CN107602781A - A kind of esters promote the preparation method of solidifying Early-strength polycarboxylate superplasticizer - Google Patents
A kind of esters promote the preparation method of solidifying Early-strength polycarboxylate superplasticizer Download PDFInfo
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Abstract
The invention discloses the preparation method that a kind of esters promote solidifying Early-strength polycarboxylate superplasticizer, comprise the following steps：(1) esterification monomer is prepared；(2) copolyreaction.The preparation method of the present invention, which utilizes, prepares remaining methyl methacrylate and hydrophobic minor comonomer in esterification monomer, preparing esterification monomer under the same conditions, further early powerful monomer is obtained with the method for ester exchange, this function monomer is introduced directly into copolyreaction to be reacted with other monomers etc., early powerful monomer is introduced in copolymerization stage and promotees solidifying function monomer, so that carrying anion, cation and fluorin radical on polycarboxylic acids strand, concrete coagulating time can be shortened and improve early age strength of concrete.
Description
Technical field
The invention belongs to build additive technical field, and in particular to a kind of esters promote solidifying Early-strength polycarboxylate superplasticizer
Preparation method.
Background technology
Prefabricated components, such as metro shield section of jurisdiction are to make concrete injection die for molding, then transport to building site
Assembled.In order to improve the production efficiency of factory, it is necessary to which concrete component short time interior energy is stripped from mould, this is required
Concrete has higher early strength and shorter setting time.Technical scheme disclosed in CN101921083A uses traditional nothing
Machine salt is compounded with polycarboxylate water-reducer, improves early age strength of concrete, but water reducer volume made from this method is high, also drops
Low late strength of concrete.Technical scheme disclosed in CN106749959A using maleic anhydride and organic amine be acylated instead
It should obtain maleic acid mono amide monomer, then the monomer and APEO polymeric monomer are copolymerized to obtain early-strength polycarboxylic acids and subtracted
Aqua, this method complex process, and obtain product and fail the effective setting time for shortening concrete, it is limited in prefabricated structure
Application in part concrete.
Therefore, develop it is a with diminishing, to promote solidifying, super hardening polycarboxylate water-reducer just aobvious particularly important, not only may be used
To improve the service behaviour of concrete, accelerate the development of early strength and shorten setting time, improve production efficiency, can also subtract
Lack the dosage of cement, construct and wipe one's face under normal temperature, shorten the steam curing time and even cancel steam curing, greatly save the energy,
Reduce energy consumption.
The content of the invention
It is an object of the invention to overcome prior art defect, there is provided a kind of esters promote solidifying Early-strength polycarboxylate superplasticizer
Preparation method.
Technical scheme is as follows：
A kind of esters promote the preparation method of solidifying Early-strength polycarboxylate superplasticizer, comprise the following steps：
(1) esterification monomer is prepared：By weight, by 100 parts of molecular weight be 2000~5000 polyethyleneglycol first
It is anti-that ether, 10~20 parts of methyl methacrylates, 0.3~1.6 part of catalyst and 0.3~1.3 part of mixing polymerization inhibitor are added to first
Answer in device, under nitrogen protection, 4~6h of isothermal reaction at 40~100 DEG C, then disposable 3.0~5.0 parts of addition is hydrophobic
Minor comonomer, continue the constant temperature esterification at 40~100 DEG C and react 1~3h, after reaction cools to 30~40 DEG C after terminating, add certain
The concentration of the water regulation solution of amount is 70~85%, that is, is obtained containing polyethylene glycol monomethyl ethermethacrylic acid esters, early powerful list
The esterification monomer of body and methyl methacrylate mixture；Above-mentioned catalyst is the concentrated sulfuric acid, concentrated phosphoric acid, p-methyl benzenesulfonic acid, amino
Sulfonic acid, DMAP, dibutyltin diacetate or isopropyl titanate；Above-mentioned mixing polymerization inhibitor by o-tert-butylphenol with
Phenthazine is formed by 0.5~1.5: 0.7~1.5 mass ratio；
(2) copolyreaction：By weight, first by esterification monomer, 3~6 parts of unsaturated sulphurs made from 100 parts of steps (1)
Hydrochlorate, 2~5 parts of solidifying function monomers of rush and 48~55 parts of water are well mixed in the first Dropping feeder；1~5 part of initiator and 30
Part water is well mixed in the second Dropping feeder；1~4 part of chain-transferring agent is well mixed in the 3rd Dropping feeder with 30 parts of water；
Again by the material in 1/3 the first Dropping feeder, the material in 1/3 the second Dropping feeder, 1/3 the 3rd Dropping feeder
Material is added in the second reaction unit, when being warming up to 45 DEG C~80 DEG C, starts simultaneously at and the first Dropping feeder, the second dropwise addition is added dropwise
Remaining material in device and the 3rd Dropping feeder, is dripped off in 0.5~1.0h, disposable after completion of dropwise addition to add 0.2~0.8 part
Regulation auxiliary agent in the second reaction unit, 0.5~1.5h of isothermal reaction, reaction product with alkaline matter adjust pH to 6.0~
7.0, that is, obtain the esters and promote solidifying Early-strength polycarboxylate superplasticizer；Above-mentioned hydrophobic minor comonomer shrinks for 1,1- dihydros perfluoroalkyl
Glycerin ether or 1,1- dihydro perfluoroalkyl are to methanesulfonate ester；Above-mentioned unsaturated sulfonic acid salt is 3- allyloxy -2- hydroxyls -1- third
Alkyl sulfonic acid sodium or 2- acrylamide-2-methyl propane sulfonics；Above-mentioned unsaturated sulfonic acid salt is 3- allyloxy -2- hydroxyl -1- propane
Sodium sulfonate or 2- acrylamide-2-methyl propane sulfonics.
In a preferred embodiment of the invention, the initiator is hydrogen peroxide, ammonium persulfate, the isobutyl of azo two
Base amidine hydrochloride or the isobutyl imidazoline hydrochloride of azo two.
In a preferred embodiment of the invention, the chain-transferring agent be TGA, isopropanol, sodium formate, 3~
Isooctyl mercaptopropionate, lauryl mercaptan or 3~mercaptopropionic acid.
In a preferred embodiment of the invention, the regulation auxiliary agent is carboxymethyl cellulose, methylcellulose or
Hydroxyethyl cellulose.
In a preferred embodiment of the invention, the alkaline matter is sodium hydroxide, calcium hydroxide, hydroxide
At least one of potassium, calcium oxide, ammoniacal liquor, monoethanolamine.
Beneficial effects of the present invention：
1st, preparation method of the invention, which utilizes, prepares remaining methyl methacrylate and hydrophobic minor comonomer in esterification monomer,
Preparing esterification monomer under the same conditions, further obtaining early powerful monomer with the method for ester exchange, this function monomer is straight
Connect to be incorporated into copolyreaction and reacted with other monomers etc., introduce early powerful monomer in copolymerization stage and promote solidifying function list
Body so that anion, cation and fluorin radical are carried on polycarboxylic acids strand, concrete coagulating time can be shortened and improve coagulation
Native early strength.
2nd, the present invention adds regulation auxiliary agent in copolymerization stage can improve concrete thixotropy, improve working performance of concrete,
There is the prefabricated components concrete of high request to concrete thixotropy suitable for metro shield section of jurisdiction etc..
Embodiment
Technical scheme is further detailed and described below by way of embodiment.
Embodiment 1
(1) prepared by esterification monomer：By weight, it is 2400 poly glycol monomethyl ether and 13 parts by 100 parts of molecular weight
Methyl methacrylate, 0.4 part of DMAP and 0.7 part mixing polymerization inhibitor be added to equipped with condensing unit first
In reaction unit, under nitrogen protection, the constant temperature 4.5h at 50 DEG C, 3.0 parts of 1,1- dihydro perfluoroalkyls are then disposably added
Glycidol ether, continue to be esterified 2h under the reaction conditions, after reaction terminates, the concentration for adding 29.0 parts of water regulation solution is
80%, that is, obtain containing polyethylene glycol monomethyl ethermethacrylic acid esters, early powerful monomer and methyl methacrylate mixture
Esterification monomer；
(2) copolyreaction：By weight, first by 100 parts of esterification monomers, 5 parts of 3- allyloxy -2- hydroxyls -1- third
Alkyl sulfonic acid sodium, 2.5 parts of 2- methylacryoyloxyethyls phosphocholine, 50 parts of water are well mixed in the first Dropping feeder；3
The azo diisobutyl amidine hydrochloride of part is well mixed in the second Dropping feeder with 30 parts of water；3 parts of TGA and 30
The water of part is well mixed in the 3rd Dropping feeder；The material in 1/3 the first Dropping feeder, the second of 1/3 are added dropwise again and filled
Material in the material put, 1/3 the 3rd Dropping feeder is added in the second reaction unit, when being warming up to 50 DEG C, is opened simultaneously
Begin that remaining material in the first Dropping feeder, the second Dropping feeder, the 3rd Dropping feeder is added dropwise, dripped off in 0.5h, completion of dropwise addition
The disposable carboxymethyl cellulose for adding 0.6 part is in the second reaction unit, isothermal reaction 1.5h；It is 23 parts to add parts by weight
The sodium hydroxide of 30% mass concentration, that is, obtain the esters that concentration is 40% and promote solidifying Early-strength polycarboxylate superplasticizer.
Embodiment 2
(1) prepared by esterification monomer：By weight, it is 3000 poly glycol monomethyl ether and 16 parts by 100 parts of molecular weight
Methyl methacrylate, 0.6 part of dibutyltin diacetate and 0.7 part mixing polymerization inhibitor be added to equipped with condensing unit first
In reaction unit, under nitrogen protection, the constant temperature 5.0h at 80 DEG C, 4.0 parts of 1,1- dihydro perfluoroalkyls are then disposably added
To methanesulfonate ester, continue to be esterified 2.5h under the reaction conditions, after reaction terminates, add 30.0 parts of water and adjust the dense of solution
Spend for 80%, that is, obtain containing polyethylene glycol monomethyl ethermethacrylic acid esters, early powerful monomer and methyl methacrylate mixing
The esterification monomer of thing；
(2) copolyreaction：By weight, first by 100 parts of esterification monomers, 4 parts of 2- acrylamide -2- methyl-prop sulphurs
Acid, 3 parts of acryloxyethyldimethyl benzyl ammonium chloride, 53 parts of water are well mixed in the first Dropping feeder；3.5 parts
Hydrogen peroxide is well mixed in the second Dropping feeder with 30 parts of water；2.5 parts of isopropanol be well mixed with 30 parts of water in
In 3rd Dropping feeder；Again by material in 1/3 the first Dropping feeder, the material in 1/3 the second Dropping feeder, 1/3
Material in 3rd Dropping feeder is added in the second reaction unit, when being warming up to 55 DEG C, starts simultaneously at dropwise addition first and dress is added dropwise
Put, remaining material in the second Dropping feeder, the 3rd Dropping feeder, dripped off in 1h, completion of dropwise addition disposably adds 0.4 part of hydroxyl
Ethyl cellulose is in the second reaction unit, isothermal reaction 1h；The ammoniacal liquor that parts by weight are 35 parts is added, that is, obtains concentration as 40%
The esters promote solidifying Early-strength polycarboxylate superplasticizer.
Embodiment 3
(1) prepared by esterification monomer：By weight, it is 4000 poly glycol monomethyl ether and 18 parts by 100 parts of molecular weight
Methyl methacrylate, 1.2 parts of p-methyl benzenesulfonic acid and 0.9 part mixing polymerization inhibitor be added to equipped with condensing unit first reaction
In device, under nitrogen protection, the constant temperature 5.5h at 60 DEG C is then disposable to add 3.5 parts of 1,1- dihydros perfluoroalkyls shrinks
Glycerin ether, continue to be esterified 2.5h under the reaction conditions, after reaction terminates, the concentration for adding 35.0 parts of water regulation solution is
80%, that is, obtain containing polyethylene glycol monomethyl ethermethacrylic acid esters, early powerful monomer and methyl methacrylate mixture
Esterification monomer；
(2) copolyreaction：By weight, first by 100 parts of esterification monomers, 4.5 parts of 3- allyloxy -2- hydroxyls -1-
Propane sulfonic acid sodium, 4.5 parts of 2- methylacryoyloxyethyls phosphocholine, 49 parts of water are well mixed in the first Dropping feeder
In；4.5 parts of ammonium persulfate is well mixed in the second Dropping feeder with 30 parts of water；3.5 parts of 3~isooctyl mercaptopropionate
It is well mixed with 30 parts of water in the 3rd Dropping feeder；Again by the material in 1/3 the first Dropping feeder, the second of 1/3 the drop
The material in material, 1/3 the 3rd Dropping feeder in feeder apparatus is added in the second reaction unit, when being warming up to 65 DEG C, together
When start that the first Dropping feeder, the second Dropping feeder, remaining material in the 3rd Dropping feeder is added dropwise, drip off, be added dropwise in 1.0h
Terminate the disposable methylcellulose for adding 0.7 part in the second reaction unit, isothermal reaction 1.0h；It is 25 parts to add parts by weight
Monoethanolamine, that is, obtain the esters that concentration is 40% and promote solidifying Early-strength polycarboxylate superplasticizer.
Embodiment 4
The esters of the gained of embodiment 1~3 are promoted into solidifying Early-strength polycarboxylate superplasticizer and control sample (common polycarboxylic acids diminishing
Agent), using standard cement, according to GB 8076~2008《Concrete admixture》, survey concrete slump and other performances.It is mixed
Coagulating native match ratio is：Cement 360kg/m3, sand 770kg/m3, stone 1038kg/m3, acquired results are as shown in table 1.
Embodiment performance comparison under the conditions of the different addition quantity of table 1
Result of the test illustrates that the present invention introduces early powerful monomer in copolymerization stage and promotees solidifying function monomer so that poly- carboxylic
Anion, cation and fluorin radical are carried on acid molecule chain, concrete coagulating time can be shortened and improve early age strength of concrete,
Suitable for the prefabricated components concrete such as metro shield section of jurisdiction.
Those of ordinary skill in the art understand, when technical scheme changes in following ranges, remain able to
To same as the previously described embodiments or similar technical scheme, protection scope of the present invention is still fallen within：
A kind of esters promote the preparation method of solidifying Early-strength polycarboxylate superplasticizer, comprise the following steps：
(1) esterification monomer is prepared：By weight, by 100 parts of molecular weight be 2000~5000 polyethyleneglycol first
It is anti-that ether, 10~20 parts of methyl methacrylates, 0.3~1.6 part of catalyst and 0.3~1.3 part of mixing polymerization inhibitor are added to first
Answer in device, under nitrogen protection, 4~6h of isothermal reaction at 40~100 DEG C, then disposable 3.0~5.0 parts of addition is hydrophobic
Minor comonomer, continue the constant temperature esterification at 40~100 DEG C and react 1~3h, after reaction cools to 30~40 DEG C after terminating, add certain
The concentration of the water regulation solution of amount is 70~85%, that is, is obtained containing polyethylene glycol monomethyl ethermethacrylic acid esters, early powerful list
The esterification monomer of body and methyl methacrylate mixture；Above-mentioned catalyst is the concentrated sulfuric acid, concentrated phosphoric acid, p-methyl benzenesulfonic acid, amino
Sulfonic acid, DMAP, dibutyltin diacetate or isopropyl titanate；Above-mentioned mixing polymerization inhibitor by o-tert-butylphenol with
Phenthazine is formed by 0.5~1.5: 0.7~1.5 mass ratio；
(2) copolyreaction：By weight, first by esterification monomer, 3~6 parts of unsaturated sulphurs made from 100 parts of steps (1)
Hydrochlorate, 2~5 parts of solidifying function monomers of rush and 48~55 parts of water are well mixed in the first Dropping feeder；1~5 part of initiator and 30
Part water is well mixed in the second Dropping feeder；1~4 part of chain-transferring agent is well mixed in the 3rd Dropping feeder with 30 parts of water；
Again by the material in 1/3 the first Dropping feeder, the material in 1/3 the second Dropping feeder, 1/3 the 3rd Dropping feeder
Material is added in the second reaction unit, when being warming up to 45 DEG C~80 DEG C, starts simultaneously at and the first Dropping feeder, the second dropwise addition is added dropwise
Remaining material in device and the 3rd Dropping feeder, is dripped off in 0.5~1.0h, disposable after completion of dropwise addition to add 0.2~0.8 part
Regulation auxiliary agent in the second reaction unit, 0.5~1.5h of isothermal reaction, reaction product with alkaline matter adjust pH to 6.0~
7.0, that is, obtain the esters and promote solidifying Early-strength polycarboxylate superplasticizer；Above-mentioned hydrophobic minor comonomer shrinks for 1,1- dihydros perfluoroalkyl
Glycerin ether or 1,1- dihydro perfluoroalkyl are to methanesulfonate ester；Above-mentioned unsaturated sulfonic acid salt is 3- allyloxy -2- hydroxyls -1- third
Alkyl sulfonic acid sodium or 2- acrylamide-2-methyl propane sulfonics；Above-mentioned unsaturated sulfonic acid salt is 3- allyloxy -2- hydroxyl -1- propane
Sodium sulfonate or 2- acrylamide-2-methyl propane sulfonics.
Preferably, the initiator is hydrogen peroxide, ammonium persulfate, azo diisobutyl amidine hydrochloride or the isobutyl of azo two
Imidazoline hydrochloride；The chain-transferring agent is TGA, isopropanol, sodium formate, 3~isooctyl mercaptopropionate, dodecyl
Mercaptan or 3~mercaptopropionic acid；The regulation auxiliary agent is carboxymethyl cellulose, methylcellulose or hydroxyethyl cellulose；The alkali
Property material be sodium hydroxide, calcium hydroxide, potassium hydroxide, calcium oxide, ammoniacal liquor, at least one of monoethanolamine.
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 (5)
1. a kind of esters promote the preparation method of solidifying Early-strength polycarboxylate superplasticizer, it is characterised in that：Comprise the following steps：
(1) esterification monomer is prepared：By weight, by 100 parts of molecular weight be 2000~5000 poly glycol monomethyl ether, 10
~20 parts of methyl methacrylates, 0.3~1.6 part of catalyst and 0.3~1.3 part of mixing polymerization inhibitor are added to the first reaction unit
In, under nitrogen protection, 4~6h of isothermal reaction at 40~100 DEG C, then disposably add 3.0~5.0 parts of hydrophobic small lists
Body, continue the constant temperature esterification at 40~100 DEG C and react 1~3h, after reaction cools to 30~40 DEG C after terminating, add a certain amount of
Water regulation solution concentration be 70~85%, that is, obtain containing polyethylene glycol monomethyl ethermethacrylic acid esters, early powerful monomer and
The esterification monomer of methyl methacrylate mixture；Above-mentioned catalyst be the concentrated sulfuric acid, concentrated phosphoric acid, p-methyl benzenesulfonic acid, sulfamic acid,
DMAP, dibutyltin diacetate or isopropyl titanate；Above-mentioned mixing polymerization inhibitor is by o-tert-butylphenol and fen thiophene
Piperazine is formed by 0.5~1.5: 0.7~1.5 mass ratio；
(2) copolyreaction：By weight, first by esterification monomer made from 100 parts of steps (1), 3~6 portions of unsaturated sulfonic acid salt,
2~5 parts of solidifying function monomers of rush and 48~55 parts of water are well mixed in the first Dropping feeder；1~5 part of initiator mixes with 30 parts of water
Close uniformly in the second Dropping feeder；1~4 part of chain-transferring agent is well mixed in the 3rd Dropping feeder with 30 parts of water；Again by 1/3
The first Dropping feeder in material, the material in 1/3 the second Dropping feeder, the material in 1/3 the 3rd Dropping feeder add
Enter into the second reaction unit, when being warming up to 45 DEG C~80 DEG C, start simultaneously at be added dropwise the first Dropping feeder, the second Dropping feeder and
Remaining material in 3rd Dropping feeder, is dripped off in 0.5~1.0h, the disposable regulation for adding 0.2~0.8 part after completion of dropwise addition
Auxiliary agent is in the second reaction unit, 0.5~1.5h of isothermal reaction, and reaction product adjusts pH to 6.0~7.0 with alkaline matter, i.e.,
Obtain the esters and promote solidifying Early-strength polycarboxylate superplasticizer；Above-mentioned hydrophobic minor comonomer is 1,1- dihydro perfluoroalkyl glycidol ethers
Or 1,1- dihydro perfluoroalkyl are to methanesulfonate ester；Above-mentioned unsaturated sulfonic acid salt is 3- allyloxy -2- hydroxyl -1- propane sulfonic acids
Sodium or 2- acrylamide-2-methyl propane sulfonics；Above-mentioned unsaturated sulfonic acid salt is 3- allyloxy -2- hydroxyl -1- propane sulfonic acid sodium
Or 2- acrylamide-2-methyl propane sulfonics.
2. preparation method as claimed in claim 1, it is characterised in that：The initiator is hydrogen peroxide, and ammonium persulfate is even
Nitrogen diisobutyl amidine hydrochloride or the isobutyl imidazoline hydrochloride of azo two.
3. preparation method as claimed in claim 1, it is characterised in that：The chain-transferring agent is TGA, isopropanol, first
Sour sodium, 3~isooctyl mercaptopropionate, lauryl mercaptan or 3~mercaptopropionic acid.
4. preparation method as claimed in claim 1, it is characterised in that：The regulation auxiliary agent is carboxymethyl cellulose, methyl
Cellulose or hydroxyethyl cellulose.
5. preparation method as claimed in claim 1, it is characterised in that：The alkaline matter be sodium hydroxide, calcium hydroxide,
At least one of potassium hydroxide, calcium oxide, ammoniacal liquor, monoethanolamine.
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Application publication date: 20180119 |