CN108707211A - A kind of collapse protection type solid polycarboxylic acid water reducing agent and preparation method thereof - Google Patents
A kind of collapse protection type solid polycarboxylic acid water reducing agent and preparation method thereof Download PDFInfo
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- CN108707211A CN108707211A CN201810743647.1A CN201810743647A CN108707211A CN 108707211 A CN108707211 A CN 108707211A CN 201810743647 A CN201810743647 A CN 201810743647A CN 108707211 A CN108707211 A CN 108707211A
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- China
- Prior art keywords
- reducing agent
- protection type
- water reducing
- type solid
- polycarboxylic acid
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- 239000007787 solid Substances 0.000 title claims abstract description 51
- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000002253 acid Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000007800 oxidant agent Substances 0.000 claims abstract description 21
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 10
- 150000002148 esters Chemical class 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 17
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 229940043237 diethanolamine Drugs 0.000 claims description 3
- 229940031098 ethanolamine Drugs 0.000 claims description 3
- 229960004418 trolamine Drugs 0.000 claims description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims description 2
- NQSLZEHVGKWKAY-UHFFFAOYSA-N 6-methylheptyl 2-methylprop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C(C)=C NQSLZEHVGKWKAY-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- JPAOMENBKRZQDR-UHFFFAOYSA-N CC=CC.[Na] Chemical compound CC=CC.[Na] JPAOMENBKRZQDR-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 229940083608 sodium hydroxide Drugs 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical group OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims 2
- 239000000243 solution Substances 0.000 claims 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims 1
- 239000002211 L-ascorbic acid Substances 0.000 claims 1
- 235000000069 L-ascorbic acid Nutrition 0.000 claims 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229960005070 ascorbic acid Drugs 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims 1
- 235000003642 hunger Nutrition 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical group [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229960003975 potassium Drugs 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 230000003467 diminishing effect Effects 0.000 abstract description 3
- 238000012856 packing Methods 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- -1 polyoxy Polymers 0.000 description 5
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical class CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920005646 polycarboxylate Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical class CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 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 description 1
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000004808 allyl alcohols Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- MRIZMKJLUDDMHF-UHFFFAOYSA-N cumene;hydrogen peroxide Chemical class OO.CC(C)C1=CC=CC=C1 MRIZMKJLUDDMHF-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229940093932 potassium hydroxide Drugs 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000004575 stone Substances 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
- C04B24/2688—Copolymers containing at least three different monomers
- C04B24/2694—Copolymers containing at least three different monomers 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
- C04B2103/302—Water reducers
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)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a kind of collapse protection type solid polycarboxylic acid water reducing agents for belonging to technical field of concrete additives and preparation method thereof.The collapse protection type solid polycarboxylic acid water reducing agent is prepared by unsaturated polyoxyethylene ether polymeric monomer, organic oxidizing agent, unsaturated carboxylic acid class minor comonomer, unsaturated esters minor comonomer, organic reducing agent, chain-transferring agent and neutralizer；Under low-dosage there is high diminishing, the significant performance of high-thin arch dam and guarantor to collapse, stability is good, durability is long, and solid forms can substantially reduce packing charges and transportation cost.
Description
Technical field
The invention belongs to technical field of concrete additives, more particularly to a kind of collapse protection type solid polycarboxylic acid water reducing agent and its
Preparation method.
Background technology
Polycarboxylate high performance water-reducing agent has become the indispensable part of modern concrete at present, with molecule
The advantages that structure design degree of freedom is big, greenization production, shows high diminishing under the conditions of low-dosage, low slump loss, extensively
It is general to be applied in all kinds of concrete works technical fields.And presently commercially available product is mostly solvent type (a concentration of 10%-50%)
Or powder-type (being obtained by high temperature spray-drying), wherein the solvent type packing cost and traffic expense for not only increasing product
With, and it is unfavorable for long-distance transportation and outlet；Although powder-type is better than liquid in packaging and transport, by fluid product
During high temperature spray-drying, part polycarboxylate water-reducer is caused to crosslink, original molecular structure is destroyed, product
Original performance substantially reduces, and also needs that interleaving agent is added in production cycle length, high energy consumption, reaction process, and production cost is high.
Solid polycarboxylic acid water reducing agent is gradually replacing liquid and the powdery polycarboxylic acid water-reducing agent by dusting captures
Market.Currently, although solid polycarboxylic acid water reducing agent in the market reduces transportation cost, but most of preparation process is complicated, instead
It answers system to contain organic solvent, environmentally protective requirement cannot be reached, organic solvent is removed again so that equipment cost is high, technique
Complexity, energy consumption of reaction are big；Performance declines after melting again；Therefore a kind of low cost is researched and developed, preparation process is simple, low energy consumption, ring
Protect pollution-free, high performance solid polycarboxylic acid water reducing agent has become new situations instantly.
Invention content
The purpose of the present invention is to provide a kind of collapse protection type solid polycarboxylic acid water reducing agent and preparation method thereof, particular technique sides
Case is as follows：
A kind of collapse protection type solid polycarboxylic acid water reducing agent, is calculated in mass percent, including 65%~85% unsaturated polyoxy second
Alkene ether polymeric monomer, 0.3%~0.5% is organic and/or inorganic oxidizer, 0.4%~0.8% azo oxidant, 3.5%~
14% unsaturated carboxylic acid class minor comonomer, 10%~18% unsaturated esters minor comonomer, 0.3%~0.7% organic reducing agent,
0.15%~0.5% chain-transferring agent, 1%~2.5% neutralizer, the sum of each component mass percent are equal to 100%.
The unsaturation polyoxyethylene ether polymeric monomer is allyl alcohol polyethenoxy ether, isoamyl alcohol polyoxyethylene ether or methyl
One or more in allyl polyethenoxy ether, weight average molecular weight is 1200~4000.
The oxidant is one or more in organic oxidizing agent, azo oxidant or inorganic oxidizer, wherein having
Machine oxidant is one or more, the azo oxygen in benzoyl peroxide, tert-butyl hydroperoxide or isopropyl benzene hydroperoxide
Agent is azodiisobutyronitrile, azobisisoheptonitrile, azo-bis-iso-dimethyl, and inorganic oxidizer is persulfate.
The unsaturated carboxylic acid class minor comonomer be acrylic acid, methacrylic acid, maleic anhydride or itaconic acid in one kind or
It is a variety of.
The unsaturation esters minor comonomer is acrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate, metering system
Sour hydroxyl ethyl ester, hydroxy propyl methacrylate, hy-droxybutyl, Isooctyl acrylate monomer, isooctyl methacrylate or methyl-prop
It is one or more in e pioic acid methyl ester.
The organic reducing agent is L-AA, N, accelerine or N, one kind or more in N- diethylanilines
Kind.
The chain-transferring agent is one or more in thioacetic acid, mercaptopropionic acid or methylpropene sodium sulfonate.
The neutralizer is one kind or more in potassium hydroxide, sodium hydroxide, ethanol amine, diethanol amine or triethanolamine
Kind.
The preparation method of the collapse protection type solid polycarboxylic acid water reducing agent includes the following steps：
(1) unsaturated polyoxyethylene ether polymeric monomer is stirred to melting under the conditions of 60-75 DEG C；
(2) unsaturated carboxylic acid class minor comonomer and organic or inorganic oxidant are added sequentially to the unsaturated polyoxy second of melting
In alkene ether polymeric monomer, stirs evenly, obtain mixed solution A；
(3) the mixed solution B that is made of chain-transferring agent and organic reducing agent is added dropwise into mixed solution A, be then added dropwise by
The mixed solution C of unsaturated carboxylic acid class minor comonomer and unsaturated esters minor comonomer composition, after 2 minutes, is added azo oxidant,
Wherein 2h, 1.5h is added dropwise in mixed solution B, mixed solution C respectively, and insulation reaction 1h is added dropwise；
(4) it is added in neutralizer and product is poured out while hot, is cooled down under room temperature after reacting 3-5 minutes with polymerizate
Obtain the collapse protection type solid polycarboxylic acid water reducing agent of effective solid content >=97%.
The step (1) is 1 with the unsaturated carboxylic acid class minor comonomer mass ratio being added in step (2):(2-5), it is entire anti-
Reaction temperature maintains between 65-80 DEG C during answering.
The above-mentioned collapse protection type solid polycarboxylic acid water reducing agent being prepared can add solid according to different construction demands
Powder is made in liquid, and powder, which can be directly incorporated into dry-mixed mortar, is uniformly mixed use, and tablet, which can be diluted with water, to be configured to respectively
The liquid water-reducing agent of kind concentration or solid content uses, and during form changes, will not reduce water-reducing agent script performance.
Beneficial effects of the present invention are：Collapse protection type solid polycarboxylic acid water reducing agent provided by the invention has height under low-dosage
Diminishing, the significant performance of high-thin arch dam and guarantor are collapsed, and stability is good, durability is long, solid forms can substantially reduce packing charges and
Transportation cost；Preparation method is easy to operate, takes that short energy consumption is low, reaction temperature is moderate, the reaction time is short, high conversion rate and green
It is pollution-free.
Specific implementation mode
The present invention provides a kind of collapse protection type solid polycarboxylic acid water reducing agents and preparation method thereof, with reference to specific embodiment party
The present invention is described further for formula.
Embodiment 1
Step 1：360g allyl alcohol polyethenoxy ethers (weight average molecular weight 1200), heating are added in four-hole boiling flask reaction kettle
Make its fusing to stirring at a temperature of 60 DEG C；
Step 2：14.7g maleic anhydrides are sequentially added in the melting allyl alcohol polyethenoxy ether polymeric monomer obtained to step 1
It with 1.75g isopropyl benzene hydroperoxides, stirs evenly, obtains mixed solution A；
Step 3：It is first added dropwise into step 2 mixed solution A by 2.0gN, N- diethylanilines and 1.2g mercaptopropionic acids and is lacked
The mixed solution B for measuring water composition, is then added dropwise the mixed solution being made of 58.8g maleic anhydrides and 91.8g acrylates
2.5g azo-bis-iso-dimethyls are added in C after 2 minutes, 2h, 1.5h is added dropwise in wherein mixed solution B, mixed solution C respectively, drip
Bi Baowen 1h are added, entire reaction process system temperature maintains between 65-70 DEG C；
Step 4：The potassium hydroxide aqueous solution neutralization reaction product that 9g mass fractions are 60% is added, after reacting 3-5 minutes,
Product is poured out while hot, is cooled down under room temperature, obtained solid is the collapse protection type solid polycarboxylic acids of effective solid content >=97%
Water-reducing agent.
Embodiment 2
Step 1：360g methyl allyl polyoxyethylene ethers (weight average molecular weight 2400) are added in four-hole boiling flask reaction kettle,
Stirring makes its fusing at a temperature of being heated to 65 DEG C；
Step 2：The melting methyl allyl polyoxyethylene ether polymeric monomer obtained to step 1 sequentially adds 5.4g metering systems
Acid and 1.4g tert-butyl hydroperoxide, stir evenly, obtain mixed solution A；
Step 3：It is first added dropwise into step 2 mixed solution A by 1.9g N, N- diethylanilines and 2.2g methacrylic sulfonic acids
The mixed solution B of sodium and a small amount of water composition, is then added dropwise by 26.83g methacrylic acids and 52.2g hydroxyethyl methacrylate groups
At mixed solution C, after 2 minutes be added 2.6g azobisisoheptonitrile, wherein mixed solution B, mixed solution C be added dropwise respectively 2h,
1.5h, is added dropwise heat preservation 1h, and entire reaction process system temperature maintains between 70-75 DEG C；
Step 4：6.5g triethanolamine neutralization reaction products are added, after reacting 3-5 minutes, while hot pour out product, room temperature
Under the conditions of it is cooling, obtained solid is the collapse protection type solid polycarboxylic acid water reducing agent of effective solid content >=97%.
Embodiment 3
Step 1：360g isoamyl alcohol polyoxyethylene ethers (weight average molecular weight 2400) are added in four-hole boiling flask reaction kettle, add
Heat to stirring at a temperature of 70 DEG C makes its fusing；
Step 2：6.75g acrylic acid is sequentially added in the melting isoamyl alcohol polyoxyethylene ether polymeric monomer obtained to step 1
It with 1.6g ammonium persulfates, stirs evenly, obtains mixed solution A；
Step 3：It is first added dropwise into step 2 mixed solution A by 1.9g N, N- diethylanilines and 1.2g mercaptopropionic acids and is lacked
The mixed solution B for measuring water composition, is then added dropwise the mixed solution C being made of 20.25g acrylic acid and 52.2g hydroxy-ethyl acrylates,
2.8g azodiisobutyronitriles are added after 2 minutes, wherein mixed solution B, mixed solution C is added dropwise 2h, 1.5h, guarantor is added dropwise respectively
Warm 1h, entire reaction process system temperature maintain between 75-80 DEG C；
Step 4：The sodium hydrate aqueous solution neutralization reaction product that 10g mass fractions are 60% is added, reacts 3-5 minutes
Afterwards, product is poured out while hot, is cooled down under room temperature, obtained solid is the poly- carboxylic of collapse protection type solid of effective solid content >=97%
Sour water-reducing agent.
Embodiment 4
Step 1：360g isoamyl alcohol polyoxyethylene ethers (weight average molecular weight 3000) are added in four-hole boiling flask reaction kettle, add
Heat to stirring at a temperature of 70 DEG C makes its fusing；
Step 2：9.75g itaconic acids are sequentially added in the melting isoamyl alcohol polyoxyethylene ether polymeric monomer obtained to step 1
It with 2.0g ammonium persulfates, stirs evenly, obtains mixed solution A；
Step 3：It is first added dropwise into step 2 mixed solution A by 2.5g N, accelerine and 1.1g mercaptopropionic acids and is lacked
The mixed solution B for measuring water composition, is then added dropwise the mixed solution C being made of 29.25g itaconic acids and 46.8g hydroxypropyl acrylates,
3.7g azodiisobutyronitriles are added after 2 minutes, wherein mixed solution B, mixed solution C is added dropwise 2h, 1.5h, guarantor is added dropwise respectively
Warm 1h, entire reaction process system temperature maintain between 75-80 DEG C；
Step 4：7.5g diethanol amine neutralization reaction products are added, after reacting 3-5 minutes, while hot pour out product, room temperature
Under the conditions of it is cooling, obtained solid is the collapse protection type solid polycarboxylic acid water reducing agent of effective solid content >=97%.
Embodiment 5
Step 1：360g isoamyl alcohol polyoxyethylene ethers (weight average molecular weight 4000) are added in four-hole boiling flask reaction kettle, add
Heat to stirring at a temperature of 75 DEG C makes its fusing；
Step 2：Sequentially added in the melting isoamyl alcohol polyoxyethylene ether polymeric monomer obtained to step 1 5.4g acrylic acid with
1.8g ammonium persulfates, stir evenly, and obtain mixed solution A；
Step 3：It is first added dropwise into step 2 mixed solution A by 2.0g N, accelerine and 1.0g mercaptopropionic acids and is lacked
The mixed solution B for measuring water composition, is then added dropwise the mixed solution C being made of 10.8g acrylic acid and 49.68g Isooctyl acrylate monomers,
3.5g azobisisoheptonitrile is added after 2 minutes, wherein mixed solution B, mixed solution C is added dropwise 2h, 1.5h, guarantor is added dropwise respectively
Warm 1h, entire reaction process system temperature maintain between 80-85 DEG C；
Step 4：6.0g ethanol amine neutralization reaction products are added, after reacting 3-5 minutes, while hot pour out product, room temperature item
Cooling under part, obtained solid is the collapse protection type solid polycarboxylic acid water reducing agent of effective solid content >=97%.
Experimental example 1
Using the collapse protection type solvent polycarboxylate water-reducer sample of commercially available better performances as reference examples, Examples 1 to 5 is prepared into
Collapse protection type solid polycarboxylic acid water reducing agent sample, the reference examples sample arrived carries out flowing degree of net paste of cement test, concrete performance is surveyed
Examination.
(1) experiment is with reference to GB8077/T-2000《Methods for testing uniformity of concrete admixture》, using reference cement, folding
Gu volume is 0.18%, the paste flowing degree of Examples 1 to 5 and reference examples in reference cement is measured；
(2) experiment is with reference to GB8076-2008《Concrete admixture》And GB/T50080-2002《Normal concrete mixture
Method for testing performance standard》, to sample obtained by Examples 1 to 5 and reference examples with certain domestic commercially available preferable poly- carboxylic of water reducing type
Sour high-performance water reducing agent presses 6:4 ratios are compounded, and testing concrete performance is carried out to it；Concrete mix (kg/cm3) is equal
For ordinary cement：Sand：Stone：Water=350:840:980:160 (mass ratioes), the solid volume of water-reducing agent folding is 0.18%, slump control
In 210 ± 10mm, the polycarboxylic acid slump retaining agent sample of the result and commercially available better performances tested is compared system, as a result such as table
Shown in 1：
1 pulp flowage results of property of table and concrete performance result
The collapse protection type solid polycarboxylic acid water reducing agent of Examples 1 to 5 synthesis is in use, by the solid polycarboxylic acid water reducing agent of sheet
It is dissolved in water as the liquid water-reducing agent of identical solid content, without apparent impurity after dissolving, and script property retention is constant；It can by table 1
To find out, the collapse protection type solid polycarboxylic acid water reducing agent of Examples 1 to 5 synthesis has under conditions of volume is 0.18% than city
Sell the lower slump-loss of product and slump holding capacity.
Claims (10)
1. a kind of collapse protection type solid polycarboxylic acid water reducing agent, which is characterized in that be calculated in mass percent, including 65%~85% insatiable hunger
With polyoxyethylene ether polymeric monomer, 0.3%~0.5% is organic and/or inorganic oxidizer, 0.4%~0.8% azo oxidant,
3.5%~14% unsaturated carboxylic acid class minor comonomer, 10%~18% unsaturated esters minor comonomer, 0.3%~0.7% organic reducing
Agent, 0.15%~0.5% chain-transferring agent, 1%~2.5% neutralizer, the sum of each component mass percent are equal to 100%.
2. collapse protection type solid polycarboxylic acid water reducing agent according to claim 1, which is characterized in that the unsaturation polyoxyethylene
Ether polymeric monomer be allyl alcohol polyethenoxy ether, isoamyl alcohol polyoxyethylene ether or methyl allyl polyoxyethylene ether in one kind or
A variety of, weight average molecular weight is 1200~4000.
3. collapse protection type solid polycarboxylic acid water reducing agent according to claim 1, which is characterized in that the oxidant is organic oxygen
One or more in agent, azo oxidant or inorganic oxidizer, wherein organic oxidizing agent is benzoyl peroxide, tertiary fourth
One or more in base hydrogen peroxide or isopropyl benzene hydroperoxide, azo oxidant is azodiisobutyronitrile, azo two is different
Heptonitrile, azo-bis-iso-dimethyl, inorganic oxidizer are persulfate.
4. collapse protection type solid polycarboxylic acid water reducing agent according to claim 1, which is characterized in that the unsaturated carboxylic acid class is small
Monomer is one or more in acrylic acid, methacrylic acid, maleic anhydride or itaconic acid.
5. collapse protection type solid polycarboxylic acid water reducing agent according to claim 1, which is characterized in that the small list of the unsaturation esters
Body be acrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxy propyl methacrylate,
It is one or more in hy-droxybutyl, Isooctyl acrylate monomer, isooctyl methacrylate or methyl methacrylate.
6. collapse protection type solid polycarboxylic acid water reducing agent according to claim 1, which is characterized in that the organic reducing agent is L-
Ascorbic acid, N, accelerine or N, it is one or more in N- diethylanilines.
7. collapse protection type solid polycarboxylic acid water reducing agent according to claim 1, which is characterized in that the chain-transferring agent is sulfydryl
It is one or more in acetic acid, mercaptopropionic acid or methylpropene sodium sulfonate.
8. collapse protection type solid polycarboxylic acid water reducing agent according to claim 1, which is characterized in that the neutralizer is hydroxide
It is one or more in potassium, sodium hydroxide, ethanol amine, diethanol amine or triethanolamine.
9. the preparation method of claim 1~8 any one of them collapse protection type solid polycarboxylic acid water reducing agent, which is characterized in that institute
The method of stating includes the following steps：
(1) unsaturated carboxylic acid class minor comonomer and organic or inorganic oxidant are added sequentially to the unsaturated polyoxyethylene ether of melting
In polymeric monomer, the solution A that is uniformly mixed；
(2) the mixed solution B being made of chain-transferring agent and organic reducing agent is added dropwise into solution A, is then added dropwise by unsaturated carboxylic
The mixed solution C of acids minor comonomer and unsaturated esters minor comonomer composition, after 2 minutes, is added azo oxidant, is added dropwise
Insulation reaction；
(3) it is added in neutralizer and polymerizate, collapse protection type solid polycarboxylic acid water reducing agent is obtained after cooling.
10. preparation method according to claim 9, which is characterized in that the step (1) is added not with step (2)
Saturated carboxylic acid class minor comonomer mass ratio is 1:(2-5).
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| CN111170671A (en) * | 2018-11-13 | 2020-05-19 | 北京市建筑工程研究院有限责任公司 | Preparation method of slump-retaining solid polycarboxylate superplasticizer |
| CN111592265A (en) * | 2019-02-21 | 2020-08-28 | 天水师范学院 | Method and device for preparing slump-retaining type polycarboxylate superplasticizer |
| CN111909327A (en) * | 2020-08-18 | 2020-11-10 | 衡阳市九州建材有限公司 | Production and preparation method of polycarboxylate superplasticizer powder |
| CN112851877A (en) * | 2020-12-31 | 2021-05-28 | 陕西友邦新材料科技有限公司 | Solid polycarboxylic acid water reducing agent and preparation method thereof |
| CN113201099A (en) * | 2021-03-16 | 2021-08-03 | 江苏超力建材科技有限公司 | Ultra-long slump retaining type polycarboxylate superplasticizer and preparation method thereof |
| CN113292687A (en) * | 2021-06-29 | 2021-08-24 | 安徽海螺新材料科技有限公司 | High-performance slump-retaining polycarboxylate superplasticizer and preparation method thereof |
| CN113429527A (en) * | 2021-04-28 | 2021-09-24 | 江苏万邦新材料科技有限公司 | Powdery polycarboxylate superplasticizer capable of rapidly dispersing dry-mixed mortar and preparation method thereof |
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| CN111170671A (en) * | 2018-11-13 | 2020-05-19 | 北京市建筑工程研究院有限责任公司 | Preparation method of slump-retaining solid polycarboxylate superplasticizer |
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| CN113201099A (en) * | 2021-03-16 | 2021-08-03 | 江苏超力建材科技有限公司 | Ultra-long slump retaining type polycarboxylate superplasticizer and preparation method thereof |
| CN113429527A (en) * | 2021-04-28 | 2021-09-24 | 江苏万邦新材料科技有限公司 | Powdery polycarboxylate superplasticizer capable of rapidly dispersing dry-mixed mortar and preparation method thereof |
| CN113292687A (en) * | 2021-06-29 | 2021-08-24 | 安徽海螺新材料科技有限公司 | High-performance slump-retaining polycarboxylate superplasticizer and preparation method thereof |
| CN113603839A (en) * | 2021-08-27 | 2021-11-05 | 贵州凯襄新材料有限公司 | Composite polycarboxylic acid water reducing agent and preparation method and application thereof |
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