CN107459611A - A kind of preparation method of long-acting polycarboxylic acid slump retaining agent - Google Patents
A kind of preparation method of long-acting polycarboxylic acid slump retaining agent Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
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- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2652—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles
- C04B24/2658—Nitrogen containing polymers, e.g. polyacrylamides, polyacrylonitriles containing polyether side chains
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- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
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- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
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- C08F275/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers containing phosphorus, selenium, tellurium or a metal as defined in group C08F30/00
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/308—Slump-loss preventing agents
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
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Abstract
The invention discloses a kind of preparation method of long-acting polycarboxylic acid slump retaining agent, comprise the following steps：(1) preparation of performed polymer；(2) esterification；(3) copolyreaction；(4) neutralization reaction.The present invention by it is bright by esters of unsaturated carboxylic acids, unsaturated phosphate and unsaturated acid anhydride under medium temperature it is free-radical polymerized synthesis with certain degree of polymerization performed polymer, and high temperature esterification performed polymer, so as to introduce phosphate group and ester group in polycarboxylate water-reducer molecule structure；It is copolymerized by normal temperature and introduces amide groups, the sequential structure of polycarboxylic acids molecule is adjusted by regulating and controlling material dropping order and time, so as to obtain the copolymerization product with differentiation molecular structure, it is effectively controlled the priority hydrolysis rate of ester group and amide groups, so as to improve the later stage function of slump protection of concrete, make it that still there is preferable function of slump protection after 3 hours.
Description
Technical field
The invention belongs to build additive technical field, and in particular to a kind of preparation method of long-acting polycarboxylic acid slump retaining agent.
Background technology
Polycarboxylate water-reducer has the advantages that water-reducing rate height, molecular structure can design, are green, promotes large volume and mixes
The development of solidifying soil, self-compacting concrete, high-strength high-performance concrete, turn into the emphasis and focus of research.But running into
During the materials such as cement complicated and changeable, sand, stone, the phenomenon that polycarboxylic acids dehydragent loses its high-performance benefits can often occur.
Such as there is the problems such as concrete slump loss is fast, concrete workability is poor.In addition, the temperature also holding to concrete slump
Have a great influence, temperature is high, and hydrated reaction of cement is fast, and the consumption of additive is accelerated, and concrete slump loss is bigger, it is general and
Speech, temperature often rise 10 DEG C, slump-loss rate increase 10%-40%.In ready-mixed concrete industry, concrete passes through high temperature
Under, the too fast phenomenon of slump-loss often occurs in transport for a long time, influences engineering construction and quality.
Existing slump retaining agent can only partly meet the short time of normal concrete in concrete application in the market
(in 1-2h) slump requirement, it is difficult to meet that the long-time (more than 3h) of the long-distance transportation of some special engineering concrete is protected
Collapse demand.
The content of the invention
It is an object of the invention to overcome prior art defect, there is provided a kind of preparation method of long-acting polycarboxylic acid slump retaining agent.
Technical scheme is as follows：
A kind of preparation method of long-acting polycarboxylic acid slump retaining agent, comprises the following steps：
(1) preparation of performed polymer：Unsaturated acid anhydride is added in the first reaction vessel, is passed through 40~60 DEG C of insulations of nitrogen
1-2h, then the mixed solution and initiator perbenzoic acid benzene fourth of esters of unsaturated carboxylic acids and unsaturated phosphate are added dropwise respectively
Ester, it is added dropwise in 3h, continues nitrogen and purge 2~3h, obtain performed polymer；Wherein, unsaturated acid anhydride is maleic anhydride, dimethyl horse
Come acid anhydrides, itaconic anhydride or succinic anhydride, esters of unsaturated carboxylic acids is hydroxy-ethyl acrylate, hydroxyethyl methacrylate, acrylic acid
Hydroxypropyl acrylate, hydroxy propyl methacrylate, hy-droxybutyl, methyl methacrylate, methyl acrylate, ethyl acrylate, first
At least one of base ethyl acrylate, butyl acrylate and butyl methacrylate, unsaturated phosphate are acrylic acid hydroxypropyl
Base phosphate or acrylic phosphite ester, the mol ratio of esters of unsaturated carboxylic acids, unsaturated phosphate and unsaturated acid anhydride is 1: 0.1
~1.5: 0.5~2, initiator account for esters of unsaturated carboxylic acids, unsaturated phosphate and unsaturated acid anhydride gross mass 0.5~
2.5%.
(2) esterification：Performed polymer obtained by unsaturated alcohol, step (1) and catalyst are added to the second reaction vessel
Middle mixing, under nitrogen protection, 3~6h of isothermal reaction at 90-120 DEG C, during which with vacuumizing or lead to method of the nitrogen with water
Water is removed, reaction is down to room temperature after terminating, obtains esterification products；Wherein, unsaturated alcohol be vinyl alcohol, 3- methyl -3- butylene -
The mass ratio of 1- alcohol, allyl alcohol or 2- methallyl alcohols, unsaturated alcohol and performed polymer is 1~5: 1, and catalyst amount is insatiable hunger
With the 0.5~3.0% of alcohol and performed polymer gross mass；
(3) copolyreaction：First monomer is dissolved in water and forms the first solution, it is molten that molecular weight regulator is dissolved in water formation second
Liquid, reducing agent are dissolved in water and form the 3rd solution, and second comonomer is dissolved in water and forms the 4th solution, and step is added in the 3rd reaction vessel
Suddenly the polyether monomer and water of esterification products, molecular weight 800~4000 made from (3), stirring at normal temperature add oxidation to being uniformly dissolved
Agent, then above-mentioned first to fourth solution is added dropwise, its dropwise addition order is as follows：It is the first solution first, next to that second and the 3rd molten
Liquid, is finally the 4th solution, and second and the 3rd solution and first 15~30min of solution interval be added dropwise, the 4th solution and second
It is added dropwise with the 3rd 15~30min of solution interval, the time for adding of the first Solutions Solution is 1.5~3.5h, second and the 3rd solution
Time for adding be 2~4h, the time for adding of the 4th solution is 1.5~3.5h；Continue 0.5~2h of reaction after completion of dropwise addition, obtain
To copolymerization product；Wherein, polyether monomer is isoamyl alcohol polyoxyethylene ether, prenol polyoxyethylene poly-oxygen propylene aether, methyl
Allyl alcohol polyethenoxy ether, methacrylic polyoxyethylene poly-oxygen propylene aether, at least one of allyl alcohol polyethenoxy ether, first
Monomer is acrylic acid and/or methacrylic acid, second comonomer be acrylamide, Methacrylamide, N hydroxymethyl acrylamide,
At least one of 2~methyl propane sulfonic acid acrylamide and N, N- methylene-bisacrylamide, the dosage of molecular weight regulator
For the 0.2~1.5% of polyether monomer quality, the dosage of Oxidizing and Reducing Agents is the 0.3~2.0% of polyether monomer quality,
The dosage of first monomer and second comonomer is respectively the 2.0~8.0% and 0.5~5% of polyether monomer quality, esterification products
Dosage is the 5.0~15.0% of polyether monomer quality；
(4) neutralization reaction：Copolymerization product obtained by step (3) is neutralized to pH value as 5~7 with liquid caustic soda, produced described
Long-acting polycarboxylic acid slump retaining agent.
In a preferred embodiment of the invention, the catalyst be benzene sulfonic acid, p-methyl benzenesulfonic acid, ethylsulfonic acid and
At least one of 98% concentrated sulfuric acid.
In a preferred embodiment of the invention, the oxidant be ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate and
At least one of hydrogen peroxide.
In a preferred embodiment of the invention, the reducing agent is ascorbic acid, sodium formaldehyde sulfoxylate, sodium hypophosphite, first
At least one of aldehyde sodium bisulphite.
In a preferred embodiment of the invention, the molecular weight regulator be 2 mercapto ethanol, 2- TGAs,
At least one of 3- mercaprols, 3- mercaptopropionic acids, tertiary sodium phosphate, sodium formate, sodium acetate.
In a preferred embodiment of the invention, the dropwise addition whole process of first to fourth solution is used and at the uniform velocity dripped
Add.
Beneficial effects of the present invention：
1st, the present invention by it is bright by esters of unsaturated carboxylic acids, unsaturated phosphate and unsaturated acid anhydride under medium temperature free radical
Copolymerization has the performed polymer of certain degree of polymerization, and high temperature esterification performed polymer, so as in polycarboxylate water-reducer molecule structure
Phosphate group and ester group are introduced, and the adsorption capacity of phosphate group is strong relatively strong, can reduce absorption of the clay to other groups, so as to
Reduction water reducer contains mud, powder containing quantity to aggregate and causes to lose the problem of fast greatly.
2nd, the present invention is copolymerized by normal temperature and introduces amide groups, and polycarboxylic acids is adjusted by regulating and controlling material dropping order and time
The sequential structure of molecule, so as to obtain the copolymerization product with differentiation molecular structure, it is effectively controlled ester group and amide groups
Priority hydrolysis rate, so as to improve the later stage function of slump protection of concrete, make it that still there is preferable slump retaining after 3 hours
Energy.
Embodiment
Technical scheme is further detailed and described below by way of embodiment.
Embodiment 1
(1) preparation of performed polymer：50.00g maleic anhydrides are added in the first reaction vessel, are passed through 40 DEG C of insulations of nitrogen
2h, then initiator perbenzoic acid butyl benzenesulfonamide, hydroxypropyl acrylate, hydroxy propyl methacrylate and acrylic acid hydroxypropyl is added dropwise
Mixed solution (wherein 2.27g perbenzoic acids butyl benzenesulfonamide, 64.00g hydroxypropyl acrylates, the 104.00g methyl of phosphate
Hydroxypropyl acrylate, 65.00g acrylic acid Hydroxypropyl phosphates ester), it is added dropwise in 3h, continues nitrogen purging 3h, reaction terminates,
Produce performed polymer.
(2) esterification：It is anti-that 80.00g vinyl alcohols, 56.00g performed polymers and 4.10g p-methyl benzenesulfonic acid are added to second
Answer in container and mix, under nitrogen protection, the isothermal reaction 6h at 90 DEG C, during which removed with vacuumizing or lead to method of the nitrogen with water
Go water, reaction to be down to room temperature after terminating, that is, obtain esterification products.
(3) copolyreaction：4.00g acrylic acid is dissolved in 30.00g water and forms the first solution, 0.66g TGAs are dissolved in
30.00g water forms the second solution, and 0.35g ascorbic acid is dissolved in 30.00g water and forms the 3rd solution, 0.45gN, N- di-2-ethylhexylphosphine oxides
Acrylamide is dissolved in 30.00g water and forms the 4th solution.12.00g esterifications made from step (3) are added in the 3rd reaction vessel
Product, the isoamyl alcohol polyoxyethylene ether that molecular weight 120.00g is 2400 and 80.00g water, stirring at normal temperature add to being uniformly dissolved
Enter 1.20g hydrogen peroxide, then first to fourth above-mentioned solution is at the uniform velocity added dropwise successively, its dropwise addition order is as follows：It is first first
Solution, it is finally the 4th solution next to that second and the 3rd solution, and second and the 3rd solution and the first solution interval 30min
It is added dropwise, the 4th solution and second and the 3rd solution interval 30min dropwise addition, the time for adding of the first Solutions Solution is 2.5h, second
Time for adding with the 3rd solution is 3h, and the time for adding of the 4th solution is 2.5h.Continue to react 1h after completion of dropwise addition, be total to
Poly- product.
(4) neutralization reaction：It is 5~7 that the copolymerization product obtained by step (3) is neutralized into pH value with liquid caustic soda, is produced described
Long-acting polycarboxylic acid slump retaining agent.
Embodiment 2
(1) preparation of performed polymer：63.50g dimethyl maleic anhydrides are added in the first reaction vessel, are passed through 60 DEG C of nitrogen
Be incubated 1h, then be added dropwise initiator perbenzoic acid butyl benzenesulfonamide, methyl methacrylate and acrylic phosphite ester mixing it is molten
Liquid (wherein 1.72g perbenzoic acids butyl benzenesulfonamide, 50.65g methyl methacrylates, 61.00g acrylic phosphite ester), 3h
Inside it is added dropwise, continues nitrogen purging 2h, reaction terminates, and produces performed polymer.
(2) esterification：43.10g3- methyl-3-butene-1-alcohols, 76.00g performed polymers and 3.15g benzene sulfonic acids are added
Mixed into the second reaction vessel, under nitrogen protection, the isothermal reaction 3h at 120 DEG C, during which with vacuumizing or lead to nitrogen band
The method of water removes water, and reaction is down to room temperature after terminating, that is, obtains esterification products.
(3) copolyreaction：5.00g acrylic acid is dissolved in 30.00g water and forms the first solution, 0.7g tertiary sodium phosphates are dissolved in
30.00g water forms the second solution, and 0.25g rongalites are dissolved in 30.00g water and form the 3rd solution, 0.20g acryloyls
Amine and 0.20gN- NMAs are dissolved in 30.00g water and form the 4th solution.Step is added in the 3rd reaction vessel
(3) 18.00g esterification products made from, the methacrylic polyoxyethylene poly-oxygen propylene aether that molecular weight 90.00g is 2400 and
100.00g water, stirring at normal temperature add 0.85g ammonium persulfate 1.20g and 0.66g sodium hypophosphites to being uniformly dissolved, then even successively
First to fourth above-mentioned solution is added dropwise in speed, and its dropwise addition order is as follows：It is the first solution first, next to that second and the 3rd molten
Liquid, is finally the 4th solution, and second and the 3rd solution and the first solution interval 30min be added dropwise, the 4th solution and second and the
Three solution interval 20min are added dropwise, and the time for adding of the first Solutions Solution is 3h, second and the 3rd the time for adding of solution be
3.5h, the time for adding of the 4th solution is 3h.Continue to react 0.5h after completion of dropwise addition, obtain copolymerization product.
(4) neutralization reaction：It is 5~7 that the copolymerization product obtained by step (3) is neutralized into pH value with liquid caustic soda, is produced described
Long-acting polycarboxylic acid slump retaining agent.
Embodiment 3
(1) preparation of performed polymer：56.90g itaconic anhydrides are added in the first reaction vessel, are passed through 50 DEG C of insulations of nitrogen
2h, then initiator perbenzoic acid butyl benzenesulfonamide, hydroxy-ethyl acrylate and butyl methacrylate, acrylic acid hydroxypropyl phosphorus is added dropwise
Mixed solution (wherein 3.55g perbenzoic acids butyl benzenesulfonamide, 60.30g hydroxy-ethyl acrylates, the 54.00g metering systems of acid esters
Acid butyl ester, 62.00g acrylic acid Hydroxypropyl phosphates ester), it is added dropwise in 3h, continues nitrogen purging 2h, reaction terminates, produced pre-
Aggressiveness.
(2) esterification：The concentrated sulfuric acid of 58.00g allyl alcohols, 67.00g performed polymers and 2.10g98% is added to second
Mixed in reaction vessel, under nitrogen protection, the isothermal reaction 4h at 110 DEG C, during which with vacuumizing or lead to side of the nitrogen with water
Method removes water, and reaction is down to room temperature after terminating, that is, obtains esterification products.
(3) copolyreaction：By 4.00g acrylic acid, 4.00g methacrylic acids are dissolved in 20.00g water and form the first solution,
1.00g mercaptopropionic acids are dissolved in 20.00g water and form the second solution, and 0.40g sodium formaldehyde sulfoxylates are dissolved in 20.00g water and form the 3rd solution,
0.80g2~methyl propane sulfonic acid acrylamide is dissolved in 20.00g water and forms the 4th solution.Step is added in the 3rd reaction vessel
(3) 15.00g esterification products, allyl alcohol polyethenoxy ether and 90.00g water that molecular weight 150.00g is 2400, normal temperature made from
Stirring adds 1.20g ammonium persulfates to being uniformly dissolved, then first to fourth above-mentioned solution is at the uniform velocity added dropwise successively, and its dropwise addition is suitable
Sequence is as follows：Be the first solution first, be finally the 4th solution next to that second and the 3rd solution, and second and the 3rd solution with
First solution interval 20min be added dropwise, the 4th solution with second and the 3rd solution interval 30min dropwise addition, the drop of the first Solutions Solution
Be 1.5h between added-time, second and the 3rd the time for adding of solution be 2h, the time for adding of the 4th solution is 1.5h.After completion of dropwise addition
Continue to react 1h, obtain copolymerization product.
(4) neutralization reaction：It is 5~7 that the copolymerization product obtained by step (3) is neutralized into pH value with liquid caustic soda, is produced described
Long-acting polycarboxylic acid slump retaining agent.
Embodiment 4
(1) preparation of performed polymer：50.10g succinic anhydrides are added in the first reaction vessel, are passed through 55 DEG C of insulations of nitrogen
1.5h, then initiator perbenzoic acid butyl benzenesulfonamide, hydroxy propyl methacrylate, methyl acrylate and acrylic acid hydroxypropyl is added dropwise
Mixed solution (wherein 1.20g perbenzoic acids butyl benzenesulfonamide, 74.60g hydroxy propyl methacrylates, the 43.00g third of phosphate
E pioic acid methyl ester, 60.00g acrylic phosphite ester), it is added dropwise in 3h, continues nitrogen purging 3h, reaction terminates, and produces pre-polymerization
Body.
(2) esterification：77.50g2- methallyl alcohols, 86.00g performed polymers and 1.88g ethylsulfonic acids are added to
Mixed in two reaction vessels, under nitrogen protection, the isothermal reaction 5h at 100 DEG C, during which with vacuumizing or lead to nitrogen with water
Method removes water, and reaction is down to room temperature after terminating, that is, obtains esterification products.
(3) copolyreaction：6.00g methacrylic acids are dissolved in 25.00g water and form the first solution, 1.20g lauryl mercaptans are molten
The second solution is formed in 25.00g water, 0.88g sodium hydrogensulfites are dissolved in 25.00g water and form the 3rd solution, 0.15g metering systems
Acid amides and 0.40gN, N- methylene-bisacrylamide are dissolved in 25.00g water and form the 4th solution.Added in the 3rd reaction vessel
15.00g esterification products, the isoamyl alcohol polyoxyethylene ether that molecular weight 100.00g is 2400 and 80.00g made from step (3)
Water, stirring at normal temperature adds 1.50g sodium peroxydisulfates to being uniformly dissolved, then first to fourth above-mentioned solution is at the uniform velocity added dropwise successively, its
Dropwise addition order is as follows：It is the first solution first, is finally the 4th solution next to that second and the 3rd solution, and second and the 3rd
Solution and the first solution interval 30min are added dropwise, and the 4th solution and second and the 3rd solution interval 15min dropwise addition, the first solution are molten
The time for adding of liquid is 2h, second and the 3rd the time for adding of solution be 2.5h, the time for adding of the 4th solution is 2.5h.It is added dropwise
Continue to react 1h after end, obtain copolymerization product.
(4) neutralization reaction：It is 5~7 that the copolymerization product obtained by step (3) is neutralized into pH value with liquid caustic soda, is produced described
Long-acting polycarboxylic acid slump retaining agent.
(polycarboxylic acids of commercially available excellent performance is protected to collapse the long-acting polycarboxylic acid slump retaining agent and comparative example that the synthesis of embodiment 1~4 is obtained
Agent) concrete performance measure is carried out, concrete mix is shown in Table 1, and acquired results are as shown in table 2：
The concrete raw material of table 1 and match ratio
The embodiment performance comparison of table 2
Understand from the above, add the concrete of long-acting polycarboxylic acid slump retaining agent prepared by the present invention, it is possible to achieve when long
Between protect and collapse effect.
Those of ordinary skill in the art understand, when technical parameter of the invention and raw material components change in following ranges,
Remain to access same as the previously described embodiments or similar technique effect, still belong to and protection scope of the present invention：
A kind of preparation method of long-acting polycarboxylic acid slump retaining agent, it is characterised in that：Comprise the following steps：
(1) preparation of performed polymer：Unsaturated acid anhydride is added in the first reaction vessel, is passed through 40~60 DEG C of insulations of nitrogen
1-2h, then the mixed solution and initiator perbenzoic acid benzene fourth of esters of unsaturated carboxylic acids and unsaturated phosphate are added dropwise respectively
Ester, it is added dropwise in 3h, continues nitrogen and purge 2~3h, obtain performed polymer；Wherein, unsaturated acid anhydride is maleic anhydride, dimethyl horse
Come acid anhydrides, itaconic anhydride or succinic anhydride, esters of unsaturated carboxylic acids is hydroxy-ethyl acrylate, hydroxyethyl methacrylate, acrylic acid
Hydroxypropyl acrylate, hydroxy propyl methacrylate, hy-droxybutyl, methyl methacrylate, methyl acrylate, ethyl acrylate, first
At least one of base ethyl acrylate, butyl acrylate and butyl methacrylate, unsaturated phosphate are acrylic acid hydroxypropyl
Base phosphate or acrylic phosphite ester, the mol ratio of esters of unsaturated carboxylic acids, unsaturated phosphate and unsaturated acid anhydride is 1: 0.1
~1.5: 0.5~2, initiator account for esters of unsaturated carboxylic acids, unsaturated phosphate and unsaturated acid anhydride gross mass 0.5~
2.5%；
(2) esterification：Performed polymer obtained by unsaturated alcohol, step (1) and catalyst are added to the second reaction vessel
Middle mixing, under nitrogen protection, 3~6h of isothermal reaction at 90-120 DEG C, during which with vacuumizing or lead to method of the nitrogen with water
Water is removed, reaction is down to room temperature after terminating, obtains esterification products；Wherein, unsaturated alcohol be vinyl alcohol, 3- methyl -3- butylene -
The mass ratio of 1- alcohol, allyl alcohol or 2- methallyl alcohols, unsaturated alcohol and performed polymer is 1~5: 1, and catalyst amount is insatiable hunger
With the 0.5~3.0% of alcohol and performed polymer gross mass；
(3) copolyreaction：First monomer is dissolved in water and forms the first solution, it is molten that molecular weight regulator is dissolved in water formation second
Liquid, reducing agent are dissolved in water and form the 3rd solution, and second comonomer is dissolved in water and forms the 4th solution, and step is added in the 3rd reaction vessel
Suddenly the polyether monomer and water of esterification products, molecular weight 800~4000 made from (3), stirring at normal temperature add oxidation to being uniformly dissolved
Agent, then above-mentioned first to fourth solution is added dropwise, its dropwise addition order is as follows：It is the first solution first, next to that second and the 3rd molten
Liquid, is finally the 4th solution, and second and the 3rd solution and first 15~30min of solution interval be added dropwise, the 4th solution and second
It is added dropwise with the 3rd 15~30min of solution interval, the time for adding of the first Solutions Solution is 1.5~3.5h, second and the 3rd solution
Time for adding be 2~4h, the time for adding of the 4th solution is 1.5~3.5h；Continue 0.5~2h of reaction after completion of dropwise addition, obtain
To copolymerization product；Wherein, polyether monomer is isoamyl alcohol polyoxyethylene ether, prenol polyoxyethylene poly-oxygen propylene aether, methyl
Allyl alcohol polyethenoxy ether, methacrylic polyoxyethylene poly-oxygen propylene aether, at least one of allyl alcohol polyethenoxy ether, first
Monomer is acrylic acid and/or methacrylic acid, second comonomer be acrylamide, Methacrylamide, N hydroxymethyl acrylamide,
At least one of 2~methyl propane sulfonic acid acrylamide and N, N- methylene-bisacrylamide, the dosage of molecular weight regulator
For the 0.2~1.5% of polyether monomer quality, the dosage of Oxidizing and Reducing Agents is the 0.3~2.0% of polyether monomer quality,
The dosage of first monomer and second comonomer is respectively the 2.0~8.0% and 0.5~5% of polyether monomer quality, esterification products
Dosage is the 5.0~15.0% of polyether monomer quality；
(4) neutralization reaction：Copolymerization product obtained by step (3) is neutralized to pH value as 5~7 with liquid caustic soda, produced described
Long-acting polycarboxylic acid slump retaining agent.
Preferably, the catalyst is at least one in benzene sulfonic acid, p-methyl benzenesulfonic acid, ethylsulfonic acid and 98% concentrated sulfuric acid
Kind, the oxidant is at least one of ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate and hydrogen peroxide, and the reducing agent is
At least one of ascorbic acid, sodium formaldehyde sulfoxylate, sodium hypophosphite, rongalite, the molecular weight regulator are 2- sulfydryls
At least one of ethanol, 2- TGAs, 3- mercaprols, 3- mercaptopropionic acids, tertiary sodium phosphate, sodium formate, sodium acetate, it is described
The dropwise addition whole process of first to fourth solution is used and is at the uniform velocity added dropwise.
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 (6)
- A kind of 1. preparation method of long-acting polycarboxylic acid slump retaining agent, it is characterised in that：Comprise the following steps：(1) preparation of performed polymer：Unsaturated acid anhydride is added in the first reaction vessel, is passed through 40~60 DEG C of insulation 1-2h of nitrogen, The mixed solution and initiator perbenzoic acid butyl benzenesulfonamide of esters of unsaturated carboxylic acids and unsaturated phosphate, 3h is added dropwise respectively again Inside it is added dropwise, continues nitrogen and purge 2~3h, obtain performed polymer；Wherein, unsaturated acid anhydride is maleic anhydride, dimethyl maleic acid Acid anhydride, itaconic anhydride or succinic anhydride, esters of unsaturated carboxylic acids are hydroxy-ethyl acrylate, hydroxyethyl methacrylate, acrylic acid hydroxypropyl Ester, hydroxy propyl methacrylate, hy-droxybutyl, methyl methacrylate, methyl acrylate, ethyl acrylate, methyl-prop At least one of olefin(e) acid ethyl ester, butyl acrylate and butyl methacrylate, unsaturated phosphate are acrylic acid hydroxypropyl phosphorus Acid esters or acrylic phosphite ester, the mol ratio of esters of unsaturated carboxylic acids, unsaturated phosphate and unsaturated acid anhydride for 1: 0.1~ 1.5: 0.5~2, initiator accounts for the 0.5~2.5% of esters of unsaturated carboxylic acids, unsaturated phosphate and unsaturated acid anhydride gross mass；(2) esterification：Performed polymer obtained by unsaturated alcohol, step (1) and catalyst are added in the second reaction vessel and mixed Close, under nitrogen protection, 3~6h of isothermal reaction at 90-120 DEG C, during which removed with vacuumizing or lead to method of the nitrogen with water Water, reaction are down to room temperature after terminating, obtain esterification products；Wherein, unsaturated alcohol be vinyl alcohol, 3- methyl-3-butene-1-alcohols, The mass ratio of allyl alcohol or 2- methallyl alcohols, unsaturated alcohol and performed polymer is 1~5: 1, and catalyst amount is unsaturated alcohol With the 0.5~3.0% of performed polymer gross mass；(3) copolyreaction：First monomer is dissolved in water and forms the first solution, molecular weight regulator is dissolved in water and forms the second solution, Reducing agent is dissolved in water and forms the 3rd solution, and second comonomer is dissolved in water and forms the 4th solution, and step is added in the 3rd reaction vessel (3) polyether monomer and water of esterification products, molecular weight 800~4000 made from, stirring at normal temperature add oxidation to being uniformly dissolved Agent, then above-mentioned first to fourth solution is added dropwise, its dropwise addition order is as follows：It is the first solution first, next to that second and the 3rd molten Liquid, is finally the 4th solution, and second and the 3rd solution and first 15~30min of solution interval be added dropwise, the 4th solution and second It is added dropwise with the 3rd 15~30min of solution interval, the time for adding of the first Solutions Solution is 1.5~3.5h, second and the 3rd solution Time for adding be 2~4h, the time for adding of the 4th solution is 1.5~3.5h；Continue 0.5~2h of reaction after completion of dropwise addition, obtain To copolymerization product；Wherein, polyether monomer is isoamyl alcohol polyoxyethylene ether, prenol polyoxyethylene poly-oxygen propylene aether, methyl Allyl alcohol polyethenoxy ether, methacrylic polyoxyethylene poly-oxygen propylene aether, at least one of allyl alcohol polyethenoxy ether, first Monomer is acrylic acid and/or methacrylic acid, second comonomer be acrylamide, Methacrylamide, N hydroxymethyl acrylamide, At least one of 2~methyl propane sulfonic acid acrylamide and N, N- methylene-bisacrylamide, the dosage of molecular weight regulator For the 0.2~1.5% of polyether monomer quality, the dosage of Oxidizing and Reducing Agents is the 0.3~2.0% of polyether monomer quality, The dosage of first monomer and second comonomer is respectively the 2.0~8.0% and 0.5~5% of polyether monomer quality, the use of esterification products Measure as the 5.0~15.0% of polyether monomer quality；(4) neutralization reaction：Copolymerization product obtained by step (3) is neutralized to pH value as 5~7 with liquid caustic soda, produced described long-acting Polycarboxylic acid slump retaining agent.
- 2. preparation method as claimed in claim 1, it is characterised in that：The catalyst is benzene sulfonic acid, p-methyl benzenesulfonic acid, ethyl At least one of sulfonic acid and 98% concentrated sulfuric acid.
- 3. preparation method as claimed in claim 1, it is characterised in that：The oxidant is ammonium persulfate, potassium peroxydisulfate, over cure At least one of sour sodium and hydrogen peroxide.
- 4. preparation method as claimed in claim 1, it is characterised in that：The reducing agent is ascorbic acid, sodium formaldehyde sulfoxylate, hypophosphorous acid At least one of sodium, rongalite.
- 5. preparation method as claimed in claim 1, it is characterised in that：The molecular weight regulator is 2 mercapto ethanol, 2- mercaptos At least one of guanidine-acetic acid, 3- mercaprols, 3- mercaptopropionic acids, tertiary sodium phosphate, sodium formate, sodium acetate.
- 6. preparation method as claimed in claim 1, it is characterised in that：The dropwise addition whole process of first to fourth solution uses At the uniform velocity it is added dropwise.
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