CN113004470B - Method for producing additive for hydraulic composition - Google Patents
Method for producing additive for hydraulic composition Download PDFInfo
- Publication number
- CN113004470B CN113004470B CN202011490275.XA CN202011490275A CN113004470B CN 113004470 B CN113004470 B CN 113004470B CN 202011490275 A CN202011490275 A CN 202011490275A CN 113004470 B CN113004470 B CN 113004470B
- Authority
- CN
- China
- Prior art keywords
- polymerization inhibitor
- additive
- hydraulic compositions
- polyether ester
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000203 mixture Substances 0.000 title claims abstract description 74
- 239000000654 additive Substances 0.000 title claims abstract description 44
- 230000000996 additive effect Effects 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 84
- 239000000178 monomer Substances 0.000 claims abstract description 81
- 239000003112 inhibitor Substances 0.000 claims abstract description 70
- 229920001515 polyalkylene glycol Polymers 0.000 claims abstract description 50
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 46
- 150000002148 esters Chemical class 0.000 claims abstract description 46
- 229920000570 polyether Polymers 0.000 claims abstract description 46
- 238000005886 esterification reaction Methods 0.000 claims abstract description 32
- 239000003377 acid catalyst Substances 0.000 claims abstract description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 11
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 4
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 36
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 12
- 125000004437 phosphorous atom Chemical group 0.000 claims description 12
- 238000007334 copolymerization reaction Methods 0.000 claims description 10
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 9
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 7
- 229950000688 phenothiazine Drugs 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 229930192627 Naphthoquinone Natural products 0.000 claims description 4
- 150000002791 naphthoquinones Chemical class 0.000 claims description 4
- 125000006353 oxyethylene group Chemical group 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- 150000008301 phosphite esters Chemical class 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 17
- 238000001879 gelation Methods 0.000 abstract description 15
- 230000032050 esterification Effects 0.000 abstract description 9
- 238000003860 storage Methods 0.000 abstract description 5
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 3
- 229920006163 vinyl copolymer Polymers 0.000 description 39
- 238000006243 chemical reaction Methods 0.000 description 31
- 238000012360 testing method Methods 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- -1 napyrenyl Chemical group 0.000 description 23
- 238000002360 preparation method Methods 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 21
- 150000003254 radicals Chemical class 0.000 description 14
- 238000004898 kneading Methods 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000005259 measurement Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- 239000004568 cement Substances 0.000 description 9
- 229920001451 polypropylene glycol Polymers 0.000 description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 8
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 8
- 239000002202 Polyethylene glycol Substances 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 229920001223 polyethylene glycol Polymers 0.000 description 7
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000011398 Portland cement Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 5
- 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 4
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 238000007142 ring opening reaction Methods 0.000 description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229940098779 methanesulfonic acid Drugs 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910021487 silica fume Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 101100145148 Coccidioides immitis (strain RS) RPC-82 gene Proteins 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 125000002511 behenyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 239000011400 blast furnace cement Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000002592 cumenyl group Chemical group C1(=C(C=CC=C1)*)C(C)C 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011396 hydraulic cement Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- SBGKURINHGJRFN-UHFFFAOYSA-N hydroxymethanesulfinic acid Chemical compound OCS(O)=O SBGKURINHGJRFN-UHFFFAOYSA-N 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- FZYCEURIEDTWNS-UHFFFAOYSA-N prop-1-en-2-ylbenzene Chemical compound CC(=C)C1=CC=CC=C1.CC(=C)C1=CC=CC=C1 FZYCEURIEDTWNS-UHFFFAOYSA-N 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- SUBJHSREKVAVAR-UHFFFAOYSA-N sodium;methanol;methanolate Chemical compound [Na+].OC.[O-]C SUBJHSREKVAVAR-UHFFFAOYSA-N 0.000 description 1
- DGTOAFBVEDTEBA-UHFFFAOYSA-N sodium;prop-1-ene Chemical compound [Na+].[CH2-]C=C DGTOAFBVEDTEBA-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229940035024 thioglycerol Drugs 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
-
- 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
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
-
- 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
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)
- Macromonomer-Based Addition Polymer (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Polyethers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Provided is a method for producing an additive for hydraulic compositions, which is low in cost and high in performance, wherein clogging of pipes due to gelation is prevented in an esterification step, and the performance of a polyether ester monomer due to gelation or the like is not reduced, and the stability of the polyether ester monomer upon storage is high. A method for producing an additive for hydraulic compositions, comprising a step 1 and a step 2, wherein the step 1 is a step of subjecting an unsaturated carboxylic acid and a specific one-terminal-blocked polyalkylene glycol to an esterification reaction in the presence of an acid catalyst, a polymerization inhibitor A, a polymerization inhibitor B and a polymerization inhibitor C under heating and reduced pressure in the absence of a solvent to obtain a polyether ester monomer, and the step 2 is a step of subjecting the obtained polyether ester monomer and a vinyl monomer copolymerizable with the polyether ester monomer to a radical polymerization in an aqueous solvent.
Description
Technical Field
The present invention relates to a method for producing an additive for hydraulic compositions. More specifically, the present invention relates to a method for producing a low-cost and high-performance additive for hydraulic compositions, which prevents clogging of pipes due to gelation or the like and deterioration of the performance of polyether ester monomers as intermediate raw materials in an esterification step and has high stability in storage.
Background
Conventionally, water-soluble vinyl copolymers have been known as additives for hydraulic compositions, which can impart excellent fluidity with little slump loss to hydraulic compositions and can sufficiently ensure the compressive strength of cured products obtained by curing hydraulic compositions.
In order to make the water-soluble vinyl copolymer exhibit excellent properties as an additive for hydraulic compositions, it is required to improve the quality of polyether ester monomers as intermediate materials.
As means for improving the quality of the polyether ester monomer, the following methods have been proposed. That is, the following method for producing a water-soluble vinyl copolymer is proposed: as the raw material, a single-end-substituted polyalkylene glycol in which the acetic acid equivalent concentration of the remaining free acid is set to a certain value or less by purification treatment is used, and in the absence of a solvent, the single-end-substituted polyalkylene glycol is subjected to an esterification reaction with an unsaturated carboxylic acid in the presence of at least one of p-benzoquinone and phenothiazine to obtain a high-quality polyether ester monomer, and then the polyether ester monomer and a vinyl monomer are subjected to radical polymerization to produce a water-soluble vinyl copolymer (see patent document 1).
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2002-265594
Disclosure of Invention
Problems to be solved by the invention
However, in the technique disclosed in patent document 1, there are the following problems: in the esterification step, gelation occurs due to gelation, and clogging of piping occurs. In addition, the technique disclosed in patent document 1 has the following problems: the properties of the polyether ester monomer are lowered due to the gelation, etc., and the stability of the polyether ester monomer upon storage is lowered, and the properties of the additive for hydraulic compositions obtained are also lowered.
Accordingly, the present invention has been made to solve the problems of the prior art, and an object of the present invention is to provide a method for producing a low-cost and high-performance additive for hydraulic compositions, which prevents clogging of pipes due to gelation in an esterification step, and which does not deteriorate the performance of polyether ester monomers due to gelation or the like, and which has high stability in storage.
Means for solving the problems
The present inventors have studied to solve the above-mentioned problems, and as a result, have found that a production method which has passed through the following steps 1 and 2 is preferable, wherein in step 1, in the esterification step of an unsaturated carboxylic acid with a one-terminal-blocked polyalkylene glycol, esterification is carried out in the presence of an acid catalyst and a specific polymerization inhibitor in the absence of a solvent; in step 2, the polyether ester monomer obtained in step 1 is radical polymerized with a vinyl monomer. According to the present invention, the following method for producing an additive for hydraulic compositions is provided.
[1] A method for producing an additive for hydraulic compositions, comprising the following steps 1 and 2,
step 1: a step of subjecting an unsaturated carboxylic acid to an esterification reaction with a one-terminal-blocked polyalkylene glycol represented by the following general formula (1) in the absence of a solvent in the presence of an acid catalyst, a polymerization inhibitor A, a polymerization inhibitor B and a polymerization inhibitor C and under heating and reduced pressure to obtain a polyether ester monomer,
[ chemical formula 1]
In the general formula (1), R 1 Represents an alkyl group having 1 to 22 carbon atoms or an aromatic group having 6 to 30 carbon atoms, AO represents an oxyalkylene group having 2 or 3 carbon atoms, n represents an integer of 1 to 300,
polymerization inhibitor A: a polymerization inhibitor which does not contain phosphorus atoms and has a vapor pressure of 0.01Pa or more at 25 ℃,
polymerization inhibitor B: a polymerization inhibitor which does not contain phosphorus atoms and has a vapor pressure of less than 0.01Pa at 25 ℃,
polymerization inhibitor C: a polymerization inhibitor containing phosphorus atoms,
step 2: and (2) a step of subjecting the polyether ester monomer obtained in the step (1) and a vinyl monomer copolymerizable with the polyether ester monomer to radical polymerization in an aqueous solvent to obtain an additive for hydraulic compositions.
[2] The method for producing an additive for hydraulic compositions according to the above [1], wherein the unsaturated carboxylic acid is at least one selected from the group consisting of acrylic acid and methacrylic acid.
[3] The method for producing an additive for hydraulic compositions according to the above [1] or [2], wherein the polymerization inhibitor A contains at least one selected from the group consisting of p-benzoquinone, naphthoquinone and quinone hydroquinone (quinone).
[4] The method for producing an additive for hydraulic compositions according to any one of the above [1] to [3], wherein the polymerization inhibitor A contains p-benzoquinone.
[5] The method for producing an additive for hydraulic compositions according to any one of the above [1] to [4], wherein the polymerization inhibitor B contains phenothiazine.
[6] The method for producing an additive for hydraulic compositions according to any one of the above [1] to [5], wherein the polymerization inhibitor C contains at least one selected from the group consisting of phosphorous acid and phosphite esters.
[7] The method for producing an additive for hydraulic compositions according to any one of the above [1] to [6], wherein the polymerization inhibitor A is added in an amount of 0.01 to 0.5 mass% relative to the one-terminal-blocked polyalkylene glycol,
the polymerization inhibitor B is added in a proportion of 0.005 to 0.5 mass% relative to the one-terminal-blocked polyalkylene glycol,
the polymerization inhibitor C is added in a proportion of 0.05 to 0.5 mass% relative to the one-terminal-blocked polyalkylene glycol.
[8] The method for producing an additive for hydraulic compositions according to any one of the above [1] to [7], wherein 95 mol% or more of all the oxyalkylene groups in the AO of the general formula (1) in the one-terminal-blocked polyalkylene glycol are oxyethylene groups having 2 carbon atoms.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the method for producing the additive for hydraulic compositions of the present invention, there is an effect that it is possible to produce a low-cost and high-performance additive for hydraulic compositions which prevents clogging of pipes caused by gelation in an esterification step and which does not have deterioration in the performance of polyether ester monomers caused by gelation or the like, and the resulting additive for hydraulic compositions has high stability in storage.
Detailed Description
Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments. Accordingly, it is to be understood that the following embodiments may be appropriately modified and improved based on the common knowledge of those skilled in the art without departing from the gist of the present invention. In the following examples and the like, "%" means "% by mass" and "parts" means "parts by mass" unless otherwise specified.
The method for producing the additive for hydraulic compositions according to the present embodiment is performed by steps 1 and 2. First, step 1 will be described. The unsaturated carboxylic acid includes acrylic acid, methacrylic acid, crotonic acid, and the like, and particularly, at least one selected from the group consisting of acrylic acid and methacrylic acid is preferable.
The one-terminal-blocked polyalkylene glycol is represented by the following general formula (1).
[ chemical formula 2]
(in the general formula (1), R 1 Represents an alkyl group having 1 to 22 carbon atoms or an aromatic group having 6 to 30 carbon atoms, AO represents an oxyalkylene group having 2 or 3 carbon atoms, and n represents an integer of 1 to 300. )
In the general formula (1), R 1 Is an alkyl group having 1 to 22 carbon atoms or an aromatic group having 6 to 30 carbon atoms. Examples of the alkyl group having 1 to 22 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl and the like. Examples of such an aromatic group having 6 to 30 carbon atoms include phenyl, naphthyl, benzyl, anthracenyl, pyrenyl, napyrenyl, methylnaphthyl, ethylnaphthyl, propylnaphthyl, butylnaphthyl, pentylnaphthyl, hexylnaphthaleneA group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a (mono-, di-or tri) styrylphenyl group, a cumenyl group, a (mono-, di-or tri) benzyl group, a diphenyl group, etc.
AO is an oxyalkylene group having 2 or 3 carbon atoms. Examples of such an oxyalkylene group include an oxyethylene group and an oxypropylene group. In the case of two or more kinds of oxyalkylene groups, any of addition forms such as random addition, block addition, alternate addition and the like may be used. n is an integer of 1 to 300. It is preferable that 95 mol% or more of all the oxyalkylene groups are oxyethylene groups having 2 carbon atoms.
As such a single-terminal-blocked polyalkylene glycol represented by the general formula (1), examples thereof include methoxypolyethylene glycol, methoxypolyethylene glycol polypropylene glycol, ethoxypolyethylene glycol polypropylene glycol, propoxypolyethylene glycol polypropylene glycol, butoxypolyethylene glycol polypropylene glycol, lauryloxypolyethylene glycol polypropylene glycol benzyloxy polyethylene glycol, benzyloxy polyethylene glycol polypropylene glycol, phenoxy polyethylene glycol polypropylene glycol, alkylphenoxy polyethylene glycol polypropylene glycol, (mono-, di-, or tri) styrylphenoxy polyethylene glycol polypropylene glycol, and the like.
In this embodiment, in the absence of a solvent, the polyether ester monomer is obtained by esterifying the one-terminal-blocked polyalkylene glycol represented by the general formula (1) with an unsaturated carboxylic acid while using an acid catalyst and distilling off the produced water under heating and reduced pressure in the presence of the acid catalyst, the polymerization inhibitor A, the polymerization inhibitor B and the polymerization inhibitor C.
The polymerization inhibitor A is a polymerization inhibitor which does not contain phosphorus atoms (i.e., does not contain phosphorus atoms) and has a vapor pressure of 0.01Pa or more at 25 ℃. Examples of such a polymerization inhibitor A include p-benzoquinone (vapor pressure at 25 ℃ C.: 13 Pa), naphthoquinone (vapor pressure at 25 ℃ C.: 0.0225 Pa), quinone hydroquinone (quinone) (1:1 mixture of p-benzoquinone having a vapor pressure at 25 ℃ C. Of 13Pa and hydroquinone having a vapor pressure at 25 ℃ C. Of 0.0225 Pa), and the like. Among them, p-benzoquinone is particularly preferable.
The polymerization inhibitor B is a polymerization inhibitor which does not contain phosphorus atoms (i.e., does not contain phosphorus atoms) and has a vapor pressure of less than 0.01Pa at 25 ℃. Examples of such a polymerization inhibitor B include phenothiazine (vapor pressure at 25 ℃ C.: 0.000119 Pa) and the like.
The polymerization inhibitor C is a polymerization inhibitor containing phosphorus atoms, i.e., a polymerization inhibitor containing phosphorus atoms. Examples of such a polymerization inhibitor C include phosphorous acid and phosphite esters. Examples of the phosphite include tributyl phosphite and triphenyl phosphite.
In the reaction system, the polymerization inhibitor a is preferably present in an amount equivalent to 0.01 to 0.5 mass%, more preferably in an amount equivalent to 0.06 to 0.45 mass%, with respect to the one-terminal-blocked polyalkylene glycol represented by the general formula (1). If the amount of the polymerization inhibitor a present in the reaction system is less than 0.01 mass% relative to the one-terminal-blocked polyalkylene glycol represented by the general formula (1), the effect of preventing gelation in the piping and voids after vaporization may not be sufficiently exhibited. If the amount exceeds 0.5 mass%, the radical copolymerization reaction may not proceed smoothly when the polyether ester monomer obtained in step 2 is used as an intermediate raw material to produce a vinyl copolymer as an additive for hydraulic compositions.
In the reaction system, the polymerization inhibitor B is preferably present in an amount equivalent to 0.005 to 0.5 mass%, more preferably in an amount equivalent to 0.005 to 0.10 mass%, and most preferably in an amount equivalent to 0.005 to 0.05 mass%, with respect to the one-terminal-blocked polyalkylene glycol represented by the general formula (1). If the polymerization inhibitor B is present in the reaction system in an amount of less than 0.005 mass% relative to the one-terminal-blocked polyalkylene glycol represented by the general formula (1), the effect of preventing gelation of the liquid portion may not be sufficiently exhibited. In addition, if the amount exceeds 0.5 mass%, the radical copolymerization reaction may not proceed smoothly when the polyether ester monomer obtained in step 2 is used as an intermediate raw material to produce a vinyl copolymer.
In the reaction system, the polymerization inhibitor C is preferably present in an amount equivalent to 0.005 to 0.5 mass%, more preferably in an amount equivalent to 0.05 to 0.3 mass%, with respect to the one-terminal-blocked polyalkylene glycol represented by the general formula (1). If the polymerization inhibitor C is present in the reaction system in an amount of less than 0.005 mass% relative to the one-terminal-blocked polyalkylene glycol represented by the general formula (1), the effect of preventing gelation of the liquid portion may not be sufficiently exhibited. In addition, if the amount exceeds 0.5 mass%, the radical copolymerization reaction may not proceed smoothly when the polyether ester monomer obtained in step 2 is used as an intermediate raw material to produce a vinyl copolymer.
In the esterification reaction, the heating temperature is preferably 105℃to 140℃and the pressure is preferably 15Pa to 0.5kPa. Under such heating conditions, the temperature is preferably raised slowly or stepwise to the above temperature range. Further, it is more preferable to gradually or stepwise decrease (i.e., decompress) the pressure to the above pressure range.
In the esterification reaction, an acid catalyst is used as a catalyst. As such an acid catalyst, sulfuric acid, p-toluenesulfonic acid, phosphoric acid, methanesulfonic acid, and the like, for example, may be used alone or in combination. The amount of the acid catalyst to be used is preferably set to 1 to 50 mol% with respect to the one-terminal-blocked polyalkylene glycol represented by the general formula (1).
In the esterification reaction, the raw material ratio (molar ratio) of the one-terminal-blocked polyalkylene glycol represented by the general formula (1) to the unsaturated carboxylic acid is preferably set to one-terminal-blocked polyalkylene glycol/unsaturated carboxylic acid=1/1.5 to 1/8 (molar ratio) represented by the general formula (1). After the esterification reaction, the excess unsaturated carboxylic acid may be distilled off, or if the unsaturated carboxylic acid remains, the unsaturated carboxylic acid may be used in step 2. When the unsaturated carboxylic acid is used in step 2 with the unsaturated carboxylic acid remaining, the amount of the excessive unsaturated carboxylic acid can be quantified by various analyses, and polymerization can be performed in a desired compounding ratio in step 2. As the analysis method, various chromatography methods or acid values can be used. The esterification rate after completion of the esterification reaction can be analyzed by a known method. The esterification rate after completion of the esterification reaction can be analyzed by, for example, a method using various chromatography methods or a method for measuring a hydroxyl value (JIS K0070).
Next, step 2 will be described. And (2) carrying out free radical copolymerization reaction on the polyether ester monomer obtained in the step (1) and a vinyl monomer capable of copolymerizing with the polyether ester monomer in an aqueous solvent. As the vinyl monomer copolymerizable with the polyether ester monomer, there may be mentioned unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, itaconic acid, fumaric acid, and mono (2- (meth) acryloyloxyethyl) succinate, and salts thereof; the copolymerizable vinyl monomer such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, styrene, acrylamide, and (meth) allylsulfonic acid and salts thereof is not particularly limited. Examples of the salt of each vinyl monomer include alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as calcium salts and magnesium salts; amine salts such as ammonium salt, diethanolamine salt and triethanolamine salt.
The ratio of the polyetherester monomer to the vinyl monomer copolymerizable with the polyetherester monomer at the time of radical copolymerization is not particularly limited. When the polyetherester monomer is subjected to the radical copolymerization reaction with at least one of (meth) acrylic acid and a salt thereof, it is preferable that the polyetherester monomer is set to 5 to 95 mass%, the at least one of (meth) acrylic acid and a salt thereof is set to 5 to 95 mass%, and the other copolymerizable monomers are set to 0 to 10 mass% (however, they are 100 mass% in total).
As the radical copolymerization reaction, for example, the reaction described in JP-A-8-290948 can be used. Specifically, an aqueous solution containing the polyether ester monomer obtained in step 1, a vinyl monomer copolymerizable with the polyether ester monomer, and a chain transfer agent is prepared, a radical initiator is added thereto under a nitrogen atmosphere, and radical copolymerization is performed at a reaction temperature of 50 ℃ to 90 ℃ for 4 hours to 8 hours, whereby a vinyl copolymer can be obtained. In this case, examples of the chain transfer agent include water-soluble chain transfer agents such as 2-mercaptoethanol, mercaptopropionic acid, and mercaptoacetic acid, and water-insoluble chain transfer agents such as α -methylstyrene dimer and dodecanethiol. Further, as the radical initiator, hydrogen peroxide is exemplified; persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; water-soluble radical initiators such as 2,2' -azobis (2-amidinopropane) dihydrochloride. In order for the free radical initiator to function effectively, reducing agents may also be used. Examples of the reducing agent Include Iron (II) sulfate heptahydrate, L-ascorbic acid, sulfite, hydroxymethanesulfinic acid (salt), and phosphinate.
The mass average molecular weight of the vinyl copolymer obtained by the radical copolymerization (mass average molecular weight in terms of polyethylene glycol by GPC method, and the same applies hereinafter) is preferably 3500 to 100000, more preferably 5000 to 40000.
The vinyl copolymer obtained as described above is an additive for hydraulic compositions which can be used in various hydraulic cement compositions (usually mortar or concrete) containing cement or a fine powder mixed material as a binder in addition to cement. Examples of the cement include various portland cements such as ordinary portland cement, early strength portland cement, and medium heat portland cement; blast furnace cement, fly ash cement, silica fume cement and the like. Examples of the fine powder mixture include limestone powder, calcium carbonate, silica fume, blast furnace slag fine powder, fly ash, and the like.
In the present embodiment, the amount of the additive for hydraulic compositions used is usually 0.01 to 2.5 parts by mass, preferably 0.05 to 1.5 parts by mass, in terms of solid content, per 100 parts by mass of the binder composed of cement or a mixture of cement and fine powder. In the present embodiment, the additive for hydraulic compositions is usually added and used together with kneading water at the time of preparing the additive for hydraulic compositions.
Examples
Test class 1 (preparation of single end blocked polyalkylene glycol (PAG):
preparation of the one-terminal blocked polyalkylene glycol (P-1):
240.3g (2 mol) of diethylene glycol monomethyl ether was charged into the autoclave, and the inside of the autoclave was sufficiently replaced with nitrogen. After adding 3.6g of 28% sodium methoxide methanol solution as a catalyst, 1760g (40 mol) of ethylene oxide was pressed under a pressure of 0.4MPa while maintaining the reaction temperature at 110℃to 120℃with stirring, thereby performing a ring-opening addition reaction. After the ring-opening addition reaction, the reaction mixture was aged at the same temperature (the reaction temperature) for 1 hour. Further, 0.72g of 85% phosphoric acid was added, dehydrated under reduced pressure for 1 hour at 110℃under heating, cooled to 80℃and then pressure-filtered under nitrogen atmosphere, whereby a one-terminal-blocked polyalkylene glycol (P-1) was obtained as a filtrate.
Preparation of Shan Moduan polyalkylene glycol (P-4):
302.5g of a commercially available stilbenephenol was charged into an autoclave, 1.3g of potassium hydroxide was added as a catalyst, and then the inside of the autoclave was sufficiently replaced with nitrogen. While stirring, dehydration was carried out under reduced pressure at 100℃for 1 hour, and then the reaction temperature was maintained at 110℃to 120℃and 968g of ethylene oxide was pressed under a pressure of 0.4MPa, whereby a ring-opening addition reaction was carried out. After the completion of the ring-opening addition reaction, the mixture was aged at the same temperature (the above reaction temperature) for 1 hour, and further 1.0g of a silicic acid/alumina-based adsorbent (Kyowa 700SL, co., ltd.) was added, dehydrated under reduced pressure at 110℃for 1 hour, cooled to 80℃and then pressure-filtered under nitrogen atmosphere. A single-end-blocked polyalkylene glycol (P-4-2) was obtained as a filtrate. Then, the one-terminal-blocked polyalkylene glycol (P-1) was mixed with the one-terminal-blocked polyalkylene glycol (P-4-2) at a mass ratio of 90/10, thereby obtaining the one-terminal-polyalkylene glycol (P-4).
Preparation of the one-terminal blocked polyalkylene glycol (P-2), (P-3), (P-5) and (P-6):
as with the above-mentioned one-terminal-blocked polyalkylene glycol (P-1), one-terminal-blocked polyalkylene glycols (P-2), (P-3), (P-5) and (P-6) were produced. The prepared single end-capped polyalkylene glycols (PAGs) are summarized and shown in table 1.
TABLE 1
Mixture of P-1 and P-4-2 (mass ratio 90/10)
P-1 to P-6 in Table 1 are explained below.
P-1: polyoxyethylene (n=22) monomethyl ether
P-2: polyoxyethylene (n=9) monomethyl ether
P-3: polyoxyethylene (n=45) monomethyl ether
P-4: mixture mass ratio of polyoxyethylene (n=22) monomethyl ether to polyoxyethylene (n=22) mono (distyrene phenol) ether of 90/10
P-5: polyoxyethylene (n=68) monomethyl ether
P-5: polyoxyethylene (n=21) oxypropylene (n=1) monomethyl ether
Test class 2 (preparation of polyetherester monomer):
example 1 (preparation of polyetherester monomer (MM-1)):
600.0g (0.6 mol) of the one-terminal-blocked polyalkylene glycol (P-1) prepared in test group 1, 155.0g (1.8 mol) of methacrylic acid, 1.2g of P-benzoquinone (vapor pressure of 13Pa at 25 ℃), 0.06g of phenothiazine (vapor pressure of 0.000119Pa at 25 ℃), 0.72g of triphenyl phosphite, and 5.8g (0.06 mol) of methanesulfonic acid were charged into a 1L glass-made reaction vessel. Then, while stirring, the temperature was gradually increased and reduced in pressure, water produced by the esterification reaction was distilled off as a water/methacrylic acid azeotropic mixture to the outside of the reaction system, and the esterification reaction was carried out at a temperature of 120℃under a pressure of 1.5kPa for 6 hours. After the completion of the reaction, methacrylic acid was distilled off, and the resultant was analyzed, whereby a polyether ester monomer (MM-1) having an esterification reaction rate of 98% was obtained.
Examples 2 to 11 (preparation of polyetherester monomers (MM-2) to (MM-11)):
examples 2 to 11 (polyether ester monomers (MM-2) to (MM-11)) were prepared in the same manner as in example 1 (polyether ester monomer (MM-1)) except that the modification was made as shown in Table 2.
Comparative example 1 (preparation of polyetherester monomer (RM-1)):
600.0g (0.6 mol) of the one-terminal-blocked polyalkylene glycol (P-1) prepared in test class 1, 155.0g (1.8 mol) of methacrylic acid, 1.0g of P-benzoquinone (vapor pressure of 13Pa at 25 ℃) and 5.7g of concentrated sulfuric acid were charged into a reaction vessel. Then, while stirring, the temperature was gradually increased and reduced in pressure, and water produced by the esterification reaction was distilled off as a water/methacrylic acid azeotropic mixture to the outside of the reaction system, and the esterification reaction was carried out under the conditions of a temperature of 130℃and a pressure of 1.0kPa for 5 hours. After the completion of the reaction, methacrylic acid was distilled off, and the resultant was analyzed, whereby the polyether ester monomer (RM-1) having an esterification reaction rate of 97% was obtained.
Comparative example 2 (preparation of polyetherester monomer (RM-2)):
600.0g (0.6 mol) of the one-terminal-blocked polyalkylene glycol (P-1) prepared in test class 1, 155.0g (1.8 mol) of methacrylic acid, 0.72g of triphenyl phosphite, and 5.7g of concentrated sulfuric acid were charged into a reaction vessel. Then, while stirring, the temperature was gradually increased to carry out the esterification reaction, but since a large amount of insoluble gel was precipitated during the process, the esterification reaction was stopped.
Comparative example 3 (preparation of polyetherester monomer (RM-3)):
600.0g (0.6 mol) of the one-terminal-blocked polyalkylene glycol (P-1) prepared in test class 1, 155.0g (1.8 mol) of methacrylic acid, 0.06g of phenothiazine (vapor pressure at 25℃of 0.000119 Pa), and 5.7g of concentrated sulfuric acid were charged into a reaction vessel. Then, while stirring, the temperature was gradually increased and reduced in pressure, and water produced by the esterification reaction was distilled off as a water/methacrylic acid azeotropic mixture to the outside of the reaction system, and the esterification reaction was carried out under a pressure of 2.0kPa at a temperature of 130 ℃ for 7 hours. After the completion of the reaction, methacrylic acid was distilled off, and the resultant was analyzed, whereby the polyether ester monomer (RM-3) having an esterification reaction rate of 98% was obtained.
Comparative examples 4 to 8 (preparation of polyetherester monomers (RM-4) to (RM-8)):
the production of polyether ester monomers (RM-4) to (RM-8) of comparative examples 4 to 8 was carried out in the same manner as in comparative example 1 (polyether ester monomer (RM-1)) except that the kind of the one-terminal polyalkylene glycol and the amount of the unsaturated carboxylic acid, and the kind and amount of the polymerization inhibitor were changed as shown in Table 2.
The contents of the polyether ester monomers (MM-1) to (MM-11) and (RM-1) to (RM-8) prepared are summarized and shown in tables 2 and 3.
TABLE 2
Q-1 and the like in Table 2 are explained below.
Mass% relative to P: the amount of the polymerization inhibitor to be used (mass%) with respect to the one-terminal-blocked polyalkylene glycol
Proportion (mol%) of acid catalyst: the amount of the acid catalyst to be used (mole%) relative to the total amount of the one-terminal-blocked polyalkylene glycol and the unsaturated carboxylic acid
Q-1: methacrylic acid
Q-2: acrylic acid
S-1: methanesulfonic acid
S-2: para-toluene sulfonic acid
S-3: mixtures of p-toluene sulfonic acid and sulfuric acid (molar ratio 1:1)
S-4: sulfuric acid
A-1: p-benzoquinone (vapor pressure of 13Pa at 25 ℃ C.)
A-2: naphthoquinone (vapor pressure of 0.0225Pa at 25 ℃ C.)
A-3: quinone hydroquinone (1:1 mixture of p-benzoquinone with a vapor pressure of 13Pa at 25 ℃ and hydroquinone with a vapor pressure of 0.0893Pa at 25 ℃)
B-1: phenothiazine (25 ℃ vapor pressure 0.000119 Pa)
C-1: triphenyl phosphite
C-2: phosphorous acid
C-3: tributyl phosphite
TABLE 3
In Table 3, regarding "sieving residue", the polyether ester monomer immediately after the esterification reaction (referred to as "immediately after the reaction" in Table 3) and a sample obtained by charging 600g of the polyether ester monomer into a 1L polypropylene container and storing the same in a sealed state in an incubator at 60℃for 2 weeks (referred to as "after 2 weeks at 60℃in Table 3) were measured and evaluated. The measurement was performed by using a JIS test sieve (made of stainless steel, nominal opening 300 μm). Specifically, after all samples in the polypropylene container were placed on the JIS test sieve, the amount of residue remaining on the sieve was measured, and the residue ratio was calculated from the amount of residue.
Based on the calculated residue ratio, the determination of the sieving residue is performed by the following criteria.
A: the residue rate is less than 1%
B: the residue rate is more than 1% and less than 3%
C: the residue rate is above 3%
Test class 3 (preparation of vinyl copolymer as additive for hydraulic compositions):
the mass average molecular weight of the copolymer shown below was measured by gel permeation chromatography under the following measurement conditions.
< measurement conditions >
The device comprises: shodex GPC-101 (manufactured by Showa electric company).
Column: OHPak SB-G+SB-806M HQ+SB-806M HQ (manufactured by Showa electric company).
A detector: differential Refractometer (RI).
Eluent: 50mM sodium nitrate aqueous solution.
Flow rate: 0.7 mL/min.
Column temperature: 40 ℃.
Sample concentration: an eluent solution with a sample concentration of 0.5 wt%.
Standard substance: polyethylene oxide, polyethylene glycol.
Example 12 (preparation of vinyl copolymer (PC-1)):
153.8g of ion-exchanged water was added to a 1L glass reaction vessel, and the atmosphere was replaced with nitrogen gas while stirring. A solution of 345.2g of the polyether ester monomer (MM-1) obtained in test class 2, 39.5g of methacrylic acid, 3.4g of 3-mercaptopropionic acid, and 272.3g of water was added dropwise over 2 hours while maintaining the temperature of the reaction system at 65℃by a hot water bath under a nitrogen atmosphere. Meanwhile, it took 3 hours to drop 55.8g of a 10% aqueous sodium persulfate solution, thereby conducting polymerization. Then, the polymerization was continued at 65℃for 1 hour to complete the polymerization, and after cooling, a 30% aqueous sodium hydroxide solution was added so as to have a pH of 6, and the mixture was diluted with ion-exchanged water to obtain an aqueous solution having a concentration of 40% of the vinyl copolymer. The vinyl copolymer was analyzed under the above-mentioned measurement conditions, and as a result, a vinyl copolymer (PC-1) having a mass average molecular weight of 23100 was obtained.
Example 13 (preparation of vinyl copolymer (PC-2)):
153.8g of ion-exchanged water was added to a 1L glass reaction vessel, and the mixture was uniformly dissolved while stirring, and then the atmosphere was replaced with nitrogen. The temperature of the reaction system was kept at 70℃by a hot water bath under a nitrogen atmosphere, and it took 4 hours to drop a solution of 329.5g of the polyether ester monomer (MM-2) obtained in test class 2, 36.6g of acrylic acid, 19.2g of hydroxyethyl acrylate, 3.8g of 3-mercaptopropionic acid, and 273.1g of ion-exchanged water. Meanwhile, it took 5 hours to drop 55.8g of a 10% aqueous sodium persulfate solution, thereby conducting polymerization. Then, the mixture was aged at the same temperature (70 ℃ C.) for 1 hour to complete the polymerization reaction. After cooling, a 30% aqueous sodium hydroxide solution was added so as to have a pH of 5, and further diluted with ion-exchanged water, to obtain an aqueous solution having a concentration of 40% of the vinyl copolymer. The vinyl copolymer was analyzed under the above-mentioned measurement conditions, and as a result, a vinyl copolymer (PC-2) having a mass average molecular weight of 20500 was obtained.
Example 14 (preparation of vinyl copolymer (PC-3)):
148.1g of the polyether ester monomer (MM-3) obtained in test class 2, 30.0g of methacrylic acid, 9.4g of methyl acrylate, 4.1g of 3-mercaptopropionic acid, and 181.0g of ion-exchanged water were charged into a reaction vessel, uniformly dissolved while stirring, and then the atmosphere was replaced with nitrogen. Under nitrogen atmosphere, the temperature of the reaction system was kept at 60℃by a hot water bath, 31.4g of 6.2% aqueous sodium persulfate solution was added dropwise to start polymerization, polymerization was continued for 8 hours to complete polymerization, and after cooling, 30% aqueous sodium hydroxide solution was added to bring the pH to 7, and further dilution with ion-exchanged water was performed to obtain a 40% aqueous solution of a vinyl copolymer. The vinyl copolymer was analyzed under the above-mentioned measurement conditions, and as a result, a vinyl copolymer (PC-3) having a mass average molecular weight of 18600 was obtained.
Example 15 (preparation of vinyl copolymer (PC-4)):
170.4g of the polyether ester monomer (MM-4) obtained in test class 2, 19.1g of methacrylic acid, 1.9g of sodium allylsulfonate, 1.7g of thioglycerol, and 172.4g of ion-exchanged water were charged into a reaction vessel. Subsequently, the mixture was uniformly dissolved while stirring, and then the atmosphere was replaced with nitrogen. Under a nitrogen atmosphere, the temperature of the reaction system was maintained at 70℃by a hot water bath, 31.4g of a 5% hydrogen peroxide solution was added dropwise to start polymerization, and the polymerization reaction was continued for 5 hours to complete the polymerization, followed by cooling. After cooling, a 30% aqueous sodium hydroxide solution was added so as to have a pH of 7, and further diluted with ion-exchanged water, to obtain a 40% aqueous solution of the vinyl copolymer. The vinyl copolymer was analyzed under the above-mentioned measurement conditions, and as a result, a vinyl copolymer (PC-4) having a mass average molecular weight of 26700 was obtained.
Examples 16 to 22 (preparation of vinyl copolymers (PC-5) to (PC-11)):
the vinyl copolymers (PC-5) to (PC-11) of examples 16 to 22 were produced in the same manner as in example 12 (production of vinyl copolymer (PC-1)) except that the changes were made as shown in Table 4.
Comparative example 9 (preparation of vinyl copolymer (RPC-1))
The preparation of the vinyl copolymer (RPC-1) of comparative example 9 was carried out in the same manner as in example 12 (preparation of the vinyl copolymer (PC-1)) except that the polyether ester monomer (RM-1) obtained in test class 2 was used in place of the polyether ester monomer (MM-1).
Comparative examples 10 to 15 (preparation of vinyl copolymers (RPC-2) to (RPC-7)):
the production of vinyl copolymers (RPC-3) to (RPC-7) of comparative examples 11 to 15 was carried out in the same manner as in comparative example 9 (production of vinyl copolymer (RPC-1)) except that the modification was carried out as shown in Table 4. The contents of the respective vinyl copolymers (PC-1) to (PC-11) and vinyl copolymers (RPC-1) to (RPC-7) obtained are summarized and shown in Table 4.
TABLE 4
HEA, MA, SAS and BA in Table 4 are explained below.
HEA: hydroxy ethyl acrylate
MA: acrylic acid methyl ester
SAS: allyl sodium sulfonate
BA: butyl acrylate
Test class 4 (preparation of concrete composition as hydraulic composition):
preparation of the concrete composition:
concrete compositions of each test example were prepared as follows under the formulation conditions described in table 5. Ordinary portland cement (specific gravity=3.16), fine aggregate (large-well river sand, specific gravity=2.58) and coarse aggregate (okazaki crushed stone, specific gravity=2.66) were sequentially put into a 50L disc-type forced kneading mixer, and dry-kneaded for 15 seconds. Subsequently, the vinyl copolymer as an additive for hydraulic compositions prepared in test class 3 was added together with kneading water and kneaded for 120 seconds. At this time, an antifoaming agent (trade name: AFK-2, manufactured by Shibata oil and fat Co., ltd.) was added in an amount of 0.0005% to 0.002% relative to cement, and an air amount regulator (trade name: AE-300, manufactured by Shibata oil and fat Co., ltd.) was added in an amount of 0.0005% to 0.002% relative to cement in the mixture 1 so that the target air amount was 4.0% to 5.0%, and in the mixture 2, kneading was performed without adding the air amount regulator.
TABLE 5
Evaluation of concrete composition:
the following evaluations were performed on the concrete of each test example prepared. The results are summarized and shown in table 6.
Slump:
after immediately after kneading (i.e., 0 minutes after kneading) and after standing for 30 minutes after kneading, measurement was carried out in accordance with JIS-A1101, respectively.
Slump flow:
after immediately after kneading (i.e., 0 minutes after kneading) and after standing for 30 minutes after kneading, measurement was carried out in accordance with JIS-A1150, respectively.
Air amount:
after immediately after kneading (i.e., 0 minutes after kneading) and after standing for 30 minutes after kneading, measurement was carried out in accordance with JIS-A1128, respectively.
Compressive strength:
according to JIS-A1108, a steel mold having a diameter of 100mm and a height of 200mm was filled with a concrete composition in a thermostatic chamber having a temperature of 20℃and a humidity of 80%, and the mold was cured and released at a age of 1 day. Subsequently, the aging in water was performed by an aging tank having a water temperature of 20 ℃ until the age of the material reached 28 days. After aging, the test body aged for 28 days was measured for compressive strength.
TABLE 6
In test examples 1 to 5, 7 to 11 and comparative test examples 1 to 6, "slump" was evaluated, and in test example 6 and comparative test example 7, "slump flow" was evaluated.
(results)
As shown in table 3, the residue rate of examples 1 to 11 in which the esterification reaction was carried out in the presence of the polymerization inhibitor a, the polymerization inhibitor B, and the polymerization inhibitor C was smaller, and gelation could be prevented, as compared with comparative examples 1 to 6 and comparative example 8 in which the polymerization inhibitor a, the polymerization inhibitor B, and the polymerization inhibitor C were not used at all. In addition, as shown in table 6, test examples 1 to 11 having passed steps 1 and 2 can bring slump (or slump flow) and air amount within a predetermined range, and can obtain excellent compressive strength, as compared with comparative examples 1 to 7 in which polymerization inhibitor a, polymerization inhibitor B and polymerization inhibitor C were not used at all in step 1. In comparative example 7, although the evaluation of "sieving residue" was a good result, the polymerization reaction in step 2 became insufficient due to the excessive amount of the polymerization inhibitor. Therefore, when the polymer is used as a monomer for an additive for hydraulic compositions (dispersant for hydraulic compositions) to produce an additive for hydraulic compositions (dispersant for hydraulic compositions), a desired polymer cannot be obtained, and slump is reduced (see comparative test example 6). Here, when comparative example 14 and example 12 were compared, the same polymerization was performed, but the weight average molecular weight of the polymer obtained in comparative example 14 was smaller than that of example 12. As described above, in comparative example 14, there is a disadvantage that the function as an additive for hydraulic compositions (dispersant for hydraulic compositions) is lowered (high-performance additive for hydraulic compositions cannot be obtained). In example 10, the addition ratio of the polymerization inhibitor C to the one-terminal-blocked polyalkylene glycol was less than 0.05 mass%, in example 11, the addition ratio of the polymerization inhibitor a to the one-terminal-blocked polyalkylene glycol was less than 0.01 mass%, and the addition ratio of the polymerization inhibitor B to the one-terminal-blocked polyalkylene glycol was 0.005 mass%. Therefore, when compared with other examples, these examples 10 and 11 did not sufficiently exert the effect of preventing gelation to be deteriorated.
Industrial applicability
The method for producing the additive for hydraulic compositions of the present invention can produce a high-performance additive for hydraulic compositions.
Claims (6)
1. A method for producing an additive for hydraulic compositions, comprising the following step 1 and the following step 2,
step 1: a step of subjecting an unsaturated carboxylic acid to an esterification reaction with a one-terminal-blocked polyalkylene glycol represented by the following general formula (1) in the absence of a solvent in the presence of an acid catalyst, a polymerization inhibitor A, a polymerization inhibitor B and a polymerization inhibitor C under heating and reduced pressure to obtain a polyether ester monomer,
[ chemical formula 1]
In the general formula (1), R 1 Represents an alkyl group having 1 to 22 carbon atoms or an aromatic group having 6 to 30 carbon atoms, AO represents an oxyalkylene group having 2 or 3 carbon atoms, n represents an integer of 1 to 300,
polymerization inhibitor A: a polymerization inhibitor which does not contain phosphorus atoms and has a vapor pressure of 0.01Pa or more at 25 ℃,
polymerization inhibitor B: a polymerization inhibitor which does not contain phosphorus atoms and has a vapor pressure of less than 0.01Pa at 25 ℃,
polymerization inhibitor C: a polymerization inhibitor containing phosphorus atoms,
step 2: a step of subjecting the polyether ester monomer obtained in the step 1 and a vinyl monomer copolymerizable with the polyether ester monomer to radical copolymerization in an aqueous solvent to obtain an additive for hydraulic compositions,
wherein the unsaturated carboxylic acid is at least one selected from the group consisting of acrylic acid and methacrylic acid,
the polymerization inhibitor A is added in a proportion of 0.01 to 0.5 mass% relative to the one-terminal-blocked polyalkylene glycol,
the polymerization inhibitor B is added in a proportion of 0.005 to 0.5 mass% relative to the one-terminal-blocked polyalkylene glycol,
the polymerization inhibitor C is added in a proportion of 0.005 to 0.5 mass% relative to the one-terminal-blocked polyalkylene glycol.
2. The method for producing an additive for hydraulic compositions according to claim 1, wherein the polymerization inhibitor A contains at least one selected from the group consisting of p-benzoquinone, naphthoquinone and quinone hydroquinone.
3. The method for producing an additive for hydraulic compositions according to claim 1 or 2, wherein the polymerization inhibitor a contains p-benzoquinone.
4. The method for producing an additive for hydraulic compositions according to claim 1 or 2, wherein the polymerization inhibitor B contains phenothiazine.
5. The method for producing an additive for hydraulic compositions according to claim 1 or 2, wherein the polymerization inhibitor C comprises at least one selected from the group consisting of phosphorous acid and phosphite esters.
6. The method for producing an additive for hydraulic compositions according to claim 1 or 2, wherein 95 mol% or more of all the oxyalkylene groups in the AO in the general formula (1) in the one-terminal-blocked polyalkylene glycol are oxyethylene groups having 2 carbon atoms.
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| JP2002003586A (en) * | 2000-06-23 | 2002-01-09 | Dainippon Ink & Chem Inc | Unsaturated polyester and method of producing the same |
| JP2003002720A (en) * | 1999-10-08 | 2003-01-08 | Takemoto Oil & Fat Co Ltd | Cement dispersing agent |
| JP2005015338A (en) * | 2004-08-25 | 2005-01-20 | Takemoto Oil & Fat Co Ltd | Cement dispersing agent |
| JP2007146125A (en) * | 2005-11-02 | 2007-06-14 | Nof Corp | Curing agent for radical polymerization type thermosetting resin, molding material containing the agent, and curing method for the material |
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| JP3327809B2 (en) * | 1996-04-03 | 2002-09-24 | 株式会社日本触媒 | Cement dispersant, method for dispersing cement and cement composition |
| IT1283082B1 (en) * | 1996-05-30 | 1998-04-07 | Hoechst Sara Spa | PROCEDURE FOR THE SYNTHESIS OF RESINS CONTAINING UNSATURAL ZONES OF TYPE (MET) ACRYLIC HARDENABLE BY RADIATION OR HEAT AND |
| JP3518795B2 (en) * | 1997-06-10 | 2004-04-12 | 株式会社日本触媒 | Method for producing polyalkylene glycol (meth) acrylate |
| DE19753322A1 (en) * | 1997-12-02 | 1999-06-10 | Basf Ag | Radiation-curable compositions based on epoxy (meth) acrylates |
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| JP2003002720A (en) * | 1999-10-08 | 2003-01-08 | Takemoto Oil & Fat Co Ltd | Cement dispersing agent |
| JP2002003586A (en) * | 2000-06-23 | 2002-01-09 | Dainippon Ink & Chem Inc | Unsaturated polyester and method of producing the same |
| JP2005015338A (en) * | 2004-08-25 | 2005-01-20 | Takemoto Oil & Fat Co Ltd | Cement dispersing agent |
| JP2007146125A (en) * | 2005-11-02 | 2007-06-14 | Nof Corp | Curing agent for radical polymerization type thermosetting resin, molding material containing the agent, and curing method for the material |
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