CN104761176A - Compound polycarboxylate superplasticizer and preparation method thereof - Google Patents
Compound polycarboxylate superplasticizer and preparation method thereof Download PDFInfo
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Abstract
The invention provides a compound polycarboxylate superplasticizer and a preparation method thereof. The compound polycarboxylate superplasticizer comprises a polycarboxylate superplasticizer mother solution, wherein the polycarboxylate superplasticizer mother solution is obtained by the steps of mixing a terminal hydroxyl esterifiable polyether macromonomer, water, an initiator, a chain transfer agent and acrylic acid, reacting while heating and neutralizing until the pH value is up to 6-7; and the terminal hydroxyl esterifiable polyether macromonomer is obtained by carrying out esterification reaction on the terminal hydroxyl of a polyether macromonomer and carboxyl of macromolecular carboxylic acid under the catalytic action of a catalyst. The terminal hydroxyl esterifiable polyether macromonomer takes the macromolecular carboxylic acid as a terminal blocking group of the polyether macromonomer, so that the physical size of the tail end of a side chain is greatly increased, then, the physical size of the tail end of the side chain of the polycarboxylate superplasticizer mother solution synthesized and prepared by using the terminal hydroxyl esterifiable polyether macromonomer is greatly increased, the polycarboxylate superplasticizer mother solution is not easily inserted to a laminated structure of clay, and furthermore, a mud-resistant effect is achieved. Then, the polycarboxylate superplasticizer mother solution is compound to form the compound polycarboxylate superplasticizer provided by the invention, so that the working performance of concrete is better ensured.
Description
Technical field
The present invention relates to polycarboxylate water-reducer technical field, particularly relate to composite polycarboxylate water-reducer and preparation method thereof.
Background technology
Water reducer is current investigation and application the most a kind of concrete admixture, and admixture has become the 5th kind of important component part in concrete except cement, sand, stone, water.Poly carboxylic acid, as water reducer of new generation, has that volume is low, function of slump protection good, concrete contraction percentage is low, molecular structure adjustability is strong, production technique is simple and to advantages such as the close friends of environment.Be acknowledged as concrete admixture developing direction from now on.
In actual use, because polycarboxylate water-reducer side chain easily inserts in the laminate structure of clay, cause polycarboxylate water-reducer being greatly affected containing the dispersing property in the concrete of clay, cause its anti-mud poor, and then cause concrete over-all properties to decline.
Summary of the invention
For above-mentioned defect and the problem of prior art, the object of this invention is to provide composite polycarboxylate water-reducer and preparation method thereof.The polyether macromonomer of terminal hydroxy group esterification that what the polyether macromonomer in the polycarboxylate superplasticizer mother liquor raw material that composite polycarboxylate water-reducer of the present invention adopts adopted is, it utilizes macromolecular carboxylic acid as the capping group of polyethers, add the physical size of polycarboxylate water-reducer side chain terminal greatly, make it not easily insert in the laminate structure of clay, thus reach the effect of anti-mud.The side chain solving existing polycarboxylate water-reducer easily inserts in the laminate structure of clay, causes its anti-mud poor, and then the technical problem causing concrete over-all properties to decline.
In order to achieve the above object, the invention provides following technical scheme:
Composite polycarboxylate water-reducer, comprise polycarboxylate superplasticizer mother liquor, wherein, described polycarboxylate superplasticizer mother liquor is by after the polyether macromonomer of terminal hydroxy group esterification and water, initiator, chain-transfer agent and vinylformic acid Hybrid Heating being reacted, then adds in basic solution and obtain behind pH value to 6 ~ 7; Wherein, the polyether macromonomer of described terminal hydroxy group esterification is under the katalysis of catalyzer, and the terminal hydroxy group of polyether macromonomer and the carboxyl of macromolecular carboxylic acid carry out that esterification obtains.
Further, the mol ratio of described polyether macromonomer and macromolecular carboxylic acid is 1 ﹕ 0.2 ~ 1.
Further, the mol ratio of described polyether macromonomer and macromolecular carboxylic acid is 1 ﹕ 0.5.
Further, described macromolecular carboxylic acid is the alkyl carboxylic acid of carbonatoms 16 ~ 32 or is the carboxylic acid containing phenyl ring.
Particularly, described macromolecular carboxylic acid can adopt but be not limited to Palmiticacid, stearic acid or phenylformic acid.
Further, the weight-average molecular weight of described polyether macromonomer is 1000 ~ 5000.
Particularly, described polyether macromonomer can adopt isopentene group Soxylat A 25-7 (TPEG) or isobutenyl Soxylat A 25-7 (HPEG).
Further, in described esterification, controlling temperature of reaction is 80 DEG C ~ 130 DEG C, and esterification time is 2 ~ 5h.
Further, the consumption of described catalyzer is 2% ~ 6% of the quality of described polyether macromonomer.
Particularly, described catalyzer adopts tosic acid or thionamic acid.
Further, in the esterification reaction, also water entrainer is added.The consumption foundation esterification reaction raw materials consumption of the water entrainer added and the ability integration analytical calculation of water entrainer obtain.Particularly, in the present invention, the consumption of described water entrainer can be 10% ~ 20% of the quality of described polyether macromonomer.Water entrainer described in the present invention can adopt hexanaphthene.The water that esterification generates is taken out of reaction system in time, and the forward accelerating esterification carries out, and improves esterification efficiency.
Further, in the esterification reaction, also stopper is added; The consumption of described stopper is 0.05% ~ 0.5% of the quality of described polyether macromonomer.Prevent the double-bond polymerization of polyether macromonomer.Particularly, Resorcinol or thiodiphenylamine etc. can be adopted.
Further, the polyether macromonomer of described terminal hydroxy group esterification and the mol ratio of initiator are 1 ﹕ 0.01 ~ 0.3; The polyether macromonomer of described terminal hydroxy group esterification and the mol ratio of chain-transfer agent are 1 ﹕ 0.05 ~ 0.8; The polyether macromonomer of described terminal hydroxy group esterification and acrylic acid mol ratio are 1 ﹕ 2 ~ 7.
Particularly, the consumption of described water is determined according to the polyether macromonomer of terminal hydroxy group esterification, initiator, chain-transfer agent and acrylic acid total mass, makes the solid content of the polycarboxylate superplasticizer mother liquor be obtained by reacting be 35% ~ 50%.Namely the consumption of described water and the ratio M of total mass are 1 ~ 2.
Further, described initiator can adopt ammonium persulfate, Potassium Persulphate or Vc-H
2o
2initiator system etc.The consumption that different initiators uses in reaction process is different.When described initiator adopts ammonium persulfate or Potassium Persulphate, the polyether macromonomer of described terminal hydroxy group esterification and the mol ratio of initiator are 1 ﹕ 0.1 ~ 0.3; Be preferably 1 ﹕ 0.2.When described initiator adopts Vc-H
2o
2during initiator system, the polyether macromonomer of described terminal hydroxy group esterification and the mol ratio of initiator are 1 ﹕ 0.01 ~ 0.1, are preferably, 1 ﹕ 0.022; Wherein, Vc-H
2o
2vc ﹕ H in initiator system
2o
2mol ratio is 0.1 ~ 0.25 ﹕ 1.
Further, described chain-transfer agent can adopt Thiovanic acid/propionic acid, methylpropene sodium sulfonate etc.When adopting Thiovanic acid/propionic acid, the polyether macromonomer of described terminal hydroxy group esterification and the mol ratio of chain-transfer agent are 1 ﹕ 0.05 ~ 0.3; Be preferably 1 ﹕ 0.11.When adopting methylpropene sodium sulfonate, the polyether macromonomer of described terminal hydroxy group esterification and the mol ratio of chain-transfer agent are 1 ﹕ 0.1 ~ 0.8; Be preferably 1 ﹕ 0.3.
Further, the polyether macromonomer of described terminal hydroxy group esterification and acrylic acid mol ratio are 1 ﹕ 4.
Further, described composite polycarboxylate water-reducer is the mixture comprising polycarboxylate superplasticizer mother liquor, water, defoamer, air entrapment agent and retardant, wherein, in the mixture, the mass percentage of the nonvolatile substances in described polycarboxylate superplasticizer mother liquor is 8% ~ 15%.The polymkeric substance that the polyether macromonomer of what nonvolatile substances wherein referred to is polycarboxylate superplasticizer mother liquor middle-end hydroxy esterification and chain-transfer agent and acroleic acid polymerization are obtained by reacting.
Preferably, in the mixture, the mass percentage of the nonvolatile substances in described polycarboxylate superplasticizer mother liquor is 10%.
Further, the mass percentage of described defoamer is 0.01% ~ 0.1%, air entrapment agent 0.01% ~ 0.1%, and the mass percentage of retardant is 0.5% ~ 8%.
Further preferably, the mass percentage of described defoamer is 0.02% ~ 0.08%, air entrapment agent 0.02% ~ 0.08%, and the mass percentage of retardant is 1% ~ 5%.
Further preferably, the mass percentage of described defoamer is 0.05%, air entrapment agent 0.05%, and the mass percentage of retardant is 2%.
Particularly, described defoamer adopts existing conventional silicone based, the defoamer of organic silicon modified by polyether class.
Particularly, described air entrapment agent adopts sodium lauryl sulphate (K
12), triterpenoid saponin, Sodium dodecylbenzene sulfonate etc. existing routine adopt air entrapment agent.
Particularly, described retardant adopts the retardant that the existing routine such as Sunmorl N 60S, white sugar or citric acid adopts.
The preparation method of composite polycarboxylate water-reducer of the present invention: realized by following steps:
Step one, prepare the polyether macromonomer of terminal hydroxy group esterification: the raw material that the polyether macromonomer of terminal hydroxy group esterification described above adopts is mixed to get mixture, then by mixture esterification under 80 DEG C ~ 130 DEG C conditions, obtains the polyether macromonomer of terminal hydroxy group esterification;
Step 2, the polyether macromonomer of terminal hydroxy group esterification step one obtained and water mixing and stirring, drip initiator, chain-transfer agent and vinylformic acid respectively after being heated to 20 DEG C ~ 60 DEG C, drip rear insulation reaction 1 ~ 3h, mixture after must reacting;
Step 3, after reaction, add basic solution in mixture, the pH value of mixture after reaction is neutralized in 6 ~ 7 scopes, obtains polycarboxylate superplasticizer mother liquor;
Step 4, polycarboxylate superplasticizer mother liquor being added water obtains the polycarboxylate superplasticizer mother liquor that solid content is 8% ~ 15%, and then adds defoamer, air entrapment agent and retardant, stirs, namely obtains composite polycarboxylate water-reducer.
Further, in step 2, time for adding controls at 2 ~ 5h, and the time for adding controlling initiator 0.5h more than acrylic acid time for adding.
In step 3, described basic solution can adopt organic alkali lye of the inorganic alkali lye or trolamine and so on such as sodium hydroxide solution.
Composite polycarboxylate water-reducer of the present invention is added into the application in concrete as concrete admixture.
Further, with the ratio of 1% ~ 5% of gelling material weight in concrete, composite polycarboxylate water-reducer is added in concrete.
Particularly, in concrete, gelling material mainly refers to cement, also has breeze, flyash etc. in concrete, to play the material of cementation gelling material.
The polyether macromonomer of terminal hydroxy group esterification that what the polyether macromonomer in the polycarboxylate superplasticizer mother liquor raw material that composite polycarboxylate water-reducer of the present invention adopts adopted is, it utilizes macromolecular carboxylic acid as the capping group of polyethers, add the physical size of polycarboxylate water-reducer side chain terminal greatly, make it not easily insert in the laminate structure of clay, thus reach the effect of anti-mud.And then ensure that concrete serviceability.
Further, the composite polycarboxylate water-reducer that the proportioning recorded according to utilizing the present invention obtains, it can be used as concrete admixture to be added in concrete, improves concrete serviceability.
Further, the macromolecular carboxylic acid's wide material sources adopted in the preparation of the polyether macromonomer of terminal hydroxy group esterification, low price, stable in properties, has no side effect.
Embodiment
Below in conjunction with embodiments of the invention, be clearly and completely described technical scheme of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Embodiment 1
The polyether macromonomer of the terminal hydroxy group esterification of the present embodiment 1 is under the katalysis of catalyzer, and the terminal hydroxy group of polyether macromonomer and the carboxyl of macromolecular carboxylic acid carry out that esterification obtains; The mol ratio of described polyether macromonomer and macromolecular carboxylic acid is 1 ﹕ 0.2 ~ 1; The temperature of reaction of described esterification is 80 DEG C ~ 130 DEG C.Wherein said polyether macromonomer adopts isopentene group Soxylat A 25-7 (TPEG) or isobutenyl Soxylat A 25-7 (HPEG).Particularly, catalyzer can adopt tosic acid or thionamic acid, and its consumption is determined according to the consumption of polyether macromonomer; Particularly, the consumption of described catalyzer can be 2% ~ 6% of the quality of described polyether macromonomer.
Particularly, described catalyzer adopts tosic acid or thionamic acid.
The structural formula of the polyether macromonomer of terminal hydroxy group esterification is as follows:
r
1for sub-methoxyl group or inferior ethoxyl, R
2removing the alkyl of remainder after carbon in decarboxylate or containing the group of phenyl ring for macromolecular carboxylic acid; N gets positive integer.R
1during for sub-methoxyl group, employing be isobutenyl Soxylat A 25-7 (HPEG); R
1during for inferior ethoxyl, employing be isopentene group Soxylat A 25-7 (TPEG).
Particularly, when macromolecular carboxylic acid adopts Palmiticacid, R
2it is the alkyl of 15 carbon; When adopting stearic acid, R
2it is the alkyl of 17 carbon; When adopting phenylformic acid, R
2for phenyl ring.Certainly, macromolecular carboxylic acid is not limited to adopt above-mentioned three kinds, every meet carbonatoms 16 ~ 32 alkyl carboxylic acid or be all applicable to the embodiment of the present invention 1 for the carboxylic acid containing phenyl ring.
That is, the numerical value of the polymerization degree n in polyether macromonomer is certain, the polyether macromonomer of the different terminal hydroxy group esterification of 6 kinds of structures can be obtained, specific as follows:
Monomer 1: isopentene group Soxylat A 25-7 and Palmiticacid esterification obtain;
Monomer 2: isopentene group Soxylat A 25-7 and stearic acid esterification obtain;
Monomer 3: isopentene group Soxylat A 25-7 and phenylformic acid esterification obtain;
Monomer 4: isobutenyl Soxylat A 25-7 and Palmiticacid esterification obtain;
Monomer 5: isobutenyl Soxylat A 25-7 and stearic acid esterification obtain;
Monomer 6: isobutenyl Soxylat A 25-7 and phenylformic acid esterification obtain;
Concrete preparation method is as follows:
The raw material (polyether macromonomer, macromolecular carboxylic acid and catalyzer) that the polyether macromonomer of described terminal hydroxy group esterification adopts is mixed to get mixture, then by mixture esterification 2 ~ 5 hours under 80 DEG C ~ 130 DEG C (be preferably 100 DEG C) conditions, the polyether macromonomer of terminal hydroxy group esterification is obtained.
Embodiment 2
Because esterification is reversible reaction, if the H generated in esterification reaction process
2o is accumulated in reaction vessel, can accelerate the generation of its reversed reaction.Therefore, in order to improve esterification efficiency, on the raw material basis of the polyether macromonomer of the terminal hydroxy group esterification adopted in embodiment 1, also add water entrainer in the raw material of the polyether macromonomer of the present embodiment 2 terminal hydroxy group esterification, the consumption of described water entrainer is 10% ~ 20% of the quality of described polyether macromonomer.Particularly, hexanaphthene can be adopted.
Further, in order to stop the double-bond polymerization of reaction raw materials polyether macromonomer in reaction process, in the esterification reaction, also stopper is added; The consumption of described stopper is 0.05% ~ 0.5% of the quality of described polyether macromonomer.Particularly, Resorcinol or thiodiphenylamine etc. can be adopted.
The preparation method of the polyether macromonomer of the terminal hydroxy group esterification of the present embodiment 2 is as follows:
By raw material (polyether macromonomer, macromolecular carboxylic acid and catalyzer that the polyether macromonomer of described terminal hydroxy group esterification adopts, water entrainer and stopper) be mixed to get mixture, then by mixture esterification 2 ~ 5 hours under 80 DEG C ~ 130 DEG C (be preferably 100 DEG C) conditions, the polyether macromonomer of terminal hydroxy group esterification is obtained.
The structural formula of the polyether macromonomer of the terminal hydroxy group esterification of the present embodiment 2 is the same with the structure in embodiment 1.Just in esterification reaction process, speed of reaction improves.
Embodiment 3
Polycarboxylate superplasticizer mother liquor is by after the polyether macromonomer of the terminal hydroxy group esterification described in embodiment 1 and water, initiator, chain-transfer agent and vinylformic acid Hybrid Heating being reacted, then adds in basic solution and obtain behind pH value to 6 ~ 7.
The polyether macromonomer of the terminal hydroxy group esterification adopted in polycarboxylate superplasticizer mother liquor of the present invention and water, initiator, chain-transfer agent and acrylic acid blending ratio adopt existing blending ratio, and existing initiator, chain-transfer agent.But as embodiment, the present embodiment 3 gives concrete adoption rate, but it can not limit polycarboxylate superplasticizer mother liquor of the present invention.
The mol ratio numerical value of the polyether macromonomer of the water adopted in the present embodiment 3, initiator, chain-transfer agent and acrylic acid molar weight and described terminal hydroxy group esterification, refers to shown in table 1.Wherein, the consumption of water and the ratio M of polyether macromonomer, initiator, chain-transfer agent and acrylic acid total mass are 1.5.
Table 1
In upper table 1, Vc-H
2o
2vc ﹕ H in initiator system
2o
2mol ratio is 0.1 ~ 0.25 ﹕ 1.
The initiator adopted in polycarboxylate superplasticizer mother liquor of the present invention and chain-transfer agent are not limited to material cited in table 1.
The preparation method of the polycarboxylate superplasticizer mother liquor of the present embodiment 3, is realized by following steps:
Step one, by the molar ratio provided in table 1 and ratio M, prepare each raw material; Then by the polyether macromonomer of terminal hydroxy group esterification and water mixing and stirring, initiator, chain-transfer agent and vinylformic acid is dripped respectively after being heated to 20 DEG C ~ 60 DEG C, time for adding controls at 2 ~ 5h, and the time for adding controlling initiator 0.5h more than acrylic acid time for adding, drip rear insulation reaction 1 ~ 3h, mixture after must reacting;
Step 2, after reaction, add basic solution in mixture, the pH value of mixture after reaction is neutralized in 6 ~ 7 scopes, obtains polycarboxylate superplasticizer mother liquor.
Solid content in the polycarboxylate superplasticizer mother liquor of the present embodiment 3 prepared by above-mentioned preparation method is about 40%.Described solid content is more specifically called " nonvolatile substances content ".
Particularly, in step 2, described basic solution can adopt sodium hydroxide solution.
Embodiment 4
Composite polycarboxylate water-reducer, it is the mixture comprising polycarboxylate superplasticizer mother liquor, defoamer, air entrapment agent and retardant that embodiment 3 is recorded, wherein, in the mixture, the mass percentage of the nonvolatile substances in described polycarboxylate superplasticizer mother liquor is 8% ~ 15%.Be preferably, in the mixture, the mass percentage of the nonvolatile substances in described polycarboxylate superplasticizer mother liquor is 10%.The mass percentage of described defoamer is 0.01% ~ 0.1%, air entrapment agent 0.01% ~ 0.1%, and the mass percentage of retardant is 0.5% ~ 8%.The consumption of retardant decides according to temperature.
Particularly, described defoamer adopts existing conventional silicone based, the defoamer of organic silicon modified by polyether class.Described air entrapment agent adopts sodium lauryl sulphate (K
12), triterpenoid saponin, Sodium dodecylbenzene sulfonate etc. existing routine adopt air entrapment agent.The retardant that described retardant adopts the existing routine such as Sunmorl N 60S, white sugar or citric acid to adopt.
Its preparation method is as follows: polycarboxylate superplasticizer mother liquor added water and obtain the polycarboxylate superplasticizer mother liquor (namely nonvolatile substances content is the polycarboxylate superplasticizer mother liquor of 8% ~ 15%) that solid content is 8% ~ 15%, and then add defoamer, air entrapment agent and retardant, stir.
Embodiment 5
The present embodiment 5 is Application Example, is the composite polycarboxylate water-reducer recorded in embodiment 4 is added in concrete application as concrete admixture.With the ratio of 2% of gelling material weight in concrete, the composite polycarboxylate water-reducer of embodiment 4 is added in concrete.
Particularly, in the sample 3-3 in the table 1 of embodiment 3, adopt the polyether macromonomer of the terminal hydroxy group esterification of 3 kinds of structures of monomer 1 to 3 in embodiment 1 respectively, obtain 3 kinds of polycarboxylate superplasticizer mother liquor; Corresponding to monomer 1 to 3, by 3 kinds of polycarboxylate superplasticizer mother liquor accordingly referred to as mother liquor 1 to 3.Preparation method adopts the method recorded in embodiment 3.The concrete mol ratio of mother liquor 1 to 3 is as follows, polyethers great mono-Ti ﹕ Vc-H of terminal hydroxy group esterification
2o
2the sour ﹕ vinylformic acid of initiation system ﹕ mercapto base third is 1 ﹕ 0.022 ﹕ 0.11 ﹕ 4.Wherein Vc-H
2o
2vc ﹕ H in initiator system
2o
2mol ratio is 0.022:0.09 (i.e. 0.24 ﹕ 1).
As a comparison, prepared a contrast mother liquor, adopted isopentene group Soxylat A 25-7, Vc-H
2o
2initiator system.Thiohydracrylic acid and vinylformic acid are as raw material, and proportioning is the same, adopt the preparation method recorded in embodiment 3 to prepare contrast mother liquor.
And then by mother liquor 1 to 3, contrast mother liquor, be formulated as composite polycarboxylate water-reducer 1-3 and the composite polycarboxylate water-reducer of contrast, referred to as composite 1-3 and contrast composite 1 according to the method recorded in embodiment 4.
Concrete proportioning is: the solid content in mother liquor 1 to 3 is 10%, and the mass percentage of described defoamer is 0.05%, air entrapment agent 0.05%, and the mass percentage of retardant is 2%.Described defoamer adopts existing conventional silicone based.Described air entrapment agent adopts sodium lauryl sulphate (K
12).Described retardant adopts Sunmorl N 60S.
The composite polycarboxylate water-reducer of above-mentioned composite 1-3 and contrast composite 1 is added into the application in concrete as concrete admixture.The composite polycarboxylate water-reducer of composite 1-3 and contrast composite 1 is added in concrete by ratio respectively that account for gelling material weight 2% in concrete with composite polycarboxylate water-reducer, obtains concrete 1-3 and contrast concrete 1.Wherein, the sand in concrete raw material adopts the sand of different silt contents.
According to the concrete standard of C30, at 25 DEG C, detect the index such as the concrete slump, time of coagulation and intensity after the composite polycarboxylate water-reducer adding composite 1-3 and contrast composite 1 respectively, detected result is as shown in the table:
Table 2 to be sand silt contents be 0% concrete performance index detected result:
Table 2
Table 3 to be sand silt contents be 5% concrete performance index detected result:
Table 3
Table 4 to be sand silt contents be 10% concrete performance index detected result:
Table 4
Can be drawn by the test result of table 2, add composite 1-3 and contrast composite 1 composite polycarboxylate water-reducer after the concrete slump, time of coagulation and intensity basically identical.
Can be drawn by the test result of table 3 and table 4, add the concrete slump/divergence after the composite polycarboxylate water-reducer of composite 1-3 be obviously better than add contrast composite 1 after concrete.Ensure that concrete serviceability.
By the concrete slump/divergence performance perameter after the composite polycarboxylate water-reducer that adds composite 1-3 in contrast table 2 to table 4, visible, the sand silt content of the sand used in concrete is little on concrete serviceability impact impact.And add in the concrete after contrast composite 1, the sand silt content of sand is very large on concrete serviceability impact impact, and along with the increase of sand silt content, the concrete slump obtained/divergence performance perameter data obviously decline.
And the concrete time of coagulation of adding after the composite polycarboxylate water-reducer of composite 1-3 and contrast composite 1 and intensity are obviously not different, level is substantially suitable.
The above; be only the specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; change can be expected easily or replace, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should described be as the criterion with the protection domain of claim.
Claims (10)
1. composite polycarboxylate water-reducer, comprise polycarboxylate superplasticizer mother liquor, to it is characterized in that: described polycarboxylate superplasticizer mother liquor is by after the polyether macromonomer of terminal hydroxy group esterification and water, initiator, chain-transfer agent and vinylformic acid Hybrid Heating being reacted, then add in basic solution and obtain behind pH value to 6 ~ 7; Wherein, the polyether macromonomer of described terminal hydroxy group esterification is under the katalysis of catalyzer, and the terminal hydroxy group of polyether macromonomer and the carboxyl of macromolecular carboxylic acid carry out that esterification obtains.
2. composite polycarboxylate water-reducer according to claim 1, is characterized in that: the mol ratio of described polyether macromonomer and macromolecular carboxylic acid is 1 ﹕ 0.2 ~ 1.
3. according to the composite polycarboxylate water-reducer one of claim 1 to 2 Suo Shu, it is characterized in that: described macromolecular carboxylic acid is the alkyl carboxylic acid of carbonatoms 16 ~ 32 or is the carboxylic acid containing phenyl ring.
4. composite polycarboxylate water-reducer according to claim 3, is characterized in that: the weight-average molecular weight of described polyether macromonomer is 1000 ~ 5000.
5. according to the composite polycarboxylate water-reducer one of claim 1 to 2 Suo Shu, it is characterized in that: the consumption of described catalyzer is 2% ~ 6% of the quality of described polyether macromonomer.
6. according to the composite polycarboxylate water-reducer one of claim 1 to 2 Suo Shu, it is characterized in that: in the esterification reaction, also add water entrainer and stopper; The consumption of described water entrainer is 10% ~ 20% of the quality of described polyether macromonomer; The consumption of described stopper is 0.05% ~ 0.5% of the quality of described polyether macromonomer.
7. according to the composite polycarboxylate water-reducer one of claim 1 to 2 Suo Shu, it is characterized in that: the polyether macromonomer of described terminal hydroxy group esterification and the mol ratio of initiator are 1 ﹕ 0.01 ~ 0.3; The polyether macromonomer of described terminal hydroxy group esterification and the mol ratio of chain-transfer agent are 1 ﹕ 0.05 ~ 0.8; The polyether macromonomer of described terminal hydroxy group esterification and acrylic acid mol ratio are 1 ﹕ 2 ~ 7.
8. according to the composite polycarboxylate water-reducer one of claim 1 to 2 Suo Shu, it is characterized in that: described composite polycarboxylate water-reducer is the mixture comprising polycarboxylate superplasticizer mother liquor, defoamer, air entrapment agent and retardant; Wherein, in the mixture, the mass percentage of the nonvolatile substances in described polycarboxylate superplasticizer mother liquor is 8% ~ 15%.
9. the preparation method of composite polycarboxylate water-reducer of the present invention, be is characterized in that: realized by following steps:
Step one, prepare the polyether macromonomer of terminal hydroxy group esterification: the raw material that the polyether macromonomer of terminal hydroxy group esterification described in any one in the claims 1 to 6 adopts is mixed to get mixture, then by mixture esterification under 80 DEG C ~ 130 DEG C conditions, the polyether macromonomer of terminal hydroxy group esterification is obtained;
Step 2, according to the consumption proportion described in claim 1 or 7, the polyether macromonomer of the terminal hydroxy group esterification that step one is obtained and water mixing and stirring, initiator, chain-transfer agent and vinylformic acid is dripped respectively after being heated to 20 DEG C ~ 60 DEG C, drip rear insulation reaction 1 ~ 3h, mixture after must reacting;
Step 3, after reaction, add basic solution in mixture, the pH value of mixture after reaction is neutralized in 6 ~ 7 scopes, obtains polycarboxylate superplasticizer mother liquor;
Step 4, polycarboxylate superplasticizer mother liquor being added water obtains the polycarboxylate superplasticizer mother liquor that solid content is 8% ~ 15%, and then adds defoamer, air entrapment agent and retardant, stirs, namely obtains composite polycarboxylate water-reducer.
10. the preparation method of composite polycarboxylate water-reducer of the present invention according to claim 9, it is characterized in that: in step 2, time for adding controls at 2 ~ 5h, and the time for adding controlling initiator 0.5h more than acrylic acid time for adding.
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| CN106966629A (en) * | 2017-04-13 | 2017-07-21 | 贵州科之杰新材料有限公司 | A kind of preparation method of polycarboxylate superplasticizer mother liquor |
| CN107188448A (en) * | 2017-05-25 | 2017-09-22 | 辽宁省建设科学研究院有限责任公司 | A kind of preparation method of nano-material modified powdery polycarboxylic acid high-performance water reducer |
| CN110759663A (en) * | 2019-10-23 | 2020-02-07 | 安徽海螺新材料科技有限公司 | Preparation method and application of anti-mud polycarboxylate superplasticizer |
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| CN112898577A (en) * | 2020-12-25 | 2021-06-04 | 科之杰新材料集团有限公司 | Defoaming type polycarboxylate superplasticizer for cement concrete and preparation method thereof |
| CN115403297A (en) * | 2022-09-30 | 2022-11-29 | 深圳市五山新材料股份有限公司 | Polycarboxylate superplasticizer for improving workability |
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