CN106519142A - Mud resistant type polycarboxylate superplasticizer with controllable molecular structure and preparation method of mud resistant type polycarboxylate superplasticizer - Google Patents
Mud resistant type polycarboxylate superplasticizer with controllable molecular structure and preparation method of mud resistant type polycarboxylate superplasticizer Download PDFInfo
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- CN106519142A CN106519142A CN201611020577.4A CN201611020577A CN106519142A CN 106519142 A CN106519142 A CN 106519142A CN 201611020577 A CN201611020577 A CN 201611020577A CN 106519142 A CN106519142 A CN 106519142A
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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
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2605—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
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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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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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
- 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
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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
- C08F2438/00—Living radical polymerisation
- C08F2438/01—Atom Transfer Radical Polymerization [ATRP] or reverse ATRP
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Abstract
The invention discloses a mud resistant type polycarboxylate superplasticizer with a controllable molecular structure and a preparation method of the mud resistant type polycarboxylate superplasticizer. A star-shaped initiator is obtained from cyclodextrin through esterification to initiate atom transfer radical polymerization of (methyl) polyethylene glycol acrylate and (methyl) sodium acrylate, a copolymer of (methyl) polyethylene glycol acrylate and (methyl) sodium acrylate is obtained and further processed, and the polycarboxylate superplasticizer with the solid content being 20% is obtained. The prepared polycarboxylate superplasticizer has the multiple advantages of controllable molecular structure, high water-reducing rate, good liquidity and dispersity, high soil adaptability and the like, can meet higher construction requirements and has broad application prospect.
Description
Technical field
A kind of a kind of the present invention relates to polycarboxylate water-reducer and preparation method thereof, more particularly to the anti-mud that molecular structure is controllable
Type polycarboxylate water-reducer and preparation method thereof, belongs to concrete additives in building materials technical field.
Background technology
Polycarboxylate water-reducer as third generation high performance concrete water reducer, with volume it is low, water-reducing rate is high, function of slump protection
The outstanding advantages such as good, molecular structure adjustability is strong, high performance potentiality are big, have been successfully applied to high-speed railway, bridge, tunnel at present
In a series of Important Projects such as road.But, high-efficiency water-reducing agent of poly-carboxylic acid also runs into many technical barriers in actual applications, such as right
The adaptability of cement/admixture, the sensitivity to water reducer consumption and water consumption, and the aspect such as clay content of gathering materials, temperature
Affect etc..
Numerous studies and engineering practice show, when clay content of gathering materials is higher, concrete performance can be had a negative impact,
Being mainly manifested in reduces the diminishing dispersive property of water reducer, affects the workability of concrete mix.For avoiding clay content of gathering materials
The negative effect that height is caused to concrete, at present conventional solution mainly gather materials high to clay content are rinsed or excess
Admixture water reducer.Although gather materials higher to clay content is rinsed can fundamentally solve shadow of the soil to concrete performance
Aggregate grading can be damaged when ringing, but rinsing, and flushing can also increase operation, affect the construction period.Though super mix water reducer in certain journey
The negative effect that clay content height is caused is solved on degree, but is well constructed sometimes for ensureing that concrete mix still has in a short time
Performance, super water reducer of mixing would generally make concrete bleeding and isolation initially occur, and super mix water reducer and can increase cost.Sandstone material
Mud in material is mainly montmorillonite soil and Kaolin, with higher specific surface area and layer structure so as to have precedence over cement suction
Attached water reducer and Free water, so as to cause that the slump-loss of concrete is big, rheological characteristic is poor, durability and intensity declines etc. and to ask
Topic.
Due to the designability of polycarboxylate water-reducer molecule structure it is strong, by the optimum organization control of difference in functionality construction unit
Backbone polymerization degree processed, side chain lengths, functional group's species prepare high-performance diminishing realizing the high performance of polycarboxylate water-reducer
Agent, can solve the problems, such as site operation.Polycarboxylate water-reducer with comb-type structure, is with polyacrylic acid as main chain, on main chain
It is grafted with the adsorption groups such as the side bases such as carboxyl and Polyethylene oxide and side chain, carboxyl to adsorb in hydrated cementitious particle surface, shape
Into there is certain thickness polymer adsorbed layers；Polyoxyethylene chain can then provide sterically hindered.When cement granules are close to each other,
The sterically hindered effect provided by side chain can prevent being close between cement granules and reunite, so as to play dispersion cement
Grain, the effect for improving mobility.Therefore the multifunctionality of the polycarboxylate water-reducer of different structure, high reaction activity and larger sky
Between volume, increasingly obtain the attention of researcher and application person.Construct the diminishing agent molecule of spatial configuration or space is bigger
Group or segment introduce polycarboxylate water-reducer and are expected to make the dispersion effect of water reducer more excellent.
Star water reducer is the class star polymerization with polyfunctional group Organic substance as core, with polycarboxylic acids linear macromolecule as arm
Thing, this kind of polymer have the property of star-like macromolecules and the property of linear polymer molecules concurrently.Due to terminal hydrophyllic group and highly -branched
The presence of structure, star polymer is compared with linear polymer with good dissolubility；The intramolecular of star polymer contains
Substantial amounts of short-chain branch, intermolecular winding are few, and intermolecular force is little, and its intrinsic viscosity is much smaller than linear molecule；Star polymer
It is with three-dimensional globular structure and intermolecular without winding, therefore linear polymer of the spatial volume relatively with molecular weight is bigger, with more
Strong sterically hindered effect, therefore star structure water reducer has higher adaptability and cement dispersibility.Chinese patent
CN102887979A reports a kind of method of synthesizing polycarboxylic acid concrete high-performance water reducing agent, using polyhydric alcohol and (methyl)
Acrylic acid prepares star polymerizable activity end by esterification, then with unsaturated polyoxyethylene ether, molecular weight regulator, insatiable hunger
It is obtained by Raolical polymerizable under initiator effect with carboxylic acid monomer.Chinese patent CN102002134B reports one kind
Dissaving polymer and hyperbranched type poly carboxylic acid series water reducer and preparation method and application, with acrylic acid methyl ester., ethanolamine, 2-
Bromoethanol, malonic acid are Material synthesis bromine end group hyperbranched poly (amine -ester) molecule, are reacted acrylic acid, single methoxy using ATRP
Base allyl polyglycol is grafted on poly- (amine -ester) molecule, obtains dissaving polymer.Chinese patent CN105669913A is public
A kind of preparation method of the controllable star polycarboxylate water-reducer of molecular structure is opened, polyol polyhydroxylated molecule will have been contained anti-with halogen acyl halide
Atom transfer radical polymerization (ATRP) initiator should be prepared, further causes unsaturated acids minor comonomer and unsaturated polymeric monomer
ATRP polymerization.Chinese patent CN105669912A reports a kind of star polycarboxylate water-reducer of knowing clearly, and will divide containing many alcoholic extract hydroxyl groups
It is sub that reversible addition-fracture transfer polymerization (RAFT) chain-transferring agent of star is prepared by esterification with carboxylic chain-transferring agent,
Obtained by causing the RAFT polymerizations of unsaturated acids minor comonomer and unsaturated polymeric monomer.
Sterically hindered larger molecule or group are introduced into polycarboxylate water-reducer molecule and can preferably solve polycarboxylic acids diminishing
Adaptability problem of the agent to soil.Cyclodextrin (CD) is direct-connected starch in the cyclodextrin glucose group-transfer produced by bacillus cereuss
A series of general name of the cyclic oligosaccharides generated under enzyme effect, usually contains 6～12 D- glucopyranose units, wherein studies
It is more and have important practical usage is the molecule containing 6,7,8 glucose units, be referred to as α-CD, β-CD, γ-
CD, and the application of β-CD is more extensive.β-CD molecular structures are tapered slightly, and cone has great amount of hydroxy group and aobvious hydrophilic outside chamber, cone
Intracavity is in hydrophobicity, and its molecular weight is 1135, and a diameter of 0.8nm in space, cavity depth are about 0.7～0.8nm, with significant
Space steric effect.Cyclodextrin is introduced in polycarboxylate water-reducer molecule as functional groups, can give polycarboxylate water-reducer good
Good anti-mud.Chinese patent CN104086114B reports a kind of concrete admixture based on cyclodextrin functional group, leads to
Cross cyclodextrin, the polyethers of the polyester containing unsaturated double-bond or unsaturated double-bond and not of the replacement of monomethacrylate glycidyl ether
Unsaturated carboxylic monomer copolymerization is obtained.Chinese patent CN102153711B reports a kind of slow-setting polycarboxylic acid water reducing agent, by allyl
The grafting of base Sulfonateses monomer, acrylic monomer, methacrylic acid MPEG-550 ester polymeric monomer and maleic anhydride
β-CD polymeric monomers are obtained by Raolical polymerizable.Chinese patent CN102229479B reports the diminishing of polycarboxylic acids containing water-retaining type
Agent, is obtained by aqueous free radical copolymerization using allyl polyglycol, acrylic acid, methylpropene sodium sulfonate etc..It is Chinese special
Sharp CN103333300B reports a kind of polycarboxylate water-reducer of stelliform connection topology configuration, star cyclodextrin prepared by esterification
Acrylate, acrylic acid, monomethyl polyethylene glycol acrylate ester and methylpropene sodium sulfonate are by free-radical polymerized and obtain.It is above-mentioned
In report, the monomer reaction active site containing cyclodextrin is more, and each reflecting point can participate in Raolical polymerizable, be easily caused poly-
Product crosslinking is closed, and polycarboxylic acids molecule is made without dispersive property.Chinese patent CN104817663A discloses one kind and can suppress montmorillonite
The polycarboxylate water-reducer of side effect, polymerized monomer are a kind of functional monomer containing β-CD, and its significant architectural feature is only
There is a polymerization activity point, the water reducer prepared using the monomer has linear structure, β-CD are located at polymer lateral chain, can
Avoid the crosslinking of polymerizate.
To sum up, the polycarboxylate water-reducer of most of patent descriptions is mainly changed by transformationreation raw material or process conditions at present
Kind performance, seldom having change polymer architecture by Molecular Design or realize its excellent application using new polymerization
Performance.Synthesis based on current polycarboxylate water-reducer mainly adopt radical polymerization, the molecular weight distribution for obtaining compared with
Width, and activity polymerizating technology has the advantages that molecular structure can be designed, molecular weight is controllable and narrow molecular weight distribution, if by activity poly
Conjunction technology is applied to the preparation of polycarboxylate water-reducer, has important meaning for the controllable polycarboxylate water-reducer of molecular structure is constructed
Justice.Jing is retrieved, and patent CN103482897A, patent CN102002134B and patent CN105669913A are reported using ATRP skills
Art prepares polycarboxylate water-reducer, and patent CN105669912A and patent CN105153375A are reported to be prepared using RAFT polymerizations and gathered
Carboxylic acid water reducer.But there is not yet with cyclodextrin and its derivant as initiator, polycarboxylic acids diminishing is prepared using activity polymerizating technology
The report of agent.
The content of the invention
For the deficiencies in the prior art, the problem to be solved in the present invention is to provide a kind of controllable anti-chamotte mould of molecular structure and gathers
Carboxylic acid water reducer and preparation method thereof.
The controllable anti-chamotte mould polycarboxylate water-reducer of molecular structure described in this patent, it is characterised in that：The water reducer is
The compound of general structure shown in formula (I)：
Wherein：
R1, R2, R3Or R4=H or CH3；
M, n represent the degree of polymerization：M=10～100, n=9～65；X, y represent the molar percentage of monomer：X=20～
40%, y=60～80%.
The preparation method of the controllable anti-chamotte mould polycarboxylate water-reducer of molecular structure of the present invention, is to be esterified beta-schardinger dextrin-
Star initiator is obtained, causes the atom transferred free radical of (methyl) polyalkylene glycol acrylate ester and (methyl) tert-butyl acrylate
Polymerization, further hydrolysis obtain (methyl) polyalkylene glycol acrylate ester and (methyl) acrylic acid copolymer.Its concrete steps is such as
Under：
(1) preparation of star initiator：Beta-schardinger dextrin-and halogen acyl halide are mixed under ice-water bath react 60～
After 120min, reaction 24 hours is stirred at room temperature, reactant liquor is precipitated in petroleum ether after terminating, obtains final product star and draw by reaction
Agent is sent out, wherein beta-schardinger dextrin-is 1 with the mol ratio of halogen acyl halide:(7～15), halogen acyl halide are 2- bromine isobutyl acylbromides, 2- bromines third
Acylbromide or bromoacetyl bromide；
(2) preparation of the controllable anti-chamotte mould polycarboxylate water-reducer of molecular structure：Star initiator that step (1) is obtained with
(methyl) polyalkylene glycol acrylate ester, (methyl) acrylic acid mixed dissolution, add sodium hydroxide solution to adjust pH7～8, after deoxygenation
Catalyst and part is added, under nitrogen atmosphere, 60～90 DEG C of 5～10h of reaction, dialysis removes the monomer of residual and other are miscellaneous
Matter, obtains the copolymer of star (methyl) polyalkylene glycol acrylate ester and (methyl) sodium acrylate, and adjusts and obtain solid content and be
20%, that is, the controllable anti-chamotte mould polycarboxylate water-reducer of molecular structure is obtained；
Wherein：Described star initiator, (methyl) polyalkylene glycol acrylate ester, (methyl) acrylic acid, catalyst, part
Mol ratio be mol ratio be 1:(30～150):(100～500):(1～10):(1～10)；The catalyst is CuBr
(cuprous bromide) or CuCl；The part is PMDETA (pentamethyl-diethylenetriamine), Me6TREN (three [2- (dimethylamino) second
Base] amine) or bpy (bipyridyl).
In the preparation method of the controllable anti-chamotte mould polycarboxylate water-reducer of above-mentioned molecular structure：Step (2) star is caused
The mol ratio that agent, (methyl) polyalkylene glycol acrylate ester, (methyl) acrylic acid, catalyst, the mol ratio of part are is preferably 1:
(30～80):(100～150):7:7.Further, the star initiator, (methyl) polyalkylene glycol acrylate ester, (methyl)
The mol ratio that acrylic acid, catalyst, the mol ratio of part are is most preferably 1:35:105:7:7.
In the preparation method of the controllable anti-chamotte mould polycarboxylate water-reducer of above-mentioned molecular structure：Step (2) catalyst is excellent
Select CuBr (cuprous bromide)；The part is preferred PMDETA (pentamethyl-diethylenetriamine).
In the preparation method of the controllable anti-chamotte mould polycarboxylate water-reducer of above-mentioned molecular structure：Described (methyl) acrylic acid gathers
The molecular weight of glycol ester is preferably 500～3000g/mol.
The present invention prepares the controllable poly- carboxylic of molecular structure with cyclodextrin esterification products as initiator using activity polymerizating technology
A kind of acids water reducer, there is provided new method for preparing polycarboxylate water-reducer, while give polycarboxylate water-reducer new function.
The invention has the beneficial effects as follows：
1. the present invention adopts ATRP technologies, and the polycarboxylate water-reducer compound with regular structure for obtaining, molecular weight are controllable, molecular weight distribution
It is narrow；
2. star polycarboxylate water-reducer can be effectively increased absorbability of the diminishing agent molecule to cement granules, at the same with compared with
Strong affinity, dispersibility are higher, improve the mobility of concrete；
3. with beta-schardinger dextrin-as core, polycarboxylic acids linear molecule is arm to star water reducer, and its viscosity is far below same molecular amount
Linear molecule, intermolecular force is little, with higher adaptability and dispersibility；
4., with polyhydric alcohol small molecular phase ratio, beta-schardinger dextrin-itself has larger space steric hindrance, therefore with beta-schardinger dextrin-as core
Diminishing agent molecule hardly enter the interlayer of soil, effectively suppress the adsorption of the polycarboxylate water-reducer of soil pair, improve
Adaptability of the water reducer to soil.
The anti-chamotte mould polycarboxylate water-reducer that the present invention is provided has that molecular structure is controllable, water-reducing rate is high, mobility and dispersion
Property is good, to various advantages such as soil strong adaptability, higher construction requirement can be met, had a good application prospect.
Specific embodiment
Below by the specific embodiment for being given it will be further appreciated that the present invention, but following embodiments are not to this
The restriction of bright protection domain.
Embodiment 1：
(1) preparation of star initiator
Beta-schardinger dextrin-(11.35g, 0.01mo) is dissolved in into 60mL anhydrous in DMF (DMF), is added to
In 100mL there-necked flasks, triethylamine (7.07g, 0.07mol) is subsequently adding as proton absorbent.In ice-water bath under nitrogen atmosphere
Middle stirring 0.5h.2- bromine isobutyl acylbromides (16.1g, 0.07mol) are dissolved in into 10mL dry DMFs, constant pressure funnel is subsequently adding
In, dropwise it is added drop-wise in there-necked flask.After completion of dropping, in room temperature reaction 24h under nitrogen atmosphere.React reactant liquor mistake after terminating
Filter, filtrate is placed in separatory funnel, is first washed the triethylamine salt for removing residual with saturated sodium bicarbonate solution, then is used deionization
Neutrality is washed to, and precipitates, filter, wash, dissolve, sink again in cold diethyl ether being dropped to after rotating the most of solvent of removing after being dried
Form sediment, refilter, washing again, in triplicate, dried in vacuum overnight at 50 DEG C obtains the star initiator (labelling containing end group bromine
For SI1).
(2) preparation of star polycarboxylate water-reducer (the controllable anti-chamotte mould polycarboxylate water-reducer of molecular structure) SP1
The star initiator (SI1) that step (1) is obtained (0.01mol), methacrylic acid macrogol ester (molecular weight
1500g/mol, 0.35mol) and methacrylic acid (1.05mol), it is dissolved in dimethyl sulfoxide (DMSO), mixing and stirring, plus
Enter the sodium hydroxide solution that mass concentration is 20% and adjust pH7～8.Under nitrogen protection, circulate through freezing-pump-thaw
Three deoxygenations, add PMDETA0.01mol and CuBr0.01mol, make initiator, methacrylic acid macrogol ester, methyl
Sodium acrylate, catalyst, the mol ratio of part are 1:35:105:7:7,70 DEG C are reacted 10h in a nitrogen atmosphere.By product
It is placed in bag filter, 36 hours (changing water once every 12h) of dialysing in deionized water.Surplus solution in bag filter is concentrated,
Obtain the polycarboxylate water-reducer (being labeled as SP1) that solid content is 20%, the as controllable anti-chamotte mould polycarboxylic acids diminishing of molecular structure
Agent.
(3) paste flowing degree test
With reference to GB8077-2000《Methods for testing uniformity of concrete admixture》, to roll over solid content as cement quality
0.2%th, when the ratio of mud is 0.29, paste flowing degree is 289mm (being shown in Table 1).
(4) anti-Property of Clay test
The fixed ratio of mud is 0.5, and when not mixed water reducer and clay, paste flowing degree is 182mm；The ratio of mud is 0.5,
The solid volume of water reducer is the 0.2% of cement quality, measures paste flowing degree for 302mm；The ratio of mud is 0.5, water reducer solid content
For the 0.2% of cement quality, the solid volume of clay for cement quality 1% when, measure paste flowing degree for 278mm, net slurry loss
Rate=(302-278)/(302-182)=20.0% (being shown in Table 1).
Embodiment 2：
The present embodiment prepares star polycarboxylate water-reducer (being labeled as SP2) according to 1 identical mode of embodiment, and difference only exists
In step (2), the molecular weight of methacrylic acid macrogol ester is 1000g/mol.
The present embodiment tests paste flowing degree and anti-soil performance according to 1 identical mode of embodiment, and test result is shown in Table
1。
Embodiment 3：
The present embodiment prepares star polycarboxylate water-reducer (being labeled as SP3) according to 1 identical mode of embodiment, and difference only exists
In step (2), the molecular weight of methacrylic acid macrogol ester is 500g/mol.
The present embodiment tests paste flowing degree and anti-soil performance according to 1 identical mode of embodiment, and test result is shown in Table
1。
Embodiment 4：
The present embodiment prepares star polycarboxylate water-reducer (being labeled as SP4) according to 1 identical mode of embodiment, and difference only exists
In step (1), 2- bromine isobutyl acylbromides are 23.0g (0.1mol), and thus obtained star initiator is labeled as SI2.
The present embodiment tests paste flowing degree and anti-soil performance according to 1 identical mode of embodiment, and test result is shown in Table
1。
Embodiment 5：
The present embodiment prepares star polycarboxylate water-reducer (being labeled as SP5) according to 4 identical mode of embodiment, and difference only exists
In step (2), the molecular weight of methacrylic acid macrogol ester is 1000g/mol.
The present embodiment tests paste flowing degree and anti-soil performance according to 1 identical mode of embodiment, and test result is shown in Table
1。
Embodiment 6：
The present embodiment prepares star polycarboxylate water-reducer (being labeled as SP6) according to 4 identical mode of embodiment, and difference only exists
In step (2), the molecular weight of methacrylic acid macrogol ester is 500g/mol.
The present embodiment tests paste flowing degree and anti-soil performance according to 1 identical mode of embodiment, and test result is shown in Table
1。
Embodiment 7：
The present embodiment prepares star polycarboxylate water-reducer (being labeled as SP7) according to 4 identical mode of embodiment, and difference only exists
In step (2) amount of methacrylic acid macrogol ester be 0.35mol, methacrylic acid be 1.225mol.
The present embodiment tests paste flowing degree and anti-soil performance according to 1 identical mode of embodiment, and test result is shown in Table
1。
Embodiment 8：
The present embodiment prepares star polycarboxylate water-reducer (being labeled as SP8) according to 4 identical mode of embodiment, and difference only exists
In step (2) amount of methacrylic acid macrogol ester be 0.49mol, methacrylic acid amount be 1.47mol, make initiation
Agent, methacrylic acid macrogol ester, Sodium methacrylate., catalyst, the mol ratio of part are 1：49：147：7：7.
The present embodiment tests paste flowing degree and anti-soil performance according to 1 identical mode of embodiment, and test result is shown in Table
1。
Embodiment 9：
The present embodiment prepares star polycarboxylate water-reducer (being labeled as SP9) according to 4 identical mode of embodiment, and difference only exists
In step (2) in a nitrogen atmosphere 80 DEG C reaction 8h.
The present embodiment tests paste flowing degree and anti-soil performance according to 1 identical mode of embodiment, and test result is shown in Table
1。
Embodiment 10：
The present embodiment prepares star polycarboxylate water-reducer (being labeled as SP10) according to 4 identical mode of embodiment, and difference is only
It is that the middle catalyst for adding of step (2) and part are respectively CuBr0.01mol, bpy0.01mol, initiator, methacrylic acid
Macrogol ester, Sodium methacrylate., catalyst, the mol ratio of part are maintained as 1：35：105：7：7, the present embodiment according to
1 identical mode of embodiment tests paste flowing degree and anti-soil performance, and test result is shown in Table 1.
The paste flowing degree of 1 star polycarboxylate water-reducer of table and anti-mud test result
Claims (6)
1. the controllable anti-chamotte mould polycarboxylate water-reducer of a kind of molecular structure, it is characterised in that：The water reducer is knot shown in formula (I)
The compound of structure formula：
Wherein：
R1, R2, R3Or R4=H or CH3；
M, n represent the degree of polymerization：M=10～100, n=9～65；X, y represent the molar percentage of monomer：X=20～40%, y
=60～80%.
2. the preparation method of the controllable anti-chamotte mould polycarboxylate water-reducer of molecular structure described in claim 1, step is：
(1) preparation of star initiator：Beta-schardinger dextrin-and halogen acyl halide are mixed into 60～120min of reaction under ice-water bath
Afterwards, reaction 24 hours is stirred at room temperature, and reactant liquor is precipitated in petroleum ether after terminating by reaction, obtains final product star initiator,
Wherein beta-schardinger dextrin-is 1 with the mol ratio of halogen acyl halide:(7～15), halogen acyl halide be 2- bromine isobutyl acylbromides, 2 bromo propionyl bromide or
Bromoacetyl bromide；
(2) preparation of the controllable anti-chamotte mould polycarboxylate water-reducer of molecular structure：The star initiator that step (1) is obtained and (first
Base) polyalkylene glycol acrylate ester, (methyl) acrylic acid mixed dissolution, add sodium hydroxide solution adjust pH7～8, after deoxygenation again
Catalyst and part is added, under nitrogen atmosphere, 60～90 DEG C of 5～10h of reaction, dialysis remove the monomer and other impurity of residual,
Obtain the copolymer of star (methyl) polyalkylene glycol acrylate ester and (methyl) sodium acrylate, and adjust and obtain solid content and be
20%, that is, the controllable anti-chamotte mould polycarboxylate water-reducer of molecular structure is obtained；
Wherein：Described star initiator, (methyl) polyalkylene glycol acrylate ester, (methyl) acrylic acid, catalyst, part rub
You are 1 than the mol ratio for being:(30～150):(100～500):(1～10):(1～10)；The catalyst is CuBr (brominations
It is cuprous) or CuCl (Cu-lyt .)；The part is PMDETA (pentamethyl-diethylenetriamine), Me6TREN (three [2- (diformazan ammonia
Base) ethyl] amine) or bpy (bipyridyl).
3. the preparation method of the controllable anti-chamotte mould polycarboxylate water-reducer of molecular structure according to claim 2, it is characterised in that：
Step (2) the star initiator, (methyl) polyalkylene glycol acrylate ester, (methyl) acrylic acid, catalyst, the mol ratio of part
For mol ratio be 1:(30～80):(100～150):7:7.
4. the preparation method of the controllable anti-chamotte mould polycarboxylate water-reducer of molecular structure according to claim 3, it is characterised in that：
Step (2) the star initiator, (methyl) polyalkylene glycol acrylate ester, (methyl) acrylic acid, catalyst, the mol ratio of part
For mol ratio be 1:35:105:7:7.
5. the preparation method of the controllable anti-chamotte mould polycarboxylate water-reducer of molecular structure according to claim 2, it is characterised in that：
Step (2) catalyst is CuBr (cuprous bromide)；The part is PMDETA (pentamethyl-diethylenetriamine).
6. according to claim 2,3 or 4 star both sexes polycarboxylate water-reducer preparation method, it is characterised in that：Described
The molecular weight of (methyl) polyalkylene glycol acrylate ester is 500～3000g/mol.
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