CN102276192B - Grouting material containing phenol modified aliphatic water reducer and preparation method thereof - Google Patents
Grouting material containing phenol modified aliphatic water reducer and preparation method thereof Download PDFInfo
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- CN102276192B CN102276192B CN2011101204430A CN201110120443A CN102276192B CN 102276192 B CN102276192 B CN 102276192B CN 2011101204430 A CN2011101204430 A CN 2011101204430A CN 201110120443 A CN201110120443 A CN 201110120443A CN 102276192 B CN102276192 B CN 102276192B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 109
- 239000000463 material Substances 0.000 title claims abstract description 105
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 77
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 72
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 63
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000004568 cement Substances 0.000 claims abstract description 43
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 20
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-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 14
- 235000010262 sodium metabisulphite Nutrition 0.000 claims abstract description 14
- 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
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 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
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 125000001931 aliphatic group Chemical group 0.000 claims description 27
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 20
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 18
- 239000004576 sand Substances 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 238000002347 injection Methods 0.000 claims description 8
- 239000007924 injection Substances 0.000 claims description 8
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 8
- 150000002790 naphthalenes Chemical class 0.000 claims description 8
- 230000008961 swelling Effects 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 6
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 claims description 5
- 235000010265 sodium sulphite Nutrition 0.000 claims description 5
- 229950000244 sulfanilic acid Drugs 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 101710194948 Protein phosphatase PhpP Proteins 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 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 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000006004 Quartz sand Substances 0.000 abstract description 4
- 230000000740 bleeding effect Effects 0.000 abstract description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 abstract 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 abstract 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 abstract 1
- 239000004567 concrete Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 14
- 239000002245 particle Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- DGVVJWXRCWCCOD-UHFFFAOYSA-N naphthalene;hydrate Chemical compound O.C1=CC=CC2=CC=CC=C21 DGVVJWXRCWCCOD-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000006277 sulfonation reaction Methods 0.000 description 4
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229960001436 calcium saccharate Drugs 0.000 description 2
- UGZVNIRNPPEDHM-SBBOJQDXSA-L calcium;(2s,3s,4s,5r)-2,3,4,5-tetrahydroxyhexanedioate Chemical compound [Ca+2].[O-]C(=O)[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O UGZVNIRNPPEDHM-SBBOJQDXSA-L 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 238000006482 condensation reaction Methods 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
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000011372 high-strength concrete Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 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 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000001912 cyanamides Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000009429 distress 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
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004574 high-performance concrete Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000010412 perfusion Effects 0.000 description 1
- 239000011178 precast concrete Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 235000019633 pungent taste Nutrition 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 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
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention provides a cement-based grouting material containing a phenol modified aliphatic water reducer and a preparation method thereof, wherein the water reducer contains, by weight, 350-500 parts of cement clinker, 80-130 parts of fly ash, 20-30 parts of an expanding agent, 80-120 parts of gypsum, 1-2 parts of a pH value regulator, 8-15 parts of the phenol modified aliphatic water reducer, and 300-500 parts of quartz sand. The weight part is calculated based on the total weight part of the grouting material. The phenol modified aliphatic water reducer is made from the following raw materials according to the following weight ratio: the ratio of formaldehyde to acetone to sodium hydrosulphite or sodium bisulfite to phenol to sodium pyrosulfite to sodium hydroxide to sodium sulfanilate to water is 200-400:80-120:80-180:10-20:60-90:1-2:20-35:400-600. The grouting material has high strength and low bleeding rate, and its strength performance is less affected by severe weather.
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 phenol-modified aliphatic water reducing agent and preparation method thereof.
Background technology
Concrete structure is big because of its fragility, in practical applications, tends to take place cracking phenomena, 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 need be used the combining site on high performance grouting material perfusion wall screw and machinery bed or steelwork and basis etc.
Distress in concrete commonly used is repaired with the injection material of reinforcing a lot, divides from material type, mainly contains two big types of chemical grouting material and cement-based grouting materials.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 is high, transportation and store inconvenience, construction technology is complicated, has toxicity in various degree mostly; Comprise pungency, corrodibility, sensitization and shortcoming such as inflammable and explosive; Simultaneously, cause environmental pollution because of test, constructing operation and discharging dead meal etc. 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, is prone to the deposition bleed, and volumetric shrinkage is arranged during sclerosis.In addition, after the strengthening of foundation grouting, slurry has certain shrink, ftractures once more easily.Therefore, those skilled in the art are devoted to overcome through 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; But the raising that cement-based grouting material intensity under necessity, especially the winter severe cold condition that improves is again still arranged 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 concrete technology field, water reducer is one of admixture that improves rheological property of concrete in modern times, has been taken as five component of concrete except that cement, sand, stone and water.
High efficiency water reducing agent is one of main raw material of producing high-strength, high performance concrete.The high efficiency water reducing agent that uses on the home market at present mainly contains naphthalene water reducer, sulfonated melamine water reducer, sulfamate based water reducer and poly carboxylic acid series water reducer.
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 got into; Advantageously promoted the development of concrete technology, the outstanding feature of these two series of high efficiency water reducers is that water-reducing rate is high, and 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 that high-strength, superelevation is strong, high durability concrete, but its fatal shortcoming is that slump-loss is big, 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 dispersivity of concrete (cement), slump retaining is good, and easy modification, so its high performance potentiality are big, be considered to the regeneration product of high efficiency water reducing agent, but its price is higher, has limited its use range.
Aliphatic high-efficiency water reducing agent is a kind of novel high efficiency water reducing agent that grows up in the eighties in 20th century, and it is a main raw material with monomers such as ketone, aldehyde and sulphite, becomes the polymeric fatty compounds of group through the oversulfonate condensation.Because its volume is little; Sodium sulphate content is few; Not containing has the villaumite of corrosive nature not have advantages such as crystallization with winter to reinforcing bar, has obtained in recent years widely and has used, and particularly aspect high-strength concrete castinplace pile, precast concrete and high-strength concrete, uses more.
Aliphatic high-efficiency water reducing agent reaction mechanism more complicated, though different processes and prescription can be produced aliphatic water reducing agent, various The comprehensive performance differ greatly.The factor that influences the aliphatic water reducing agent performance has: raw material composition, feed way, temperature of reaction, reaction density etc.At present; Though the aliphatic water reducing agent of many types is arranged on the market; But the aliphatic water reducing agent volume is little, pollution is little, price is relatively cheap for satisfying, can provide again concrete good strengthen the property and also there is very big room for improvement in the product of slump retention.Bring thus, also there is very big room for improvement in the modification that contains the injection material of said water reducer.
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 is than like product, and is early strong, strengthen the property significantly, and slump retention value is high, and the slump through the time loss little.Further, the present invention provides a kind of cement-based grouting material that contains this water reducer and preparation method thereof, and this injection material intensity is high, and bleeding rate is low, and strength property receives the influence of severe cold weather little.
The cement-based grouting material that contains phenol-modified aliphatic water reducing agent of the present invention comprises by weight: cement clinker 350～500; Flyash 80～130, swelling agent 20～30, gypsum 80～120; PH value regulator 1～2; Phenol-modified aliphatic water reducing agent 8～15, silica sand 300～500, said parts by weight calculate and get based on the gross weight umber of said injection material; Said phenol-modified aliphatic water reducing agent is prepared from according to the following weight ratio following raw material: formaldehyde: acetone: S-WAT or sodium sulfite anhy 96: phenol: Sodium Pyrosulfite: sodium hydroxide: Sodium sulfanilate: water=200-400: 80-120: 80-180: 10-20: 60-90: 1-2: 20-35: 400-600.
Preferably, said formaldehyde: acetone: S-WAT or sodium sulfite anhy 96: phenol: Sodium Pyrosulfite: sodium hydroxide: Sodium sulfanilate: water=200-400: 80-120: 100-160: 12-16: 60-90: 1-2: 20-35: 500-600.
Preferably, the parts by weight of said cement clinker are 380～420, and the parts by weight of said water reducer are 9～11.Preferably, said cement clinker is a Portland clinker.Preferably, said swelling agent comprises sulplo-aluminate, and further preferably, said swelling agent is sulplo-aluminate, more preferably calcium sulphoaluminate.Preferably, the said pH value regulator mixed thing that to be boric acid and tripoly phosphate sodium STPP obtain according to 1: 2 ratio.
Preferably; Said silica sand comprises thick silica sand, middle silica sand and three kinds of level branches of fine quartz sand; The amount ratio of three kinds of level branches is 45～60: 35～50: 10～20; Wherein the particle size range of thick silica sand is＞3mm～5mm, and the particle size range of middle silica 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 silica sands that will satisfy above-mentioned qualification and can further improves concrete intensity, reduces bleeding rate.
The present invention provides a kind of preparation method of cement-based grouting material in addition, and comprising the step that each component is mixed, the preparation method of wherein said phenol-modified aliphatic water reducing agent comprises the steps:
(1) preparation of A material
Make phenol, Sodium sulfanilate and formaldehyde in water, react, obtain the A material;
(2) preparation of B material
Prepare the B material by water, acetone, formaldehyde, Sodium Pyrosulfite, S-WAT and sodium hydroxide;
(3) hybrid reaction
The A material is slowly joined in the B material, and insulation reaction obtains said phenol-modified aliphatic water reducing agent.
Preferably, the preparation of said B material comprises:
(i) acetone, formaldehyde and Sodium Pyrosulfite are mixed, get material B-1;
(ii) water, S-WAT, sodium hydroxide and Sodium Pyrosulfite are mixed, get material B-2;
After (iii) material B-2 being warming up to 45-55 ℃, to wherein dripping material B-1, elevated temperature reacts, and obtains the B material.
Preferably, the preparation of said A material comprises: after water, phenol, Sodium sulfanilate are mixed, in mixed solution, drip formaldehyde; The adding speed of control formaldehyde; Make the temperature of reaction system be no more than 105 ℃, after dropwising, maintain the temperature at 95-105 ℃ of reaction 2-3 hour.
Preferably, material B-1 being added drop-wise to the time used among the material B-2 is 6-8 hour.
Preferably said A material and B material are 90-98 ℃ of following insulation reaction.
The present invention provides a kind of cement-based grouting material that contains composite water reducer in addition, and it comprises aforesaid phenol-modified aliphatic water reducing agent, and naphthalene series high-efficiency water-reducing agent and/or slow setting component.This composite water reducer has the effect of good control concrete slump loss, and it is with respect to independent naphthalene water reducer, and slump retention value can improve about 2%.
Preferably; Phenol-modified aliphatic water reducing agent: naphthalene series high-efficiency water-reducing agent: slow setting component=20～50: 10～40: 0～10; More preferably phenol-modified aliphatic water reducing agent: naphthalene series high-efficiency water-reducing agent: slow setting component=30～50: 20～30: 2～6, said ratio is a weight ratio.
Preferably; Said naphthalene series high-efficiency water-reducing agent is made up of C material and D material; Wherein the C material is prepared from naphthalene, the vitriol oil, formaldehyde, water and sodium hydroxide, and the D material is prepared from phenol, sodium hydroxide, formaldehyde, thionamic acid, Sulphanilic Acid, and the C material is 20: 1～5: 1 with the weight ratio of D material.Preferably, said C material is prepared from by following weight ratio following raw material: naphthalene: the vitriol oil of 98 weight %: water: formaldehyde: the aqueous sodium hydroxide solution of 50 weight %=20～30: 20～30: 12～18: 12～20: 20～30.
Further preferably, said C material is prepared from by following weight ratio following raw material: naphthalene: the vitriol oil of 98 weight %: water: formaldehyde: the aqueous sodium hydroxide solution of 50 weight %=20～25: 20～25: 12～15: 14～17: 20～25.Said slow setting component can be calcium saccharate.
Further preferably, said D material is prepared from by following weight ratio following raw material: phenol: sodium hydroxide: formaldehyde: thionamic acid: Sulphanilic Acid=18～21: 9～10: 28～31: 28～31: 10～12.
Further preferably, the preparation process of said C material comprises: 1) with the naphthalene fusion; 2) in the fused naphthalene, drip the vitriol oil and carry out sulfonation reaction, the rate of addition of the preferred vitriol oil is to make the temperature of reaction system between 150～165 ℃, and reaction was preferably carried out 3～4 hours; 3) with step 2) sulfonated products that obtains adds the water hydrolysis, and the total acidity of selective hydrolysis afterreaction system is 26%～30%; 4) product in the step 3) is cooled to 100～120 ℃, drip formaldehyde and carry out condensation, the rate of addition of formaldehyde preferably makes the temperature of reaction system be no more than 115 ℃; 5) add aqueous sodium hydroxide solution in the product that in step 4), obtains, carry out neutralization reaction, preferred in the pH value of after product be 8～10.
Further preferably, the preparation process of said D material comprises: phenol is joined in the aqueous sodium hydroxide solution, and the back that stirs adds thionamic acid; Continue to stir; Evenly add part formaldehyde in the back to mixing solutions, react one section between the back add Sulphanilic Acid, follow; Residual formaldehyde is added, continue reaction and obtain liquid product.Wherein need not the external heat source heat supply in the reaction process, circulation obtains initial reaction stage institute heat requirement from reaction later stage liberated heat.
Embodiment
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, deducts 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
The preparation of A material:
In 400Kg water, 160Kg phenol, No. 1 reaction kettle of 295Kg Sodium sulfanilate input, mix, be warming up to 50 ℃; At the uniform velocity drip 280Kg formaldehyde, the control rate of addition makes temperature of reaction system be no more than 105 ℃; Reacted 2.5 hours down at 98-105 ℃ then, it is subsequent use to obtain the A material.
The preparation of B material:
To volume is to add 1100Kg acetone, 3200Kg formaldehyde and 440Kg Sodium Pyrosulfite in 5000 liters No. 2 reaction kettles, mix, material B-1.
To volume is to add 4300Kg water in 10000 liters of No. 3 reaction kettles, and 1100Kg S-WAT, 13Kg sodium hydroxide and 390Kg Sodium Pyrosulfite mix, and obtain material B-2.
The temperature of material B-2 is increased to 50 ℃, begins to drip material B-1, the rate of addition of control B-1; Make B-1 drip 7 hours times spent, keep temperature of reaction system at 50-55 ℃ simultaneously, after dropwising; Elevated temperature is to 90-95 ℃, and isothermal reaction 2 hours obtains the B material.
Hybrid reaction
In the B material, drip the A material, under 90-94 ℃, isothermal reaction 2 hours promptly gets phenol-modified aliphatic water reducing agent.
Preparation embodiment 2
Other step is identical with preparation embodiment 1, and difference is to replace with the 1600Kg sodium sulfite anhy 96 S-WAT of 1100Kg among the preparation embodiment 1.
Preparation embodiment 3
Other step is identical with preparation embodiment 1, and difference is to replace with 200Kg phenol the phenol of 160Kg among the preparation embodiment 1.
Preparation embodiment 4
Other step is identical with preparation embodiment 1, and difference drips the A material in the B material, under 95-98 ℃, and isothermal reaction 2 hours.
Preparation Comparative Examples 1
Other step is identical with preparation embodiment 1, and difference is to replace 160Kg phenol among the preparation embodiment 1 with the 160Kg Resorcinol.。
Preparation Comparative Examples 2
Other step is identical with preparation embodiment 1, and difference is not add phenol.
Preparation Comparative Examples 3
Other step is identical with preparation embodiment 1, and difference is not add Sodium sulfanilate.
Preparation Comparative Examples 4
Other step is identical with preparation embodiment 1, and difference does not add Sodium Pyrosulfite.
Preparation Comparative Examples 5
Use the method for CN101531479A embodiment 1 to prepare aliphatic water reducing agent.
Table 1:
Performance after adding to water reducer of the present invention and Comparative Examples water reducer in the Lafarge cement respectively relatively
Preparation embodiment 5
One, the preparation of naphthalene water reducer
The preparation of C material
The 1600Kg naphthalene is put in the molten-bath, and the fusion heating when treating that temperature is elevated to 90 ℃ of left and right sides, is pressed into the sulfonation still with the fused naphthalene, keep-ups pressure smaller or equal to 0.1MPa.With after being pressed into naphthalene in the sulfonation still and being warming up to 130～135 ℃, the vitriol oil that adds 1600Kg carries out sulfonation reaction, reacts 3.5 hours.Then, add the reaction that is hydrolyzed of 1000Kg water, when the acidity of reaction system proceeded to 28% left and right sides, adding 1000Kg formaldehyde carried out condensation reaction, and setting-up point is controlled at 100～110 ℃.After condensation reaction was carried out 3 hours, add 1600Kg concentration and be 50% aqueous sodium hydroxide solution and neutralize, make the pH of reaction system reach 8～10.
The preparation of D material
The sodium hydroxide of 3000kg water and about 300Kg is joined in the reaction kettle, and the back that stirs adds 600Kg phenol, continues then to stir; Add the 1050Kg thionamic acid, stirred 40 minutes, 300Kg formaldehyde is added drop-wise in the reaction system reacted about 1 hour; Add the 350Kg Sulphanilic Acid; Then 700Kg formaldehyde is added drop-wise in the reaction system, continues to react half a hour, obtain product liquid.Need not in the reaction process to provide to add heat, turn back to reaction kettle through circulation line after only will reacting the heat collection that produces.Through measuring, wherein the molecular weight of gained condensation product is about 6000.
With C material and the mixed of D material according to 10: 1, be blended in 100～110 ℃, carry out under the normal pressure.
Two, the preparation of Compositional type water reducer
With the naphthalene water reducer of the phenol-modified water reducer of preparation embodiment 1 preparation and the above-mentioned preparation of this embodiment mixed, obtain described Compositional type water reducer according to 40: 25.
Preparation embodiment 6
Other is identical with preparation embodiment 5, and difference is to replace the naphthalene water reducer for preparing among the above-mentioned preparation embodiment 5 with disclosed naphthalene water reducer in the CN101863635A embodiment.
Preparation embodiment 7
Other is identical with preparation embodiment 5, and the calcium saccharate of further adding 3% is as the slow setting component in the Compositional type water reducer that difference is in preparation embodiment 5, to obtain.
Table 2:
Performance after the composite water reducer that obtains among the embodiment 5-7 adds in the Lafarge cement respectively relatively
Embodiment 1
A kind of preparation method of cement-based grouting material is provided, and this method makes through 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 12 of preparation embodiment 1, average particle size particle size is the middle silica 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 difference is that the water reducer with preparation embodiment 5 replaces the water reducer of preparation embodiment 1.
Embodiment 6
Other is identical with embodiment 1, and difference is that the water reducer with preparation embodiment 6 replaces the water reducer of preparation embodiment 1.
Embodiment 7
Other is identical with embodiment 1, and difference is that the water reducer with preparation embodiment 7 replaces the water reducer of preparation embodiment 1.
Embodiment 8
Other is identical with embodiment 1, silica sand in 450 weight parts about fine quartz sand 70 weight parts about difference is to use average particle size particle size as 1mm, middle silica sand 200 weight parts about 2.5mm and thick silica sand 180 weight parts about 4mm replace average particle size particle size among the embodiment 1 as 2.5mm.
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 12 weight parts.
Table 2:
The performance of embodiment 1-8 and the said cement-based grouting material of Comparative Examples 1-5 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 (14)
1. cement-based grouting material that contains phenol-modified aliphatic water reducing agent, it comprises by weight: cement clinker 350～500, flyash 80～130; Swelling agent 20～30; Gypsum 80～120, pH value regulator 1～2, phenol-modified aliphatic water reducing agent 8～15; Silica sand 300～500, said parts by weight calculate and get based on the gross weight umber of said injection material; Said phenol-modified aliphatic water reducing agent is prepared from according to the following weight ratio following raw material: formaldehyde: acetone: S-WAT or sodium sulfite anhy 96: phenol: Sodium Pyrosulfite: sodium hydroxide: Sodium sulfanilate: water=200-400: 80-120: 80-180: 10-20: 60-90: 1-2: 20-35: 400-600.
2. the described cement-based grouting material of claim 1, wherein said formaldehyde: acetone: S-WAT or sodium sulfite anhy 96: phenol: Sodium Pyrosulfite: sodium hydroxide: Sodium sulfanilate: water=200-400: 80-120: 100-160: 12-16: 60-90: 1-2: 20-35: 500-600.
3. claim 1 or 2 described cement-based grouting materials, the parts by weight of wherein said cement clinker are 380～420, the parts by weight of said water reducer are 9～11.
4. claim 1 or 2 described cement-based grouting materials, wherein said cement clinker is a Portland clinker.
5. claim 1 or 2 described cement-based grouting materials, wherein said swelling agent comprises sulplo-aluminate.
6. claim 1 or 2 described cement-based grouting materials, wherein said swelling agent is a calcium sulphoaluminate.
7. claim 1 or 2 described cement-based grouting materials, the wherein said pH value regulator mixed thing that to be boric acid and tripoly phosphate sodium STPP obtain according to 1: 2 ratio.
8. the preparation method of a cement-based grouting material; Comprising with cement clinker, flyash, swelling agent, gypsum, pH value regulator, phenol-modified aliphatic water reducing agent, silica sand according to the uniform step of each described mixed of claim 1-3, the preparation method of wherein said phenol-modified aliphatic water reducing agent comprises the steps:
(1) preparation of A material
Make phenol, Sodium sulfanilate and formaldehyde in water, react, obtain the A material;
(2) preparation of B material
Prepare the B material by water, acetone, formaldehyde, Sodium Pyrosulfite, S-WAT and sodium hydroxide;
(3) hybrid reaction
The A material is slowly joined in the B material, and insulation reaction obtains said phenol-modified aliphatic water reducing agent.
9. the described method of claim 8, the preparation of wherein said B material comprises:
(i) acetone, formaldehyde and Sodium Pyrosulfite are mixed, get material B-1;
(ii) water, S-WAT, sodium hydroxide and Sodium Pyrosulfite are mixed, get material B-2;
After (iii) material B-2 being warming up to 45-55 ℃, to wherein dripping material B-1, elevated temperature reacts, and obtains the B material.
10. claim 8 or 9 described methods; The preparation of wherein said A material comprises: after water, phenol, Sodium sulfanilate are mixed; In mixed solution, drip formaldehyde, the adding speed of control formaldehyde makes the temperature of reaction system be no more than 105 ℃; After dropwising, maintain the temperature at 95-105 ℃ of reaction 2-3 hour.
11. a cement-based grouting material that contains composite water reducer, it comprises by weight: cement clinker 350～500, flyash 80～130; Swelling agent 20～30; Gypsum 80～120, pH value regulator 1～2, composite water reducer 8～15; Silica sand 300～500, said parts by weight calculate and get based on the gross weight umber of said injection material; Said composite water reducer comprises the phenol-modified aliphatic water reducing agent described in the claim 1, and naphthalene series high-efficiency water-reducing agent and/or slow setting component.
12. the described cement-based grouting material of claim 11, wherein said phenol-modified aliphatic water reducing agent: naphthalene series high-efficiency water-reducing agent: slow setting component=20～50: 10～40: 0～10, said ratio is a weight ratio.
13. the described cement-based grouting material of claim 12, wherein said phenol-modified aliphatic water reducing agent: naphthalene series high-efficiency water-reducing agent: slow setting component=30～50: 20～30: 2～6, said ratio is a weight ratio.
14. the described cement-based grouting material of claim 12; Wherein said naphthalene series high-efficiency water-reducing agent is made up of C material and D material; Wherein the C material is prepared from naphthalene, the vitriol oil, formaldehyde, water and sodium hydroxide; The D material is prepared from phenol, sodium hydroxide, formaldehyde, thionamic acid, Sulphanilic Acid, and the C material is 20: 1～5: 1 with the weight ratio of D material.
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| CN104478271B (en) * | 2014-12-09 | 2017-05-03 | 重庆建研科之杰新材料有限公司 | Aliphatic water reducer and preparation method thereof |
| CN110028642A (en) * | 2018-12-19 | 2019-07-19 | 江苏苏博特新材料股份有限公司 | A kind of sulfamate polymeric dispersant and preparation method thereof and its application in ceramic slurries |
| CN111978034B (en) * | 2020-07-02 | 2022-05-31 | 江苏省建筑工程质量检测中心有限公司 | Anti-permeation high-strength high-volume-stability concrete, preparation method thereof and application of concrete as cushion block for protective layer |
| CN112608058B (en) * | 2020-12-03 | 2022-10-21 | 科之杰新材料集团浙江有限公司 | Concrete micro-foaming agent and preparation method thereof |
| CN118792026A (en) * | 2024-09-14 | 2024-10-18 | 四川方能油气工程技术服务有限公司 | A plugging material for oil and gas drilling and its preparation method and application |
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| US20030172850A1 (en) * | 2002-03-13 | 2003-09-18 | Byong-Wa Chun | Beneficiated water reducing compositions |
| CN101186459A (en) * | 2007-12-04 | 2008-05-28 | 北京工业大学 | Method and application of manufacturing aliphatic high-efficiency water reducer by using industrial by-products |
| CN101531479A (en) * | 2009-04-03 | 2009-09-16 | 南京瑞迪高新技术公司 | Method for preparing low cost aliphatic high efficiency water reducing agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030172850A1 (en) * | 2002-03-13 | 2003-09-18 | Byong-Wa Chun | Beneficiated water reducing compositions |
| CN101186459A (en) * | 2007-12-04 | 2008-05-28 | 北京工业大学 | Method and application of manufacturing aliphatic high-efficiency water reducer by using industrial by-products |
| CN101531479A (en) * | 2009-04-03 | 2009-09-16 | 南京瑞迪高新技术公司 | Method for preparing low cost aliphatic high efficiency water reducing agent |
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