CN106519141B - A kind of width molecular weight distribution high-adaptability type polycarboxylic acid slump retaining agent masterbatch - Google Patents
A kind of width molecular weight distribution high-adaptability type polycarboxylic acid slump retaining agent masterbatch Download PDFInfo
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- CN106519141B CN106519141B CN201611004970.4A CN201611004970A CN106519141B CN 106519141 B CN106519141 B CN 106519141B CN 201611004970 A CN201611004970 A CN 201611004970A CN 106519141 B CN106519141 B CN 106519141B
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- slump retaining
- retaining agent
- polycarboxylic acid
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- solution
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- 239000002253 acid Substances 0.000 title claims abstract description 39
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 37
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 18
- 238000009826 distribution Methods 0.000 title claims abstract description 18
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000003999 initiator Substances 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 150000007513 acids Chemical class 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 11
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 11
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 11
- -1 acrylic ester Chemical class 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 230000003020 moisturizing effect Effects 0.000 claims description 5
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 5
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 4
- JPAOMENBKRZQDR-UHFFFAOYSA-N CC=CC.[Na] Chemical compound CC=CC.[Na] JPAOMENBKRZQDR-UHFFFAOYSA-N 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- 229930091371 Fructose Natural products 0.000 claims description 3
- 239000005715 Fructose Substances 0.000 claims description 3
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 3
- 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 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- 230000002045 lasting effect Effects 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims 1
- 241000255964 Pieridae Species 0.000 claims 1
- 239000008103 glucose Substances 0.000 claims 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims 1
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 239000004568 cement Substances 0.000 abstract description 25
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 6
- 239000011707 mineral Substances 0.000 abstract description 6
- 229920005646 polycarboxylate Polymers 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 239000012452 mother liquor Substances 0.000 abstract 1
- 230000011218 segmentation Effects 0.000 abstract 1
- 230000006641 stabilisation Effects 0.000 abstract 1
- 238000011105 stabilization Methods 0.000 abstract 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 241000233855 Orchidaceae Species 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 6
- 239000001530 fumaric acid Substances 0.000 description 6
- 235000010755 mineral Nutrition 0.000 description 5
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical group [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- SPFMQWBKVUQXJV-BTVCFUMJSA-N (2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanal;hydrate Chemical group O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O SPFMQWBKVUQXJV-BTVCFUMJSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229960000673 dextrose monohydrate Drugs 0.000 description 3
- 230000003467 diminishing effect Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000011398 Portland cement Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 238000004873 anchoring Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000003642 hunger Nutrition 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- PYGXUPRQBBNETH-UHFFFAOYSA-N acetic acid;2-hydroxypropyl prop-2-enoate Chemical compound CC(O)=O.CC(O)COC(=O)C=C PYGXUPRQBBNETH-UHFFFAOYSA-N 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 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
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
-
- 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
- C04B2103/308—Slump-loss preventing agents
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a kind of wide molecular weight distribution high-adaptability type polycarboxylic acid slump retaining agent masterbatch.It is different from general polycarboxylic acid slump retaining agent preparation method, minor comonomer solution is added dropwise with multifrequency speed, and time for adding control is desirably to obtain backbone length segmentation arrangement, the equally distributed polycarboxylic acid slump retaining agent molecular structure of branch in 4 ~ 5h.This high-adaptability type mother liquor is for cement, mineral admixture, the sandstone ground changeable situation of material qualities such as material, when being used in combination individually or with other polycarboxylate water-reducers, shows that initial water-reducing rate is high, middle and later periods slump retaining is good and the feature of volume stabilization.
Description
Technical field
The invention belongs to cement-based gelling material additive technical field, for cement, mineral admixture, sandstone ground material
The changeable situation of equal material qualities is related to a kind of wide molecular weight distribution high-adaptability type polycarboxylic acid slump retaining agent masterbatch.
Background technology
Cement performance depends on C in clinker3S and C3A mineral contents, specific surface area, mineral admixture volume and kind, and
The influence power of factors is followed successively by sandstone, cement, mineral admixture, and it is that concrete admixture fluctuates therewith to correspond
It is larger.Strong absorption material inferior can accelerate hydrated cementitious, water-reducing agent to be wrapped up by cement granules or hydrated product, steric hindrance effect
It is violent decaying should to be acted on electrical charge rejection.
The method for solving concrete flowability loss at present is that compounding polycarboxylic acid slump retaining agent and conventional set retarder are next real mostly
Now protect collapse, it is this guarantor collapse measure to according to cement, material otherness easily occurs guarantor collapse effect can not be by construction requirement time controlled released
Or hysteresis quality release, it shows as high flowability concrete slump and instead increases or even isolate sedimentation, middle low slump after being perfused
Concrete slump retaining is not connected or slump-retaining difference.
For cement, mineral admixture, sandstone the material qualities such as material it is changeable in the case of, concrete adaptability influence because
Element depends primarily on the internal factor of concrete raw material stability, this is appropriate to the occasion using the poly- carboxylic of wide molecular weight distribution high-adaptability type
Sour slump retaining agent, backbone length diversification, is in multigroup arrangement, and short-chain branch anchoring group binary three-dimensional is uniformly distributed, wide adaptability,
Stability is good.
103073215 A of patent CN disclose a kind of preparation method of the high-efficiency water-reducing agent of poly-carboxylic acid of Narrow Molecular Weight Distribution,
Preparation method uses water soluble starter and water-soluble active chain-transferring agent, at a certain temperature the just polyethers list containing double bond
Body, alkene-carboxylic acid and its salt carry out Controlled Living Radical Polymerization, and obtained high-efficiency water-reducing agent of poly-carboxylic acid narrow molecular weight distribution can
It adjusts on demand.This method is compared with the synthetic method of other high-efficiency water-reducing agent of poly-carboxylic acid, obtained high-efficiency water-reducing agent of poly-carboxylic acid
Molecular weight distribution and its controllability all have greatly improved, and can synthesize the product of different molecular weight on demand, be respectively provided with excellent
It is early strong, protect the performances such as collapse, enhance.
104177561 A of patent CN disclose a kind of preparation side of the polycarboxylate water-reducer with slow release and resistance to mud
Method, the polycarboxylate water-reducer have the following advantages：(1) contain ester unstable under cement strong alkali environment in products molecule structure
Base and amide group；(2) amide groups has sealing process because hydrolyzing the amine cation generated to the soil with negative electrical charge, reaches resistance to
Mud effect；(3) there is thickening effect to cement slurry, and delay the aquation of cement granules；(3) this product water-reducing rate is high, the slump
Through when holder it is good, it is high to the tolerance of mud scholar.
105085822 A of patent CN provide a kind of anti-chamotte mould polycarboxylate water-reducer and its normal temperature preparation method, by insatiable hunger
With fatty alcohol polyethenoxy ether class polymeric monomer, unsaturated carboxylic acid, cationic quaternary ammonium salt and quaternary ammonium acrylate in room temperature, normal pressure
Under the conditions of formed using free radical solution copolymerization, can effectively reduce negative effect of the viscous scholar to concrete, there is sustained release, anti-
The features such as mud, adaptability are good, and have dispersion and dispersion holding performance well to the concrete of the mud containing different type.
Invention content
Technical problem to be solved by the invention is to provide wide molecular weight distribution high-adaptability type polycarboxylic acid slump retaining agent masterbatch.
The present invention can match different polycarboxylic acids to a certain extent by packet design polycarboxylic acid slump retaining agent molecular backbone length
Water-reducing agent molecular components are satisfied with polycarboxylate water-reducer and the slump retaining agent of certain backbone length point under different hydrated environments and medium
Son matching is reasonable, and to meet initial adsorption amount, and the hydrolysis of the slump retaining agent later stage of other backbone lengths remains to auxiliary polycarboxylic acids diminishing
Agent molecule collective effect is in cement granules；Above-mentioned design concept utmostly stablizes polycarboxylic-acid slump retaining agent molecule in different absorption
Absorption dispersibility in the case of mass-energy power, amount are changeable and repulsion ability.
A kind of width molecular weight distribution high-adaptability type polycarboxylic acid slump retaining agent masterbatch, is polymerized by following each components, total matter
Amount is 1000 parts, is as follows：
1) 325~335 parts of polyether macromonomers and 200~250 parts of water are added in reaction kettle, it is lasting to stir, until molten
Liquid is without obvious bulk or sheet material；Temperature in the kettle is controlled at 5~25 DEG C, disposably puts into 2.0~5.0 parts of hydrogen peroxide and 2.1
~4.5 parts of sulphonic acids minor comonomers；
2) hydrogen peroxide is added in 10min, starts that initiator, minor comonomer solution is added dropwise successively；Initiator is by 5.0~10.0 parts
Organic weak reductant and 100~120 parts of water compositions；Minor comonomer solution by 4.9~10.5 parts of sulphonic acids minor comonomers, 5.0~
10.0 parts of fumaric acid, 30.0~45.0 parts of acrylic ester monomers and 60~90 parts of water compositions；Initiator time for adding is than small list
Liquid solution is 0.5 hour more；
During minor comonomer solution is added dropwise, the minor comonomer amount of solution of half, intermediate 1/3 time is added in preceding 1/3 time
The minor comonomer amount of solution of one third is added, 1/6th minor comonomer amount of solution is added in rear 1/3 time；
3) after completion of dropwise addition, 1~2h is cured, when reaction solution temperature is less than 30 DEG C, 6~10 parts of liquid caustic soda, moisturizing is added
10~15h is stood after stirring evenly.
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 is sentenced from the angle of slump retaining
Disconnected, preferably isoamyl alcohol polyoxyethylene ether, the one or two kinds of of vinyl butyl ether polyoxyethylene ether form；The polyethers is big
Monomer judges from the balanced angle of reactivity ratio, preferably the isoamyl alcohol polyoxyethylene ether of 2400 molecular weight.
The hydrogen peroxide is that mass percent is 27.5% industrial grade hydrogen peroxide.
The sulphonic acids minor comonomer is sodium vinyl sulfonate, Sodium Allyl Sulfonate, methylpropene sodium sulfonate, styrene sulfonic acid
One or more of compositions of sodium, 2- acrylamide-2-methyl propane sulfonics；The sulphonic acids minor comonomer is preferably that molecular weight is smaller
One or two kinds of compositions of minor comonomer, i.e. sodium vinyl sulfonate, Sodium Allyl Sulfonate.
The fumaric acid, i.e. fumaric acid.
The organic weak reductant is one or two kinds of compositions of Dextrose Monohydrate, fructose.
The acrylic ester monomer be hydroxy-ethyl acrylate, hydroxypropyl acrylate, methyl acrylate, ethyl acrylate,
One or more of compositions of methyl methacrylate.
The minor comonomer solution time for adding is 4.0~5.0h.
The beneficial effects of the invention are as follows：
1. being different from the sulfydryl class chain-transferring agent and acrylic acid unitary unsaturated carboxylic acid class that general polycarboxylic acid slump retaining agent uses
Minor comonomer, wide molecular weight distribution high-adaptability type polycarboxylic acid slump retaining agent system use enough sulphonic acids minor comonomers and binary insatiable hunger
With carboxylic acid-fumaric acid primitive is anchored as short-chain branch；The use of unsaturated dicarboxylic acid class minor comonomer, enough amounts that can have more than needed are come
Design sulphonic acids minor comonomer and organic weak reductant component；The organic weak reductant small molecule that do not react completely is removed and plays lubrication
Effect, also adsorbent is filled in adsorbate as priority, ensures the diminishing effect of diminishing agent molecule.
2. small monomer solution takes frequency conversion speed to be added dropwise in synthesis technology, sulphonic acids minor comonomer, which removes, makees anchoring group component
Outside, chain-transferring agent effect is also played, 30% sulphonic acids minor comonomer is disposably added in bottom material, it is ensured that time for adding leading portion
Afterwards, enough chain tra nsfer dosage ensures backbone length otherness in the reasonable scope；Acrylic ester monomer diversification is set
Meter is matched with the ester based monomer of different hydrolysis time points, to meet absorption-peptizaiton under different hydrated environments and medium.
Specific implementation mode
Embodiment 1：
A kind of width molecular weight distribution high-adaptability type polycarboxylic acid slump retaining agent masterbatch, by following each components by mass percentage
It is polymerized, raw material gross mass is 1000 parts, and each component and technological parameter are as follows：
Bottom material：The methyl allyl polyoxyethylene ether of 2400 molecular weight：329, water：220；
Hydrogen peroxide solution：27.5% industrial grade hydrogen peroxide：3.0, water：10；
Methylpropene sodium sulfonate：2.25；
It is molten that initiator, minor comonomer are sequentially added after hydrogen peroxide solution and methylpropene sodium sulfonate are added at one time, in 10min
Liquid；
Initiator：Dextrose Monohydrate：9.2, water：110；
Minor comonomer solution：Methylpropene sodium sulfonate：5.25 fumaric acid：7.9, hydroxy-ethyl acrylate：22.8, acrylic acid first
Ester：18.7 water：65；
Initiator time for adding：4.5h；
Minor comonomer solution time for adding 4.0h；
The minor comonomer amount of solution of half is added in preceding 1/3 period, in 1/3 time be added one third minor comonomer it is molten
/ 6th minor comonomer amount of solution is added in liquid measure, rear 1/3 period；
Initiator solution is at the uniform velocity added dropwise；
Soaking time：1.5h；
When reaction solution temperature is less than 30 degree, it is slowly added to liquid caustic soda 7, moisturizing 189.9；
10h is stood after stirring evenly to get finished product.
Embodiment 2：
Bottom material：The isoamyl alcohol polyoxyethylene ether of 2400 molecular weight：327, water：235；
Hydrogen peroxide solution：27.5% industrial grade hydrogen peroxide：4.2, water：10；
Sodium vinyl sulfonate：3.0；
It is molten that initiator, minor comonomer are sequentially added after hydrogen peroxide solution and sodium vinyl sulfonate are added at one time, in 10min
Liquid；
Initiator：Dextrose Monohydrate：8.6, water：110；
Minor comonomer solution：Sodium vinyl sulfonate：7.0, fumaric acid：10.0 hydroxy-ethyl acrylate：15.7, acrylic acid hydroxypropyl
Ester：15.5 methyl methacrylate：8.2, water：70；
Initiator time for adding：5.0h；
Minor comonomer solution time for adding 4.5h；
The minor comonomer amount of solution of half is added in preceding 1/3 period, in 1/3 time be added one third minor comonomer it is molten
/ 6th minor comonomer amount of solution is added in liquid measure, rear 1/3 period；
Initiator solution is at the uniform velocity added dropwise；
Soaking time：2.0h；
When reaction solution temperature is less than 30 degree, it is slowly added to liquid caustic soda 8, moisturizing 167.8；
12h is stood after stirring evenly to get finished product.
Embodiment 3：
Bottom material：The vinyl butyl ether polyoxyethylene ether of 2400 molecular weight：333, water：250；
Hydrogen peroxide solution：27.5% industrial grade hydrogen peroxide：3.5, water：10；
Sodium Allyl Sulfonate：4.05；
Hydrogen peroxide solution and Sodium Allyl Sulfonate, which are added at one time in rear 10min, sequentially adds initiator, minor comonomer solution；
Initiator：Fructose：9.7, water：120；
Minor comonomer solution：Sodium Allyl Sulfonate：9.45 hydroxy-ethyl acrylate：20.5 methyl acrylate：10.8 acrylic acid
Ethyl ester：8.5, water：80；
Initiator time for adding：5.5h；
Minor comonomer solution time for adding 5.0h；
The minor comonomer amount of solution of half is added in preceding 1/3 period, in 1/3 time be added one third minor comonomer it is molten
/ 6th minor comonomer amount of solution is added in liquid measure, rear 1/3 period；
Initiator solution is at the uniform velocity added dropwise；
Soaking time：2.0h；
When reaction solution temperature is less than 30 degree, it is slowly added to liquid caustic soda 10, moisturizing 130.5；
14.5h is stood after stirring evenly to get finished product.
In addition to the implementation, the present invention can also have other embodiment.It is all to use equivalent substitution or equivalent transformation shape
At technical solution, fall within the scope of protection required by the present invention.
Common slump retaining agent and wide molecular weight distribution high-adaptability type polycarboxylic acid slump retaining agent masterbatch in examples detailed above are tested respectively
Embodiment 1, the flowing degree of net paste of cement under 2,3 same dosages and 1,2,3h fluidities.Experiment cement used is that China new 42.5 is general
Silicon cement, 42.5 ordinary portland cement of Ge Zhou Ba, blue 42.5 ordinary portland cements in capital, with reference to GB/8076-2008《Concrete admixture》Test
Pulp flowage.
New flowing degree of net paste of cement influences the different water-reducing agents of table 1 to China
The different water-reducing agents of table 2 influence Ge Zhou Ba flowing degree of net paste of cement
The different water-reducing agents of table 3 influence capital orchid flowing degree of net paste of cement
By table 1-3 statistics indicate that, common slump retaining agent for Hua Xin, Ge Zhou Ba, capital orchid cement show it is different it is initial,
1,2,3h mobility, Zhong jing orchid cement adsorb that additive polymer molecule ability is big, and initially without mobility, 1h is opened ordinary cement
Begin release, 2h fluidities start it is weak, 3h be intended to fluidity disappearance；But capital orchid cement initially has certain fluidity, and 1h reaches
To peak, 2h is i.e. without fluidity；The slump retaining agent of example 1,2,3 shows to stablize relatively for Hua Xin, Ge Zhou Ba, capital orchid cement
Fluidity and guarantor collapse Long-term change trend, in the case of the orchid cement of Zhong jing, 2h still has the mobility that can be satisfied with working performance.It is comprehensive
Upper described, under different cement, the performance of 1,2,3 function of slump protection of example is relatively stable, adaptable.
The GPC data of wide molecular weight distribution high-adaptability type polycarboxylic acid slump retaining agent masterbatch embodiment 1 is as shown in table 4 below,
Middle-molecular-weihydroxyethyl is distributed index D=M (w)/M (n)=2.550 of degree of scatter.
4 embodiment 1GPC test results of table
The GPC data of common polycarboxylic acid slump retaining agent masterbatch is as shown in table 5 below, wherein the index of molecular weight distribution degree of scatter
D=M (w)/M (n)=1.461.
5 common slump retaining agent GPC test results of table
It is the polymer of uniform molecular weight, its bigger molecular weight distribution of numeric ratio 1 of D is wider, polydispersity journey when D=1
Degree is bigger.It can be seen that embodiment 1 meets wide molecular weight distribution high-adaptability type polycarboxylic acid slump retaining agent masterbatch design concept.
Claims (7)
1. a kind of width molecular weight distribution high-adaptability type polycarboxylic acid slump retaining agent masterbatch, which is characterized in that polymerize by following each components
It forms, gross mass is 1000 parts, is as follows：
1) 325 ~ 335 parts of polyether macromonomers and 200 ~ 250 parts of water are added in reaction kettle, it is lasting to stir, until solution is without bright
Aobvious blocky or sheet material；Temperature in the kettle is controlled at 5 ~ 25 DEG C, disposably puts into 2.0 ~ 5.0 parts of hydrogen peroxide and 2.1 ~ 4.5 parts of sulphurs
Acids minor comonomer；
2) hydrogen peroxide is added in 10min, starts that initiator, minor comonomer solution is added dropwise successively；Initiator is organic by 5.0 ~ 10.0 parts
Class weak reductant and 100 ~ 120 parts of water compositions；Minor comonomer solution is by 4.9 ~ 10.5 parts of sulphonic acids minor comonomers, 5.0 ~ 10.0 parts of rich horses
Acid, 30.0 ~ 45.0 parts of acrylic ester monomers and 60 ~ 90 parts of water compositions；Initiator time for adding is 0.5 small more than minor comonomer solution
When；
During minor comonomer solution is added dropwise, the minor comonomer amount of solution of half is added in preceding 1/3 time, and intermediate 1/3 time is added
/ 6th minor comonomer amount of solution is added in the minor comonomer amount of solution of one third, rear 1/3 time；
3) after completion of dropwise addition, 1 ~ 2h is cured, when reaction solution temperature is less than 30 DEG C, 6 ~ 10 parts of liquid caustic soda is added, moisturizing stirring is equal
10 ~ 15h is stood after even.
2. polycarboxylic acid slump retaining agent masterbatch according to claim 1, which is characterized in that the polyether macromonomer is poly- for allyl
One kind of ethylene oxide ether, methyl allyl polyoxyethylene ether, isoamyl alcohol polyoxyethylene ether, vinyl butyl ether polyoxyethylene ether
Or several compositions.
3. polycarboxylic acid slump retaining agent masterbatch according to claim 1, which is characterized in that the hydrogen peroxide is that mass percent is
27.5% industrial grade hydrogen peroxide.
4. polycarboxylic acid slump retaining agent masterbatch according to claim 1, which is characterized in that the sulphonic acids minor comonomer is vinyl
One kind of sodium sulfonate, Sodium Allyl Sulfonate, methylpropene sodium sulfonate, sodium styrene sulfonate, 2- acrylamide-2-methyl propane sulfonics
Or several compositions.
5. polycarboxylic acid slump retaining agent masterbatch according to claim 1, which is characterized in that the organic weak reductant is a water
One or two kinds of compositions of glucose, fructose.
6. polycarboxylic acid slump retaining agent masterbatch according to claim 1, which is characterized in that the acrylic ester monomer is propylene
One or more of compositions of sour hydroxyl ethyl ester, hydroxypropyl acrylate, methyl acrylate, ethyl acrylate, methyl methacrylate.
7. polycarboxylic acid slump retaining agent masterbatch according to claim 1, which is characterized in that the minor comonomer solution time for adding is
4.0~5.0 h。
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