CN104761176B - Compound polycarboxylate water-reducer and preparation method thereof - Google Patents
Compound polycarboxylate water-reducer and preparation method thereof Download PDFInfo
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Abstract
The invention provides compounding polycarboxylate water-reducer and preparation method thereof.Compounding polycarboxylate water-reducer includes polycarboxylate superplasticizer mother liquor, and polycarboxylate superplasticizer mother liquor is after being reacted by the polyether macromonomer for being esterified terminal hydroxy group with water, initiator, chain-transferring agent and acrylic acid Hybrid Heating, then neutralizes pH value to obtaining after 6~7；Wherein, the polyether macromonomer of the terminal hydroxy group esterification is under the catalytic action of catalyst, and the terminal hydroxy group of polyether macromonomer and the carboxyl of macromolecular carboxylic acid carry out what esterification obtained.The polyether macromonomer of terminal hydroxy group esterification uses end-capping group of the macromolecular carboxylic acid as polyether macromonomer, greatly add the physical size of side chain terminal, and then considerably increase the physical size of the side chain terminal by its synthetically prepared polycarboxylate superplasticizer mother liquor, it is set to be not easy to insert in the layer structure of clay, so as to reach the effect of anti-mud.It is compounding polycarboxylate water-reducer of the invention to be compounded again, more ensure that the service behaviour of concrete.
Description
Technical field
The present invention relates to polycarboxylate water-reducer technical field, more particularly to compounding polycarboxylate water-reducer and preparation method thereof.
Background technology
Water reducer is current research and a kind of most widely used concrete admixture, and additive turns into be removed in concrete
The 5th kind of important component beyond cement, sand, stone, water.Polycarboxylic acids has that volume is low, protects and collapses as water reducer of new generation
Performance is good, concrete contraction percentage is low, molecular structure adjustability is strong, simple production process and the advantages that the close friend to environment.It is public
It is considered the developing direction of concrete admixture from now on.
In actual use, easily inserted due to polycarboxylate water-reducer side chain in the layer structure of clay, cause to gather
Dispersive property of the carboxylic acid water reducer in the concrete containing clay is greatly affected, and causes its anti-mud poor, and then lead
The combination property of concrete is caused to decline.
The content of the invention
For the drawbacks described above and problem of prior art, it is an object of the invention to provide compounding polycarboxylate water-reducer and its system
Preparation Method.What the polyether macromonomer in the polycarboxylate superplasticizer mother liquor raw material that the compounding polycarboxylate water-reducer of the present invention uses used
It is the polyether macromonomer of terminal hydroxy group esterification, it is the end-capping group by the use of macromolecular carboxylic acid as polyethers, is greatly added poly-
The physical size of carboxylic acid water reducer side chain terminal, it is set to be not easy to insert in the layer structure of clay, so as to reach the effect of anti-mud.
The side chain for solving existing polycarboxylate water-reducer is easily inserted in the layer structure of clay, causes its anti-mud poor, and then cause
The technical problem that the combination property of concrete declines.
In order to achieve the above object, the present invention provides following technical scheme：
Polycarboxylate water-reducer, including polycarboxylate superplasticizer mother liquor are compounded, wherein, the polycarboxylate superplasticizer mother liquor is to pass through
By the polyether macromonomer of terminal hydroxy group esterification with after water, initiator, chain-transferring agent and the reaction of acrylic acid Hybrid Heating, adding alkalescence
In solution and pH value is to obtaining after 6~7；Wherein, the polyether macromonomer of the terminal hydroxy group esterification is the catalysis work in catalyst
Under, the terminal hydroxy group of polyether macromonomer and the carboxyl of macromolecular carboxylic acid carry out what esterification obtained.
Further, the mol ratio of the polyether macromonomer and macromolecular carboxylic acid are 1 ﹕ 0.2~1.
Further, the mol ratio of the polyether macromonomer and macromolecular carboxylic acid are 1 ﹕ 0.5.
Further, the macromolecular carboxylic acid is the alkyl carboxylic acid of carbon number 16~32 or is the carboxylic acid containing phenyl ring.
Specifically, the macromolecular carboxylic acid can use but be not limited to palmitic acid, stearic acid or benzoic acid.
Further, the weight average molecular weight of the polyether macromonomer is 1000~5000.
Specifically, the polyether macromonomer can use isopentene group APEO (TPEG) or isobutenyl polyoxy
Vinethene (HPEG).
Further, in the esterification, controlling reaction temperature is 80 DEG C~130 DEG C, and esterification time is 2~5h.
Further, the dosage of the catalyst is the 2%~6% of the quality of the polyether macromonomer.
Specifically, the catalyst uses p-methyl benzenesulfonic acid or sulfamic acid.
Further, in the esterification reaction, it is also added into water entrainer.The dosage of the water entrainer of addition is former according to esterification
The analysis of the ability integration of material dosage and water entrainer is calculated.Specifically, in the present invention, the dosage of the water entrainer can be with
For the 10%~20% of the quality of the polyether macromonomer.Heretofore described water entrainer can use hexamethylene.Esterification
The water of generation is taken out of reaction system in time, is accelerated the positive progress of esterification, is improved esterification efficiency.
Further, in the esterification reaction, it is additionally added polymerization inhibitor；The dosage of the polymerization inhibitor is the polyether macromonomer
The 0.05%~0.5% of quality.Prevent the double-bond polymerization of polyether macromonomer.Specifically, hydroquinones or fen thiophene can be used
Piperazine etc..
Further, the polyether macromonomer of the terminal hydroxy group esterification and the mol ratio of initiator are 1 ﹕ 0.01~0.3；It is described
The polyether macromonomer of terminal hydroxy group esterification and the mol ratio of chain-transferring agent are 1 ﹕ 0.05~0.8；The polyethers of the terminal hydroxy group esterification is big
The mol ratio of monomer and acrylic acid is 1 ﹕ 2~7.
Specifically, polyether macromonomer, initiator, chain-transferring agent and acrylic acid of the dosage of the water according to terminal hydroxy group esterification
Gross mass depending on, the solid content for making the polycarboxylate superplasticizer mother liquor that reaction obtains is 35%~50%.I.e. described water
The ratio M of dosage and gross mass is 1~2.
Further, the initiator can use ammonium persulfate, potassium peroxydisulfate or Vc-H2O2Initiation system etc..It is different
The dosage that uses during the course of the reaction of initiator it is different.When the initiator uses ammonium persulfate or potassium peroxydisulfate
When, the polyether macromonomer of the terminal hydroxy group esterification and the mol ratio of initiator are 1 ﹕ 0.1~0.3；Preferably 1 ﹕ 0.2.When described
Initiator uses Vc-H2O2During initiation system, the polyether macromonomer of the terminal hydroxy group esterification and the mol ratio of initiator are 1 ﹕ 0.01
~0.1, be preferably, 1 ﹕ 0.022；Wherein, Vc-H2O2Vc ﹕ H in initiation system2O2Mol ratio is 0.1~0.25 ﹕ 1.
Further, the chain-transferring agent can use TGA/propionic acid, methylpropene sodium sulfonate etc..When using mercapto
During guanidine-acetic acid/propionic acid, the polyether macromonomer of the terminal hydroxy group esterification and the mol ratio of chain-transferring agent are 1 ﹕ 0.05~0.3；It is preferred that
For 1 ﹕ 0.11.When using methylpropene sodium sulfonate, the polyether macromonomer of the terminal hydroxy group esterification and the mol ratio of chain-transferring agent
For 1 ﹕ 0.1~0.8；Preferably 1 ﹕ 0.3.
Further, the polyether macromonomer of the terminal hydroxy group esterification and the mol ratio of acrylic acid are 1 ﹕ 4.
Further, the compounding polycarboxylate water-reducer, it is to include polycarboxylate superplasticizer mother liquor, water, defoamer, air entraining agent
With the mixture of retarder, wherein, in the mixture, the quality percentage of the non-volatile matter in the polycarboxylate superplasticizer mother liquor
Content is 8%~15%.What non-volatile matter therein referred to be polycarboxylate superplasticizer mother liquor middle-end hydroxy esterification polyethers it is big
Monomer and chain-transferring agent and acroleic acid polymerization react obtained polymer.
Preferably, in the mixture, the weight/mass percentage composition of the non-volatile matter in the polycarboxylate superplasticizer mother liquor is
10%.
Further, the weight/mass percentage composition of the defoamer is 0.01%~0.1%, air entraining agent 0.01%~0.1%,
The weight/mass percentage composition of retarder is 0.5%~8%.
It is further preferred that the weight/mass percentage composition of the defoamer is 0.02%~0.08%, air entraining agent 0.02%~
0.08%, the weight/mass percentage composition of retarder is 1%~5%.
It is further preferred that the weight/mass percentage composition of the defoamer is 0.05%, and air entraining agent 0.05%, the matter of retarder
It is 2% to measure percentage composition.
Specifically, the defoamer uses existing conventional organic silicon, the defoamer of organic silicon modified by polyether class.
Specifically, the air entraining agent uses lauryl sodium sulfate (K12), triterpenoid saponin, neopelex etc. it is existing
There is the air entraining agent routinely used.
Specifically, the retarder is using existing retarder routinely used such as sodium gluconate, white sugar or citric acids
.
The preparation method of the compounding polycarboxylate water-reducer of the present invention：Through the following steps that realize：
Step 1: prepare the polyether macromonomer of terminal hydroxy group esterification：The polyether macromonomer that terminal hydroxy group described above is esterified is adopted
Raw material mixes to obtain mixture, is then esterified mixture under the conditions of 80 DEG C~130 DEG C, obtains the polyethers of terminal hydroxy group esterification
Polymeric monomer；
Step 2: the polyether macromonomer that the terminal hydroxy group that step 1 obtains is esterified is mixed evenly with water, 20 are heated to
DEG C~60 DEG C after initiator, chain-transferring agent and acrylic acid are added dropwise respectively, drip rear 1~3h of insulation reaction, mixed after must reacting
Thing；
Step 3: adding alkaline solution into mixture after reaction, the pH value of mixture after reaction is neutralized to 6~7 models
In enclosing, polycarboxylate superplasticizer mother liquor is obtained；
Step 4: add water to obtain the polycarboxylate superplasticizer mother liquor that solid content is 8%~15% polycarboxylate superplasticizer mother liquor,
Then add defoamer, air entraining agent and retarder, stir, that is, obtain compounding polycarboxylate water-reducer.
Further, in step 2, time for adding is controlled in 2~5h, and controls the time for adding of initiator to compare acrylic acid
The more 0.5h of time for adding.
In step 3, the alkaline solution can use the inorganic alkali lye or triethanolamine such as sodium hydroxide solution etc
Organic alkali lye.
The application that the compounding polycarboxylate water-reducer of the present invention is added in concrete as concrete admixture.
Further, with 1%~5% ratio of binder materials weight in concrete, compounding polycarboxylate water-reducer is added
Add in concrete.
Specifically, binder materials is primarily referred to as cement in concrete, and also miberal powder, flyash etc. rises cementing in concrete
The material of effect is binder materials.
Polyether macromonomer in the polycarboxylate superplasticizer mother liquor raw material that the compounding polycarboxylate water-reducer of the present invention uses uses
Be terminal hydroxy group esterification polyether macromonomer, it is the end-capping group by the use of macromolecular carboxylic acid as polyethers, is greatly added
The physical size of polycarboxylate water-reducer side chain terminal, it is set to be not easy to insert in the layer structure of clay, so as to reach the effect of anti-mud
Fruit.And then it ensure that the service behaviour of concrete.
Further, the compounding polycarboxylate water-reducer obtained according to the proportioning recorded using the present invention, as coagulation
Native additive is added in concrete, improves the service behaviour of concrete.
Further, the macromolecular carboxylic acid's wide material sources used in the preparation of the polyether macromonomer of terminal hydroxy group esterification, price
Cheaply, property is stable, has no toxic side effect.
Embodiment
Below in conjunction with embodiments of the invention, technical scheme is clearly and completely described, it is clear that
Described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.Based on the implementation in the present invention
Example, the every other embodiment that those of ordinary skill in the art are obtained under the premise of creative work is not made, is belonged to
The scope of protection of the invention.
Embodiment 1
The present embodiment 1 terminal hydroxy group esterification polyether macromonomer, be under the catalytic action of catalyst, polyether macromonomer
Terminal hydroxy group and the carboxyl of macromolecular carboxylic acid carry out what esterification obtained；The polyether macromonomer and the mol ratio of macromolecular carboxylic acid
For 1 ﹕ 0.2~1；The reaction temperature of the esterification is 80 DEG C~130 DEG C.Wherein described polyether macromonomer uses isopentene group
APEO (TPEG) or isobutenyl APEO (HPEG).Specifically, catalyst can use p-methyl benzenesulfonic acid
Or sulfamic acid, depending on its dosage is according to the dosage of polyether macromonomer；Specifically, the dosage of the catalyst can be described poly-
The 2%~6% of the quality of ether polymeric monomer.
Specifically, the catalyst uses p-methyl benzenesulfonic acid or sulfamic acid.
The structural formula of the polyether macromonomer of terminal hydroxy group esterification is as follows：
R1For methylene epoxide or inferior ethoxyl, R2For macromolecular carboxylic
Acid removes in decarboxylate remaining alkyl or the group containing phenyl ring after carbon；N takes positive integer.R1For methylene epoxide when, use
It is isobutenyl APEO (HPEG)；R1For inferior ethoxyl when, using isopentene group APEO (TPEG).
Specifically, when macromolecular carboxylic acid uses palmitic acid, R2For the alkyl of 15 carbon；During using stearic acid, R2For 17 carbon
Alkyl；During using benzoic acid, R2For phenyl ring.Certainly, macromolecular carboxylic acid is not limited to using above-mentioned three kinds, every to meet carbon original
The alkyl carboxylic acid of subnumber 16~32 is applied to the embodiment of the present invention 1 for the carboxylic acid containing phenyl ring.
That is, in the case that the numerical value of the polymerization degree n in polyether macromonomer is certain, 6 kinds of different ends of structure can be obtained
The polyether macromonomer of hydroxy esterification, it is specific as follows：
Monomer 1：Isopentene group APEO and palmitic acid are esterified to obtain；
Monomer 2：Isopentene group APEO and stearic acid are esterified to obtain；
Monomer 3：Isopentene group APEO and benzoic acid are esterified to obtain；
Monomer 4：Isobutenyl APEO and palmitic acid are esterified to obtain；
Monomer 5：Isobutenyl APEO and stearic acid are esterified to obtain；
Monomer 6：Isobutenyl APEO and benzoic acid are esterified to obtain；
Specific preparation method is as follows：
The raw material (polyether macromonomer, macromolecular carboxylic acid and catalyst) that the polyether macromonomer that the terminal hydroxy group is esterified uses
Mixture is mixed to obtain, then mixture is esterified 2~5 hours under the conditions of 80 DEG C~130 DEG C (being preferably 100 DEG C), held
The polyether macromonomer of hydroxy esterification.
Embodiment 2
Because esterification is reversible reaction, if the H generated in esterification reaction process2O is accumulated in reaction vessel, can be added
The generation of its fast back reaction.Therefore, in order to improve esterification efficiency, the polyethers of the terminal hydroxy group esterification used in embodiment 1
On the basis of the raw material of polymeric monomer, water entrainer is also added into the raw material of the polyether macromonomer of the terminal hydroxy group of the present embodiment 2 esterification, it is described
The dosage of water entrainer is the 10%~20% of the quality of the polyether macromonomer.Specifically, hexamethylene can be used.
Further, in order to prevent the double-bond polymerization of reaction raw materials polyether macromonomer during the course of the reaction, in esterification
In, it is also added into polymerization inhibitor；The dosage of the polymerization inhibitor is the 0.05%~0.5% of the quality of the polyether macromonomer.Specifically
Ground, hydroquinones or phenthazine etc. can be used.
The preparation method of the polyether macromonomer of the terminal hydroxy group esterification of the present embodiment 2 is as follows：
Raw material that the polyether macromonomer that the terminal hydroxy group is esterified uses (polyether macromonomer, macromolecular carboxylic acid and catalyst,
Water entrainer and polymerization inhibitor) mixture is mixed to obtain, mixture is then esterified 2 under the conditions of 80 DEG C~130 DEG C (being preferably 100 DEG C)
~5 hours, obtain the polyether macromonomer of terminal hydroxy group esterification.
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.Simply exist
In esterification reaction process, reaction rate improves.
Embodiment 3
Polycarboxylate superplasticizer mother liquor, it is by the polyether macromonomer and the water that are esterified the terminal hydroxy group described in embodiment 1, draws
After sending out agent, chain-transferring agent and the reaction of acrylic acid Hybrid Heating, add in alkaline solution and pH value is to obtaining after 6~7.
The polyether macromonomer and water, initiator, chain of the terminal hydroxy group esterification used in the polycarboxylate superplasticizer mother liquor of the present invention
The mixed proportion of transfer agent and acrylic acid uses existing mixed proportion, and existing initiator, chain-transferring agent.But
As embodiment, the present embodiment 3 gives specific adoption rate, but it can not limit the polycarboxylate superplasticizer mother liquor of the present invention.
The mole of the water, initiator, chain-transferring agent and the acrylic acid that are used in the present embodiment 3 and terminal hydroxy group esterification
The mol ratio numerical value of polyether macromonomer, is referred to shown in table 1.Wherein, the dosage of water and polyether macromonomer, initiator, chain tra nsfer
The ratio M of the gross mass of agent and acrylic acid is 1.5.
Table 1
In upper table 1, Vc-H2O2Vc ﹕ H in initiation system2O2Mol ratio is 0.1~0.25 ﹕ 1.
The initiator that uses and chain-transferring agent are not limited to cited in upper table 1 in the polycarboxylate superplasticizer mother liquor of the present invention
Material.
The preparation method of the polycarboxylate superplasticizer mother liquor of the present embodiment 3, through the following steps that realize：
Step 1: by the molar ratio and ratio M that are provided in table 1, prepare each raw material；Then polyethers terminal hydroxy group being esterified
Polymeric monomer is mixed evenly with water, and initiator, chain-transferring agent and acrylic acid is added dropwise after being heated to 20 DEG C~60 DEG C respectively, is added dropwise
Time control in 2~5h, and control the time for adding of initiator than acrylic acid time for adding more than 0.5h, be incubated after dripping anti-
1~3h is answered, mixture after must reacting；
Step 2: adding alkaline solution into mixture after reaction, the pH value of mixture after reaction is neutralized to 6~7 models
In enclosing, polycarboxylate superplasticizer mother liquor is obtained.
Solid content in the polycarboxylate superplasticizer mother liquor of the present embodiment 3 that the method for being prepared as described above is prepared is left 40%
It is right.The solid content is more specifically referred to as " non-volatile matter content ".
Specifically, in step 2, the alkaline solution can use sodium hydroxide solution.
Embodiment 4
Compound polycarboxylate water-reducer, be include embodiment 3 record polycarboxylate superplasticizer mother liquor, defoamer, air entraining agent and
The mixture of retarder, wherein, in the mixture, the quality percentage of the non-volatile matter in the polycarboxylate superplasticizer mother liquor contains
Measure as 8%~15%.Preferably, in the mixture, the quality percentage of the non-volatile matter in the polycarboxylate superplasticizer mother liquor
Content is 10%.The weight/mass percentage composition of the defoamer is 0.01%~0.1%, air entraining agent 0.01%~0.1%, retarder
Weight/mass percentage composition be 0.5%~8%.The dosage of retarder determines according to temperature.
Specifically, the defoamer uses existing conventional organic silicon, the defoamer of organic silicon modified by polyether class.
The air entraining agent uses lauryl sodium sulfate (K12), triterpenoid saponin, neopelex etc. it is existing routinely use draw
Gas agent.The retarder is using existing retarder routinely used such as sodium gluconate, white sugar or citric acids.
Its preparation method is as follows：Polycarboxylate superplasticizer mother liquor plus water are obtained into the polycarboxylic acids that solid content is 8%~15% to subtract
Aqua mother liquor (polycarboxylate superplasticizer mother liquor that i.e. non-volatile matter content is 8%~15%), then adds defoamer, draws
Gas agent and retarder, stir, you can.
Embodiment 5
The present embodiment 5 is Application Example, is that the compounding polycarboxylate water-reducer described in embodiment 4 is additional as concrete
The application that agent is added in concrete.With 2% ratio of binder materials weight in concrete, by the poly- carboxylic of the compounding of embodiment 4
Sour water reducer is added in concrete.
Specifically, 3 kinds of structures of monomer 1 to 3 in embodiment 1 are respectively adopted in the sample 3-3 in the table 1 of embodiment 3
The polyether macromonomer of terminal hydroxy group esterification, obtains 3 kinds of polycarboxylate superplasticizer mother liquors；Corresponding to monomer 1 to 3, by 3 kinds of polycarboxylic acids diminishings
Agent mother liquor is accordingly abbreviated as mother liquor 1 to 3.Preparation method is using the method described in embodiment 3.Specific mole of mother liquor 1 to 3
Proportioning is as follows, the mono- Ti ﹕ Vc-H of polyethers great of terminal hydroxy group esterification2O2Primosome Xi ﹕ Qiu base Bing Suan ﹕ acrylic acid is the ﹕ of 1 ﹕, 0.022 ﹕ 0.11
4.Wherein Vc-H2O2Vc ﹕ H in initiation system2O2Mol ratio is 0.022:0.09 (i.e. 0.24 ﹕ 1).
As a comparison, a contrast mother liquor is prepared for, using isopentene group APEO, Vc-H2O2Initiation system.Sulfydryl
Propionic acid and acrylic acid are same as above as raw material, proportioning, and contrast mother liquor is prepared using the preparation method described in embodiment 3.
Then again mother liquor 1 to 3, contrast mother liquor are formulated as compounding polycarboxylic acids diminishing according to the method described in embodiment 4
Agent 1-3 and contrast compounding polycarboxylate water-reducer, are abbreviated as compounding 1-3 and contrast compounding 1.
Specifically proportioning is：Solid content in mother liquor 1 to 3 is 10%, and the weight/mass percentage composition of the defoamer is 0.05%,
Air entraining agent 0.05%, the weight/mass percentage composition of retarder is 2%.The defoamer uses existing conventional organic silicon.It is described
Air entraining agent uses lauryl sodium sulfate (K12).The retarder uses sodium gluconate.
Above-mentioned compounding 1-3 and contrast compounding 1 compounding polycarboxylate water-reducer are added to coagulation as concrete admixture
Application in soil.With compound polycarboxylate water-reducer account for the ratio of binder materials weight 2% in concrete respectively will compounding 1-3 and right
Compounding polycarboxylate water-reducer than compounding 1 is added in concrete, obtains concrete 1-3 and contrast concrete 1.Wherein, coagulation
Sand in the raw material of soil uses the sand of different clay contents.
According to the standard of C30 concrete, at 25 DEG C, the compounding polycarboxylic acids to adding compounding 1-3 and contrast compounding 1 respectively
The indexs such as the slump, setting time and the intensity of the concrete after water reducer are detected, and testing result is as shown in the table：
Table 2 is the performance indications testing result for the concrete that sand clay content is 0%：
Table 2
Table 3 is the performance indications testing result for the concrete that sand clay content is 5%：
Table 3
Table 4 is the performance indications testing result for the concrete that sand clay content is 10%：
Table 4
It can be drawn by the test result of table 2, it is mixed after the compounding polycarboxylate water-reducer of addition compounding 1-3 and contrast compounding 1
The slump, setting time and the intensity for coagulating soil are basically identical.
It can be drawn by the test result of table 3 and table 4, the concrete after addition compounding 1-3 compounding polycarboxylate water-reducer
The slump/divergence is substantially better than addition contrast and compounds the concrete after 1.It ensure that the service behaviour of concrete.
The slump/expansion of the concrete after compounding 1-3 compounding polycarboxylate water-reducer is added into table 4 by contrast table 2
Latitude of emulsion performance parameter, it is seen then that the sand clay content of the sand used in concrete influences little on the service behaviour of concrete.And
In concrete after addition contrast compounding 1, the sand clay content of sand the service behaviour of concrete is influenceed it is very big, with sand
The increase of clay content, the slump/divergence performance parameter data of obtained concrete are decreased obviously.
And add setting time and the intensity of the concrete after compounding 1-3 and the compounding polycarboxylate water-reducer of contrast compounding 1
Do not have it is significantly different, it is horizontal substantially suitable.
The foregoing is only a specific embodiment of the invention, but protection scope of the present invention is not limited thereto, any
Those familiar with the art the invention discloses technical scope in, change or replacement can be readily occurred in, should all be contained
Cover within protection scope of the present invention.Therefore, protection scope of the present invention described should be defined by scope of the claims.
Claims (8)
1. polycarboxylate water-reducer is compounded, including polycarboxylate superplasticizer mother liquor, it is characterised in that：The polycarboxylate superplasticizer mother liquor is
After being reacted by the polyether macromonomer for being esterified terminal hydroxy group with water, initiator, chain-transferring agent and acrylic acid Hybrid Heating, add
In alkaline solution and pH value is to obtaining after 6~7；Wherein, the polyether macromonomer of the terminal hydroxy group esterification is urging in catalyst
Under change effect, the terminal hydroxy group of polyether macromonomer and the carboxyl of macromolecular carboxylic acid carry out what esterification obtained；
Wherein, the mol ratio of the polyether macromonomer and macromolecular carboxylic acid are 1 ﹕ 0.2~0.5；The macromolecular carboxylic acid is that carbon is former
The alkyl carboxylic acid of subnumber 16~32 is the carboxylic acid containing phenyl ring.
2. compounding polycarboxylate water-reducer according to claim 1, it is characterised in that：The Weight-average molecular of the polyether macromonomer
Measure as 1000~5000.
3. compounding polycarboxylate water-reducer according to claim 1, it is characterised in that：The dosage of the catalyst is described poly-
The 2%~6% of the quality of ether polymeric monomer.
4. compounding polycarboxylate water-reducer according to claim 1, it is characterised in that：In the esterification reaction, it is also added into band
Aqua and polymerization inhibitor；The dosage of the water entrainer is the 10%~20% of the quality of the polyether macromonomer；The polymerization inhibitor
Dosage is the 0.05%~0.5% of the quality of the polyether macromonomer.
5. compounding polycarboxylate water-reducer according to claim 1, it is characterised in that：The big list of polyethers of the terminal hydroxy group esterification
The mol ratio of body and initiator is 1 ﹕ 0.01~0.3；The polyether macromonomer of the terminal hydroxy group esterification and the mol ratio of chain-transferring agent
For 1 ﹕ 0.05~0.8；The polyether macromonomer of the terminal hydroxy group esterification and the mol ratio of acrylic acid are 1 ﹕ 2~7.
6. compounding polycarboxylate water-reducer according to claim 1, it is characterised in that：The compounding polycarboxylate water-reducer is bag
Include the mixture of polycarboxylate superplasticizer mother liquor, defoamer, air entraining agent and retarder；Wherein, in the mixture, the polycarboxylic acids subtracts
The weight/mass percentage composition of non-volatile matter in aqua mother liquor is 8%~15%.
7. compound the preparation method of polycarboxylate water-reducer, it is characterised in that：Through the following steps that realize：
Step 1: prepare the polyether macromonomer of terminal hydroxy group esterification：By terminal hydroxy group described in any one in the claims 1 to 4
The raw material that the polyether macromonomer of esterification uses mixes to obtain mixture, and then mixture is esterified under the conditions of 80 DEG C~130 DEG C, is obtained
To the polyether macromonomer of terminal hydroxy group esterification；
Step 2: the consumption proportion described according to claim 1 or 5, the polyethers that the terminal hydroxy group that step 1 is obtained is esterified is big
Monomer is mixed evenly with water, and initiator, chain-transferring agent and acrylic acid are added dropwise respectively after being heated to 20 DEG C~60 DEG C, drips
1~3h of insulation reaction afterwards, mixture after must reacting；
Step 3: adding alkaline solution into mixture after reaction, the pH value of mixture after reaction is neutralized in the range of 6~7,
Obtain polycarboxylate superplasticizer mother liquor；
Step 4: water is added to obtain the polycarboxylate superplasticizer mother liquor that solid content is 8%~15% polycarboxylate superplasticizer mother liquor, then
Add defoamer, air entraining agent and retarder, stir, that is, obtain compounding polycarboxylate water-reducer.
8. the preparation method of compounding polycarboxylate water-reducer according to claim 7, it is characterised in that：In step 2, it is added dropwise
Time control in 2~5h, and control the time for adding of initiator than acrylic acid time for adding more than 0.5h.
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| CN201510146030.8A CN104761176B (en) | 2015-03-31 | 2015-03-31 | Compound polycarboxylate water-reducer and preparation method thereof |
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| CN201510146030.8A CN104761176B (en) | 2015-03-31 | 2015-03-31 | Compound polycarboxylate water-reducer and preparation method thereof |
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| CN107188448B (en) * | 2017-05-25 | 2019-04-16 | 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 |
| 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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