CN108034027A - A kind of comb shape polycarboxylate water-reducer and preparation method thereof - Google Patents
A kind of comb shape polycarboxylate water-reducer and preparation method thereof Download PDFInfo
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- CN108034027A CN108034027A CN201711499367.2A CN201711499367A CN108034027A CN 108034027 A CN108034027 A CN 108034027A CN 201711499367 A CN201711499367 A CN 201711499367A CN 108034027 A CN108034027 A CN 108034027A
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- 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
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- 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
- C04B2103/302—Water reducers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
A kind of comb shape polycarboxylate water-reducer and preparation method thereof, the preparation method includes：(1) ethers polymeric monomer and esters polymeric monomer are placed in reaction vessel, heating stirs evenly；(2) by (methyl) acrylic acid, initiator and small molecule nitrogen containing monomer M1, small molecule sulfur-bearing monomer M2, is added dropwise in reaction vessel, temperature reaction；(3) after the solution of step (2) is kept the temperature, it is 7 to add lye adjustment pH value, is cooled to room temperature.This water-reducing agent has the excellent slump and divergence.
Description
Technical field
The present invention relates to polycarboxylate water-reducer field.
Background technology
Investigated from long side chain polymeric monomer, the high-efficiency water-reducing agent of poly-carboxylic acid applied currently on the market is divided into three classes, with APEG
(allyl polyglycol) is the polyether-type high efficiency water reducing agent of long side chain；It is the poly- of long side chain with MPEG (methoxy poly (ethylene glycol))
Ester-type efficient water-reducing agent；The third is to obtain carboxylic acid using two class polyether macromonomer of APEG and MPEG or derivatives thereof polymerization at the same time
High efficiency water reducing agent.
For Molecular Design feature, star polycarboxylate water-reducer and comb shape polycarboxylate water-reducer can be divided into.This
Kind branch bifurcation structure, can give full play to space steric effect, effectively prevent water-reducing agent macromolecular by hydrolysis product of cement bag
Consumption is wrapped up in, more preferable effect can be shown in terms of cement aggregation is prevented, improve cement mortar stability.
CN101602834A discloses a kind of preparation method of polycarboxylic acid concrete dispersers, comprises the following steps：(1)
Free radicals copolymerization reaction, monomer A and monomer C according to 1.01: 1-1.5: 1 molar ratio, under conditions of using monomer B as solvent
Free radicals copolymerization reaction is carried out, wherein monomer A is (alkyl) vinyl alkyl acid esters CH2=C (R1) OC (=O) (CH2) nCH3,
R1 represents hydrogen atom or methyl, and n is the number of methylene, is 0-2, monomer B is monoalkoxy polyalkylene glycol ethers HO-
(CH2-CH2-O) p- (CH (CH3)-CH2-O) q-R2, R2 represents the alkyl of 1-20 carbon atom, and p represents the addition of ethylene oxide
Quantity, is 1-200, and q represents the addition quantity of propylene oxide, is 0-25；Monomer C is maleic anhydride；Monomer B's and monomer C rubs
Your ratio is 0.1: 1-1: 1, the reaction of (2) graft esterification, polymer heating made from step 1 is esterified, to be introduced by monomer C
Anhydride group on grafted monomers B；(3) after esterification, diluent is added to reaction product, and add alkaline matter tune
Whole pH value is 6-8.This method avoid volatile organic solvent, technique are simple.
CN103482897A discloses a kind of block polycarboxylic acid concrete high efficiency water reducing agent and its system with ordered structure
Preparation Method, comprises the following steps：1) after monomer A is sufficiently mixed with catalyst, ligand, solvent, it is passed through nitrogen N2By O in solution2Row
Go out, then initiator is disposably added rapidly in above-mentioned solution, in N2The lower progress atom transfer controllable free-radical of protection gathers
Reaction is closed, its reaction temperature is 30-90 DEG C, reaction time 0.5-12h, obtains homopolymer macromolecular solution, the molecule of monomer A
Structure meets general formula 1. CH2=C (R1)COO(AO)nR2, 2. the molecular structure of homopolymer meets general formulaIn formula, R1=CH3Or H, R2The alkyl of=H or 1-4 carbon atom；AO is the oxygen of 2-4 carbon atom
Change the mixture of alkenyl or two or more this oxyalkylene groups, n is the average addition molal quantity of AO, it is whole for 5-50's
Number.2) the homopolymer macromolecular solution for preparing step 1 is added in monomer B, and copolymerization, generation are mixed under conditions of nitrogen protection
Block polycarboxylic acids, monomer B are unsaturated carboxylic acid, its structure meets general formula 3. CH2=C (R3)COOM；The constructor of block polycarboxylic acids
Close general formula 4.The document thinks that the molecular weight of polymer is in single dispersing, is mixed in very low
In the range of amount, i.e. the 0.08-0.2% of cementitious material, you can to improve the mobility of concrete.
CN105754045A discloses a kind of silane coupler modified polycarboxylate water-reducer and preparation method thereof：1) by 350
The polyether macromonomer of part is placed in reaction vessel, after 5-15 parts of acrylic acid of addition stir evenly, adds 0.5-5 parts of silicon containing double bond
Alkane coupling agent, is stirred to solution without obvious bulk or sheet material；The polyether macromonomer for methyl allyl polyoxyethylene ether,
The one or more of isoamyl alcohol polyoxyethylene ether, modified isoamyl alcohol polyoxyethylene ether；2) solution obtained by step 1), is being stirred
Mix down and 2.5-6 parts of oxidants, 2.5-3.5 parts of initiators and 20-37 parts of minor comonomers are added dropwise successively, minor comonomer solution time for adding is
1-4h；The minor comonomer is acrylic acid, methylpropene sodium sulfonate, 2- acrylamide-2-methyl propane sulfonics, itaconic acid, rich horse
Acid, the one or more of maleic anhydride；3) after the solution curing 1-2h of step 2), add liquid caustic soda and neutralize, stablize pH value 6, then
1-3 parts are added to stir evenly without double bond silane coupling agent.This application file is contained by being introduced in polycarboxylic acids molecular backbone
The functional group of siloxane structure, provides and a kind of is chemically bonded with gelling material particles for the side chain of comb shape polycarboxylate water-reducer
The anchoring ability of strong interaction, the increase of the anchoring ability, can promote water-reducing agent adaptability, slump retaining to significantly increase, and one
Determine to extend use of the water-reducing agent in mineral micro powder field of dispersions in degree.
CN106146859A is related to a kind of four arm high-efficiency water-reducing agent of poly-carboxylic acid and preparation method thereof, free using atom transfer
The condition and step of high-efficiency polycarboxylic acid water reducer with excellent anti-mud performance of the method synthesis with four arm configurations of base polymerization
It is as follows：(1) in the single port bottle of 50mL, add a certain amount of tetrahydroxylic alcohol, 0 DEG C be cooled to through ice-water bath, by dropping funel by
Drop instills suitable alpha-brominated isobutyl acylbromide, after being added dropwise to complete, is warming up to room temperature, reacts 16h, and reaction terminates, and it is dry to carry out separation
The dry product that obtains is the small molecule initiator with four-functional group；(2) it is obtained that step (1) is separately added into 50mL single port bottles
Small molecule initiator, monomer A, ligand, stirring and dissolving, under nitrogen protection, completes freezing one three times and vacuumizes a course of defrosting,
Catalyst is added, stirs evenly and is repeated a further three times freezing and one vacuumizes a course of defrosting, after defrosting, be warming up to certain temperature stirring
18h；After reaction, separated, polymerizate I is dried to obtain under vacuum condition；(3) the obtained polymerization of step (2) is utilized
Product I continues to trigger atom transfer radical polymerization as macromole evocating agent：Add polymerizate I, monomer B, ligand, molten
Agent, stirring and dissolving, under nitrogen protection, completes freezing one three times and vacuumizes a course of defrosting, add catalyst, stir evenly again
Freezing one vacuumizes a defrosting in triplicate, after defrosting, is placed in 85 DEG C of oil baths and stirs 18h；After reaction, separated,
Polymerizate II is dried to obtain under vacuum condition, polymerizate II is the AB type diblock copolymers with four arm configurations；(4) water
Solution reaction：Polymerizate II made from step (3) is dissolved in acid solution, stirs 10h at room temperature, after reaction, will be anti-
Liquid concentrated by rotary evaporation is answered, product precipitates acquisition in absolute methanol, obtains having four after white precipitate is dried under vacuum
The polycarboxylate water-reducer of arm configuration.Compared with traditional comb shape polycarboxylate water-reducer, polycarboxylic acids can be solved to a certain extent and is subtracted
The problem of aqua is more sensitive to soil in concrete and causes hydraulic performance decline because of soil presence, it is higher to be particularly suitable for clay content
Concrete.
To sum up, the design either in structure, or polymerization, the selection of polymerized monomer, new polycarboxylic acid water reducer
All the time it is the hot spot of a research, for the control of technological process, the pursuit of diminishing efficiency never changes.
The content of the invention
The present invention is it has been unexpectedly found that nitrogenous by ethers polymeric monomer, esters polymeric monomer, (methyl) acrylic acid, small molecule
Monomer M1, the thin shape polycarboxylate water-reducer that small molecule sulfur-bearing monomer M2 is prepared be used for concrete in enable to the slump and
Autgmentability improves at the same time.
Therefore, the application provides a kind of thin shape polycarboxylate water-reducer first, it is by ethers polymeric monomer, esters polymeric monomer, (first
Base) acrylic acid, small molecule nitrogen containing monomer M1, small molecule sulfur-bearing monomer M2 are prepared.
The present invention provides a kind of preparation method of comb shape polycarboxylate water-reducer, comprises the following steps that：(1) by ethers polymeric monomer
It is placed in esters polymeric monomer in reaction vessel, heating stirs evenly；(2) it is (methyl) acrylic acid, initiator and small molecule is nitrogenous
Monomer M1, small molecule sulfur-bearing monomer M2, is added dropwise in reaction vessel, temperature reaction；(3) after the solution of step (2) is kept the temperature, add
Enter lye and adjust pH value to 6-8, preferably 7, be cooled to room temperature.The ethers polymeric monomer is methyl allyl polyoxyethylene ether, different
Pentenol polyoxyethylene ether, the one or more being modified in isoamyl alcohol polyoxyethylene ether；Esters polymeric monomer is methacrylic acid
One or both of poly glycol monomethyl ether ester (MPEGMA), dipolyethylene glycol maleate.
Small molecule nitrogen containing monomer M1 is N- vinyl formamides, N- vinyl acetamides, N- vinyl propionamides, N- hydroxyl first
Base acrylamide, the one or more of N methacrylamide, are preferably N hydroxymethyl acrylamide.Small molecule sulfur-bearing monomer M2
For methylpropene sodium sulfonate, the one or more in 2- acrylamide-2-methyl propane sulfonics.
Ethers polymeric monomer, esters polymeric monomer, (methyl) acrylic acid, small molecule nitrogen containing monomer M1, small molecule sulfur-bearing monomer M2
Molar ratio be 1: 0.8-1.2: 2-5: 1.5-3.5: 3-5, preferably molar ratio be 1: 1: 3: 2: 3.Initiator amount is monomer
The 1-3wt% of total dosage, initiator are ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate etc..
Ethers polymeric monomer, the molecular weight of esters polymeric monomer is 500-1000.
Lye is NaOH solution, KOH solution, ethylenediamine or triethanolamine.
Preferably, (methyl) acrylic acid, the time for adding of small molecule nitrogen containing monomer M1, small molecule sulfur-bearing monomer M2 are 3-
4h, the time for adding of initiator is 3.5-4.5h, it is further preferred that monomer is dripped prior to initiator.
Optionally, chain-transferring agent is added in step (2), selected from thioacetic acid, mercaptopropionic acid.
Preferably, step (1) is warming up to 40-50 DEG C, and step (2) is warming up to 70-80 DEG C.
Preferably, the reaction time of step (2) is 1-2h, and the soaking time of step (3) is 1-2h.
Preferably, after reaction, it is diluted with water to reaction product.
Gained water-reducing agent of the invention has the excellent slump/divergence.
Embodiment
Embodiment 1
(1) ethers polymeric monomer TPEG and esters polymeric monomer MPEGMA are placed in reaction vessel, it is equal is warming up to 40 DEG C of stirrings
It is even；(2) by acrylic acid, initiator potassium persulfate and small molecule nitrogen containing monomer M1, small molecule sulfur-bearing monomer M2, is added dropwise to reaction and holds
In device, 70 DEG C of reaction 1.5h are warming up to, the wherein monomer dropping time is 3h, and initiator time for adding is 3.5h, and monomer is prior to drawing
Hair agent drips；(3) by after the solution insulation 1h of step (2), it is 7 to add KOH solution adjustment pH value, is cooled to room temperature.M1 is
N- vinyl formamides.M2 is methylpropene sodium sulfonate.Ethers polymeric monomer, esters polymeric monomer, acrylic acid, small molecule nitrogen containing monomer
The molar ratio of M1, small molecule sulfur-bearing monomer M2 are 1: 1: 3: 2: 3.
Embodiment 2
M1 is N hydroxymethyl acrylamide, the other the same as in Example 1.
Embodiment 3
Ethers polymeric monomer, esters polymeric monomer, acrylic acid, small molecule nitrogen containing monomer M1, mole of small molecule sulfur-bearing monomer M2
Than for 1: 1: 2: 2: 3, the other the same as in Example 1.
Embodiment 4
Ethers polymeric monomer, esters polymeric monomer, acrylic acid, small molecule nitrogen containing monomer M1, mole of small molecule sulfur-bearing monomer M2
Than for 1: 1: 3: 1.5: 3, the other the same as in Example 1.
Embodiment 5
Ethers polymeric monomer, esters polymeric monomer, acrylic acid, small molecule nitrogen containing monomer M1, mole of small molecule sulfur-bearing monomer M2
Than for 1: 1: 3: 3.5: 3, the other the same as in Example 1.
Comparative example 1
All using ethers polymeric monomer, the other the same as in Example 1.
Comparative example 2
All using esters polymeric monomer, the other the same as in Example 1.
Comparative example 3
M1 is replaced with into M2, i.e., using only M2 monomers, the other the same as in Example 1.
Comparative example 4
M2 is replaced with into M1, i.e., using only M1 monomers, the other the same as in Example 1.
Comparative example 5
M1, the other the same as in Example 1 are replaced with acrylamide.
Experiment determines divergence and the slump such as institute of table 1 that each embodiment and comparative example are shown in concrete system
Show.The test uses GB/T 50080-2016.
1 concrete flowability energy result of table
Claims (10)
1. a kind of thin shape polycarboxylate water-reducer, it is nitrogenous by ethers polymeric monomer, esters polymeric monomer, (methyl) acrylic acid, small molecule
Monomer M1, small molecule sulfur-bearing monomer M2 are prepared.
2. a kind of preparation method of comb shape polycarboxylate water-reducer, comprises the following steps that：
(1) ethers polymeric monomer and esters polymeric monomer are placed in reaction vessel, heating stirs evenly；
(2) by (methyl) acrylic acid, initiator and small molecule nitrogen containing monomer M1, small molecule sulfur-bearing monomer M2, is added dropwise to reaction and holds
In device, temperature reaction；
(3) after the solution of step (2) is kept the temperature, add lye and adjust pH value to 6-8, be cooled to room temperature；
The ethers polymeric monomer is methyl allyl polyoxyethylene ether, and isoamyl alcohol polyoxyethylene ether, is modified prenol polyoxy
The one or more of vinethene；Esters polymeric monomer is Methylacrylic acid polyethylene glycol single armor ether ester (MPEGMA), maleic acid double focusing
The one or two of glycol monoethyl ether ester；
Small molecule nitrogen containing monomer M1 is N- vinyl formamides, N- vinyl acetamides, N- vinyl propionamides, N- methylols third
Acrylamide, the one or more of N methacrylamide, are preferably N hydroxymethyl acrylamide；
Small molecule sulfur-bearing monomer M2 is methylpropene sodium sulfonate, the one or more in 2- acrylamide-2-methyl propane sulfonics；
Esters polymeric monomer, (methyl) acrylic acid, the molar ratio of small molecule nitrogen containing monomer M1, small molecule sulfur-bearing monomer M2 are 1: 0.8-
1.2∶2-5∶1.5-3.5∶3-5。
3. the method as described in claim 1, it is characterised in that：Initiator amount be the total dosage of monomer 1-3wt%, initiator
For ammonium persulfate, potassium peroxydisulfate or sodium peroxydisulfate, the lye are NaOH solution, KOH solution, ethylenediamine or triethanolamine.
4. the method as described in claim 1, it is characterised in that：Ethers polymeric monomer, the molecular weight of esters polymeric monomer is 500-
1000。
5. the method as described in claim 1, it is characterised in that：(methyl) acrylic acid, small molecule nitrogen containing monomer M1, small molecule contain
The time for adding of sulphur monomer M2 is 3-4h, and the time for adding of initiator is 3.5-4.5h, it is further preferred that monomer is prior to triggering
Agent drips.
6. the method as described in claim 1, it is characterised in that：Chain-transferring agent is added in step (2), selected from thioacetic acid, mercapto
Base propionic acid.
7. the method as described in claim 1, it is characterised in that：Step (1) is warming up to 40-50 DEG C, and step (2) is warming up to 70-
80℃。
8. the method as described in claim 1, it is characterised in that：The reaction time of step (2) is 1-2h, the insulation of step (3)
Time is 1-2h.
9. the method as described in claim 1, it is characterised in that：After reaction, it is diluted with water to reaction product.
10. the comb shape polycarboxylate water-reducer being prepared according to claim 1-9 either method.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111777350A (en) * | 2020-05-28 | 2020-10-16 | 滕宏军 | High-performance polycarboxylate superplasticizer |
| WO2022134317A1 (en) * | 2020-12-22 | 2022-06-30 | 科之杰新材料集团有限公司 | Corrosion-resistant ether polycarboxylate water reducer and preparation method therefor |
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| CN101708973A (en) * | 2009-11-04 | 2010-05-19 | 山东华伟银凯建材有限公司 | Water-plastic retaining polycarboxylic acid water reducer and method for preparing same |
| CN102503226A (en) * | 2011-10-19 | 2012-06-20 | 中建商品混凝土有限公司 | High slump retaining type polycarboxylic acid water reducing agent with sustained-release effect and preparation method thereof |
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| CN101708973A (en) * | 2009-11-04 | 2010-05-19 | 山东华伟银凯建材有限公司 | Water-plastic retaining polycarboxylic acid water reducer and method for preparing same |
| CN102503226A (en) * | 2011-10-19 | 2012-06-20 | 中建商品混凝土有限公司 | High slump retaining type polycarboxylic acid water reducing agent with sustained-release effect and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111777350A (en) * | 2020-05-28 | 2020-10-16 | 滕宏军 | High-performance polycarboxylate superplasticizer |
| WO2022134317A1 (en) * | 2020-12-22 | 2022-06-30 | 科之杰新材料集团有限公司 | Corrosion-resistant ether polycarboxylate water reducer and preparation method therefor |
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