CN105153375A - Method for synthesizing polycarboxylate superplasticizer through RAFT method - Google Patents
Method for synthesizing polycarboxylate superplasticizer through RAFT method Download PDFInfo
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Abstract
The invention discloses a method for synthesizing polycarboxylate superplasticizer through a RAFT method. According to the method, firstly, macro-monomers A are added into a reaction kettle, water is added, water bath heating is performed till the temperature is 65-85 DEG C, and constant-temperature stirring is performed; then, a trithio ester chain transferring agent is dissolved in a mixed solution of micro-monomers B and water, the mixture is dropwise added into the reaction kettle at constant speed, and meanwhile an initiator aqueous solution is dropwise added; after all the needed matter is dropwise added, a stirring reaction lasts for 3-5 h under the continuous constant-temperature stirring condition of 65-85 DEG C; after the reaction ends, an alkali solution and water are added to adjust PH to 6-7, and the polycarboxylate superplasticizer is obtained after reaction products are cooled to room temperature. By means of the method, the molecular-structure-controllable polycarboxylate superplasticizer can be prepared, the molecular weight is controllable, the molecular weight distribution range is narrow, polymer molecule design can also be performed, and the method has great significance in research and development of the polycarboxylate superplasticizer synthetic technology.
Description
Technical field
The present invention relates to polycarboxylate water-reducer, particularly utilize reversible addion-fragmentation chain transfer to be polymerized the method for (RAFT) method synthesis polycarboxylate water-reducer (PCE), belong to concrete chemical admixture technical field.
Background technology
Water reducer is described as concrete 5th kind of component, in concrete evolution, play important effect.Polycarboxylate water-reducer has the application advantages such as volume in concrete is low, water-reducing rate is high, Slump Time losing of Large is little, concrete contraction percentage is little, and the synthesis advantage that its own molecular structure mutability is strong, has become the focus of recent domestic research.A lot of scholar is attempting the molecular structure information dissecting PCE, PCE molecular structure comprises the contents such as molecular weight, molecular weight distribution, functional group, side chain density, and result of study shows that the change of each molecular structure information all can produce larger impact to the performance of PCE.Visible, to the research of PCE molecular structure, there is very high value.
The synthesis of current polycarboxylate water-reducer adopts radical polymerization.The method is formed by decomposition of initiator and causes free radical, cause free radical rapidly and monomer add and be shaped as long-chain free radical, long-chain free radical by and other combined with radical and termination reaction, easily there is chain transfer reaction in long-chain free radical, causes the premature termination of chain free radical.So Raolical polymerizable is generally made up of elementary reactions such as chain initiation, chainpropagation, chain terminations, also may with chain transfer reaction.
The molecular weight distribution that radical polymerization obtains is wider, realize controlled living polymerization difficulty larger.Reason mainly contains two aspects: (1) rate of chain growth substantially exceeds trigger rate, free radical forms rear rapid polymerization single polymerization monomer and forms polymer chain, " microenvironment " around when next free radical is formed just becomes complete difference, causes mass difference very large (molecular weight distribution is wide).(2) number of free radical is higher, easily various reaction occurs each other, especially easily double-basis termination reaction occurs, wherein coupling reaction relative molecular weight distribution (PDI) theoretical value is 1.5, disproportionation termination PDI theoretical value is 2, causes molecular weight distribution wide.So, the control to PCE radical polymerization be realized, the free radical first formed will be avoided on the one hand to consume rapidly monomer and form polymer chain, cause " the reaction microenvironment " of the free radical of rear formation that larger change occurs.The life-span of free radical should be extended, make each macromolecular chain be formed under identical condition as far as possible.The concentration of free radical to be controlled on the other hand, while keeping basic rate of polymerization, significantly reduce the probability that double-basis stops.
Current RAFT polymerization process successfully achieves mass polymerization and organic solution polymerization, is mainly used in the special Macroscopic single crystal of the structures such as non-water-soluble star-like, combed, but uses the report of the method synthetic polymer also few.In the report of existing aqueous solution RAFT living polymerization, research report various of monomer single stage method being formed to polymkeric substance is less.Polycarboxylate water-reducer is the water-soluble cross-linked graftomer that two or more monomer one-step polymerization is formed, and the requirement of polymerizing condition is more special.
Summary of the invention
The object of the invention is intended to overcome prior art Problems existing, provides a kind of and prepares that molecular weight is controlled, the method with RAFT method synthesis polycarboxylate water-reducer of its PDI<1.3 of narrow molecular weight distribution.
The present invention adopts the principle of the polycarboxylate water-reducer of RAFT method synthetic molecular weight narrowly distributing to be: in RAFT reaction, add three thioesters as chain transfer agents, and it can form the intermediate of dormancy with Propagating Radical.On the one hand, because the chain transfer constant of three thioesters is very large, addition with it before a large amount of monomer of free radical consumption, system " reaction microenvironment " does not have that great changes will take place, the polymerization environment of the free radical that front and back are formed is similar, the molecular weight obtaining polymerisate is also similar with molecular structure, then narrow molecular weight distribution.Hypopus cracking can go out Propagating Radical on the other hand, after the Propagating Radical that cracking goes out and monomer addition very fast again with three thioesters additions, the concentration of the growing chain in system is in a lower level always, the irreversible double-basis limited between growing chain free radical stops side reaction, and molecular weight distribution is controlled.
The present invention proposes RAFT legal system for the synthetic route of polycarboxylate water-reducer and technique.On the basis adding the efficient chain-transfer agent of three thioesters, by reducing free radical trigger rate to the adjustment of initiator system.In addition, the present invention also makes a change traditional PCE polymerization technique, and on the one hand, aqueous solution chain-transfer agent being dissolved in minor comonomer guarantees that it dissolves and drips smoothly; On the other hand, by factor such as adjustment temperature and feed time etc., the basis of bonding transformation rate ensure that the balance of chainpropagation and chain tra nsfer speed.Finally realized addition and the cracking of chain-transfer agent and Propagating Radical by above method, obtain the PCE that molecular structure is controlled.
The object of the invention is achieved by the following technical programs:
A method for RAFT method synthesis polycarboxylate water-reducer, is characterized in that comprising the steps:
(1) added in reactor by polymeric monomer A, and add water, heating in water bath is to 65 ~ 85 DEG C, and constant temperature stirs;
(2) three thioesters chain-transfer agents are dissolved in the mixed solution of minor comonomer B and water, are at the uniform velocity added drop-wise in described reactor, drip initiator solution simultaneously; The mol ratio of polymeric monomer A and minor comonomer B is 1:3 ~ 1:6; The molar percentage that described initiator accounts for minor comonomer B is 0.2% ~ 1%; The mol ratio of described initiator and three thioesters chain-transfer agents is 1:1 ~ 1:8;
(3) under 65 ~ 85 DEG C of lasting constant temperature agitation conditions, drip after terminating, Keep agitation reaction 3-5h; After reaction terminates, add alkaline solution and water adjustment PH to 6 ~ 7, after being cooled to room temperature, namely obtain polycarboxylate water-reducer;
Described polymeric monomer A is one or more of the polyethers with logical formula I;
Wherein: R
1represent hydrogen or have the alkyl of 1 ~ 3 carbon atom, phenyl or alkane phenyl; R
2for EO or PO; N represents the average addition mole number of oxyalkylene group, is the Arbitrary Digit in 10 ~ 100;
Described initiator is one or more in persulphate, water-soluble azo initiator X, and the structure of described persulphate is for shown in logical formula II:
Described water-soluble azo initiator X is Xl, X2, X3 or X4; Wherein the structure of Xl is for shown in logical formula III:
The structure of X2 is for shown in logical formula IV:
The structure of X3 is for shown in general formula (V):
The structure of X4 is for shown in logical formula VI:
Wherein, R
3for Na
+, K
+or NH
4 +one;
R
4for-(CH
2)
2sO
3h ,-(CH
2)
2cOOH or
R
5for
R
6for
R
7for
Described minor comonomer B is one or more of vinylformic acid, methacrylic acid and methylpropene sodium sulfonate;
Described water is deionized water;
Described three thioesters chain-transfer agents are S ?S ' ?bis-(a, a ' ?bis-first base ?a " ?acetic acid) ?trithiocarbonate (BDATT).
For realizing the object of the invention further, preferably, the water yield added in reactor ensures that the concentration of aqueous solution of polymeric monomer A is 20wt% ~ 65wt%.
Preferably, described initiator accounts for the molar percentage of minor comonomer B is 0.25% ~ 1%.
Preferably, the mol ratio of described polymeric monomer A and minor comonomer B is 1:3 ~ 1:5.
Preferably, the mol ratio of described initiator and three thioesters chain-transfer agents is 1:2 ~ 1:6.
Preferably, three thioesters are dissolved in the mixed solution of minor comonomer B and water, and the time of dropping is 2 ~ 3.5h.
Preferably, the concentration of initiator solution is 0.1wt% ~ 10wt%, and time for adding is 2 ~ 3.5h.
Preferably, described deionization resistivity of water is 18.2M Ω .cm.
Relative to prior art, tool of the present invention has the following advantages:
1) the present invention adopts water-soluble RAFT agent, has very high chain transfer efficiency, can realize the reversible chain tra nsfer between Propagating Radical and chain-transfer agent, controls number of free radical in polymerization system, and then effectively controls radical polymerization.
2) polymerization process flow process of the present invention is simple, easy to control, and obtained polycarboxylate water-reducer molecular weight is controlled, narrow molecular weight distribution.
3) RAFT method of the present invention has the advantages such as the restriction that suitable monomers scope is wide, reaction conditions is gentle, be not subject to polymerizing condition, and the structures such as the block of polymkeric substance, grafting, combed, star-like, random and gradient can be controlled, become one of effective means of the controlled polymkeric substance of composite structure.
4) the present invention is that the preparation of polycarboxylate water-reducer provides a kind of new polymerization process, has good investigation and application prospect.
Accompanying drawing explanation
Fig. 1 is embodiment 3 synthetic sample is polymerized PCE infrared spectra comparison diagram with the conventional free radical of market sale;
Fig. 2 is that embodiment 3 synthetic sample is polymerized PCE GPC with the conventional free radical of market sale contrasts collection of illustrative plates.
Embodiment
For understanding the present invention better, below in conjunction with embodiment and accompanying drawing, the invention will be further described, but embodiments of the present invention are not limited thereto.
The preparation of embodiment 1 polycarboxylate water-reducer
(1) add TPEG polymeric monomer 120g in a kettle., add water 117.5g, reactor is placed in water-bath and is heated to 80 DEG C, and Keep agitation;
(2) vinylformic acid 14.4g mixes with 40g water, is added in mixed solution by 2.256gBDATT and dissolves, at the uniform velocity drip 3h;
(3) be dissolved in 20g water by 0.5424g azo diisobutyl amidine dihydrochloride, and in step (2), solution starts at the uniform velocity to be added drop-wise in the reactor of step (1) simultaneously, time for adding is 3h;
(4), after dropping terminates, constant temperature stirring reaction 4h is continued;
(5), after reaction terminates, add the NaOH aqueous solution of massfraction 30% and the water of 10g, drop to room temperature and namely obtain polycarboxylate water-reducer.
The preparation of embodiment 2 polycarboxylate water-reducer
(1) add TPEG polymeric monomer 120g in a kettle., add water 137.5g, reactor is placed in water-bath and is heated to 80 DEG C, and Keep agitation;
(2) vinylformic acid 14.4g mixes with 30g water, is added in mixed solution by 2.256gBDATT and dissolves, at the uniform velocity drip 3h;
(3) be dissolved in 20g water by 0.2282g ammonium persulphate, and in step (2), solution starts at the uniform velocity to be added drop-wise in the reactor of step (1) simultaneously, time for adding is 3h;
(4), after dropping terminates, constant temperature stirring reaction 5h is continued;
(5), after reaction terminates, add the NaOH aqueous solution of massfraction 30%, drop to room temperature and namely obtain polycarboxylate water-reducer.
The preparation of embodiment 3 polycarboxylate water-reducer
(1) add TPEG polymeric monomer 120g in a kettle., add water 117.5g, reactor is placed in water-bath and is heated to 80 DEG C, and Keep agitation;
(2) vinylformic acid 14.4g mixes with 40g water, is added in mixed solution by 1.128gBDATT and dissolves, at the uniform velocity drip 3h;
(3) be dissolved in 20g water by 0.1356g azo diisobutyl amidine dihydrochloride, and in step (2), solution starts at the uniform velocity to be added drop-wise in the reactor of step (1) simultaneously, time for adding is 3h;
(4), after dropping terminates, constant temperature stirring reaction 5h is continued;
(5), after reaction terminates, add the NaOH aqueous solution of massfraction 30% and the water of 10g, drop to room temperature and namely obtain polycarboxylate water-reducer.
Fig. 1 is the infrared spectra comparison diagram that the PCE for preparing of the present embodiment and conventional free radical polymerization prepare PCE.Display Liang Zhong sample functional group is consistent, and the vibration peak of the C=O in carboxyl is at 1643cm
-1near; Various C-H vibration performance peak is at 2910cm
-1near; COO-vibration peak is positioned at 1560cm
-1near; 1100cm
-1near there is the stretching vibration peak of C-O-C in polyoxyethylene groups long-chain.There is the group such as carboxyl, polyoxyethylene groups in this product molecule structure, conform to designed polycarboxylate water-reducer molecular structure.
Fig. 2 is the GPC comparison diagram that the PCE for preparing of the present embodiment and conventional free radical polymerization prepare PCE (Hua Lixin LX-Q type polycarboxylate water-reducer).The clear appearance time demonstrating polymkeric substance and residual monomer, can find out that sample (in the figure No. 1) monodispersity that RAFT method is synthesized is better than conventional free radical polymerization PCE (in figure No. 2), in data presentation figure, the PDI of RAFT method synthetic sample is 1.209, belong to narrow ditribution, and the PDI contrasting sample is 1.392, belong to wide distribution.Other sample of the present invention's synthesis is consistent with this sample rule, and sample segment monodispersity is better.Comprehensive analysis, the polymkeric substance of RAFT method success synthetic molecular weight narrowly distributing, it is consistent that this polymers functionality and residual monomer and the conventional free radical of market sale are polymerized PCE, and postmenstruation, application test was proved again, can affirm that polymkeric substance is polycarboxylate water-reducer.
The preparation of embodiment 4 polycarboxylate water-reducer
(1) add TPEG polymeric monomer 120g in a kettle., add water 117.5g, reactor is placed in water-bath and is heated to 80 DEG C, and Keep agitation;
(2) methacrylic acid 14.4g mixes with 40g water, is added in mixed solution by 0.987gBDATT and dissolves, at the uniform velocity drip 3h;
(3) be dissolved in 20g water by 0.1356g azo diisobutyl amidine dihydrochloride, and in step (2), solution starts at the uniform velocity to be added drop-wise in the reactor of step (1) simultaneously, time for adding is 3h;
(4), after dropping terminates, constant temperature stirring reaction 4h is continued;
(5), after reaction terminates, add the NaOH aqueous solution of massfraction 30% and the water of 10g, drop to room temperature and namely obtain polycarboxylate water-reducer.
The preparation of embodiment 5 polycarboxylate water-reducer
(1) add TPEG polymeric monomer 120g in a kettle., add water 100g, reactor is placed in water-bath and is heated to 80 DEG C, and Keep agitation;
(2) vinylformic acid 14.4g mixes with 40g water, is added in mixed solution by 0.846gBDATT and dissolves, at the uniform velocity drip 3h;
(3) be dissolved in 20g water by 0.2712g azo diisobutyl amidine dihydrochloride, and in step (2), solution starts at the uniform velocity to be added drop-wise in the reactor of step (1) simultaneously, time for adding is 3h;
(4), after dropping terminates, constant temperature stirring reaction 4h is continued;
(5), after reaction terminates, add the NaOH aqueous solution of massfraction 20% and the water of 30g, drop to room temperature and namely obtain polycarboxylate water-reducer.
The preparation of embodiment 6 polycarboxylate water-reducer
(1) add TPEG polymeric monomer 120g in a kettle., add water 117.5g, reactor is placed in water-bath and is heated to 80 DEG C, and Keep agitation;
(2) vinylformic acid 14.4g mixes with 40g water, is added in mixed solution by 0.846gBDATT and dissolves, at the uniform velocity drip 3h;
(3) be dissolved in 20g water by 0.2282g ammonium persulphate, and in step (2), solution starts at the uniform velocity to be added drop-wise in the reactor of step (1) simultaneously, time for adding is 3h;
(4), after dropping terminates, constant temperature stirring reaction 6h is continued;
(5), after reaction terminates, add the NaOH aqueous solution of massfraction 30% and the water of 10g, drop to room temperature and namely obtain polycarboxylate water-reducer.
The preparation of embodiment 7 polycarboxylate water-reducer
(1) add TPEG polymeric monomer 120g in a kettle., add water 117.5g, reactor is placed in water-bath and is heated to 80 DEG C, and Keep agitation;
(2) vinylformic acid 14.4g mixes with 40g water, is added in mixed solution by 0.846gBDATT and dissolves, at the uniform velocity drip 3h;
(3) be dissolved in 20g water by 0.1356g azo diisobutyl amidine dihydrochloride, and in step (2), solution starts at the uniform velocity to be added drop-wise in the reactor of step (1) simultaneously, time for adding is 3h;
(4), after dropping terminates, constant temperature stirring reaction 3.5h is continued;
(5), after reaction terminates, add the NaOH aqueous solution of massfraction 30% and the water of 10g, drop to room temperature and namely obtain polycarboxylate water-reducer.
The preparation of embodiment 8 polycarboxylate water-reducer
(1) add APEG polymeric monomer 120g in a kettle., add water 117.5g, reactor is placed in water-bath and is heated to 65 DEG C, and Keep agitation;
(2) vinylformic acid 14.4g mixes with 40g water, is added in mixed solution by 0.987gBDATT and dissolves, at the uniform velocity drip 3.5h;
(3) be dissolved in 20g water by 0.1356g azo diisobutyl amidine dihydrochloride, and in step (2), solution starts at the uniform velocity to be added drop-wise in the reactor of step (1) simultaneously, time for adding is 3.5h;
(4), after dropping terminates, constant temperature stirring reaction 4h is continued;
(5), after reaction terminates, add the NaOH aqueous solution of massfraction 30% and the water of 10g, drop to room temperature and namely obtain polycarboxylate water-reducer.
The preparation of embodiment 9 polycarboxylate water-reducer
(1) add APEG polymeric monomer 120g in a kettle., add water 117.5g, reactor is placed in water-bath and is heated to 70 DEG C, and Keep agitation;
(2) methacrylic acid 17.22g mixes with 40g water, is added in mixed solution by 0.564gBDATT and dissolves, at the uniform velocity drip 3h;
(3) be dissolved in 20g water by 0.5424g azo diisobutyl amidine dihydrochloride, and in step (2), solution starts at the uniform velocity to be added drop-wise in the reactor of step (1) simultaneously, time for adding is 3h;
(4), after dropping terminates, constant temperature stirring reaction 4h is continued;
(5), after reaction terminates, add the NaOH aqueous solution of massfraction 40% and the water of 10g, drop to room temperature and namely obtain polycarboxylate water-reducer.
The preparation of embodiment 10 polycarboxylate water-reducer
(1) add TPEG polymeric monomer 120g in a kettle., add water 137.5g, reactor is placed in water-bath and is heated to 80 DEG C, and Keep agitation;
(2) vinylformic acid 14.4g mixes with 30g water, is added in mixed solution by 0.705gBDATT and dissolves, at the uniform velocity drip 2h;
(3) be dissolved in 20g water by 0.1356g azo diisobutyl amidine dihydrochloride, and in step (2), solution starts at the uniform velocity to be added drop-wise in the reactor of step (1) simultaneously, time for adding is 2h;
(4), after dropping terminates, constant temperature stirring reaction 5h is continued;
(5), after reaction terminates, add the NaOH aqueous solution of massfraction 30%, drop to room temperature and namely obtain polycarboxylate water-reducer.
The preparation of embodiment 11 polycarboxylate water-reducer
(1) add HPEG polymeric monomer 120g in a kettle., add water 117.5g, reactor is placed in water-bath and is heated to 85 DEG C, and Keep agitation;
(2) methacrylic acid 21.52g mixes with 40g water, is added in mixed solution by 1.128gBDATT and dissolves, at the uniform velocity drip 3h;
(3) be dissolved in 20g water by 0.1352g Potassium Persulphate, and in step (2), solution starts at the uniform velocity to be added drop-wise in the reactor of step (1) simultaneously, time for adding is 3h;
(4), after dropping terminates, constant temperature stirring reaction 5h is continued;
(5), after reaction terminates, add the NaOH aqueous solution of massfraction 30% and the water of 10g, drop to room temperature and namely obtain polycarboxylate water-reducer.
The preparation of embodiment 12 polycarboxylate water-reducer
(1) add TPEG polymeric monomer 120g in a kettle., add water 117.5g, reactor is placed in water-bath and is heated to 85 DEG C, and Keep agitation;
(2) vinylformic acid 18.02g mixes with 40g water, is added in mixed solution by 1.692gBDATT and dissolves, at the uniform velocity drip 3h;
(3) be dissolved in 20g water by 0.2382g Sodium Persulfate, and in step (2), solution starts at the uniform velocity to be added drop-wise in the reactor of step (1) simultaneously, time for adding is 3h;
(4), after dropping terminates, constant temperature stirring reaction 3.5h is continued;
(5), after reaction terminates, add the NaOH aqueous solution of massfraction 30% and the water of 10g, drop to room temperature and namely obtain polycarboxylate water-reducer.
Implementation result:
Gained water reducer narrow molecular weight distribution of the present invention, molecular weight is controlled, and the PCE that in Example, the traditionally free radical polymerisation process of representative sample and market sale synthesizes carries out application performance contrast experiment.
The experiment of cement mortar water-reducing rate is carried out with reference to " Methods for testing uniformity of concrete admixture " (GB/T8077-2012).The mortar divergence experiment of embodiment is carried out with reference to " Technical code for application of admixture in concrete " (GB50119-2013), experiment adopts tower board P II 52.5R cement, iso standard sand, II grade of flyash, mortar mix ratio is water: cement: flyash: sand=1:0.96:0.87:0.18, the solid volume of effective folding of water reducer is 0.505g, and experimental performance the results are shown in Table 1.Molecular weight Mw and PDI (Polydispersity coefficient) all uses gel chromatograph to record.
Table 1 result shows, present method can effectively regulate polycarboxylate water-reducer molecular weight, and molecular weight can be controlled in close limit.Can see, the polycarboxylate water-reducer water-reducing rate of present method synthesis is higher, dispersed and dispersion retentivity is good, and portioned product performance is better than existing market product on sale.
It is close that the present invention picks out molecular weight from RAFT method and conventional free radical polymerization synthetic sample (synthon raw material and proportioning identical), the batch sample that molecular weight distribution is different, comparative analysis molecular weight distribution, on the impact of sand-cement slurry degree of mobilization and gradual loss, the results are shown in Table 2.Can find out, in two samples that molecular weight is close, the mortar divergence of the sample of narrow molecular weight distribution is higher.This is owing to be adsorbed by cement granules and to play the poly carboxylic acid molecule of optimum dispersion effect general all in a suitable molecular weight ranges, molecular weight distribution is narrower, also just mean that the poly carboxylic acid molecule dropped in this molecular weight ranges is more, the dispersing property of such product is also better.
Table 1 application performance experimental result
The mortar divergence of the sample that the close molecular weight distribution of table 2 molecular weight is different
Claims (8)
1., by a method for RAFT method synthesis polycarboxylate water-reducer, it is characterized in that comprising the steps:
(1) added in reactor by polymeric monomer A, and add water, heating in water bath is to 65 ~ 85 DEG C, and constant temperature stirs;
(2) three thioesters chain-transfer agents are dissolved in the mixed solution of minor comonomer B and water, are at the uniform velocity added drop-wise in described reactor, drip initiator solution simultaneously; The mol ratio of polymeric monomer A and minor comonomer B is 1:3 ~ 1:6; The molar percentage that described initiator accounts for minor comonomer B is 0.2% ~ 1%; The mol ratio of described initiator and three thioesters chain-transfer agents is 1:1 ~ 1:8;
(3) under 65 ~ 85 DEG C of lasting constant temperature agitation conditions, drip after terminating, Keep agitation reaction 3-5h; After reaction terminates, add alkaline solution and water adjustment PH to 6 ~ 7, after being cooled to room temperature, namely obtain polycarboxylate water-reducer;
Described polymeric monomer A is one or more of the polyethers with logical formula I;
logical formula I
Wherein: R
1represent hydrogen or have the alkyl of 1 ~ 3 carbon atom, phenyl or alkane phenyl; R
2for EO or PO; N represents the average addition mole number of oxyalkylene group, is the Arbitrary Digit in 10 ~ 100;
Described initiator is one or more in persulphate, water-soluble azo initiator X, and the structure of described persulphate is for shown in logical formula II:
logical formula II
Described water-soluble azo initiator X is Xl, X2, X3 or X4; Wherein the structure of Xl is for shown in logical formula III:
logical formula III
The structure of X2 is for shown in logical formula IV:
logical formula IV
The structure of X3 is for shown in general formula (V):
general formula (V)
The structure of X4 is for shown in logical formula VI:
logical formula VI
Wherein, R
3for Na
+, K
+or NH
4 +one;
R
4for
R
5for
R
6for
R
7for
Described minor comonomer B is one or more of vinylformic acid, methacrylic acid and methylpropene sodium sulfonate;
Described water is deionized water;
Described three thioesters chain-transfer agents are S ?S ' ?bis-(a, a ' ?bis-first base ?a " ?acetic acid) ?trithiocarbonate (BDATT).
2. the method for RAFT method synthesis polycarboxylate water-reducer according to claim 1, is characterized in that: the water yield added in reactor ensures that the concentration of aqueous solution of polymeric monomer A is 20wt% ~ 65wt%.
3. the method for RAFT method synthesis polycarboxylate water-reducer according to claim 1, is characterized in that: the molar percentage that described initiator accounts for minor comonomer B is 0.25% ~ 1%.
4. the method for RAFT method synthesis polycarboxylate water-reducer according to claim 1, is characterized in that: the mol ratio of described polymeric monomer A and minor comonomer B is 1:3 ~ 1:5.
5. the method for RAFT method synthesis polycarboxylate water-reducer according to claim 1, is characterized in that: the mol ratio of described initiator and three thioesters chain-transfer agents is 1:2 ~ 1:6.
6. the method for RAFT method synthesis polycarboxylate water-reducer according to claim 1, it is characterized in that: three thioesters are dissolved in the mixed solution of minor comonomer B and water, the time of dropping is 2 ~ 3.5h.
7. the method for RAFT method synthesis polycarboxylate water-reducer according to claim 1, is characterized in that: the concentration of initiator solution is 0.1wt% ~ 10wt%, and time for adding is 2 ~ 3.5h.
8. the method for RAFT method synthesis polycarboxylate water-reducer according to claim 1, is characterized in that: described deionization resistivity of water is 18.2M Ω .cm.
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| CN105669912A (en) * | 2016-03-03 | 2016-06-15 | 江苏中铁奥莱特新材料有限公司 | Method for preparing star polycarboxylate water reducing agent |
| CN106519143A (en) * | 2016-12-19 | 2017-03-22 | 贵州石博士科技有限公司 | Preparation method of star-shaped polycarboxylate water reducer |
| CN107337771A (en) * | 2016-12-22 | 2017-11-10 | 江苏苏博特新材料股份有限公司 | A kind of three block polycarboxylate water-reducer and preparation method thereof |
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| CN109467654A (en) * | 2018-11-09 | 2019-03-15 | 安徽森普新型材料发展有限公司 | Four arm block polycarboxylate water-reducers of one kind and preparation method thereof |
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| CN105669912B (en) * | 2016-03-03 | 2018-03-13 | 江苏中铁奥莱特新材料股份有限公司 | A kind of method for preparing star-like poly carboxylic acid series water reducer |
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| US11548967B2 (en) | 2017-12-29 | 2023-01-10 | Sobute New Materials Co., Ltd. | Preparation method for polycarboxylate water reducer having regular sequence structure |
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| CN109467654A (en) * | 2018-11-09 | 2019-03-15 | 安徽森普新型材料发展有限公司 | Four arm block polycarboxylate water-reducers of one kind and preparation method thereof |
| CN109705289B (en) * | 2018-11-09 | 2021-11-30 | 安徽森普新型材料发展有限公司 | Block imidazole type polycarboxylate superplasticizer and preparation method thereof |
| CN110437387A (en) * | 2019-07-24 | 2019-11-12 | 天津大学 | Copolymer of poly (methyl) acrylic acid polyether ester containing dithio-carboxylate group, preparation method and application thereof |
| CN110437387B (en) * | 2019-07-24 | 2022-03-11 | 天津大学 | Copolymer of poly (methyl) acrylic acid polyether ester containing dithio-carboxylate group, preparation method and application thereof |
| CN112759724A (en) * | 2020-12-30 | 2021-05-07 | 河北双诚建筑工程检测有限公司 | Preparation method of polycarboxylic acid water reducer |
| CN114014993A (en) * | 2021-11-16 | 2022-02-08 | 北京化工大学 | Preparation method of low-temperature polymerization high-performance polycarboxylate superplasticizer |
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