JP2005231949A - Additive for cement - Google Patents
Additive for cement Download PDFInfo
- Publication number
- JP2005231949A JP2005231949A JP2004043412A JP2004043412A JP2005231949A JP 2005231949 A JP2005231949 A JP 2005231949A JP 2004043412 A JP2004043412 A JP 2004043412A JP 2004043412 A JP2004043412 A JP 2004043412A JP 2005231949 A JP2005231949 A JP 2005231949A
- Authority
- JP
- Japan
- Prior art keywords
- group
- cement
- carbon atoms
- weight
- formula
- 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.)
- Granted
Links
- 239000004568 cement Substances 0.000 title claims abstract description 97
- 239000000654 additive Substances 0.000 title claims abstract description 48
- 230000000996 additive effect Effects 0.000 title claims abstract description 45
- 150000001875 compounds Chemical class 0.000 claims abstract description 66
- 239000000203 mixture Substances 0.000 claims abstract description 56
- 125000005702 oxyalkylene group Chemical group 0.000 claims abstract description 41
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 38
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 34
- 229920000570 polyether Polymers 0.000 claims abstract description 34
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 19
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 22
- 229920001577 copolymer Polymers 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 125000006353 oxyethylene group Chemical group 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 12
- 125000002947 alkylene group Chemical group 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 9
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 6
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000001033 ether group Chemical group 0.000 claims description 4
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 4
- 239000012615 aggregate Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims description 3
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 3
- 229920001521 polyalkylene glycol ether Polymers 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims 1
- 239000010802 sludge Substances 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 239000002440 industrial waste Substances 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 23
- 239000004570 mortar (masonry) Substances 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- -1 oxybutylene group Chemical group 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 17
- 229910001873 dinitrogen Inorganic materials 0.000 description 17
- 238000003786 synthesis reaction Methods 0.000 description 17
- 150000003839 salts Chemical class 0.000 description 16
- 238000007664 blowing Methods 0.000 description 13
- 239000004567 concrete Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 150000002430 hydrocarbons Chemical group 0.000 description 11
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 10
- 238000010276 construction Methods 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 230000001603 reducing effect Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 229920002873 Polyethylenimine Polymers 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000005086 pumping Methods 0.000 description 6
- 239000004576 sand Substances 0.000 description 6
- 238000007259 addition reaction Methods 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000011398 Portland cement Substances 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- LAIUFBWHERIJIH-UHFFFAOYSA-N 3-Methylheptane Chemical compound CCCCC(C)CC LAIUFBWHERIJIH-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 235000019738 Limestone Nutrition 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000000853 cresyl group Chemical group C1(=CC=C(C=C1)C)* 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000011372 high-strength concrete Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 239000006028 limestone Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229940050176 methyl chloride Drugs 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 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 2
- 239000006072 paste Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910021487 silica fume Inorganic materials 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-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
- FASUFOTUSHAIHG-UHFFFAOYSA-N 3-methoxyprop-1-ene Chemical compound COCC=C FASUFOTUSHAIHG-UHFFFAOYSA-N 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 229910015900 BF3 Inorganic materials 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
- 229910001369 Brass Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 125000002511 behenyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 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
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000000470 constituent Substances 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
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 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
- 238000001035 drying Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- DUDCYUDPBRJVLG-UHFFFAOYSA-N ethoxyethane methyl 2-methylprop-2-enoate Chemical compound CCOCC.COC(=O)C(C)=C DUDCYUDPBRJVLG-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 239000011440 grout Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000033001 locomotion Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 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
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 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
- 125000001624 naphthyl group Chemical group 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
- 125000001117 oleyl 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])=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
- 150000001451 organic peroxides Chemical class 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
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 229920000333 poly(propyleneimine) Polymers 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000003449 preventive effect Effects 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
- 230000005070 ripening Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 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
- 239000004575 stone Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 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
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
本発明は、特定のポリエーテル系化合物を含有するセメント用添加剤および該セメント用添加剤を含有するセメント組成物に関する。さらに、本発明は、特定のポリエーテル系化合物とポリカルボン酸系化合物を含有するセメント用添加剤および該セメント用添加剤を含有するセメント組成物に関する。 The present invention relates to a cement additive containing a specific polyether compound and a cement composition containing the cement additive. Furthermore, the present invention relates to a cement additive containing a specific polyether compound and a polycarboxylic acid compound, and a cement composition containing the cement additive.
近年、建築物に対して耐震性、高層化などが求められる中で、高強度、超高強度コンクリートの要求が高まり、セメント組成物中の水の使用量を少なくする必要性が増している。
コンクリートに代表されるセメント組成物は基本材料であるセメント、水、骨材をミキサーで練り混ぜて製造し、打ち込み場所まで運搬し、型枠中へ打ち込み、養生してセメントの水和反応による硬化を起こさせて、硬化物を得るが、製造、運搬及び施工に必要な流動性が悪いために、工場で製造されたセメント組成物を運搬する際、セメント組成物がホッパーやバケット等に付着して閉塞したり、工事現場到着時にセメント組成物をアジテータ車から排出することができなかったり、これらが可能な場合でも非常に時間がかかる等の問題点を抱えている。
また、洗浄するにも付着分が多いと非常に時間を要するとともに、洗浄水を多量に必要とし、洗浄廃水やスラッジなどの廃棄物が増えるためその処理に多大な費用と時間がかかるだけでなく、環境への負荷も大きいため問題となる。
一方、セメントの施工は、セメントペースト、モルタルおよびコンクリート等のセメント組成物をポンプを用いて圧送したり、バケットを使用したりすることにより、打設の場所に移動する手法である。最近の大規模コンクリート構造物の施工では、多量のコンクリートを効率よく搬送するため、搬送能力の大きなポンプや径の大きな配管を用いたり、配管を幾つにも分岐させ打設面積を増大させた分岐管工法等の新たなポンプ施工法が開発されている。また、大都市圏でみられるような高層コンクリート建築物等の建造には、高強度発現性や自己充填性等の特殊な性能を有する高強度コンクリート等が使用されている。
しかしながら、前記の新たなポンプ施工法および特殊な性能を有するコンクリートは、ポンプ圧送した場合に、そのコンクリートの配合、環境、施工条件等によっては、配管内に付着して圧送圧が増大し、場合によっては圧送が停滞し、最悪の場合はポンプの閉塞に至るおそれもある。
配管内への付着を防止するために、コンクリート中の粉体量や細骨材量を増加したり、練り混ぜ水量を低減したり、増粘剤を添加する方法が提案されている（特許文献１参照）が、これらの手法は、コンクリートのバケットやホッパーへの付着、ポンプの圧送圧力の上昇、粉体量の増大による硬化体の耐久性の低下などを生じ、十分な改善方法とはなっていない。さらに、コンクリートのポンプ圧送助剤としてポリカルボン酸系分散剤とポリエチレングリコールからなるセメント混和剤が提案されている（例えば、特許文献２参照）が、コンクリートの付着の増大をさせ、アジテータ車から排出する際、もしくはポンプ圧送する際の流動性の低下を十分に防止することができない。
In recent years, demands for high-strength and ultra-high-strength concrete are increasing as buildings are required to have earthquake resistance and high-rise, and the need to reduce the amount of water used in the cement composition is increasing.
Cement compositions represented by concrete are manufactured by mixing basic materials such as cement, water, and aggregate with a mixer, transporting them to the place where they are placed, placing them in a mold, curing them, and hardening them by hydration of the cement. However, since the fluidity required for production, transportation and construction is poor, the cement composition adheres to the hopper, bucket, etc. when transporting the cement composition manufactured in the factory. And when the construction site arrives, the cement composition cannot be discharged from the agitator vehicle, and even when these are possible, it takes time.
In addition, cleaning requires a lot of time if there is a large amount of adhesion, and requires a large amount of cleaning water, which increases the amount of waste such as cleaning wastewater and sludge. This is a problem because the load on the environment is large.
On the other hand, the construction of cement is a method in which a cement composition such as cement paste, mortar and concrete is pumped using a pump or moved to a place of placement by using a bucket. In recent construction of large-scale concrete structures, in order to efficiently transport a large amount of concrete, a pump with a large transport capacity or a pipe with a large diameter is used, or a branch that branches into several pipes to increase the installation area. New pump construction methods such as the pipe method have been developed. In addition, high-strength concrete having special properties such as high-strength development and self-filling properties are used for the construction of high-rise concrete buildings and the like found in metropolitan areas.
However, when the above-mentioned new pump construction method and concrete having special performance are pumped, depending on the concrete mix, environment, construction conditions, etc., the pressure will increase due to adhesion in the pipe. Depending on the situation, the pumping may stagnate, and in the worst case, the pump may be blocked.
In order to prevent adhesion in the pipe, methods have been proposed in which the amount of powder and fine aggregate in concrete is increased, the amount of mixed water is reduced, and a thickener is added (Patent Literature). However, these methods cause adhesion of concrete to buckets and hoppers, an increase in pumping pressure, a decrease in the durability of the cured body due to an increase in the amount of powder, and so on. Not. Furthermore, a cement admixture composed of a polycarboxylic acid-based dispersant and polyethylene glycol has been proposed as a pumping aid for concrete (see, for example, Patent Document 2), which increases the adhesion of concrete and discharges it from an agitator vehicle. It is not possible to sufficiently prevent a decrease in fluidity at the time of pumping or pumping.
本発明の課題は、セメント組成物の施工時の移送に用いるバケットやホッパー等への付着分を低下させ、セメント組成物の作業性を向上させるとともに産業廃棄物である洗浄廃水やスラッジを低減するセメント用添加剤を提供することである。 An object of the present invention is to reduce adhesion to a bucket or hopper used for transfer of a cement composition during construction, to improve the workability of the cement composition and to reduce cleaning wastewater and sludge that are industrial waste. It is to provide an additive for cement.
すなわち、本発明は、以下に示されるものである。
（１）式（１）または式（２）で示されるポリエーテル系化合物（Ａ）を含むセメント用添加剤。
That is, the present invention is as follows.
(1) An additive for cement containing the polyether compound (A) represented by the formula (1) or (2).
（ただし、式中、Ｚは窒素原子に結合した活性水素を４０〜２５０個持つ２０個以上の窒素原子を有する化合物の残基、Ａ1Ｏはその８０モル％以上がオキシエチレン基である炭素数２〜４のオキシアルキレン基の１種または２種以上で、２種以上の場合にはランダム状でもブロック状でも良く、ａはＡ1Ｏで示される炭素数２〜４のオキシアルキレン基の平均付加モル数でａ＝１〜５０であり、Ａ2Ｏはその８０モル％以上が炭素数３または４のオキシアルキレン基である炭素数２〜４のオキシアルキレン基の１種または２種以上で、２種以上の場合にはランダム状でもブロック状でも良く、ｂはＡ2Ｏで示される炭素数２〜４のオキシアルキレン基の平均付加モル数でｂ＝１〜５０であり、ａとｂとの関係が１＜ｂ／ａ≦５０であり、Ｒ1は水素原子または炭素数１〜８の炭化水素基であり、ｎ＝４０〜２５０である。）
（２）式（１）または式（２）で示されるポリエーテル系化合物（Ａ）において、Ａ1Ｏがオキシエチレン基であり、Ａ2Ｏが炭素数３または４のオキシアルキレン基であり、かつＲ１が水素原子であることを特徴とする前記のセメント用添加剤。
（３）式（１）または式（２）で示されるポリエーテル系化合物（Ａ）において、Ｚで示される窒素原子に結合した活性水素を４０〜２５０個持つ２０個以上の窒素原子を有する化合物が、ポリアルキレンポリアミンまたはポリアルキレンイミンであることを特徴とする前記のセメント用添加剤。
（４）前記のいずれか１項に記載のセメント用添加剤１〜９５重量％およびポリカルボン酸系化合物（ＰＣ）５〜９９重量％を含むセメント用添加剤。
（５）ポリカルボン酸系化合物（ＰＣ）が式（３）で示されるポリアルキレングリコールエ−テルに基づく構成単位（ア）５０〜９９重量％、式（４）で示されるジカルボン酸または無水マレイン酸に基づく構成単位（イ）１〜５０重量％および共重合可能な他の単量体に基づく構成単位（ウ）０〜３０重量％を有する共重合体である前記のセメント用添加剤。
(Wherein, Z is a residue of a compound having 20 or more nitrogen atoms having 40 to 250 active hydrogens bonded to the nitrogen atom, and A 1 O is a carbon whose 80 mol% or more is an oxyethylene group. One or two or more of the oxyalkylene groups of 2 to 4 and in the case of 2 or more, they may be random or block, and a is an oxyalkylene group of 2 to 4 carbon atoms represented by A 1 O. The average added mole number is a = 1 to 50, and A 2 O is one or two or more of C 2-4 oxyalkylene groups in which 80 mol% or more is a C 3 or 4 oxyalkylene group. In the case of two or more kinds, it may be random or block, and b is an average added mole number of an oxyalkylene group having 2 to 4 carbon atoms represented by A 2 O, where b = 1 to 50, b is 1 <b / a ≦ 50 and R 1 is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and n = 40 to 250.)
(2) In the polyether compound (A) represented by formula (1) or formula (2), A 1 O is an oxyethylene group, A 2 O is an oxyalkylene group having 3 or 4 carbon atoms, And R 1 is a hydrogen atom. The cement additive as described above.
(3) A compound having 20 or more nitrogen atoms having 40 to 250 active hydrogens bonded to a nitrogen atom represented by Z in the polyether compound (A) represented by the formula (1) or (2) Is a polyalkylene polyamine or a polyalkyleneimine, the above-mentioned additive for cement.
(4) A cement additive comprising 1 to 95% by weight of the cement additive according to any one of the above and 5 to 99% by weight of a polycarboxylic acid compound (PC).
(5) The structural unit (a) based on the polyalkylene glycol ether represented by the formula (3) in which the polycarboxylic acid compound (PC) is 50 to 99% by weight, the dicarboxylic acid or maleic anhydride represented by the formula (4) The above-mentioned additive for cement, which is a copolymer having 1 to 50% by weight of the structural unit (i) based on an acid and 0 to 30% by weight of the structural unit (c) based on another copolymerizable monomer.
（ただし、Ｒ2、Ｒ3およびＲ4はそれぞれ独立に水素原子またはメチル基を表し、Ｒ5は炭素数１〜４のアルキレン基を表し、Ｒ6は水素原子または炭素数１〜２２の炭化水素基、ＡＯは炭素数２〜４のオキシアルキレン基の１種または２種以上で、２種以上の場合はブロック状でもランダム状でも良く、ｐは炭素数２〜４のオキシアルキレン基の平均付加モル数でｐ＝１〜１５０である。） (However, R 2 , R 3 and R 4 each independently represents a hydrogen atom or a methyl group, R 5 represents an alkylene group having 1 to 4 carbon atoms, and R 6 represents a hydrogen atom or a carbon atom having 1 to 22 carbon atoms. A hydrogen group and AO are 1 type or 2 types or more of a C2-C4 oxyalkylene group, and when it is 2 or more types, it may be a block form or a random form, p is an average of a C2-C4 oxyalkylene group (The number of moles added is p = 1 to 150.)
（ただし、Ｘは−ＯＭ2または−Ｙ−（ＡＯ）rＲ7〔式（５）〕を表し、Ｍ1およびＭ2はそれぞれ独立に水素原子、アルカリ金属、アルカリ土類金属、アンモニウムまたは有機アンモニウムを表し、Ｙはエーテル基またはイミノ基を表し、Ｒ7は水素原子または炭素数１〜２２の炭化水素基、ＡＯは炭素数２〜４のオキシアルキレン基の１種または２種以上で、２種以上の場合はブロック状でもランダム状でも良く、ｒは炭素数２〜４のオキシアルキレン基の平均付加モル数でｒ＝１〜１５０である。）
（６） ポリカルボン酸系化合物（ＰＣ）が式（６）で示されるポリアルキレングリコールエステルに基づく構成単位（エ）５０〜９９重量％、式（７）で示されるモノカルボン酸に基づく構成単位（オ）１〜５０重量％および共重合可能な他の単量体に基づく構成単位（ウ）０〜３０重量％を有する共重合体である前記のセメント用添加剤。
(Where X represents —OM 2 or —Y— (AO) r R 7 [formula (5)], and M 1 and M 2 each independently represent a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, or organic. Y represents an ether group or an imino group, R 7 represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, AO represents one or more of an oxyalkylene group having 2 to 4 carbon atoms, In the case of 2 or more types, it may be a block shape or a random shape, and r is an average added mole number of an oxyalkylene group having 2 to 4 carbon atoms, and r = 1 to 150.)
(6) The structural unit based on the polycarboxylic acid compound (PC) based on the polyalkylene glycol ester represented by the formula (6) (d) 50 to 99% by weight, the monocarboxylic acid represented by the formula (7) (E) The above additive for cement, which is a copolymer having 1 to 50% by weight and a structural unit (c) based on another copolymerizable monomer (c) of 0 to 30% by weight.
（ただし、Ｒ8は水素原子またはメチル基を表し、Ｒ9は水素原子または炭素数１〜２２の炭化水素基を表し、ＡＯは炭素数２〜４のオキシアルキレン基の１種または２種以上で、２種以上の場合はブロック状でもランダム状でも良く、ｓは炭素数２〜４のオキシアルキレン基の平均付加モル数でｓ＝１〜１５０である。） (However, R 8 represents a hydrogen atom or a methyl group, R 9 represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, and AO is one or more kinds of oxyalkylene groups having 2 to 4 carbon atoms. In the case of 2 or more types, it may be block or random, and s is the average number of added moles of the oxyalkylene group having 2 to 4 carbon atoms, and s = 1 to 150.)
（ただし、Ｒ10は水素原子またはメチル基を表し、Ｍ3は水素原子、アルカリ金属、アルカリ土類金属、アンモニウムまたは有機アンモニウムを表す。）
（７）前記のセメント用添加剤、骨材、水およびセメントからなるセメント組成物。
（８）セメントに対する水の比率が、重量比で５０％以下であることを特徴とする前記のセメント組成物。
(However, R 10 represents a hydrogen atom or a methyl group, and M 3 represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, or organic ammonium.)
(7) A cement composition comprising the above cement additive, aggregate, water, and cement.
(8) The said cement composition characterized by the ratio of the water with respect to cement being 50% or less by weight ratio.
本発明のセメント用添加剤はセメントペースト、セメントグラウト、モルタル、コンクリート等のセメント組成物に対して用いることができ、ホッパーもしくはバケット内の付着分も少なく、ポンプ圧送によるセメント組成物の移送もスムーズに行うことができ、建設現場における作業性、施工性を高めることができる。また、セメント組成物の付着分が少ないため、従来排出していた産業廃棄物である洗浄廃水やスラッジを低減することができる。 The cement additive of the present invention can be used for cement compositions such as cement paste, cement grout, mortar, concrete, etc., has little adhesion in the hopper or bucket, and smooth transfer of the cement composition by pumping. It is possible to improve the workability and workability at the construction site. Moreover, since there is little adhesion of a cement composition, the washing | cleaning waste water and sludge which are the industrial waste conventionally discharged | emitted can be reduced.
本発明のセメント用添加剤は、式（１）または式（２）で示されるポリエーテル系化合物（Ａ）を含有するものである。
式（１）または式（２）で示されるポリエーテル系化合物（Ａ）において、Ｚは窒素原子に結合した活性水素を４０〜２５０個持つ２０個以上の窒素原子を有する化合物の残基である。窒素原子に結合した活性水素を４０〜２５０個持つ２０個以上の窒素原子を有する化合物としては、ポリエチレンイミン、ポリプロピレンイミン、ポリ−１，１−ジメチルエチレンイミン、ポリ−１，２−ブチレンイミン、ポリ−２，３−ブチレンイミン等のポリアルキレンイミンやポリアリルアミンが挙げられる。好ましくは、数平均分子量１,５００〜１０,０００のポリエチレンイミンである。より好ましくは数平均分子量１,５００〜５,０００のポリエチレンイミンである。なお、窒素原子に結合した活性水素を４０〜２５０個持つ２０個以上の窒素原子を有する化合物は１種または２種以上を混合して用いても良い。
The additive for cement of the present invention contains the polyether compound (A) represented by the formula (1) or the formula (2).
In the polyether compound (A) represented by the formula (1) or (2), Z is a residue of a compound having 20 or more nitrogen atoms having 40 to 250 active hydrogens bonded to the nitrogen atom. . Examples of the compound having 20 or more nitrogen atoms having 40 to 250 active hydrogen atoms bonded to the nitrogen atom include polyethyleneimine, polypropyleneimine, poly-1,1-dimethylethyleneimine, poly-1,2-butyleneimine, Examples include polyalkyleneimines such as poly-2,3-butyleneimine and polyallylamine. Polyethyleneimine having a number average molecular weight of 1,500 to 10,000 is preferable. More preferred is polyethyleneimine having a number average molecular weight of 1,500 to 5,000. In addition, the compound which has 20 or more nitrogen atoms which have 40-250 active hydrogen couple | bonded with the nitrogen atom may mix and use 1 type or 2 types or more.
式（１）または式（２）で示されるポリエーテル系化合物（Ａ）においてＡ1Ｏは、その８０モル％以上がオキシエチレン基である炭素数２〜４のオキシアルキレン基の１種または２種以上で、２種以上の場合には、ランダム状でもブロック状でも良い。炭素数２〜４のオキシアルキレン基としては、オキシエチレン基、オキシプロピレン基、オキシブチレン基が挙げられ、オキシプロピレン基としては、１，２―オキシプロピレン基が好ましく、オキシブチレン基としては、１，２−オキシブチレン基が好ましい。Ａ１Ｏはその８０モル％以上がオキシエチレン基と限定されるのは、この範囲から外れると本発明のセメント用添加剤によるセメント組成物の付着低減効果が低くなるためであり、Ａ１Ｏがオキシエチレン基のみの場合がさらに好ましい。
Ａ2Ｏは、その８０モル％以上が炭素数３または４のオキシアルキレン基である炭素数２〜４のオキシアルキレン基の１種または２種以上で、２種以上の場合には、ランダム状でもブロック状でも良く、炭素数２〜４のオキシアルキレン基としては、オキシエチレン基、オキシプロピレン基、オキシブチレン基が挙げられ、オキシプロピレン基としては、１，２―オキシプロピレン基が好ましく、オキシブチレン基としては、１，２−オキシブチレン基が好ましい。Ａ2Ｏは、その８０モル％以上が炭素数３または４のオキシアルキレン基と限定されるのは、この範囲から外れると、本発明のセメント用添加剤によるセメント組成物の付着低減効果が低くなるためであり、Ａ2Ｏが炭素数３または４のオキシアルキレン基からなる場合がさらに好ましい。
In the polyether compound (A) represented by the formula (1) or (2), A 1 O is one or two of oxyalkylene groups having 2 to 4 carbon atoms in which 80 mol% or more thereof is an oxyethylene group. In the case of two or more species, it may be random or block. Examples of the oxyalkylene group having 2 to 4 carbon atoms include an oxyethylene group, an oxypropylene group, and an oxybutylene group. The oxypropylene group is preferably a 1,2-oxypropylene group, and the oxybutylene group is 1 , 2-oxybutylene group is preferred. A 1 to O is more than the 80 mol% is limited oxyethylene groups is for adhering reducing effect of the cement composition according to the cement additive of the present invention deviates from this range is low, A 1 O More preferably, is only an oxyethylene group.
A 2 O is one or more oxyalkylene groups having 2 to 4 carbon atoms, in which 80 mol% or more thereof is an oxyalkylene group having 3 or 4 carbon atoms. However, the oxyalkylene group having 2 to 4 carbon atoms may be an oxyethylene group, an oxypropylene group, or an oxybutylene group, and the oxypropylene group is preferably a 1,2-oxypropylene group. As the butylene group, a 1,2-oxybutylene group is preferable. The fact that 80 mol% or more of A 2 O is limited to an oxyalkylene group having 3 or 4 carbon atoms is less than this range, the adhesion reducing effect of the cement composition by the cement additive of the present invention is low. More preferably, A 2 O is composed of an oxyalkylene group having 3 or 4 carbon atoms.
ａおよびｂは、それぞれＡ1ＯおよびでＡ2Ｏで示される炭素数２〜４のオキシアルキレン基の平均付加モル数で、それぞれ１〜５０であり、好ましくは１〜３０である。ａおよびｂがこの範囲から外れると、セメント組成物の付着低減効果が低くなるため好ましくない。
また、Ａ1Ｏで示される炭素数２〜４のオキシアルキレン基の平均付加モル数ａとＡ2Ｏで示される炭素数２〜４のオキシアルキレン基の平均付加モル数ｂとは、１＜ｂ／ａ≦５０の関係も満たすことが好ましい。ｂ／ａは、ポリエーテル系化合物（Ａ）におけるポリエーテル鎖の親水性の高い部分Ａ1Ｏと、ポリエーテル鎖の親水性の低い部分Ａ2Ｏとのバランスを意味しており、ｂ／ａが１未満であるとセメント組成物の付着低減効果が低くなるため好ましくない。ｂ／ａが５０を超えると、ポリエーテル系化合物（Ａ）の水溶性が乏しくなるため好ましくない。ｂ／ａとして好ましくは、１＜ｂ／ａ≦３０であり、さらに好ましくは１＜ｂ／ａ≦１０である。
式（１）または式（２）のＲ1は、水素原子または炭素数１〜８の炭化水素基であり、炭化水素基としては、メチル基、エチル基、プロピル基、イソプロピル基、アリル基、ブチル基、イソブチル基、ｔ−ブチル基、アミル基、イソアミル基、へキシル基、へプチル基、オクチル基、２−エチルヘキシル基、フェニル基、ベンジル基、クレジル基などが挙げられ、これらは１種のみでも良く、２種以上でも良い。好ましくは、水素原子、メチル基、エチル基、プロピル基、イソプロピル基、アリル基、ブチル基など炭素数１〜４の炭化水素基で、さらに好ましくは、水素原子またはメチル基である。Ｒ1で示される炭化水素基の炭素数が８を超えると、製造しにくいため好ましくない。
a and b are the average addition mole number of the oxyalkylene group having 2 to 4 carbon atoms represented by each of A 1 O and with A 2 O, 1 to 50, respectively, and preferably 1 to 30. If a and b are out of this range, the effect of reducing the adhesion of the cement composition is lowered, which is not preferable.
The average addition mole number a of the oxyalkylene group having 2 to 4 carbon atoms represented by A 1 O and the average addition mole number b of the oxyalkylene group having 2 to 4 carbon atoms represented by A 2 O are 1 < It is also preferable to satisfy the relationship of b / a ≦ 50. b / a means the balance between the highly hydrophilic part A 1 O of the polyether chain and the low hydrophilic part A 2 O of the polyether chain in the polyether compound (A), and b / a If a is less than 1, the effect of reducing the adhesion of the cement composition is lowered, which is not preferable. When b / a exceeds 50, the water solubility of the polyether compound (A) becomes poor. Preferably, b / a is 1 <b / a ≦ 30, and more preferably 1 <b / a ≦ 10.
R 1 in Formula (1) or Formula (2) is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an allyl group, Examples include butyl group, isobutyl group, t-butyl group, amyl group, isoamyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, phenyl group, benzyl group, cresyl group, etc. Or two or more. Preferably, it is a C1-C4 hydrocarbon group such as a hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, allyl group, butyl group, and more preferably a hydrogen atom or a methyl group. If the number of carbon atoms of the hydrocarbon group represented by R 1 exceeds 8, it is not preferable because it is difficult to produce.
また、式（１）または式（２）で示されるポリエーテル系化合物（Ａ）の重量平均分子量は、１５,０００〜２００,０００であり、好ましくは２５,０００〜２００,０００である。
式（１）または式（２）で示されるポリエーテル系化合物（Ａ）は、式（１）または式（２）のＺに由来する窒素原子に結合した活性水素を４０〜２５０個持つ２０個以上の窒素原子を有する化合物に、アルキレンオキシドを付加することによって製造することができる。
アルキレンオキシドの付加反応は、触媒の存在下で行うことができ、場合によっては触媒を使用しなくても良い。アルキレンオキシド付加反応の触媒としては、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化マグネシウム等のアルカリ金属及びアルカリ土類金属の水酸化物などの他に、ナトリウム、カリウム、ナトリウムハイドライド、ナトリウムメトキシド、カリウムメトキシド、ナトリウムエトキシド、カリウムエトキシドなどのアルカリ金属化合物や、トリエチルアミンなどのアルキルアミン、トリエタノールアミンなどのアルカノールアミンを用いることができる。また、上記のアルカリ触媒の他に、三ふっ化ほう素や四塩化錫などのルイス酸触媒を用いても良い。アルキレンオキシドの付加反応は、例えば、アルゴン、窒素などの不活性ガス存在下、５０〜２００℃、０．０２ＭＰａ〜１．０ＭＰａで原料の窒素原子を有する化合物に対し、触媒の存在下、場合によっては無触媒で、アルキレンオキシドを連続して加圧添加して製造することができる。
オキシアルキレン基由来の水酸基にＲ1で示される炭化水素基を導入する方法に特に制限はなく、公知の方法を用いることができる。例えば、上記で得たポリアルキレンイミンのアルキレンオキシド付加物に、水酸化ナトリウム、水酸化カリウム等のアルカリ金属の水酸化物等のアルカリ触媒を用い、塩化メチル、臭化メチルなど炭化水素のハロゲン化物を用いたエーテル化反応により得ることができる。
The weight average molecular weight of the polyether compound (A) represented by the formula (1) or the formula (2) is 15,000 to 200,000, preferably 25,000 to 200,000.
The polyether compound (A) represented by the formula (1) or (2) has 20 active hydrogen atoms bonded to nitrogen atoms derived from Z in the formula (1) or formula (2). It can manufacture by adding an alkylene oxide to the compound which has the above nitrogen atoms.
The addition reaction of alkylene oxide can be performed in the presence of a catalyst, and in some cases, the catalyst may not be used. Examples of the catalyst for the addition reaction of alkylene oxide include alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and magnesium hydroxide, as well as sodium, potassium, sodium hydride and sodium. Alkali metal compounds such as methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, alkylamines such as triethylamine, and alkanolamines such as triethanolamine can be used. In addition to the above alkali catalyst, a Lewis acid catalyst such as boron trifluoride or tin tetrachloride may be used. For example, the addition reaction of alkylene oxide is carried out in the presence of a catalyst in the presence of a catalyst with respect to a compound having a nitrogen atom as a raw material at 50 to 200 ° C. and 0.02 MPa to 1.0 MPa in the presence of an inert gas such as argon or nitrogen. Is non-catalyzed and can be produced by continuously adding alkylene oxide under pressure.
There is no particular limitation on the method for introducing the hydrocarbon group represented by R 1 into the hydroxyl group derived from the oxyalkylene group, and a known method can be used. For example, using an alkylene oxide adduct of polyalkyleneimine obtained above with an alkali catalyst such as an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, a hydrocarbon halide such as methyl chloride or methyl bromide Can be obtained by an etherification reaction.
本発明に用いるポリカルボン酸系化合物（ＰＣ）としては、構成成分とする単量体としてマレイン酸またはその誘導体、アクリル酸、メタクリル酸またはその誘導体を有する共重合体が挙げられ、例えば、マレイン酸−スチレンスルホン酸塩の共重合物またはその塩、無水マレイン酸−スチレン共重合物、その加水分解物またはその塩、無水マレイン酸−オレフイン共重合物、その加水分解物またはその塩、ポリオキシアルキレンモノアルキルエーテル（メタ）アクリレート−（メタ）アクリル酸共重合物またはその塩、ポリオキシアルキレンモノ（メタ）アリルエーテル−マレイン酸共重合物またはその塩、ポリオキシアルキレンモノアルキルモノ（メタ）アリルエーテル−無水マレイン酸共重合物、その加水分解物またはその塩等が挙げられる。これらは1種または２種以上を混合して使用しても良い。 Examples of the polycarboxylic acid compound (PC) used in the present invention include maleic acid or a derivative thereof, and a copolymer having acrylic acid, methacrylic acid or a derivative thereof as a constituent monomer. -Styrene sulfonate copolymer or salt thereof, maleic anhydride-styrene copolymer, hydrolyzate thereof or salt thereof, maleic anhydride-olefin copolymer, hydrolyzate thereof or salt thereof, polyoxyalkylene Monoalkyl ether (meth) acrylate- (meth) acrylic acid copolymer or salt thereof, polyoxyalkylene mono (meth) allyl ether-maleic acid copolymer or salt thereof, polyoxyalkylene monoalkyl mono (meth) allyl ether -Maleic anhydride copolymer, its hydrolyzate or its salt, etc. It is. You may use these 1 type or in mixture of 2 or more types.
この中でも、以下の共重合体を用いることが好ましい。
１）式（３）で示されるポリアルキレングリコールエーテルに基づく構成単位（ア）５０〜９９重量％と、式（４）で示されるジカルボン酸または無水マレイン酸に基づく構成単位（イ）１〜５０重量％および共重合可能な他の単量体に基づく構成単位（ウ）０〜３０重量％を有する共重合体
構成単位（ア）構成単位（イ）および構成単位（ウ）の比において好ましくは、構成単位（ア）７５〜９９重量％、構成単位（イ）１〜２５重量％である。構成単位（ウ）は構成単位（ア）と構成単位（イ）の和に対して１０以下である。この範囲であると、減水性とスランプ保持性に優れる。
２）式（６）で示されるポリアルキレングリコールエステルに基づく構成単位（エ）５０〜９９重量％と式（７）で示されるモノカルボン酸に基づく構成単位（オ）１〜５０重量％および共重合可能な他の単量体に基づく構成単位（ウ）０〜３０重量％を有する共重合体
構成単位（ア）構成単位（イ）および構成単位（ウ）の比において、好ましくは構成単位（ア）６５〜９９重量％、構成単位（イ）１〜３５重量％である。構成単位（ウ）は構成単位（ア）と構成単位（イ）の和に対して１０重量％以下である。この範囲であると、減水性とスランプ保持性に優れる。
Among these, it is preferable to use the following copolymers.
1) 50 to 99% by weight of the structural unit (a) based on the polyalkylene glycol ether represented by the formula (3) and 1 to 50 based on the dicarboxylic acid or maleic anhydride represented by the formula (4) Copolymer having 0 to 30% by weight of structural unit (c) based on weight percent and other copolymerizable monomers, preferably in the ratio of structural unit (a) structural unit (b) and structural unit (c) The structural unit (a) is 75 to 99% by weight, and the structural unit (a) is 1 to 25% by weight. The structural unit (c) is 10 or less with respect to the sum of the structural unit (a) and the structural unit (a). Within this range, the water-reducing property and the slump retention property are excellent.
2) The structural unit (e) based on the polyalkylene glycol ester represented by the formula (6) (50 to 99% by weight), the structural unit (e) based on the monocarboxylic acid represented by the formula (7) and 1 to 50% by weight Copolymer having 0 to 30% by weight of structural unit (c) based on other polymerizable monomer In the ratio of structural unit (a) structural unit (b) and structural unit (c), preferably the structural unit ( A) 65 to 99% by weight and structural unit (a) 1 to 35% by weight. The structural unit (c) is 10% by weight or less based on the sum of the structural unit (a) and the structural unit (a). Within this range, the water-reducing property and the slump retention property are excellent.
式（３）において、Ｒ2、Ｒ3およびＲ4はそれぞれ独立に水素原子またはメチル基である。
式（３）、式（５）および式（６）において、ＡＯは炭素数２〜４のオキシアルキレン基であり、オキシエチレン基、オキシプロピレン基、オキシブチレン基が挙げられ、好ましくはオキシエチレン基またはオキシプロピレン基であり、より好ましくはオキシエチレン基である。
Ｒ5は炭素数１〜４のアルキレン基であり、メチレン基、エチレン基、トリメチレン基、プロピレン基、テトラメチレン基、ブチレン基があり、プロピレン基としては、１−プロピレン基、２−プロピレン基が好適であり、ブチレン基としては、１，２−ブチレン基、２，３−ブチレン基が好適である。Ｒ5の炭素数が４を超えると原料の入手が困難なため好ましくない。
ｐは炭素数２〜４のオキシアルキレン基の付加モル数であり、１〜１５０であり、好ましくは１０〜１００である。
In the formula (3), R 2 , R 3 and R 4 are each independently a hydrogen atom or a methyl group.
In the formula (3), formula (5) and formula (6), AO is an oxyalkylene group having 2 to 4 carbon atoms, and examples thereof include an oxyethylene group, an oxypropylene group and an oxybutylene group, preferably an oxyethylene group. Or it is an oxypropylene group, More preferably, it is an oxyethylene group.
R 5 is an alkylene group having 1 to 4 carbon atoms, and includes a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, and a butylene group. The propylene group includes a 1-propylene group and a 2-propylene group. The butylene group is preferably a 1,2-butylene group or a 2,3-butylene group. If the number of carbon atoms in R 5 exceeds 4, it is not preferable because it is difficult to obtain raw materials.
p is the number of added moles of an oxyalkylene group having 2 to 4 carbon atoms, and is 1 to 150, preferably 10 to 100.
式（４）および式（７）のＭ1、Ｍ2およびＭ3は水素原子、アルカリ金属、アルカリ土類金属、アンモニウムまたは有機アンモニウムである。アルカリ金属としてはリチウム、ナトリウム、カリウム、ルビジウム等が挙げられる。
アルカリ土類金属としては、マグネシウム、カルシウムが挙げられる。
有機アンモニウムとしては、有機アミン由来のアンモニウムであり、有機アミンとしては、例えばモノエタノールアミン、ジエタノールアミン、トリエタノールアミンなどのアルカノールアミン、メチルアミン、ジメチルアミン、トリエチルアミン、エチルアミン、ジエチルアミン、トリエチルアミンなどのアルキルアミンが挙げられ、好ましくはモノエタノールアミン、メチルアミン、エチルアミン、ジエチルアミンである。
M 1 , M 2 and M 3 in formula (4) and formula (7) are a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or organic ammonium. Examples of the alkali metal include lithium, sodium, potassium, rubidium and the like.
Examples of the alkaline earth metal include magnesium and calcium.
The organic ammonium is an ammonium derived from an organic amine. Examples of the organic amine include alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, alkylamines such as methylamine, dimethylamine, triethylamine, ethylamine, diethylamine and triethylamine. Among them, monoethanolamine, methylamine, ethylamine, and diethylamine are preferable.
式（４）のＸは−ＯＭ2または−Ｙ−（ＡＯ）rＲ7〔式（５）〕である。Ｙはエーテル基またはイミノ基であり、エーテル基は−Ｏ−を表し、イミノ基は−ＮＨ−を表す。
式（３）、式（５）および式（６）のＲ6、Ｒ7およびＲ9は水素原子または炭素数1〜２２の炭化水素基であり、炭素数１〜２２の炭化水素基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、第三ブチル基、アミル基、イソアミル基、ヘキシル基、ヘプチル基、２−エチルヘキシル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、イソトリデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基、オレイル基、ドコシル基、フェニル基、ベンジル基、クレジル基、ブチルフェニル基、オクチルフェニル基、ノニルフェニル基、ナフチル基等がある。好ましくは、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、第三ブチル基など炭素数１〜４の炭化水素基である。Ｒ6、Ｒ7およびＲ9で示される炭化水素基の炭素数が２２を超えると、親水性が十分でなくなるので好ましくない。
式（６）において、Ｒ8は水素原子またはメチル基である。
式（５）において、ｒは炭素数２〜４のオキシアルキレン基の平均付加モル数で１〜１５０であり、好ましくは３〜１００である。
式（６）において、ｓは炭素数２〜４のオキシアルキレン基の平均付加モル数で１〜１５０であり、好ましくは３〜１００である。
X in Formula (4) is —OM 2 or —Y— (AO) r R 7 [Formula (5)]. Y is an ether group or imino group, the ether group represents —O—, and the imino group represents —NH—.
R 6 , R 7 and R 9 in formula (3), formula (5) and formula (6) are hydrogen atoms or hydrocarbon groups having 1 to 22 carbon atoms. , Methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, amyl group, isoamyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, Undecyl, dodecyl, isotridecyl, tetradecyl, hexadecyl, octadecyl, oleyl, docosyl, phenyl, benzyl, cresyl, butylphenyl, octylphenyl, nonylphenyl, naphthyl, etc. . Preferably, it is a C1-C4 hydrocarbon group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, or a tertiary butyl group. When the hydrocarbon group represented by R 6 , R 7 and R 9 has more than 22 carbon atoms, the hydrophilicity becomes insufficient, which is not preferable.
In the formula (6), R 8 is a hydrogen atom or a methyl group.
In the formula (5), r is an average added mole number of an oxyalkylene group having 2 to 4 carbon atoms, preferably 1 to 150, and preferably 3 to 100.
In the formula (6), s is an average added mole number of an oxyalkylene group having 2 to 4 carbon atoms, preferably 1 to 150, and preferably 3 to 100.
ポリカルボン酸系化合物（ＰＣ）において、構成単位（ウ）の由来となる共重合可能な他の単量体としては、アクリル酸およびその塩、メタクリル酸及びその塩、アリルスルホン酸及びその塩、メタリルスルホン酸及びその塩、ｐ−スチレンスルホン酸及びその塩、アクリルアミド、メタクリルアミド、アクリル酸エステル、メタクリル酸エステル、スチレン、酢酸ビニル、イソブチレン等が挙げられる。共重合可能な他の単量体は加えても加えなくとも良い。これらは単独でも２種以上用いても良い。
本発明のセメント用添加剤に用いるポリカルボン酸系化合物の重量平均分子量は、５００〜１００，０００であり、好ましくは５，０００〜３０，０００である。重量平均分子量が１００，０００を超える化合物は、粘度が高くなるため取り扱いがしづらく好ましくない。
In the polycarboxylic acid compound (PC), other copolymerizable monomers from which the structural unit (U) is derived include acrylic acid and its salt, methacrylic acid and its salt, allylsulfonic acid and its salt, Examples include methallylsulfonic acid and its salt, p-styrenesulfonic acid and its salt, acrylamide, methacrylamide, acrylic ester, methacrylic ester, styrene, vinyl acetate, and isobutylene. Other copolymerizable monomers may or may not be added. These may be used alone or in combination of two or more.
The weight average molecular weight of the polycarboxylic acid compound used in the additive for cement of the present invention is 500 to 100,000, preferably 5,000 to 30,000. A compound having a weight average molecular weight exceeding 100,000 is not preferable because it has a high viscosity and is difficult to handle.
また、本発明のセメント用添加剤に用いるポリカルボン酸系化合物は、公知の方法により、重合開始剤を用いて重合することにより得ることができる。重合の方法については、塊状重合でも溶液重合でも良い。溶液重合で水を溶剤として用いる場合は、過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウムなどの過硫酸塩や、過酸化水素、水溶性のアゾ系開始剤を用いることができ、その際に亜硫酸水素ナトリウム、ヒドロキシルアミン塩酸塩、チオ尿素、次亜リン酸ナトリウムなどの促進剤を併用することもできる。また、溶液重合でメタノール、エタノール、イソプロパノールなどの低級アルコール、ｎ−ヘキサン、２−エチルヘキサン、シクロヘキサンなどの脂肪族炭化水素、トルエン、キシレン等の芳香族炭化水素、アセトン、メチルエチルケトン、酢酸エチル等の有機溶剤を用いた重合の場合や塊状重合の際には、ベンゾイルペルオキシド、ジ−ｔ−ブチルペルオキシド、ｔ−ブチルペルオキシイソブチレートなどの有機過酸化物やアゾイソブチロニトリルなどのアゾ系化合物を用いることができる。また、その際にはチオグリコール酸、メルカプトエタノールなどの連鎖移動剤を用いることもできる。 Moreover, the polycarboxylic acid-type compound used for the additive for cements of this invention can be obtained by superposing | polymerizing by a well-known method using a polymerization initiator. The polymerization method may be bulk polymerization or solution polymerization. When water is used as a solvent in solution polymerization, persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate, hydrogen peroxide, and water-soluble azo initiators can be used. Accelerators such as sodium, hydroxylamine hydrochloride, thiourea and sodium hypophosphite can be used in combination. Also, in solution polymerization, lower alcohols such as methanol, ethanol and isopropanol, aliphatic hydrocarbons such as n-hexane, 2-ethylhexane and cyclohexane, aromatic hydrocarbons such as toluene and xylene, acetone, methyl ethyl ketone, ethyl acetate, etc. In the case of polymerization using an organic solvent or bulk polymerization, organic peroxides such as benzoyl peroxide, di-t-butyl peroxide and t-butylperoxyisobutyrate, and azo compounds such as azoisobutyronitrile Can be used. In this case, a chain transfer agent such as thioglycolic acid or mercaptoethanol can also be used.
本発明のセメント用添加剤は、式（１）または式（２）で示されるポリエーテル系化合物（Ａ）のみを単独で用いることができ、式（１）または式（２）で示されるポリエーテル系化合物（Ａ）とポリカルボン酸系化合物（ＰＣ）とを組み合わせても良く、式（１）または式（２）で示されるポリエーテル系化合物（Ａ）とポリカルボン酸系化合物（ＰＣ）の組成割合は、ポリエーテル系化合物（Ａ）１〜９５重量％とポリカルボン酸系化合物（ＰＣ）５〜９９重量％であり、好ましくはポリエーテル系化合物（Ａ）５〜５０重量％とポリカルボン酸系化合物（ＰＣ）５０〜９５重量％であり、ポリエーテル系化合物（Ａ）が１重量％より少ないとセメント組成物の付着低減効果が見られないために多量の添加が必要となり好ましくない。ポリカルボン酸系化合物（ＰＣ）に対してポリエーテル系化合物（Ａ）が５０重量％より多いと、多量に添加することとなり、それに見合う付着低減効果は見られないため経済的な面では好ましくない。 As the additive for cement of the present invention, only the polyether compound (A) represented by the formula (1) or the formula (2) can be used alone, and the polyester represented by the formula (1) or the formula (2) can be used. The ether compound (A) and the polycarboxylic acid compound (PC) may be combined, and the polyether compound (A) represented by the formula (1) or the formula (2) and the polycarboxylic acid compound (PC). The composition ratio of the polyether compound (A) is 1 to 95% by weight and the polycarboxylic acid compound (PC) is 5 to 99% by weight, preferably 5 to 50% by weight of the polyether compound (A) and poly The amount of the carboxylic acid compound (PC) is 50 to 95% by weight, and if the amount of the polyether compound (A) is less than 1% by weight, an effect of reducing the adhesion of the cement composition is not seen, so a large amount of addition is necessary, which is not preferable. . If the amount of the polyether compound (A) is more than 50% by weight with respect to the polycarboxylic acid compound (PC), it will be added in a large amount, and an adhesion reduction effect corresponding to that will not be seen. .
本発明のセメント用添加剤は、そのままの形態で用いることもできるが、水希釈して用いることもできる。水に希釈させて用いる場合は、セメント組成物の練り混ぜ水に希釈溶解させて使用でき、練り混ぜ水の注水と同時に添加して使用することもでき、注水後から練り上がりまでの間に添加して使用することもでき、一旦練り上がったセメント組成物に後から添加して使用することもできる。
本発明のセメント組成物には、水、セメントおよび本発明の添加剤を含み、必要に応じて砂、砂利などの骨材、粘土など他の増量材などを配合することもできる。セメントとしては、普通、早強、中庸熟、ビーライト等のポルトランドセメントや、これらポルトランドセメントに、高炉スラグ、シリカフューム、石灰石等の鉱物系粉体を配合した混合セメント、石膏等が挙げられる。また、上記の各種セメントに、さらに、高炉スラグ、シリカヒューム、フライアッシュ、石灰石などの鉱物系粉体各種粉体を配合しても良い。骨材についても特に制限されることもなく、川砂、山砂、陸砂、砕砂、川砂利、砕石、人工骨材、コンクリート再生骨材など通常用いられている骨材を使用でき、その種類、配合比率は適宜選択して使用できる。
The cement additive of the present invention can be used as it is, but it can also be diluted with water. When diluted in water, it can be used after diluting and dissolving in the mixing water of the cement composition. It can also be used by adding it simultaneously with the pouring of the mixing water. It can also be used, and it can also be used after adding to the cement composition once kneaded.
The cement composition of the present invention contains water, cement and the additive of the present invention, and if necessary, aggregates such as sand and gravel, and other extenders such as clay can be blended. Examples of the cement include Portland cements such as normal, early strength, medium ripening, and belite, and mixed cements and gypsum in which these Portland cements are blended with mineral powders such as blast furnace slag, silica fume, and limestone. Further, various types of mineral powders such as blast furnace slag, silica fume, fly ash, and limestone may be blended with the various cements. There is no particular restriction on the aggregate, and river sand, mountain sand, land sand, crushed sand, river gravel, crushed stone, artificial aggregate, concrete recycled aggregate, etc. can be used, the type, The mixing ratio can be appropriately selected and used.
セメント組成物に用いる添加剤は本発明のセメント用添加剤を用い、セメント用添加剤はセメント組成物中でセメントなどの粉体に対して０．０１〜１０重量％、好ましくは０．０２〜３重量％であり、０．０１重量％では、効果が得られないので好ましくなく、１０重量％を超えて使用しても効果の向上はみられない。
また、セメント組成物の水の比率は、セメントに対して、水１５〜３００重量％であるが、セメント組成物中の水の比率が低い場合で、流動性が急激に下がり、本発明の効果を発揮しやすい範囲として、好ましくは水が１５〜５０重量％であり、さらに好ましくは、水が２０〜４５重量％である。セメント組成物に使用するセメント用添加剤は、セメント組成物中で、セメントと他の水硬性材料の重量に対して０．０１〜５重量％、好ましくは０．０２〜３重量％であり、０．０１重量％では、十分な分散効果が得られないので好ましくない。
本発明のセメント用添加剤は、その効果を損なわない程度で、必要に応じて他の添加剤と併用することができる。他の添加剤としては、例えば、ナフタレンスルホン酸ホルムアルデヒド縮合物の塩、メラミンスルホン酸ホルムアルデヒド縮合物の塩、リグニンスルホン酸の塩、芳香族スルホン酸ホルムアルデヒド縮合物の塩、変性リグニンスルホン酸の塩、ポリオキシアルキレンアリールエーテル誘導体、オキシカルボン酸の塩など他の減水剤、空気連行剤、消泡剤、分離低減剤、凝結遅延剤、凝結促進剤、膨張剤、乾燥収縮低減剤、防錆剤などを挙げることができる。
The additive used for the cement composition is the additive for cement of the present invention, and the cement additive is 0.01 to 10% by weight, preferably 0.02 to 10% by weight based on the powder of cement or the like in the cement composition. 3% by weight, and 0.01% by weight is not preferable because the effect cannot be obtained, and the use of more than 10% by weight does not improve the effect.
Further, the ratio of water in the cement composition is 15 to 300% by weight of water with respect to the cement. However, when the ratio of water in the cement composition is low, the fluidity is drastically lowered, and the effect of the present invention is achieved. Is preferably 15 to 50% by weight of water, and more preferably 20 to 45% by weight of water. The cement additive used in the cement composition is 0.01 to 5% by weight, preferably 0.02 to 3% by weight, based on the weight of cement and other hydraulic materials in the cement composition, An amount of 0.01% by weight is not preferable because a sufficient dispersion effect cannot be obtained.
The cement additive of the present invention can be used in combination with other additives as required, as long as the effect is not impaired. Other additives include, for example, naphthalene sulfonic acid formaldehyde condensate salt, melamine sulfonic acid formaldehyde condensate salt, lignin sulfonic acid salt, aromatic sulfonic acid formaldehyde condensate salt, modified lignin sulfonic acid salt, Other water reducing agents such as polyoxyalkylene aryl ether derivatives, oxycarboxylic acid salts, air entraining agents, antifoaming agents, separation reducing agents, setting retarders, setting accelerators, swelling agents, drying shrinkage reducing agents, rust preventives, etc. Can be mentioned.
以下に、実施例を挙げて本発明を説明する。なお、合成例に用いた式（１）または式（２）で示される化合物の構造を表１に示す。 Hereinafter, the present invention will be described with reference to examples. Table 1 shows the structures of the compounds represented by formula (1) or formula (2) used in the synthesis examples.
［注１］｛／｝は、ランダム状付加を表す。
［注２］化合物のモルは全てモル比を表す。
［注３］ＥＯ、ＰＯおよびＢＯは、それぞれオキシエチレン基、オキシプロピレン基および１，２−オキシブチレン基を表す。
［注４］Ｚを残基とする化合物中のＭｎは数平均分子量を表す。
[Note 1] {/} represents random addition.
[Note 2] All moles of the compound represent a molar ratio.
[Note 3] EO, PO and BO represent an oxyethylene group, an oxypropylene group and a 1,2-oxybutylene group, respectively.
[Note 4] Mn in the compound having Z as a residue represents a number average molecular weight.
合成例１（ポリエーテル系化合物（ａ）の合成）
攪拌機、圧力計、安全弁、破裂弁、ガス吹き込み管、排気管、冷却コイル、蒸気ジャケットを装備したステンレス製（ＳＵＳ３１６Ｌ）の耐圧反応装置に、数平均分子量１，８００のポリエチレンイミン（商品名：エポミンＳＰ−０１８（株）日本触媒製）１６０ｇと水酸化ナトリウム３．２ｇを仕込み、系内の空気を窒素ガスで置換したのち、撹拌下、８０℃まで昇温後、８０〜１２０℃、０．０５〜０．５ＭＰa（ゲージ圧）でエチレンオキシド８１８ｇをガス吹き込み管より窒素ガスにより加圧添加を行った。添加終了後、同条件で６時間反応させた。窒素ガスを吹き込みながら、７０〜８０℃、１３ｋＰa以下で０．５時間処理を行った。続いて、８０℃まで昇温後、８０〜１２０℃、０．０５〜０．５ＭＰa（ゲージ圧）の条件下でプロピレンオキシド１６３７ｇをガス吹き込み管より窒素ガスにより加圧添加を行った。添加終了後、同条件で８時間反応させた。窒素ガスを吹き込みながら、７０〜８０℃、１３ｋＰa以下で０．５時間処理を行い、表１に示した式（１）のポリエーテル系化合物（ａ）を得た。
Synthesis Example 1 (Synthesis of polyether compound (a))
A stainless steel (SUS316L) pressure-resistant reactor equipped with a stirrer, pressure gauge, safety valve, burst valve, gas blowing pipe, exhaust pipe, cooling coil, steam jacket, polyethyleneimine with a number average molecular weight of 1,800 (trade name: Epomin) SP-018 (manufactured by Nippon Shokubai Co., Ltd.) 160 g and sodium hydroxide 3.2 g were charged, and the air in the system was replaced with nitrogen gas. After stirring, the temperature was raised to 80 ° C., then 80 to 120 ° C., 0. 818 g of ethylene oxide was added under pressure with nitrogen gas from a gas blowing tube at a pressure of 05 to 0.5 MPa (gauge pressure). After completion of the addition, the reaction was performed for 6 hours under the same conditions. While blowing nitrogen gas, the treatment was performed at 70 to 80 ° C. and 13 kPa or less for 0.5 hour. Subsequently, after the temperature was raised to 80 ° C., 1637 g of propylene oxide was pressurized and added with nitrogen gas from a gas blowing tube under the conditions of 80 to 120 ° C. and 0.05 to 0.5 MPa (gauge pressure). After completion of the addition, the reaction was allowed to proceed for 8 hours under the same conditions. While blowing nitrogen gas, treatment was performed at 70 to 80 ° C. and 13 kPa or less for 0.5 hour to obtain a polyether compound (a) of the formula (1) shown in Table 1.
合成例２（ポリエーテル系化合物（ｂ）の合成）
合成例１と同様の反応装置に、数平均分子量１，８００のポリエチレンイミン（商品名：エポミンＳＰ−０１８（株）日本触媒製）７２ｇと水酸化ナトリウム１．４ｇを仕込み、系内の空気を窒素ガスで置換したのち、撹拌下、８０℃まで昇温後、８０〜１２０℃、０．０５〜０．５ＭＰa（ゲージ圧）でエチレンオキシド４４２ｇをガス吹き込み管より窒素ガスにより加圧添加した。添加終了後、同条件で２時間反応させた。窒素ガスを吹き込みながら、７０〜８０℃、１３ＭＰa以下で０．５時間処理を行った。続いて、８０℃まで昇温後、８０〜１２０℃、０．０５〜０．５ＭＰa（ゲージ圧）の条件下でプロピレンオキシド１９４２ｇをガス吹き込み管より窒素ガスにより加圧添加した。添加終了後、同条件で３時間反応させた。窒素ガスを吹き込みながら、７０〜８０℃、１３ｋＰa以下で０．５時間処理を行った。次に水酸化カリウム４０ｇを加え、系内の空気を窒素ガスで置換したのち、８０℃で撹拌しながらメチルクロライド２５ｇを圧入した。添加終了後、８０℃〜１２０℃で６時間反応させた。窒素ガスを吹き込みながら、７０〜８０℃、１３ｋＰa以下で０．５時間処理を行った。減圧下、吸着剤処理により、生じた塩を取り除いた。表１に示した式（１）のポリエーテル系化合物（ｂ）を得た。
Synthesis Example 2 (Synthesis of polyether compound (b))
In a reactor similar to Synthesis Example 1, 72 g of polyethyleneimine having a number average molecular weight of 1,800 (trade name: Epomin SP-018 manufactured by Nippon Shokubai Co., Ltd.) and 1.4 g of sodium hydroxide were charged. After substituting with nitrogen gas, the temperature was raised to 80 ° C. with stirring, and then 442 g of ethylene oxide was added under pressure with nitrogen gas from a gas blowing tube at 80 to 120 ° C. and 0.05 to 0.5 MPa (gauge pressure). After completion of the addition, the reaction was carried out for 2 hours under the same conditions. While blowing nitrogen gas, the treatment was performed at 70 to 80 ° C. and 13 MPa or less for 0.5 hour. Subsequently, after the temperature was raised to 80 ° C., 1942 g of propylene oxide was pressure-added with nitrogen gas from a gas blowing tube under the conditions of 80 to 120 ° C. and 0.05 to 0.5 MPa (gauge pressure). After completion of the addition, the reaction was carried out for 3 hours under the same conditions. While blowing nitrogen gas, the treatment was performed at 70 to 80 ° C. and 13 kPa or less for 0.5 hour. Next, 40 g of potassium hydroxide was added, the air in the system was replaced with nitrogen gas, and then 25 g of methyl chloride was injected while stirring at 80 ° C. After completion of the addition, the reaction was carried out at 80 to 120 ° C. for 6 hours. While blowing nitrogen gas, the treatment was performed at 70 to 80 ° C. and 13 kPa or less for 0.5 hour. The generated salt was removed by adsorbent treatment under reduced pressure. A polyether compound (b) of the formula (1) shown in Table 1 was obtained.
合成例３（ポリエーテル系化合物（ｃ）の合成）
合成例１で用いたのと同様の反応装置に、数平均分子量３，０００のポリエチレンイミン（商品名：エポミンＳＰ−０３０（株）日本触媒製）１２０ｇと水酸化ナトリウム２．４ｇを仕込み、系内の空気を窒素ガスで置換したのち、８０℃まで昇温後、８０〜１２０℃でエチレンオキシド４９０ｇとプロピレンオキシド１６２ｇを混合したものを、０．０５〜０．５ＭＰa（ゲージ圧）で徐々に圧入して付加反応を行った。添加終了後、同条件で６時間反応させた。続いて、撹拌下、８０℃まで昇温後、８０〜１２０℃、０．０５〜０．５ＭＰa（ゲージ圧）の条件下で１，２−ブチレンオキシド２００８ｇをガス吹き込み管より窒素ガスにより徐々に圧入して付加反応を行った。添加終了後、同条件で６時間反応させた。窒素ガスを吹き込みながら、７０〜８０℃、１３ＫＰa以下で０．５時間処理を行い、表１に示した式（１）のポリエーテル系化合物（ｃ）を得た。
Synthesis Example 3 (Synthesis of polyether compound (c))
A reactor similar to that used in Synthesis Example 1 was charged with 120 g of polyethyleneimine having a number average molecular weight of 3,000 (trade name: Epomin SP-030 manufactured by Nippon Shokubai Co., Ltd.) and 2.4 g of sodium hydroxide. After replacing the air inside with nitrogen gas, the temperature was raised to 80 ° C., and then a mixture of 490 g of ethylene oxide and 162 g of propylene oxide was gradually injected at 0.05 to 0.5 MPa (gauge pressure) at 80 to 120 ° C. Then, an addition reaction was performed. After completion of the addition, the reaction was performed for 6 hours under the same conditions. Subsequently, after stirring up to 80 ° C. with stirring, 2008 g of 1,2-butylene oxide was gradually added with nitrogen gas from a gas blowing tube under the conditions of 80 to 120 ° C. and 0.05 to 0.5 MPa (gauge pressure). The addition reaction was performed by press-fitting. After completion of the addition, the reaction was performed for 6 hours under the same conditions. While blowing nitrogen gas, treatment was performed at 70 to 80 ° C. and 13 KPa or less for 0.5 hour to obtain a polyether compound (c) of the formula (1) shown in Table 1.
合成例４（ポリカルボン酸系化合物（イ）の合成）
温度計、攪拌機、冷却管および窒素導入管を装着した３リットル四つ口フラスコに、ポリオキシエチレン（平均付加モル数；２３）メチルエーテルメタクリレート７６２ｇ、無水マレイン酸７３．３ｇおよびイオン交換水１，０３５ｇを秤取り、窒素ガス雰囲気下、６０〜６５℃に加温し、均一に溶解させた。続いて、過硫酸アンモニウム１２．０ｇをイオン交換水２００ｇに溶解させた溶液を、６０〜６５℃で６時間かけて滴下した。滴下終了後さらに３時間撹拌反応させ、得られた反応物を４０％水酸化ナトリウム水溶液で中和してポリカルボン酸系化合物（イ）を含む水溶液を得た。水溶液１０ｇを１２０±２℃に調整した恒温槽で２時間放置後の重量変化により求めた水溶液の固形分は４０．１％であり、ＧＰＣ（ポリエチレングリコールを標準体として換算）により求めた重量平均分子量２３，５００であった。
Synthesis Example 4 (Synthesis of polycarboxylic acid compound (a))
Into a 3 liter four-necked flask equipped with a thermometer, stirrer, condenser and nitrogen inlet tube, 762 g of polyoxyethylene (average added mole number; 23) methyl ether methacrylate, 73.3 g of maleic anhydride and ion-exchanged water 1, 035 g was weighed and heated to 60 to 65 ° C. in a nitrogen gas atmosphere to dissolve uniformly. Subsequently, a solution prepared by dissolving 12.0 g of ammonium persulfate in 200 g of ion-exchanged water was dropped at 60 to 65 ° C. over 6 hours. After completion of the dropwise addition, the mixture was further reacted with stirring for 3 hours, and the resulting reaction product was neutralized with a 40% aqueous sodium hydroxide solution to obtain an aqueous solution containing a polycarboxylic acid compound (I). The solid content of the aqueous solution obtained by weight change after standing for 2 hours in a thermostat adjusted to 120 ± 2 ° C. of 10 g of the aqueous solution is 40.1%, and the weight average obtained by GPC (converted using polyethylene glycol as a standard) The molecular weight was 23,500.
合成例５（ポリカルボン酸系化合物（ロ）の合成）
温度計、攪拌機、冷却管および窒素導入管を装着した３リットル四つ口フラスコに、
ポリオキシエチレン（平均付加モル数；３３）アリルメチルエーテル７６７ｇ、無水マレイン酸５３．９ｇ、メタクリル酸メチル２．４５ｇ、メルカプトエタノール２．７ｇおよびトルエン１５０ｇを秤取り、開始剤としてジ−ｔ−ブチルペルオキシド４．７ｇをトルエン５０ｇに溶解させて滴下して、８０〜８５℃で８時間反応させた。続いて８０〜９０℃の範囲で、窒素ガスを吹き込みながら２７ｋＰａ以下の減圧下でトルエンを除去した。反応物を６０℃まで冷却後、イオン交換水１２４０ｇを加え、ポリカルボン酸系化合物（ロ）を含む水溶液を得た。水溶液１０ｇを１２０±２℃に調整した恒温槽で２時間放置後の重量変化により求めた水溶液の固形分は４０．１重量％であり、ＧＰＣ（ポリエチレングリコールを標準体として換算）により求めた重量平均分子量は１９，８００であった。
Synthesis Example 5 (Synthesis of polycarboxylic acid compound (b))
To a 3 liter four-necked flask equipped with a thermometer, stirrer, condenser and nitrogen inlet,
Polyoxyethylene (average number of moles added: 33) 767 g of allyl methyl ether, 53.9 g of maleic anhydride, 2.45 g of methyl methacrylate, 2.7 g of mercaptoethanol and 150 g of toluene were weighed and di-t-butyl was used as an initiator. 4.7 g of peroxide was dissolved in 50 g of toluene and dropped, and reacted at 80 to 85 ° C. for 8 hours. Subsequently, toluene was removed under a reduced pressure of 27 kPa or less while blowing nitrogen gas in the range of 80 to 90 ° C. After cooling the reaction product to 60 ° C., 1240 g of ion-exchanged water was added to obtain an aqueous solution containing a polycarboxylic acid compound (B). The solid content of the aqueous solution obtained by weight change after standing for 2 hours in a thermostat adjusted to 120 ± 2 ° C. of 10 g of the aqueous solution was 40.1% by weight, and the weight obtained by GPC (converted using polyethylene glycol as a standard). The average molecular weight was 19,800.
配合例１
１リットルビーカーに合成例１で合成したポリエーテル系化合物（ａ）を２０ｇ、および合成例４で合成した共重合体１８０ｇ、イオン交換水２６０ｇを秤取り、３０分撹拌、混合しセメント用添加剤を得た。
配合例２〜４
配合例１と同様にして、表２の重量％比に基づいて配合を行い、セメント用添加剤を得た。
Formulation Example 1
20 g of the polyether compound (a) synthesized in Synthesis Example 1 and 180 g of the copolymer synthesized in Synthesis Example 4 and 260 g of ion-exchanged water were weighed in a 1 liter beaker and stirred for 30 minutes, and mixed. Got.
Formulation Examples 2-4
In the same manner as in Formulation Example 1, blending was performed based on the weight% ratio in Table 2 to obtain a cement additive.
実施例１
配合例１で得られたセメント用添加剤に、さらに消泡剤（ディスホームＣＣ−１１８ 日本油脂（株）製）を添加した。ＪＩＳＲ５２０１記載のモルタルミキサにセメント［普通ポルトランドセメント］７５０ｇ、細骨材［君津産山砂］１,５００ｇを秤取り、低速回転で３０秒間空練りを行ったのち、前記セメント用添加剤を１９．５ｇ添加した水道水３００ｇを加えて低速回転で６０秒間練り混ぜ後、高速回転で１分間練り混ぜモルタル組成物を調整した。調整したモルタルは、フロー試験Ｊ１４ロート試験を行った。尚、モルタル調整および各試験は２０±３℃に調整した試験室で行った。
「フロー試験」
１５秒間に１５回の落下運動は与えない以外はＪＩＳＲ５２０１に準拠してフロー試験を行った。
「Ｊ１４ロート試験」
モルタルを、土木学会基準に準拠した上部内径７０ｍｍ、下部内径１４ｍｍ、高さ４２０ｍｍで内容積約６４０ｍｌの真鍮製の漏斗（以下、Ｊ１４ロートと呼ぶ）に充填し、上面をペーストナイフで均一にならした。下部の栓をはずし、下部よりモルタル組成物を落下させはじめてから、すべて流出し終わるまでの時間を測定し、Ｊ１４ロート落下時間とした。また、試験終了後のＪ１４ロートの重量を測定し、付着したモルタルの重量を算出し、Ｊ１４ロート付着量とした。
Example 1
An antifoaming agent (Dishome CC-118, manufactured by NOF Corporation) was further added to the cement additive obtained in Formulation Example 1. 750 g of cement [ordinary Portland cement] and 1,500 g of fine aggregate [Kimitsu mountain sand] were weighed in a mortar mixer described in JIS R5201, and kneaded at low speed for 30 seconds, and then 19.5 g of the cement additive. 300 g of added tap water was added and kneaded for 60 seconds at low speed, and then kneaded for 1 minute at high speed to prepare a mortar composition. The adjusted mortar was subjected to a flow test J14 funnel test. The mortar adjustment and each test were performed in a test room adjusted to 20 ± 3 ° C.
"Flow test"
A flow test was performed in accordance with JIS R5201 except that 15 falling motions were not given in 15 seconds.
"J14 funnel test"
Fill the mortar into a brass funnel (hereinafter referred to as a J14 funnel) with an inner diameter of 70 mm, a lower inner diameter of 14 mm, a height of 420 mm and an internal volume of approximately 640 ml in accordance with the Japan Society of Civil Engineers standards. did. The bottom plug was removed, and the time from when the mortar composition began to fall from the bottom to when it completely flowed out was measured, and this was taken as the J14 funnel dropping time. Moreover, the weight of the J14 funnel after completion | finish of a test was measured, the weight of the adhered mortar was computed, and it was set as the J14 funnel adhesion amount.
実施例２〜６
配合例２〜４で得られたセメント用添加剤を使用し、実施例１と同様の方法で、表２の添加量によりモルタル試験を行った。得られた結果を表４に示す。
Examples 2-6
Using the cement additives obtained in Formulation Examples 2 to 4, a mortar test was conducted in the same manner as in Example 1 with the addition amounts shown in Table 2. Table 4 shows the obtained results.
比較例１
合成例４で得られた共重合体を２００ｇ、イオン交換水２００ｇを秤取り、３０分間撹拌混合し、セメント用添加剤とし、消泡剤を添加して、実施例１と同様の方法にてモルタル試験を行った。得られた結果を表４に示す。
比較例２〜５
合成例４、５で得られた共重合体の溶液と表１のポリエーテル系化合物（１）の（ｈ）、（ｊ）をそれぞれ使用し、配合例１に従い配合し、実施例１と同様の方法で、表３の添加量によりモルタル試験を行った。得られた結果を表４に示す。
Comparative Example 1
In the same manner as in Example 1, 200 g of the copolymer obtained in Synthesis Example 4 and 200 g of ion-exchanged water were weighed, mixed with stirring for 30 minutes, added as an additive for cement, and added with an antifoaming agent. A mortar test was performed. Table 4 shows the obtained results.
Comparative Examples 2-5
Using the solution of the copolymer obtained in Synthesis Examples 4 and 5 and (h) and (j) of the polyether compound (1) in Table 1, respectively, and blending according to Blending Example 1, the same as in Example 1 In this way, a mortar test was conducted with the addition amount shown in Table 3. Table 4 shows the obtained results.
表４の結果から、本発明のセメント用添加剤を用いた実施例のモルタル組成物は、フロー値およびＪ１４ロート落下時間は同程度であるが、Ｊ１４ロートに付着するモルタル組成物が少なく、取り扱いやすいと判断される。
一方、比較例のセメント用添加剤を用いたモルタル組成物は、実施例と同程度のフロー値であるが、実施例と比べてＪ１４ロートに付着するモルタル組成物の量が多く、取り扱いにくいと判断された。比較例１では、セメント用添加剤の成分が、ポリカルボン酸系化合物（ＰＣ）のみであり、Ｊ１４ロートにおけるモルタル組成物の落下に時間を要し、Ｊ１４ロート内のモルタル組成物の付着分も多い。
実施例１と比較例２では、フロー値とＪ１４ロートにおける落下時間が同程度であるが、ポリエーテル系化合物（Ａ）におけるオキシアルキレン基部分の構造が、親水性の高い基（Ａ１Ｏ）ａと、親水性の低い基（Ａ２Ｏ）ｂとの両方を有している実施例１の方が、親水性の高い基（Ａ１Ｏ）ａのみからなる比較例２よりも、Ｊ１４ロート中のモルタル組成物の付着分が低減しており、取り扱いやすいと判断される。比較例３ではポリエーテル系化合物（Ａ）におけるアルキレンオキシドの平均付加モル数が多すぎるため、Ｊ１４ロート内のモルタル組成物の付着分を減少させる効果が低い。比較例４は、親水性の高い基と親水性の低い基のバランスが悪いため、フロー値とＪ１４ロートにおける落下時間が同程度に対し、モルタル組成物の付着分を減少させる効果が低い。
From the results of Table 4, the mortar compositions of the examples using the cement additive of the present invention have the same flow value and J14 funnel dropping time, but the mortar compositions adhering to the J14 funnel are few and handled. Judged to be easy.
On the other hand, the mortar composition using the cement additive of the comparative example has the same flow value as the example, but the amount of the mortar composition adhering to the J14 funnel is larger than that of the example and is difficult to handle. It was judged. In Comparative Example 1, the component of the cement additive is only a polycarboxylic acid compound (PC), and it takes time to drop the mortar composition in the J14 funnel, and the amount of adhesion of the mortar composition in the J14 funnel is also as follows. Many.
In Example 1 and Comparative Example 2, the flow value and the drop time in the J14 funnel are approximately the same, but the structure of the oxyalkylene group part in the polyether compound (A) is a highly hydrophilic group (A 1 O). In Example 1, which has both a and a low hydrophilic group (A 2 O) b , J14 is higher than Comparative Example 2 consisting only of a high hydrophilic group (A 1 O) a. The adhesion of the mortar composition in the funnel is reduced, and it is judged that it is easy to handle. In Comparative Example 3, since the average number of added moles of alkylene oxide in the polyether compound (A) is too large, the effect of reducing the adhesion of the mortar composition in the J14 funnel is low. In Comparative Example 4, since the balance between the highly hydrophilic group and the low hydrophilic group is poor, the effect of reducing the adhesion of the mortar composition is low with respect to the flow value and the drop time in the J14 funnel.
Claims (8)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS6027638A (en) * | 1983-07-19 | 1985-02-12 | 花王株式会社 | Cement dispersant |
| JP2000109357A (en) * | 1998-08-07 | 2000-04-18 | Nippon Shokubai Co Ltd | Cement composition |
| JP2003165755A (en) * | 2001-09-19 | 2003-06-10 | Nmb Co Ltd | Agent for improving workability of cement composition and water-reducing admixture for cement containing the same |
| JP2003226566A (en) * | 2002-02-06 | 2003-08-12 | Nippon Shokubai Co Ltd | Concrete composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6027638A (en) * | 1983-07-19 | 1985-02-12 | 花王株式会社 | Cement dispersant |
| JP2000109357A (en) * | 1998-08-07 | 2000-04-18 | Nippon Shokubai Co Ltd | Cement composition |
| JP2003165755A (en) * | 2001-09-19 | 2003-06-10 | Nmb Co Ltd | Agent for improving workability of cement composition and water-reducing admixture for cement containing the same |
| JP2003226566A (en) * | 2002-02-06 | 2003-08-12 | Nippon Shokubai Co Ltd | Concrete composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012132017A (en) * | 2006-09-13 | 2012-07-12 | Toho Chem Ind Co Ltd | Novel polycarboxylic acid polymer |
| JP2013216917A (en) * | 2006-09-13 | 2013-10-24 | Toho Chem Ind Co Ltd | Novel polycarboxylic acid polymer |
| JP5424084B2 (en) * | 2006-09-13 | 2014-02-26 | 東邦化学工業株式会社 | Novel polycarboxylic acid polymer |
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