CN106496443B - A kind of polycarboxylate water-reducer masterbatch of sulfonic acid phosphate double-strand transferance - Google Patents
A kind of polycarboxylate water-reducer masterbatch of sulfonic acid phosphate double-strand transferance Download PDFInfo
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- CN106496443B CN106496443B CN201610959789.2A CN201610959789A CN106496443B CN 106496443 B CN106496443 B CN 106496443B CN 201610959789 A CN201610959789 A CN 201610959789A CN 106496443 B CN106496443 B CN 106496443B
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 33
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 23
- 239000010452 phosphate Substances 0.000 title claims abstract description 23
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 title claims abstract description 14
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 11
- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910001868 water Inorganic materials 0.000 claims abstract description 23
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 17
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 12
- 229920000570 polyether Polymers 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 22
- 239000003999 initiator Substances 0.000 claims description 16
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 13
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 13
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 12
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical group FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 11
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- JPAOMENBKRZQDR-UHFFFAOYSA-N CC=CC.[Na] Chemical compound CC=CC.[Na] JPAOMENBKRZQDR-UHFFFAOYSA-N 0.000 claims description 5
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical group CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 239000000498 cooling water Substances 0.000 claims description 2
- 230000002045 lasting effect Effects 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 238000011017 operating method Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000004568 cement Substances 0.000 abstract description 15
- 238000004873 anchoring Methods 0.000 abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 230000002860 competitive effect Effects 0.000 abstract description 3
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 239000012452 mother liquor Substances 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 3
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract 1
- 229910001882 dioxygen Inorganic materials 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000003467 diminishing effect Effects 0.000 description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- -1 ether ester Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 235000010323 ascorbic acid Nutrition 0.000 description 3
- 239000011668 ascorbic acid Substances 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 230000003020 moisturizing effect Effects 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- WCASXYBKJHWFMY-UHFFFAOYSA-N crotyl alcohol Chemical compound CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 235000013379 molasses Nutrition 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 239000001116 FEMA 4028 Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 1
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 1
- 229960004853 betadex Drugs 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical class OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
-
- 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2605—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
-
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/302—Water reducers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a kind of polycarboxylate water-reducer masterbatch of sulfonic acid phosphate double-strand transferance, synthetic raw material gross mass is 1000 parts, its usage ratio are as follows: polyether macromonomer dosage is 345 ~ 350, acrylic acid dosage is 32.0 ~ 40.0, sulfonic group chain-transferring agent: 3.0 ~ 8.0, phosphate chain-transferring agent: 1.0 ~ 5.0, dioxygen water consumption is 2.0 ~ 5.0, Victoria C dosage is 0.35 ~ 0.75, remaining is water.The polycarboxylate water-reducer that the present invention synthesizes is i.e. polymerizable at low temperature, and carboxyl, sulfonic group, phosphate are arranged alternately, and absorption anchoring ability is stronger, and product shows water-reducing rate height, the characteristics of wide adaptability.The grinding aid that this modified mother liquor is used suitable for cement production process contains competitive Adsorption ability greater than carboxyl, the retarder of sulfydryl or salt electrolyte.
Description
Technical field
The present invention relates to a kind of cement-based gelling material polycarboxylate water-reducers, are adapted to grinding aid component and water-reducing agent phase
A kind of bad cement of capacitive, and in particular to polycarboxylate water-reducer masterbatch of sulfonic acid phosphate double-strand transferance.
Background technique
Grinding aid is usually the components such as hydramine type organic, molasses, salt electrolyte, table of such component to cement granules
Face can have certain influence, and then the absorption of cement particle surface is caused to generate variation, the water-reducing effect and cement of water-reducing agent
The adsorbance on grain surface is closely related.In addition, gypsum and C in alcamines organic destruction cement in grinding aid3Best of A
Match, molasses class has a minimal effect to the solution rate of sulfate radical in cement, and salt electrolyte accelerates cement early hydration, and with subtract
Competitive adsorption occurs for aqua.The variation of grinding aid component, causes water-reducing agent there are a certain range of fluctuation, and grinding aid component is multiple
Miscellaneous or volume is excessively high, and failure phenomenon even occurs in water-reducing agent, i.e. the bad problem of compatibility easily occurs in grinding aid and water-reducing agent.
Single unsaturated carboxyl minor comonomer and sulfydryl class chain-transferring agent are generallyd use in common high performance water-reducer system.?
In high performance water-reducer component, introduce unsaturated sulfonic acid base minor comonomer, sulfonic group electronegativity is stronger compared with carboxyl, easily in the form of hydrogen is good for and
Water molecules are got up, and this hydrogen bond association power is relatively firm.Phosphate increases water-reducing agent molecular backbone termination process
The anchoring ability of water-reducing agent short-side chain, and then diminishing agent molecule is improved in the competitive Adsorption ability of cement particle surface.
102731009 A of CN, which is disclosed, provides a kind of sulfonyl modified carboxylic acid water-reducing agent and preparation method thereof, described to subtract
The raw material for preparing of aqua includes: allyl alcohol polyethenoxy ether or methyl allyl alcohol polyoxyethylene ether, acrylic acid, methacrylic sulfonic acid
Sodium, ammonium persulfate, NaOH, water.The water-reducing agent environmental protection, little loss of slump, water-reducing rate are high, and preparation process is simple, cost
It is cheap.
102153711 A of CN discloses that the present invention relates to a kind of preparation methods of slow-setting polycarboxylic acid water reducing agent.Its content
It is by allyl sulphonic acid salt monomer, acrylic monomer, Methylacrylic acid polyethylene glycol single armor ether ester polymeric monomer and maleic acid
Acid anhydride is grafted β-cyclodextrin polymeric monomer and obtains a kind of slow-setting polycarboxylic acid water reducing agent by free radicals copolymerization reaction.It is of the present invention
Preparation method has the characteristics that technique uniqueness, excellent product performance.
102718426 A of CN discloses the present invention and provides a kind of modified carboxylic acid class water-reducing agent, and preparing raw material includes: alkene
Propyl alcohol polyoxyethylene ether or methyl allyl alcohol polyoxyethylene ether, acrylic acid, methylpropene sodium sulfonate, initiator, chain-transferring agent, alkali
Property neutralizer, water.The water-reducing agent environmental protection, little loss of slump, water-reducing rate are high, and preparation process is simple, low in cost.This hair
It is bright to also disclose the preparation method of modified carboxylic acid class water-reducing agent.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of polycarboxylic acids diminishings of sulfonic acid phosphate double-strand transferance
Masterbatch is polymerized by following each components, and total mass of raw material is 1000 parts, and each component includes:
Polyether macromonomer: 345~350；
Acrylic acid: 32.0~40.0；
Sulfonic group chain-transferring agent: 3.0~8.0；
Phosphate chain-transferring agent: 1.0~5.0；
Hydrogen peroxide: 2.0~5.0；
Victoria C: 0.35~0.75；
Water: remaining.
The polyether macromonomer is allyl polyethenoxy ether, methyl allyl polyoxyethylene ether, prenol polyoxy second
One or more of compositions of alkene ether, vinyl butyl ether polyoxyethylene ether；
The polyether macromonomer preferably protects the collapse stronger polyether macromonomer of ability, i.e. isoamyl alcohol polyoxyethylene ether, second
One or two kinds of compositions of alkenyl butyl ether polyoxyethylene ether.
The hydrogen peroxide is that mass fraction is 27.5% industrial grade hydrogen peroxide, and dosage is 2.0~5.0；
The sulfonic group chain-transferring agent is sodium vinyl sulfonate, acrylic sodium sulfonate, methylpropene sodium sulfonate, styrene
One or more of compositions of sodium sulfonate, 2- acrylamide-2-methyl propane sulfonic；The sulfonic group chain-transferring agent is preferably molecule
Measure lesser sulfonic group chain-transferring agent, the i.e. one or more of sodium vinyl sulfonate, acrylic sodium sulfonate, methylpropene sodium sulfonate
Composition；
The sulfonic group chain-transferring agent dosage is 3.0~5.5, and acrylic acid is preferably 36~40；The sulfonic group chain
Transfer agent dosage is 5.5~8, and acrylic acid is preferably 32~36.
The phosphate chain-transferring agent is sodium hypophosphite, and dosage is 1.0~5.0；
Initiator is the water solution mixture of sulfonic group chain-transferring agent and Victoria C；
When the Victoria C dosage is 0.35~0.55, sodium hypophosphite dosage is preferably 3.0~5.0；The Victoria C dosage
When being 0.55~0.75, sodium hypophosphite dosage is preferably 1.0~3.0；
The preparation method of the polycarboxylate water-reducer masterbatch of sulfonic acid phosphate double-strand transferance of the present invention, including such as
Lower operating procedure:
Polyether macromonomer is placed in reaction vessel, it is lasting to stir, until solution is without obvious bulk or sheet material.
Hydrogen peroxide and phosphate chain-transferring agent are disposably placed in and dissolved in complete polyether macromonomer solution, then
10min domestic demand sequentially adds initiator and minor comonomer solution, and minor comonomer solution time for adding is 4~5h, and initiator lags behind small
It is dripped after 10~20min of monomer solution, the minor comonomer solution is acrylic acid solution；
Cooling water circulation is not opened, liquid alkaline neutralization is not added, being placed in reaction kettle after 10~15h can release.
The present invention has prevented the strong chain-transferring agent of sulfydryl class and has used, using the compound work of the weak chain-transferring agent of phosphoric acid sulfonic group binary
With design concept is to introduce initial anchoring property of the phosphoric acid sulfonic group to improve Water-reducing Admixtures To Cements slurry, keeps simultaneously
The quality and dosage of polyether macromonomer, to improve the dispersion retentivity of cement slurry.
The beneficial effects of the present invention are:
1. selecting the lesser unsaturated sulfonic acid base minor comonomer of molecular weight, sulfonic distribution is close on increase short-chain branch as far as possible
Degree, to improve diminishing agent molecule in the adsorption capacity of cement particle surface；Additionally using sodium hypophosphite as chain-transferring agent, sulfonic acid
The design of the compound use of phosphate chain-transferring agent and longer time for adding promotes diminishing agent molecule short-chain branch structure distribution more
Uniformly.
2. using the compound use of neutral reduction agent-Victoria C and weak property reducing agent-sodium hypophosphite, hypophosphorous acid in synthetic system
Sodium is removed as weak reductant auxiliary Victoria C effect, it is ensured that high performance water-reducer conversion ratio further increases；The sealing end of phosphate acts on,
Diminishing agent molecule can be enhanced in the anchorage effect of cement particle surface, promote the anti-mud performance of sulfate resistance of diminishing agent molecule.
Specific embodiment
Below by example, the present invention will be further elaborated, and following the description is not right only for explaining the present invention
Content is defined.
Embodiment 1
A kind of polycarboxylate water-reducer masterbatch of sulfonic acid phosphate double-strand transferance, it is characterised in that: the water-reducing agent is by pressing
Following each components of mass percent are polymerized, total mass of raw material 1000, and each component and technological parameter are as follows:
Bottom material: the isoamyl alcohol polyoxyethylene ether of 2400 molecular weight: 345, water: 200；
Oxidizing agent solution: hydrogen peroxide: 3.0, water: 5；
Sodium hypophosphite: 1.2
Oxidizing agent solution, sodium hypophosphite are added at one time in rear 10min and initiator, minor comonomer solution are successively added dropwise, and cause
After 10min is added dropwise in agent, start that minor comonomer solution is added dropwise；
Initiator: sodium vinyl sulfonate: 3.5, ascorbic acid: 0.68, water: 120；
Minor comonomer solution: acrylic acid: 38.5, water: 50；
Initiator time for adding: 4.5h；
Minor comonomer solution time for adding 4.0h；
Moisturizing: 233.12.
It keeps the temperature 10h and releases reaction kettle.
Embodiment 2
Bottom material: the vinyl butyl ether polyoxyethylene ether of 2400 molecular weight: 348, water: 220；
Oxidizing agent solution: hydrogen peroxide: 3.5, water: 5；
Sodium hypophosphite: 3.5
Oxidizing agent solution, sodium hypophosphite are added at one time in rear 10min and initiator, minor comonomer solution are successively added dropwise, and cause
After 10min is added dropwise in agent, start that minor comonomer solution is added dropwise；
Initiator: acrylic sodium sulfonate: 5.7, ascorbic acid: 0.52, water: 120；
Minor comonomer solution: acrylic acid: 35.6, water: 50；
Initiator time for adding: 5.5h；
Minor comonomer solution time for adding 5.0h；
Moisturizing: 208.18.
It keeps the temperature 15h and releases reaction kettle.
Embodiment 3
Bottom material: the vinyl butyl ether polyoxyethylene ether of 2400 molecular weight: 346, water: 250；
Oxidizing agent solution: hydrogen peroxide: 4.8, water: 10；
Sodium hypophosphite: 4.7
Oxidizing agent solution, sodium hypophosphite are added at one time in rear 10min and initiator, minor comonomer solution are successively added dropwise, and cause
After 10min is added dropwise in agent, start that minor comonomer solution is added dropwise；
Initiator: methylpropene sodium sulfonate: 7.8, ascorbic acid: 0.20, water: 115；
Minor comonomer solution: acrylic acid: 32.8, water: 50；
Initiator time for adding: 5.0h；
Minor comonomer solution time for adding 4.5h；
Moisturizing: 178.7.
It keeps the temperature 12h and releases reaction kettle.
The polycarboxylate water-reducer masterbatch and common polycarboxylic acids of the double-strand transferance of examples detailed above sulfonic acid phosphate are tested respectively
Concrete initial slump/divergence under water-reducing agent mother liquor comparable sodium and through when the slump/divergence.Test cement used
For 42.5 ordinary portland cement of Ge Zhou Ba, clay content is larger in sandstone, with reference to GB/8076-2008 " concrete admixture " testing standard.
Different water-reducing agents influence concrete flowability
According to above-mentioned concrete it is initial and through when mobility compare, the polycarboxylic acids diminishing of sulfonic acid phosphate double-strand transferance
The initial fluidity of masterbatch example 1,2,3 is relatively a little bigger compared with ordinary water-reducing agent mother liquor, and protects more significant, anti-mud performance of collapsing
It is excellent；The reason is that the compound use of sulfonic acid phosphate chain-transferring agent leads to anchoring ability diversification and anchoring ability is more
By force, the dropwise addition technique of longer time for adding promotes diminishing agent molecule short-chain branch structure distribution uniform, protects the ability of collapsing and is ensured.
Claims (2)
1. a kind of polycarboxylate water-reducer masterbatch of sulfonic acid phosphate double-strand transferance, is polymerized by following each components, raw material
Gross mass is 1000 parts, and each component includes:
Polyether macromonomer: 345 ~ 350；
Acrylic acid: 32.0 ~ 40.0；
Sulfonic group chain-transferring agent: 3.0 ~ 8.0；
Phosphate chain-transferring agent: 1.0 ~ 5.0；
Hydrogen peroxide: 2.0 ~ 5.0；
Victoria C: 0.35 ~ 0.75；
Water: remaining；
The polyether macromonomer be allyl polyethenoxy ether, methyl allyl polyoxyethylene ether, isoamyl alcohol polyoxyethylene ether,
One or more of compositions of vinyl butyl ether polyoxyethylene ether；
The hydrogen peroxide is that mass fraction is 27.5% industrial grade hydrogen peroxide；
The sulfonic group chain-transferring agent is one kind or several of sodium vinyl sulfonate, acrylic sodium sulfonate, methylpropene sodium sulfonate
Kind composition；
The phosphate chain-transferring agent is sodium hypophosphite.
2. the preparation method of the polycarboxylate water-reducer masterbatch of sulfonic acid phosphate double-strand transferance described in claim 1, special
Sign is, including following operating procedure:
Polyether macromonomer is placed in reaction vessel, it is lasting to stir, until solution is without obvious bulk or sheet material；
Hydrogen peroxide and phosphate chain-transferring agent are disposably placed in and dissolved in complete polyether macromonomer solution, then 10min
Domestic demand sequentially adds initiator and minor comonomer solution, and minor comonomer solution time for adding is 4 ~ 5h, and it is molten that initiator lags behind minor comonomer
It is dripped after 10 ~ 20min of liquid, the initiator is the water solution mixture of sulfonic group chain-transferring agent and Victoria C, and the minor comonomer is molten
Liquid is acrylic acid solution；
Cooling water circulation is not opened, liquid alkaline neutralization is not added, being placed in reaction kettle after 10 ~ 15h can release.
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| CN103992443A (en) * | 2014-05-19 | 2014-08-20 | 科之杰新材料集团有限公司 | Method for preparing polycarboxylate water reducing agent by normal-temperature mixing process |
| CN104497223A (en) * | 2014-12-23 | 2015-04-08 | 李鼎 | Water reducing agent synthesized at normal temperature through taking phosphorous-containing compound as chain transfer agent, as well as preparation method thereof |
| CN105776933A (en) * | 2014-12-22 | 2016-07-20 | 上海东大化学有限公司 | Mud-resisting type polycarboxylate-type water reducer and preparation method and use method thereof |
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| CN103992443A (en) * | 2014-05-19 | 2014-08-20 | 科之杰新材料集团有限公司 | Method for preparing polycarboxylate water reducing agent by normal-temperature mixing process |
| CN105776933A (en) * | 2014-12-22 | 2016-07-20 | 上海东大化学有限公司 | Mud-resisting type polycarboxylate-type water reducer and preparation method and use method thereof |
| CN104497223A (en) * | 2014-12-23 | 2015-04-08 | 李鼎 | Water reducing agent synthesized at normal temperature through taking phosphorous-containing compound as chain transfer agent, as well as preparation method thereof |
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