CN105153375B - A kind of method with RAFT methods synthesis polycarboxylate water-reducer - Google Patents
A kind of method with RAFT methods synthesis polycarboxylate water-reducer Download PDFInfo
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- CN105153375B CN105153375B CN201510603477.3A CN201510603477A CN105153375B CN 105153375 B CN105153375 B CN 105153375B CN 201510603477 A CN201510603477 A CN 201510603477A CN 105153375 B CN105153375 B CN 105153375B
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- 239000003638 reducing agent Substances 0.000 title claims abstract description 58
- 229920005646 polycarboxylate Polymers 0.000 title claims abstract description 44
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 20
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 17
- 230000002194 synthesizing Effects 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 67
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 239000000178 monomer Substances 0.000 claims abstract description 33
- 238000007792 addition Methods 0.000 claims abstract description 23
- 239000003999 initiator Substances 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 150000007970 thio esters Chemical group 0.000 claims abstract description 15
- 239000008236 heating water Substances 0.000 claims abstract description 3
- 230000002045 lasting Effects 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 4
- JPAOMENBKRZQDR-UHFFFAOYSA-N CC=CC.[Na] Chemical compound CC=CC.[Na] JPAOMENBKRZQDR-UHFFFAOYSA-N 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L Sulphite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- 238000002360 preparation method Methods 0.000 description 14
- -1 azo diisobutyl amidine Chemical class 0.000 description 10
- 238000010526 radical polymerization reaction Methods 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000004567 concrete Substances 0.000 description 7
- 230000001902 propagating Effects 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000011083 cement mortar Substances 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000000379 polymerizing Effects 0.000 description 2
- 230000002441 reversible Effects 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000006276 transfer reaction Methods 0.000 description 2
- 0 C*C(*)(*)N=NC(C)(*)C(C)=* Chemical compound C*C(*)(*)N=NC(C)(*)C(C)=* 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L Potassium persulfate Chemical class [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L Sodium persulfate Chemical class [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 229920000578 graft polymer Polymers 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000002427 irreversible Effects 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
Abstract
The invention discloses a kind of methods with RAFT methods synthesis polycarboxylate water-reducer.This method first adds in polymeric monomer A in reaction kettle, and adds in water, and to 65~85 DEG C, constant temperature stirs heating water bath；Then, three thioesters chain-transferring agents are dissolved in the mixed liquor of minor comonomer B and water, be at the uniform velocity added drop-wise in the reaction kettle, while initiator solution is added dropwise；Under 65~85 DEG C of lasting constant temperature stirring conditions, after completion of dropwise addition, it is persistently stirred to react 3 5h；After reaction, it adds in aqueous slkali and water adjusts PH to 6~7, polycarboxylate water-reducer is obtained after being cooled to room temperature；This method can prepare the controllable polycarboxylate water-reducer of molecular structure, and not only molecular weight is controllable, narrow molecular weight distribution, can also carry out Polymer supported catalyst, and the research and development to polycarboxylate water-reducer synthetic technology are meaningful great.
Description
Technical field
The present invention relates to polycarboxylate water-reducers, more particularly to polymerize (RAFT) method using reversible addion-fragmentation chain transfer and close
Into the method for polycarboxylate water-reducer (PCE), belong to concrete chemical admixture technical field.
Background technology
Water-reducing agent is known as the 5th kind of component of concrete, is played an important role in the evolution of concrete.It is poly-
Carboxylic acid water reducer has the applications such as volume is low in concrete, water-reducing rate is high, Slump Time losing of Large is small, concrete contraction percentage is small
Advantage and the strong synthesis advantage of own molecular structure changeability have become the hot spot of recent domestic research.It is many to learn
For person in the molecular structure information for attempting to dissect PCE, it is close that PCE molecular structures include molecular weight, molecular weight distribution, functional group, side chain
The contents such as degree, result of study show that the change of each molecular structure information all can generate large effect to the performance of PCE.It can
See that there is very high value to the research of PCE molecular structures.
The synthesis of polycarboxylate water-reducer at present is using radical polymerization.This method is formed by decomposition of initiator and caused
Free radical causes free radical and forms long-chain free radical with monomer addition rapidly, and long-chain free radical with other free radicals by combining
And reaction is terminated, long-chain free radical easily occurs chain transfer reaction, leads to the termination in advance of chain free radical.So free radical polymerization
The elementary reactions such as reaction is generally caused by chain, chain growth, chain termination form, it is also possible to chain transfer reaction.
The polymer molecular weight wider distribution that free radical polymerization obtains will realize that controllable living polymerization difficulty is larger.It is former
Because mainly there is two aspects：(1) rate of chain growth substantially exceeds trigger rate, free radical rapid polymerized monomer formation polymerization after being formed
Object chain, during the formation of next free radical around " microenvironment " just become entirely different, lead to the very big (molecular weight point of mass difference
Cloth is wide).(2) number of free radical is higher, and various reactions easily occur each other, is particularly susceptible and biradical termination reaction occurs, wherein
Coupled reaction relative molecular weight distribution (PDI) theoretical value 1.5, disproportionation termination PDI theoretical values 2 cause molecular weight distribution wide.
So to realize the control to PCE free radical polymerizations, on the one hand to avoid the free radical being initially formed consume rapidly monomer formed it is poly-
Object chain is closed, " the reaction microenvironment " of the free radical formed after causing varies widely.The service life of free radical should be extended, made as possible
Each macromolecular chain is formed under identical condition.On the other hand the concentration of free radical is controlled, keeps basic polymerization speed
While rate, the probability of biradical termination is greatly lowered.
RAFT polymerizations have been successfully realized bulk polymerization and organic solution polymerization at present, are mainly used in non-aqueous
Property the special Macroscopic single crystal of structures such as star-like, combed in, but using this method synthetic polymer report also not
It is more.In the report of existing aqueous solution RAFT living polymerizations, the research report that polymer is formed to various of monomer one-step method is less.
Polycarboxylate water-reducer is the water-soluble cross-linked graft polymers that two or more monomer one-step polymerizations are formed, and the requirement of polymerizing condition is more
It is special.
Invention content
The object of the invention is intended to overcome the problems, such as of the existing technology, provides and a kind of prepares that molecular weight is controllable, molecular weight point
Its narrow PDI of cloth<1.3 method with RAFT methods synthesis polycarboxylate water-reducer.
The present invention is using the principle of polycarboxylate water-reducer of RAFT method synthetic molecular weight narrowly distributings：In RAFT reactions,
Three thioesters are added in as chain transfer agents, it can form the intermediate of suspend mode with Propagating Radical.On the one hand, due to three thioesters
Chain transfer constant it is very big, the addition therewith before free radical consumes a large amount of monomers, system " reaction microenvironment " is without occurring very
Big variation, the polymerization environment of the free radical of front and rear formation is similar, and molecular weight and the molecular structure for obtaining polymerizate are also similar, then
Narrow molecular weight distribution.Another aspect hypopus can crack out Propagating Radical, the Propagating Radical cracked out and monomer addition
Afterwards quickly again with three thioesters additions, the concentration of the growing chain in system has been at a relatively low level, limits growing chain
Irreversible biradical termination side reaction between free radical, molecular weight distribution are controlled.
The present invention proposes the synthetic route and technique that RAFT methods prepare polycarboxylate water-reducer.Adding in the efficient chain of three thioesters
On the basis of transfer agent, by reducing free radical trigger rate to the adjustment for causing system.In addition to this, the present invention is also to tradition
PCE polymerization techniques make a change, on the one hand, by chain-transferring agent be dissolved in minor comonomer aqueous solution ensure its dissolve and smoothly drip
Add；On the other hand, by adjusting factors such as temperature and feed times, ensure to ensure on the basis of monomer conversion chain growth and
The balance of chain tra nsfer rate.The addition and cracking of chain-transferring agent and Propagating Radical are finally realized by above method, is divided
The controllable PCE of minor structure.
The object of the invention is achieved by the following technical programs：
A kind of method with RAFT methods synthesis polycarboxylate water-reducer, it is characterised in that include the following steps：
(1) polymeric monomer A is added in reaction kettle, and adds in water, to 65~85 DEG C, constant temperature stirs heating water bath；
(2) three thioesters chain-transferring agents are dissolved in the mixed liquor of minor comonomer B and water, are at the uniform velocity added drop-wise to the reaction kettle
In, while initiator solution is added dropwise；The molar ratio of polymeric monomer A and minor comonomer B are 1:3~1:6；The initiator accounts for minor comonomer
The molar percentage of B is 0.2%~1%；The molar ratio of the initiator and three thioesters chain-transferring agents is 1:1~1:8；
(3) under 65~85 DEG C of lasting constant temperature stirring conditions, after completion of dropwise addition, persistently it is stirred to react 3-5h；Reaction terminates
Afterwards, it adds in aqueous slkali and water adjusts PH to 6~7, polycarboxylate water-reducer is obtained after being cooled to room temperature；
The polymeric monomer A be have general formula (I) polyethers it is one or more；
Wherein：R1It represents hydrogen or has the alkyl, phenyl or alkane phenyl of 1~3 carbon atom；R2For EO or PO；N is represented
The average addition molal quantity of oxyalkylene group is the arbitrary number in 10~100；
The initiator is persulfate, one or more, the knot of the persulfate in water-soluble azo initiator X
Structure is shown in general formula (II)：
The water-soluble azo initiator X is Xl, X2, X3 or X4；Wherein the structure of Xl is shown in general formula (III)：
The structure of X2 is shown in general formula (IV)：
The structure of X3 is shown in general formula (V)：
The structure of X4 is shown in general formula (VI)：
Wherein, R3For Na+、K+Or NH4 +One kind；
R4For-(CH2)2SO3H、-(CH2)2COOH or
R5For
R6For
R7For
The minor comonomer B is the one or more of acrylic acid, methacrylic acid and methylpropene sodium sulfonate；
The water is deionized water；
The three thioesters chain-transferring agent is S-S '-two (a, a '-dimethyl-a "-acetic acid)-trithiocarbonate (BDATT).
Further to realize the object of the invention, it is preferable that the water added in reaction kettle ensures that the aqueous solution of polymeric monomer A is dense
It spends for 20wt%~65wt%.
Preferably, the molar percentage that the initiator accounts for minor comonomer B is 0.25%~1%.
Preferably, the molar ratio of the polymeric monomer A and minor comonomer B is 1:3~1:5.
Preferably, the molar ratio of the initiator and three thioesters chain-transferring agents is 1:2~1:6.
Preferably, three thioesters are dissolved in the mixed liquor of minor comonomer B and water, and the time of dropwise addition is 2~3.5h.
Preferably, a concentration of 0.1wt%~10wt% of initiator solution, time for adding are 2~3.5h.
Preferably, the resistivity of the deionized water is 18.2M Ω .cm.
Relative to the prior art, the invention has the advantages that：
1) present invention is had very high chain transfer efficiency, can be realized Propagating Radical using water-soluble RAFT agent
Reversible chain tra nsfer between chain-transferring agent controls number of free radical in polymerization system, and then effectively controls free radical polymerization.
2) polymerization flow of the present invention is simple, easy to control, and polycarboxylate water-reducer molecule amount obtained is controllable, molecular weight point
Cloth is narrow.
3) RAFT methods of the present invention have that suitable monomers range is wide, reaction condition is mild, it is excellent not limited etc. by polymerizing condition
Point, and the structures such as block, grafting, combed, star-like, random and gradient of controllable polymer become composite structure controllably
One of effective means of polymer.
4) present invention provides a kind of new polymerization for the preparation of polycarboxylate water-reducer, has research well and answers
Use prospect.
Description of the drawings
Fig. 1 is the infrared spectrum comparison diagram that 3 synthetic sample of embodiment polymerize PCE with the conventional free radical of market sale；
Fig. 2 is the GPC comparison collection of illustrative plates that 3 synthetic sample of embodiment polymerize PCE with the conventional free radical of market sale.
Specific embodiment
To more fully understand the present invention, with reference to embodiment and attached drawing, the invention will be further described, but the present invention
Embodiment it is without being limited thereto.
The preparation of 1 polycarboxylate water-reducer of embodiment
(1) TPEG polymeric monomer 120g are added in a kettle, add in water 117.5g, reaction kettle is placed in water-bath and is heated
To 80 DEG C, and continue to stir；
(2) acrylic acid 14.4g is uniformly mixed with 40g water, and 2.256gBDATT is added in mixed liquor and is dissolved, is at the uniform velocity added dropwise
3h；
(3) by 0.5424g azo diisobutyl amidine dihydrochlorides be dissolved in 20g water and step (2) in solution open simultaneously
Beginning is at the uniform velocity added drop-wise in the reaction kettle of step (1), time for adding 3h；
(4) after completion of dropwise addition, continue constant temperature and be stirred to react 4h；
(5) after reaction, the NaOH aqueous solutions of mass fraction 30% and the water of 10g are added in, drops to room temperature up to poly- carboxylic
Sour water-reducing agent.
The preparation of 2 polycarboxylate water-reducer of embodiment
(1) TPEG polymeric monomer 120g are added in a kettle, add in water 137.5g, reaction kettle is placed in water-bath and is heated
To 80 DEG C, and continue to stir；
(2) acrylic acid 14.4g is uniformly mixed with 30g water, and 2.256gBDATT is added in mixed liquor and is dissolved, is at the uniform velocity added dropwise
3h；
(3) by 0.2282g ammonium persulfates be dissolved in 20g water and step (2) in solution start simultaneously at and be at the uniform velocity added drop-wise to step
Suddenly in the reaction kettle of (1), time for adding 3h；
(4) after completion of dropwise addition, continue constant temperature and be stirred to react 5h；
(5) after reaction, the NaOH aqueous solutions of mass fraction 30% are added in, drop to room temperature up to polycarboxylate water-reducer.
The preparation of 3 polycarboxylate water-reducer of embodiment
(1) TPEG polymeric monomer 120g are added in a kettle, add in water 117.5g, reaction kettle is placed in water-bath and is heated
To 80 DEG C, and continue to stir；
(2) acrylic acid 14.4g is uniformly mixed with 40g water, and 1.128gBDATT is added in mixed liquor and is dissolved, is at the uniform velocity added dropwise
3h；
(3) by 0.1356g azo diisobutyl amidine dihydrochlorides be dissolved in 20g water and step (2) in solution open simultaneously
Beginning is at the uniform velocity added drop-wise in the reaction kettle of step (1), time for adding 3h；
(4) after completion of dropwise addition, continue constant temperature and be stirred to react 5h；
(5) after reaction, the NaOH aqueous solutions of mass fraction 30% and the water of 10g are added in, drops to room temperature up to poly- carboxylic
Sour water-reducing agent.
Fig. 1 is the infrared spectrum comparison diagram that PCE manufactured in the present embodiment prepares PCE with conventional free radical polymerization.Display
Liang Zhong samples functional group is consistent, and the vibration peak of the C=O in carboxyl is in 1643cm-1Near；Various C-H vibration performances peaks exist
2910cm-1Near；COO- vibration peaks are located at 1560cm-1Near；1100cm-1Nearby there is C-O-C in polyoxyethylene groups long-chain
Stretching vibration peak.There are the groups such as carboxyl, polyoxyethylene groups in the product molecule structure, with designed polycarboxylate water-reducer molecule
Structure is consistent.
For PCE manufactured in the present embodiment and conventional free radical polymerization preparation PCE, (Hua Lixin LX-Q type polycarboxylic acids subtracts Fig. 2
Aqua) GPC comparison diagrams.Appear clearly from the appearance time of polymer and residual monomer, it can be seen that the sample of RAFT methods synthesis
Product (in figure No. 1) monodispersity is better than conventional free radical polymerization PCE (in figure No. 2), and data show RAFT method synthetic samples in figure
PDI for 1.209, belong to narrow ditribution, and the PDI of comparative sample is 1.392, belongs to wide distribution.Other samples that the present invention synthesizes
Consistent with the sample rule, sample segment monodispersity is more preferable.Comprehensive analysis, RAFT methods success synthetic molecular weight narrowly distributing gather
It is consistent with the conventional free radical polymerization PCE of market sale to close object, the polymers functionality and residual monomer, and postmenstruation application examination
Evidence is tested, it is polycarboxylate water-reducer that can affirm polymer.
The preparation of 4 polycarboxylate water-reducer of embodiment
(1) TPEG polymeric monomer 120g are added in a kettle, add in water 117.5g, reaction kettle is placed in water-bath and is heated
To 80 DEG C, and continue to stir；
(2) methacrylic acid 14.4g is uniformly mixed with 40g water, and 0.987gBDATT is added in mixed liquor and is dissolved, at the uniform velocity
3h is added dropwise；
(3) by 0.1356g azo diisobutyl amidine dihydrochlorides be dissolved in 20g water and step (2) in solution open simultaneously
Beginning is at the uniform velocity added drop-wise in the reaction kettle of step (1), time for adding 3h；
(4) after completion of dropwise addition, continue constant temperature and be stirred to react 4h；
(5) after reaction, the NaOH aqueous solutions of mass fraction 30% and the water of 10g are added in, drops to room temperature up to poly- carboxylic
Sour water-reducing agent.
The preparation of 5 polycarboxylate water-reducer of embodiment
(1) TPEG polymeric monomer 120g are added in a kettle, add in water 100g, reaction kettle is placed in water-bath and is heated to
80 DEG C, and continue to stir；
(2) acrylic acid 14.4g is uniformly mixed with 40g water, and 0.846gBDATT is added in mixed liquor and is dissolved, is at the uniform velocity added dropwise
3h；
(3) by 0.2712g azo diisobutyl amidine dihydrochlorides be dissolved in 20g water and step (2) in solution open simultaneously
Beginning is at the uniform velocity added drop-wise in the reaction kettle of step (1), time for adding 3h；
(4) after completion of dropwise addition, continue constant temperature and be stirred to react 4h；
(5) after reaction, the NaOH aqueous solutions of mass fraction 20% and the water of 30g are added in, drops to room temperature up to poly- carboxylic
Sour water-reducing agent.
The preparation of 6 polycarboxylate water-reducer of embodiment
(1) TPEG polymeric monomer 120g are added in a kettle, add in water 117.5g, reaction kettle is placed in water-bath and is heated
To 80 DEG C, and continue to stir；
(2) acrylic acid 14.4g is uniformly mixed with 40g water, and 0.846gBDATT is added in mixed liquor and is dissolved, is at the uniform velocity added dropwise
3h；
(3) by 0.2282g ammonium persulfates be dissolved in 20g water and step (2) in solution start simultaneously at and be at the uniform velocity added drop-wise to step
Suddenly in the reaction kettle of (1), time for adding 3h；
(4) after completion of dropwise addition, continue constant temperature and be stirred to react 6h；
(5) after reaction, the NaOH aqueous solutions of mass fraction 30% and the water of 10g are added in, drops to room temperature up to poly- carboxylic
Sour water-reducing agent.
The preparation of 7 polycarboxylate water-reducer of embodiment
(1) TPEG polymeric monomer 120g are added in a kettle, add in water 117.5g, reaction kettle is placed in water-bath and is heated
To 80 DEG C, and continue to stir；
(2) acrylic acid 14.4g is uniformly mixed with 40g water, and 0.846gBDATT is added in mixed liquor and is dissolved, is at the uniform velocity added dropwise
3h；
(3) by 0.1356g azo diisobutyl amidine dihydrochlorides be dissolved in 20g water and step (2) in solution open simultaneously
Beginning is at the uniform velocity added drop-wise in the reaction kettle of step (1), time for adding 3h；
(4) after completion of dropwise addition, continue constant temperature and be stirred to react 3.5h；
(5) after reaction, the NaOH aqueous solutions of mass fraction 30% and the water of 10g are added in, drops to room temperature up to poly- carboxylic
Sour water-reducing agent.
The preparation of 8 polycarboxylate water-reducer of embodiment
(1) APEG polymeric monomer 120g are added in a kettle, add in water 117.5g, reaction kettle is placed in water-bath and is heated
To 65 DEG C, and continue to stir；
(2) acrylic acid 14.4g is uniformly mixed with 40g water, and 0.987gBDATT is added in mixed liquor and is dissolved, is at the uniform velocity added dropwise
3.5h；
(3) by 0.1356g azo diisobutyl amidine dihydrochlorides be dissolved in 20g water and step (2) in solution open simultaneously
Beginning is at the uniform velocity added drop-wise in the reaction kettle of step (1), time for adding 3.5h；
(4) after completion of dropwise addition, continue constant temperature and be stirred to react 4h；
(5) after reaction, the NaOH aqueous solutions of mass fraction 30% and the water of 10g are added in, drops to room temperature up to poly- carboxylic
Sour water-reducing agent.
The preparation of 9 polycarboxylate water-reducer of embodiment
(1) APEG polymeric monomer 120g are added in a kettle, add in water 117.5g, reaction kettle is placed in water-bath and is heated
To 70 DEG C, and continue to stir；
(2) methacrylic acid 17.22g is uniformly mixed with 40g water, and 0.564gBDATT is added in mixed liquor and is dissolved, at the uniform velocity
3h is added dropwise；
(3) by 0.5424g azo diisobutyl amidine dihydrochlorides be dissolved in 20g water and step (2) in solution open simultaneously
Beginning is at the uniform velocity added drop-wise in the reaction kettle of step (1), time for adding 3h；
(4) after completion of dropwise addition, continue constant temperature and be stirred to react 4h；
(5) after reaction, the NaOH aqueous solutions of mass fraction 40% and the water of 10g are added in, drops to room temperature up to poly- carboxylic
Sour water-reducing agent.
The preparation of 10 polycarboxylate water-reducer of embodiment
(1) TPEG polymeric monomer 120g are added in a kettle, add in water 137.5g, reaction kettle is placed in water-bath and is heated
To 80 DEG C, and continue to stir；
(2) acrylic acid 14.4g is uniformly mixed with 30g water, and 0.705gBDATT is added in mixed liquor and is dissolved, is at the uniform velocity added dropwise
2h；
(3) by 0.1356g azo diisobutyl amidine dihydrochlorides be dissolved in 20g water and step (2) in solution open simultaneously
Beginning is at the uniform velocity added drop-wise in the reaction kettle of step (1), time for adding 2h；
(4) after completion of dropwise addition, continue constant temperature and be stirred to react 5h；
(5) after reaction, the NaOH aqueous solutions of mass fraction 30% are added in, drop to room temperature up to polycarboxylate water-reducer.
The preparation of 11 polycarboxylate water-reducer of embodiment
(1) HPEG polymeric monomer 120g are added in a kettle, add in water 117.5g, reaction kettle is placed in water-bath and is heated
To 85 DEG C, and continue to stir；
(2) methacrylic acid 21.52g is uniformly mixed with 40g water, and 1.128gBDATT is added in mixed liquor and is dissolved, at the uniform velocity
3h is added dropwise；
(3) by 0.1352g potassium peroxydisulfates be dissolved in 20g water and step (2) in solution start simultaneously at and be at the uniform velocity added drop-wise to step
Suddenly in the reaction kettle of (1), time for adding 3h；
(4) after completion of dropwise addition, continue constant temperature and be stirred to react 5h；
(5) after reaction, the NaOH aqueous solutions of mass fraction 30% and the water of 10g are added in, drops to room temperature up to poly- carboxylic
Sour water-reducing agent.
The preparation of 12 polycarboxylate water-reducer of embodiment
(1) TPEG polymeric monomer 120g are added in a kettle, add in water 117.5g, reaction kettle is placed in water-bath and is heated
To 85 DEG C, and continue to stir；
(2) acrylic acid 18.02g is uniformly mixed with 40g water, and 1.692gBDATT is added in mixed liquor and is dissolved, is at the uniform velocity added dropwise
3h；
(3) by 0.2382g sodium peroxydisulfates be dissolved in 20g water and step (2) in solution start simultaneously at and be at the uniform velocity added drop-wise to step
Suddenly in the reaction kettle of (1), time for adding 3h；
(4) after completion of dropwise addition, continue constant temperature and be stirred to react 3.5h；
(5) after reaction, the NaOH aqueous solutions of mass fraction 30% and the water of 10g are added in, drops to room temperature up to poly- carboxylic
Sour water-reducing agent.
Implementation result：
Gained water-reducing agent narrow molecular weight distribution of the invention, molecular weight is controllable, and representative sample is sold with market in Example
The PCE synthesized according to conventional free radical polymerization sold carries out application performance contrast experiment.
Reference《Methods for testing uniformity of concrete admixture》(GB/T8077-2012) it is real to carry out cement mortar water-reducing rate
It tests.Reference《Technical code for application of admixture in concrete》(GB50119-2013) the mortar divergence experiment of embodiment is carried out, it is real
It tests using II 52.5R cement of tower board P, 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-reducing agent is 0.505g, and experimental performance the results are shown in Table 1.Molecular weight Mw and PDI
(Polydispersity coefficient) is measured using gel permeation chrommatograph.
Table 1 the result shows that, this method can effectively adjust polycarboxylate water-reducer molecule amount, and molecular weight can be controlled in it is narrow
In the range of.It can be seen that the polycarboxylate water-reducer water-reducing rate of this method synthesis is higher, dispersibility and dispersion retentivity are good, part
Properties of product are better than existing market product on sale.
The present invention chooses from RAFT methods and conventional free radical polymerization synthetic sample (synthon raw material and proportioning are identical)
Select that molecular weight is close, the different a collection of sample of molecular weight distribution, comparative analysis molecular weight distribution to cement mortar fluidity and
The influence of gradual loss, the results are shown in Table 2.As can be seen that in two samples similar in molecular weight, the sample of narrow molecular weight distribution
Mortar divergence higher.This is because it is adsorbed by cement granules and plays the role of the polycarboxylic acids molecule of optimum dispersion generally all one
In a suitable molecular weight ranges, molecular weight distribution is narrower, also means that the polycarboxylic acids point fallen in this molecular weight ranges
Son is more, and the dispersion performance of such product is also better.
1 application performance experimental result of table
The mortar divergence of the different sample of the close molecular weight distribution of 2 molecular weight of table
Claims (8)
- A kind of 1. method with RAFT methods synthesis polycarboxylate water-reducer, it is characterised in that include the following steps：(1) polymeric monomer A is added in reaction kettle, and adds in water, to 65~85 DEG C, constant temperature stirs heating water bath；(2) three thioesters chain-transferring agents are dissolved in the mixed liquor of minor comonomer B and water, be at the uniform velocity added drop-wise in the reaction kettle, together When initiator solution is added dropwise；The molar ratio of polymeric monomer A and minor comonomer B are 1:3~1:6；The initiator accounts for rubbing for minor comonomer B Your percentage is 0.2%~1%；The molar ratio of the initiator and three thioesters chain-transferring agents is 1:1~1:8；(3) under 65~85 DEG C of lasting constant temperature stirring conditions, after completion of dropwise addition, persistently it is stirred to react 3-5h；After reaction, add Enter aqueous slkali and water adjusts PH to 6~7, polycarboxylate water-reducer is obtained after being cooled to room temperature；The polymeric monomer A be have general formula (I) polyethers it is one or more；General formula (I)Wherein：R1It represents hydrogen or has the alkyl, phenyl or alkane phenyl of 1~3 carbon atom；R2For EO or PO；N represents oxidation The average addition molal quantity of alkenyl is the arbitrary number in 10~100；The initiator is persulfate, one or more in water-soluble azo initiator X, and the structure of the persulfate is Shown in general formula (II)：General formula (II)The water-soluble azo initiator X is Xl, X2, X3 or X4；Wherein the structure of Xl is shown in general formula (III)：General formula (III)The structure of X2 is shown in general formula (IV)：General formula (IV)The structure of X3 is shown in general formula (V)：General formula (V)The structure of X4 is shown in general formula (VI)：General formula (VI)Wherein, R3For Na+、K+Or NH4 +One kind；R4ForR5ForR6ForR7ForThe minor comonomer B is the one or more of acrylic acid, methacrylic acid and methylpropene sodium sulfonate；The water is deionized water；The three thioesters chain-transferring agent is S-S '-two (a, a '-dimethyl-a "-acetic acid)-trithiocarbonate (BDATT).
- 2. the method for RAFT methods synthesis polycarboxylate water-reducer according to claim 1, it is characterised in that：It is added in reaction kettle Water ensure that the concentration of aqueous solution of polymeric monomer A is 20wt%~65wt%.
- 3. the method for RAFT methods synthesis polycarboxylate water-reducer according to claim 1, it is characterised in that：The initiator accounts for The molar percentage of minor comonomer B is 0.25%~1%.
- 4. the method for RAFT methods synthesis polycarboxylate water-reducer according to claim 1, it is characterised in that：The polymeric monomer A Molar ratio with minor comonomer B is 1:3~1:5.
- 5. the method for RAFT methods synthesis polycarboxylate water-reducer according to claim 1, it is characterised in that：The initiator and The molar ratio of three thioesters chain-transferring agents is 1:2~1:6.
- 6. the method for RAFT methods synthesis polycarboxylate water-reducer according to claim 1, it is characterised in that：Three thioesters are dissolved in small In the mixed liquor of monomer B and water, the time of dropwise addition is 2~3.5h.
- 7. the method for RAFT methods synthesis polycarboxylate water-reducer according to claim 1, it is characterised in that：Initiator solution A concentration of 0.1wt%~10wt%, time for adding be 2~3.5h.
- 8. the method for RAFT methods synthesis polycarboxylate water-reducer according to claim 1, it is characterised in that：The deionized water Resistivity be 18.2M Ω .cm.
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| CN106519143B (en) * | 2016-12-19 | 2018-01-26 | 贵州石博士科技有限公司 | A kind of preparation method of star-like polycarboxylate water-reducer |
| CN107337771B (en) * | 2016-12-22 | 2020-03-27 | 江苏苏博特新材料股份有限公司 | Triblock polycarboxylate superplasticizer and preparation method thereof |
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| CN107828061A (en) * | 2017-10-26 | 2018-03-23 | 陕西科技大学 | One kind contains compound long short-side chain polycarboxylate salt dispersant and its aqueous solution RAFT synthetic methods |
| CN108059697B (en) * | 2017-12-29 | 2019-12-27 | 江苏苏博特新材料股份有限公司 | Preparation method of polycarboxylate superplasticizer with regular sequence structure |
| CN111040089A (en) * | 2018-10-15 | 2020-04-21 | 辽宁奥克化学股份有限公司 | Synthesis method of solid polycarboxylate superplasticizer |
| 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 |
| 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 |
| 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 |
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