CN115745468A - Starch-based slump retaining water reducer and preparation method thereof - Google Patents
Starch-based slump retaining water reducer and preparation method thereof Download PDFInfo
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- CN115745468A CN115745468A CN202310017738.8A CN202310017738A CN115745468A CN 115745468 A CN115745468 A CN 115745468A CN 202310017738 A CN202310017738 A CN 202310017738A CN 115745468 A CN115745468 A CN 115745468A
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- starch
- parts
- water reducer
- slump retaining
- retaining water
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- 229920002472 Starch Polymers 0.000 title claims abstract description 127
- 239000008107 starch Substances 0.000 title claims abstract description 127
- 235000019698 starch Nutrition 0.000 title claims abstract description 127
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- -1 hydroxyl ester Chemical class 0.000 claims abstract description 43
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229920000642 polymer Polymers 0.000 claims abstract description 32
- 150000004676 glycans Chemical class 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 229920001282 polysaccharide Polymers 0.000 claims abstract description 27
- 239000005017 polysaccharide Substances 0.000 claims abstract description 27
- 238000005886 esterification reaction Methods 0.000 claims abstract description 26
- 230000032050 esterification Effects 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 239000004593 Epoxy Substances 0.000 claims abstract description 18
- 229930182470 glycoside Natural products 0.000 claims abstract description 18
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 18
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 17
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000015556 catabolic process Effects 0.000 claims abstract description 14
- 238000006731 degradation reaction Methods 0.000 claims abstract description 14
- 239000003112 inhibitor Substances 0.000 claims abstract description 14
- 230000015271 coagulation Effects 0.000 claims abstract description 13
- 238000005345 coagulation Methods 0.000 claims abstract description 13
- 239000002270 dispersing agent Substances 0.000 claims abstract description 12
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 43
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- 230000002255 enzymatic effect Effects 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 229920000856 Amylose Polymers 0.000 claims description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003377 acid catalyst Substances 0.000 claims description 6
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 150000002191 fatty alcohols Chemical class 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 235000013336 milk Nutrition 0.000 claims description 5
- 239000008267 milk Substances 0.000 claims description 5
- 210000004080 milk Anatomy 0.000 claims description 5
- 230000001737 promoting effect Effects 0.000 claims description 5
- 239000004382 Amylase Substances 0.000 claims description 4
- 108090000637 alpha-Amylases Proteins 0.000 claims description 4
- 102000004139 alpha-Amylases Human genes 0.000 claims description 4
- 229940024171 alpha-amylase Drugs 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 3
- 108010019077 beta-Amylase Proteins 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004567 concrete Substances 0.000 abstract description 33
- 239000002253 acid Substances 0.000 abstract description 16
- 239000004721 Polyphenylene oxide Substances 0.000 abstract description 4
- 229920000570 polyether Polymers 0.000 abstract description 4
- 150000001735 carboxylic acids Chemical class 0.000 abstract 1
- 239000004568 cement Substances 0.000 description 21
- 239000000463 material Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 16
- 230000000694 effects Effects 0.000 description 15
- 230000008569 process Effects 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 12
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000011112 process operation Methods 0.000 description 9
- 229930182478 glucoside Natural products 0.000 description 6
- 230000036571 hydration Effects 0.000 description 6
- 238000006703 hydration reaction Methods 0.000 description 6
- 239000004576 sand Substances 0.000 description 6
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 5
- 229960005070 ascorbic acid Drugs 0.000 description 5
- 235000010323 ascorbic acid Nutrition 0.000 description 5
- 239000011668 ascorbic acid Substances 0.000 description 5
- 239000011790 ferrous sulphate Substances 0.000 description 5
- 235000003891 ferrous sulphate Nutrition 0.000 description 5
- 238000006206 glycosylation reaction Methods 0.000 description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 5
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- 229920002261 Corn starch Polymers 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 239000011942 biocatalyst Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000008120 corn starch Substances 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003248 enzyme activator Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- PYIDGJJWBIBVIA-UYTYNIKBSA-N lauryl glucoside Chemical compound CCCCCCCCCCCCO[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O PYIDGJJWBIBVIA-UYTYNIKBSA-N 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-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
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 238000007865 diluting Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
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- 229940088598 enzyme Drugs 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 150000008131 glucosides Chemical class 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 125000003563 glycoside group Chemical group 0.000 description 1
- 150000002338 glycosides Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- 235000019426 modified starch Nutrition 0.000 description 1
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- 125000005702 oxyalkylene group Chemical group 0.000 description 1
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- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention provides a starch-based slump retaining water reducer and a preparation method thereof, wherein the preparation raw materials of the starch-based slump retaining water reducer comprise the following components in parts by weight: 150-250 parts of polysaccharide polymer esterified liquid, 11-22 parts of carboxyl-terminated vinyl epoxy ether, 0.8-1 part of initiator, 4-11 parts of acrylic acid, 10-15 parts of hydroxyl ester monomer, 0-0.3 part of reducing agent, 0.3-0.7 part of chain transfer agent and 1-3 parts of coagulation accelerating component; the preparation raw materials of the polysaccharide polymer esterification liquid comprise the following components in parts by weight: enzymolysis starch, short straight chain degradation starch and alkyl glycoside mixture, dispersant, unsaturated carboxylic acid and/or unsaturated anhydride, esterification catalyst and polymerization inhibitor. The starch-based slump retaining water reducer performs unsaturated acid esterification on a mixture of enzymolysis starch, short straight chain degradation starch and alkyl glycoside, so that a group with an unsaturated bond is grafted on a starch chain, the starch chain can be polymerized with a polyether monomer to form a comb-shaped structure, and the starch-based slump retaining water reducer can play a role in reducing water when added into concrete.
Description
Technical Field
The invention relates to the field of concrete building materials, in particular to a starch-based slump loss resistant water reducer and a preparation method thereof.
Background
National infrastructure and real estate are in a rapid development stage, the demand for concrete is increased gradually, sandstone materials are increasingly scarce, part of natural river sand is limited to mining, machine-made sand gradually replaces river sand to occupy the market, the quality of cement and stone on the market is increasingly complex, half of materials have the problems of large mud content and high powder content, and in addition, in order to meet the long-time construction requirements of concrete, a large amount of water reducing agent and slump retaining agent must be compounded in an additive. Many slump retaining agents have good slump retaining effect at the initial stage, but have poor slump retaining effect at the later stage, so that concrete pumping construction is difficult, and new requirements are provided for long-acting slump retaining of the water reducing agent. In addition, the air entraining agent is one of the most common additives in the concrete at present, can introduce a large amount of stable micro bubbles in the concrete mixing process, the micro bubbles are similar to balls, the workability of fresh concrete can be improved, and in hardened concrete, the introduced bubbles are beneficial to improving the frost resistance, the compactness and the impermeability of the concrete. The existing air entraining agent is mainly used by compounding with a water reducing agent, is relatively complicated to use, and always has the defects of non-ideal air entraining effect or relatively quick air loss.
With the rapid development of concrete technology towards green, environmental protection and high cost performance, higher and more comprehensive requirements are provided for the water reducing agent which is an important component in the concrete. The traditional concrete high-efficiency water reducing agent is gradually replaced by a polycarboxylic acid water reducing agent with more excellent performance due to larger mixing amount, low water reducing rate and high concrete slump loss, but the polycarboxylic acid high-performance water reducing agent has excellent water reducing performance and workability, is the mainstream in the current market, but the raw material sources of the polycarboxylic acid high-efficiency water reducing agent are petroleum and petrochemical products, consumes a large amount of petrochemical resources and has high carbon emission, and in addition, the polycarboxylic acid water reducing agent is also found to have the problem of insufficient slump retaining performance due to material problems in partial application. Therefore, the development of the high-cost-performance slump retaining agent which takes green natural degradable raw materials as main raw materials and has excellent slump retaining performance, insensitive use conditions and wider application range has very important significance.
Disclosure of Invention
In view of the above, the invention provides a starch-based slump retaining water reducing agent to improve the slump retention performance of concrete.
In order to achieve the purpose, the technical scheme of the invention is realized in such a way.
A starch-based slump retaining water reducer is prepared from the following raw materials in parts by weight: 150-250 parts of polysaccharide polymer esterified liquid, 11-22 parts of carboxyl-terminated vinyl epoxy ether, 0.8-1 part of initiator, 4-11 parts of acrylic acid, 10-15 parts of hydroxyl ester monomer, 0-0.3 part of reducing agent, 0.3-0.7 part of chain transfer agent and 1-3 parts of coagulation accelerating component;
the preparation raw materials of the polysaccharide polymer esterification liquid comprise the following components in parts by weight: 90-120 parts of enzymolysis starch, 30-60 parts of short straight chain degradation starch and alkyl glycoside mixture, 75-150 parts of dispersing agent, 25-35 parts of unsaturated carboxylic acid and/or unsaturated anhydride, 3-5 parts of esterification catalyst and 0.04-0.4 part of polymerization inhibitor.
Further, the hydroxy ester monomer comprises at least one of hydroxyethyl methacrylate, hydroxypropyl methacrylate and hydroxyethyl acrylate.
Further, the coagulation promoting component comprises at least one of diethanolamine, triethanolamine or triisopropanolamine.
Further, the unsaturated carboxylic acid comprises at least one of acrylic acid, itaconic acid and maleic acid, and the unsaturated anhydride comprises at least one of itaconic anhydride and maleic anhydride.
Further, the esterification catalyst is at least one of concentrated sulfuric acid, boric acid, organic sulfonic acid and sulfate.
Further, the dispersant comprises dimethyl sulfoxide, and/or the polymerization inhibitor comprises a polyhydric phenol polymerization inhibitor.
Further, the molecular weight of the enzymolysis starch is 2500-13000, and/or the molecular weight of the mixture of the short amylose degradation starch and the alkyl glycoside is 800-1600.
The application also provides a preparation method of the starch-based slump retaining water reducer, which comprises the steps of taking a mixed solution of enzymolysis starch, a mixture of short straight chain degraded starch and alkyl glycoside, a dispersing agent and deionized water, adding unsaturated carboxylic acid or anhydride, an esterification catalyst and a polymerization inhibitor, heating to 80-120 ℃, stirring and mixing, and reacting fully to obtain polysaccharide polymer esterified liquid; mixing the polysaccharide polymer esterified solution with carboxyl-terminated vinyl epoxy ether, heating to 55-65 ℃, adding an initiator, and uniformly stirring; and then dropwise adding a mixed aqueous solution of acrylic acid and hydroxyl ester monomers and a mixed aqueous solution of a reducing agent and a chain transfer agent, keeping the temperature and continuously stirring after the dropwise adding is finished, adding a coagulation accelerating component and stirring after the reaction is finished, adjusting the pH =6-7, adding dilution water and uniformly stirring to obtain the starch-based slump retaining water reducer.
Further, the preparation method of the enzymatic starch comprises the following steps:
preparing starch milk with solid content of 20-40%, heating to 40-60 deg.C, adjusting pH =3.5-6, adding pullulan-amylase, and keeping the temperature; adjusting pH to 4-7.5, heating to 60-110 deg.C, controlling starch gelatinization time for 20-60 min, adding alpha-amylase and/or beta-amylase, and keeping temperature; cooling and filtering, and drying and grinding the filtrate in vacuum to obtain the enzymatic starch.
Further, the preparation method of the short amylose degraded starch and alkyl glycoside mixture comprises the following steps:
mixing the enzymatic starch and fatty alcohol, stirring uniformly, adding an acid catalyst, heating to 90-120 ℃, vacuumizing to 1.5-2kPa for 30-60 min, cooling, filtering to remove filtrate, distilling to remove alcohol, and drying to obtain the mixture of the short amylose degraded starch and the alkyl glycoside.
The starch-based slump retaining water reducer performs unsaturated acid esterification on a mixture of enzymolysis starch, short and straight chain degradation starch and alkyl glycoside to graft a group with an unsaturated bond on a starch chain, the obtained polysaccharide polymer esterified liquid has an unsaturated bond, the polysaccharide polymer esterified liquid is polymerized with carboxyl-terminated vinyl epoxy ether, acrylic acid and hydroxyl ester monomers to generate a polymer with the function of dispersing cement particles, the working performance and the workability of concrete can be continuously maintained, the slump loss is small over time, a certain air entraining effect is achieved, the proper air entraining amount can be provided in the concrete, the size of introduced air bubbles is moderate, the stability is high, the plasticity of the concrete is improved by introducing the air bubbles, and the slump retaining is facilitated. The starch-based slump retaining water reducer is prepared from environment-friendly starch materials, and has the advantages of greenness, low carbon and high cost performance.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The experimental procedures in the following examples are conventional unless otherwise specified. The test materials used in the following examples were purchased from a conventional biochemical reagent store unless otherwise specified. In addition, except for the specific description of the present embodiment, the terms and processes referred to in the present embodiment should be understood according to the common knowledge and conventional methods in the prior art.
A starch-based slump retaining water reducer comprises the following raw materials in parts by weight: 150-250 parts of polysaccharide polymer esterified liquid, 11-22 parts of carboxyl-terminated vinyl epoxy ether, 0.8-1 part of initiator, 4-11 parts of acrylic acid, 10-15 parts of hydroxyl ester monomer, 0-0.3 part of reducing agent, 0.3-0.7 part of chain transfer agent and 1-3 parts of coagulation promoting component; the preparation raw materials of the polysaccharide polymer esterification liquid comprise the following components in parts by weight: 90-120 parts of enzymolysis starch, 30-60 parts of short straight chain degradation starch and alkyl glycoside mixture, 75-150 parts of dispersing agent, 25-35 parts of unsaturated carboxylic acid or anhydride, 3-5 parts of esterification catalyst and 0.04-0.4 part of polymerization inhibitor.
The invention adopts unsaturated acid to esterify and modify the mixture of enzymolysis starch, short straight chain degradation starch and alkyl glucoside to prepare polysaccharide polymer esterification liquid, the starch chain after esterification modification has unsaturated bond, and can be polymerized with polyether monomer and unsaturated acid into polymer with comb structure, the main chain of the polymer is formed by the addition of the esterification modification starch, esterification alkyl glucoside and acrylic acid, the side chain is formed by carboxyl-terminated vinyl epoxy ether and hydroxyl ester monomer, and the polymer has the function of dispersing cement particles.
When concrete is mixed, the starch-based slump retaining water reducer is added, carboxylic acid groups on the main chain of polymer molecules of the starch-based slump retaining water reducer can be adsorbed with metal ions on the surfaces of cement particles, so that the polymer molecules are anchored on the surfaces of the cement particles, negative charges are carried on the surfaces of the cement particles, an electrostatic repulsion effect is formed, the cement particles are dispersed mutually, a flocculation structure is disintegrated, wrapped water is released to participate in flowing, and the fluidity of a concrete mixture is effectively increased. Meanwhile, long side chains of the carboxyl-terminated vinyl epoxy ether are spread out, and the long side chains generate steric hindrance effect among cement particles to hinder coagulation among the cement particles, so that the cement particles are dispersed, and the mixing performance of concrete is improved. Meanwhile, the alkyl glycoside group on the main chain has a surface activity effect, a large number of uniformly distributed bubbles can be introduced when concrete is mixed, and due to the compressibility of the bubbles, the expansion pressure generated by icing can be relieved, and meanwhile, the bubbles can accommodate the migration of free water, so that the osmotic pressure can be greatly relieved, the bleeding and segregation of concrete mixtures are reduced, the workability and plasticity are improved, the slump maintenance is facilitated, and the frost resistance and durability of hardened concrete can be obviously improved.
The inventor finds that the molecular weight of common starch is larger, even can reach hundreds of thousands of millions, the polymerization degree is higher, and the grafted unsaturated acid can not be effectively adsorbed, so that the starch adopts starch subjected to enzymolysis to a certain degree, the molecular weight of the enzymolysis starch is 2500-13000, the molecular weight of the mixture of short straight chain degradation starch and alkyl glycoside is 800-1600, and the main chain formed by the starch has a better adsorption effect.
The side chain of the starch-based slump retaining water reducer is composed of carboxyl-terminated vinyl epoxy ether and a hydroxyl ester monomer. Ester groups of the hydroxyl ester monomers can be continuously hydrolyzed under the strong alkaline action of the cement slurry solution to gradually generate new carboxyl anions, the newly generated carboxyl anions drive water reducer molecules to continuously adsorb the surfaces of cement particles and hydration products, so that the loss of fluidity caused by the hydration action of cement over time is effectively counteracted, and a good fluidity maintaining effect is shown.
The structural formula of the carboxyl-terminated vinyl epoxy ether is specifically H 2 C=CR 1 -B-(AO) n R 2 ，R 1 Is a hydrogen atom or a methyl group, R 2 Is COOH, B is COO, O (CH) 2 ) m O、CH 2 O or CH 2 CH 2 O, m =2 to 4, AO is at least one of oxyalkylene groups of 2 to 4 carbon atoms, and n is an average molar number of addition of AO and is an integer of 3 to 8. Alkenyl at one end of carboxyl-terminated vinyl epoxy ether, and terminal alkenyl and ester of unsaturated acid and hydroxy ester monomerEster groups of the modified starch are copolymerized to form water reducing agent molecules, and carboxyl groups at the other end can form firm electrovalence bond combination with a cationic region on the surface of cement particles, so that a polyether chain segment can form a stable and firm adsorption and winding layer on the surface of the cement particles, and the functions of water reducing, isolating and dispersing are achieved.
Because abundant hydroxyl in a polysaccharide polymer structure can form an unstable complex with free calcium ions in cement so as to influence the formation of a cement hydration product calcium hydroxide, the cement hydration product calcium hydroxide has certain coagulation time prolonging effect and hydration heat release temperature rise inhibition effect, but in order to maintain the coagulation time within a reasonable range, a certain non-alkali metal salt coagulation-promoting component is required to be supplemented, so that an alcohol amine compound is selected as the coagulation-promoting component to be compounded with the alcohol amine compound, and the coagulation time is effectively regulated while the hydration temperature rise inhibition function of the alcohol amine compound is kept. The set accelerating component preferably comprises at least one of diethanolamine, triethanolamine, or triisopropanolamine.
The unsaturated carboxylic acid or anhydride is preferably organic acid with stronger acidity, has better adsorption effect, and can be selected from at least one of acrylic acid, itaconic anhydride, maleic acid and maleic anhydride.
The esterification catalyst has an effect of catalyzing the esterification reaction to proceed, so that the esterification reaction is more efficient, and may preferably include at least one of concentrated sulfuric acid, boric acid, organic sulfonic acid, and sulfate. The dispersing agent can disperse the degraded starch, so that the degraded starch can be uniformly suspended in the solution, and the esterification is more sufficient. While it is preferable to use a dissolution type dispersant capable of dissolving starch to have a more stable state, the present invention preferably uses a dispersant including dimethyl sulfoxide (DMSO), which is an excellent organic solvent having good chemical and thermal stability, has good dispersion to starch polysaccharides, and increases the speed of chemical reaction. The polymerization inhibitor can effectively prevent polymerization addition between unsaturated acids, so that the unsaturated acids can be fully esterified with the degraded starch, and a polyhydric phenol polymerization inhibitor such as benzenediol can be preferably used as the polymerization inhibitor.
The degraded starch has unsaturated bonds after being modified by the esterification of unsaturated acid, and can be polymerized and added with the unsaturated acid and the monomers forming the side chains under a redox system, the initiator for polymerization preferably comprises at least one of hydrogen peroxide, ammonium ceric nitrate and ammonium persulfate and ferrous sulfate, and the reducing agent can preferably be ascorbic acid. The chain transfer agent is used to control the molecular weight of the polymer, and preferably at least one selected from the group consisting of thioglycolic acid, mercaptopropionic acid, mercaptoethanol, and sodium hypophosphite may be used.
The application also provides a preparation method of the starch-based slump retaining water reducer, which particularly preferably comprises the following process steps of:
s1, injecting 300 parts of water into a reaction kettle, starting stirring, slowly adding 75-200 parts of starch into the reaction kettle to prepare starch milk with the solid content of 20-40%, heating the reaction kettle to 40-60 ℃, adjusting the pH =3.5-6 of the starch milk, and adding a biocatalyst A: pullulan-amylase, catalytically degraded for 20-80 minutes, at which time part of the 1, 6-glucosidic bonds of the starch are hydrolysed. Adjusting the pH value to 4-7.5, raising the temperature of the reaction kettle to 60-110 ℃, controlling the starch gelatinization time to 20-60 minutes, adding a biocatalyst B: alpha-amylase and/or beta-amylase, catalytic degradation for 30-90 minutes, when the starch part of the 1, 4-glycosidic bond is hydrolyzed. Cooling, filtering to remove impurity protein in starch, and spray drying the filtrate to obtain degraded starch with molecular weight of 2500-13000.
The water in the step can adopt one or a combination of more than two of deionized water, tap water and underground water, preferably tap water, such as deionized water alone, and can also be added with 0.01-0.03 per mill of a biological enzyme activator, wherein the biological enzyme activator is one or a combination of two of calcium oxide, calcium chloride and calcium hydroxide. The pH regulator may be acetic acid, sodium bicarbonate, or sodium hydroxide.
S2: adding the degraded starch into the fatty alcohol according to the mass ratio of 1; adding an acid catalyst into the mixed solution according to 0.5-1.5% of the total mass of the starch and the fatty alcohol, continuously stirring uniformly, slowly heating to 90-120 ℃, vacuumizing and maintaining the pressure to 1.5-2kPa for glycosylation reaction, wherein the reaction time is 30-60 min; and then cooling, filtering to remove the acid catalyst, distilling to remove alcohol, and drying to obtain the mixture of the short straight chain degraded starch and the alkyl glucoside. The molecular weight of the mixture of the short straight chain degraded starch and the alkyl glycoside prepared in the step is 800-1600, and the fatty alcohol can be at least one of n-octanol, n-nonanol, n-decanol, n-undecanol and n-dodecanol with the carbon chain length of 8-12.
S3, taking 90-120 parts of degraded starch, 30-60 parts of short straight chain degraded starch and alkyl glycoside mixture, adding 30 parts of unsaturated carboxylic acid or anhydride, 3.5 parts of esterification catalyst and 0.4 part of polymerization inhibitor into the mixed solution of 75-150 parts of dispersing agent and 0-75 parts of deionized water, heating to 80-120 ℃, stirring and mixing, and reacting for 60-180 minutes to obtain polysaccharide polymer esterified liquid with the solid content of 55%. The step is to introduce reactive double bond groups on two polysaccharide molecules with different molecular weights, so that unsaturated polyether and unsaturated carboxylic acid can be effectively grafted to a polysaccharide polymer main chain in the next free radical polymerization process.
S4, adding 150-250 parts of polysaccharide polymer esterified liquid and 11-22 parts of carboxyl-terminated vinyl epoxy ether into a reaction kettle, heating to 60 ℃, adding 0.8-1 part of initiator under stirring, and beginning to synchronously dropwise add materials A and B, wherein the material A is as follows: 4-11 parts of acrylic acid, 10-15 parts of hydroxyl ester monomer and 20 parts of deionized water solution, and the dripping time is 120-150 minutes; the material B is as follows: 0-0.3 part of reducing agent, 0.3-0.7 part of chain transfer agent and 30 parts of deionized water, wherein the dripping time is 150-180 minutes, the mixture is kept warm and is continuously stirred for reaction for 60-90 minutes after the dripping is finished, 1-3 parts of coagulation promoting component are added after the reaction is finished, the pH value is adjusted to 6-7 by using a pH regulator after the stirring is carried out for 10-30 minutes, and the diluting water is added and is stirred for 5-10 minutes to obtain the starch-based slump retaining water reducing agent with the solid content of 40%.
The starch is degraded by a biological enzyme process, residual glucose residues in degradation products are used for being subjected to glycosylation reaction with fatty alcohol to obtain alkyl glucoside, proper air entraining performance can be provided in concrete, introduced bubbles are moderate in size and high in stability, the workability and the workability of the concrete can be effectively improved, short straight-chain starch except the alkyl glucoside obtained after the starch and the glycosylation reaction is degraded in the first step and is subjected to esterification modification with unsaturated carboxylic acid or anhydride, then the short straight-chain starch is subjected to free radical polymerization with monomers such as carboxyl-terminated vinyl epoxy ether, unsaturated carboxylic acid and hydroxyl ester to obtain semitransparent milky liquid, and finally a certain amount of coagulation promoting components are compounded to obtain the starch-based slump retaining water reducer.
The following describes in detail specific embodiments of the present invention.
Example 1
The embodiment of the invention provides a starch-based slump retaining water reducer, which comprises the following specific preparation steps:
s1, weighing 75g of common corn starch, adding the common corn starch into a reaction kettle containing 300g of tap water to prepare 20% starch milk, heating to 55 ℃, adjusting the pH to be =4.5 +/-0.2, adding 0.15g of pullulan-amylase, performing catalytic degradation for 30 minutes, adjusting the pH to be 6 +/-0.2, heating the reaction kettle to 90 ℃, controlling starch gelatinization time to be 20 minutes, adding 0.03g of alpha-amylase, performing catalytic degradation for 60 minutes, cooling, filtering out impurities, spray-drying filtrate, and grinding to obtain the enzymatic starch.
S2, adding 50g of enzymolytic starch into a reaction kettle containing 125g of n-dodecanol, stirring to uniformly disperse the enzymolytic starch, adding 1.25g of sulfuric acid into the mixed solution, continuously stirring uniformly, slowly heating to 100 ℃, vacuumizing, maintaining the pressure to 1.5-2kPa, and carrying out glycosylation reaction for 40 min; and after the reaction is finished, cooling, filtering to remove the acid catalyst, distilling to remove alcohol, and drying to obtain the mixture of the short straight chain degraded starch and the dodecyl glucoside.
S3, adding 120g of the mixture of the enzymatic starch, 30g of the short-chain and straight-chain degraded starch and the dodecyl glucoside into 120g of DMSO and 30g of deionized water, stirring and dispersing for 20 minutes, adding 30g of methacrylic acid, 3.5g of sulfuric acid (98%) and 0.4g of hydroquinone under a stirring state, heating to 120 ℃, stirring and mixing for 180 minutes to obtain the polysaccharide polymer esterified solution.
S4, adding 200g of polysaccharide polymer esterified liquid and 11g of carboxyl-terminated vinyl epoxy ether into a reaction kettle, heating to 60 ℃, adding 0.45g of hydrogen peroxide, 0.45g of ammonium persulfate and 0.13g of ferrous sulfate solution (1% concentration) while stirring, and starting to synchronously dropwise add materials A and B, wherein the material A is as follows: 4g of acrylic acid, 10g of hydroxyethyl acrylate and 20g of deionized water solution, and the dripping time is 150 minutes; the material B is as follows: 0.2g of ascorbic acid, 0.35g of mercaptopropionic acid and 30g of deionized water, wherein the dripping time is 180 minutes, the stirring reaction is continued for 90 minutes under the condition of heat preservation after the dripping is finished, 2.5g of triethanolamine is added after the reaction is finished, the pH value is adjusted to be 6-7 by using a pH regulator after the stirring is carried out for 15 minutes, 73g of dilution water is added, and the stirring is carried out for 10 minutes, so that the starch-based slump retaining water reducer with the solid content of 40% is obtained.
Example 2
The embodiment of the invention provides a starch-based slump retaining water reducer, which comprises the following specific preparation steps:
s1, the process operation steps are completely the same as those of the S1 process in the example 1.
S2, adding 100g of the enzymatic starch into a reaction kettle containing 250g of n-octanol, stirring to uniformly disperse the starch, adding 2.5g of sulfuric acid into the mixed solution, continuously stirring uniformly, slowly heating to 120 ℃, vacuumizing and maintaining the pressure to 1.5-2kPa to perform glycosylation reaction, wherein the reaction time is 60min; and after the reaction is finished, cooling, filtering to remove the acid catalyst, distilling to remove alcohol, and drying to obtain the mixture of the short amylose degraded starch and the octaalkyl glucoside.
And S3, adding a mixture of 75g of the enzymatic starch, 75g of the short straight chain degraded starch and the octaalkyl glycoside into 135g of DMSO and 15g of deionized water, stirring and dispersing for 20 minutes, adding 30g of methacrylic acid, 3.5g of sulfuric acid (98 percent) and 0.4g of hydroquinone under a stirring state, heating to 120 ℃, stirring and mixing for 180 minutes to obtain the polysaccharide polymer esterified solution.
S4, the operation steps are completely the same as those of the S4 process in the example 1.
Example 3
The embodiment of the invention provides a starch-based slump retaining water reducer, which comprises the following specific preparation steps:
s1, the process operation steps are completely the same as those of the S1 process in the example 1.
S2, the process operation steps are completely the same as those of the S2 process in the example 1.
S3, the process operation steps are completely the same as those of the S3 process in the example 1.
S4, adding 200g of polysaccharide polymer esterified liquid and 22g of carboxyl-terminated vinyl epoxy ether into a reaction kettle, heating to 60 ℃, adding 0.48g of hydrogen peroxide, 0.48g of ammonium persulfate and 0.15g of ferrous sulfate solution (1% concentration) while stirring, and synchronously dropwise adding materials A and B, wherein the material A is as follows: 4g of acrylic acid, 10g of hydroxyethyl acrylate and 20g of deionized water solution, and the dripping time is 150 minutes; the material B is as follows: 0.24g of ascorbic acid, 0.39g of mercaptopropionic acid and 30g of deionized water, wherein the dripping time is 180 minutes, the stirring and the reaction are continued for 90 minutes after the dripping is finished, 2.5g of triethanolamine is added after the reaction is finished, the pH is adjusted to be 6-7 by using a pH regulator after the stirring is carried out for 15 minutes, 75g of dilution water is added, and the stirring is carried out for 10 minutes, so that the starch-based slump retaining water reducing agent with the solid content of 40% is obtained.
Example 4
The embodiment of the invention provides a starch-based slump retaining water reducer, which comprises the following specific preparation steps:
s1, the process operation steps are completely the same as those of the S1 process in the example 1.
S2, the process operation steps are completely the same as those of the S2 process in the example 1.
S3, the operation steps are completely the same as those of the S3 process in the example 1.
S4, adding 200g of polysaccharide polymer esterified liquid and 11g of carboxyl-terminated vinyl epoxy ether into a reaction kettle, heating to 60 ℃, adding 0.45g of hydrogen peroxide, 0.45g of ammonium persulfate and 0.13g of ferrous sulfate solution (1% concentration) while stirring, and starting to synchronously dropwise add materials A and B, wherein the material A is as follows: dripping 10g of acrylic acid, 15g of hydroxyethyl acrylate and 20g of deionized water solution for 150 minutes; the material B is as follows: 0.2g of ascorbic acid, 0.35g of mercaptopropionic acid and 30g of deionized water, wherein the dripping time is 180 minutes, the stirring reaction is continued for 90 minutes under the condition of heat preservation after the dripping is finished, 2.5g of triethanolamine is added after the reaction is finished, the pH value is adjusted to be 6-7 by using a pH regulator after the stirring is carried out for 15 minutes, 74g of dilution water is added, and the stirring is carried out for 10 minutes, so that the starch-based slump retaining water reducer with the solid content of 40% is obtained.
Example 5
The embodiment of the invention provides a starch-based slump retaining water reducer, which comprises the following specific preparation steps:
s1, the process operation steps are completely the same as those of the S1 process in the example 1.
S2, the process operation steps are completely the same as those of the S2 process in the example 1.
S3, the process operation steps are completely the same as those of the S3 process in the example 1.
S4, adding 200g of polysaccharide polymer esterified liquid and 22g of carboxyl-terminated vinyl epoxy ether into a reaction kettle, heating to 60 ℃, adding 0.48g of hydrogen peroxide, 0.48g of ammonium persulfate and 0.15g of ferrous sulfate solution (1% concentration) while stirring, and starting to synchronously dropwise add materials A and B, wherein the material A is as follows: dripping 10g of acrylic acid, 10g of hydroxyethyl acrylate and 20g of deionized water solution for 150 minutes; the material B is as follows: 0.24g of ascorbic acid, 0.39g of mercaptopropionic acid and 30g of deionized water, wherein the dripping time is 180 minutes, the stirring and the reaction are continued for 90 minutes after the dripping is finished, 2.5g of triethanolamine is added after the reaction is finished, the pH is adjusted to be 6-7 by using a pH regulator after the stirring is carried out for 15 minutes, 74g of dilution water is added, and the stirring is carried out for 10 minutes, so that the starch-based slump retaining water reducing agent with the solid content of 40% is obtained.
Comparative example 1
A high-performance polycarboxylic slump retaining agent disclosed in patent CN 106947029B is adopted.
Comparative example 2
A high-performance polycarboxylic acid water-reducing slump-retaining agent disclosed in patent CN102532437B is adopted.
Comparative example 3
The high-performance polycarboxylic acid water-reducing slump-retaining agent of the comparative example 2 is adopted, and is compounded with a rosin air-entraining agent accounting for 0.005 percent of the mass of cement.
The following are the performance tests of the invention:
the cement is NZ P.O.42.5 cement; the sand is artificial machine-made sand, and the fineness modulus of the sand is 2.6; the stones are crushed stones with the thickness of 5-10 mm and crushed stones with the thickness of 10-20mm, and concrete performance tests are carried out according to the Standard of the test methods for mechanical properties of ordinary concrete (GB/T50080-2002). The products of the five groups of examples and the two groups of comparative examples are subjected to a mixing ratio experiment by adopting C30, the mixing ratio of concrete tests is shown in Table 1, and the test data in Table 2 are that the water reducing mother liquor GK-P6 of the company and the slump retaining mother liquor of the examples and the comparative examples have a solid ratio of 6:4, testing by compounding, wherein the mixing amount is 0.27% (water reducing and slump retaining).
TABLE 1 concrete mix proportion
Table 2 concrete slump loss and air content comparison of examples and comparative examples
As can be seen from the data in Table 2, the starch-based slump loss reducing agent prepared in examples 1 to 5 has good long-term dispersion retention ability, good later slump retention ability and less loss, has good workability and fluidity, can retain plasticity for a long time, and has the best effect on each component.
The slump-retaining agents prepared in comparative examples 1-2 were comparable in early fluidity to the slump-retaining agents prepared in the examples, but had rapid slump loss in the later period, indicating that the concrete slump-retaining agents prepared according to the present invention have dispersion-retaining ability for a longer period of time.
In addition, the air content difference between the embodiment and the comparative example is combined with slump loss, so that the water reducer disclosed by the invention has excellent air entraining and air stabilizing capabilities, is very suitable for concrete with higher frost resistance regulations in alpine regions, and does not need to be compounded with an air entraining agent during use.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
Claims (10)
1. A starch-based slump retaining water reducer is characterized in that: the preparation raw materials of the starch-based slump retaining water reducer comprise the following components in parts by weight: 150-250 parts of polysaccharide polymer esterified liquid, 11-22 parts of carboxyl-terminated vinyl epoxy ether, 0.8-1 part of initiator, 4-11 parts of acrylic acid, 10-15 parts of hydroxyl ester monomer, 0-0.3 part of reducing agent, 0.3-0.7 part of chain transfer agent and 1-3 parts of coagulation promoting component;
the preparation raw materials of the polysaccharide polymer esterification liquid comprise the following components in parts by weight: 90-120 parts of enzymolysis starch, 30-60 parts of short straight chain degradation starch and alkyl glycoside mixture, 75-150 parts of dispersing agent, 25-35 parts of unsaturated carboxylic acid and/or unsaturated anhydride, 3-5 parts of esterification catalyst and 0.04-0.4 part of polymerization inhibitor.
2. The starch-based slump retaining water reducer according to claim 1, characterized in that: the hydroxyl ester monomer comprises at least one of hydroxyethyl methacrylate, hydroxypropyl methacrylate and hydroxyethyl acrylate.
3. The starch-based slump retaining water reducer according to claim 1, characterized in that: the set accelerating component comprises at least one of diethanolamine, triethanolamine or triisopropanolamine.
4. The starch-based slump retaining water reducer according to claim 1, characterized in that: the unsaturated carboxylic acid comprises at least one of acrylic acid, itaconic acid and maleic acid, and the unsaturated anhydride comprises at least one of itaconic anhydride and maleic anhydride.
5. The starch-based slump retaining water reducer according to claim 1, characterized in that: the esterification catalyst is at least one of concentrated sulfuric acid, boric acid, organic sulfonic acid and sulfate.
6. The starch-based slump retaining water reducer according to claim 1, characterized in that: the dispersant comprises dimethyl sulfoxide, and/or the polymerization inhibitor comprises a polyhydric phenol polymerization inhibitor.
7. The starch-based slump retaining water reducer according to any one of claims 1 to 6, wherein: the molecular weight of the enzymolysis starch is 2500-13000, and/or the molecular weight of the short amylose degradation starch and alkyl glycoside mixture is 800-1600.
8. A preparation method of a starch-based slump retaining water reducer is characterized by comprising the following steps:
taking a mixed solution of the enzymolysis starch, the mixture of the short straight chain degradation starch and the alkyl glycoside, a dispersant and deionized water, adding unsaturated carboxylic acid and/or unsaturated anhydride, an esterification catalyst and a polymerization inhibitor, heating to 80-120 ℃, stirring and mixing, and reacting fully to obtain polysaccharide polymer esterification solution;
mixing the polysaccharide polymer esterified solution with carboxyl-terminated vinyl epoxy ether, heating to 55-65 ℃, adding an initiator, and uniformly stirring; and then dropwise adding a mixed aqueous solution of acrylic acid and hydroxyl ester monomers and a mixed aqueous solution of a reducing agent and a chain transfer agent, keeping the temperature and continuously stirring after the dropwise adding is finished, adding a coagulation accelerating component after the reaction is finished, stirring, adjusting the pH to be =6-7, adding dilution water, and uniformly stirring to obtain the starch-based slump retaining water reducer.
9. The preparation method of the starch-based slump retaining water reducer according to claim 8, characterized by comprising the following steps: the preparation method of the enzymatic starch comprises the following steps:
preparing starch milk with solid content of 20-40%, heating to 40-60 deg.C, adjusting pH =3.5-6, adding pullulan-amylase, and keeping the temperature;
adjusting pH to 4-7.5, heating to 60-110 deg.C, controlling starch gelatinization time for 20-60 min, adding alpha-amylase and/or beta-amylase, and keeping temperature;
cooling and filtering, and drying and grinding the filtrate in vacuum to obtain the enzymatic starch.
10. The preparation method of the starch-based slump loss resistant water reducer according to claim 9, characterized by comprising the following steps: the preparation method of the short amylose degraded starch and alkyl glycoside mixture comprises the following steps:
mixing the enzymatic starch and fatty alcohol, stirring uniformly, adding an acid catalyst, heating to 90-120 ℃, vacuumizing to 1.5-2kPa for 30-60 min, cooling, filtering to remove filtrate, distilling to remove alcohol, and drying to obtain the mixture of the short amylose degraded starch and the alkyl glycoside.
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| CN116444196A (en) * | 2023-06-15 | 2023-07-18 | 北京鼎瀚中航建设有限公司 | Composite water reducing agent and application thereof |
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