる硬化体に凍結融解作用に対する強い抵抗性を発揮させるためには、調製するコンクリートはその連行空気量を３〜６容量％にしたＡＥコンクリートとするのが好ましい。かかる連行空気量の調製は、前記したＡ成分、Ｂ成分及びＣ成分のうちで、連行空気量に影響の大きいＣ成分の含有割合を調節することによって調製することができる。 In the method of the present invention, it is preferable that the concrete to be prepared is AE concrete having an entrained air amount of 3 to 6% by volume in order to make the obtained hardened body exhibit strong resistance to freezing and thawing. Such an entrained air amount can be prepared by adjusting the content ratio of the C component having a large influence on the entrained air amount among the A component, the B component, and the C component described above.
本発明の方法では、以上説明したように、セメント、未燃カーボンを８〜２５質量％の高濃度で含有するフライアッシュ、細骨材、粗骨材、水及び混和剤を練り混ぜてコンクリートを調製するが、この際、本発明の効果を損なわない範囲内で、必要に応じて前記した混和剤以外に、凝結促進剤、凝結遅延剤、防水剤、防腐剤、防錆剤等の他の添加剤を併用することができる。 In the method of the present invention, as described above, cement, fly ash, fine aggregate, coarse aggregate, water and an admixture containing 8 to 25% by mass of unburned carbon are mixed to produce concrete. In this case, within the range not impairing the effect of the present invention, in addition to the above-mentioned admixture, other additives such as a setting accelerator, a setting retarder, a waterproofing agent, an antiseptic, a rusting agent, etc. Additives can be used in combination.
以上説明した本発明の方法によると、未燃カーボンを８〜２５質量％の高濃度で含有するフライアッシュを用いる場合であっても、１）所要の流動性を得るための高性能減水剤乃至高性能ＡＥ減水剤の使用量の増大を抑え、２）流動性の経時的な低下（スランプロス）を防止し、３）所要の連行空気量を得るためのＡＥ剤の使用量の増大を抑えて、４）得られる硬化体に凍結融解作用に対する強い抵抗性を与え、５）得られる硬化体に充分な強度を与えるという以上の１）〜５）の機能を同時に有するコンクリートを調製することができるという効果がある。 According to the method of the present invention described above, even when fly ash containing unburned carbon at a high concentration of 8 to 25% by mass is used, 1) a high-performance water reducing agent for obtaining required fluidity Suppress the increase in the amount of high-performance AE water reducing agent used, 2) prevent the fluidity from decreasing over time (slump loss), and 3) suppress the increase in the amount of AE agent used to obtain the required amount of entrained air. 4) giving the hardened body obtained strong resistance to freeze-thaw action, and 5) preparing concrete having the functions 1) to 5) at the same time of giving sufficient strength to the obtained hardened body. There is an effect that can be done.
以下、本発明の構成及び効果をより具体的にするため、実施例等を挙げるが、本発明が該実施例に限定されるというものではない。なお、以下の実施例等において、別に記載しない限り、％は質量％を、また部は質量部を意味する。 Hereinafter, in order to make the configuration and effects of the present invention more specific, examples and the like will be described. However, the present invention is not limited to the examples. In the following examples and the like, unless otherwise indicated,% means mass%, and part means mass part.
試験区分１（混和剤の調製に用いる各成分の合成）
・Ａ成分として用いるグラフト共重合体（ａ−１）の合成
無水マレイン酸１２０ｇ（１．２モル）及びα−アリル−ω−メチル−ポリ（ｎ＝３３）オキシエチレン１５２４ｇ（１．０モル）を反応容器に仕込み、攪拌しながら均一に溶解した後、雰囲気を窒素置換した。反応系の温度を温水浴にて７０℃に保ち、アゾビスイソブチロニトリル３ｇを投入して、ラジカル重合反応を開始した。更にアゾビスイソブチロニトリル５ｇを分割投入し、ラジカル重合反応を４時間継続して反応を完結した。得られた共重合体を分析したところ、原料換算で、無水マレイン酸／α−アリル−ω−メチル−ポリオキシエチレン（ｎ＝３３）＝５５／４５（モル比）の割合で有する、質量平均分子量２６０００の共重合体であった。次いで、この共重合体１００ｇと、オレイルアルコール１モルに対してエチレンオキサイド６モル及びプロピレンオキサイド４３モルの割合でブロック状に付加したα−オレイル−ω−ヒドロキシ−ポリオキシエチレン（ｎ＝６）ポリオキシプロピレン（ｍ＝４３）２．８ｇと、触媒としてトリブチルアミン２ｇとを反応容器に仕込み、雰囲気を窒素置換した。反応系の温度を攪拌しながら９０℃に保ち、４時間グラフト反応を続け、グラフト共重合体（ａ−１）を得た。
Test Category 1 (Synthesis of each component used for preparation of admixture)
Synthesis of graft copolymer (a-1) used as component A Maleic anhydride 120 g (1.2 mol) and α-allyl-ω-methyl-poly (n = 33) oxyethylene 1524 g (1.0 mol) Was uniformly dissolved while stirring, and the atmosphere was replaced with nitrogen. The temperature of the reaction system was kept at 70 ° C. in a warm water bath, and 3 g of azobisisobutyronitrile was added to initiate radical polymerization reaction. Further, 5 g of azobisisobutyronitrile was added in portions, and the radical polymerization reaction was continued for 4 hours to complete the reaction. When the obtained copolymer was analyzed, it was a mass average having a ratio of maleic anhydride / α-allyl-ω-methyl-polyoxyethylene (n = 33) = 55/45 (molar ratio) in terms of raw materials. The copolymer had a molecular weight of 26000. Next, 100 g of this copolymer and α-oleyl-ω-hydroxy-polyoxyethylene (n = 6) poly added in a block form at a ratio of 6 mol of ethylene oxide and 43 mol of propylene oxide to 1 mol of oleyl alcohol. 2.8 g of oxypropylene (m = 43) and 2 g of tributylamine as a catalyst were charged into a reaction vessel, and the atmosphere was replaced with nitrogen. While maintaining the temperature of the reaction system at 90 ° C., the graft reaction was continued for 4 hours to obtain a graft copolymer (a-1).
・Ａ成分として用いるグラフト共重合体（ａ−２）〜（ａ−４）及び（ｒ−１）〜（ｒ−５）の合成
グラフト共重合体（ａ−１）の合成と同様にして、グラフト共重合体（ａ−２）〜（ａ−４）及び（ｒ−１）〜（ｒ−５）を合成した。
Synthesis of graft copolymers (a-2) to (a-4) and (r-1) to (r-5) used as component A In the same manner as the synthesis of graft copolymer (a-1), Graft copolymers (a-2) to (a-4) and (r-1) to (r-5) were synthesized.
・Ａ成分として用いるグラフト共重合体の塩（ａ−５）の合成
前記のグラフト共重合体（ａ−１）の４０％水溶液２５０ｇを反応容器に仕込み、攪拌しながら３０％水酸化ナトリウム水溶液１０ｇを徐々に加えて、部分中和処理を行ない、グラフト共重合体の部分中和塩（ａ−５）を得た。グラフト共重合体の部分中和塩（ａ−５）の中和度は５０％であった。
-Synthesis of graft copolymer salt (a-5) used as component A 250 g of 40% aqueous solution of the above graft copolymer (a-1) was charged into a reaction vessel, and 10 g of 30% aqueous sodium hydroxide solution was stirred. Was gradually added to carry out a partial neutralization treatment to obtain a partially neutralized salt (a-5) of the graft copolymer. The degree of neutralization of the partially neutralized salt (a-5) of the graft copolymer was 50%.
・グラフト共重合体の塩（ａ−６）の合成
前記のグラフト共重合体（ａ−３）の４０％水溶液２５０ｇを反応容器に仕込み、攪拌しながら３０％水酸化ナトリウム水溶液４３ｇを徐々に加えて、完全中和処理を行ない、グラフト共重合体の塩（ａ−６）を得た。以上で合成した各グラフト共重合体等の内容を表１にまとめて示した。
-Synthesis of graft copolymer salt (a-6) A reaction vessel was charged with 250 g of a 40% aqueous solution of the graft copolymer (a-3), and 43 g of a 30% aqueous sodium hydroxide solution was gradually added while stirring. Then, a complete neutralization treatment was performed to obtain a graft copolymer salt (a-6). The contents of each of the graft copolymers synthesized above are summarized in Table 1.
表１において、
＊１：第１工程で得た共重合体１００部に対してグラフト反応させた化２で示されるポリエーテル化合物等の部
＊２：水酸化ナトリウム
ｄ−１：α−アリル−ω−メチル−ポリオキシエチレン（ｎ＝３３）
ｄ−２：α−アリル−ω−メチル−ポリオキシエチレン（ｎ＝７０）
ｄ−３：α−アリル−ω−アセチル−ポリオキシエチレン（ｎ＝１０）
ｄ−４：α−アリル−ω−アセチル−ポリオキシエチレン（ｎ＝５０）
ｅ−１：スチレン
ｆ−１：α−オレイル−ω−ヒドロキシ−ポリオキシエチレン（ｎ＝６）−ポリオキシプロピレン（ｍ＝４３）
ｆ−２：α−ラウリル−ω−ヒドロキシ−ポリオキシエチレン（ｎ＝３）−ポリオキシプロピレン（ｍ＝３２）
ｄｒ−１：α−アリル−ω−アセチル−ポリオキシエチレン（ｎ＝１６０）
ｆｒ−１：α−ラウリル−ω−ヒドロキシ−ポリオキシエチレン（ｎ＝１５）
ｆｒ−２：α−オレイル−ω−ヒドロキシ−ポリオキシエチレン（ｎ＝５０）
In Table 1,
* 1: Part of the polyether compound or the like represented by Chemical Formula 2 grafted to 100 parts of the copolymer obtained in the first step * 2: Sodium hydroxide d-1: α-allyl-ω-methyl- Polyoxyethylene (n = 33)
d-2: α-allyl-ω-methyl-polyoxyethylene (n = 70)
d-3: α-allyl-ω-acetyl-polyoxyethylene (n = 10)
d-4: α-allyl-ω-acetyl-polyoxyethylene (n = 50)
e-1: Styrene f-1: α-Oleyl-ω-hydroxy-polyoxyethylene (n = 6) -polyoxypropylene (m = 43)
f-2: α-lauryl-ω-hydroxy-polyoxyethylene (n = 3) -polyoxypropylene (m = 32)
dr-1: α-allyl-ω-acetyl-polyoxyethylene (n = 160)
fr-1: α-lauryl-ω-hydroxy-polyoxyethylene (n = 15)
fr-2: α-oleyl-ω-hydroxy-polyoxyethylene (n = 50)
試験区分２（混和剤の調製）
・混和剤（Ｐ−１）の調製
Ａ成分として試験区分１で合成したグラフト共重合体（ａ−１）７５部、Ｂ成分としてラウリルアミンエチレンオキサイド付加物（ｂ−１）２３部及びＣ成分としてオクチルリン酸モノエステルカリウム塩（ｃ−１）２部を混合して混和剤（Ｐ−１）を調製した。
Test Category 2 (Preparation of admixture)
-Preparation of admixture (P-1) 75 parts of graft copolymer (a-1) synthesized in Test Category 1 as component A, 23 parts of laurylamine ethylene oxide adduct (b-1) as component B, and component C As an admixture (P-1), 2 parts of octyl phosphate monoester potassium salt (c-1) was mixed.
混和剤（Ｐ−１）〜（Ｐ−１２）及び（Ｒ−１）〜（Ｒ−１４）の調製
混和剤（Ｐ−１）と同様にして、混和剤（Ｐ−１）〜（Ｐ−１２）及び（Ｒ−１）〜（Ｒ−１４）を調製した。以上で調製した各混和剤の内容を表２にまとめて示した。
Preparation of Admixtures (P-1) to (P-12) and (R-1) to (R-14) In the same manner as Admixture (P-1), Admixtures (P-1) to (P-) 12) and (R-1) to (R-14) were prepared. The contents of the admixtures prepared above are summarized in Table 2.
表２において、
Ｐ−１〜Ｐ−１２：実施例で用いる混和剤
Ｒ−１〜Ｒ−１４：比較例で用いる混和剤
ａ−１〜ａ−６，ｒ−１〜ｒ−５：試験区分１で合成したグラフト共重合体等
ｂ−１：ラウリルアミンのエチレンオキサイド（４モル）付加物
ｂ−２：ラウリルアミンのエチレンオキサイド（８モル）付加物
ｂ−３：ステアリルアミンのエチレンオキサイド（１２モル）付加物
ｃ−１：オクチルリン酸モノエステルのカリウム塩
ｃ−２：テトラデシルリン酸モノエステルのナトリウム塩
ｃ−３：ドデシルリン酸モノエステルのナトリウム塩
＊３：ロジン塩系ＡＥ剤（竹本油脂社製の商品名ＡＥ３００）
＊４：ポリカルボン酸系高性能ＡＥ減水剤（竹本油脂社製の商品名チューポールＨＰ−８）
＊５：ナフタレンスルホン酸系高性能減水剤（竹本油脂社製の商品名ポールファイン５１０ＡＮ）
In Table 2,
P-1 to P-12: Admixtures used in Examples R-1 to R-14: Admixtures used in Comparative Examples a-1 to a-6, r-1 to r-5: synthesized in Test Category 1 Graft copolymer etc. b-1: Ethylene oxide (4 mol) adduct of laurylamine b-2: Ethylene oxide (8 mol) adduct of laurylamine b-3: Ethylene oxide (12 mol) adduct of stearylamine c-1: Potassium salt of octyl phosphate monoester c-2: Sodium salt of tetradecyl phosphate monoester c-3: Sodium salt of dodecyl phosphate monoester * 3: Rosin salt AE agent (manufactured by Takemoto Yushi Co., Ltd.) Product name AE300)
* 4: Polycarboxylic acid-based high-performance AE water reducing agent (Brand name Tupol HP-8 manufactured by Takemoto Yushi Co., Ltd.)
* 5: Naphthalenesulfonic acid-based high-performance water reducing agent (trade name Pole Fine 510AN manufactured by Takemoto Yushi Co., Ltd.)
試験区分３（未燃カーボンを高濃度で含有するフライアッシュを用いたコンクリートの調製及び評価）
・実施例１〜１５及び比較例１〜１６
表３に記載した配合条件で、５０Ｌのパン型強制練りミキサーに普通ポルトランドセメント（密度＝３．１６、ブレーン値３３００）、フライアッシュ（中国電力水島火力発電所産、密度＝２．１２ｇ／cm３、ブレーン値３６５０、未燃カーボン量１２．５％）、細骨材（大井川水系砂、密度＝２．５８ｇ／cm３）及び粗骨材（岡崎産砕石、密度＝２．６８ｇ／cm３）を順次投入して１５秒間空練りした。次いで、目標スランプが１８±１cm、目標空気量が４〜５％の範囲となるよう、試験区分２で調製した混和剤を水と共に投入して練り混ぜ、各例のコンクリートを調製した。混和剤の使用量と共に、各例で調製したコンクリートの内容を表４にまとめて示した。
Test category 3 (Preparation and evaluation of concrete using fly ash containing unburned carbon in high concentration)
-Examples 1-15 and Comparative Examples 1-16
Under the compounding conditions shown in Table 3, a 50 L pan-type forced kneader was mixed with ordinary Portland cement (density = 3.16, brain value 3300), fly ash (produced by Chugoku Electric Power Mizushima Thermal Power Plant, density = 2.12 g / cm 3 , Blaine value 3650, unburned carbon amount 12.5%), fine aggregate (Oikawa water sand, density = 2.58 g / cm 3 ) and coarse aggregate (Okazaki crushed stone, density = 2.68 g / cm 3 ) Were put in order and kneaded for 15 seconds. Next, the admixture prepared in Test Category 2 was added together with water and kneaded so that the target slump was 18 ± 1 cm and the target air amount was in the range of 4 to 5%, thereby preparing concrete for each example. Table 4 summarizes the contents of the concrete prepared in each example, along with the amount of admixture used.
表３において、
＊６：粉体はセメントとフライアッシュの合計量
In Table 3,
* 6: Powder is the total amount of cement and fly ash
・調製したコンクリートの物性評価
各例で調製したコンクリートについて、空気量、スランプ、スランプ残存率を下記のように求め、結果を表４にまとめて示した。また各例で調製したコンクリートの硬化体について、圧縮強度及び凍結融解抵抗性指数を下記のように求め、結果を表５にまとめて示した。
-Physical property evaluation of prepared concrete About the concrete prepared in each case, the air content, slump, and slump residual rate were calculated | required as follows, and the result was put together in Table 4 and shown. Moreover, about the hardened | cured material of the concrete prepared in each example, the compressive strength and the freeze-thaw resistance index were calculated | required as follows, and the result was put together in Table 5 and shown.
空気量：練り混ぜ直後のコンクリート及び更に９０分間静置後のコンクリートについて、ＪＩＳ−Ａ１１２８に準拠して測定した。
スランプ：空気量の測定と同時に、ＪＩＳ−Ａ１１０１に準拠して測定した。
スランプ残存率：（９０分間静置後のスランプ／練り混ぜ直後のスランプ）×１００で求めた。
・凍結融解耐久性指数：各例のコンクリートについて、ＪＩＳ−Ａ１１２９の付属書２に準拠して測定した値を用い、ＡＳＴＭ−Ｃ６６６−７５の耐久性指数で計算した数値を示した。この数値は、最大値が１００で、１００に近いほど、凍結融解に対する抵抗性が優れていることを示す。
・圧縮強度：各例のコンクリートについて、ＪＩＳ−Ａ１１０８に準拠し、材齢７日と材齢２８日で測定した。
Air amount: Measured in accordance with JIS-A1128 for concrete immediately after mixing and concrete after standing for 90 minutes.
Slump: Measured according to JIS-A1101 simultaneously with the measurement of the air amount.
Slump residual ratio: (slump after standing for 90 minutes / slump just after mixing) × 100.
-Freeze-thaw durability index: About the concrete of each example, the numerical value calculated by the durability index of ASTM-C666-75 was shown using the value measured based on the appendix 2 of JIS-A1129. This numerical value indicates that the maximum value is 100, and the closer to 100, the better the resistance to freezing and thawing.
Compressive strength: The concrete of each example was measured at a material age of 7 days and a material age of 28 days in accordance with JIS-A1108.
表４において、
＊７：セメント１００部に対する混和剤の使用部
In Table 4,
* 7: Admixture used for 100 parts of cement
Claims (5)
Ａ成分：１）下記の第１工程及び第２工程を経て得られるグラフト共重合体、２）更に下記の第３工程を経て得られるグラフト共重合体の塩、以上の１）及び２）から選ばれる一つ又は二つ以上。
第１工程：無水マレイン酸と下記の化１で示される単量体とを合計で９５モル％以上含有し且つ無水マレイン酸／該単量体＝５０／５０〜６５／３５（モル比）の割合で含有するラジカル重合性単量体混合物を溶剤の非存在下でラジカル重合して、質量平均分子量５０００〜７００００の共重合体を得る工程。
第２工程：第１工程で得た共重合体１００質量部当たり、下記の化２で示されるポリエーテル化合物を０．０５〜５質量部の割合でグラフト反応して、グラフト共重合体を得る工程。
第３工程：第２工程で得たグラフト共重合体を、塩基性化合物で部分中和又は完全中和処理して、グラフト共重合体の塩を得る工程。
Ｒ１：メチル基又はアセチル基
Ｒ２：炭素数８〜２０の脂肪族炭化水素基
Ａ１：分子中に１〜１５０個のオキシエチレン単位のみ又は合計２〜１５０個のオキシエチレン単位とオキシプロピレン単位とで構成された（ポリ）オキシアルキレン基を有する（ポリ）アルキレングリコールから全ての水酸基を除いた残基
Ａ２：分子中に合計２３〜７０個のオキシエチレン単位とオキシプロピレン単位とで構成され且つ該オキシエチレン単位と該オキシプロピレン単位とがブロック状に結合したポリオキシアルキレン基を有するポリアルキレングリコールから全ての水酸基を除いた残基）
Ｂ成分：下記の化３で示される有機アミンエチレンオキサイド付加物
Ｒ３：炭素数８〜２０の脂肪族炭化水素基
ｎ，ｍ：１以上の整数であって、且つ４≦ｎ＋ｍ≦１２を満足する整数）
Ｃ成分：下記の化４で示される有機リン酸エステル
Ｒ４：炭素数８〜２０の脂肪族炭化水素基
Ｍ１，Ｍ２：水素原子、アルカリ金属、アルカリ土類金属、アンモニウム又は有機アミン） Upon unburned carbon to prepare a concrete with a fly ash containing a high concentration of 8 to 25 wt%, A components of such fly ash weight unit used to be a 40~100kg / m 3, also under Symbol the 62-89 wt%, 10-35 wt% of component B described below and C the following ingredients will be contained in a proportion of 0.3 to 3 wt%, and 100% by weight of these three components in total A method for preparing concrete, wherein the admixture to be contained is used at a ratio of 0.1 to 3 parts by mass per 100 parts by mass of cement.
Component A: 1) Graft copolymer obtained through the following first step and second step, 2) Graft copolymer salt obtained through the following third step, from the above 1) and 2) One or more selected.
First step: maleic anhydride and monomers represented by the following chemical formula 1 are contained in a total of 95 mol% or more and maleic anhydride / the monomer = 50/50 to 65/35 (molar ratio). A step of radically polymerizing a radically polymerizable monomer mixture contained in a proportion in the absence of a solvent to obtain a copolymer having a mass average molecular weight of 5000 to 70000.
Second step: A graft copolymer is obtained by graft-reacting a polyether compound represented by the following chemical formula 2 at a ratio of 0.05 to 5 parts by mass per 100 parts by mass of the copolymer obtained in the first step. Process.
Third step: A step of partially or completely neutralizing the graft copolymer obtained in the second step with a basic compound to obtain a salt of the graft copolymer.
R 1 : Methyl group or acetyl group R 2 : Aliphatic hydrocarbon group having 8 to 20 carbon atoms A 1 : Only 1 to 150 oxyethylene units or 2 to 150 total oxyethylene units and oxypropylene in the molecule Residue obtained by removing all hydroxyl groups from a (poly) alkylene glycol having a (poly) oxyalkylene group composed of units A 2 : composed of a total of 23 to 70 oxyethylene units and oxypropylene units in the molecule And a residue obtained by removing all hydroxyl groups from a polyalkylene glycol having a polyoxyalkylene group in which the oxyethylene unit and the oxypropylene unit are bonded in a block form)
Component B: Organic amine ethylene oxide adduct represented by the following chemical formula 3
R 3 : an aliphatic hydrocarbon group having 8 to 20 carbon atoms, n, m: an integer of 1 or more and an integer satisfying 4 ≦ n + m ≦ 12 )
Component C: Organophosphate represented by the following chemical formula 4
R 4 : aliphatic hydrocarbon group having 8 to 20 carbon atoms M 1 , M 2 : hydrogen atom, alkali metal, alkaline earth metal, ammonium or organic amine)
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