CN102211909B - Cement-based grouting material containing polyether carboxylic acid type water reducing agent and preparation method of cement-based grouting material - Google Patents
Cement-based grouting material containing polyether carboxylic acid type water reducing agent and preparation method of cement-based grouting material Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 239000004568 cement Substances 0.000 title claims abstract description 42
- 239000000463 material Substances 0.000 title claims abstract description 37
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims abstract description 18
- 239000004721 Polyphenylene oxide Substances 0.000 title abstract 4
- 229920000570 polyether Polymers 0.000 title abstract 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 43
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 32
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003999 initiator Substances 0.000 claims abstract description 18
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 17
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 10
- 239000010881 fly ash Substances 0.000 claims abstract description 5
- 239000010440 gypsum Substances 0.000 claims abstract description 5
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000004576 sand Substances 0.000 claims description 13
- 239000000377 silicon dioxide Substances 0.000 claims description 13
- JPAOMENBKRZQDR-UHFFFAOYSA-N CC=CC.[Na] Chemical compound CC=CC.[Na] JPAOMENBKRZQDR-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 230000008961 swelling Effects 0.000 claims description 7
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 6
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 claims description 5
- 101150065749 Churc1 gene Proteins 0.000 claims description 5
- 102100038239 Protein Churchill Human genes 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [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
- 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
- 238000003756 stirring Methods 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
- 238000010792 warming Methods 0.000 claims description 3
- WROUWQQRXUBECT-UHFFFAOYSA-M 2-ethylacrylate Chemical compound CCC(=C)C([O-])=O WROUWQQRXUBECT-UHFFFAOYSA-M 0.000 claims description 2
- -1 polypropylene Polymers 0.000 abstract description 6
- 239000006004 Quartz sand Substances 0.000 abstract description 4
- 230000000740 bleeding effect Effects 0.000 abstract description 4
- CAQWNKXTMBFBGI-UHFFFAOYSA-N C.[Na] Chemical compound C.[Na] CAQWNKXTMBFBGI-UHFFFAOYSA-N 0.000 abstract 1
- 239000004743 Polypropylene Substances 0.000 abstract 1
- 229920001155 polypropylene Polymers 0.000 abstract 1
- 239000004567 concrete Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 13
- 239000002245 particle Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- 230000014759 maintenance of location Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000010276 construction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
- 239000004159 Potassium persulphate Substances 0.000 description 2
- 150000001336 alkenes Chemical class 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
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 235000019394 potassium persulphate Nutrition 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
- 239000002904 solvent Substances 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- WEHZNZTWKUYVIY-UHFFFAOYSA-N 3-oxabicyclo[3.2.2]nona-1(7),5,8-triene-2,4-dione Chemical compound O=C1OC(=O)C2=CC=C1C=C2 WEHZNZTWKUYVIY-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical group ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 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
- 239000003513 alkali Substances 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000001912 cyanamides Chemical class 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 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
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 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
- 239000004574 high-performance concrete Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000010412 perfusion Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 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
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229920005552 sodium lignosulfonate Polymers 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-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
- 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
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention provides a cement-based grouting material containing polyether carboxylic acid type water reducing agent and a preparation method of the cement-based grouting material. The cement-based grouting material containing the polyether carboxylic acid type water reducing agent comprises the following components in part by weight: 350 to 500 parts of cement clinker, 80 to 130 parts of fly ash, 20 to 30 parts of expanding agent, 80 to 120 parts of gypsum, 1 to 2 parts of pH regulator, 8 to 15 parts of water reducing agent and 300 to 500 parts of quartz sand, wherein the water reducing agent is the polyether carboxylic acid type water reducing agent prepared from the following components: polypropylene alcohol ether, maleic anhydride, methyl sodium allylsulfonate, acrylamide, acrylic-2-hydroxyethyl ester, initiator and water. The grouting material has high strength and low bleeding rate.
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 particular variety polyether-type carboxylic-acid water reducer 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.
Common water reducer mainly contains xylogen ring phosphate-gallate series, naphthalene system, trimeric cyanamide system, sulfamate system and polycarboxylic acid 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 cpds such as sodium abietate, sodium lignosulfonate, stearate; It mainly is to be used to improve Concrete Construction property, 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 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 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, is considered to the regeneration product of high efficiency water reducing agent.
External polycarboxylic acid high efficiency water reducing agent is widely used in the concrete preparation, and product type is main with maleic anhydride series mainly.With Japan is example, and the product compound method is mainly: the first step, under the nitrogen protection condition, methyl alcohol and oxyethane react under certain temperature and pressure, in reaction vessel, add NaOH, elevated temperature decompression dehydration again.Subsequently, in mixture, add a certain amount of chlorallylene, when mixture basicity is reduced to a stationary value, use the HCl neutralise mixt, separate obtaining allyl ethers.Second step: as solvent, under nitrogen protection, the allyl ethers and the maleic anhydride that obtain with the first step reaction carry out polyreaction, steam and remove toluene solvant, obtain maleic anhydride series high performance concrete water reducer with toluene.
The domestic relevant report that the polycarboxylic acid high efficiency water reducing agent is also arranged in recent years.Its use raw material generally by unsaturated carboxylic acid class (vinylformic acid, methylacrylic acid, maleic anhydride), polyoxy alkene (T 46155, polyoxyethylene glycol etc.), unsaturated carboxylate type, contain the unsaturated monomer of sulfonic acid group etc.; Its synthesis step generally be divided into two the step carry out.As the polycarboxylic acid water reducing agents for efficient aerocrote reported among the CN1316398A tosic acid do catalyzer, Resorcinol do stopper, BPO do the initiator condition little with the methylacrylic acid polymerization reaction take place, obtain bleed type high efficiency water reducing agent except that desolvating question response is accomplished basically after.The water reducer that this method obtains is only soluble in alkali lye and is insoluble in water, brings very big inconvenience to use.CN1800076A also discloses a kind of acrylic acid or the like multiple copolymer analog high efficiency water reducing agent; The shared umber of its each raw material is: 100 parts of vinylformic acid or derivatives thereofs, 150～450 parts of polyoxy alkenes, sulfonic acid are 10～80 parts in verivate, 450～800 parts of deionized water solvents, 0.5～6 part of catalyzer, 0.1～5 part of stopper, 5～30 parts of Virahol chain-transfer agents, 0.5～5 part of initiator, and the add-on of NaOH solution is to make the pH value of product reach 6～8.But the method reaction process that this patent provided is difficult to control, and water-reducing rate and slump retention value still are not very desirable yet.
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 preparation technology is simple, and is with low cost.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.
Cement-based grouting material 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; Polyether-type carboxylic-acid water reducer 8～15, silica sand 300～500, the carboxylic-acid water reducer of wherein said polyether-type carboxylic-acid water reducer for being prepared from: Vestolen PP 7052 alcohol ether, MALEIC ANHYDRIDE, methylpropene sodium sulfonate, acrylic amide, 2-Hydroxy ethyl acrylate, initiator and water following component.Preferably, the weight ratio of each component is in the said polyether-type carboxylic-acid water reducer: Vestolen PP 7052 alcohol ether: MALEIC ANHYDRIDE: methylpropene sodium sulfonate: acrylic amide: 2-Hydroxy ethyl acrylate: initiator: water=25-40: 3-6: 1-6: 0.5-4: 1-5: 0.5-4: 100.
Further preferably, the weight ratio of each component is in the said polyether-type carboxylic-acid water reducer: Vestolen PP 7052 alcohol ether: MALEIC ANHYDRIDE: methylpropene sodium sulfonate: acrylic amide: 2-Hydroxy ethyl acrylate: initiator: water=30-35: 3.5-4: 2-3: 1-2: 2-3: 1-2: 100.
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.
Preferred said Vestolen PP 7052 alcohol ether is CH
2=CHCH
2O (CH
2CH
2O)
nH, wherein n=10-60.Preferred said initiator is ammonium persulphate, Potassium Persulphate or Sodium Persulfate.
The present invention provides a kind of preparation method of cement-based grouting material 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 regulator 1～2; Polyether-type carboxylic-acid water reducer 8～15, silica sand 300～400, wherein said polyether-type carboxylic-acid water reducer is prepared from following component: Vestolen PP 7052 alcohol ether, MALEIC ANHYDRIDE, methylpropene sodium sulfonate, acrylic amide, 2-Hydroxy ethyl acrylate, initiator and water.Preferably, the weight ratio of each component is in the said polyether-type carboxylic-acid water reducer: Vestolen PP 7052 alcohol ether: MALEIC ANHYDRIDE: methylpropene sodium sulfonate: acrylic amide: 2-Hydroxy ethyl acrylate: initiator: water=25-40: 3-6: 1-6: 0.5-4: 1-5: 0.5-4: 100.
The preparation method of said polyether-type carboxylic-acid water reducer comprises:
Step 1: propylene alcohol ether, MALEIC ANHYDRIDE and methylpropene sodium sulfonate are mixed with the aqueous solution, join in the reaction kettle, stir, be warming up to 80～100 ℃;
Step 2: drip acrylic amide and the aqueous solution of 2-Hydroxy ethyl acrylate formation and the aqueous solution of initiator in the mixture that in step 1, obtains, maintain the temperature at 80～100 ℃ in the dropping process, the dropping time is 2～5 hours;
Step 3: after dropwising, 80～100 ℃ following isothermal reaction 2-8 hour;
Step 4: filter.
Preferably, in the said aqueous solution of step 1, with respect to the water of 100 weight parts, the parts by weight of propylene alcohol ether, MALEIC ANHYDRIDE and methylpropene sodium sulfonate are respectively: 100-150 weight part, 15-25 weight part, 1-15 weight part.
Preferably, in the aqueous solution that said acrylic amide of step 2 and 2-Hydroxy ethyl acrylate form, with respect to the water of 100 weight parts, the parts by weight of acrylic amide and 2-Hydroxy ethyl acrylate are respectively 12-18 weight part and 15-25 weight part.In the step 2 in the initiator solution initiator concentration be 2-5 weight %.Preferably, the time of dropping described in the step 2 is 3-4 hour, and constant temperature time described in the step 3 is 4-5 hour.
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, 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
Step 1: with 320Kg propylene alcohol ether CH
2=CHCH
2O (CH
2CH
2O)
nH (wherein n=10-60), 420Kg MALEIC ANHYDRIDE and 50Kg methylpropene sodium sulfonate join in the 300Kg water and are mixed with the aqueous solution, join in the reaction kettle, stir, and are warming up to 90 ℃;
Step 2: the aqueous solution and the 860Kg concentration that drips 13Kg acrylic amide and 26Kg 2-Hydroxy ethyl acrylate and the formation of 140Kg water in the mixture that in step 1, obtains is the aqueous solution of 3% Potassium Persulphate initiator; Maintain the temperature at 90 ℃ in the dropping process, the dropping time is 3-3.5 hour;
Step 3: after dropwising, about 5 hours of 80～100 ℃ of following isothermal reactions;
Step 4: filter.
Productive rate is 94%.The slump retention value and the water-reducing rate value of products obtained therefrom are seen table 1.
Preparation embodiment 2
Other step is identical with preparation embodiment 1, and difference is to use 320Kg propylene alcohol ether to replace the CH of n value as 200-300
2=CHCH
2O (CH
2CH
2O)
nH replaces the CH of n=10-60 among the preparation embodiment 1
2=CHCH
2O (CH
2CH
2O)
nH.Productive rate is 90%.The slump retention value and the water-reducing rate value of products obtained therefrom are seen table 1.
Preparation embodiment 3
Other step is identical with preparation embodiment 1, and difference is the consumption of acrylic amide is reduced to 8Kg.Productive rate is 80%.The slump retention value and the water-reducing rate value of products obtained therefrom are seen table 1.
Preparation embodiment 4
Other step is identical with preparation embodiment 1, and difference is in the step 2 temperature to be remained on 80 ℃, rather than 90 ℃.Productive rate is 93%.The slump retention value and the water-reducing rate value of products obtained therefrom are seen table 1.
Preparation Comparative Examples 1
Other step is identical with preparation embodiment 1, and difference is to replace 420Kg MALEIC ANHYDRIDE described in the step 1 with the 420Kg terephthalic anhydride.Productive rate is 95%.The slump retention value and the water-reducing rate value of products obtained therefrom are seen table 1.
Preparation Comparative Examples 2
Other step is identical with preparation embodiment 1, and difference is not add MALEIC ANHYDRIDE.Productive rate is 95%.The slump retention value and the water-reducing rate value of products obtained therefrom are seen table 1.
Preparation Comparative Examples 3
Other step is identical with preparation embodiment 1, and difference is not add acrylic amide.Productive rate is 90%.The slump retention value and the water-reducing rate value of products obtained therefrom are seen table 1.
Preparation Comparative Examples 4
Other step is identical with preparation embodiment 1, and difference is to replace 2-Hydroxy ethyl acrylate with Virahol.
Table 1:
Performance after adding to water reducer of the present invention and the said water reducer of Comparative Examples in the Lafarge cement respectively relatively
Explain: " * " representative reaction is carried out smoothly
On behalf of reaction process, "-" be difficult to control
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 8 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, 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 8 weight parts.
Table 2:
The performance of embodiment 1-5 and the said 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 (13)
1. cement-based grouting material that contains polyether-type carboxylic-acid water reducer; It contains by weight: cement clinker 350～500; Flyash 80～130, swelling agent 20～30, gypsum 80～120; PH value regulator 1～2; Water reducer 6～15, silica sand 300～500, wherein said water reducer is prepared from for the component the following weight ratio: polyether-type carboxylic-acid water reducer: Vestolen PP 7052 alcohol ether: MALEIC ANHYDRIDE: methylpropene sodium sulfonate: acrylic amide: 2-Hydroxy ethyl acrylate: initiator: water=25-40: 3-6: 1-6: 0.5-4: 1-5: 0.5-4: 100.
2. cement-based grouting material according to claim 1, wherein said cement clinker are Portland clinker.
3. cement-based grouting material according to claim 1, wherein said swelling agent comprises sulplo-aluminate.
4. cement-based grouting material according to claim 1, wherein said swelling agent are calcium sulphoaluminate.
5. cement-based grouting material according to claim 1, the wherein said pH value regulator mixed thing that to be boric acid and tripoly phosphate sodium STPP obtain according to 1: 2 ratio.
6. cement-based grouting material according to claim 1, the parts by weight of said cement clinker are 380～420, and the parts by weight of said water reducer are 9～11.
7. according to each described cement-based grouting material of claim 1～6, the weight ratio of wherein said each component of water reducer is: Vestolen PP 7052 alcohol ether: MALEIC ANHYDRIDE: methylpropene sodium sulfonate: acrylic amide: 2-Hydroxy ethyl acrylate: initiator: water=30-35: 3.5-4: 2-3: 1-2: 2-3: 1-2: 100.
8. according to the described cement-based grouting material of claim 1～6 each each, wherein said Vestolen PP 7052 alcohol ether is CH
2=CHCH
2O (CH
2CH
2O)
nH, wherein n=10-60.
9. according to the preparation method of the described cement-based grouting material of claim 1～8 each each, comprising with each component blended step.
10. method according to claim 9, the preparation process of wherein said water reducer comprises:
Step 1: Vestolen PP 7052 alcohol ether, MALEIC ANHYDRIDE and methylpropene sodium sulfonate are mixed with the aqueous solution, join in the reaction kettle, stir, be warming up to 80～100 ℃;
Step 2: drip acrylic amide and the aqueous solution of 2-Hydroxy ethyl acrylate formation and the aqueous solution of initiator in the mixture that in step 1, obtains, maintain the temperature at 80～100 ℃ in the dropping process, the dropping time is 2～5 hours;
Step 3: after dropwising, 80～100 ℃ following isothermal reaction 2-8 hour;
Step 4: filter.
11. method according to claim 10; Wherein in the said aqueous solution of step 1; With respect to the water of 100 weight parts, the parts by weight of Vestolen PP 7052 alcohol ether, MALEIC ANHYDRIDE and methylpropene sodium sulfonate are respectively: 100-150 weight part, 15-25 weight part, 1-15 weight part.
12. according to claim 10 or 11 each described methods; Wherein the preparation process of B material is: in the aqueous solution that said acrylic amide of step 2 and 2-Hydroxy ethyl acrylate form; With respect to the water of 100 weight parts, the parts by weight of acrylic amide and 2-Hydroxy ethyl acrylate are respectively 12-18 weight part and 15-25 weight part.
13. method according to claim 10, wherein in the step 2 in the initiator solution initiator concentration be 2-5 weight %, the time of dropping described in the step 2 is 3-4 hour, constant temperature time described in the step 3 is 4-5 hour.
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