CN106188423B - A kind of sustained-release polycarboxylic super plasticizer and preparation method thereof - Google Patents
A kind of sustained-release polycarboxylic super plasticizer and preparation method thereof Download PDFInfo
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- CN106188423B CN106188423B CN201610593905.3A CN201610593905A CN106188423B CN 106188423 B CN106188423 B CN 106188423B CN 201610593905 A CN201610593905 A CN 201610593905A CN 106188423 B CN106188423 B CN 106188423B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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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- C—CHEMISTRY; METALLURGY
- 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
- C04B24/24—Macromolecular compounds
- C04B24/243—Phosphorus-containing polymers
- C04B24/246—Phosphorus-containing polymers containing polyether side chains
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
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- C—CHEMISTRY; METALLURGY
- 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
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/30—Water reducers, plasticisers, air-entrainers, flow improvers
- C04B2103/32—Superplasticisers
Abstract
The invention discloses a kind of sustained-release polycarboxylic super plasticizer and preparation method thereof, which is that unsaturated carboxylic acid, unsaturated polyether and beta-unsaturated esters are carried out under the effect of oxidant, reducing agent and chain-transferring agent made from free radicals copolymerization reaction.Beta-unsaturated esters molecular weight of the present invention is smaller, and preparation process is simple, easily-controllable, and yield is high, three-waste free discharge.There are two kinds of ester bonds that the hydroxyl of carboxyl and phosphate group and polyalcohol is formed in the small-molecular-weight beta-unsaturated esters, form the ester bond of the different gradient hydrolysis abilities under alkaline environment, after sustained-release polycarboxylic super plasticizer is made as raw material by the use of it, the ester bond of this gradient hydrolysis ability has ensured the sustained release of concrete system sustained-release polycarboxylic super plasticizer, makes super plasticizer that there is superior diminishing and guarantor to collapse effect.
Description
Technical field
The present invention relates to a kind of sustained-release polycarboxylic super plasticizers and preparation method thereof, and in particular to a kind of special with structure
Small-molecular-weight sustained-release polycarboxylic super plasticizer and preparation method thereof for raw material of beta-unsaturated esters, belong to building material technology
Field.
Background technology
High performance concrete because of good workability and durability, and be widely applied to China's high ferro, water conservancy, tunnel,
The large-scale construction engineerings such as bridge build in, wherein, poly carboxylic acid series super plasticizer be the indispensable component of high performance concrete it
One, it is known as third generation Concrete superplastizer.Poly carboxylic acid series super plasticizer is with volume is low, water-reducing rate is high, the slump is kept
The advantages that property is good, Molecular Design degree of freedom is big, environmentally protective, becomes hot spot and the exploitation of concrete admixture area research
Emphasis.
As architectural engineering is higher and higher to the requirement of concrete material application property, when being kept to high performance concrete workability
Between require increasingly to grow, how to effectively control concrete slump loss it is minimum or do not lose be at present both at home and abroad scientific research institutions and
The problem of water-reducing agent enterprise urgent need to resolve.
At present, slow-release type polycarboxylate super plasticizer protects landslide face in diminishing and has been achieved for certain achievement, such as
CN104261719A with unsaturated polyether monomer, unsaturated acid monomer, unsaturated phosphate ester monomer, chain-transferring agent, initiator and
Deionized water is raw material, under the conditions of 40-80 DEG C, 4-6h is added dropwise, the polycarboxylic acids with phosphate ester structure is prepared in heat preservation 2h
Water-reducing agent, but the patent in preparation process using heating systems, it is higher to equipment requirement, and generated time is longer, energy consumption compared with
Greatly, cost is higher.
105367720 A of patent CN are with prenol polyether monomer, acrylic acid, acrylic acid hydroxy alkyl ester, unsaturated phosphoric acid
Ester, unsaturated alcohol ether are raw material, and using hydrogen peroxide as initiator, sodium formaldehyde sulphoxylate or ascorbic acid are reducing agent, with mercapto
Guanidine-acetic acid is molecular weight regulator, causes free radical polymerization at a temperature of 5-40 DEG C, is prepared for a kind of slow-release type polycarboxylate and subtracts
Aqua.But the unsaturated phosphate ester that the patent uses is 2- methacryloxyethyls phosphate or 2- methacryloxies
Propyl phosphate, preparation process want thermal dehydration, and esterification yield is low, production process energy consumption and of high cost, are unfavorable for industrialized production,
And additive amount is smaller in slow-release type polycarboxylate water reducer preparation process, which is added in concrete, mixed in control
It is limited in terms of solidifying soil later-slump loss, it is difficult to meet requirement of engineering.
Invention content
For the deficiency that poly carboxylic acid series super plasticizer now is difficult to control in later concrete slump-loss, the present invention carries
A kind of sustained-release polycarboxylic super plasticizer is supplied, the plasticiser is with simultaneously containing phosphate-based and unsaturated acyl oxygroup unsaturation
Ester is raw material, and beta-unsaturated esters hydrolysis ability under alkaline environment is good, and gained super plasticizer protects time lengthening of collapsing, and efficiently solves
The thorny problem faced in engineering.
The present invention also provides the preparation method of above-mentioned sustained-release polycarboxylic super plasticizer, this method process safety is simple,
It is environmentally protective, low energy consumption.
Sustained-release polycarboxylic super plasticizer of the present invention be unsaturated carboxylic acid, unsaturated polyether and beta-unsaturated esters oxidant,
Made from reducing agent and the lower progress free radicals copolymerization reaction of chain-transferring agent effect, this method process safety is simple, environmentally protective, energy
Consume low, products obtained therefrom guarantor water-reducing effect of collapsing is good, efficiently solves the thorny problem faced in engineering.Specific technical solution is as follows：
Sustained-release polycarboxylic super plasticizer of the present invention is made of the raw material of following parts by weight：Unsaturated carboxylic acid 20~
43 parts, 300~360 parts of unsaturated polyether, 25~35 parts of beta-unsaturated esters, 2.2~5 parts of oxidant, 0.6~1.5 part of reducing agent, chain
0.5~2.5 part of transfer agent.
The raw materials used in the present invention beta-unsaturated esters are a kind of small-molecular-weight beta-unsaturated esters of new structure, with following formula I institute
The structural formula shown：
Wherein, R1And R2Separately expression-H or-(CH2)xCOOH, and R1And R2It is asynchronously-H, R3Expression-H or-
OH；X=0,1 or 2, n=0 or 1.
Beta-unsaturated esters of the present invention are dibasic acid esters, and molecular weight is smaller, and relative molecular mass is less than 600, belongs to small-molecular-weight insatiable hunger
And ester, hydrolysis ability is good under alkaline environment, and the guarantor that the raw material as super plasticizer is conducive to improve super plasticizer is collapsed ability.
Preferably, the beta-unsaturated esters R3For-OH.
Preferably, beta-unsaturated esters x=0.
In sustained-release polycarboxylic super plasticizer of the present invention, the unsaturated carboxylic acid is acrylic acid, methacrylic acid, Malaysia
It is one or more in acid, fumaric acid and itaconic acid.
In sustained-release polycarboxylic super plasticizer of the present invention, the unsaturated polyether is that relative molecular mass is 1600~4000
Isobutene alcohol polyoxyethylene ether or isoamyl alcohol polyoxyethylene ether.
In sustained-release polycarboxylic super plasticizer of the present invention, the oxidant of the free radicals copolymerization reaction is ammonium persulfate, mistake
One or both of sodium sulphate, potassium peroxydisulfate and hydrogen peroxide.
In sustained-release polycarboxylic super plasticizer of the present invention, the reducing agent of the free radicals copolymerization reaction is sodium hydrogensulfite,
One or both of sodium formaldehyde sulphoxylate and ascorbic acid.
In sustained-release polycarboxylic super plasticizer of the present invention, the chain-transferring agent of the free radicals copolymerization reaction is thioacetic acid,
Mercaptopropionic acid, sodium hypophosphite or methacrylic sulfonic acids sodium.
The preparation method of sustained-release polycarboxylic super plasticizer of the present invention, includes the following steps：
（1）Unsaturated carboxylic acid is soluble in water, A material are obtained, reducing agent is soluble in water with chain-transferring agent, obtain B material；
（2）Unsaturated polyether and beta-unsaturated esters is soluble in water, oxidant is then added in, after stirring evenly, starts that A is added dropwise
Material and B material, wherein A drops add 1.5~3 hours, and B drops add 2~3.5 hours, and A material continue room temperature after expecting equal completion of dropwise addition with B
Reaction 1~2 hour adjusts solid content to 35-45%, obtains sustained-release polycarboxylic super plasticizer after reaction.
When preparing beta-unsaturated esters, hydroxyl in polyalcohol first and phosphorus pentoxide or phosphorus oxychloride reaction, then with unsaturation
Anhydride reaction forms two kinds of ester groups of phosphate and unsaturated acid ester.Beta-unsaturated esters specifically include following preparation process：
A. under catalyst action esterification occurs for phosphorus pentoxide or phosphorus oxychloride and polyalcohol, is formed shown in formula II
Esterification products, R in formula3Expression-H or-OH, n=0 or 1；
B. the esterification products of step a and unsaturated acid anhydride carry out esterification, obtain the beta-unsaturated esters shown in Formulas I, in formula, R1
And R2Separately expression-H or-(CH2)xCOOH, and R1And R2It is asynchronously-H, R3Expression-H or-OH；X=0,1 or 2, n=0
Or 1；
。
When preparing beta-unsaturated esters, phosphorus pentoxide or phosphorus oxychloride in the reaction of polyalcohol need in the presence of a catalyst into
Row, the catalyst are polyoxometallic acid salt catalyst, such as phosphotungstate load type active carbon.
When preparing beta-unsaturated esters, catalyst amount for phosphorus pentoxide or phosphorus oxychloride quality 2 ~ 5%, preferably 2-3%.
When preparing beta-unsaturated esters, each parts by weight of raw materials dosage relation is：12 ~ 15 parts of phosphorus pentoxide or phosphorus oxychloride are more
First 5 ~ 11 parts of alcohol, 8 ~ 12 parts of unsaturated acid anhydride, preferably：14 ~ 15 parts of phosphorus pentoxide or phosphorus oxychloride, 6 ~ 10 parts of polyalcohol,
9 ~ 10 parts of unsaturated acid anhydride.
When preparing beta-unsaturated esters, the polyalcohol is glycerine, 1,3-PD or ethylene glycol, preferably glycerine or second
Glycol.
When preparing beta-unsaturated esters, the unsaturated acid anhydride is preferably maleic anhydride.
When preparing beta-unsaturated esters, above-mentioned steps a and b are reacted under gas shield.
In above-mentioned steps a, it is 55-70 DEG C to answer temperature, reaction time 4-5h；In step b, reaction temperature is 70-80 DEG C,
Reaction time is 6-8h.
When preparing beta-unsaturated esters, step a after reaction, can be directly added into reaction solution unsaturated acid anhydride continue into
Row reaction, without after the product of step a is detached again with unsaturated acids anhydride reactant.
When preparing sustained-release polycarboxylic super plasticizer, each raw material carries out free radicals copolymerization reaction, which need not heat,
It can be carried out under room temperature.
Further, the preparation method of sustained-release polycarboxylic super plasticizer may comprise steps of：
（1）Each raw material is weighed by weight：20~43 parts of unsaturated carboxylic acid, 300~360 parts of unsaturated polyether, unsaturation
25~35 parts of ester, 2.2~5 parts of oxidant, 0.6~1.5 part of reducing agent, 0.5~2.5 part of chain-transferring agent；
（2）Unsaturated carboxylic acid is dissolved in 50~70 parts by weight water, obtains A material, reducing agent and chain-transferring agent are dissolved in 80~
In 120 parts by weight water, B material are obtained；
（3）Unsaturated polyether, beta-unsaturated esters and 300 parts by weight water are stirred together to dissolving, oxidant is then added in, stirs
After mixing uniformly, start that A material and B material is added dropwise, wherein A material time for adding is 1.5~3 hours, and B material time for adding is small for 2~3.5
When, A material and B expect that the reaction was continued 1~2 hour after equal completion of dropwise addition；
（4）After reaction, it is 35-45wt% with deionized water adjustment solid content, obtains sustained-release polycarboxylic super plasticizer
Product.
Further, step（4）In, it is 39-41wt% preferably to adjust solid content.
Preferably, each parts by weight of raw materials dosage is：22~23 parts of unsaturated carboxylic acid, 350~360 parts of unsaturated polyether, no
30~32 parts of saturated ester, 3.5~4.0 parts of oxidant, 1.0~1.5 parts of reducing agent, 1.2~1.5 parts of chain-transferring agent.
Beneficial effects of the present invention are：
1. the present invention provides a kind of beta-unsaturated esters of relatively small molecular weight, preparation process is simple, easily-controllable, and yield is high, nothing
Three waste discharge.In the small-molecular-weight beta-unsaturated esters there are the hydroxyl of carboxyl and phosphate group and polyalcohol formed two kinds of ester bonds,
The ester bond of the different gradient hydrolysis abilities under alkaline environment is formd, sustained-release polycarboxylic super plasticizer is made by the use of it as raw material
Afterwards, the ester bond of this gradient hydrolysis ability has ensured the sustained release of concrete system sustained-release polycarboxylic super plasticizer, makes to surpass
There is plasticiser superior diminishing and guarantor to collapse effect, overcome that existing unsaturated phosphate ester cost performance is low and unsaturated carboxylic acid list
Ester hydrolysis ability it is limited and influence gained poly carboxylic acid series water reducer performance the defects of.
2. sustained-release polycarboxylic super plasticizer of the present invention is by unsaturated carboxylic acid, unsaturated polyether and small-molecular-weight beta-unsaturated esters
It is made under the effect of oxidant, reducing agent and chain-transferring agent by free radicals copolymerization reaction, preparation process is safe and simple, green ring
It protects, need not heat, esterification yield is high, low energy consumption, at low cost, suitable industrial scale production.The sustained-release polycarboxylic being prepared
Super plasticizer in concrete system can sustained release go on a tour from phosphate radical and polyalcohol, extend induction period of hydrated cementitious,
Hinder hydrated cementitious；A large amount of carboxyl and alcoholic extract hydroxyl group can be also released in super plasticizer molecule, continues to play the role of dispersion, make
Super plasticizer is protected the ability of collapsing and is substantially improved, and also has in later concrete and protects ability of collapsing well.
Specific embodiment
To make technical scheme of the present invention and advantage clearer, illustrated further below by specific embodiment,
Following embodiments are only exemplary, its content are not defined.
The structural formula of beta-unsaturated esters of the present invention shown in formula I, R1And R2Separately expression-H or-(CH2)xCOOH, and
R1And R2It is asynchronously-H；R3Expression-H or-OH；X=0,1 or 2, n=0 or 1.Below by specific embodiment to various different knots
The beta-unsaturated esters of structure illustrate.
Embodiment 1
Prepare sustained-release polycarboxylic super plasticizer：
By 14.20g phosphorus pentoxides, 9.21g glycerine and 0.42g phosphate-tungstic acid salt load type active carbons, it is added to
In three-necked flask, after carrying out nitrogen displacement three times, stirring is started.Controlling reaction temperature keeps the temperature 4 hours, after reaction at 60 ~ 70 DEG C
Add in maleic anhydride 9.8g, and carry out nitrogen displacement three times after, keep reaction temperature for 70~80 DEG C reaction 6 hours after discharge,
Beta-unsaturated esters are obtained, are denoted as DT-A.Gained beta-unsaturated esters structural formula is as shown in formula I, R1For-H, R2For-COOH, R3For-OH, n=1.
Deionized water 300g, unsaturation are added in the 1000ml four-hole boiling flasks for being configured with electric mixing device, peristaltic pump
Ester DT-A30g, isopentene group polyoxyethylene ether（Relative molecular weight is 3000）360g, stirring, which is warming up to, to be completely dissolved, then
The initiation liquid being made by 3.5g hydrogen peroxide and 15g deionized waters is disposably added in, after stirring 5min starts that A material and B material, A is added dropwise
Material is made of 23g acrylic acid, 60g deionized waters, is at the uniform velocity dripped off in 3 hours, and B is expected by 1.0g vitamin Cs, 1.2g mercaptopropionic acids
It forms with 85g water, was at the uniform velocity dripped off in 3.5 hours.A expects and B is expected after being added dropwise to complete, and continues room temperature reaction 2 hours, is mended after reaction
Deionized water 160g stirs 30min, and solid content is measured through determination of solid content instrument, obtains the slow-release that solid content is 39.5wt%
Polycarboxylic acid super-plasticizer is denoted as HPC-A.
Embodiment 2
Prepare sustained-release polycarboxylic super plasticizer：
By 14.20g phosphorus pentoxides, 7.61g1,3-propanediol and 0.32g phosphate-tungstic acid salt load type active carbons add
Enter into three-necked flask, after carrying out nitrogen displacement three times, start stirring.Controlling reaction temperature keeps the temperature 4.5 hours at 55 ~ 60 DEG C,
After reaction add in maleic anhydride 9.80g, and carry out nitrogen displacement three times after, keep reaction temperature for 75~80 DEG C react 6 hours
After discharge, obtain beta-unsaturated esters, be denoted as DT-B, gained beta-unsaturated esters structural formula is as shown in formula I, wherein R1For-H, R2For-COOH, R3
For-H, n=1.
Deionized water 300g, unsaturation are added in the 1000ml four-hole boiling flasks for being configured with electric mixing device, peristaltic pump
Ester DT-B32g, isopentene group polyoxyethylene ether（Relative molecular weight is 3000）360g, stirring, which is warming up to, to be completely dissolved.Then
The initiation liquid being made by 3.5g hydrogen peroxide and 15g deionized waters is disposably added in, after stirring 5min starts that A material and B material, A is added dropwise
Material is made of 22g acrylic acid, 60g deionized waters, is at the uniform velocity dripped off in 3 hours, and B is expected by 1.0g vitamin Cs, 1.3g mercaptopropionic acids
It forms with 85g water, was at the uniform velocity dripped off in 3.5 hours.A expects and B is expected after being added dropwise to complete, and continues room temperature reaction 2 hours, is mended after reaction
Deionized water 162g stirs 30min, measures solid content through determination of solid content instrument, obtains the poly- carboxylic of slow-release of solid content 39.2%
Sour super plasticizer, is denoted as HPC-B.
Embodiment 3
Prepare sustained-release polycarboxylic super plasticizer：
By 14.20g phosphorus pentoxides, 6.21g ethylene glycol and 0.38g phosphate-tungstic acid salt load type active carbons, it is added to
In three-necked flask, after carrying out nitrogen displacement three times, stirring is started.Controlling reaction temperature keeps the temperature 4.5 hours at 55 ~ 60 DEG C, reaction
Afterwards add in maleic anhydride 9.80g, and carry out nitrogen displacement three times after, keep reaction temperature for 75~80 DEG C reaction 6 hours after go out
Material, obtains beta-unsaturated esters, is denoted as DT-C, gained beta-unsaturated esters structural formula is as shown in formula I, wherein R1For-H, R2For-COOH, n=0.
Method according to embodiment 1 prepares sustained-release polycarboxylic super plasticizer, the difference is that beta-unsaturated esters used are DT-C,
Products obtained therefrom solid content is 39.5%, is denoted as HPC-C.
Comparative example
Method according to embodiment 1 prepares sustained-release polycarboxylic super plasticizer, unlike：Beta-unsaturated esters used are 2- first
Base acryloyl-oxyethyl phosphate.
In order to verify improvement of the structure beta-unsaturated esters of the present invention to super plasticizer performance, following test is carried out：
Example 1, embodiment 2, embodiment 3 and comparative example super plasticizer 1.2g, experimental water 87g, reference cement
300g, according to GB/T8077-2012《Concrete admixture homogeneity test method》Standard surveys flowing degree of net paste of cement
It is fixed.Experimental result is shown in Table 1.
As seen from the results in Table 1, compared to comparative example, embodiment 1-3 120min, 180min and 240min fluidity through when
Comparative example is substantially better than in terms of loss, it can be seen that, the introducing of small-molecular-weight beta-unsaturated esters significantly improves sustained-release polycarboxylic
The slump retaining of super plasticizer compared with comparative example, there is superior diminishing and guarantor to collapse effect.
The foregoing is only a preferred embodiment of the present invention, it will be appreciated by those of skill in the art that
In the case of not departing from the present inventive concept and range that claims are limited, various modifications can be made to the present invention, are added
It sums it up and replaces.
Claims (11)
1. a kind of sustained-release polycarboxylic super plasticizer, it is characterized in that being made of the raw material of following parts by weight：Unsaturated carboxylic acid 20~
43 parts, 300~360 parts of unsaturated polyether, 25~35 parts of beta-unsaturated esters, 2.2~5 parts of oxidant, 0.6~1.5 part of reducing agent, chain
0.5~2.5 part of transfer agent, the beta-unsaturated esters have the structural formula shown in following formula I：
Wherein, R1And R2Separately expression-H or-(CH2)xCOOH, and R1And R2It is asynchronously-H, R3Expression-H or-OH；x=
0th, 1 or 2, n=0 or 1.
2. sustained-release polycarboxylic super plasticizer according to claim 1, it is characterized in that：In formula I, R3For-OH.
3. sustained-release polycarboxylic super plasticizer according to claim 1, it is characterized in that：In formula I, x=0.
4. sustained-release polycarboxylic super plasticizer according to claim 1, it is characterized in that：Its solid content is 35-45%.
5. a kind of preparation method of sustained-release polycarboxylic super plasticizer described in claim 1, it is characterized in that including the following steps：
（1）Unsaturated carboxylic acid is soluble in water, A material are obtained, reducing agent is soluble in water with chain-transferring agent, obtain B material；
（2）Unsaturated polyether and beta-unsaturated esters is soluble in water, then add in oxidant, after stirring evenly, start be added dropwise A material and
B expects that wherein A drops add 1.5~3 hours, and B drops add 2~3.5 hours, continues room temperature reaction 1 after A material and the equal completion of dropwise addition of B material
~2 hours, solid content is adjusted after reaction to 35-45%, obtains sustained-release polycarboxylic super plasticizer.
6. preparation method according to claim 5, it is characterized in that：The unsaturated carboxylic acid for acrylic acid, methacrylic acid,
It is one or more in maleic acid, fumaric acid and itaconic acid；The unsaturated polyether is that relative molecular mass is 1600~4000
Isobutene alcohol polyoxyethylene ether or isoamyl alcohol polyoxyethylene ether；The oxidant is ammonium persulfate, sodium peroxydisulfate, persulfuric acid
One or both of potassium and hydrogen peroxide；The reducing agent is sodium hydrogensulfite, sodium formaldehyde sulphoxylate and ascorbic acid
One or both of；The chain-transferring agent is thioacetic acid, mercaptopropionic acid, sodium hypophosphite or methacrylic sulfonic acids sodium.
7. preparation method according to claim 5, it is characterized in that：The beta-unsaturated esters are made in accordance with the following methods：
A. under catalyst action esterification occurs for phosphorus pentoxide or phosphorus oxychloride and polyalcohol, is formed and is esterified shown in formula II
Product, R in formula3Expression-H or-OH, n=0 or 1；
B. step（1）Esterification products and unsaturated acid anhydride carry out esterification, obtain the beta-unsaturated esters shown in Formulas I, in formula, R1With
R2Separately expression-H or-(CH2)xCOOH, and R1And R2It is asynchronously-H, R3Expression-H or-OH；X=0,1 or 2, n=0 or
1；
。
8. preparation method according to claim 7, it is characterized in that：When preparing beta-unsaturated esters, the polyalcohol for glycerine,
1,3- propylene glycol or ethylene glycol；The catalyst is polyoxometallic acid salt catalyst；The unsaturated acid anhydride is maleic anhydride.
9. preparation method according to claim 8, it is characterized in that：When preparing beta-unsaturated esters, the polyalcohol is glycerine
Or ethylene glycol.
10. preparation method according to claim 1, it is characterized in that：When preparing beta-unsaturated esters, each parts by weight of raw materials dosage
For：12 ~ 15 parts of phosphorus pentoxide or phosphorus oxychloride, 5 ~ 11 parts of polyalcohol, 8 ~ 12 parts of unsaturated acid anhydride.
11. preparation method according to claim 1, it is characterized in that：When preparing beta-unsaturated esters, step a and b are protected in gas
It is reacted under shield；In step a, reaction temperature is 55-70 DEG C, reaction time 4-5h；In step b, reaction temperature 70-80
DEG C, reaction time 6-8h.
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| CN110642988B (en) * | 2018-06-26 | 2021-11-30 | 科之杰新材料集团有限公司 | Preparation method of early-strength ether polycarboxylate superplasticizer |
| CN108997151B (en) * | 2018-08-30 | 2021-08-24 | 济南大学 | Preparation method of unsaturated ester containing alkylamine group, obtained product and application |
| CN109354654B (en) * | 2018-08-30 | 2021-09-24 | 济南大学 | Early-strength polycarboxylate superplasticizer and preparation method thereof |
| CN113929832B (en) * | 2020-06-29 | 2023-02-14 | 博特建材（天津）有限公司 | Polyfunctional group superplasticizer for ultrahigh-performance concrete and preparation method thereof |
| CN113135686A (en) * | 2021-04-25 | 2021-07-20 | 重庆富普新材料有限公司 | Ultra-long slump retaining type polycarboxylic acid pumping agent and preparation method thereof |
| CN113636773A (en) * | 2021-06-01 | 2021-11-12 | 贵州石博士科技股份有限公司 | Composite concrete retarder and preparation method thereof |
| CN113603840B (en) * | 2021-09-06 | 2023-09-19 | 抚顺东科精细化工有限公司 | Preparation method of rust-proof slow-release polycarboxylic acid superplasticizer |
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