CN109704619B - Sulfamate high-efficiency water reducing agent and preparation process thereof - Google Patents
Sulfamate high-efficiency water reducing agent and preparation process thereof Download PDFInfo
- Publication number
- CN109704619B CN109704619B CN201910056998.XA CN201910056998A CN109704619B CN 109704619 B CN109704619 B CN 109704619B CN 201910056998 A CN201910056998 A CN 201910056998A CN 109704619 B CN109704619 B CN 109704619B
- Authority
- CN
- China
- Prior art keywords
- parts
- mixed solution
- sulfamate
- reducing agent
- regulator
- 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.)
- Active
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 103
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 59
- 239000000463 material Substances 0.000 claims abstract description 30
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 22
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 230000002378 acidificating effect Effects 0.000 claims abstract description 15
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 15
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims abstract description 13
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims abstract description 13
- 229940001584 sodium metabisulfite Drugs 0.000 claims abstract description 13
- 235000010262 sodium metabisulphite Nutrition 0.000 claims abstract description 13
- 238000013329 compounding Methods 0.000 claims abstract description 11
- KSVSZLXDULFGDQ-UHFFFAOYSA-M sodium;4-aminobenzenesulfonate Chemical compound [Na+].NC1=CC=C(S([O-])(=O)=O)C=C1 KSVSZLXDULFGDQ-UHFFFAOYSA-M 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 10
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 claims abstract description 7
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 18
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 18
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 239000008098 formaldehyde solution Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 11
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 11
- 229960000583 acetic acid Drugs 0.000 claims description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 9
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 9
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 9
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 9
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims description 8
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 6
- 238000006277 sulfonation reaction Methods 0.000 claims description 6
- 239000008030 superplasticizer Substances 0.000 claims description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 5
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 235000004279 alanine Nutrition 0.000 claims description 4
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- WDHYRUBXLGOLKR-UHFFFAOYSA-N phosphoric acid;prop-2-enoic acid Chemical compound OC(=O)C=C.OP(O)(O)=O WDHYRUBXLGOLKR-UHFFFAOYSA-N 0.000 claims description 4
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 4
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 4
- 229960005055 sodium ascorbate Drugs 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims description 3
- 239000011755 sodium-L-ascorbate Substances 0.000 claims description 3
- 235000019187 sodium-L-ascorbate Nutrition 0.000 claims description 3
- 229960003767 alanine Drugs 0.000 claims description 2
- 229960004106 citric acid Drugs 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 17
- 239000002253 acid Substances 0.000 abstract description 10
- DGVVJWXRCWCCOD-UHFFFAOYSA-N naphthalene;hydrate Chemical compound O.C1=CC=CC2=CC=CC=C21 DGVVJWXRCWCCOD-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000376 reactant Substances 0.000 abstract description 9
- 230000007547 defect Effects 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 3
- 239000004567 concrete Substances 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 26
- 239000004568 cement Substances 0.000 description 24
- 230000000694 effects Effects 0.000 description 24
- -1 monocyclic aromatic derivative phenol compounds Chemical class 0.000 description 15
- 229910019142 PO4 Inorganic materials 0.000 description 13
- 239000010452 phosphate Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 11
- 239000004576 sand Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 5
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000004574 high-performance concrete Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 150000007942 carboxylates Chemical class 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000002734 clay mineral Substances 0.000 description 3
- 208000012839 conversion disease Diseases 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 229920000867 polyelectrolyte Polymers 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000000979 retarding effect Effects 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- RYVFEFXJFWSQHB-UHFFFAOYSA-N 2-(hydroxymethyl)naphthalen-1-ol Chemical compound C1=CC=CC2=C(O)C(CO)=CC=C21 RYVFEFXJFWSQHB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229910052925 anhydrite Inorganic materials 0.000 description 2
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229950000244 sulfanilic acid Drugs 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 0.000 description 1
- 102000003839 Human Proteins Human genes 0.000 description 1
- 108090000144 Human Proteins Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940000635 beta-alanine Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000007336 electrophilic substitution reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 229940048084 pyrophosphate Drugs 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Images
Abstract
The invention relates to a sulfamate high-efficiency water reducing agent, which relates to the technical field of building engineering materials and comprises the following raw materials in percentage by weight: 15-20% of sodium sulfanilate, 10-15% of sodium metabisulfite, 10-15% of naphthol, 1-5% of itaconic acid, 1-2% of alkaline pH regulator, 0.5-1% of acidic pH regulator, 20-30% of formaldehyde, 6-10% of first auxiliary agent and the balance of water. The preparation process comprises the following steps: 1) under the action of a catalyst, the reactants generate sulfamate and naphthalenesulfonate at about 90-95 ℃ and about 145-155 ℃ respectively to obtain a fifth mixed solution; 2) preparing a first auxiliary agent; 3) and compounding the first auxiliary agent and the fifth mixed solution to obtain the liquid sulfamate high-efficiency water reducing agent. According to the invention, through compounding the sulfamate water reducing agent, the naphthalene water reducing agent and the polycarboxylic acid water reducing agent, the defect that the sulfamate water reducing agent is too sensitive to the mixing amount is overcome, and the slump retaining property and the adaptability are improved.
Description
Technical Field
The invention relates to the technical field of building engineering materials, in particular to a sulfamate high-efficiency water reducing agent and a preparation process thereof.
Background
The concrete is a material prepared according to experience, and the raw material selection, the preparation process and the construction application are simple. The concrete technology has been greatly developed in the last 70 th century, and the light, high-strength, durable, economical and practical high-performance concrete technology gradually replaces the conventional concrete and is used for civil engineering structures such as large buildings, bridges, tunnels, drilling platforms and the like. Nowadays, the high-efficiency water reducing agent becomes an indispensable component for preparing high-performance concrete, the water consumption of the concrete material can be reduced by more than 30% by adding the high-efficiency water reducing agent into the concrete material, the high-performance concrete doped with the high-efficiency water reducing agent is easy to flex-pour, vibrate and not separate, and the high-performance concrete doped with the high-efficiency water reducing agent also has the characteristics of high early strength, good long-term mechanical property, high toughness, good volume stability and long service life under severe use conditions.
The sulfamate high-efficiency water reducing agent is a monocyclic aromatic high-efficiency water reducing agent, which is mainly prepared by condensing sulfanilic acid, monocyclic aromatic derivative phenol compounds and formaldehyde under acidic or alkaline conditions and is called AS high-efficiency water reducing agent. The AS high-efficiency water reducing agent is a non-air-entraining water reducing agent, the water reducing rate can reach 30% under very low doping amount, and a concrete mixture doped with the AS high-efficiency water reducing agent can keep good concrete slump after 90-120 min.
Disclosure of Invention
The invention aims to provide a sulfamate high-efficiency water reducing agent and a preparation process thereof.
The above object of the present invention is achieved by the following technical solutions:
a sulfamate high-efficiency water reducing agent comprises the following raw materials in percentage by weight: 15-20% of sodium sulfanilate, 10-15% of sodium metabisulfite, 10-15% of naphthol, 1-5% of itaconic acid, 1-2% of alkaline pH regulator, 0.5-1% of acidic pH regulator, 20-30% of formaldehyde, 6-10% of first auxiliary agent and the balance of water.
By adopting the technical scheme, sodium sulfanilate, naphthol and itaconic acid can be subjected to graft copolymerization under the catalysis of sodium metabisulfite, so that carboxyl is connected to a molecular chain of sulfamate, the adaptability of the water reducer is improved, the defect that the sulfamate water reducer is too sensitive to the doping amount is overcome, and the slump retaining effect is improved.
Because a large number of carboxyl groups exist on the molecular chain of the sulfamate, the carboxyl groups have certain chelating capacity and are changed into-COO in water-The water reducing agent can have stronger adsorption effect with cement particles and stronger electrostatic repulsion effect with clay, so that the water reducing agent is suitable for the condition that the clay mineral content in the sand and gravel ground material is higher, and the slump retaining effect is improved. Meanwhile, the carboxyl has extremely strong hydrophilicity, so that the water reducing agent adsorbed on the surface of cement particles and water molecules can form a stable solvated water film, and the water film hasHas good lubricating effect, and can effectively reduce the sliding resistance among cement particles, thereby further improving the fluidity of concrete.
And the carboxyl can be stretched in the aqueous solution, and a hydrophilic three-dimensional adsorption layer with a certain thickness can be formed on the surface of the adsorbed cement particles. When the cement particles are close to each other, the adsorption layers begin to overlap, namely, a steric hindrance effect is generated among the cement particles, the more the overlap is, the larger the steric hindrance repulsive force is, the larger the obstruction to the coagulation effect among the cement particles is, and the slump of the concrete is kept good. The stability of the dispersing system can also be maintained by this steric repulsion.
When the cement paste is in an alkaline condition, carboxyl in the water reducing agent is hydrolyzed to generate free carboxylic acid molecules and HO-X-OH, wherein the free carboxylic acid molecules and mineral substances or hydrate on the outer surface of cement grains act to generate a compact carboxylate layer to prevent water molecules from entering the interior of the compact carboxylate layer, so that the normal hydration of the cement is restrained, the hydration speed of the compact carboxylate layer is slowed down, and the slump retaining effect is achieved. And free carboxylic acid molecules have a diffusion effect on cement. And HO-X-OH also has a certain delay effect on cement hydration, and the water reducing agent has better performance under the combined action of the HO-X-OH and the HO-X-OH.
Itaconic acid is known as methylene succinic acid, which is an unsaturated dibasic organic acid and can be used as a sour agent, a pH regulator, and a metal chelating agent. Solubility: soluble in water, ethanol and acetone, and slightly soluble in chloroform, benzene and diethyl ether. Is not easy to volatilize and can be decomposed by overheating. The double bond of itaconic acid and carboxyl are in conjugate relation, which makes itaconic acid very active, and can be polymerized with other monomers with different numbers besides self-polymerization.
Sodium metabisulfite is a sulfite that acts as a sulfonating agent and, due to its oxidizing properties, acts as an oxidizing agent.
Naphthols are chemically similar to phenols, and electrophilic substitution of aromatic rings and reaction of phenolic hydroxyl groups can also occur. Unlike phenol, naphthol can be substituted with amino to produce naphthylamine and coupled with diazonium salt. Meanwhile, the boiling point of naphthol is 285-286 ℃, so that naphthol is not easy to volatilize, and phenols are prevented from volatilizing in the heating process to influence the generation of effective components of reactants.
The invention is further configured to: the first auxiliary agent comprises the following raw materials in parts by weight: 450 parts of methyl allyl polyoxyethylene ether 300-containing material, 150 parts of acrylic acid 100-containing material, 40-60 parts of acrylic acid phosphate, 2-6 parts of hydroxyethyl acrylate, 0.5-2.0 parts of initiator, 0.5-1.5 parts of L-sodium ascorbate, 0.3-1.5 parts of mercaptopropionic acid and 550 parts of water 300-containing material.
By adopting the technical scheme, the methyl allyl polyoxyethylene ether, the acrylic acid and the acrylic acid phosphate ester are subjected to graft copolymerization, and the phosphate ester short branched chain is introduced into the macromonomer, so that the phosphate ester short branched chain and the macromonomer long branched chain are mutually staggered, the adaptability and the workability of the water reducing agent are improved, the water reducing agent is suitable for the condition of higher clay mineral content in the sandstone ground material, and the slump retaining effect is improved.
And because phosphate radicals in the phosphate ester have two negative charges, a phosphate ester monomer is introduced to the main chain of the comb polymer, and stronger electrostatic repulsion is generated between the stronger adsorption of the phosphate ester and cement particles and clay, so that the mud resistance of the water reducing agent is improved, the water reducing agent is suitable for the condition of higher clay mineral content in sand and gravel ground materials, and the slump retaining effect is improved.
Meanwhile, as the phosphate ester hydrophilic group has very strong polarity, the auxiliary agent adsorbed on the surface of the cement particles and water molecules can form a stable solvated water film, and the water film has good lubricating effect and can effectively reduce the sliding resistance among the cement particles, thereby further improving the fluidity of the concrete.
The L-sodium ascorbate is used as a reducing agent and can form a redox system with an initiator to reduce the threshold energy of the polymerization reaction, thereby compensating the reduction of the stress release rate and reducing the energy consumption.
Mercaptopropionic acid is used as a chain transfer agent to improve the grafting reaction efficiency of methyl allyl polyoxyethylene ether and acrylic acid esterification and the yield of the comb-type macromonomer. The mercaptopropionic acid can transfer the active center of an acrylic acid free radical to a sulfonic group, a polyoxyethylene chain and a phosphate group, so that the four monomers can be arranged and distributed at intervals, and the writing synergistic effect of the four monomers is completely exerted. Meanwhile, the transfer of the active center can reduce the polymerization degree and adjust the molecular weight distribution of the water reducing agent.
The invention is further configured to: the first auxiliary agent also comprises the following raw materials in parts by weight: 1.0-5.0 parts of sodium tripolyphosphate, 10-20 parts of methacryloyloxyethyl trimethyl ammonium chloride, 2-4 parts of concentrated sulfuric acid and 10-50 parts of liquid caustic soda.
By adopting the technical scheme, because the naphthalene water reducer is acidic and the polycarboxylic acid water reducer is alkaline, if products are replaced between the two series of water reducers, all water reducer storage and conveying pipelines, metering systems and mixers need to be thoroughly cleaned, otherwise, the using effect of the water reducers can be seriously influenced. By adding the cationic polyelectrolyte which can be generated by the reaction of the methacryloyloxyethyl trimethyl ammonium chloride and acrylic acid, and the cationic polyelectrolyte can react with the main components in the naphthalene-based high-efficiency water reducing agent, the polycarboxylic acid water reducing agent and the naphthalene-based water reducing agent are not mutually gram and can be compatible, certain compounding or mixing is performed, the operation of workers is facilitated, and the adaptability and the workability of the water reducing agent are improved.
The sodium tripolyphosphate can be used as a phosphate chain transfer agent to improve the grafting rate of the phosphate short branched chain, and can also be used as a retarder to improve the slump retaining property of cement and slow down the cement solidification.
The invention is further configured to: the initiator comprises hydrogen peroxide and ammonium persulfate, wherein the hydrogen peroxide accounts for 20-50% of the total amount of the initiator, and the ammonium persulfate accounts for 50-80% of the total amount of the initiator.
By adopting the technical scheme, the hydrogen peroxide can generate hydroxyl radicals at high temperature in the presence of the catalyst to initiate the free radical polymerization of the monomer, but the consumption of the hydrogen peroxide can influence the reaction conversion rate and the molecular weight of the product, thereby influencing the dispersion effect of the water reducer. When the amount of hydrogen peroxide is less than 20%, the conversion rate of the reaction is lowered, resulting in a low effective content of the product and poor dispersibility. When the amount of the hydrogen peroxide is more than 50%, the number of decomposed free radicals is increased, the chain termination probability is increased, the molecular weight is too low, the steric hindrance effect of the water reducing agent is reduced, and the dispersion efficiency is deteriorated.
Ammonium persulfate is easily dissolved in water and easily decomposed by heat, and can be hydrolyzed into ammonium bisulfate and hydrogen peroxide in aqueous solution. By adding hydrogen peroxide, the decomposition amount of ammonium persulfate can be reduced, and the content of ammonium persulfate in the aqueous solution can be increased, so that the reaction conversion rate and the molecular weight of the product can be improved.
And the redox system generated by the ammonium persulfate and the L-sodium ascorbate can improve the reaction conversion rate and the molecular weight of a product, and the prepared water reducing agent has good initial net slurry fluidity and better flow retention performance.
The invention is further configured to: the pH regulator comprises a sodium hydroxide solution and a calcium hydroxide solution, wherein the sodium hydroxide solution accounts for 60-80% of the total amount of the pH regulator, and the calcium hydroxide solution accounts for 20-40% of the total amount of the pH regulator.
By adopting the technical scheme, the method is used for adjusting the pH value of the solution and improving the stability of the water reducing agent system.
The sodium sulfate content in the water reducing agent has certain influence on the performance of the concrete. The existence of the over-high sodium sulfate can weaken the dispersing performance of the water reducing agent, reduce the compatibility of cement, increase the slump loss of concrete mixtures and other negative effects, and the sodium sulfate is easy to crystallize at low temperature, reduces the fluidity of the material and easily blocks pipelines. Adding calcium hydroxide solution to make Ca2+With SO in solution4 2-And SO3 2-Reacting to generate CaSO which is not dissolved in water4Precipitation and CaSO3Precipitating to reduce Na in naphthalene dispersant2SO4And Na2SO3. Simultaneously, the CaSO does not need to be filtered after the pH value is adjusted4Precipitation and CaSO3Precipitating to make it directly enter into the final product.
When the calcium hydroxide solution is more than 40 percent, the CaSO4Precipitation and CaSO3Excessive precipitation can affect the plasticity retention of cement, CaSO4Precipitation and CaSO3Too much will lower the plasticity retention of the cement.
The invention is further configured to: the acidic pH regulator comprises one of citric acid, alanine, glacial acetic acid and pyrophosphoric acid.
By adopting the technical scheme, the pH value of the solution is adjusted, the stability of the water reducing agent system is improved, and the next reaction is not influenced.
Citric acid, also known as citric acid trinaphthalene, is a retarding and plasticity-maintaining agent, and has good remittance, stability, environmental protection and excellent retarding and plasticity-maintaining effects in a plurality of retarding and plasticity-maintaining agents.
Alanine is the basic unit of protein, one of the 20 amino acids that make up human proteins, and has two isomers, alpha-alanine and beta-alanine.
Pyrophosphoric acid is a colorless viscous liquid, and forms crystals after long-term storage, and is colorless glass. Pyrophosphate has strong coordination property and is used as a catalyst, a sequestering agent and the like.
Glacial acetic acid, i.e. anhydrous acetic acid, acetic acid is one of the important organic acids, organic compounds. It solidifies into ice at low temperature, commonly known as glacial acetic acid. Volume expansion upon solidification may cause the container to rupture. Pure acetic acid freezes into ice crystals below the melting point, so anhydrous acetic acid is also known as glacial acetic acid.
A preparation method of a sulfamate high-efficiency water reducing agent comprises the following steps:
s1: equally dividing water in the raw materials into three parts, equally dividing an alkaline pH regulator into five parts;
s2: preparing a formaldehyde solution, taking 1 part of water in S1, adding formaldehyde according to the weight percentage, and heating and stirring to form the formaldehyde solution;
s3, adding 2 parts of water in S1 into a reaction container, adding sodium metabisulfite, sodium sulfanilate, naphthol and itaconic acid into the reaction container according to the weight percentage, heating while stirring, keeping the temperature at 75-95 ℃, and adding 3 parts of alkaline pH regulator in S1 after uniformly stirring to form a first mixed solution;
s4: adding two thirds of the total weight of the formaldehyde solution prepared in the step S2 into the first mixed solution, stirring and heating the mixture, keeping the temperature at 90-95 ℃, and reacting for 2-6 hours to form a second mixed solution;
s5: adding the acidic pH regulator into the second mixed solution according to the weight percentage, heating to 145-155 ℃ within 10-20min, and then preserving the heat at 145-155 ℃ for sulfonation reaction to form a third mixed solution;
s6: cooling the third mixed solution to 100-110 ℃, adding one third of the total weight of the formaldehyde solution prepared in the S2 into the third mixed solution, and performing heat preservation and condensation to form a fourth mixed solution;
s7: adding 2 parts of alkaline pH regulator into the fourth mixed solution, and regulating the pH value of the fourth mixed solution to obtain a fifth mixed solution containing sulfamate and naphthalenesulfonate;
s8: preparing a first auxiliary agent according to a proportion;
s9: and compounding the fifth mixed solution prepared in the step S7 with the first auxiliary agent to obtain the liquid sulfamate high-efficiency water reducing agent.
By adopting the technical scheme, S2: the preparation method is used for preparing the formaldehyde solution and is convenient to use.
S3: at 75-95 ℃, sodium metabisulfite, sodium sulfanilate and naphthol are condensed to generate a compound under an acidic condition, and carboxyl on itaconic acid is grafted and copolymerized on the compound under the catalysis of the sodium metabisulfite, so that the carboxyl and a macromonomer long chain branch chain are staggered with each other, the space resistance of the copolymer is improved, and the adaptability and the slump retention of the water reducing agent are improved. When the temperature is lower than 75 ℃, the reaction does not proceed or proceeds slowly, and the generation of reactants is influenced. When the temperature is higher than 95 ℃, the reaction is sulfonated, and more byproducts are generated to influence the generation of reactants.
Adding alkaline pH regulator to regulate the pH value of the solution to make the pH value of the solution alkaline. Under the acidic condition, the three components are easy to be condensed to generate a body type product with high molecular weight, so that the final performance of the product is influenced.
S4: at 90-95 ℃, naphthol can enhance the attack capability of formaldehyde under the alkaline condition, hydroxide ions in water of H on phenolic hydroxyl react to enable the phenolic hydroxyl to form oxygen ions, the activity of H on the ortho position of naphthol is improved, formaldehyde is easy to replace H on the ortho position of naphthol to generate hydroxymethyl naphthol, and the hydroxymethyl naphthol reacts with active hydrogen on sulfanilic acid to generate the sulfamate water reducer.
When the temperature is too low, the activation energy which needs to be overcome by the reaction cannot be reached, and the polycondensation reaction is not enough; when the temperature is too high, the molecular weight of the product is lowered, and there are some other side reactions, and the dispersion property is deteriorated.
Generally, the molecular weight of the copolycondensation reactant increases with the reaction time, and the performance of the water reducing agent is closely related to the molecular weight. The concrete high-efficiency water reducing agent is a polymer electrolyte containing monocyclic, polycyclic or aromatic heterocyclic rings, and the polymerization degree of the concrete high-efficiency water reducing agent generally has better performance within the range of 1500-10000. When the reaction time is prolonged, the molecular weight is increased, the viscosity of the product is increased, the dispersing performance of the product is reduced, and even water-insoluble gel is generated, so that the performance of the water reducing agent is lost.
The excessive formaldehyde can accelerate the crosslinking reaction and reduce the sulfonation degree, so that the structure of the condensation compound is changed, and the effect is influenced.
S5: the pH value of the solution is adjusted to be acidic, the sulfonation reaction is carried out on the residual naphthol, the sodium sulfanilate and the sodium metabisulfite in the mixture in the S4 at 145-155 ℃ to generate the naphthalene sulfonate, so that the sulfamate water reducing agent can be compounded with the naphthalene water reducing agent, the defect that the sulfamate water reducing agent is too sensitive to the doping amount is overcome, and the slump retaining property and the adaptability are improved.
The temperature is rapidly raised to 145-155 ℃, and the final performance of the product is influenced because the naphthol, the sodium sulfanilate and the sodium metabisulfite are condensed at the temperature lower than 145 ℃ under an acidic condition to generate a body-type product with high molecular weight. Temperatures above 155 ℃ lower the molecular weight of the product and there may be some other side reactions and poor dispersion properties.
S6: reacting at the temperature of 100 ℃ and 110 ℃, and carrying out condensation reaction on formaldehyde and naphthalenesulfonate to obtain a naphthalenesulfonate formaldehyde condensate, thereby obtaining the naphthalene water reducer.
Prevent the formaldehyde from self-polymerizing when the temperature of the formaldehyde is too high, which affects the generation of the naphthalene sulfonate formaldehyde condensate and the effective components in the naphthalene water reducing agent.
When the temperature is lower than 100 ℃, formaldehyde reacts with naphthol to substitute polyhydroxy, the crosslinking reaction is accelerated, the sulfonation degree is reduced, and the structure of a condensation compound is changed, so that the effect is influenced.
S7: the pH value is adjusted to make the pH value of the solution alkaline, so as to inhibit the hydrolysis of the effective components of the reactant, and reduce the effect of the reactant.
S9: by compounding the sulfamate water reducer, the naphthalene water reducer and the polycarboxylic acid water reducer, the defect that the sulfamate water reducer is too sensitive to the mixing amount is overcome, and the slump retaining property and the adaptability are improved. Because sulfate ions can have certain influence on cement, a phosphate monomer is introduced to the comb-shaped polymer main chain, and the combination degree of phosphate and cement in the phosphate monomer is higher, so that the influence of the sulfate ions on the cement can be reduced, and the slump of the concrete is kept good.
The invention is further configured to: the specific operation of the first auxiliary agent in the step S8 is as follows:
1) equally dividing acrylic acid in the raw material into three parts;
2) adding the methyl allyl polyoxyethylene ether, the initiator, the acrylic acid phosphate, the sodium tripolyphosphate, the water and 1 part of the acrylic acid in the step 1 into a reaction container according to the parts by weight, and reacting to form a sixth mixed solution;
3) adding the material A and the material B into the sixth mixed solution in sequence according to the parts by weight to form a seventh mixed solution; the material A comprises hydroxyethyl acrylate and 2 parts of acrylic acid in the step 1; the material B comprises mercaptopropionic acid and sodium L-ascorbate;
4) adding methacryloyloxyethyl trimethyl ammonium chloride and concentrated sulfuric acid into the seventh mixed solution in sequence according to the parts by weight for reaction to form eighth mixed solution;
5) adding liquid caustic soda into the eighth mixed solution according to the parts by weight, and adjusting the pH value of the eighth mixed solution to obtain the first auxiliary agent
By adopting the technical scheme, the step one is to configure the material A and the material B, so that the material A and the material B can be conveniently taken by workers.
And 2, carrying out a grafting reaction on the methyl allyl polyoxyethylene ether and the acrylic phosphate to generate a comb-type macromonomer with a phosphoric acid short branched chain.
And 3, carrying out esterification grafting reaction on the methyl allyl polyoxyethylene ether and acrylic acid to generate the comb-type macromonomer with carboxyl.
And 4, generating the cationic polyelectrolyte.
And 5, adjusting the pH value to make the pH value of the solution alkaline, and inhibiting the hydrolysis of the effective components of the reactant to reduce the effect of the reactant.
In conclusion, the beneficial technical effects of the invention are as follows:
1. by compounding the sulfamate water reducer, the naphthalene water reducer and the polycarboxylic acid water reducer, the defect that the sulfamate water reducer is too sensitive to the mixing amount is overcome, and the slump retaining property and the adaptability are improved;
2. by controlling the reaction temperature, the sulfamate and the naphthalenesulfonate can be prepared in the same reaction vessel, thereby facilitating the work of workers and reducing the production cost of enterprises;
3. by adding itaconic acid and introducing carboxyl on a sulfamate molecular chain, the adaptability of the water reducer is improved, the defect that a sulfamate water reducer is too sensitive to the mixing amount is overcome, and the slump retaining effect is improved.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The invention is described in detail below with reference to the figures and examples.
Referring to fig. 1, the sulfamate high-efficiency water reducing agent comprises the following raw materials in percentage by weight: 18% of sodium sulfanilate, 13% of sodium metabisulfite, 13% of naphthol, 3% of itaconic acid, 1.5% of an alkaline pH regulator, 0.8% of an acidic pH regulator, 25% of formaldehyde, 8% of a first auxiliary agent and the balance of water.
The preparation method comprises the following steps:
s1: equally dividing water in the raw materials into three parts, and equally dividing an alkaline pH regulator in the raw materials into five parts; the alkaline pH regulator comprises 20 wt% of sodium hydroxide solution and 30 wt% of calcium hydroxide solution, wherein the sodium hydroxide solution accounts for 70% of the total amount of the pH regulator, and the calcium hydroxide solution accounts for 30% of the total amount of the pH regulator;
s2: preparing a formaldehyde solution, taking 1 part of water in S1, adding 25% of formaldehyde according to the weight percentage, and heating and stirring to form the formaldehyde solution;
s3, adding 2 parts of water in S2 into a reaction container, adding 13% of sodium metabisulfite, 18% of sodium sulfanilate, 13% of naphthol and 3% of itaconic acid into the reaction container according to the weight percentage, stirring and heating the mixture, keeping the temperature at 85 ℃, and adding 3 parts of alkaline pH regulator in S1 after uniformly stirring the mixture to form a first mixed solution;
s4: adding two thirds of the total weight of the formaldehyde solution prepared in the step S2 into the first mixed solution, stirring and heating the mixture, keeping the temperature at 92 ℃, and reacting for 4 hours to form a second mixed solution;
s5: adding 0.8 percent of citric acid into the second mixed solution according to the weight percentage, heating to 150 ℃ within 15min, and then preserving heat at 150 ℃ for sulfonation reaction to form a third mixed solution;
s6: cooling the third mixed solution to 105 ℃, adding one third of the total weight of the formaldehyde solution prepared in the S2 into the third mixed solution, and carrying out heat preservation condensation to form a fourth mixed solution;
s7: adding 2 parts of alkaline pH regulator into the fourth mixed solution, and regulating the pH value of the fourth mixed solution to obtain a fifth mixed solution containing sulfamate and naphthalenesulfonate;
s8: preparing a first auxiliary agent in proportion:
1) equally dividing 126 parts of acrylic acid in the raw material into three parts;
2) adding 370 parts of methyl allyl polyoxyethylene ether, 0.42 part of hydrogen peroxide, 0.78 part of ammonium persulfate, 50 parts of acrylic phosphate, 3 parts of sodium tripolyphosphate, 425 parts of water and 1 part of acrylic acid in the step 1 into a reaction container for reaction to form a sixth mixed solution;
3) adding the material A and the material B into the sixth mixed solution in sequence to form a seventh mixed solution; the material A comprises 4 parts of hydroxyethyl acrylate and 2 parts of acrylic acid in the step 1; the material B comprises 0.9 part of mercaptopropionic acid and 1 part of sodium L-ascorbate;
4) adding 15 parts of methacryloyloxyethyl trimethyl ammonium chloride and 3 parts of concentrated sulfuric acid into the seventh mixed solution in sequence to react to form eighth mixed solution;
5) adding 30 parts of liquid caustic soda with the mass concentration of 40% into the eighth mixed solution, and adjusting the pH value of the eighth mixed solution to obtain a first auxiliary agent;
s9: mixing the fifth mixed solution prepared in the step S7 with the first auxiliary agent according to the weight ratio of 3.5: 1, compounding to obtain the liquid sulfamate high-efficiency water reducing agent.
Examples 2-5 example 1 differs in that: the sulfamate high-efficiency water reducing agent comprises the following raw materials in percentage by weight:
examples 10-13 differ from example 1 in that the alkaline pH adjuster comprises the following raw materials in weight percent:
| examples | Example 10 | Example 11 | Example 12 | Example 13 |
| Sodium hydroxide | 60％ | 65％ | 75％ | 80％ |
| Calcium hydroxide | 40％ | 35％ | 25％ | 20％ |
Examples 14-26 differ from example 1 in that the acidic pH adjusting agent comprises the following raw materials in weight percent:
| examples | Citric acid | Alanine | Glacial acetic acid | Pyrophosphoric acid |
| Example 14 | 100 | 0 | 0 | 0 |
| Example 15 | 0 | 100 | 0 | 0 |
| Example 16 | 0 | 0 | 100 | 0 |
| Example 17 | 0 | 0 | 0 | 100 |
Examples 18-21 differ from example 1 in that the temperatures in step 3 are as follows:
| examples | Example 18 | Example 19 | Example 20 | Example 21 |
| Temperature/. degree.C | 75 | 80 | 90 | 95 |
Examples 22-25 differ from example 1 in that the temperatures in step 4 are as follows:
| examples | Example 22 | Example 23 | Example 24 | Example 25 |
| Temperature/. degree.C | 90 | 91 | 94 | 95 |
Examples 26-29 differ from example 1 in that the reaction times in step 4 are as follows:
| examples | Example 26 | Example 27 | Example 28 | Example 29 |
| Time/h | 2 | 3 | 5 | 6 |
Examples 30-33 differ from example 1 in that the ramp times in step 5 are as follows:
| examples | Example 30 | Example 31 | Example 32 | Example 33 |
| Time/min | 10 | 12 | 18 | 20 |
Examples 34-37 differ from example 1 in that the temperatures in step 5 are as follows:
| examples | Example 34 | Example 35 | Example 36 | Example 37 |
| Temperature/. degree.C | 145 | 148 | 152 | 155 |
Examples 38-41 differ from example 1 in that the temperatures in step 6 are as follows:
| examples | Example 38 | Example 39 | Example 40 | EXAMPLE 41 |
| Temperature/. degree.C | 100 | 102 | 108 | 110 |
Examples 42-45 differ from example 1 in that the weight ratio of the sulfamate superplasticizer to the first adjuvant compounded in step 9 is:
| examples | Example 42 | Example 43 | Example 44 | Example 45 |
| Weight ratio of | 3:1 | 3.2:1 | 3.8:1 | 4:1 |
Comparative example
Comparative example 1 differs from example 1 in that no first auxiliary agent was added.
Comparative example 2 differs from example 1 in that methacryloyloxyethyltrimethylammonium chloride was not added to the first auxiliary.
Comparative example 3 differs from the examples in that S5 and S6 were not performed.
Comparative example 4 differs from comparative example 3 in that the first aid is not added.
Comparative example 5 is a typical sulfamate superplasticizer on the market.
C30 concrete experiments: comparing the water reducing agents prepared in examples 1-3 and comparative examples 1-4 with the water reducing agent in comparative example 5, adopting ordinary portland cement, river sand, machine-made sand and broken stones (with the particle size of 5-25mm and continuous particle size fraction), wherein the concrete mixing ratio is as follows: 280kg/m cement360kg/m of fly ash3448kg/m of river sand3Machine-made sand 300kg/m31122kg/m of crushed stone3160kg/m of water3The concrete was mixed under the above conditions, and the slump retention was measured by adjusting the amount of admixture to control the initial slump to 220. + -. 10 mm.
Slump test:
1) the slump cone, the spade and the mixing plate are firstly smeared with wet cloth. The collapse cylinder is horn-shaped with an upper opening diameter of 100mm, a lower opening diameter of 200mm and a height of 300 mm.
2) Weighing the following materials in proportion: weighing concrete and sand, pouring the concrete and sand on a mixing plate, uniformly stirring, weighing stones, and mixing. And (3) opening the center of the material pile, pouring half of the required water and the water reducing agent, carefully and uniformly mixing, pouring the rest water, and continuously mixing until the mixture is uniform. The mixing time is about 4-5 min.
3) Placing the slump constant cylinder on a non-water-absorbing rigid flat plate, placing a funnel on the slump constant cylinder, stepping on a pedal, and loading the mixture into the slump constant cylinder in three layers, wherein the filling height of each layer is about one third of the height of the slump constant cylinder. Each layer was tamped 25 times with a tamper along a helix from edge to center without impact. Each plunge should be evenly distributed across the interface. When the concrete at the side of the cylinder is inserted and tamped, the tamping rod can be slightly inclined. When the bottom layer is inserted and pounded, the tamping rod should penetrate the whole depth, and when the other two layers are inserted and pounded, the tamping rod should penetrate the bottom layer and be inserted into the lower layer by about 20mm-30 mm.
4) After filling, the excess mix is scraped off with a trowel and the mouth of the cylinder is smoothed and the concrete around the bottom of the cylinder is removed. Immediately lifting the collapse cylinder within 5-10s to avoid transverse and torsional force on the concrete. The whole process from the start of charging to the lifting of the slump cone should be completed within 150 s.
5) And (3) placing the slump cone beside the cone concrete sample, horizontally placing a straight ruler facing the mixture on the top of the cone, and measuring the vertical distance from the bottom surface of the straight ruler to the highest point of the sample by using a steel ruler, wherein the vertical distance is the slump of the concrete mixture, the accurate value is 1mm, and the result is approximately corrected to be 5mm which is the closest. When one side of the concrete sample collapses or is sheared and damaged, the sample is taken again for another measurement. If this still occurs for the second time, it is an indication that the workability of the concrete is not good and should be recorded.
6) And after 1h, measuring the vertical distance from the bottom surface of the straight scale to the highest point of the test sample by using the steel ruler again, wherein the vertical distance is the 1h slump of the concrete mixture.
| Test sample | Mixing amount/% | Initial slump (mm) | Slump of 1h (mm) |
| Example 1 | 1.65 | 225 | 220 |
| Example 2 | 1.72 | 225 | 220 |
| Example 3 | 1.68 | 220 | 215 |
| Comparative example 1 | 1.89 | 220 | 200 |
| Comparative example 2 | 2.27 | 230 | 190 |
| Comparative example 3 | 1.82 | 225 | 205 |
| Comparative example 4 | 1.97 | 220 | 210 |
| Comparative example 5 | 2.25 | 230 | 195 |
As can be seen from the above table, with the water-reducing agent prepared in the examples of the present invention, both the 1-hour slump and the slump loss were smaller than those of comparative examples 1 to 5, indicating that the slump retaining property was excellent.
The water reducing agent prepared in the embodiment of the invention can reach the same initial properties at a lower mixing amount, which shows that the water reducing agent has higher water reducing rate.
Compared with the comparative example 1, the embodiment 1 shows that the water reducing rate and the slump retaining property of the sulfamate high-efficiency water reducing agent can be improved by compounding the sulfamate high-efficiency water reducing agent and the polycarboxylic acid water reducing agent.
The comparison among the example 1, the comparative example 2 and the comparative example 3 shows that the addition of the methacryloyloxyethyl trimethyl ammonium chloride can reduce the phase gram between the polycarboxylic acid water reducer and the naphthalene water reducer and improve the compounding effect of the sulfamate high-efficiency water reducer and the polycarboxylic acid water reducer.
Comparing example 1 with comparative example 4, it is demonstrated that the water reducing rate and slump retaining property can be improved by compounding the sulfamate water reducing agent, the naphthalene water reducing agent and the polycarboxylic acid water reducing agent.
Comparing example 1 with comparative example 5, the water reducing agent prepared in the example of the invention has higher water reducing rate and slump retention than the sulfamate high-efficiency water reducing agent commonly used on the market.
The difference between the comparative example 7 and the example 1 is that the addition amount of the sulfamate superplasticizer is 3% in the detection method.
The difference between the comparative example 8 and the example 1 is that in the detection method, the addition amount of the sulfamate high-efficiency water reducing agent is 1%.
| Test sample | Mixing amount/％ | Initial slump (mm) | Slump of 1h (mm) |
| Example 1 | 1.65 | 225 | 220 |
| Comparative example 7 | 3 | 225 | 218 |
| Comparative example 8 | 1 | 225 | 217 |
Compared with the comparative examples 7 and 8, the slump value of the comparative examples 7 and 8 for 1h is smaller than that of the example 1, but the difference is small, so that the defect that the sulfamate water reducer, the naphthalene water reducer and the polycarboxylic acid water reducer are excessively sensitive to the mixing amount is overcome, and the adaptability of the sulfamate water reducer is improved.
The embodiments of the present invention are preferred embodiments of the present invention, and the scope of the present invention is not limited by these embodiments, so: all equivalent changes made according to the structure, shape and principle of the invention are covered by the protection scope of the invention.
Claims (6)
1. The sulfamate high-efficiency water reducing agent is characterized by comprising the following raw materials in percentage by weight: 15-20% of sodium sulfanilate, 10-15% of sodium metabisulfite, 10-15% of naphthol, 1-5% of itaconic acid, 1-2% of alkaline pH regulator, 0.5-1% of acidic pH regulator, 20-30% of formaldehyde, 6-10% of first auxiliary agent and the balance of water;
the first auxiliary agent comprises the following raw materials in parts by weight: 450 parts of methyl allyl polyoxyethylene ether, 150 parts of acrylic acid, 40-60 parts of acrylic acid phosphate, 2-6 parts of hydroxyethyl acrylate, 0.5-2.0 parts of initiator, 0.5-1.5 parts of L-sodium ascorbate, 0.3-1.5 parts of mercaptopropionic acid, 550 parts of water, 1.0-5.0 parts of sodium tripolyphosphate, 10-20 parts of methacryloyloxyethyl trimethyl ammonium chloride, 2-4 parts of concentrated sulfuric acid and 10-50 parts of liquid alkali.
2. The sulfamate superplasticizer of claim 1, characterized in that: the initiator comprises hydrogen peroxide and ammonium persulfate, wherein the hydrogen peroxide accounts for 20-50% of the total amount of the initiator, and the ammonium persulfate accounts for 50-80% of the total amount of the initiator.
3. The sulfamate superplasticizer of claim 1, characterized in that: the alkaline pH regulator comprises a sodium hydroxide solution and a calcium hydroxide solution, wherein the sodium hydroxide solution accounts for 60-80% of the total amount of the alkaline pH regulator, and the calcium hydroxide solution accounts for 20-40% of the total amount of the alkaline pH regulator.
4. The sulfamate superplasticizer of claim 1, characterized in that: the acidic pH regulator comprises one of citric acid, alanine, glacial acetic acid and pyrophosphoric acid.
5. The preparation process of the sulfamate high-efficiency water reducer as claimed in any one of claims 1 to 4, is characterized in that: the method comprises the following steps:
s1: equally dividing water in the raw materials into three parts, equally dividing an alkaline pH regulator into five parts;
s2: preparing a formaldehyde solution, taking 1 part of water in S1, adding formaldehyde according to the weight percentage, and heating and stirring to form the formaldehyde solution;
s3: adding 2 parts of water in S1 into a reaction vessel, adding sodium metabisulfite, sodium sulfanilate, naphthol and itaconic acid into the reaction vessel according to the weight percentage, heating while stirring, keeping the temperature at 75-95 ℃, uniformly stirring, and then adding 3 parts of alkaline pH regulator in S1 to form a first mixed solution;
s4: adding two thirds of the total weight of the formaldehyde solution prepared in the step S2 into the first mixed solution, stirring and heating the mixture, keeping the temperature at 90-95 ℃, and reacting for 2-6 hours to form a second mixed solution;
s5: adding the acidic pH regulator into the second mixed solution according to the weight percentage, heating to 145-155 ℃ within 10-20min, and then preserving the heat at 145-155 ℃ for sulfonation reaction to form a third mixed solution;
s6: cooling the third mixed solution to 100-110 ℃, adding one third of the total weight of the formaldehyde solution prepared in the S2 into the third mixed solution, and performing heat preservation and condensation to form a fourth mixed solution;
s7: adding 2 parts of alkaline pH regulator into the fourth mixed solution, and regulating the pH value of the fourth mixed solution to obtain a fifth mixed solution containing sulfamate and naphthalenesulfonate;
s8: preparing a first auxiliary agent according to a proportion;
s9: and compounding the fifth mixed solution prepared in the step S7 with the first auxiliary agent to obtain the liquid sulfamate high-efficiency water reducing agent.
6. The preparation process of the sulfamate high-efficiency water reducer according to claim 5, characterized in that: the specific operation of configuring the first auxiliary agent in S8 is as follows:
1) equally dividing acrylic acid in the raw material into three parts;
2) adding the methyl allyl polyoxyethylene ether, the initiator, the acrylic acid phosphate, the sodium tripolyphosphate, the water and 1 part of the acrylic acid in the step 1 into a reaction container according to the parts by weight, and reacting to form a sixth mixed solution;
3) adding the material A and the material B into the sixth mixed solution in sequence according to the parts by weight to form a seventh mixed solution; the material A comprises hydroxyethyl acrylate and 2 parts of acrylic acid in the step 1; the material B comprises mercaptopropionic acid and sodium L-ascorbate;
4) adding methacryloyloxyethyl trimethyl ammonium chloride and concentrated sulfuric acid into the seventh mixed solution in sequence according to the parts by weight for reaction to form eighth mixed solution;
5) and adding liquid caustic soda into the eighth mixed solution according to the parts by weight, and adjusting the pH value of the eighth mixed solution to obtain the first auxiliary agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910056998.XA CN109704619B (en) | 2019-01-19 | 2019-01-19 | Sulfamate high-efficiency water reducing agent and preparation process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910056998.XA CN109704619B (en) | 2019-01-19 | 2019-01-19 | Sulfamate high-efficiency water reducing agent and preparation process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109704619A CN109704619A (en) | 2019-05-03 |
| CN109704619B true CN109704619B (en) | 2021-04-30 |
Family
ID=66262505
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910056998.XA Active CN109704619B (en) | 2019-01-19 | 2019-01-19 | Sulfamate high-efficiency water reducing agent and preparation process thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109704619B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110358026B (en) * | 2019-08-20 | 2021-12-21 | 武汉奥克化学有限公司 | Viscosity-reducing polycarboxylate superplasticizer and preparation method thereof |
| CN115108751B (en) * | 2022-07-14 | 2023-03-21 | 武汉工程大学 | Dispersing agent for premixed fluid solidified soil and preparation method and application thereof |
| CN117049813B (en) * | 2023-10-12 | 2023-12-26 | 莱芜市兆信新材料股份有限公司 | Gypsum water reducer and preparation method and application thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100398481C (en) * | 2004-05-12 | 2008-07-02 | 刘明华 | Method for batch polymerization preparation of sulphamate composite high-efficiency water reducing agent and its acid and alkali |
| EP2644578A1 (en) * | 2012-03-30 | 2013-10-02 | Technische Universität München | Copolymer for dispersant for cement, dispersant for cement, and cement composition |
| CN102807653B (en) * | 2012-08-21 | 2014-09-17 | 南京瑞迪高新技术有限公司 | Co-polycarboxylic acid high efficiency water reducer capable of compounding with naphthalene formaldehyde water reducer and method for preparing same |
| CN103723943B (en) * | 2013-12-19 | 2015-12-02 | 江苏苏博特新材料股份有限公司 | A kind of utilize industrial by-products to prepare cement dispersants method and application |
| CN105367720B (en) * | 2015-11-25 | 2018-09-28 | 科之杰新材料集团有限公司 | A kind of diminishing collapse protective poly-carboxylic acid water reducing agent and preparation method thereof |
| CN105439488B (en) * | 2015-12-30 | 2018-05-08 | 浙江建研科之杰新材料有限公司 | A kind of dedicated water reducing type aliphatic water reducing agent of pile pile and preparation method thereof |
-
2019
- 2019-01-19 CN CN201910056998.XA patent/CN109704619B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109704619A (en) | 2019-05-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2771666C (en) | Formulation and its use | |
| CN110938176B (en) | Super-long slump loss resistant cement-based polycarboxylate superplasticizer mother liquor and application thereof | |
| CN109704619B (en) | Sulfamate high-efficiency water reducing agent and preparation process thereof | |
| JP2012505812A (en) | Dynamic copolymers for maintaining workability of cementitious compositions | |
| EP1615860A2 (en) | Solid supported comb-branched copolymers as an additive for gypsum compositions | |
| CN109369859B (en) | Concrete tackifying type viscosity regulator and preparation method thereof | |
| KR101470307B1 (en) | Concrete chemical admixtures and Method for nontoxic concrete used recovered remicon water | |
| EP1511699A1 (en) | Additive for hydraulically setting systems, the hydraulically setting mixtures and the use thereof | |
| RU2613372C2 (en) | Hydraulic composition | |
| JP2003221266A (en) | Cement admixture | |
| CN108218284B (en) | Concrete water reducing agent composition | |
| CN103613307B (en) | Slump type polycarboxylate superplasticizer and preparation method thereof | |
| CN109320714B (en) | Special small-molecule superplasticizer for medium-low slump concrete and preparation method thereof | |
| CN114044856A (en) | Mud-blocking type polycarboxylate superplasticizer and preparation method thereof | |
| JPH0118028B2 (en) | ||
| JP4877691B2 (en) | Method of constructing cement admixture and cement composition | |
| JP4785267B2 (en) | Cement admixture and cement composition using the same | |
| WO2016158921A1 (en) | Dispersant composition for hydraulic composition | |
| JP6905795B2 (en) | Sprayed concrete composition and its manufacturing method | |
| CN109021179B (en) | Phosphonic acid-based polymer, preparation method thereof and phosphate mother liquor | |
| EP2292567A1 (en) | Dispersant for a hydraulic composite | |
| JP5019734B2 (en) | Cement admixture and method for producing the same | |
| CN113248663B (en) | Early-strength functional monomer, early-strength polycarboxylate superplasticizer and preparation method thereof | |
| JP4448274B2 (en) | Method of constructing cement admixture and cement composition | |
| CN109535347B (en) | Preparation method of block water-retaining concrete admixture |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |