CN104231188B - A kind of esters polycarboxylic acid slump retaining agent and preparation method thereof - Google Patents
A kind of esters polycarboxylic acid slump retaining agent and preparation method thereof Download PDFInfo
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- CN104231188B CN104231188B CN201410487655.6A CN201410487655A CN104231188B CN 104231188 B CN104231188 B CN 104231188B CN 201410487655 A CN201410487655 A CN 201410487655A CN 104231188 B CN104231188 B CN 104231188B
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Abstract
The invention discloses a kind of esters polycarboxylic acid slump retaining agent and preparation method thereof, its molecular weight is 20000~150000, and its structural formula is as follows：Wherein, R1For H or CH3, R2For H or COOM, R3For the alkyl of 2~4 carbon, M is H or Na or K or NH4.The esters polycarboxylic acid slump retaining agent of the present invention both can be used alone, and can also solve existing polycarboxylic admixture with existing polycarboxylic admixture compounding use and protect collapse difference or the technical barrier such as the workability variation after slump retaining agent is compounded, easy bleeding；The esters polycarboxylic acid slump retaining agent of the present invention is when applied to concrete, compared to ethers polycarboxylic acids product, workability is more preferable, also more difficult bleeding, this can be very good compensate for easily cause workability variation after wide variety of ethers polycarboxylic acid slump retaining agent incorporation concrete currently on the market, the problem of easy bleeding.
Description
Technical field
The invention belongs to building material technical field, and in particular to a kind of esters polycarboxylic acid slump retaining agent and preparation method thereof.
Background technology
Polycarboxylate water-reducer gradually substitutes the two generation water reducers such as naphthalene system to turn into wide variety of concrete admixture, although
Polycarboxylate water-reducer has the advantages that water-reducing rate is big, function of slump protection is good, it is smaller that the drying shrinkage of concrete is influenceed, but actually should
During, because the quality of sand, stone material is uneven, the sand of some places, stone clay content are very high, and some places are due to day
The scarcity of right sand, have no alternative but employment mechanism sand, and the amount containing stone flour and grading in Machine-made Sand do not control well so that it is poly-
Also there is the problems such as slump-loss is big, workability is poor, easy bleeding in application of the carboxylic acid water reducer in some engineerings.
The content of the invention
It is an object of the invention to overcome prior art defect, there is provided a kind of esters polycarboxylic acid slump retaining agent.
Another object of the present invention is to provide the preparation method of above-mentioned esters polycarboxylic acid slump retaining agent.
The concrete technical scheme of the present invention is as follows：
A kind of esters polycarboxylic acid slump retaining agent, its molecular weight is 20000~150000, and its structural formula is as follows：
Wherein, R1For H or CH3, R2For H or COOM, R3For the alkyl of 2~4 carbon, M is H or Na or K or NH4。
A kind of preparation method of above-mentioned esters polycarboxylic acid slump retaining agent, comprises the following steps：
(1) bifunctionality monomer is prepared：Unsaturated carboxylic acid and/or acid anhydrides, unsaturated carboxylic acid hydroxy ester and polymerization inhibitor are mixed
Close, under nitrogen protection, be warming up to 40~60 DEG C, add catalyst, be warming up to 100~140 DEG C, then 0.5~3h of constant temperature, during which
Water is removed with vacuumizing or leading to method of the nitrogen with water, constant temperature is down to room temperature after terminating, obtains the first mixture, above-mentioned unsaturation
Molecular weight≤200 of carboxylic acid and/or acid anhydrides and unsaturated carboxylic acid hydroxy ester, and mol ratio is 1:2~7, the dosage of catalyst is
The 0.5%~5.0% of unsaturated carboxylic acid and/or acid anhydrides and unsaturated carboxylic acid hydroxy ester gross mass, polymerization inhibitor dosage are unsaturation
The 0.5%~5.0% of carboxylic acid and/or acid anhydrides and unsaturated carboxylic acid hydroxy ester gross mass；
(2) copolyreaction：By the first mixture made from step (1) with esterification polymeric monomer with 1~2:1~2 mass ratio
Mixing, adds molecular weight regulator, obtains the second mixture, and the aqueous solution of second mixture and initiator is instilled in water
Row reaction, it is 30~80 DEG C to keep reaction temperature, and time for adding is 1.0~6.0 hours, and it is small that 0.5~3.0 is incubated after being added dropwise
When, produce copolymerization product；The esterification polymeric monomer is the methoxypolyglycol polymer or methoxyl group of molecular weight 600~4000
(the esterification of at least one of esterification products of polyethylene glycol propylene glycol copolymers and acrylic acid, methacrylic acid or maleic anhydride
Polymeric monomer synthesizes with reference to following literature methods：The mixed acid such as Guo Qiurong, Fang Yunhui, Jiang Zhuojun esterification method prepares polycarboxylic acids with big list
Body [J] New Building Materials 2012 (1)：49-52；The MPEG series high-performance dehydragent molecules such as Ke Yuliang, Zhang little Fang, Fang Yunhui
Influence [J] New Building Materials 2014 (2) of the structure to cement granules dispersiveness：13-15,22；Yu Feiyu, Guo Xinqi, fiber crops are elegant
Star direct melt esterification prepares macromonomer [J] New Building Materials 2008 (11) among Polycarboxylic Superplasticizer：80-
83), the total amount of water used in above-mentioned reaction make it that the mass concentration of the copolymerization product is 20~70%, and the dosage of the initiator is
The 0.5~3.0% of first mixture and esterification polymeric monomer gross mass, the dosage of the molecular weight regulator for the first mixture and
It is esterified the 0.2~3.0% of polymeric monomer gross mass；
(3) neutralization reaction：Copolymerization product made from step (2) is adjusted into pH to 5~7 with alkali, produces the poly- carboxylic of the esters
Sour slump retaining agent.
In a preferred embodiment of the invention, the step (1) is：By unsaturated carboxylic acid and/or acid anhydrides, insatiable hunger
Mixed with carboxylic hydroxy group's ester and polymerization inhibitor, under nitrogen protection, be warming up to 50~60 DEG C, add catalyst, it is warming up to 105~
130 DEG C, then 1~2h of constant temperature, during which with vacuumizing or leading to method removing water of the nitrogen with water, constant temperature is down to room temperature after terminating, obtained
To the first mixture, molecular weight≤150 of above-mentioned unsaturated carboxylic acid and/or acid anhydrides and unsaturated carboxylic acid hydroxy ester, and mol ratio
For 1:2~5, the dosage of catalyst for unsaturated carboxylic acid and/or acid anhydrides and unsaturated carboxylic acid hydroxy ester gross mass 0.5%~
4.0%, polymerization inhibitor dosage is the 0.5%~4.0% of unsaturated carboxylic acid and/or acid anhydrides and unsaturated carboxylic acid hydroxy ester gross mass.
In a preferred embodiment of the invention, the step (2) is：By the first mixture made from step (1)
With esterification polymeric monomer with 1~1.5:1~1.5 mass ratio mixing, adds molecular weight regulator, obtains the second mixture, by this
The aqueous solution of second mixture and initiator, which is instilled in water, to be reacted, and it is 30~70 DEG C to keep reaction temperature, and time for adding is
1.5~5.0 hours, 0.5~2.0 hour is incubated after being added dropwise, produces copolymerization product；The total amount of water causes used in above-mentioned reaction
The mass concentration of the copolymerization product is 20~60%, and the dosage of the initiator is the first mixture and esterification polymeric monomer gross mass
0.5~2.0%, the dosage of the molecular weight regulator for the first mixture and be esterified polymeric monomer gross mass 0.2~
2.0%.
In a preferred embodiment of the invention, the unsaturated carboxylic acid and/or acid anhydrides are acrylic acid, metering system
At least one of acid, maleic anhydride.
In a preferred embodiment of the invention, the unsaturated carboxylic acid hydroxy ester is hydroxy-ethyl acrylate, propylene
At least one of sour hydroxypropyl acrylate, hy-droxybutyl, hydroxyethyl methacrylate, hydroxy propyl methacrylate.
In a preferred embodiment of the invention, the catalyst is the concentrated sulfuric acid, benzene sulfonic acid, p-methyl benzenesulfonic acid, second
At least one of base sulfonic acid.
In a preferred embodiment of the invention, the polymerization inhibitor be hydroquinones, phenthazine, in diphenylamines extremely
Few one kind.
In a preferred embodiment of the invention, the initiator is water-soluble inorganic peroxide initiator, water-soluble
Property redox initiation system or water-soluble azo initiator；It is further preferred that the water-soluble inorganic peroxide initiator
For at least one of ammonium persulfate, potassium peroxydisulfate, it is hydrogen peroxide~sodium formaldehyde sulfoxylate that the water soluble, redox, which triggers system, double
At least one of oxygen water~ascorbic acid, persulfate~sodium hydrogensulfite, the water-soluble azo initiator are azo two
In isobutyl amidine hydrochloride, azo dicyclohexyl formonitrile HCN hydrochloride, azo dicyano valeric acid, azo dicyclohexyl formonitrile HCN
It is at least one.
In a preferred embodiment of the invention, the molecular weight regulator is TGA, mercaptopropionic acid, isopropyl
At least one of alcohol, tertiary sodium phosphate, sodium formate, sodium acetate, lauryl mercaptan.
The beneficial effects of the invention are as follows：
1st, esters polycarboxylic acid slump retaining agent of the invention both can be used alone when applied to concrete, can also with it is existing
There is polycarboxylic admixture compounding use, compared to ethers polycarboxylic acid slump retaining agent product, can be very good to make up extensive currently on the market
Workability variation is easily caused after the ethers polycarboxylic acid slump retaining agent incorporation concrete of application, the problem of easy bleeding；
2nd, the present invention carries out esterification using unsaturated carboxylic acid and/or acid anhydrides and unsaturated carboxylic acid hydroxy ester and prepares bifunctionality
Monomer, bifunctionality monomer is prepared with the amidatioon of alkenyl acid or esterification compared to diamines or glycol, due to list need to only occur
Side esterification can be prepared by bifunctionality monomer, therefore reaction is more easy to carry out, and the time for reacting required is also shorter；
3rd, the synthetic raw material of the bifunctionality monomer obtained by step (1) of the present invention belongs to small molecule, and molecular weight is smaller,
Steric hindrance is corresponding smaller, is also easier to synthesize compared to bifunctionality polymeric monomer；
4th, the preparation method of esters polycarboxylic acid slump retaining agent of the invention introduces bifunctionality monomer, product can be caused to have one
Other esters structures introduced when fixed crosslinking, these crosslinking points and copolymerization are (when esterification polymeric monomer and bifunctionality monomer synthesize
Possible remaining unsaturated carboxylic acid hydroxy ester) can gradually it be hydrolyzed under the alkalescence condition of concrete, discharge certain diminishing effect
Fruit, realizes the effect of control slump loss, and because the speed of each structure hydrolysis is different, thus protect collapse effect duration can
To be adjusted according to actual conditions, better adaptability.
Embodiment
It is further detailed and describes below by way of embodiment technical scheme.
The molecular weight of esters polycarboxylic acid slump retaining agent obtained by following embodiments is 20000~150000, and its structural formula
It is as follows：
Wherein, R1For H or CH3, R2For H or COOM, R3For the alkyl of 2~4 carbon, M is H or Na or K or NH4。
Embodiment 1
(1) bifunctionality monomer is prepared：By 72.00g acrylic acid, 360.00g hydroxy-ethyl acrylates and 11.74g to benzene two
Phenol mixes, and under nitrogen protection, is warming up to 60 DEG C, adds the 12.07g concentrated sulfuric acids, be warming up to 110 DEG C, then constant temperature 2h, during which with logical
Method of the nitrogen with water removes the water of dereaction generation, and constant temperature is down to room temperature after terminating, obtains the first mixture；
(2) copolyreaction：First mixture 100.00g made from step (1) is gathered with molecular weight for 1200 methoxyl group
Ethylene glycol methacrylatoethyl 69.00g is mixed, and is added TGA 1.17g, is obtained the second mixture, and this second is mixed
Thing, aqueous hydrogen peroxide solution (wherein, hydrogen peroxide 3.43g, water 20.00g) and aqueous ascorbic acid (wherein, ascorbic acid
0.50g, water 20.00g) instill in 219.19g water and reacted, it is 40 DEG C to keep reaction temperature, and time for adding is 3.0 hours,
1.0 hours are incubated after being added dropwise, produces copolymerization product；
(3) neutralization reaction：Copolymerization product made from step (2) is adjusted into pH to 5~7 with alkali, produces the poly- carboxylic of the esters
Sour slump retaining agent.
Embodiment 2
(1) bifunctionality monomer is prepared：By 86.00g methacrylic acids, 650.00g hydroxy propyl methacrylates and 9.88g
Phenthazine mixes, and under nitrogen protection, is warming up to 60 DEG C, adds 4.52g p-methyl benzenesulfonic acid, be warming up to 120 DEG C, then constant temperature 2h,
Period removes the water of dereaction generation with the method vacuumized, and constant temperature is down to room temperature after terminating, obtains the first mixture；
(2) copolyreaction：First mixture 150.00g made from step (1) is gathered with molecular weight for 2000 methoxyl group
Ethylene glycol methacrylatoethyl 120.00g is mixed, and is added tertiary sodium phosphate 1.12g, is obtained the second mixture, and this second is mixed
Thing and ammonium persulfate aqueous solution (wherein, ammonium persulfate 2.62g, water 40.00g), which are instilled in 184.71g water, to be reacted, and keeps anti-
It is 70 DEG C to answer temperature, and time for adding is 4.0 hours, is incubated 0.5 hour after being added dropwise, produces copolymerization product；
(3) neutralization reaction：Copolymerization product made from step (2) is adjusted into pH to 5~7 with alkali, produces the poly- carboxylic of the esters
Sour slump retaining agent.
Embodiment 3
(1) bifunctionality monomer is prepared：By 49.00g maleic anhydrides, 36.00g acrylic acid, 260.00g hydroxyethyl methacrylates
Propyl ester, 116.00g hydroxy-ethyl acrylates, 4.00g hydroquinones and the mixing of 2.00g phenthazine, under nitrogen protection, are warming up to 50
DEG C, 3.48g p-methyl benzenesulfonic acid is added, is warming up to 115 DEG C, then constant temperature 3h, during which removes what dereaction generated with the method vacuumized
Water, constant temperature are down to room temperature after terminating, and obtain the first mixture；
(2) copolyreaction：First mixture 150.00g made from step (1) is gathered with molecular weight for 1200 methoxyl group
Ethylene glycol maleate 160.00g is mixed, and is added mercaptopropionic acid 1.30g, is obtained the second mixture, by second mixture and mistake
Potassium sulfate solution (wherein, potassium peroxydisulfate 2.50g, water 40.00g), which is instilled in 191.72g water, to be reacted, and keeps reaction temperature
For 60 DEG C, time for adding is 3.5 hours, is incubated 1 hour after being added dropwise, produces copolymerization product；
(3) neutralization reaction：Copolymerization product made from step (2) is adjusted into pH to 5~7 with alkali, produces the poly- carboxylic of the esters
Sour slump retaining agent.
Embodiment 4
(1) bifunctionality monomer is prepared：By 43.00g methacrylic acids, 36.00g acrylic acid, 232.00g acrylic acid hydroxyl second
Ester, 216.00g hy-droxybutyls and the mixing of 12.00g diphenylamines, under nitrogen protection, are warming up to 50 DEG C, add 4.00g benzene
Sulfonic acid, 120 DEG C, then constant temperature 1h are warming up to, the water of dereaction generation is during which removed with logical method of the nitrogen with water, constant temperature drops after terminating
To room temperature, the first mixture is obtained；
(2) copolyreaction：First mixture 120.00g made from step (1) is gathered with molecular weight for 1200 methoxyl group
Ethylene glycol acrylate 140.00g is mixed, and is added isopropanol 1.80g, is obtained the second mixture, by second mixture and azo
Diisobutyl amidine hydrochloric acid saline solution (wherein, azo diisobutyl amidine hydrochloride 3.05g, water 40.00g) instills 221.24g water
In reacted, keep reaction temperature be 40 DEG C, time for adding be 3.0 hours, be incubated 1.5 hours after being added dropwise, produce be total to
Poly- product；
(3) neutralization reaction：Copolymerization product made from step (2) is adjusted into pH to 5~7 with alkali, produces the poly- carboxylic of the esters
Sour slump retaining agent.
Embodiment 5
(1) bifunctionality monomer is prepared：By 43.00g methacrylic acids, 49.00g maleic anhydrides, 260.00g metering systems
Sour hydroxyl ethyl ester, 174.00g hydroxy-ethyl acrylates, 4.00g mix to biphenol and 4.00g diphenylamines, under nitrogen protection, heating
To 60 DEG C, 10.00g ethylsulfonic acids are added, are warming up to 120 DEG C, then constant temperature 2h, during which removing dereaction with the method vacuumized generates
Water, constant temperature is down to room temperature after terminating, obtains the first mixture；
(2) copolyreaction：First mixture 100.00g made from step (1) is gathered with molecular weight for 3000 methoxyl group
Glycolmethacrylate 111.00g mix, add sodium formate 2.15g, obtain the second mixture, by second mixture,
Aqueous hydrogen peroxide solution (wherein, hydrogen peroxide 1.20g, water 20.00g) and the sodium formaldehyde sulfoxylate aqueous solution (wherein, sodium formaldehyde sulfoxylate 0.60g, water
20.00g) instill in 280.00g water and reacted, it is 50 DEG C to keep reaction temperature, and time for adding is 2.5 hours, is added dropwise
1.5 hours are incubated afterwards, produces copolymerization product；
(3) neutralization reaction：Copolymerization product made from step (2) is adjusted into pH to 5~7 with alkali, produces the poly- carboxylic of the esters
Sour slump retaining agent.
Embodiment 6
(1) bifunctionality monomer is prepared：By unsaturated carboxylic acid and/or acid anhydrides, unsaturated carboxylic acid hydroxy ester (molecular weight≤
200) and polymerization inhibitor mixes, and under nitrogen protection, is warming up to 40~60 DEG C, adds catalyst, is warming up to 100~140 DEG C, then permanent
0.5~3h of temperature, during which with vacuumizing or leading to method removing water of the nitrogen with water, constant temperature is down to room temperature after terminating, it is mixed to obtain first
Compound, molecular weight≤200 of above-mentioned unsaturated carboxylic acid and/or acid anhydrides and unsaturated carboxylic acid hydroxy ester, and mol ratio are 1:2~7,
The dosage of catalyst is the 0.5%~5.0% of unsaturated carboxylic acid and/or acid anhydrides and unsaturated carboxylic acid hydroxy ester gross mass, is inhibited
Agent dosage is the 0.5%~5.0% of unsaturated carboxylic acid and/or acid anhydrides and unsaturated carboxylic acid hydroxy ester gross mass；Preferably, it is described
Unsaturated carboxylic acid and/or acid anhydrides are at least one of acrylic acid, methacrylic acid, maleic anhydride.The unsaturated carboxylic acid hydroxyl
Base ester is hydroxy-ethyl acrylate, hydroxypropyl acrylate, hy-droxybutyl, hydroxyethyl methacrylate, methacrylic acid hydroxypropyl
At least one of ester.The catalyst is at least one of the concentrated sulfuric acid, benzene sulfonic acid, p-methyl benzenesulfonic acid, ethylsulfonic acid.It is described
Polymerization inhibitor is at least one of hydroquinones, phenthazine, diphenylamines；
(2) copolyreaction：By the first mixture made from step (1) with esterification polymeric monomer with 1~2:1~2 mass ratio
Mixing, adds molecular weight regulator, obtains the second mixture, and the aqueous solution of second mixture and initiator is instilled in water
Row reaction, it is 30~80 DEG C to keep reaction temperature, and time for adding is 1.0~6.0 hours, and it is small that 0.5~3.0 is incubated after being added dropwise
When, produce copolymerization product；The esterification polymeric monomer is the methoxypolyglycol polymer or methoxyl group of molecular weight 600~4000
At least one of esterification products of polyethylene glycol propylene glycol copolymers and acrylic acid, methacrylic acid or maleic anhydride, it is above-mentioned
The total amount of water used in reaction make it that the mass concentration of the copolymerization product is 20~70%, and the dosage of the initiator is the first mixing
The 0.5~3.0% of thing and esterification polymeric monomer gross mass, the dosage of the molecular weight regulator are big single for the first mixture and esterification
The 0.2~3.0% of body gross mass；Preferably, the initiator is water-soluble inorganic peroxide initiator, water soluble, redox
Initiation system or water-soluble azo initiator；It is further preferred that the water-soluble inorganic peroxide initiator be ammonium persulfate,
At least one of potassium peroxydisulfate, it is hydrogen peroxide~sodium formaldehyde sulfoxylate, hydrogen peroxide~anti-bad that the water soluble, redox, which triggers system,
At least one of hematic acid, persulfate~sodium hydrogensulfite, the water-soluble azo initiator are azo diisobutyl amidine salt
At least one of hydrochlorate, azo dicyclohexyl formonitrile HCN hydrochloride, azo dicyano valeric acid, azo dicyclohexyl formonitrile HCN；
The molecular weight regulator is in TGA, mercaptopropionic acid, isopropanol, tertiary sodium phosphate, sodium formate, sodium acetate, lauryl mercaptan
At least one.
(3) neutralization reaction：Copolymerization product made from step (2) is adjusted into pH to 5~7 with alkali, produces the poly- carboxylic of the esters
Sour slump retaining agent.
Esters polycarboxylic acid slump retaining agent obtained by embodiment 1 to embodiment 6 is tested, cement used is China Resources P.O
42.5 Portland cements.Flowing degree of net paste of cement test, W/C=are carried out to gained slump retaining agent according to GB/T8077-2012
0.29, roll over when solid volume is 0.20wt% (relative to cement consumption), paste flowing degree can be from initial 150~170mm through 0.5
Hour is 190~210mm, was 230~250mm through 1 hour, was 200~220mm through 2 hours；According to GB/T8076-2008 pairs
The esters polycarboxylic acid slump retaining agent of gained carries out concrete test, rolls over when solid volume is 0.20wt% (relative to cement consumption), subtracts
Water rate is above 22%, and slump 2h gradual loss amount, which is respectively less than, is equal to 10mm, and mixture workability is good, and bleeding rate is than equal
Less than or equal to 2%.
The foregoing is only a preferred embodiment of the present invention, therefore can not limit the scope that the present invention is implemented according to this, i.e.,
The equivalent changes and modifications made according to the scope of the claims of the present invention and description, all should still it belong in the range of the present invention covers.
Claims (9)
- A kind of 1. preparation method of esters polycarboxylic acid slump retaining agent, it is characterised in that：The molecular weight of the esters polycarboxylic acid slump retaining agent is 20000~150000, and its structural formula is as follows：Wherein, R1For H or CH3, R2For H or COOM, R3For the alkyl of 2~4 carbon, M is H or Na or K or NH4；Its preparation method comprises the following steps：(1) bifunctionality monomer is prepared：Unsaturated carboxylic acid and/or acid anhydrides, unsaturated carboxylic acid hydroxy ester and polymerization inhibitor are mixed, Under nitrogen protection, 40~60 DEG C are warming up to, add catalyst, be warming up to 100~140 DEG C, then 0.5~3h of constant temperature, during which with taking out The method of vacuum or logical nitrogen with water removes water, and constant temperature is down to room temperature after terminating, obtains the first mixture, above-mentioned unsaturated carboxylic acid And/or molecular weight≤200 of acid anhydrides and unsaturated carboxylic acid hydroxy ester, and mol ratio is 1: 2~7, the dosage of catalyst is insatiable hunger With the 0.5%~5.0% of carboxylic acid and/or acid anhydrides and unsaturated carboxylic acid hydroxy ester gross mass, polymerization inhibitor dosage is unsaturated carboxylic acid And/or the 0.5%~5.0% of acid anhydrides and unsaturated carboxylic acid hydroxy ester gross mass；(2) copolyreaction：First mixture made from step (1) is mixed with esterification polymeric monomer with 1~2: 1~2 mass ratio, Molecular weight regulator is added, obtains the second mixture, the aqueous solution of second mixture and initiator is instilled in water and carried out instead Should, it is 30~80 DEG C to keep reaction temperature, and time for adding is 1.0~6.0 hours, and 0.5~3.0 hour is incubated after being added dropwise, Produce copolymerization product；The esterification polymeric monomer is the ethylene glycol copolymer or polyethylene glycol propane diols of molecular weight 600~4000 At least one of esterification products of copolymer and acrylic acid, methacrylic acid or maleic anhydride, water is total used in above-mentioned reaction Amount make it that the mass concentration of the copolymerization product is 20~70%, and the dosage of the initiator is the first mixture and esterification polymeric monomer The 0.5~3.0% of gross mass, the dosage of the molecular weight regulator are the 0.2 of the first mixture and esterification polymeric monomer gross mass ~3.0%；(3) neutralization reaction：Copolymerization product made from step (2) is adjusted into pH to 5~7 with alkali, the esters polycarboxylic acids is produced and protects Collapse agent.
- A kind of 2. preparation method of esters polycarboxylic acid slump retaining agent as claimed in claim 1, it is characterised in that：The step (1) For：Unsaturated carboxylic acid and/or acid anhydrides, unsaturated carboxylic acid hydroxy ester and polymerization inhibitor are mixed, under nitrogen protection, it is warming up to 50~ 60 DEG C, catalyst is added, is warming up to 105~130 DEG C, then 1~2h of constant temperature, during which removed with vacuumizing or lead to method of the nitrogen with water Go water, constant temperature to be down to room temperature after terminating, obtain the first mixture, above-mentioned unsaturated carboxylic acid and/or acid anhydrides and unsaturated carboxylic acid hydroxyl Molecular weight≤150 of base ester, and mol ratio is 1: 2~5, the dosage of catalyst is unsaturated carboxylic acid and/or acid anhydrides and unsaturation The 0.5%~4.0% of carboxylic hydroxy group's ester gross mass, polymerization inhibitor dosage are unsaturated carboxylic acid and/or acid anhydrides and unsaturated carboxylic acid hydroxyl The 0.5%~4.0% of base ester gross mass.
- A kind of 3. preparation method of esters polycarboxylic acid slump retaining agent as claimed in claim 1, it is characterised in that：The step (2) For：First mixture made from step (1) is mixed with esterification polymeric monomer with 1~1.5: 1~1.5 mass ratio, added point Son amount conditioning agent, obtains the second mixture, the aqueous solution of second mixture and initiator is instilled in water and reacted, and keeps anti- It is 30~70 DEG C to answer temperature, and time for adding is 1.5~5.0 hours, and 0.5~2.0 hour is incubated after being added dropwise, and produces copolymerization production Thing；The total amount of water used in above-mentioned reaction make it that the mass concentration of the copolymerization product is 20~60%, and the dosage of the initiator is The 0.5~2.0% of first mixture and esterification polymeric monomer gross mass, the dosage of the molecular weight regulator for the first mixture and It is esterified the 0.2~2.0% of polymeric monomer gross mass.
- 4. a kind of preparation method of esters polycarboxylic acid slump retaining agent as described in any claim in claims 1 to 3, its feature It is：The unsaturated carboxylic acid and/or acid anhydrides are at least one of acrylic acid, methacrylic acid, maleic anhydride.
- 5. a kind of preparation method of esters polycarboxylic acid slump retaining agent as described in any claim in claims 1 to 3, its feature It is：The unsaturated carboxylic acid hydroxy ester is hydroxy-ethyl acrylate, hydroxypropyl acrylate, hy-droxybutyl, methacrylic acid At least one of hydroxyl ethyl ester, hydroxy propyl methacrylate.
- 6. a kind of preparation method of esters polycarboxylic acid slump retaining agent as described in any claim in claims 1 to 3, its feature It is：The catalyst is at least one of the concentrated sulfuric acid, benzene sulfonic acid, p-methyl benzenesulfonic acid, ethylsulfonic acid.
- 7. a kind of preparation method of esters polycarboxylic acid slump retaining agent as described in any claim in claims 1 to 3, its feature It is：The polymerization inhibitor is at least one of hydroquinones, phenthazine, diphenylamines.
- 8. a kind of preparation method of esters polycarboxylic acid slump retaining agent as described in any claim in claims 1 to 3, its feature It is：The initiator is that water-soluble inorganic peroxide initiator, water soluble, redox initiation system or water-soluble azo draw Send out agent.
- 9. a kind of preparation method of esters polycarboxylic acid slump retaining agent as described in any claim in claims 1 to 3, its feature It is：The molecular weight regulator is TGA, mercaptopropionic acid, isopropanol, tertiary sodium phosphate, sodium formate, sodium acetate, 12 sulphur At least one of alcohol.
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| CN104261721B (en) * | 2014-09-22 | 2016-06-29 | 科之杰新材料集团有限公司 | A kind of ethers polycarboxylic acid slump retaining agent and preparation method thereof |
| CN105294951B (en) * | 2015-11-25 | 2018-02-27 | 科之杰新材料集团有限公司 | A kind of preparation method of esters polycarboxylate water-reducer |
| CN107629176A (en) * | 2017-08-30 | 2018-01-26 | 常州豫春化工有限公司 | A kind of preparation method of high-efficiency water-reducing agent of poly-carboxylic acid |
| CN108003304B (en) * | 2017-12-28 | 2020-05-12 | 科之杰新材料集团有限公司 | Preparation method of cardanol modified ester polycarboxylate superplasticizer |
| CN109111146B (en) * | 2018-08-16 | 2020-08-11 | 科之杰新材料集团有限公司 | Multifunctional ester polycarboxylate superplasticizer and preparation method thereof |
| CN112390560B (en) * | 2019-08-14 | 2022-04-22 | 陕西科之杰新材料有限公司 | Low-sensitivity concrete workability regulator and preparation method thereof |
| CN112708057B (en) * | 2020-11-03 | 2022-10-25 | 科之杰新材料集团有限公司 | High-temperature-resistant anti-corrosion long-acting polycarboxylic acid slump retaining agent and preparation method thereof |
| CN112940194B (en) * | 2021-01-29 | 2022-05-24 | 武汉奥克特种化学有限公司 | Preparation method and application of inorganic pigment and filler water-based dispersant |
| CN113896845B (en) * | 2021-11-01 | 2023-07-25 | 科之杰新材料集团有限公司 | Low-sensitivity slow-release polycarboxylic acid slump retaining agent and preparation method thereof |
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| CN102515618A (en) * | 2011-11-30 | 2012-06-27 | 上海大学 | Slow release slump retaining polycarboxylate water reducer and preparation thereof |
| CN102643042A (en) * | 2012-04-20 | 2012-08-22 | 株洲加美乐素建材有限公司 | Cross-linked polycarboxylic acid water reducing agent and preparation method thereof |
| CN103723945A (en) * | 2013-11-28 | 2014-04-16 | 中建商品混凝土有限公司 | Fast hydrolyzable slow releasing polycarboxylate superplasticizer and preparation method thereof |
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