CN102267807A - Modified melamine water reducer-containing cement-based grouting material and preparation method thereof - Google Patents
Modified melamine water reducer-containing cement-based grouting material and preparation method thereof Download PDFInfo
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 77
- 239000004568 cement Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 title claims abstract description 46
- WPJGWJITSIEFRP-UHFFFAOYSA-N 1,3,5-triazine-2,4,6-triamine;hydrate Chemical class O.NC1=NC(N)=NC(N)=N1 WPJGWJITSIEFRP-UHFFFAOYSA-N 0.000 title abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 96
- 239000002904 solvent Substances 0.000 claims abstract description 32
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000004202 carbamide Substances 0.000 claims abstract description 25
- 239000006004 Quartz sand Substances 0.000 claims abstract description 24
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 19
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims abstract description 17
- 235000010262 sodium metabisulphite Nutrition 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims abstract description 9
- 239000010881 fly ash Substances 0.000 claims abstract description 6
- 239000010440 gypsum Substances 0.000 claims abstract description 6
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 105
- 239000000203 mixture Substances 0.000 claims description 46
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 33
- -1 amino phenyl sulfonyl Chemical group 0.000 claims description 24
- 150000007974 melamines Chemical class 0.000 claims description 23
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 18
- 229960004418 trolamine Drugs 0.000 claims description 18
- 230000002378 acidificating effect Effects 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 230000008961 swelling Effects 0.000 claims description 6
- 230000003750 conditioning effect Effects 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 4
- KSVSZLXDULFGDQ-UHFFFAOYSA-M sodium;4-aminobenzenesulfonate Chemical compound [Na+].NC1=CC=C(S([O-])(=O)=O)C=C1 KSVSZLXDULFGDQ-UHFFFAOYSA-M 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000012263 liquid product Substances 0.000 claims description 2
- 239000013557 residual solvent Substances 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 claims description 2
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 claims 1
- 229950000244 sulfanilic acid Drugs 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 3
- 229920000877 Melamine resin Polymers 0.000 abstract 1
- 239000003377 acid catalyst Substances 0.000 abstract 1
- FRPDXUHZSXRSCC-UHFFFAOYSA-N amino benzenesulfonate Chemical compound NOS(=O)(=O)C1=CC=CC=C1 FRPDXUHZSXRSCC-UHFFFAOYSA-N 0.000 abstract 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- 238000010276 construction Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 239000000178 monomer Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 235000019832 sodium triphosphate Nutrition 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 230000000740 bleeding effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000006277 sulfonation reaction Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 101710194948 Protein phosphatase PhpP Proteins 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 2
- 239000011398 Portland cement Substances 0.000 description 1
- LUVNLWYZXZXCIA-UHFFFAOYSA-N S(=O)(=O)(O)O.C(O)[Na].N1=C(N)N=C(N)N=C1N Chemical compound S(=O)(=O)(O)O.C(O)[Na].N1=C(N)N=C(N)N=C1N LUVNLWYZXZXCIA-UHFFFAOYSA-N 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- USDJGQLNFPZEON-UHFFFAOYSA-N [[4,6-bis(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical compound OCNC1=NC(NCO)=NC(NCO)=N1 USDJGQLNFPZEON-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- CUBCNYWQJHBXIY-UHFFFAOYSA-N benzoic acid;2-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1O CUBCNYWQJHBXIY-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001912 cyanamides Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000009429 distress Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000010412 perfusion Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 235000019633 pungent taste Nutrition 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229920005552 sodium lignosulfonate Polymers 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- ITCAUAYQCALGGV-XTICBAGASA-M sodium;(1r,4ar,4br,10ar)-1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylate Chemical compound [Na+].C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C([O-])=O ITCAUAYQCALGGV-XTICBAGASA-M 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention provides a modified melamine water reducer-containing cement-based grouting material and a preparation method thereof. The grouting material comprises: by weight, 350 to 500 parts of cement clinkers, 80 to 130 parts of fly ash, 20 to 30 parts of an expanding agent, 80 to 120 parts of gypsum, 1 to 2 parts of a pH regulator, 8 to 15 parts of a modified melamine water reducer and 300 to 500 parts of quartz sand, wherein the modified melamine water reducer is prepared from phenol, urea, an aminobenzenesulfonate, formaldehyde, melamine, sodium pyrosulfite, sodium hydroxide, triethanolamine, an acid catalyst and a solvent. The modified melamine water reducer-containing cement-based grouting material has the advantages of high strength, low cost and excellent early strength performances.
Description
Technical field
The present invention relates to a kind of material of construction and preparation method thereof, relate in particular to a kind of cement-based grouting material that contains the modified cyanurotriamide water reducer and preparation method thereof.
Background technology
Concrete structure is big because of its fragility, tends to take place cracking phenomena in engineering is used, and the concrete structure watertightness descends, seepage and concrete cracking can cause, and then influences the work-ing life of engineering.Thereby in construction and operational phase, many engineerings such as water conservancy, railway, highway, bridge etc. need injection material that the crack is repaired and reinforced inevitably.And the installation of many large-scale instruments also needs the combining site on usefulness high performance grouting material perfusion wall screw and machinery bed or steel construction and basis etc.
Distress in concrete commonly used is repaired with the injection material of reinforcing a lot, divides from material type, mainly contains chemical grouting material and cement-based grouting material two big classes.Chemical grouting material has that particle is thin, intensity is high, viscosity is low, and flowability, stability and concrete castability are good, gelling or set time can advantage such as regulate by requirement of engineering, but its cost height, transportation and storage inconvenience, construction technology complexity, has toxicity in various degree mostly, comprise pungency, corrodibility, sensitization and shortcoming such as inflammable and explosive, simultaneously, because of test, constructing operation and discharging dead meal etc. cause environmental pollution and to phreatic pollution, the application of chemical grouting material also more and more is restricted.That the cement based cement grouting material has is easy to use, intensity is high, good endurance, pollution-free, characteristics such as cost is low, the source is wide, thereby, more and more obtained using widely.But Portland cement base grouting material particle is thicker, the poor stability of slurries, easily precipitates bleed, and volumetric shrinkage is arranged during sclerosis.In addition, after the strengthening of foundation grouting, slurry has certain contraction, ftractures once more easily.Therefore, those skilled in the art are devoted to overcome by approach such as interpolation admixtures the above-mentioned defective of cement-based grouting material in recent years.Wherein, cement additive commonly used, also be concrete admixture for example the adding of water reducer help to improve above-mentioned defective, still, the necessity that improves is again still arranged, and especially the cement-based grouting material raising of epistasis energy early is the problem that those skilled in the art want to solve and be difficult to solution always.
Water reducer is called dispersion agent or fluidizer again, during owing to use the water consumption of fresh concrete is reduced, and therefore gains the name.In the modern concrete technical field, water reducer is one of admixture that improves rheological property of concrete, has been taken as five component of concrete except that cement, sand, stone and water.
Common water reducer mainly contains xylogen ring phosphate-gallate series, naphthalene system, trimeric cyanamide system, sulfamate system and polycarboxylic acid series etc.Be the application and the developing period of ordinary water-reducing agent the thirties to the sixties in 20 century, the early stage water reducer that uses is mainly organic compound such as sodium abietate, sodium lignosulfonate, stearate, it mainly is to be used to improve Concrete Construction, solves the endurance issues such as freeze-thaw-of concrete road surface.But along with improving constantly of construction requirement, the water-reducing effect of the water reducer that these are early stage can not satisfy the needs that modern project is built.
Since at first developing naphthalene sulfonic acidformaldehyde condensation product high efficiency water reducing agent and West Germany's exploitation trimeric cyanamide series high-efficiency water-reducing agent in 1964 from Japan in 1962, the exploitation and the application period of high efficiency water reducing agent have been entered, advantageously promoted the development of concrete technology, the outstanding feature of these two series of high efficiency water reducers is water-reducing rate height, the cement dispersion effect is good, it mainly acts on is to reduce unit consumption of water or unit cement consumption significantly, be used to prepare high-strength, superelevation is strong, high durability concrete, but its fatal shortcoming is that slump-loss is big, and formaldehyde volatilization environmental pollution is serious in the preparation process.And polycarboxylic acid series high efficiency water reducing agent blending amount is low, but to the good dispersity of concrete (cement), slump retaining is good, and easily modification so its high performance potentiality are big, is considered to the regeneration product of high efficiency water reducing agent, but its cost is higher, and reaction is responsive, therefore uses and is subjected to certain limitation.The melamine water reducing agent of China almost occurs simultaneously with naphthalene series high-efficiency water-reducing agent, has begun by the trial production success of Shandong cement products institute sulfonated melamine compound resin high efficiency water reducing agent SM in the latter stage seventies.High at present interior synthetic such water reducers of four step rules that adopt comprise methylolation, sulfonation, acid polycondensation, alkalescence rearrangement more.Its preparation can be divided into three phases; (1) monomer preparation: as raw material, remove certain ratio and temperature synthesizing trimethylol melamine with trimeric cyanamide, formaldehyde; (2) monomer sulfonation: with the synthetic monomer, with containing-SO in sodium bisulfite, S-WAT or the Sodium Pyrosulfite equimolecular
3The material of H carries out sulfonation reaction as sulphonating agent under alkaline condition, make monosulfonate by reaction; (3) monomer condenses: monosulfonate is placed under certain ambient condition, and condensation between the methylol and generate ehter bond makes to be connected with each other with ehter bond between the melamine methylol sodium monosulfate monomer, makes the linear polymeric that can be dissolved in water; (4) alkalescence is reset: the relative molecular mass by control reaction conditions controlling polymers makes product reach best diminishing reinforced effects.But, along with people to concrete, especially high-effective concrete quality and consumption growth of requirement, the water-reducing effect of this high efficiency water reducing agent and expensively can not satisfy the demand.
CN101386488 discloses a kind of carboxyl acid modified melamine high-efficiency water-reducing agent, wherein mainly use trimeric cyanamide, formaldehyde, thionamic acid, Whitfield's ointment, citric acid, phenol, the agent of self-control modification sulphonation and alkali as raw material, its improvement to existing water reducer mainly realizes by introducing carboxyl and phenyl ring, and wherein do not have the preparation method of the self-control modification sulphonation agent of public use, cause those skilled in the art in fact can't realize its invention; In addition, though wherein loosely described the plurality of advantages of invention with respect to prior art, do not provide concrete experimental data, those skilled in the art can't determine also whether it really can reach the effect that it is claimed.
Summary of the invention
The present invention provides a kind of novel water reducer in order to overcome above-mentioned deficiency of the prior art, and this water reducer environmental protection, slump-loss is little, water-reducing rate is high, and especially cost is lower, and good epistasis energy morning can be provided.Further, the invention provides a kind of cement-based grouting material that contains this water reducer and preparation method thereof, this injection material intensity height, cost is lower, and early epistasis can be good.
The cement-based grouting material that contains the modified cyanurotriamide water reducer of the present invention, comprise by weight: cement clinker 350～500, flyash 80～130, swelling agent 20～30, gypsum 80～120, pH value conditioning agent 1～2, modified cyanurotriamide water reducer 8～15, quartz sand 300～500, the preparation raw material of wherein said modified cyanurotriamide water reducer comprises: phenol, urea, amino phenyl sulfonyl hydrochlorate, formaldehyde, trimeric cyanamide, Sodium Pyrosulfite, sodium hydroxide, trolamine, an acidic catalyst and solvent.Preferably, described an acidic catalyst is a sulfuric acid, and preferred working concentration is 98% concentrated sulfuric acid aqueous solution; Preferably, described amino phenyl sulfonyl hydrochlorate is a Sodium sulfanilate.Preferably, the parts by weight of described cement clinker are 380～420, and the parts by weight of described water reducer are 9～11.
Preferably, described cement clinker is a Portland clinker.Preferably, described swelling agent comprises sulplo-aluminate, and further preferably, described swelling agent is sulplo-aluminate, more preferably calcium sulphoaluminate.Preferably, the described pH value conditioning agent mixed thing that to be boric acid and tripoly phosphate sodium STPP obtain according to 1: 2 ratio.
Preferably, described quartz sand comprises thick quartz sand, middle quartz sand and three kinds of fractions of fine quartz sand, the amount ratio of three kinds of fractions is 45～60: 35～50: 10～20, wherein the particle size range of thick quartz sand is＞3mm～5mm, the particle size range of middle quartz sand is 2～3mm, and the particle size range of fine quartz sand is＞0mm～2mm.The inventor finds unexpectedly, is used according to three kinds of quartz sands that will satisfy above-mentioned qualification and can further improves concrete intensity, reduces bleeding rate.
Preferably, in the described modified cyanurotriamide water reducer, each raw materials in part by weight is: phenol 35-50, urea 2.5-4, amino phenyl sulfonyl hydrochlorate 10-20, formaldehyde 20-30, trimeric cyanamide 20-30, Sodium Pyrosulfite 20-40, sodium hydroxide 0.4-1, trolamine 0.5-1.5, an acidic catalyst 0.1-0.5, the solvent of surplus.Preferably, described solvent is a water, and further preferably, the consumption of described solvent is 0.8-1.5 a times of aforementioned base materials gross weight umber.
Further preferably, in the described modified cyanurotriamide water reducer, the parts by weight of phenol are 40-45; The parts by weight of amino phenyl sulfonyl hydrochlorate are 12-15; The parts by weight of formaldehyde are 22-26; The parts by weight of urea are 3-3.5; The parts by weight of trimeric cyanamide are 22-25; The parts by weight of Sodium Pyrosulfite are 25-30; The parts by weight of sodium hydroxide are 0.5-0.7; The parts by weight of an acidic catalyst are 0.2-0.4; The parts by weight of trolamine are 0.7-1.0; And/or the parts by weight of solvent are 85-90.
The present invention provides a kind of preparation method who contains the cement-based grouting material of modified cyanurotriamide water reducer in addition, comprising the step that following raw material is mixed according to following parts by weight: cement clinker 350～500, flyash 80～130, swelling agent 20～30, gypsum 80～120, pH value conditioning agent 1～2, modified cyanurotriamide water reducer 8～15, quartz sand 300～400, the preparation raw material of wherein said modified cyanurotriamide water reducer comprises: phenol, urea, the amino phenyl sulfonyl hydrochlorate, formaldehyde, trimeric cyanamide, Sodium Pyrosulfite, sodium hydroxide, trolamine, an acidic catalyst and solvent.Preferably, described an acidic catalyst is a sulfuric acid, and preferred working concentration is 98% concentrated sulfuric acid aqueous solution; Preferably, described amino phenyl sulfonyl hydrochlorate is a Sodium sulfanilate.
Preferably, the preparation method of described modified cyanurotriamide water reducer comprises the steps:
One), at room temperature, part sodium hydroxide, phenol, amino phenyl sulfonyl hydrochlorate, formaldehyde, urea, trimeric cyanamide and partial solvent are mixed, elevated temperature to 80～100 ℃ treat that material becomes limpid follow-up continuation of insurance temperature 10～50 minutes by muddiness, must mixture I;
Two), in mixture I, continue to add partial solvent, Sodium Pyrosulfite and part sodium hydroxide mix, and temperature is increased to 90～105 ℃, be incubateds 1～2 hour, must mixtures II;
Three), in mixtures II, add an acidic catalyst and partial solvent, mix, 25 ℃ of following constant temperature 3～6 hours, mixtures III;
Four), in mixtures III, add the residual hydrogen sodium oxide, residual solvent, and trolamine mix.
Preferably, in the aforesaid method, the consumption of each raw material is counted by weight: phenol 35-50, urea 2.5-4, amino phenyl sulfonyl hydrochlorate 10-20, formaldehyde 20-30, trimeric cyanamide 20-30, Sodium Pyrosulfite 20-40, sodium hydroxide 0.4-1, trolamine 0.5-1.5, an acidic catalyst 0.1-0.5, the solvent of surplus.Preferably, described solvent is a water, and further preferably, the consumption of described solvent is 0.8-1.5 a times of aforementioned base materials gross weight umber.
In the aforesaid method, further preferably, the parts by weight of phenol are 40-45; The parts by weight of amino phenyl sulfonyl hydrochlorate are 12-15; The parts by weight of formaldehyde are 22-26; The parts by weight of urea are 3-3.5; The parts by weight of trimeric cyanamide are 22-25; The parts by weight of Sodium Pyrosulfite are 25-30; The parts by weight of sodium hydroxide are 0.5-0.7; The parts by weight of an acidic catalyst are 0.2-0.4; The parts by weight of trolamine are 0.7-1.0; And/or the parts by weight of solvent are 85-90.
Preferably, total consumption in described sodium hydroxide is 100 weight %, step 1 wherein) amount of sodium hydroxide that adds in accounts for 3～4% of total consumption, step 2) amount of sodium hydroxide that adds in accounts for 40～60% of total consumption, and step 4) in the amount of sodium hydroxide that adds account for 40～60% of total consumption.
Preferably, described solvent is a water, and the total consumption in institute's water is 100 weight %, step 1) water that adds in accounts for 55～65% of total consumption, step 2) water yield that adds in accounts for 30～45% of total consumption, step 3) water yield that adds in accounts for 0.2～0.6%, step 4) in the water yield that adds account for 0.8～1.5%.
Preferably, the preparation process of described modified cyanurotriamide water reducer comprises:
One), at room temperature, in water solvent, add the part sodium hydroxide aqueous solution, add phenol, amino phenyl sulfonyl hydrochlorate, formalin then, mix the back and add urea and trimeric cyanamide, mix, elevated temperature to 80～100 ℃ treat that material becomes limpid follow-up continuation of insurance temperature 10～50 minutes by muddiness, mixture I;
Two), continuation adds portion water solvent, Sodium Pyrosulfite and the part sodium hydroxide aqueous solution in mixture I, mixes, and temperature is increased to 90～105 ℃, is incubated 1～2 hour, gets mixtures II;
Three), in mixtures II, add the vitriol oil and the portion water solvent of 98 weight %, mix, 25 ℃ of following constant temperature 3～6 hours, mixtures III;
Four), in mixtures III, add the residual hydrogen aqueous solution of sodium oxide, and trolamine mixes.
The present invention unexpectedly finds, with phenol traditional melamine water reducing agent is carried out modification, can improve its water-reducing rate and to the performance of improving of strength of cement, further carry out modification with urea instead of part phenol, water-reducing rate and the performance of improving of strength of cement do not reduced not only, and can save cost.Further, add epistasis energy morning that a certain amount of trolamine can further improve the gained water reducer, water-reducing rate slightly improves simultaneously.Especially, with respect to CN101386488A, the present invention has replaced part phenol with urea, replaced thionamic acid with the amino phenyl sulfonyl hydrochlorate, and added trolamine, further improved water-reducing property in the final stage of reaction, save cost, and improved epistasis energy early.
In addition, the inventor unexpectedly finds, in the reaction process, controls sodium hydroxide and the additional proportion of solvent in each step, can further improve the water-reducing property of reaction yield and products therefrom.
In addition, the inventor further finds, use water reducer of the present invention, can be so that the required water yield reduces more than 20% in the cement-based grouting material use, thereby improved the intensity after described cement-based grouting material solidifies, reduced bleeding rate, especially improved the performance after the winter construction and improved epistasis energy early.
Embodiment
The testing method explanation:
The testing method of the slump: with a 100mm suitable for reading, end opening 200mm, the trumpet-shaped slump bucket of high 300mm, tamping behind the penetration concrete, pull up bucket then, concrete produces the slump phenomenon because of deadweight, deduct the height of concrete vertex after the slump with bucket high (300mm), be called slump, unit is mm.
Water-reducing rate is according to the method test of stipulating among the GB8076-2008.
Ultimate compression strength is tested according to GB/T 50448-2008; Bleeding rate is according to the regulation test of GB/T 50080 the 5.1st joint.
Preparation embodiment 1
At room temperature, adding concentration in 600Kg water is the aqueous sodium hydroxide solution 14Kg of 10 weight %, mix, adding 280Kg phenol, 860Kg amino phenyl sulfonyl hydrochlorate, 4300Kg concentration then is the formalin of 36 weight %, after continuing to mix, adds 220Kg urea and 1500Kg trimeric cyanamide, mix, elevated temperature to 80～100 ℃ treat that material becomes limpid follow-up continuation of insurance temperature 10～50 minutes by muddiness, mixture I;
Two), adding 2000Kg water, 1800Kg Sodium Pyrosulfite and 90Kg concentration are the aqueous sodium hydroxide solution of 20 weight % in mixture I, mix, and temperature is increased to 90～105 ℃, are incubated 1～2 hour, get mixtures II;
Three), in mixtures II, add the vitriol oil 20Kg of 98 weight %, add 30Kg water again, mix, 25 ℃ of following constant temperature 3 hours, mixtures III;
Four), to add concentration in mixtures III be the 80Kg aqueous sodium hydroxide solution of 25 weight %, and 50Kg trolamine mixes, and promptly obtains modification water reducer liquid product of the present invention after the cooling.
Preparation embodiment 2
Other condition is identical with embodiment 1, and difference is to use 100Kg phenol, and 400Kg urea replaces 280Kg phenol and the 220Kg urea among the embodiment 1.
Preparation embodiment 3
Other condition is identical with embodiment 1, and difference is with 280Kg phenol and 220Kg urea among 400Kg phenol and the 100Kg urea replacement embodiment 1.
Preparation embodiment 4
Other condition is identical with embodiment 1, and difference is to use 1600Kg water to replace embodiment 1 step 1) middle 600Kg water, replace embodiment 1 step 2 with 1000Kg water) middle 2000Kg water.
Preparation Comparative Examples 1
Other condition is identical with embodiment 1, and difference is with 280Kg phenol and 220Kg urea among the 500Kg phenol replacement embodiment 1.
Preparation Comparative Examples 2
Other condition is identical with embodiment 1, and difference is with 280Kg phenol and 220Kg urea among the 500Kg urea replacement embodiment 1.
Preparation Comparative Examples 3
Other condition is identical with embodiment 1, and difference is step 4) in do not add trolamine.
Application Example about water reducer of the present invention
For the effect of water reducer of the present invention is described, following table provides adds in the Lafarge cement water reducer of the present invention and the described water reducer of Comparative Examples the contrast table of cement performance to respectively.
Table 1:
Performance after adding to water reducer of the present invention and the described water reducer of Comparative Examples in the Lafarge cement respectively relatively
Embodiment 1
A kind of preparation method of cement-based grouting material is provided, and this method makes by following component is mixed according to following weight part, wherein:
Cement clinker 380, flyash 90, calcium sulphoaluminate 25, gypsum 80, boric acid 0.5, tripoly phosphate sodium STPP 1, the water reducer 10 of preparation embodiment 1, average particle size particle size is the middle quartz sand 450 about 2.5mm.
Embodiment 2
Other is identical with embodiment 1, and difference is that the water reducer with preparation embodiment 2 replaces the water reducer of preparation embodiment 1.
Embodiment 3
Other is identical with embodiment 1, and difference is that the water reducer with preparation embodiment 3 replaces the water reducer of preparation embodiment 1.
Embodiment 4
Other is identical with embodiment 1, and difference is that the water reducer with preparation embodiment 4 replaces the water reducer of preparation embodiment 1.
Embodiment 5
Other is identical with embodiment 1, and it is that to replace average particle size particle size among the embodiment 1 be quartz sand in 450 weight parts about 2.5mm for fine quartz sand 70 weight parts, middle quartz sand 200 weight parts about 2.5mm and thick quartz sand 180 weight parts about 4mm about 1mm that difference is with average particle size particle size.
Comparative Examples 1
Other is identical with embodiment 1, and difference is that the water reducer with preparation Comparative Examples 1 replaces the water reducer of preparation embodiment 1.
Comparative Examples 2
Other is identical with embodiment 1, and difference is that the water reducer with preparation Comparative Examples 2 replaces the water reducer of preparation embodiment 1.
Comparative Examples 3
Other is identical with embodiment 1, and difference is that the water reducer with preparation Comparative Examples 3 replaces the water reducer of preparation embodiment 1.
Comparative Examples 4
In the Lafarge cement of 1026 commercially available weight parts, add the water reducer that makes among the preparation embodiment 1 of 10 weight parts.
The performance of table 2 embodiment 1-5 and the described cement-based grouting material of Comparative Examples 1-4 relatively
Annotate 1:R
-7The ratio of expression 7 days test specimen compression strength value of negative temperature conservation and 28 days test specimen compression strength value of normal curing.
Claims (10)
1. cement-based grouting material that contains the modified cyanurotriamide water reducer, comprise by weight: cement clinker 350～500, flyash 80～130, swelling agent 20～30, gypsum 80～120, pH value conditioning agent 1～2, modified cyanurotriamide water reducer 8～15, quartz sand 300～500, the preparation raw material of wherein said modified cyanurotriamide water reducer comprises: phenol, urea, amino phenyl sulfonyl hydrochlorate, formaldehyde, trimeric cyanamide, Sodium Pyrosulfite, sodium hydroxide, trolamine, an acidic catalyst and solvent.Preferably, described an acidic catalyst is a sulfuric acid, and preferred working concentration is 98% concentrated sulfuric acid aqueous solution; Preferably, described amino phenyl sulfonyl hydrochlorate is a Sodium sulfanilate.Preferably, the parts by weight of described cement clinker are 380～420, and the parts by weight of described water reducer are 9～11.
2. the described cement-based grouting material of claim 1, in the described modified cyanurotriamide water reducer, each raw materials in part by weight is: phenol 35-50, urea 2.5-4, amino phenyl sulfonyl hydrochlorate 10-20, formaldehyde 20-30, trimeric cyanamide 20-30, Sodium Pyrosulfite 20-40, sodium hydroxide 0.4-1, trolamine 0.5-1.5, an acidic catalyst 0.1-0.5, the solvent of surplus.Preferably, described solvent is a water, and further preferably, the consumption of described solvent is 0.8-1.5 a times of aforementioned base materials gross weight umber.
3. claim 1 or 2 described cement-based grouting materials, in the described modified cyanurotriamide water reducer, the parts by weight of phenol are 40-45; The parts by weight of amino phenyl sulfonyl hydrochlorate are 12-15; The parts by weight of formaldehyde are 22-26; The parts by weight of urea are 3-3.5; The parts by weight of trimeric cyanamide are 22-25; The parts by weight of Sodium Pyrosulfite are 25-30; The parts by weight of sodium hydroxide are 0.5-0.7; The parts by weight of an acidic catalyst are 0.2-0.4; The parts by weight of trolamine are 0.7-1.0; And/or the parts by weight of solvent are 85-90.
4. each described cement-based grouting material of claim 1-3, wherein said quartz sand comprises thick quartz sand, middle quartz sand and three kinds of fractions of fine quartz sand, the amount ratio of three kinds of fractions is 45～60: 35～50: 10～20, wherein the particle size range of thick quartz sand is＞3mm～5mm, the particle size range of middle quartz sand is 2～3mm, and the particle size range of fine quartz sand is＞0mm～2mm.
5. preparation method who contains the cement-based grouting material of modified cyanurotriamide water reducer, comprising the step that following raw material is mixed according to following parts by weight: cement clinker 350～500, flyash 80～130, swelling agent 20～30, gypsum 80～120, pH value conditioning agent 1～2, modified cyanurotriamide water reducer 8～15, quartz sand 300～400, the preparation raw material of wherein said modified cyanurotriamide water reducer comprises: phenol, urea, the amino phenyl sulfonyl hydrochlorate, formaldehyde, trimeric cyanamide, Sodium Pyrosulfite, sodium hydroxide, trolamine, an acidic catalyst and solvent.Preferably, described an acidic catalyst is a sulfuric acid, and preferred working concentration is 98% concentrated sulfuric acid aqueous solution; Preferably, described amino phenyl sulfonyl hydrochlorate is a Sodium sulfanilate.
6. the preparation method of the described cement-based grouting material of claim 5, the preparation method of wherein said modified cyanurotriamide water reducer comprises the steps:
One), at room temperature, part sodium hydroxide, phenol, amino phenyl sulfonyl hydrochlorate, formaldehyde, urea, trimeric cyanamide and partial solvent are mixed, elevated temperature to 80～100 ℃ treat that material becomes limpid follow-up continuation of insurance temperature 10～50 minutes by muddiness, must mixture I;
Two), in mixture I, continue to add partial solvent, Sodium Pyrosulfite and part sodium hydroxide mix, and temperature is increased to 90～105 ℃, be incubateds 1～2 hour, must mixtures II;
Three), in mixtures II, add an acidic catalyst and partial solvent, mix, 25 ℃ of following constant temperature 3～6 hours, mixtures III;
Four), in mixtures III, add the residual hydrogen sodium oxide, residual solvent, and trolamine mix.The preparation process of sulfamate water reducer comprises: 1) phenol is joined in the aqueous sodium hydroxide solution; 2) add thionamic acid; 3) add the part formaldehyde reaction; 4) add Sulphanilic Acid, then, will add residual formaldehyde, continue reaction and obtain liquid product.
7. the preparation method of the described cement-based grouting material of claim 5, the preparation method of wherein said modified cyanurotriamide water reducer comprises the steps:
One), at room temperature, in water solvent, add the part sodium hydroxide aqueous solution, add phenol, amino phenyl sulfonyl hydrochlorate, formalin then, mix the back and add urea and trimeric cyanamide, mix, elevated temperature to 80～100 ℃ treat that material becomes limpid follow-up continuation of insurance temperature 10～50 minutes by muddiness, mixture I;
Two), continuation adds portion water solvent, Sodium Pyrosulfite and the part sodium hydroxide aqueous solution in mixture I, mixes, and temperature is increased to 90～105 ℃, is incubated 1～2 hour, gets mixtures II;
Three), in mixtures II, add the vitriol oil and the portion water solvent of 98 weight %, mix, 25 ℃ of following constant temperature 3～6 hours, mixtures III;
Four), in mixtures III, add the residual hydrogen aqueous solution of sodium oxide, and trolamine mixes.
8. the preparation method of each described cement-based grouting material of claim 6～7, it is characterized in that: the total consumption in described sodium hydroxide is 100 weight %, step 1 wherein) amount of sodium hydroxide that adds in accounts for 3～4% of total consumption, step 2) amount of sodium hydroxide that adds in accounts for 40～60% of total consumption, and step 4) in the amount of sodium hydroxide that adds account for 40～60% of total consumption.
Preferably, described solvent is a water, and the total consumption in institute's water is 100 weight %, step 1) water that adds in accounts for 55～65% of total consumption, step 2) water yield that adds in accounts for 30～45% of total consumption, step 3) water yield that adds in accounts for 0.2～0.6%, step 4) in the water yield that adds account for 0.8～1.5%.
9. the preparation method of the described cement-based grouting material of claim 7, it is characterized in that: the total consumption in institute's water is 100 weight %, step 1) water that adds in accounts for 55～65% of total consumption, step 2) water yield that adds in accounts for 30～45% of total consumption, step 3) water yield that adds in accounts for 0.2～0.6%, step 4) in the water yield that adds account for 0.8～1.5%.
10. cement-based grouting material, it prepares by each described method of claim 5～9.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103979820A (en) * | 2014-05-27 | 2014-08-13 | 长沙矿山研究院有限责任公司 | Early-strength water reducing agent for mine filling material and preparation method of early-strength water reducing agent |
| CN104591622A (en) * | 2015-01-06 | 2015-05-06 | 无为县严桥双龙建材厂 | Highly anti-bending and wearing-resistant lightweight concrete |
| CN107129176A (en) * | 2017-02-27 | 2017-09-05 | 武汉理工大学 | A kind of synthetic method of modified sulfamate water reducer |
| CN108996950A (en) * | 2018-08-19 | 2018-12-14 | 柳州市家富连装饰有限公司 | A kind of functional ornamentation material and preparation method thereof |
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| CN1341571A (en) * | 2001-09-29 | 2002-03-27 | 华南理工大学 | Aminosulfonic acid series high-effective water-reducing agent and its preparation method |
| CN1765811A (en) * | 2005-08-31 | 2006-05-03 | 南京瑞迪高新技术公司 | High efficiency water reducing agent for suppressing alkali-aggregate reaction efficiency and its preparation method |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1341571A (en) * | 2001-09-29 | 2002-03-27 | 华南理工大学 | Aminosulfonic acid series high-effective water-reducing agent and its preparation method |
| CN1765811A (en) * | 2005-08-31 | 2006-05-03 | 南京瑞迪高新技术公司 | High efficiency water reducing agent for suppressing alkali-aggregate reaction efficiency and its preparation method |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103979820A (en) * | 2014-05-27 | 2014-08-13 | 长沙矿山研究院有限责任公司 | Early-strength water reducing agent for mine filling material and preparation method of early-strength water reducing agent |
| CN103979820B (en) * | 2014-05-27 | 2016-01-06 | 长沙矿山研究院有限责任公司 | A kind of early strength water-reducing agent for filling in mine material and preparation method thereof |
| CN104591622A (en) * | 2015-01-06 | 2015-05-06 | 无为县严桥双龙建材厂 | Highly anti-bending and wearing-resistant lightweight concrete |
| CN107129176A (en) * | 2017-02-27 | 2017-09-05 | 武汉理工大学 | A kind of synthetic method of modified sulfamate water reducer |
| CN108996950A (en) * | 2018-08-19 | 2018-12-14 | 柳州市家富连装饰有限公司 | A kind of functional ornamentation material and preparation method thereof |
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