JP5282884B2 - Cement dispersant - Google Patents
Cement dispersant Download PDFInfo
- Publication number
- JP5282884B2 JP5282884B2 JP2008534394A JP2008534394A JP5282884B2 JP 5282884 B2 JP5282884 B2 JP 5282884B2 JP 2008534394 A JP2008534394 A JP 2008534394A JP 2008534394 A JP2008534394 A JP 2008534394A JP 5282884 B2 JP5282884 B2 JP 5282884B2
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- JP
- Japan
- Prior art keywords
- alkylene oxide
- carbon atoms
- structural unit
- acid
- group
- 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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- 239000004568 cement Substances 0.000 title claims description 72
- 239000002270 dispersing agent Substances 0.000 title claims description 57
- 239000002253 acid Substances 0.000 claims description 92
- 229920000642 polymer Polymers 0.000 claims description 74
- 229920000768 polyamine Polymers 0.000 claims description 67
- 125000002947 alkylene group Chemical group 0.000 claims description 54
- 239000004952 Polyamide Substances 0.000 claims description 53
- 229920002647 polyamide Polymers 0.000 claims description 53
- 125000004432 carbon atom Chemical group C* 0.000 claims description 42
- -1 carboxylic acid compound Chemical class 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 16
- 229920000233 poly(alkylene oxides) Polymers 0.000 claims description 16
- 229920001281 polyalkylene Polymers 0.000 claims description 15
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 10
- 150000001408 amides Chemical group 0.000 claims description 10
- 125000003277 amino group Chemical group 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 8
- 150000008065 acid anhydrides Chemical class 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 40
- 239000004567 concrete Substances 0.000 description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 37
- 239000007864 aqueous solution Substances 0.000 description 30
- 238000004519 manufacturing process Methods 0.000 description 30
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000000203 mixture Substances 0.000 description 21
- 229910052757 nitrogen Inorganic materials 0.000 description 21
- 239000000178 monomer Substances 0.000 description 19
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 description 18
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 13
- 229920001515 polyalkylene glycol Polymers 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 13
- 239000001530 fumaric acid Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000004570 mortar (masonry) Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 11
- 230000014759 maintenance of location Effects 0.000 description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 11
- 230000009467 reduction Effects 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 9
- 239000003638 chemical reducing agent Substances 0.000 description 9
- 238000004898 kneading Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 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 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 8
- 238000010926 purge Methods 0.000 description 8
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- 239000002518 antifoaming agent Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 5
- 239000011976 maleic acid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 239000011398 Portland cement Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- 125000005702 oxyalkylene group Chemical group 0.000 description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- 229920001732 Lignosulfonate Polymers 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical group NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical group NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Chemical group 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical group NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 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 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 150000002237 fumaric acid derivatives Chemical class 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011372 high-strength concrete Substances 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 150000002500 ions Chemical group 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical group NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 2
- AQGNVWRYTKPRMR-UHFFFAOYSA-N n'-[2-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical group NCCNCCNCCNCCNCCNCCN AQGNVWRYTKPRMR-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 230000001953 sensory effect Effects 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 150000005846 sugar alcohols Chemical class 0.000 description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical group NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 2
- 229960001124 trientine Drugs 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 1
- OZDGMOYKSFPLSE-UHFFFAOYSA-N 2-Methylaziridine Chemical compound CC1CN1 OZDGMOYKSFPLSE-UHFFFAOYSA-N 0.000 description 1
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 1
- IGDLZDCWMRPMGL-UHFFFAOYSA-N 2-ethenylisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(C=C)C(=O)C2=C1 IGDLZDCWMRPMGL-UHFFFAOYSA-N 0.000 description 1
- MBNVSWHUJDDZRH-UHFFFAOYSA-N 2-methylthiirane Chemical compound CC1CS1 MBNVSWHUJDDZRH-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- WHNPOQXWAMXPTA-UHFFFAOYSA-N 3-methylbut-2-enamide Chemical compound CC(C)=CC(N)=O WHNPOQXWAMXPTA-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
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- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- 229920002558 Curdlan Polymers 0.000 description 1
- 239000001879 Curdlan Substances 0.000 description 1
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical class [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- MUPFEKGTMRGPLJ-RMMQSMQOSA-N Raffinose Natural products O(C[C@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@@H](O[C@@]2(CO)[C@H](O)[C@@H](O)[C@@H](CO)O2)O1)[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 MUPFEKGTMRGPLJ-RMMQSMQOSA-N 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
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- 150000002009 diols Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2641—Polyacrylates; Polymethacrylates
- C04B24/2647—Polyacrylates; Polymethacrylates containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2652—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles
- C04B24/2658—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
- C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
- C08G65/08—Saturated oxiranes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/331—Polymers modified by chemical after-treatment with organic compounds containing oxygen
- C08G65/332—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof
- C08G65/3322—Polymers modified by chemical after-treatment with organic compounds containing oxygen containing carboxyl groups, or halides, or esters thereof acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/40—Surface-active agents, dispersants
- C04B2103/408—Dispersants
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Description
本発明は減水性、保持性、コンクリート粘性に優れるセメント分散剤に関する。 The present invention relates to a cement dispersant that is excellent in water reduction, retention, and concrete viscosity.
従来、コンクリート等のセメント配合物の流動性を確保する目的で、リグニンスルホン酸塩、ナフタレンスルホン酸ホルムアルデヒド縮合物塩、メラミンスルホン酸ホルムアルデヒド縮合物塩がセメント分散剤として使用されてきた。しかしながら上記のセメント分散剤では分散性能が充分でなく、スランプロスが著しく大きいという問題を抱えていた。
近年、ポリカルボン酸系重合体などに代表される高性能ＡＥ減水剤が、高い減水性能及びスランプロスの低減効果を兼ね備える混和剤として広く浸透している。高性能ＡＥ減水剤は従来のセメント分散剤よりも優れた減水性能を発現することが本来の特徴ではあるが、適性使用量の範囲であればコンクリートの凝結遅延に殆ど影響を与えずにスランプロスを少なくできるという特徴もあり、他の薬剤ではみられないこうした性能も重要な位置付けにある。Conventionally, lignin sulfonate, naphthalene sulfonic acid formaldehyde condensate salt, and melamine sulfonic acid formaldehyde condensate salt have been used as cement dispersants for the purpose of ensuring the fluidity of cement compounds such as concrete. However, the above cement dispersant has a problem that the dispersion performance is not sufficient and the slump loss is remarkably large.
In recent years, high-performance AE water reducing agents represented by polycarboxylic acid polymers and the like have been widely used as admixtures having both high water reducing performance and slump loss reduction effects. A high-performance AE water reducing agent is characterized by its superior water-reducing performance compared to conventional cement dispersants, but slump loss has little effect on concrete setting delay as long as it is within the appropriate usage range. These features that are not seen with other drugs are also important.
分散性能を改善するセメント分散剤としては、種々その技術が公開されている。たとえば、不飽和アルコールアルキレンオキサイド付加物と不飽和カルボン酸系単量体を必須の構成成分として含む共重合体を用いたセメント分散剤として、以下を挙げることができる：
ポリエチレングリコールモノアリルエーテル単量体（Ｉ）とマレイン酸系単量体（ＩＩ）及びこれらの単量体と共重合可能な単量体（ＩＩＩ）を特定の比率で用いて導かれた共重合体を主成分とするセメント分散剤（特許文献１）、炭素数２〜４のオキシアルキレン基１種又は２種以上の混合物を有する不飽和ポリアルキレングリコールエーテル系単量体（Ｉ）、マレイン酸系単量体（ＩＩ）及びこれらの単量体と共重合可能なその他の単量体（ＩＩＩ）を特定の共重合比で共重合させた共重合体を主成分とするセメント分散剤（特許文献２）、炭素数２〜１８のオキシアルキレン基の１種又は２種以上の混合物を有する短鎖ポリアルキレングリコールアルケニルエーテル系単量体と不飽和カルボン酸系単量体からなる共重合体（Ａ）並びに炭素数２〜１８のオキシアルキレン基の１種又は２種以上の混合物を有する長鎖ポリアルキレングリコールアルケニルエーテル系単量体と不飽和カルボン酸系単量体からなる共重合体（Ｂ）の２種の共重合体を必須成分とするセメント分散剤（特許文献３）、炭素数２〜１８のオキシアルキレン基を有する不飽和カルボン酸系単量体及び／又は不飽和酸無水物系単量体並びに不飽和アルコール系単量体の共重合により得られ、その一部にアミノ基が導入されてなる、セメント分散剤として使用可能なアミノ基含有重合体（特許文献４）、超高強度コンクリートのセメント混和剤に好適に用いることができる窒素原子を含有する不飽和単量体、炭素数２〜８のアルキレンオキシドを有する不飽和アルコールアルキレンオキシド及び不飽和カルボン酸系単量体からなる不飽和アルコールアルキレンオキシド付加物系重合体（特許文献５）。
このように、セメント分散剤として多くの共重合体が研究され提案されているものの、減水性、保持性並びにコンクリート粘性に於いて更に優れた性能を有する薬剤の開発が望まれていた。Various techniques have been disclosed as cement dispersants for improving the dispersion performance. For example, as a cement dispersant using a copolymer containing an unsaturated alcohol alkylene oxide adduct and an unsaturated carboxylic acid monomer as essential components, the following may be mentioned:
Polyethylene glycol monoallyl ether monomer (I), maleic acid monomer (II), and copolymerization derived using monomers (III) copolymerizable with these monomers in specific ratios Cement dispersant mainly composed of coal (Patent Document 1), unsaturated polyalkylene glycol ether monomer (I) having one or a mixture of two or more oxyalkylene groups having 2 to 4 carbon atoms, maleic acid Cement dispersant containing a copolymer of the main monomer (II) and other monomers (III) copolymerizable with these monomers at a specific copolymerization ratio (patent Reference 2), a copolymer comprising a short-chain polyalkylene glycol alkenyl ether monomer having an oxyalkylene group having 2 to 18 carbon atoms or a mixture of two or more thereof and an unsaturated carboxylic acid monomer ( A) and Two types of copolymers (B) comprising a long-chain polyalkylene glycol alkenyl ether monomer having an oxyalkylene group having 2 to 18 prime numbers and a mixture of two or more thereof and an unsaturated carboxylic acid monomer Cement Dispersant (Patent Document 3) comprising a copolymer of the above as an essential component, an unsaturated carboxylic acid monomer and / or an unsaturated acid anhydride monomer having an oxyalkylene group having 2 to 18 carbon atoms, and Amino group-containing polymer that can be used as a cement dispersant obtained by copolymerization of unsaturated alcohol monomers and has amino groups introduced into a part thereof (Patent Document 4), cement for ultra-high strength concrete Unsaturated monomer containing nitrogen atom, unsaturated alcohol alkylene oxide having 2 to 8 carbon atoms and unsaturated carbo which can be suitably used as admixture Acid consists monomers unsaturated alcohol alkylene oxide adduct-based polymer (Patent Document 5).
As described above, although many copolymers have been studied and proposed as cement dispersants, it has been desired to develop a drug having further superior performance in water reduction, retention and concrete viscosity.
上記特許文献２乃至５においては、不飽和アルコールアルキレンオキサイド付加物において２種以上のアルキレンオキサイド（例えばエチレンオキサイドとプロピレンオキサイド）の混合付加が提案されてはいるものの、実際の試験例はエチレンオキサイドの単独付加のアルコールを用いた結果にとどまり、ましてや、２種以上のアルキレンオキサイドを用いた場合にその付加させる順序あるいは部位については全く検討されてこなかった。
本発明はかかる従来の技術背景の下、セメント分散剤の性能を改良すべくなされたものであって、減水性、保持性に優れ、更にはコンクリート粘性が低く施工性にも配慮されたセメント分散剤を提供することを課題とする。 The present invention has been made to improve the performance of a cement dispersant under the background of such conventional technology, and is excellent in water reduction and retention, and further has low cement viscosity and consideration for workability. It is an object to provide an agent.
本発明者等は鋭意検討した結果、重合性結合部位を有する反応性アルコール誘導体及び二塩基酸系誘導体からなるポリカルボン酸系重合体において、反応性アルコール誘導体のポリアルキレンオキサイド鎖の末端部を炭素原子数３又は４のポリアルキレンオキサイド付加とし、このとき、末端部における炭素原子数３又は４のアルキレンオキサイドをアルキレンオキサイド鎖の全モル量に対して０．１乃至３０ｍｏｌ％の割合で有するものとしたポリカルボン酸系重合体が、セメント分散剤としての基本性能を著しく改善することを見出した。またこのポリカルボン酸系重合体にポリアミドポリアミンを含有することでコンクリート分散剤としての種々の性能が更に向上されることも見出した。 As a result of intensive studies, the present inventors have found that in the polycarboxylic acid polymer comprising a reactive alcohol derivative having a polymerizable binding site and a dibasic acid derivative, the terminal portion of the polyalkylene oxide chain of the reactive alcohol derivative is carbon. A polyalkylene oxide addition having 3 or 4 atoms, wherein the alkylene oxide having 3 or 4 carbon atoms in the terminal portion has a ratio of 0.1 to 30 mol% with respect to the total molar amount of the alkylene oxide chain. It has been found that the polycarboxylic acid-based polymer significantly improves the basic performance as a cement dispersant. It has also been found that various properties as a concrete dispersant can be further improved by including a polyamide polyamine in the polycarboxylic acid polymer.
すなわち本発明は、不飽和アルコールアルキレンオキサイド系化合物に由来する構成単位並びに不飽和カルボン酸系化合物に由来する構成単位を含みて構成されるポリカルボン酸系重合体からなるセメント分散剤において、該重合体の主鎖骨格に結合するグラフト鎖は主としてエチレンオキサイドから構成されるポリアルキレンオキサイド鎖を含み、該グラフト鎖の末端は水酸基であり、さらに該ポリアルキレンオキサイド鎖の水酸基側の末端部は、該グラフト鎖のアルキレンオキサイドの全モル量に対して０．１乃至３０ｍｏｌ％の割合で炭素原子数３又は４のアルキレンオキサイドを有していることを特徴とする、セメント分散剤に関する。 That is, the present invention relates to a cement dispersant comprising a polycarboxylic acid polymer comprising a structural unit derived from an unsaturated alcohol alkylene oxide compound and a structural unit derived from an unsaturated carboxylic acid compound. The graft chain bonded to the main chain skeleton of the coalescence includes a polyalkylene oxide chain mainly composed of ethylene oxide, the terminal of the graft chain is a hydroxyl group, and the terminal portion on the hydroxyl side of the polyalkylene oxide chain is The present invention relates to a cement dispersant characterized by having an alkylene oxide having 3 or 4 carbon atoms in a proportion of 0.1 to 30 mol% with respect to the total molar amount of alkylene oxide of a graft chain.
また本発明は、前記ポリカルボン酸系重合体が、下記の式（Ｉ）で示される構成単位（Ｉ）及び式（ＩＩ）で示される構成単位（ＩＩ）を含みて構成され、該構成単位（Ｉ）におけるポリアルキレンオキサイド鎖の水酸基側末端部が、炭素原子数３又は４のアルキレンオキサイドを、該アルキレンオキサイド鎖の全モル量に対して０．１乃至３０ｍｏｌ％の割合で有することを特徴とする、セメント分散剤に関する。
さらに本発明は、前記ポリカルボン酸系重合体が、前記構成単位（Ｉ）及び構成単位（ＩＩ）に加え、更に下記の式（ＩＩＩ）で表される構成単位（ＩＩＩ）を含みて構成されることを特徴とする、セメント分散剤に関する。
そして本発明は、前記のポリカルボン酸系重合体に加え、二塩基酸とポリアルキレンポリアミンを縮合させたポリアミドポリアミン及び／又は該ポリアミドポリアミンの活性イミノ基、アミノ基、アミド残基１当量に対して炭素原子数２乃至４のアルキレンオキサイドを０．１乃至１０モル付加させたポリアミドポリアミン変性物を含有することを特徴とする、セメント分散剤に関する。 In addition to the polycarboxylic acid-based polymer, the present invention provides a polyamide polyamine obtained by condensing a dibasic acid and a polyalkylene polyamine and / or an active imino group, amino group, and amide residue of 1 equivalent of the polyamide polyamine. The present invention relates to a cement dispersant characterized by containing a polyamide polyamine modified product obtained by adding 0.1 to 10 moles of an alkylene oxide having 2 to 4 carbon atoms.
本発明により、優れた減水性及びスランプ保持性能を有するだけでなく、コンクリート粘性も低いなど施工性も良好であるセメント分散剤を提供することができる。 According to the present invention, it is possible to provide a cement dispersant that not only has excellent water reduction and slump retention performance but also has good workability such as low concrete viscosity.
本発明は、不飽和アルコールアルキレンオキサイド系化合物に由来する構成単位並びに不飽和カルボン酸系化合物に由来する構成単位を含みて構成されるポリカルボン酸系重合体からなるセメント分散剤において、該重合体の主鎖骨格に結合するグラフト鎖は主としてエチレンオキサイドから構成されるポリアルキレンオキサイド鎖を含み、該グラフト鎖の末端は水酸基であり、さらに該ポリアルキレンオキサイド鎖の水酸基側の末端部は、該グラフト鎖のアルキレンオキサイドの全モル量に対して０．１乃至３０ｍｏｌ％の割合で炭素原子数３又は４のアルキレンオキサイドを有していることを特徴とする、セメント分散剤に関するものである。より詳細には、該ポリカルボン酸系重合体は上記に示す構成単位（Ｉ）及び構成単位（ＩＩ）より構成され、さらに該ポリカルボン酸系重合体は、該構成単位（Ｉ）及び（ＩＩ）に加え、ポリアミドポリアミン及び／又はポリアミドポリアミン変性物由来の上記構成単位（ＩＩＩ）を含みて構成される。このように構成されたポリカルボン酸系重合体は、主鎖骨格にポリアルキレンオキサイド鎖、ポリアミドポリアミン鎖などのグラフト鎖が結合した櫛型重合体の構造を有している。
また本発明のセメント分散剤は上記ポリカルボン酸系重合体に加え、ポリアミドポリアミン及び／又はポリアミドポリアミン変性物を含有することもできる。
以下に本発明を詳細に説明する。The present invention relates to a cement dispersant comprising a structural unit derived from an unsaturated alcohol alkylene oxide compound and a polycarboxylic acid polymer comprising a structural unit derived from an unsaturated carboxylic acid compound. The graft chain bonded to the main chain skeleton includes a polyalkylene oxide chain mainly composed of ethylene oxide, the terminal of the graft chain is a hydroxyl group, and the terminal part on the hydroxyl side of the polyalkylene oxide chain is The present invention relates to a cement dispersant characterized by having an alkylene oxide having 3 or 4 carbon atoms in a proportion of 0.1 to 30 mol% with respect to the total molar amount of alkylene oxide in the chain. More specifically, the polycarboxylic acid polymer is composed of the structural unit (I) and the structural unit (II) shown above, and the polycarboxylic acid polymer is further composed of the structural units (I) and (II). In addition, the above-mentioned structural unit (III) derived from a modified polyamide polyamine and / or modified polyamide polyamine is included. The polycarboxylic acid polymer thus configured has a comb polymer structure in which a graft chain such as a polyalkylene oxide chain or a polyamide polyamine chain is bonded to the main chain skeleton.
The cement dispersant of the present invention can also contain a polyamide polyamine and / or a polyamide polyamine-modified product in addition to the polycarboxylic acid polymer.
The present invention is described in detail below.
［構成単位（Ｉ）及び構成単位（ＩＩ）］
本発明のセメント分散剤に含有されるポリカルボン酸系重合体を構成する構成単位（Ｉ）は下記式で表される。
The structural unit (I) constituting the polycarboxylic acid polymer contained in the cement dispersant of the present invention is represented by the following formula.
上記ポリアルキレンオキサイド鎖−（ＡＯ）ａ−は好ましくは主としてエチレンオキサイドからなり、そしてその平均付加モル数は３０以上であること、より好ましくは５０以上であることが分散性能を改善する点で望ましい。
上記構成単位（Ｉ）において、ポリアルキレンオキサイド鎖の水酸基側の末端部は、炭素原子数３のプロピレンオキサイド又は炭素原子数４のブチレンオキサイドを、該アルキレンオキサイド鎖全モル数に対して０．１乃至３０ｍｏｌ％の範囲で含有する。さらに望ましくは０．１乃至２０ｍｏｌ％の範囲で、より好ましくは０．１乃至１０ｍｏｌ％又は１２乃至２０ｍｏｌ％の範囲で、最も好ましくは、０．５乃至５ｍｏｌ％又は１５乃至２０ｍｏｌ％の範囲で有することにより、減水性、スランプ保持性及びコンクリート粘性等を改良する点で好ましい。The polyalkylene oxide chain-(AO) a- is preferably mainly composed of ethylene oxide, and its average added mole number is preferably 30 or more, more preferably 50 or more in view of improving the dispersion performance. .
In the structural unit (I), the terminal portion on the hydroxyl group side of the polyalkylene oxide chain is a propylene oxide having 3 carbon atoms or a butylene oxide having 4 carbon atoms in an amount of 0.1 to the total number of moles of the alkylene oxide chain. It is contained in the range of 30 mol%. More desirably, it is in the range of 0.1 to 20 mol%, more preferably in the range of 0.1 to 10 mol% or 12 to 20 mol%, and most preferably in the range of 0.5 to 5 mol% or 15 to 20 mol%. This is preferable in terms of improving water reduction, slump retention, concrete viscosity, and the like.
上記構成単位（Ｉ）は、例えば以下の化合物に由来する構成単位である；ポリアルキレングリコールモノアリルエーテル、ポリアルキレングリコールモノアルケニルエーテル、などのポリアルキレングリコールと炭素原子数３〜８のアルケニルエーテルより形成されるアルケニルエーテル類、不飽和脂肪族アルコールアルキレンオキサイド付加物である不飽和脂肪族エーテル類等。これらのうち、最も好ましい化合物の具体例は、３−メチル−３−ブテン−１−オールのアルキレンオキサイド付加物である。
上記構成単位（Ｉ）はこれら化合物のうち単独あるいは複数の組合せに由来する構成単位であってよい。The structural unit (I) is, for example, a structural unit derived from the following compound; from polyalkylene glycols such as polyalkylene glycol monoallyl ether and polyalkylene glycol monoalkenyl ether and alkenyl ethers having 3 to 8 carbon atoms. Alkenyl ethers formed, unsaturated aliphatic ethers that are unsaturated aliphatic alcohol alkylene oxide adducts, and the like. Among these, the specific example of the most preferable compound is an alkylene oxide adduct of 3-methyl-3-buten-1-ol.
The structural unit (I) may be a structural unit derived from one or a combination of these compounds.
本発明のセメント分散剤に含有されるポリカルボン酸系重合体を構成する構成単位（ＩＩ）は下記式で表される。
上記構成単位（ＩＩ）は、具体的には、アクリル酸、メタクリル酸、フマル酸、マレイン酸、無水マレイン酸などに由来する構成単位であり、特に最良の性能を発現するためにはフマル酸を相当な割合で、例えば重合体の総質量に対して１０質量％以上含有することが良い。
上記構成単位（ＩＩ）において酸（−ＣＯＯＨ）及び／または酸塩（−ＣＯＯＭ）が含まれる場合、これらは酸の形態でも中和された形態でも良いが、部分中和又は完全中和された形態が製品形態として好ましい。Specifically, the structural unit (II) is a structural unit derived from acrylic acid, methacrylic acid, fumaric acid, maleic acid, maleic anhydride, etc. In order to express the best performance, fumaric acid is used. It is good to contain 10 mass% or more with a considerable ratio, for example with respect to the total mass of a polymer.
When the structural unit (II) contains an acid (—COOH) and / or an acid salt (—COOM), these may be in an acid form or a neutralized form, but may be partially neutralized or completely neutralized. The form is preferred as the product form.
また上記構成単位（ＩＩ）において酸誘導体（−ＣＯＯＹ）が含まれる場合、Ｙは具体的には炭素原子数１乃至２２の部分エステル又は全エステル、ポリアルキレンオキサイド付加物の部分エステル又は全エステル、（アルコキシ）ポリアルキレングリコールの部分エステル又は全エステルなどが挙げられる。より具体的には、メトキシポリエチレングリコールモノ（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート等の（アルコキシ）ポリアルキレングリコールモノ（メタ）アクリレート類、メトキシポリエチレングリコールモノマレート、メトキシポリエチレングリコールジマレート、ポリエチレングリコールモノマレート、ポリエチレングリコールジマレート等の（アルコキシ）ポリアルキレングリコールマレート類、メトキシポリエチレングリコールモノフマレート、メトキシポリエチレングリコールジフマレート、ポリエチレングリコールモノフマレート、ポリエチレングリコールジフマレート等の（アルコキシ）ポリアルキレングリコールフマレート類が挙げられる。アルキレンオキサイドは単独付加又は混合付加することができ、二種以上のアルキレンオキサイドを用いる場合にはブロック付加、ランダム付加何れの形態であっても良い。フマル酸誘導体の具体例としてはメトキシポリエチレングリコールジフマレートを挙げることができる。
上記構成単位（ＩＩ）において、フマル酸及び／又はフマル酸誘導体に由来する構成単位を含む場合には、それら構成単位は、全構成単位（ＩＩ）の全質量に対して、好ましくは１０乃至１００質量％、更に好ましくは２０乃至１００質量％、特に好ましくは３０乃至１００質量％、最も好ましくは５０乃至１００質量％の割合で含むことが望ましい。In addition, when the structural unit (II) contains an acid derivative (—COOY), Y is specifically a partial ester or a total ester having 1 to 22 carbon atoms, a partial ester or a total ester of a polyalkylene oxide adduct, Examples include (alkoxy) polyalkylene glycol partial esters or total esters. More specifically, (alkoxy) polyalkylene glycol mono (meth) acrylates such as methoxypolyethylene glycol mono (meth) acrylate and polyethylene glycol mono (meth) acrylate, methoxypolyethylene glycol monomaleate, methoxypolyethylene glycol dimaleate, polyethylene (Alkoxy) polyalkylene glycol malates such as glycol monomalate and polyethylene glycol dimaleate, (alkoxy) such as methoxypolyethylene glycol monofumarate, methoxypolyethylene glycol difumarate, polyethylene glycol monofumarate, polyethylene glycol difumarate Examples include polyalkylene glycol fumarate. Alkylene oxides can be added individually or in a mixed manner. When two or more types of alkylene oxide are used, either block addition or random addition may be used. Specific examples of the fumaric acid derivative include methoxypolyethylene glycol difumarate.
When the structural unit (II) includes a structural unit derived from fumaric acid and / or a fumaric acid derivative, the structural unit is preferably 10 to 100 with respect to the total mass of the total structural unit (II). It is desirable to include it in a proportion of mass%, more preferably 20 to 100 mass%, particularly preferably 30 to 100 mass%, and most preferably 50 to 100 mass%.
本発明のセメント分散剤は、最も好ましくは、ポリアルキレンオキサイド鎖が、平均付加モル数５０以上のエチレンオキサイド鎖の末端に、プロピレンオキサイド又はブチレンオキサイドが結合してなるポリアルキレンオキサイド鎖（該プロピレンオキサイド又はブチレンオキサイドは該アルキレンオキサイド鎖の全モル数に対して０．１乃至２０ｍｏｌ％の割合で含有する）を有する不飽和アルコールアルキレンオキサイド系化合物に由来する構成単位（Ｉ）と、フマル酸由来の構成単位を相当な割合（重合体の総質量に対して１０質量％以上）で含む構成単位（ＩＩ）からなることが望ましい。 The cement dispersant of the present invention is most preferably a polyalkylene oxide chain in which propylene oxide or butylene oxide is bonded to the terminal of an ethylene oxide chain having an average addition mole number of 50 or more. Or the butylene oxide is contained in a proportion of 0.1 to 20 mol% with respect to the total number of moles of the alkylene oxide chain) and the structural unit (I) derived from an unsaturated alcohol alkylene oxide compound, and derived from fumaric acid It is desirable to comprise the structural unit (II) containing a structural unit in a considerable proportion (10% by mass or more based on the total mass of the polymer).
［構成単位（ＩＩＩ）］
また本発明のセメント分散剤は、上記構成単位（Ｉ）及び（ＩＩ）に加えポリアミドポリアミン及び／又はポリアミドポリアミン変性物に由来する構成単位（ＩＩＩ）を含むポリカルボン酸系重合体を含有してなる。
構成単位（ＩＩＩ）は下記式で表される。
Moreover, the cement dispersant of the present invention contains a polycarboxylic acid polymer containing a structural unit (III) derived from a polyamide polyamine and / or a modified polyamide polyamine in addition to the structural units (I) and (II). Become.
The structural unit (III) is represented by the following formula.
上記構成単位（ＩＩＩ）中、Ｚを構成する上記二塩基酸としては総炭素原子数が２乃至１０の脂肪族飽和二塩基酸、例えばシュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸等が挙げられ、ポリアルキレンポリアミンとしてはエチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン、ヘキサエチレンヘプタミン、あるいはエチレン単位と窒素原子を多く含む混合体である高分子ポリエチレンポリアミンの混合物等を挙げることができる。 In the structural unit (III), the dibasic acid constituting Z is an aliphatic saturated dibasic acid having 2 to 10 carbon atoms, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, Pimelic acid, suberic acid, azelaic acid, sebacic acid, and the like. Examples of polyalkylene polyamines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexaethyleneheptamine, or ethylene units and nitrogen atoms. Examples thereof include a mixture of high-molecular polyethylene polyamines, which is a mixture containing a large amount.
上記構成単位（ＩＩＩ）は、これら二塩基酸とポリアルキレンポリアミンの縮合物であるポリアミドポリアミン及び／又は、該ポリアミドポリアミンの活性イミノ基、アミノ基、アミド残基１当量に対して、炭素原子数２乃至４のアルキレンオキサイドを０．１乃至１０モル付加させたポリアミドポリアミン変性物が、無水マレイン酸、マレイン酸、フマル酸とアミド結合を介し、結合してなる構成単位である。
これらポリアミドポリアミン又はポリアルキレンオキサイド変性ポリアミドポリアミンは水溶液で塩基性を示す性質を有するものもある為、ポリカルボン酸系重合体の中和剤として作用することもある。The structural unit (III) is a polyamide polyamine which is a condensate of these dibasic acid and polyalkylene polyamine and / or the number of carbon atoms with respect to 1 equivalent of the active imino group, amino group and amide residue of the polyamide polyamine. A polyamide polyamine modified product obtained by adding 2 to 4 alkylene oxides in an amount of 0.1 to 10 mol is a structural unit formed by bonding maleic anhydride, maleic acid, fumaric acid and an amide bond through an amide bond.
Since some of these polyamide polyamines or polyalkylene oxide-modified polyamide polyamines have a property of being basic in an aqueous solution, they may act as a neutralizing agent for the polycarboxylic acid polymer.
［各構成単位の構成割合］
上述の構成単位（Ｉ）及び構成単位（ＩＩ）からなるポリカルボン酸系重合体において、それらの構成割合は構成単位（Ｉ）：構成単位（ＩＩ）＝９５乃至６０質量％：５乃４０質量％、好ましくは構成単位（Ｉ）：構成単位（ＩＩ）＝９０乃至７０質量％：１０乃至３０質量％、最も好ましくは構成単位（Ｉ）：構成単位（ＩＩ）＝９０乃至８０質量％：１０乃至２０質量％の範囲にあることが望ましい。また、構成単位（Ｉ）乃至構成単位（ＩＩＩ）からなるポリカルボン酸系重合体においては、構成単位（Ｉ）：構成単位（ＩＩ）：構成単位（ＩＩＩ）＝９０乃至５０質量％：８乃至４０質量％：２乃至１０質量％、好ましくは、構成単位（Ｉ）：構成単位（ＩＩ）：構成単位（ＩＩＩ）＝９０乃至６０質量％：８乃至３０質量％：２乃至７質量％の範囲にあることが望ましい。（但し、構成単位（Ｉ）及び構成単位（ＩＩ）、又は、構成単位（Ｉ）乃至構成単位（ＩＩＩ）の合計は何れも１００質量％である。）[Composition ratio of each structural unit]
In the polycarboxylic acid polymer composed of the structural unit (I) and the structural unit (II) described above, the structural ratio thereof is structural unit (I): structural unit (II) = 95 to 60% by mass: 5-40 mass %, Preferably structural unit (I): structural unit (II) = 90 to 70% by mass: 10 to 30% by mass, most preferably structural unit (I): structural unit (II) = 90 to 80% by mass: 10 It is desirable to be in the range of 20 to 20% by mass. In the polycarboxylic acid polymer composed of the structural unit (I) to the structural unit (III), the structural unit (I): the structural unit (II): the structural unit (III) = 90 to 50% by mass: 8 to 40% by mass: 2 to 10% by mass, preferably, structural unit (I): structural unit (II): structural unit (III) = 90 to 60% by mass: 8 to 30% by mass: 2 to 7% by mass It is desirable to be in (However, the total of the structural unit (I) and the structural unit (II) or the structural unit (I) to the structural unit (III) is 100% by mass.)
［その他含有し得る構成単位（ＩＶ）］
上述のポリカルボン酸系重合体において、これら構成単位（Ｉ）乃至（ＩＩＩ）以外に、構成単位（ＩＶ）を含有することができる。
上記その他含有しうる構成単位（ＩＶ）の由来となる化合物としては、（メタ）アクリル酸（塩）、（メタ）アクリル酸ポリアルキレングリコールモノアルキルエーテル、（メタ）アリルスルホン酸（塩）、スチレンスルホン酸（塩）、（メタ）アクリル酸アルキル、スチレン、（メタ）アクリルアミド等の慣用のポリカルボン酸系セメント分散剤用単量体として例示される化合物であり、上記構成単位（Ｉ）乃至（ＩＩＩ）と重合体を形成可能な化合物であればその種類は特に限定されない。特に上記ポリカルボン酸系重合体にスランプ保持性を付与すべくアルカリ加水分解性の化合物に由来する構成単位を組み込むことは、特許第３７８０４６５号公報等との組合せで容易に想到できる手段の一つである。
上記構成単位（ＩＶ）の構成割合は、前記ポリカルボン酸系重合体等（構成単位（Ｉ）乃至（ＩＩＩ））：構成単位（ＩＶ）＝１００乃至７０質量％：０乃至３０質量％の範囲（但し合計１００質量％）の範囲にあることが好ましい。[Other structural units (IV) that may be contained]
In the above-mentioned polycarboxylic acid polymer, the structural unit (IV) can be contained in addition to these structural units (I) to (III).
Examples of the compound from which the other structural unit (IV) that can be contained includes (meth) acrylic acid (salt), (meth) acrylic acid polyalkylene glycol monoalkyl ether, (meth) allylsulfonic acid (salt), styrene Compounds exemplified as monomers for conventional polycarboxylic acid-based cement dispersants such as sulfonic acid (salt), alkyl (meth) acrylate, styrene, (meth) acrylamide, and the like, the structural units (I) to ( If it is a compound which can form a polymer with III), the kind will not be specifically limited. In particular, incorporation of a structural unit derived from an alkali hydrolyzable compound to impart slump retention to the polycarboxylic acid polymer is one of the means that can be easily conceived in combination with Japanese Patent No. 3780465. It is.
The structural ratio of the structural unit (IV) is a range of the polycarboxylic acid polymer or the like (structural units (I) to (III)): structural unit (IV) = 100 to 70% by mass: 0 to 30% by mass. However, it is preferably in the range of 100% by mass.
［ポリアミドポリアミン及び／またはポリアミドポリアミン変性物］
本発明のセメント分散剤は、上記ポリカルボン酸系重合体に加え、二塩基酸とポリアルキレンポリアミンを縮合させたポリアミドポリアミン及び／又は該ポリアミドポリアミンの活性イミノ基、アミノ基、アミド残基１当量に対して炭素原子数２乃至４のアルキレンオキサイドを０．１乃至１０モル付加させたポリアミドポリアミン変性物を含有することが、コンクリート粘性を改良する点で好ましい。
これらポリアミドポリアミン及び／またはポリアミドポリアミン変性物の含有比率は、上記ポリカルボン酸系重合体：ポリアミドポリアミン及び／またはポリアミドポリアミン変性物＝９８乃至９０質量％：２乃至１０質量％の範囲にあることが好ましい。[Polyamide polyamine and / or modified polyamide polyamine]
The cement dispersant of the present invention is a polyamide polyamine obtained by condensing a dibasic acid and a polyalkylene polyamine and / or an active imino group, amino group, and 1 equivalent of an amide residue in addition to the above polycarboxylic acid polymer. In view of improving the concrete viscosity, it is preferable to contain a modified polyamide polyamine obtained by adding 0.1 to 10 moles of an alkylene oxide having 2 to 4 carbon atoms.
The content ratio of these polyamide polyamine and / or polyamide polyamine modified product may be in the range of the above polycarboxylic acid polymer: polyamide polyamine and / or polyamide polyamine modified product = 98 to 90 mass%: 2 to 10 mass%. preferable.
上記ポリアミドポリアミンを構成するポリアルキレンポリアミンとしては、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン、ヘキサエチレンヘプタミン、あるいはエチレン単位と窒素原子を多く含む混合体である高分子ポリエチレンポリアミンの混合物等や、ポリエチレンイミン、ポリプロピレンイミン、ポリ−３−メチルプロピルイミン、ポリ−２−エチルプロピルイミン等の環状イミンの重合体、ポリビニルアミン、ポリアリルアミンの如き不飽和アミンの重合体等が挙げられる。更にポリアルキレンポリアミンは、エチレンイミン、プロピレンイミン、３−メチルプロピルイミン、２−エチルプロピルイミン等の環状イミン、Ｎ−ビニルアセトアミド、Ｎ−ビニルホルムアミド、Ｎ−ビニルフタルイミド等の不飽和アミド、不飽和イミドと、これらと共重合可能な不飽和化合物との共重合体であってもよい。環状イミン、不飽和アミド、不飽和イミド等と共重合可能な不飽和化合物としては、例えばジメチルアクリルアミド、スチレン、アクリル酸メチル、メタクリル酸メチル、アクリル酸、メタクリル酸、スチレンスルホン酸やこれらの塩、エチレンスルフィドやプロピレンスルフィド等の環状スルフィド化合物、オキセタン、モノ又はビスアルキルオキセタン、モノ又はビスアルキルクロロメチルオキセタン、テトラヒドロフラン、モノ又はビスアルキルテトラフロロフラン等の環状エーテル類、１，２−ジオキソフラン、トリオキソフラン等の環状ホルマール類、Ｎ−メチルエチレンイミン等のＮ置換アルキルイミン等が挙げられる。 The polyalkylene polyamines constituting the polyamide polyamine include ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, hexaethylene heptamine, or a high molecular polyethylene which is a mixture containing a large amount of ethylene units and nitrogen atoms. A mixture of polyamines, polymers of cyclic imines such as polyethyleneimine, polypropyleneimine, poly-3-methylpropylimine, poly-2-ethylpropylimine, polymers of unsaturated amines such as polyvinylamine and polyallylamine, etc. Can be mentioned. Furthermore, polyalkylene polyamines are cyclic imines such as ethyleneimine, propyleneimine, 3-methylpropylimine, 2-ethylpropylimine, unsaturated amides such as N-vinylacetamide, N-vinylformamide, N-vinylphthalimide, and unsaturated. It may be a copolymer of an imide and an unsaturated compound copolymerizable therewith. Examples of unsaturated compounds copolymerizable with cyclic imines, unsaturated amides, unsaturated imides, etc. include dimethylacrylamide, styrene, methyl acrylate, methyl methacrylate, acrylic acid, methacrylic acid, styrene sulfonic acid and their salts, Cyclic sulfide compounds such as ethylene sulfide and propylene sulfide, cyclic ethers such as oxetane, mono- or bisalkyloxetane, mono- or bisalkylchloromethyloxetane, tetrahydrofuran, mono- or bisalkyltetrafluorofuran, 1,2-dioxofuran, trioxy Examples thereof include cyclic formals such as sofuran and N-substituted alkylimines such as N-methylethyleneimine.
上記ポリアミドポリアミンを構成する二塩基酸としては、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸等の総炭素原子数が２乃至１０の脂肪族飽和二塩基酸が挙げられる。
二塩基酸としてその誘導体も使用可能であり、例えば二塩基酸無水物（例えば上記二塩基酸の無水物）、二塩基酸エステル（例えば上記二塩基酸のモノメチルエステル、モノエチルエステル、モノブチルエステル、モノプロピルエステル、ジメチルエステル、ジエチルエステル、ジブチルエステル、ジプロピルエステル等）、又は二塩基酸ジハライド（前記二塩基酸の二塩化物、二臭素化物、二ヨウ化物等）を挙げることができる。Examples of the dibasic acid constituting the polyamide polyamine include fatty acids having 2 to 10 carbon atoms in total such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. Group saturated dibasic acids.
Derivatives thereof can also be used as dibasic acids, for example, dibasic acid anhydrides (eg, anhydrides of the above dibasic acids), dibasic acid esters (eg, monomethyl esters, monoethyl esters, monobutyl esters of the above dibasic acids) , Monopropyl ester, dimethyl ester, diethyl ester, dibutyl ester, dipropyl ester, etc.), or dibasic acid dihalides (dichloride, dibromide, diiodide, etc. of the dibasic acid).
また上記ポリアミドポリアミン変性物とは、上記ポリアミドポリアミンの活性イミノ基、アミノ基、アミド残基１当量に対し炭素原子数２乃至４のアルキレンオキサイドを０．１乃至１０モル付加せしめた化合物を示す。すなわち、このアルキレンオキサイドとしては、エチレンオキサイド、プロピレンオキサイド、ブチレンオキサイド等が挙げられ、これらは単独もしくは混合して用いることができ、２種以上のアルキレンオキサイドを用いる場合にはブロック状に重合していてもランダムに重合していても良い。 The modified polyamide polyamine is a compound obtained by adding 0.1 to 10 moles of alkylene oxide having 2 to 4 carbon atoms to 1 equivalent of the active imino group, amino group, and amide residue of the polyamide polyamine. That is, examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, and the like. These can be used alone or in combination. When two or more alkylene oxides are used, they are polymerized in a block shape. Alternatively, it may be polymerized randomly.
［各構成単位及びポリカルボン酸系重合体の製造方法］
本発明のセメント分散剤であるポリカルボン酸系重合体を得るにあたり、構成単位（Ｉ）の由来となる不飽和アルコールアルキレンオキサイド付加物の製造方法、及びポリカルボン酸系重合体を得る重合方法は特に限定されない。
ただし、上記不飽和アルコールアルキレンオキサイド付加物製造時のアルキレンオキサイド付加反応においては、重合活性基（不飽和基）がその重合活性を失わない、重合活性基の位置を転移させない、及び、副生するジオール分を低減することなどに留意して製造される必要がある。なお、これら重合活性基を有するアルコールのポリアルキレンオキサイド付加物は、製造後に精製過程の有無に係わらず重合用原料とし使用することができる。
ポリカルボン酸系重合体の製造方法に於いては、溶剤重合、水溶液重合、連続式、バッチ式の何れの方法においても同様の重合物を得ることができるが、一般的に水溶液重合で行われることが多い。[Methods for producing each structural unit and polycarboxylic acid polymer]
In obtaining the polycarboxylic acid polymer which is the cement dispersant of the present invention, a method for producing an unsaturated alcohol alkylene oxide adduct derived from the structural unit (I), and a polymerization method for obtaining the polycarboxylic acid polymer are: There is no particular limitation.
However, in the alkylene oxide addition reaction during the production of the unsaturated alcohol alkylene oxide adduct, the polymerization active group (unsaturated group) does not lose its polymerization activity, does not transfer the position of the polymerization active group, and is a by-product. It needs to be manufactured with attention paid to reducing the diol content. In addition, the polyalkylene oxide adduct of alcohol having a polymerization active group can be used as a raw material for polymerization regardless of the presence or absence of a purification process after production.
In the method for producing a polycarboxylic acid-based polymer, the same polymer can be obtained by any of solvent polymerization, aqueous solution polymerization, continuous type, and batch type methods. There are many cases.
構成単位（ＩＩＩ）の製造方法は、通常のアマイド化法に従い、二塩基酸とポリアミドポリアミンを縮合させ、更にマレイン酸、フマル酸、無水マレイン酸とのアマイド基を形成し、必要に応じアルキレンオキサイドを付加する方法、二塩基酸とポリアミドポリアミンとの縮合物或いはアルキレンオキサイドを付加したアルキレンオキサイド変性ポリアミドポリアミンを形成させポリカルボン酸系重合体にグラフト化させる方法、ポリアミドポリアミンを形成後ポリカルボン酸系重合体にグラフト化させたポリマー水溶液にアルキレンオキサイドを付加する方法等を挙げることができる。 The structural unit (III) is produced by condensing a dibasic acid and a polyamide polyamine in accordance with a usual amidation method, and further forming an amide group with maleic acid, fumaric acid, and maleic anhydride, and if necessary, alkylene oxide A method of adding a polybasic acid, a polycondensate of a dibasic acid and a polyamide polyamine, or a method of forming an alkylene oxide-modified polyamide polyamine added with an alkylene oxide and grafting it to a polycarboxylic acid polymer, after forming a polyamide polyamine Examples thereof include a method of adding alkylene oxide to an aqueous polymer solution grafted to a polymer.
最終的に得られる本発明のセメント分散剤であるポリカルボン酸系重合体は、重量平均分子量（ゲルパーミエーションクロマトグラフィー法（以下「ＧＰＣ法」と呼ぶ）、ポリエチレングリコール換算）で１０，０００〜５００，０００の範囲が適当であり、この範囲を外れると減水性が著しく低下するか、あるいは所望のスランプロス低減効果を得ることができない。より好ましくは、重量平均分子量が１０，０００〜１００，０００の範囲であることが、更に減水性及びスランプ保持性を発現するため望ましい。また水溶液重合においてラジカル重合開始剤等の種類及び／又は使用量を調整することにより、分子量を制御することが可能であるが、連鎖移動剤等を併用すれば分子量分布の制御を行うことも可能である。
なお本発明におけるセメント分散剤には、ポリカルボン酸系重合体のみからなるものでも良いが、一般に、各々の重合工程、アルキレンオキサイド付加工程等で発生した未反応成分、副反応物も含めた成分も包含されている。The finally obtained polycarboxylic acid polymer which is the cement dispersant of the present invention has a weight average molecular weight (gel permeation chromatography method (hereinafter referred to as “GPC method”), in terms of polyethylene glycol) of 10,000 to The range of 500,000 is appropriate, and if it is out of this range, the water reduction is remarkably reduced or the desired slump loss reduction effect cannot be obtained. More preferably, the weight average molecular weight is in the range of 10,000 to 100,000 in order to further exhibit water reduction and slump retention. In addition, the molecular weight can be controlled by adjusting the type and / or amount of radical polymerization initiator used in aqueous solution polymerization, but the molecular weight distribution can also be controlled by using a chain transfer agent together. It is.
The cement dispersant in the present invention may be composed only of a polycarboxylic acid-based polymer, but in general, components including unreacted components and side reactants generated in each polymerization step, alkylene oxide addition step, etc. Are also included.
［セメント混和剤及び併用可能な混和剤］
本発明のセメント分散剤は、種々のコンクリート製造条件に応じ、好適な公知公用の混和剤等を採用して組合せ、セメント混和剤とすることができる。具体的には、本発明のセメント分散剤以外のセメント分散剤、空気連行剤、凝結遅延剤、促進剤、分離低減剤、増粘剤、消泡剤、収縮低減剤等である。
なお、本発明のポリカルボン酸系重合体からなるセメント分散剤とは、上述のポリカルボン酸系重合体以外に公知公用の混和剤を配合しセメント混和剤とした形態、又はコンクリート製造時に上述のポリカルボン酸系重合体と公知公用の混和剤が別々に添加され最終的にコンクリート中で混合される形態の何れをも含む。以下公知公用の混和剤を例示する。[Cement admixture and compatible admixture]
The cement dispersant of the present invention can be combined into a cement admixture by employing a suitable publicly known admixture according to various concrete production conditions. Specifically, cement dispersants other than the cement dispersant of the present invention, air entraining agents, setting retarders, accelerators, separation reducing agents, thickeners, antifoaming agents, shrinkage reducing agents, and the like.
In addition, the cement dispersant comprising the polycarboxylic acid polymer of the present invention is a form in which a publicly known admixture is blended in addition to the polycarboxylic acid polymer described above to form a cement admixture, or the above-mentioned at the time of concrete production. The polycarboxylic acid polymer and the publicly known admixture are added separately and finally mixed in concrete. The publicly known admixtures are exemplified below.
一般にセメント分散剤は、コンクリートの製造条件及び性能要求等に応じて、適宜組み合わされ使用される。本発明のセメント分散剤の場合も同様であり、セメント分散剤として単独、あるいは主剤として使用されるものであるが、スランプロスの大きいセメント分散剤の改質助剤として、或いは、初期減水性が高いセメント分散剤として併用して使用され得るものである。
本発明以外の公知のセメント分散剤としては先に挙げた特許文献１のほか、特公昭５９−１８３３８号公報、特許２６２８４８６号公報、特許第２７７４４４５号公報、特許第３２３５００２号公報、特許第３３３６４５６号公報、特許第３７８０４５６号公報などのポリカルボン酸系共重合体の塩があり、またナフタレンスルホン酸ホルマリン縮合物の塩、メラミンスルホン酸ホルマリン縮合物の塩、リグニンスルホン酸塩、グルコン酸ソーダ、糖アルコールも挙げられる。本発明のセメント分散剤と本発明以外のセメント分散剤との配合割合は１：９９〜９９：１質量％である。Generally, cement dispersants are appropriately combined and used according to concrete production conditions and performance requirements. The same applies to the cement dispersant of the present invention, which is used as a cement dispersant alone or as a main agent, but as a modification aid for a cement dispersant having a large slump loss, or has an initial water reduction. It can be used in combination as a high cement dispersant.
As well-known cement dispersants other than the present invention, in addition to the above-mentioned Patent Document 1, Japanese Patent Publication No. 59-18338, Japanese Patent No. 2628486, Japanese Patent No. 2774445, Japanese Patent No. 323002, and Japanese Patent No. 3336456. No. 3,780,456, and the like, and salts of polycarboxylic acid copolymers, naphthalene sulfonic acid formalin condensate, melamine sulfonic acid formalin condensate salt, lignin sulfonate, gluconate soda, sugar Also includes alcohol. The blending ratio of the cement dispersant of the present invention and the cement dispersant other than the present invention is 1:99 to 99: 1 mass%.
空気連行剤を具体的に例示すると＜１＞アニオン系空気連行剤、＜２＞ノニオン系空気連行剤、及び＜３＞両性系空気連行剤が挙げられる。＜１＞アニオン系空気連行剤としては高級アルコール（又はそのアルキレンオキシド付加物）の硫酸エステル塩、アルキルベンゼンスルホン酸塩、ロジン石鹸などの樹脂石鹸塩、高級アルコール（又はそのアルキレンオキシド付加物）の燐酸エステル塩など、＜２＞ノニオン系空気連行剤としてはアルキレングリコール、高級アルコールのアルキレンオキサイド付加物、脂肪酸とアルキレングルコールとのエステル、糖アルコールのアルキレングルコール付加物など、＜３＞アニオン、カチオンからなる両性系空気連行剤としてはアルキルベタイン型、アルキルアミドベタイン型、アミノ酸系両性活性剤型などが挙げられる。本空気連行剤の好ましい添加量はセメント分散剤に対し０．００１〜０．０３質量％である。 Specific examples of the air entraining agent include <1> anionic air entraining agent, <2> nonionic air entraining agent, and <3> amphoteric air entraining agent. <1> As anionic air entraining agents, sulfuric acid ester salts of higher alcohols (or alkylene oxide adducts thereof), resin soap salts such as alkylbenzene sulfonates and rosin soaps, phosphoric acid of higher alcohols (or alkylene oxide adducts thereof) <2> Nonionic air entraining agents such as ester salts include alkylene glycol, alkylene oxide adducts of higher alcohols, esters of fatty acids and alkylene glycols, alkylene glycol adducts of sugar alcohols, <3> anions and cations Examples of the amphoteric air entraining agent comprising alkylbetaine type, alkylamide betaine type, and amino acid type amphoteric activator type. The preferred amount of addition of the air entraining agent is 0.001 to 0.03% by mass with respect to the cement dispersant.
凝結遅延剤を例示すると、＜１＞無機質系凝結遅延剤：リン酸塩、珪フッ化物、酸化亜鉛、炭酸化亜鉛、塩化亜鉛、一酸化亜鉛、水酸化銅、マグネシア塩、ホウ砂、酸化ホウ素、＜２＞有機質系凝結遅延剤：ホスホン誘導体、糖類やその誘導体、オキシカルボン酸塩、リグニンスルホン酸塩が挙げられ、さらに詳しく例示するとホスホン誘導体：アミノトリ（メチレンホスホン酸）、アミノトリ（メチレンホスホン酸）５ナトリウム塩、１−ヒドロキシエチリデン−１，１−ジホスホン酸、ジエチレントリアミンペンタ（メチレンホスホン酸）及びアルカリ金属塩、アルカリ土類金属塩のホスホン酸及びその誘導体、糖類：サッカロース、マルトース、ラフィノース、ラクトース、グルコース、フラクトース、マンノース、アラビノース、キシロース、アビトース、リポーズ、オキシカルボン酸塩：グルコン酸、クエン酸、グルコヘプトン酸、リンゴ酸、酒石酸、これらのアルカリ金属塩、アルカリ土類金属塩が挙げられる。本凝結遅延剤の好ましい添加量はセメント等の結合材料に対して０．０１〜１．５質量％である。 Examples of setting retarders include: <1> inorganic setting retarders: phosphates, silicofluorides, zinc oxide, zinc carbonate, zinc chloride, zinc monoxide, copper hydroxide, magnesia salts, borax, boron oxide <2> Organic coagulation retarders: phosphonic derivatives, saccharides and derivatives thereof, oxycarboxylates, lignin sulfonates, and more specific examples include phosphonic derivatives: aminotri (methylenephosphonic acid), aminotri (methylenephosphonic acid) ) Pentasodium salt, 1-hydroxyethylidene-1,1-diphosphonic acid, diethylenetriaminepenta (methylenephosphonic acid) and alkali metal salts, phosphonic acids of alkaline earth metal salts and derivatives thereof, saccharides: saccharose, maltose, raffinose, lactose Glucose, fructose, mannose, arabinose, key Loin, Abitosu, Repose, oxycarboxylate: gluconic acid, citric acid, glucoheptonic acid, malic acid, tartaric acid, their alkali metal salts, alkaline earth metal salts. A preferable addition amount of the setting retarder is 0.01 to 1.5% by mass with respect to a binding material such as cement.
促進剤を例示すると塩化カルシウム、亜硝酸カルシウムなどで代表される無機系促進剤、アルカノールアミンなどで代表される有機系促進剤が挙げられる。本促進剤の好ましい添加量はセメント等の結合材料に対して０．５〜５質量％である。 Examples of the accelerator include inorganic accelerators represented by calcium chloride, calcium nitrite and the like, and organic accelerators represented by alkanolamine and the like. A preferable addition amount of the accelerator is 0.5 to 5% by mass with respect to a binding material such as cement.
増粘剤・分離低減剤を例示すると、＜１＞セルロース系水溶性高分子：セルロースエーテル（ＭＣなど）、＜２＞ポリアクリルアミド系水溶性高分子：ポリアクリルアミド、＜３＞バイオポリマー：カードラン、ウエランガム、＜４＞非イオン系増粘剤：ポリアルキレングリコールの脂肪酸ジエステル、ポリアルキレングリコールのウレタン縮合物などが挙げられる。本増粘・分離低減剤の好ましい配合割合はコンクリート組成物に対し０．０１〜０．５質量％である。 Examples of thickeners / separation reducing agents include: <1> Cellulose-based water-soluble polymer: cellulose ether (MC, etc.), <2> Polyacrylamide-based water-soluble polymer: Polyacrylamide, <3> Biopolymer: Curdlan , Welan gum, <4> nonionic thickener: polyalkylene glycol fatty acid diester, polyalkylene glycol urethane condensate, and the like. A preferable blending ratio of the thickening / separation reducing agent is 0.01 to 0.5% by mass with respect to the concrete composition.
消泡剤を例示すると脂肪族アルコールアルキレンオキサイド付加物、脂肪酸アルキレンオキサイド付加物、アルキレンオキサイドジ脂肪酸エステル、多価アルコールアルキレンオキサイド付加物、ポリアルキレンポリアミンアルキレンオキサイド付加物等の非イオン系消泡剤類、シリコーンオイルをエマルションとしたシリコーン系消泡剤類、高級アルコールをエマルションとした高級アルコール類、これらを主成分とした混合物などが挙げられる。本消泡剤の好ましい添加量はセメント分散剤に対し０．０１〜１質量％である。 Examples of antifoaming agents include nonionic defoaming agents such as aliphatic alcohol alkylene oxide adducts, fatty acid alkylene oxide adducts, alkylene oxide difatty acid esters, polyhydric alcohol alkylene oxide adducts, polyalkylene polyamine alkylene oxide adducts, etc. And silicone-based antifoaming agents using silicone oil as an emulsion, higher alcohols using higher alcohol as an emulsion, and mixtures containing these as main components. The preferred amount of addition of the antifoaming agent is 0.01 to 1% by mass with respect to the cement dispersant.
収縮低減剤を例示するとポリアルキレングリコール、低級アルコールアルキレンオキサイド付加物、これらが油性である場合はエマルションとしたものであり、好ましい添加量はセメント等の結合材料に対し０．１〜５質量％である。 Examples of shrinkage reducing agents include polyalkylene glycols, lower alcohol alkylene oxide adducts, and emulsions when these are oily. The preferred addition amount is 0.1 to 5% by mass with respect to the binding material such as cement. is there.
本発明のセメント分散剤はコンクリートの材料を含めた配合条件によりその添加量が変わるが、セメント質量に対し固形分換算で通常０．０５〜５．０質量％程度添加される。減水性、スランプフロー保持性を得るためには添加量が多いほど良いが、多過ぎると凝結遅延を起こし、場合によっては硬化不良を引き起こす。使用方法は一般のセメント分散剤の場合と同様であり、コンクリート混練時に原液添加するか、予め混練水に希釈して添加する。あるいはコンクリート又はモルタルを練り混ぜた後に添加し、再度均一に混練しても良い。ここで、セメント分散剤以外の成分は従来慣用のコンクリート用成分であり、セメント（例えば普通ポルトランドセメント、早強ポルトランドセメント、低熱・中庸熱ポルトランドセメント又は高炉セメント等）、骨材（すなわち細骨材及び粗骨材）、混和材（例えばシリカフューム、炭酸カルシウム粉末、高炉スラグ粉末）、膨張材及び水を挙げることができる。また本発明のセメント分散剤以外の混和剤で調合時に別に添加できる混和剤としては、前記の公知公用の空気連行剤、凝結遅延剤、促進剤、分離低減剤、増粘剤、消泡剤、収縮低減剤等があり、これらも適宜配合し得る。それら各成分の配合割合は選択された成分の種類や使用目的に応じて適宜決定され得る。 Although the addition amount of the cement dispersant of the present invention varies depending on the blending conditions including the concrete material, it is generally added in an amount of about 0.05 to 5.0% by mass in terms of solid content with respect to the cement mass. In order to obtain water-reducing properties and slump flow retention, it is better that the amount added is larger. The method of use is the same as in the case of ordinary cement dispersants, and is added to the stock solution during concrete kneading or diluted in kneading water in advance. Alternatively, concrete or mortar may be added after kneading and kneaded uniformly again. Here, the components other than the cement dispersant are conventional concrete components, such as cement (for example, ordinary Portland cement, early strong Portland cement, low heat / moderate heat Portland cement or blast furnace cement), aggregate (that is, fine aggregate). And coarse aggregates), admixtures (for example, silica fume, calcium carbonate powder, blast furnace slag powder), expansion materials and water. Moreover, as an admixture that can be added separately at the time of preparation with an admixture other than the cement dispersant of the present invention, the above-mentioned publicly known air entraining agent, setting retarder, accelerator, separation reducing agent, thickener, antifoaming agent, There are shrinkage reducing agents and the like, and these can be appropriately blended. The blending ratio of these components can be appropriately determined according to the type of the selected component and the purpose of use.
本発明者らは数多くの重合体の研究を重ねた結果、特定のアルキレンオキサイドを特定の位置及び割合で付加させた不飽和アルコールアルキレンオキサイド付加物及び不飽和カルボン酸から構成されたポリカルボン酸系重合体、およびこのポリカルボン酸系重合体とポリアミドポリアミン及び／又はポリアルキレンオキサイド変性ポリアミドポリアミンを構成単位に含んだポリカルボン酸系重合体からなるセメント分散剤が、他の類似化合物よりも優れた減水性、スランプ保持性、コンクリート粘性を有することを見出すに至った。
如何にして上述の優れた効果が得られるのか未だ解明には至っていない。その仮定の一つとして、上記構成単位の組み合わせ、特に、従来広く使用されてきた不飽和アルコールアルキレンオキサイド付加物において付加するアルキレンオキサイドの種類、位置及びその割合をコントロールしたことが上記効果の発現に寄与したものとみている。すなわち、上記不飽和アルコールアルキレンオキサイド付加物において、特にポリアルキレンオキサイド末端が親水性基（水酸基など）で形成される場合に、セメントの水和反応に前記親水性基が取り込まれ初期分散性が低下し、ひいては経過変化におけるスランプロスを招き易い結果を引き起こすとみており、このため疎水性基であるプロピレンオキサイド等を特定量、特定の位置に配置することでこうした問題点の改善につながったものとみている。
また末端に疎水性基を配置することで表面張力低下現象が発生して微細な気泡の発生が起こり、さらに、添加されたポリアミドポリアミンによって気泡の安定化が図られたなどの効果が相まってコンクリート粘性も改善されたものとみている。As a result of repeated researches on many polymers by the present inventors, a polycarboxylic acid system composed of an unsaturated alcohol alkylene oxide adduct and an unsaturated carboxylic acid in which a specific alkylene oxide is added at a specific position and ratio. A cement dispersant comprising a polymer and a polycarboxylic acid polymer containing the polycarboxylic acid polymer and a polyamide polyamine and / or a polyalkylene oxide-modified polyamide polyamine as a constituent unit is superior to other similar compounds. It has been found that it has water reduction, slump retention, and concrete viscosity.
It has not yet been elucidated how the above-mentioned excellent effects can be obtained. As one of the assumptions, controlling the combination of the above structural units, particularly the type, position, and ratio of alkylene oxide added in unsaturated alcohol alkylene oxide adducts that have been widely used in the past, has manifested the above effects. We think that it contributed. That is, in the above unsaturated alcohol alkylene oxide adduct, particularly when the polyalkylene oxide terminal is formed with a hydrophilic group (such as a hydroxyl group), the hydrophilic group is incorporated into the hydration reaction of the cement, and the initial dispersibility is lowered. As a result, we think that it will cause a slump loss in the course of change, and this has led to the improvement of these problems by placing propylene oxide, which is a hydrophobic group, in a specific amount and a specific position. I'm watching.
In addition, by placing a hydrophobic group at the end, the phenomenon of surface tension lowering occurs and fine bubbles are generated, and the added polyamide polyamine stabilizes the bubbles and the effects of concrete viscosity are combined. Is also considered improved.
次に実施例に基づいて本発明をより詳しく説明する。なお本発明は前記製造方法により得られるものであり、この実施例に限定されるものではない。
なお、特に記載のない限り、以下に示す％は質量％を表す。Next, based on an Example, this invention is demonstrated in detail. In addition, this invention is obtained by the said manufacturing method, and is not limited to this Example.
In addition, unless otherwise indicated,% shown below represents mass%.
［製造例Ａ１（ＥＯ付加ポリアミドポリアミンの製造）］
窒素導入管、温度計、コンデンサー付き検水管を備えた攪拌機付き反応容器にポリアルキレンポリアミン（東ソー社製 品名：ポリエイト）１９９ｇ及びアジピン酸６８ｇを仕込み、窒素を導入しながら攪拌し、次いで温度を１６０℃になるまで昇温した。反応を８時間継続し、酸価が１０となった時点で反応を終了した。反応脱水量は１７ｇであった。次いで水２４５ｇを加えて水溶液として６０℃まで冷却後、エチレンオキサイド８９ｇを同温度で４時間かけて付加させ、その後１時間の熟成を行い、ＥＯ付加ポリアミドポリアミンＡ１の水溶液５８４ｇ（固形分濃度：５８％）を得た。[Production Example A1 (Production of EO-added polyamide polyamine)]
Into a reaction vessel equipped with a stirrer equipped with a nitrogen introduction tube, a thermometer, and a test tube with a condenser, 199 g of polyalkylene polyamine (product name: Polyate) and 68 g of adipic acid were charged, stirred while introducing nitrogen, and then the temperature was changed to 160 The temperature was raised to 0 ° C. The reaction was continued for 8 hours, and the reaction was terminated when the acid value reached 10. The amount of reaction dehydration was 17 g. Next, after adding 245 g of water and cooling to 60 ° C. as an aqueous solution, 89 g of ethylene oxide was added over 4 hours at the same temperature, followed by aging for 1 hour, and 584 g of an aqueous solution of EO-added polyamide polyamine A1 (solid content concentration: 58 %).
［製造例Ａ２（ポリアミドポリアミンの製造）］
窒素導入管、温度計、コンデンサー付き検水管を備えた攪拌機付き反応容器にポリアルキレンポリアミン（東ソー社製 品名：ポリエイト）１９９ｇ及びアジピン酸６８ｇを仕込み、窒素を導入しながら攪拌し、次いで温度を１６０℃になるまで昇温した。反応を８時間継続し酸価が１０となった時点で反応を終了した。反応脱水量は１７ｇであった。次いで水２５０ｇを加えて水溶液として６０℃まで冷却し、ポリアミドポリアミンＡ２の水溶液５００ｇ（固形分濃度：５０％）を得た。[Production Example A2 (Production of polyamide polyamine)]
Into a reaction vessel equipped with a stirrer equipped with a nitrogen introduction tube, a thermometer, and a test tube with a condenser, 199 g of polyalkylene polyamine (product name: Polyate) and 68 g of adipic acid were charged, stirred while introducing nitrogen, and then the temperature was changed to 160 The temperature was raised to 0 ° C. The reaction was continued for 8 hours and terminated when the acid value reached 10. The amount of reaction dehydration was 17 g. Next, 250 g of water was added and cooled to 60 ° C. as an aqueous solution to obtain 500 g of an aqueous solution of polyamide polyamine A2 (solid content concentration: 50%).
［製造例Ｂ１（ポリカルボン酸系重合体の製造）］
窒素導入管、攪拌機、温度計付きステンレス製オートクレーブに３−メチル−３−ブテン−１−オール５０ＥＯ２ＰＯ付加物４０２ｇ（ブロック付加物）、イオン交換水２８６ｇ、無水マレイン酸６．６２ｇ、フマル酸５９．６ｇを攪拌しながら仕込んだ。充分に窒素置換を行い、６０℃まで昇温させた後、過硫酸ナトリウム１４％水溶液２２．２ｇを仕込み、同温度を維持しながら６時間反応させた。反応終了後８０℃まで昇温し、１時間攪拌を継続した。次いでポリアミドポリアミンＡ１水溶液２６．７ｇ、イオン交換水１７０ｇを添加し、更に１時間攪拌した。重合液を５０℃まで冷却し、４８％苛性ソーダ水溶液２５．０ｇを用いて中和し、ポリカルボン酸系重合体Ｂ１の水溶液９９８ｇ（固形分濃度：５０％、重量平均分子量：２６，０００）を得た。[Production Example B1 (Production of polycarboxylic acid polymer)]
In a stainless steel autoclave equipped with a nitrogen introduction tube, a stirrer, and a thermometer, 402 g of 3-methyl-3-buten-1-ol 50EO2PO adduct (block adduct), 286 g of ion-exchanged water, 6.62 g of maleic anhydride, 59.fumaric acid 59. 6 g was charged with stirring. After sufficiently purging with nitrogen and raising the temperature to 60 ° C., 22.2 g of a 14% aqueous solution of sodium persulfate was charged and reacted for 6 hours while maintaining the same temperature. After completion of the reaction, the temperature was raised to 80 ° C., and stirring was continued for 1 hour. Next, 26.7 g of polyamide polyamine A1 aqueous solution and 170 g of ion-exchanged water were added, and the mixture was further stirred for 1 hour. The polymerization solution was cooled to 50 ° C., neutralized with 25.0 g of 48% aqueous sodium hydroxide solution, and 998 g of an aqueous solution of polycarboxylic acid polymer B1 (solid content concentration: 50%, weight average molecular weight: 26,000). Obtained.
［製造例Ｂ２（ポリカルボン酸系重合体の製造）］
窒素導入管、攪拌機、温度計付きステンレス製オートクレーブに３−メチル−３−ブテン−１−オール５０ＥＯ２ＰＯ付加物４０２ｇ（ブロック付加物）、イオン交換水２８６ｇ、無水マレイン酸３３．１ｇ、フマル酸３３．１ｇを攪拌しながら仕込んだ。充分に窒素置換を行い、６０℃まで昇温させた後、過硫酸ナトリウム１４％水溶液２２．２ｇを仕込み、同温度を維持しながら６時間反応させた。反応終了後８０℃まで昇温し、１時間攪拌を継続した。次いでポリアミドポリアミンＡ１水溶液２６．７ｇ、イオン交換水１７０ｇを添加し、更に１時間攪拌した。重合液を５０℃まで冷却し、４８％苛性ソーダ水溶液２５．０ｇを用いて中和し、ポリカルボン酸系重合体Ｂ２の水溶液９９８ｇ（固形分濃度：５０％、重量平均分子量：２９，０００）を得た。[Production Example B2 (Production of polycarboxylic acid polymer)]
In a stainless steel autoclave equipped with a nitrogen introduction tube, a stirrer and a thermometer, 402 g of 3-methyl-3-buten-1-ol 50EO2PO adduct (block adduct), 286 g of ion-exchanged water, 33.1 g of maleic anhydride, 33.fumaric acid 33. 1 g was charged with stirring. After sufficiently purging with nitrogen and raising the temperature to 60 ° C., 22.2 g of a 14% aqueous solution of sodium persulfate was charged and reacted for 6 hours while maintaining the same temperature. After completion of the reaction, the temperature was raised to 80 ° C., and stirring was continued for 1 hour. Next, 26.7 g of polyamide polyamine A1 aqueous solution and 170 g of ion-exchanged water were added, and the mixture was further stirred for 1 hour. The polymerization solution was cooled to 50 ° C., neutralized with 25.0 g of 48% aqueous sodium hydroxide solution, and 998 g of an aqueous solution of polycarboxylic acid polymer B2 (solid content concentration: 50%, weight average molecular weight: 29,000). Obtained.
［製造例Ｂ３（ポリカルボン酸系重合体の製造）］
窒素導入管、攪拌機、温度計付きステンレス製オートクレーブに３−メチル−３−ブテン−１−オール５０ＥＯ５ＰＯ付加物４０２ｇ（ブロック付加物）、イオン交換水２８６ｇ、無水マレイン酸６．６２ｇ、フマル酸５９．６ｇを攪拌しながら仕込んだ。充分に窒素置換を行い、６０℃まで昇温させた後、過硫酸ナトリウム１４％水溶液２２．２ｇを仕込み、同温度を維持しながら６時間反応させた。反応終了後８０℃まで昇温し、１時間攪拌を継続した。次いでポリアミドポリアミンＡ２水溶液３０．４ｇ、イオン交換水１６６ｇを添加し、更に１時間攪拌した。重合液を５０℃まで冷却し、４８％苛性ソーダ水溶液２５．０ｇを用いて中和し、ポリカルボン酸系重合体Ｂ３の水溶液９９８ｇ（固形分濃度：４９％、重量平均分子量：３１，０００）を得た。[Production Example B3 (Production of polycarboxylic acid polymer)]
In a stainless steel autoclave equipped with a nitrogen introduction tube, a stirrer, and a thermometer, 402 g of 3-methyl-3-buten-1-ol 50EO5PO adduct (block adduct), 286 g of ion-exchanged water, 6.62 g of maleic anhydride, 59. fumaric acid. 6 g was charged with stirring. After sufficiently purging with nitrogen and raising the temperature to 60 ° C., 22.2 g of a 14% aqueous solution of sodium persulfate was charged and reacted for 6 hours while maintaining the same temperature. After completion of the reaction, the temperature was raised to 80 ° C., and stirring was continued for 1 hour. Next, 30.4 g of polyamide polyamine A2 aqueous solution and 166 g of ion-exchanged water were added, and the mixture was further stirred for 1 hour. The polymerization solution was cooled to 50 ° C., neutralized with 25.0 g of 48% aqueous sodium hydroxide solution, and 998 g of an aqueous solution of polycarboxylic acid polymer B3 (solid content concentration: 49%, weight average molecular weight: 31,000). Obtained.
［製造例Ｂ４（ポリカルボン酸系重合体の製造）］
窒素導入管、攪拌機、温度計付きステンレス製オートクレーブに３−メチル−３−ブテン−１−オール５０ＥＯ２ＰＯ付加物４０２ｇ（ブロック付加物）、イオン交換水２８６ｇ、無水マレイン酸５９．６ｇ、フマル酸６．６２ｇを攪拌しながら仕込んだ。充分に窒素置換を行い、６０℃まで昇温させた後、過硫酸ナトリウム１４％水溶液２２．２ｇを仕込み、同温度を維持しながら６時間反応させた。反応終了後８０℃まで昇温し、１時間攪拌を継続した。次いでポリアミドポリアミンＡ１水溶液２６．７ｇ、イオン交換水１７０ｇを添加し、更に１時間攪拌した。重合液を５０℃まで冷却し、４８％苛性ソーダ水溶液２５．０ｇを用いて中和し、ポリカルボン酸系重合体Ｂ４の水溶液９９８ｇ（固形分濃度：５０％、重量平均分子量：３０，０００）を得た。[Production Example B4 (Production of polycarboxylic acid polymer)]
In a stainless steel autoclave equipped with a nitrogen introduction tube, a stirrer, and a thermometer, 402 g of 3-methyl-3-buten-1-ol 50EO2PO adduct (block adduct), 286 g of ion-exchanged water, 59.6 g of maleic anhydride, 6. 62 g was charged with stirring. After sufficiently purging with nitrogen and raising the temperature to 60 ° C., 22.2 g of a 14% aqueous solution of sodium persulfate was charged and reacted for 6 hours while maintaining the same temperature. After completion of the reaction, the temperature was raised to 80 ° C., and stirring was continued for 1 hour. Next, 26.7 g of polyamide polyamine A1 aqueous solution and 170 g of ion-exchanged water were added, and the mixture was further stirred for 1 hour. The polymerization solution was cooled to 50 ° C., neutralized with 25.0 g of 48% sodium hydroxide aqueous solution, and 998 g of an aqueous solution of polycarboxylic acid polymer B4 (solid content concentration: 50%, weight average molecular weight: 30,000). Obtained.
［製造例Ｂ５（ポリカルボン酸系重合体の製造）］
窒素導入管、攪拌機、温度計付きステンレス製オートクレーブに３−メチル−３−ブテン−１−オール５０ＥＯ０．５ＰＯ付加物４０２ｇ（ブロック付加物）、イオン交換水２８６ｇ、無水マレイン酸３３．１ｇ、フマル酸３３．１ｇを攪拌しながら仕込んだ。充分に窒素置換を行い、６０℃まで昇温させた後、過硫酸ナトリウム１４％水溶液２２．２ｇを仕込み、同温度を維持しながら６時間反応させた。反応終了後８０℃まで昇温し、１時間攪拌を継続した。次いでポリアミドポリアミンＡ２水溶液３０．４ｇ、イオン交換水１６６ｇを添加し、更に１時間攪拌した。重合液を５０℃まで冷却し、その後エチレンオキサイドの４ｇを重合液に対し付加し、同温度で１時間熟成後、４８％苛性ソーダ水溶液２５．０ｇを用いて中和し、ポリカルボン酸系重合体Ｂ５の水溶液９９８ｇ（固形分濃度：５０％、重量平均分子量：２９，０００）を得た。[Production Example B5 (Production of polycarboxylic acid polymer)]
Nitrogen inlet tube, stirrer, stainless steel autoclave with thermometer 402 g 3-methyl-3-buten-1-ol 50EO0.5PO adduct (block adduct), 286 g ion-exchanged water, 33.1 g maleic anhydride, fumaric acid 33.1 g was charged with stirring. After sufficiently purging with nitrogen and raising the temperature to 60 ° C., 22.2 g of a 14% aqueous solution of sodium persulfate was charged and reacted for 6 hours while maintaining the same temperature. After completion of the reaction, the temperature was raised to 80 ° C., and stirring was continued for 1 hour. Next, 30.4 g of polyamide polyamine A2 aqueous solution and 166 g of ion-exchanged water were added, and the mixture was further stirred for 1 hour. The polymerization solution is cooled to 50 ° C., and then 4 g of ethylene oxide is added to the polymerization solution. After aging at the same temperature for 1 hour, the solution is neutralized with 25.0 g of a 48% aqueous sodium hydroxide solution to obtain a polycarboxylic acid polymer. 998 g of an aqueous solution of B5 (solid content concentration: 50%, weight average molecular weight: 29,000) was obtained.
［製造例Ｂ６（ポリカルボン酸系重合体の製造）］
窒素導入管、攪拌機、温度計付きステンレス製オートクレーブに３−メチル−３−ブテン−１−オール５０ＥＯ２ＰＯ付加物４０２ｇ（ブロック付加物）、イオン交換水２８６ｇ、アクリル酸６．６２、無水マレイン酸５９．６ｇを攪拌しながら仕込んだ。充分に窒素置換を行い、６０℃まで昇温させた後、過硫酸ナトリウム１４％水溶液２２．２ｇを仕込み、同温度を維持しながら６時間反応させた。反応終了後８０℃まで昇温し、１時間攪拌を継続した。５０℃まで冷却後、４８％苛性ソーダ水溶液２５．０ｇ、イオン交換水１６４ｇを添加し、更に１時間攪拌した。ポリカルボン酸系重合体Ｂ６の水溶液９６５ｇ（固形分濃度：５０％、重量平均分子量：３７，０００）を得た。[Production Example B6 (Production of polycarboxylic acid polymer)]
In a stainless steel autoclave with a nitrogen introduction tube, a stirrer, and a thermometer, 402 g of 3-methyl-3-buten-1-ol 50EO2PO adduct (block adduct), 286 g of ion-exchanged water, 6.62 acrylic acid, 59. maleic anhydride. 6 g was charged with stirring. After sufficiently purging with nitrogen and raising the temperature to 60 ° C., 22.2 g of a 14% aqueous solution of sodium persulfate was charged and reacted for 6 hours while maintaining the same temperature. After completion of the reaction, the temperature was raised to 80 ° C., and stirring was continued for 1 hour. After cooling to 50 ° C., 25.0 g of 48% sodium hydroxide aqueous solution and 164 g of ion-exchanged water were added, and the mixture was further stirred for 1 hour. 965 g (solid content concentration: 50%, weight average molecular weight: 37,000) of an aqueous solution of polycarboxylic acid polymer B6 was obtained.
［製造例Ｃ１（ポリカルボン酸系重合体の製造）］
窒素導入管、攪拌機、温度計付きステンレス製オートクレーブに３−メチル−３−ブテン−１−オール７０ＥＯ付加物４０２ｇ、イオン交換水２８６ｇ、無水マレイン酸３３．１ｇ、フマル酸３３．１ｇを攪拌しながら仕込んだ。充分に窒素置換を行い、６０℃まで昇温させた後、過硫酸ナトリウム１４％水溶液２２．２ｇを仕込み、同温度を維持しながら６時間反応させた。反応終了後８０℃まで昇温し、１時間攪拌を継続した。５０℃まで冷却後、イオン交換水１６５ｇ、４８％苛性ソーダ水溶液２５．０ｇを添加し、更に１時間攪拌した。ポリカルボン酸系重合体Ｃ１の水溶液９６６ｇ（固形分濃度：５０％、重量平均分子量：２９，０００）を得た。[Production Example C1 (Production of polycarboxylic acid polymer)]
While stirring 402 g of 3-methyl-3-buten-1-ol 70EO, 286 g of ion-exchanged water, 33.1 g of maleic anhydride, and 33.1 g of fumaric acid in a stainless steel autoclave equipped with a nitrogen introduction tube, a stirrer, and a thermometer. Prepared. After sufficiently purging with nitrogen and raising the temperature to 60 ° C., 22.2 g of a 14% aqueous solution of sodium persulfate was charged and reacted for 6 hours while maintaining the same temperature. After completion of the reaction, the temperature was raised to 80 ° C., and stirring was continued for 1 hour. After cooling to 50 ° C., 165 g of ion exchanged water and 25.0 g of 48% aqueous sodium hydroxide solution were added, and the mixture was further stirred for 1 hour. 966 g of an aqueous solution of the polycarboxylic acid polymer C1 (solid content concentration: 50%, weight average molecular weight: 29,000) was obtained.
［製造例Ｃ２（ポリカルボン酸系重合体の製造）］
窒素導入管、攪拌機、温度計付きステンレス製オートクレーブに３−メチル−３−ブテン−１−オール２ＰＯ５０ＥＯ付加物４０２ｇ（ブロック付加物）、イオン交換水２８６ｇ、無水マレイン酸３３．１ｇ、フマル酸３３．１ｇを攪拌しながら仕込んだ。充分に窒素置換を行い、６０℃まで昇温させた後、過硫酸ナトリウム１４％水溶液２２．２ｇを仕込み、同温度を維持しながら６時間反応させた。反応終了後８０℃まで昇温し、１時間攪拌を継続した。５０℃まで冷却後、イオン交換水１６５ｇ、４８％苛性ソーダ水溶液２５．０ｇを添加し、更に１時間攪拌した。ポリカルボン酸系重合体Ｃ１の水溶液９６６ｇ（固形分濃度：５０％、重量平均分子量：３０，０００）を得た。[Production Example C2 (Production of polycarboxylic acid polymer)]
In a stainless steel autoclave equipped with a nitrogen inlet tube, a stirrer, and a thermometer, 402 g of 3-methyl-3-buten-1-ol 2PO50EO adduct (block adduct), 286 g of ion-exchanged water, 33.1 g of maleic anhydride, 33.fumaric acid 33. 1 g was charged with stirring. After sufficiently purging with nitrogen and raising the temperature to 60 ° C., 22.2 g of a 14% aqueous solution of sodium persulfate was charged and reacted for 6 hours while maintaining the same temperature. After completion of the reaction, the temperature was raised to 80 ° C., and stirring was continued for 1 hour. After cooling to 50 ° C., 165 g of ion exchanged water and 25.0 g of 48% aqueous sodium hydroxide solution were added, and the mixture was further stirred for 1 hour. 966 g of an aqueous solution of the polycarboxylic acid polymer C1 (solid content concentration: 50%, weight average molecular weight: 30,000) was obtained.
［実施例１乃至５、参考例６、比較例１及び２：モルタルフロー試験］
上記製造例で得られたポリカルボン酸系重合体Ｂ１乃至Ｂ６、並びにポリカルボン酸系重合体Ｃ１及びＣ２を用い、下記に示す手順にてモルタルフロー試験を行った。
普通ポルトランドセメント（太平洋セメント社製、密度３．１６ｇ／ｃｍ３）５００ｇ、陸砂１,１７４ｇ（君津産、密度２．６４ｇ／ｃｍ３、表乾）を秤とり、ポリカルボン
酸系重合体Ｂ１をセメント質量に対し０．１５％（固形分基準）含む水２３５ｇ（水／セメント比＝４７％）を卓上モルタルミキサーで９０秒間練混ぜ、試験用のモルタルを調製した。
これらをＪＩＳ Ｒ５２０１に準じモルタルフロー値を測定すると共に、モルタルの練り感を官能評価で判断した。３０分後、６０分後に再度練混ぜを行い同様の方法でモルタルフロー値の測定及び練り感の評価を行った。
なお、同様にポリカルボン酸系重合体Ｂ２乃至Ｂ６又はＣ１又はＣ２を用いて各々試験用のモルタルを調製し、調製直後、３０分後、６０分後のモルタルフロー値の測定及び練り感の評価を行った。結果を下記表２に示す。
[Examples 1 to 5, Reference Example 6 , Comparative Examples 1 and 2: Mortar flow test]
Using the polycarboxylic acid polymers B1 to B6 obtained in the above production examples and the polycarboxylic acid polymers C1 and C2, a mortar flow test was performed according to the following procedure.
Ordinary Portland cement (manufactured by Taiheiyo Cement Co., Ltd., density 3.16 g / cm 3 ) 500 g, land sand 1,174 g (from Kimitsu, density 2.64 g / cm 3 , surface dry) was weighed and polycarboxylic acid polymer B1 235 g of water (water / cement ratio = 47%) containing 0.15% (based on solid content) with respect to the cement mass was kneaded for 90 seconds with a desktop mortar mixer to prepare a test mortar.
While measuring the mortar flow value of these according to JIS R5201, the kneading feeling of the mortar was judged by sensory evaluation. After 30 minutes and 60 minutes, the mixture was kneaded again, and the mortar flow value was measured and the feeling of kneading was evaluated in the same manner.
Similarly, test mortars were prepared using the polycarboxylic acid polymers B2 to B6, C1 or C2, respectively, and mortar flow values were measured immediately after preparation, after 30 minutes and after 60 minutes, and evaluation of kneading feeling. Went. The results are shown in Table 2 below.
［実施例７及び８、比較例３：フレッシュコンクリート試験］
上記製造例で得られたポリカルボン酸系重合体Ｂ１及びＢ２、並びにＣ１を用い、下記表３に示すコンクリート配合にて、フレッシュコンクリート試験を行った。
コンクリートの練混ぜは５５リットル強制二軸ミキサを使用し、粗骨材、セメント、細骨材に、各々のポリカルボン酸系重合体（Ｂ１、Ｂ２及びＣ１）を予め加え調製した水を加え９０秒間練混ぜた。その後、コンクリートの排出直後及び３０分後にフレッシュコンクリート試験（スランプ試験ＪＩＳ Ａ １１０１（フレッシュコンクリートの広がりをフロー値として測定）、空気量 ＪＩＳ Ａ １１２８、コンクリート粘性）を行った。なお、コンクリート粘性評価は当業界内で統一した評価方法が確立されていない為、官能評価（練り感の柔らかさ）で判断した。[Examples 7 and 8, Comparative Example 3: Fresh Concrete Test]
Using the polycarboxylic acid polymers B1 and B2 and C1 obtained in the above production examples, a fresh concrete test was conducted with the concrete composition shown in Table 3 below.
For mixing the concrete, a 55-liter forced biaxial mixer was used, and each of the polycarboxylic acid polymers (B1, B2, and C1) was added in advance to the coarse aggregate, cement, and fine aggregate, and water prepared was added. Kneaded for 2 seconds. Then, fresh concrete test (slump test JIS A 1101 (measures the spread of fresh concrete as a flow value), air amount JIS A 1128, concrete viscosity) immediately after discharging concrete and 30 minutes later. The concrete viscosity evaluation was judged by sensory evaluation (softness of kneading feeling) because a unified evaluation method was not established in the industry.
［コンクリート試験結果］
表３にコンクリ−ト配合を、表４にフレッシュコンクリート試験結果を示す。
Table 3 shows the concrete composition, and Table 4 shows the results of the fresh concrete test.
表２に示す通り、モルタル試験において、アルキレンオキサイド鎖末端にＰＯ基がブロック付加した反応性アルコールを用いた実施例１乃至５は、いずれも比較例１及び２と比較してモルタル保持性の改善が見られ、練り感も非常に柔らかいとする結果となった。
また表４に示す通り、コンクリート試験に於いても、実施例７及び８は比較例３と比べ減水性能が向上し、３０分経過後もスランプ値及びフロー値ともに変動が少なく、良好な保持性を示す結果となった。
更にコンクリート中の空気量においては、比較例と比ベて同程度の結果が得られており、起泡性及び消泡性に影響を与えることなく、フレッシュコンクリートの練り感が著しく改善されたとする結果が得られた。
なお、上記試験結果により、本発明のセメント分散剤は汎用強度レベルのコンクリート以外にも、高強度コンクリート、すなわち、水セメント比（Ｗ／Ｃ）：２０〜５０％においても使用可能な減水性能を有していることが確認された。また、凝結時間も早く、コンクリート製品への適応にも十分対応し得るものであることが認められた。
このように、本発明のセメント分散剤は、優れた減水性、スランプ保持性を有するだけでなく、コンクリート施工時に重要となる粘性の点においても優れるとする結果が得られた。
これらの結果は反応性アルコールの特定の位置に、特定量のプロピレンオキサイドを配置したことにより発揮され、さらに、適正な酸基の種類、量の選択、ポリアミドポリアミン系化合物の併用により相乗効果が発揮されたものとみられる。
As shown in Table 2, in Examples 1 to 5 using a reactive alcohol in which a PO group was block-added to the end of an alkylene oxide chain in a mortar test, both improved mortar retention compared to Comparative Examples 1 and 2. As a result, the kneading feeling was very soft.
Moreover, as shown in Table 4, also in the concrete test, the water-reducing performance of Examples 7 and 8 was improved compared to Comparative Example 3, and both the slump value and the flow value were less fluctuated even after 30 minutes, and good holding properties. The result was shown.
Furthermore, in the amount of air in the concrete, comparable results were obtained compared to the comparative example, and the feeling of kneading of fresh concrete was remarkably improved without affecting the foaming and defoaming properties. Results were obtained.
In addition, according to the above test results, the cement dispersant of the present invention has a water-reducing performance that can be used in high-strength concrete, that is, water cement ratio (W / C): 20 to 50% in addition to general-purpose strength level concrete. It was confirmed to have. In addition, it was confirmed that the setting time is fast and it can be sufficiently adapted to the concrete product.
Thus, the cement dispersant of the present invention has excellent water reducing property, not only has a slump retention ability, as a result of the excellent in terms of viscosity, which is important during the concrete construction is obtained.
These results are demonstrated by placing a specific amount of propylene oxide at a specific position of the reactive alcohol, and further, a synergistic effect is achieved by selecting the appropriate type and amount of acid groups and using a polyamidopolyamine compound in combination. It seems that it was done.
Claims (2)
該重合体の主鎖骨格に結合するグラフト鎖は主としてエチレンオキサイドから構成されるポリアルキレンオキサイド鎖を含み、該グラフト鎖の末端は水酸基であり、
該構成単位（Ｉ）におけるポリアルキレンオキサイド鎖の水酸基側末端部が、炭素原子数３又は４のアルキレンオキサイドを、該アルキレンオキサイド鎖の全モル量に対して０．１乃至３０ｍｏｌ％の割合で有することを特徴とする、セメント分散剤。
しくはＲ ６ とＲ ７ は一緒になって酸無水物を形成する。Ｍはアルカリ金属、アルカリ土類金属、アンモニウム、アルカノールアミンを表し、Ｙは炭素原子数１乃至２２の炭化水素基または−（ＡＯ）ｃ−Ｒ ８ を表し、ＡＯは炭素原子数２乃至４のアルキレンオキサイド基を表し、ｃはアルキレンオキサイドの平均付加モル数で１乃至２００の数を表し、Ｒ ８ は水素原子又は炭素原子数１乃至２２の炭化水素基を表す。）
The graft chain bonded to the main chain skeleton of the polymer includes a polyalkylene oxide chain mainly composed of ethylene oxide, and the terminal of the graft chain is a hydroxyl group,
The hydroxyl group side terminal portion of the polyalkylene oxide chain in the structural unit (I) has an alkylene oxide having 3 or 4 carbon atoms in a proportion of 0.1 to 30 mol% with respect to the total molar amount of the alkylene oxide chain. A cement dispersant characterized by that .
R 6 and R 7 together form an acid anhydride. M represents an alkali metal, alkaline earth metal, ammonium or alkanolamine, Y represents a hydrocarbon group having 1 to 22 carbon atoms or — (AO) c—R 8 , and AO represents 2 to 4 carbon atoms. Represents an alkylene oxide group, c represents an average addition mole number of the alkylene oxide and represents a number of 1 to 200, and R 8 represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms. )
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| JP4984255B2 (en) * | 2007-12-28 | 2012-07-25 | 東邦化学工業株式会社 | New cement dispersant |
| JP4984254B2 (en) * | 2007-12-28 | 2012-07-25 | 東邦化学工業株式会社 | Cement dispersant |
| JP5151620B2 (en) * | 2008-03-31 | 2013-02-27 | 日油株式会社 | Method for producing copolymer |
| MY152754A (en) * | 2009-05-20 | 2014-11-28 | Basf Se | Hydrophobically associating copolymers |
| KR101106211B1 (en) * | 2009-06-12 | 2012-01-20 | 주식회사 실크로드시앤티 | Polymer admixture for controlling hydration of concrete, and method for producing the same |
| US8586687B2 (en) * | 2010-12-17 | 2013-11-19 | Nippon Shokubai Co., Ltd. | Polyalkylene glycol-based polymer and process for producing the same |
| JP6570433B2 (en) * | 2015-11-17 | 2019-09-04 | 株式会社日本触媒 | Additive for concrete |
| CN111770942A (en) * | 2018-03-07 | 2020-10-13 | 丸善石油化学株式会社 | Core-shell type polymer microparticle, particle dispersion, and method for producing microparticle |
| CN112608422B (en) * | 2019-12-12 | 2023-02-03 | 科之杰新材料集团有限公司 | Preparation method of polycarboxylic acid workability regulator |
| CN115536828B (en) * | 2022-10-25 | 2024-05-10 | 炜宏新材料科技有限公司 | Concrete anti-dispersing agent with reticular structure, and preparation method and application thereof |
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| JPH11106247A (en) * | 1997-09-30 | 1999-04-20 | Sanyo Chem Ind Ltd | Dispersant for cement |
| JP2000191356A (en) * | 1998-12-25 | 2000-07-11 | Nippon Shiika Kk | Cement dispersant and concrete composition containing the same |
| JP2003171156A (en) * | 2001-09-28 | 2003-06-17 | Nippon Shokubai Co Ltd | Cement admixture and cement composition |
| JP2004002174A (en) * | 2002-04-25 | 2004-01-08 | Nippon Shokubai Co Ltd | Admixture for cement and its manufacturing method |
| JP2004182583A (en) * | 2002-11-19 | 2004-07-02 | Nippon Shokubai Co Ltd | Cement admixture |
| JP2005126271A (en) * | 2003-10-23 | 2005-05-19 | Nippon Shokubai Co Ltd | Concrete composition |
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| JPH11106247A (en) * | 1997-09-30 | 1999-04-20 | Sanyo Chem Ind Ltd | Dispersant for cement |
| JP2000191356A (en) * | 1998-12-25 | 2000-07-11 | Nippon Shiika Kk | Cement dispersant and concrete composition containing the same |
| JP2003171156A (en) * | 2001-09-28 | 2003-06-17 | Nippon Shokubai Co Ltd | Cement admixture and cement composition |
| JP2004002174A (en) * | 2002-04-25 | 2004-01-08 | Nippon Shokubai Co Ltd | Admixture for cement and its manufacturing method |
| JP2004182583A (en) * | 2002-11-19 | 2004-07-02 | Nippon Shokubai Co Ltd | Cement admixture |
| JP2005126271A (en) * | 2003-10-23 | 2005-05-19 | Nippon Shokubai Co Ltd | Concrete composition |
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