CN105713154B - A kind of preparation method of Early-strength polycarboxylate superplasticizer - Google Patents
A kind of preparation method of Early-strength polycarboxylate superplasticizer Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of Early-strength polycarboxylate superplasticizer；Include the following steps：After monomer a is sufficiently mixed with chain-transferring agent, initiator, water, in N2Protection is lower to carry out Invertible ideal, and products therefrom and monomer b and monomer c are in N later2Protection is lower to carry out polymerisation.Synthetic method is simple, and technological requirement is low, and production cost is small.The product produced has many advantages, such as that volume is low, water-reducing rate is high, cement adaptability is strong, good with the workability of concrete of its mixing, can significantly improve its early strength.
Description
Technical field
The present invention relates to concrete additives in building materials technical fields, and in particular to a kind of morning available for concrete
The preparation method of strong type polycarboxylate water-reducer.
Background technology
The extensive use of concrete admixture has become indispensable in addition to cement, sand, stone and water in concrete
The 5th component, the research of additive and application promote the development of new varieties concrete and concrete construction technology.Wherein subtract
Aqua is that most widely used additive kind, usage amount have been more than the 80% of additive total amount in concrete works, is existing
For the indispensable important component of concrete.Polycarboxylate water-reducer is claimed as a kind of novel high-performance water reducing agent
For super plasticizer, since its copolymer raw material sources is extensive, molecular composition can design, with volume is low, function of slump protection is good, coagulation
Outstanding advantages of native shrinking percentage is low, molecular structure adjustability is strong, production technology cleans, becomes domestic and international concrete admixture and grinds
The hot spot studied carefully and developed.
In engineer application, the addition of polycarboxylate water-reducer is primarily to improve the workability during concrete mixing
Energy.But it is observed that after polycarboxylate water-reducer is added in putting into practice, the setting time of cement system is postponed, and early stage is strong
Degree is also affected, this can not meet rapid construction, repairing and dykes and dams burst accident and meet an urgent need the requirement of construction.And with early strong work(
The water-reducing agent of energy accelerates concrete strength development speed since it can promote hydrated cementitious, improves early strength of concrete, and
It does not make significant difference to late strength of concrete, its use can conveniently, effectively solve early strength mistake during winter construction
The problems such as low and concrete is by freeze injury, and construction speed and form cycling rate are accelerated, it increases economic efficiency, has good
Application prospect.
For whole realization early there are two types of powerful technological approaches, a kind of is that the conventional water-reducing agent of synthesis is compounded with early strength agent,
It is solved the problems, such as by compounding early strong.Traditional compound early strength agent employs naphthalene water reducer composite high-early strength component mostly, and
The production of naphthalene series high-efficiency water-reducing agent can bring environment a degree of harm, and its sodium sulphate content is high.Secondly, inorganic morning
Strong agent and the poor compatibility of water-reducing agent compounding, easily layering, flocculation, influence water-reducing agent performance.In addition, traditional compound morning subtracts by force
Early strong composition is again in the majority with villaumite and sulfate in aqua, this inevitably improves alkali and steel bar corrosion occurs
Possibility, reduce the durability of concrete structure.Another kind is that synthesis has early powerful polycarboxylate water-reducer in itself,
In recent years, Sequa Corp of Switzerland, Japanese catalyst company, BASF Corp. of Germany were proposed the polycarboxylic acids with super hardening effect one after another
Water-reducing agent product, oneself prepares early strong concrete, but prepared by its water-reducing agent through producing and requiring for concrete prefabricated element
In the presence of esterification and transesterification difficulty are big, macromolecular class synthon raw material are not easy to obtain and its polymerization process conversion ratio in journey
It is low, the problems such as complex process and higher cost, therefore enter the production practical stage and also have certain difficulty.Therefore, it is now known that
Technology contain some there are structures and preparation method of early powerful polycarboxylate water-reducer.But due to raw material, work
The reason of skill route etc., economy and the feature of environmental protection constrain its industrialized application.
On the other hand, traditional free radical polymerization causes synthesized polycarboxylic acids to have the molecule of a big chunk off-design
Composition, such as molecular weight, side chain density.Therefore, it can not greatly play suction-operated and stay in the solution as invalid
Ingredient.CN 103482897 prepares the block polycarboxylic acids diminishing with ordered structure using the method for atom transfer radical polymerization
Agent, effectively solve prepared by conventional free radical polymerization random polycarboxylate water-reducer molecule structure is uncontrollable, molecular weight distribution
The problems such as wider, but post-reaction treatment metal ion and ligand are difficult, initiator-alkyl halide have to human body it is larger poison,
The shortcomings of easy oxidation by air of transient metal complex of catalyst-low-oxidation-state, storage is more difficult, valency height is not easy to obtain, makes it
There is certain difficulty into the production practical stage.
In conclusion provide the preparation that a kind of synthetic method is simple, and technological requirement is low, and production cost is small, environmental pollution is small
The method of Early-strength polycarboxylate superplasticizer is very necessary.
Invention content
The present invention is directed to its macromolecular class synthon raw material of existing Early-strength polycarboxylate superplasticizer is overcome to be not easy to obtain
And its polymerization process conversion ratio it is low the problem of, a kind of preparation method of Early-strength polycarboxylate superplasticizer, the product produced are provided
Have many advantages, such as that volume is low, water-reducing rate is high, cement adaptability is strong, and preparation process is simple, production cost is small.
The technical principle of the present invention：Early-strength polycarboxylate superplasticizer is synthesized using reversible addion-fragmentation chain transfer polymerization.
The present invention is to provide a kind of preparation methods of Early-strength polycarboxylate superplasticizer, include the following steps：
1) after monomer a is sufficiently mixed with chain-transferring agent, initiator, water, in N2The lower reversible addition-fracture chain that carries out of protection turns
Polymerization is moved, reaction temperature is not less than 95% for 60-75 DEG C, reaction time 3-10h, monomer a conversion ratio, and dialysis is removed not anti-
The monomer a and small molecule answered obtains polyether macromonomer-RAFT reagents.1. the molecular structure of wherein monomer a meets general formula：
R in formula1For H or CH3, R2For the alkyl of H or 1~4 carbon atom, AO is the oxyalkylene of 2~4 carbon atoms
The mixture of base or two or more this oxyalkylene groups, n are the average addition molal quantity of AO, are 10~53 integer；
When AO is the oxyalkylene group of different carbon atom numbers in the structural unit of homopolymer molecule, (AO) n is total to for random copolymerization or block
Poly structure.
If n is too small, space steric effect is weak, and the copolymer dispersion performance for leading to synthesis is poor；If n is too big,
Copolymerization activity is poor, and monomer conversion is low, not only causes the waste of raw material, and the copolymer dispersion performance synthesized is also poor.
The chain-transferring agent is water solubility 4- cyano -4- (phenyl formyl sulfenyl) valeric acids or 2- (phenyl formyls
Sulfenyl) propionic acid, dosage is the 1/50~1/10 of monomer a moles.
The initiator is water solubility 4,4'- azos bis- (4- cyanopentanoic acids) or azo diisobutyl amidine hydrochloride, is used
Measure 1/500~1/100 for monomer a moles.
2) polyether macromonomer-RAFT reagents, monomer b and the monomer c for obtaining step 1 are in N2It carries out polymerizeing under protection anti-
Should, reaction temperature is 60-75 DEG C, reaction time 6-12h.Monomer a and the molar ratio of (b+c) meet：A/ (b+c)=1/
The molar ratio of 0.5~1/8, wherein monomer c and monomer (b+c) meet：C/ (b+c)=1/2~1/10.
2. the molecular structure of monomer b meets general formula：
In formula, R3For H or CH3, M H, monovalent metal, (1/2) divalent metal, amino or organic amine.
Monomer c is with sulfonic polymerizable vinyl monomer, is specifically as follows methylpropene sodium sulfonate, propene sulfonic acid
Sodium, 2- acrylamide-2-methyl propane sulfonics, sodium p styrene sulfonate, but not limited to this.
Described its weight average molecular weight of early-strength co-poly carboxylic acid is 8,000~80,000.If early-strength polycarboxylic acids
Weight average molecular weight it is too small or too big, diminishing and function of slump protection can all deteriorate.
1. monomer a that formula of of the present invention represents is that have general formula 1. at least one of represented substance of structure,
It is mixed with arbitrary proportion.
Monomer b contains at least one of 2. substance that general formula represents, when monomer b contains what 2. two or more general formulas represented
During substance, it can be mixed with arbitrary proportion.
1. monomer a that formula of of the present invention represents is polyalkylene glycol mono (methyl) acrylate monomer.
It is that Asia is gathered by alkoxy when 1. monomer a that general formula represents is polyalkylene glycol mono (methyl) acrylate monomer
Alkyl diol and (methyl) acrylic acid or the lactate synthesis object with (methyl) acrylic anhydride；Or for (methyl) hydroxyalkyl acrylate with
The addition product of at least one of ethylene oxide, propylene oxide, epoxy butane substance.These monomers be used alone or with two kinds with
Upper composition is used with the form of mixtures of arbitrary proportion.When AO is the oxygen of different carbon atom numbers in the structural unit of homopolymer molecule
When changing alkenyl, (AO) n is random copolymerization or block copolymeric structure.
It can include as the specific example that monomer a is polyalkylene glycol mono (methyl) acrylate monomer：Poly- second two
Alcohol list (methyl) acrylate, (methyl) acrylic acid 2- hydroxy methacrylates, polytetramethylene glycol list (methyl) acrylate, polyethylene glycol
(methyl) acrylic acid 2- hydroxy methacrylates, polyethylene glycol polytetramethylene glycol list (methyl) acrylate, polypropylene glycol polytetramethylene glycol list
(methyl) acrylate, polyethylene glycol polypropylene glycol polytetramethylene glycol list (methyl) acrylate, methoxy poly (ethylene glycol) list (first
Base) acrylate, methoxyl group (methyl) acrylic acid 2- hydroxy methacrylates, methoxyl group polytetramethylene glycol list (methyl) acrylate, first
Oxygroup polyethylene glycol (methyl) acrylic acid 2- hydroxy methacrylates, methoxy poly (ethylene glycol) polytetramethylene glycol list (methyl) acrylate,
Methoxyl group polypropylene glycol polytetramethylene glycol list (methyl) acrylate, methoxy poly (ethylene glycol) polypropylene glycol polytetramethylene glycol list (methyl)
Acrylate, ethyoxyl polyethyleneglycol (methyl) acrylate, ethyoxyl (methyl) acrylic acid 2- hydroxy methacrylates, ethyoxyl
Polytetramethylene glycol list (methyl) acrylate, ethyoxyl polyethylene glycol (methyl) acrylic acid 2- hydroxy methacrylates, the poly- second two of ethyoxyl
Alcohol polytetramethylene glycol list (methyl) acrylate, ethyoxyl polypropylene glycol polytetramethylene glycol list (methyl) acrylate, the poly- second of ethyoxyl
Glycol polypropylene glycol polytetramethylene glycol list (methyl) acrylate, propoxyl group polyethyleneglycol (methyl) acrylate, propoxyl group gather
Propylene glycol list (methyl) acrylate, propoxyl group polytetramethylene glycol list (methyl) acrylate, propoxyl group polyethylene glycol polypropylene glycol
Single (methyl) acrylate, propoxyl group polyethylene glycol polytetramethylene glycol list (methyl) acrylate, propoxyl group polypropylene glycol polybutadiene
Alcohol list (methyl) acrylate, propoxyl group polyethylene glycol polypropylene glycol polytetramethylene glycol list (methyl) acrylate, the poly- second of butoxy
Glycol list (methyl) acrylate, butoxypolypropylene glycol list (methyl) acrylate, ethyoxyl polytetramethylene glycol list (methyl) third
Olefin(e) acid ester, butoxy polyethylene glycol (methyl) acrylic acid 2- hydroxy methacrylates, butoxy polyethylene glycol polytetramethylene glycol list (methyl)
Acrylate, butoxypolypropylene glycol polytetramethylene glycol list (methyl) acrylate, butoxy polyethylene glycol polypropylene glycol polybutadiene
Alcohol list (methyl) acrylate.
It can be as polyalkylene glycol mono (methyl) acrylate monomer of monomer a, as long as meeting the structure of general formula 1.
It is required that the different of type influence very little to prepared early-strength polycarboxylic acids performance.
The monomer b is acrylic acid and/or methacrylic acid.
The monomer c is methylpropene sodium sulfonate, sodium allylsulfonate, 2- acrylamide-2-methyl propane sulfonics and/or to benzene
Vinyl sulfonic acid sodium, but not limited to this.
The application process of Early-strength polycarboxylate superplasticizer of the present invention：Its volume is the 0.05% of total cementitious material weight
~0.5%,
Its application process of Early-strength polycarboxylate superplasticizer of the present invention is identical with existing water-reducing agent, and only volume is not slightly
Together.The art those skilled in the art generally know that the type of specific volume and used water-reducing agent has certain pass
System.
As an improvement, the volume of Early-strength polycarboxylate superplasticizer of the present invention is 0.05%~0.3%.Volume is too low,
It is then unsatisfactory to the dispersion effect of cement；Volume is excessively high, causes waste economically, and dispersion effect is not further
Increase.
Early-strength polycarboxylate superplasticizer of the present invention can also be selected from amino sulphur known in the state of the art at least one
Sour based water reducer, Lignins ordinary water-reducing agent and existing polycarboxylate dehydragent mix use.In addition, except set out above
Known cement water reducing agent, wherein can also add in air entraining agent, swelling agent, retarder, early strength agent, tackifier, economization agent and
Antifoaming agent etc..
Compared with the prior art, the present invention has the following advantages：
(1) method using the present invention has the advantages of synthetic method is simple, and technological requirement is low, and production cost is small.
(2) polycarboxylate water-reducer prepared by method using the present invention is with volume is low, water-reducing rate is high, slump-loss
It is small, the advantages that cement adaptability is strong, good with the workability of concrete of its mixing, it can significantly improve its early strength.
With reference to embodiment, technical scheme of the present invention is described in further detail.
Description of the drawings
Fig. 1 is the hydration heat curve of 4 gained early-strength polycarboxylic acids of the embodiment of the present invention and comparative example polycarboxylic acids.
Specific embodiment
Following embodiment has described in more detail the process for preparing polymerizate according to the method for the present invention, and these realities
It applies example to provide by way of illustration, its object is to allow person skilled in the art that can understand present disclosure and according to this
Implement, but these embodiments are in no way intended to limit the scope of the present invention.All equivalence changes made according to spirit of the invention are repaiied
Decorations, should be covered by the protection scope of the present invention.
In the embodiment of the present invention, reagent used is ommercially available AR, and the weight average molecular weight Mw of polymer is used
The miniDAWN Tristar aqueous gels permeation chromatographs (GPC) of Wyatt technology corporation productions carry out
It measures；Experiment condition is as follows：Column：TSK-GELSW (TOSOH companies), elutriant：0.1M NaNO3, flowing velocity：0.8ml/
Min, injection：20 μ l, 0.1% aqueous solutions (differential refraction detector).
In the embodiment of the present invention, the conversion ratio test of monomer b and monomer c uses the LC600 high performance liquid chromatography of LabTech
Instrument (HPLC) carries out.Test condition is that chromatographic column uses Kromasil C18 columns, mobile phase CH3OH/H2O=80/20 (v/
V), flow velocity 0.6mL/min, detector are differential refraction detector, and 35 DEG C of detector temperature, sample size is 20 μ L0.5% samples
The aqueous solution of product.
Embodiment 1
By 14.82g monomethyl polyethylene glycol acrylate esters (Mn=500g/mol), 0.68g 4- cyano -4- (phenyls
Formyl sulfenyl) after valeric acid and 0.06g azos diisobutyl amidine hydrochloride and 27.5g water is sufficiently mixed, it is passed through N2By O in solution2Row
Go out, in N2Protection is lower to carry out reversible addion-fragmentation chain transfer polymerisation, and reaction temperature is 60 DEG C, reaction time 10h,
Monomer a conversion ratios 98.55%, dialysis remove unreacted monomer and small molecule, obtain polyether macromonomer-RAFT reagents (Mw
=7.91kDa),
Add in 2.46g acrylic acid (conversion ratio 47.84%), 5.41g methylpropene sodium sulfonates (conversion ratio 45.35%) continue
It polymerize 12h, obtains early-strength polycarboxylic acids mother liquor (Mw=8.68kDa).
Embodiment 2
By 29.64g monomethyl polyethylene glycol acrylate esters (Mn=950g/mol), 0.28g 2- (phenyl formyl sulphur
Base) after propionic acid and 0.03g azos diisobutyl amidine hydrochloride and 55g water is sufficiently mixed, it is passed through N2By O in solution2Discharge, in N2
Protection is lower to carry out reversible addion-fragmentation chain transfer polymerisation, and reaction temperature is 70 DEG C, reaction time 6h, monomer a conversions
Rate 97.34%, dialysis remove unreacted monomer and small molecule, obtain polyether macromonomer-RAFT reagents (Mw=
43.09kDa),
Add in 39.83g acrylic acid (conversion ratio 50.95%), 79.71g sodium allylsulfonates (conversion ratio 47.04%) continue to gather
10h is closed, obtains early-strength polycarboxylic acids mother liquor (Mw=78.08kDa).
Embodiment 3
By 29.64g polyethylene glycol monomethyl ethermethacrylic acid esters (Mn=950g/mol), 0.17g 4- cyano -4- (phenyl
Thio formyl sulfenyl) valeric acid and 0.02g 4, after 4'- azos bis- (4- cyanopentanoic acids) and 55g water are sufficiently mixed, it is passed through N2It will be molten
O in liquid2Discharge, in N2Protection is lower to carry out reversible addion-fragmentation chain transfer polymerisation, and reaction temperature is 70 DEG C, the reaction time
For 8h, monomer a conversion ratios 97.62%, unreacted monomer and small molecule are removed in dialysis, obtain polyether macromonomer-RAFT examinations
Agent (Mw=31.14kDa),
Add in 11.74g methacrylic acids (conversion ratio 49.65%), 28.3g 2- acrylamide-2-methyl propane sulfonics (turn
Rate 47.84%) continue to polymerize 8h, obtain early-strength polycarboxylic acids mother liquor (Mw=34.23kDa).
Embodiment 4
By 29.64g polypropylene glycols monomethyl ether metacrylic acid ester (Mn=2400g/mol), 0.17g 4- cyano -4- (benzene
The thio formyl sulfenyl of base) valeric acid and 0.02g 4, after 4'- azos bis- (4- cyanopentanoic acids) and 55g water are sufficiently mixed, it is passed through N2It will
O in solution2Discharge, in N2Protection is lower to carry out reversible addion-fragmentation chain transfer polymerisation, and reaction temperature is 75 DEG C, during reaction
Between for 3h, unreacted monomer and small molecule are removed in monomer a conversion ratios 96.73%, dialysis, obtain polyether macromonomer-RAFT
Reagent (Mw=38.05kDa),
Add in 3.69g methacrylic acids (conversion ratio 46.12%), 6.79g methylpropene sodium sulfonates (conversion ratio 43.71%)
Continue to polymerize 6h, obtain early-strength polycarboxylic acids mother liquor (Mw=28.18kDa).
Embodiment 5
By 30.78g polyethylene glycol monomethyl ethermethacrylic acid esters (Mn=950g/mol), 0.25g 4- cyano -4- (phenyl
Thio formyl sulfenyl) valeric acid and 0.03g 4, after 4'- azos bis- (4- cyanopentanoic acids) and 65.0g water are sufficiently mixed, it is passed through N2It will
O in solution2Discharge, in N2Protection is lower to carry out reversible addion-fragmentation chain transfer polymerisation, and reaction temperature is 75 DEG C, during reaction
Between for 6h, unreacted monomer and small molecule are removed in monomer a conversion ratios 98.64%, dialysis, obtain polyether macromonomer-RAFT
Reagent (Mw=19.41kDa),
Add in 8.64g acrylic acid (conversion ratio 58.88%), 4.74g methylpropene sodium sulfonates (conversion ratio 56.37%) continue
Polymerase 17 h obtains the polycarboxylate superplasticizer mother liquor (Mw=25.27kDa) of resistance to sulfate.
Embodiment 6
By 15.6g polyethylene glycol monomethyl ethermethacrylic acid esters (Mn=1500g/mol), 0.11g 4- cyano -4- (phenyl
Thio formyl sulfenyl) valeric acid and 0.01g 4, after 4'- azos bis- (4- cyanopentanoic acids) and 36.4g water are sufficiently mixed, it is passed through N2It will
O in solution2Discharge, in N2Protection is lower to carry out reversible addion-fragmentation chain transfer polymerisation, and reaction temperature is 75 DEG C, during reaction
Between for 8h, unreacted monomer and small molecule are removed in monomer a conversion ratios 96.87%, dialysis, obtain polyether macromonomer-RAFT
Reagent (Mw=23.77kDa),
Add in 1.99g acrylic acid (conversion ratio 54.52%), 0.63g 2- acrylamide-2-methyl propane sulfonic (conversion ratios
52.01%) continue to polymerize 8h, obtain the polycarboxylate superplasticizer mother liquor (Mw=24.48kDa) of resistance to sulfate.
Comparative example
20g water is added in the four-hole boiling flask for being configured with blender, thermometer, Dropping feeder, 90 DEG C are warming up to, to reaction
50.0g polypropylene glycols monomethyl ether metacrylic acid ester (Mn=1000g/mol), 9.0g acrylic acid and 30g water is added dropwise simultaneously in device
Mixed monomer solution, the mixing of the mixed solution and 1.30g sodium hydrogensulfites and 46g water of 1.18g ammonium persulfates and 46g water
Solution, time for adding 3h keep the temperature 2h at this temperature after being added dropwise to complete, the NaOH solution for adding in 16.7g 30% neutralizes, and obtains
The polycarboxylic acids molecular weight arrived is 23.39kDa.
Application Example：
In Application Example, used cement is the small wild water in field mud P II 52.5 and middle cement PO42.5 in Jiangnan,
Sand is the middle sand of fineness modulus M=2.6.Admixture dosage is on the basis of cement quality, by the solid gauge of folding.
Test method is with reference to GB8077-2000 in application example《Methods for testing uniformity of concrete admixture》Related rule
Fixed to perform, wherein aggregate-to-cement ratio is 2:1.
Application Example
Application Example 1
Water-reducing agent of the present invention is evaluated according to GB8077-2000 standards, paste flowing degree result such as table 1.
Influence of the different polycarboxylic acids of table 1 to mortar strength
Find out from result of the test, the early-strength polycarboxylic acids being prepared by synthetic example is in two different kinds of cement
In, preferable initial dispersion and super hardening effect are respectively provided with, it is stronger to the adaptability of cement.In small wild water in field mud, than
Compression strength compared with example 8h is 6.28MPa, and compression strength for 24 hours is 27.89MPa, and the compression strength of 28d is 74.7MPa；Mix reality
It is 11.93MPa that example 4, which is applied, in the compression strength of 8h, and compression strength for 24 hours is 34.75MPa, and the compression strength of 28d is 74.5MPa.
In middle cement, the compression strength of comparative example 8h is 4.59MPa, and compression strength for 24 hours is 12.68MPa, the pressure resistance of 28d
It spends for 64.8MPa；It is 7.35MPa to mix embodiment 4 in the compression strength of 8h, and compression strength for 24 hours is 17.56MPa, and 28d's is anti-
Compressive Strength is 65.62MPa.In short, compared with common polycarboxylic admixture comparative sample, 8h and early strength significantly improves for 24 hours, and
28d later strengths are not influenced.
Application Example 2
Cement and the polycarboxylic acids of water and 0.15% volume that the ratio of mud is 0.29 are mixed and (first stirred with 500r/min
1min is mixed, then 1min is stirred with 1500r/min).The TAM Air 08Isothermal produced using TA companies of the U.S.
The micro- calorimeter of Calorimeter isothermals carries out hydration heat rate test, and controlled at 20 ± 0.1 DEG C, hydration heat is fast
Rate is as shown in Figure 1.
It can be seen that compared with conventional polycarboxylic acids (comparative example) from hydration heat curve, when mixing early-strength polycarboxylic acids, water
Induction period in slurry body hydration process is shorter, about shortens 3h, and the main exothermic peak of aquation appears earlier, this shows the poly- carboxylic of early-strength
Acid can promote the early stage hydration process of cement slurry, so as to improve hardened cement paste early strength.
Claims (8)
1. a kind of preparation method of Early-strength polycarboxylate superplasticizer, which is characterized in that include the following steps：
1) after monomer a is sufficiently mixed with chain-transferring agent, initiator, water, in N2The lower progress reversible addion-fragmentation chain transfer of protection gathers
It closes, reaction temperature is not less than 95% for 60-75 DEG C, reaction time 3-10h, monomer a conversion ratio, and dialysis is removed unreacted
Monomer a and small molecule obtain polyether macromonomer-RAFT reagents；1. the molecular structure of wherein monomer a meets general formula：
R in formula1For H or CH3, R2For the alkyl of H or 1~4 carbon atom, AO be 2~4 carbon atoms oxyalkylene group or
The mixture of the two or more this oxyalkylene group of person, n are the average addition molal quantity of AO, are 10~53 integer；When equal
When AO is the oxyalkylene group of different carbon atom numbers in the structural unit of polymers molecule, (AO) n is random copolymerization or block copolymerization knot
Structure；
The chain-transferring agent is water solubility 4- cyano -4- (phenyl formyl sulfenyl) valeric acids or 2- (phenyl formyl sulfenyl)
Propionic acid, dosage are the 1/50~1/10 of monomer a moles；
The initiator is water solubility 4,4'- azos bis- (4- cyanopentanoic acids) or azo diisobutyl amidine hydrochloride, dosage are
The 1/500~1/100 of monomer a moles；
2) polyether macromonomer-RAFT reagents, monomer b and the monomer c for obtaining step 1 are in N2Protection is lower to carry out polymerisation, instead
It is 60-75 DEG C to answer temperature, reaction time 6-12h；
Monomer a and the molar ratio of (b+c) meet：The molar ratio of a/ (b+c)=1/0.5~1/8, wherein monomer c and monomer (b+c)
Meet：C/ (b+c)=1/2~1/10；
2. the molecular structure of monomer b meets general formula：
In formula, R3For H or CH3, M H, monovalent metal, (1/2) divalent metal, amino or organic amine；
Monomer c is with sulfonic polymerizable vinyl monomer.
2. the preparation method of Early-strength polycarboxylate superplasticizer according to claim 1, which is characterized in that the early-strength
Its weight average molecular weight of co-poly carboxylic acid is 8,000~80,000.
3. the preparation method of Early-strength polycarboxylate superplasticizer according to claim 1 or 2, which is characterized in that in the present invention
1. monomer a that general formula represents is polyalkylene glycol mono (methyl) acrylate monomer.
4. the preparation method of Early-strength polycarboxylate superplasticizer according to claim 3, which is characterized in that the polyalkylene
Glycol list (methyl) acrylate monomer,
It is by alkoxy polyalkyleneglycol and (methyl) acrylic acid or the lactate synthesis object with (methyl) acrylic anhydride；
Or the addition at least one of (methyl) hydroxyalkyl acrylate and ethylene oxide, propylene oxide, epoxy butane substance
Object；
These monomers are used alone or are used with two or more compositions with the form of mixtures of arbitrary proportion；
When AO is the oxyalkylene group of different carbon atom numbers in the structural unit of homopolymer molecule, (AO) n is random copolymerization or embedding
Section copolymeric structure.
5. the preparation method of Early-strength polycarboxylate superplasticizer according to claim 3, which is characterized in that
Monomer a is polyalkylene glycol mono (methyl) acrylate monomer, selected from polyethyleneglycol (methyl) acrylate, poly- third
Glycol list (methyl) acrylate, polytetramethylene glycol list (methyl) acrylate, polyethylene glycol polypropylene glycol list (methyl) acrylic acid
Ester, polyethylene glycol polytetramethylene glycol list (methyl) acrylate, polypropylene glycol polytetramethylene glycol list (methyl) acrylate, polyethylene glycol
Polypropylene glycol polytetramethylene glycol list (methyl) acrylate, methoxy poly (ethylene glycol) list (methyl) acrylate, methoxyl group poly- the third two
Alcohol list (methyl) acrylate, methoxyl group polytetramethylene glycol list (methyl) acrylate, methoxy poly (ethylene glycol) polypropylene glycol list (first
Base) acrylate, methoxy poly (ethylene glycol) polytetramethylene glycol list (methyl) acrylate, methoxyl group polypropylene glycol polytetramethylene glycol list
(methyl) acrylate, methoxy poly (ethylene glycol) polypropylene glycol polytetramethylene glycol list (methyl) acrylate, ethyoxyl polyethylene glycol
Single (methyl) acrylate, ethyoxyl (methyl) acrylic acid 2- hydroxy methacrylates, ethyoxyl polytetramethylene glycol list (methyl) acrylic acid
Ester, ethyoxyl polyethylene glycol (methyl) acrylic acid 2- hydroxy methacrylates, ethyoxyl polyethylene glycol polytetramethylene glycol list (methyl) propylene
Acid esters, ethyoxyl polypropylene glycol polytetramethylene glycol list (methyl) acrylate, ethyoxyl polyethylene glycol polypropylene glycol polytetramethylene glycol list
(methyl) acrylate, propoxyl group polyethyleneglycol (methyl) acrylate, propoxyl group (methyl) acrylic acid 2- hydroxy methacrylates,
Propoxyl group polytetramethylene glycol list (methyl) acrylate, propoxyl group polyethylene glycol (methyl) acrylic acid 2- hydroxy methacrylates, propoxyl group
Polyethylene glycol polytetramethylene glycol list (methyl) acrylate, propoxyl group polypropylene glycol polytetramethylene glycol list (methyl) acrylate, the third oxygen
Base polyethylene glycol polypropylene glycol polytetramethylene glycol list (methyl) acrylate, butoxy polyethyleneglycol (methyl) acrylate, fourth
Oxygroup (methyl) acrylic acid 2- hydroxy methacrylates, butoxy polyethylene glycol (methyl) acrylic acid 2- hydroxy methacrylates, butoxy gather
Ethylene glycol polytetramethylene glycol list (methyl) acrylate, butoxypolypropylene glycol polytetramethylene glycol list (methyl) acrylate or butoxy
Polyethylene glycol polypropylene glycol polytetramethylene glycol list (methyl) acrylate.
6. the preparation method of Early-strength polycarboxylate superplasticizer according to claim 4, which is characterized in that
Monomer a is polyalkylene glycol mono (methyl) acrylate monomer, selected from polyethyleneglycol (methyl) acrylate, poly- third
Glycol list (methyl) acrylate, polytetramethylene glycol list (methyl) acrylate, polyethylene glycol polypropylene glycol list (methyl) acrylic acid
Ester, polyethylene glycol polytetramethylene glycol list (methyl) acrylate, polypropylene glycol polytetramethylene glycol list (methyl) acrylate, polyethylene glycol
Polypropylene glycol polytetramethylene glycol list (methyl) acrylate, methoxy poly (ethylene glycol) list (methyl) acrylate, methoxyl group poly- the third two
Alcohol list (methyl) acrylate, methoxyl group polytetramethylene glycol list (methyl) acrylate, methoxy poly (ethylene glycol) polypropylene glycol list (first
Base) acrylate, methoxy poly (ethylene glycol) polytetramethylene glycol list (methyl) acrylate, methoxyl group polypropylene glycol polytetramethylene glycol list
(methyl) acrylate, methoxy poly (ethylene glycol) polypropylene glycol polytetramethylene glycol list (methyl) acrylate, ethyoxyl polyethylene glycol
Single (methyl) acrylate, ethyoxyl (methyl) acrylic acid 2- hydroxy methacrylates, ethyoxyl polytetramethylene glycol list (methyl) acrylic acid
Ester, ethyoxyl polyethylene glycol (methyl) acrylic acid 2- hydroxy methacrylates, ethyoxyl polyethylene glycol polytetramethylene glycol list (methyl) propylene
Acid esters, ethyoxyl polypropylene glycol polytetramethylene glycol list (methyl) acrylate, ethyoxyl polyethylene glycol polypropylene glycol polytetramethylene glycol list
(methyl) acrylate, propoxyl group polyethyleneglycol (methyl) acrylate, propoxyl group (methyl) acrylic acid 2- hydroxy methacrylates,
Propoxyl group polytetramethylene glycol list (methyl) acrylate, propoxyl group polyethylene glycol (methyl) acrylic acid 2- hydroxy methacrylates, propoxyl group
Polyethylene glycol polytetramethylene glycol list (methyl) acrylate, propoxyl group polypropylene glycol polytetramethylene glycol list (methyl) acrylate, the third oxygen
Base polyethylene glycol polypropylene glycol polytetramethylene glycol list (methyl) acrylate, butoxy polyethyleneglycol (methyl) acrylate, fourth
Oxygroup (methyl) acrylic acid 2- hydroxy methacrylates, butoxy polyethylene glycol (methyl) acrylic acid 2- hydroxy methacrylates, butoxy gather
Ethylene glycol polytetramethylene glycol list (methyl) acrylate, butoxypolypropylene glycol polytetramethylene glycol list (methyl) acrylate or butoxy
Polyethylene glycol polypropylene glycol polytetramethylene glycol list (methyl) acrylate.
7. the preparation method of Early-strength polycarboxylate superplasticizer according to claim 1, which is characterized in that the monomer b is
Acrylic acid and/or methacrylic acid.
8. the preparation method of Early-strength polycarboxylate superplasticizer according to claim 1, which is characterized in that the monomer c is
Methylpropene sodium sulfonate, sodium allylsulfonate, 2- acrylamide-2-methyl propane sulfonics and/or sodium p styrene sulfonate.
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| CN103467669A (en) * | 2013-08-23 | 2013-12-25 | 北京市建筑工程研究院有限责任公司 | Early-strength polycarboxylate water-reducing agent and preparation method thereof |
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| CN103467669A (en) * | 2013-08-23 | 2013-12-25 | 北京市建筑工程研究院有限责任公司 | Early-strength polycarboxylate water-reducing agent and preparation method thereof |
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