CN106188423A - 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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- 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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- 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
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Abstract
The invention discloses a kind of sustained-release polycarboxylic super plasticizer and preparation method thereof, this super plasticizer is that unsaturated carboxylic acid, unsaturated polyether and beta-unsaturated esters carry out free radicals copolymerization reaction under oxidant, reducing agent and chain-transferring agent effect and prepare.Beta-unsaturated esters molecular weight of the present invention, preparation process is simple, easily-controllable, and productivity is high, three-waste free discharge.This small-molecular-weight beta-unsaturated esters exists two kinds of ester bonds of carboxyl and phosphate group and the hydroxyl formation of polyhydric alcohol, define the ester bond of different gradient hydrolysis abilities under alkaline environment, after making sustained-release polycarboxylic super plasticizer with it as raw material, the ester bond of this gradient hydrolysis ability has ensured the sustained release of concrete system sustained-release polycarboxylic super plasticizer, makes super plasticizer have a more excellent diminishing and guarantor is collapsed effect.
Description
Technical field
The present invention relates to a kind of sustained-release polycarboxylic super plasticizer and preparation method thereof, it is a kind of special with structure to be specifically related to
The sustained-release polycarboxylic super plasticizer that beta-unsaturated esters is raw material of small-molecular-weight and preparation method thereof, 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,
During the large-scale construction engineering such as bridge is built, wherein, poly carboxylic acid series super plasticizer be the indispensable component of high performance concrete it
One, it is described as third generation Concrete superplastizer.Poly carboxylic acid series super plasticizer has that volume is low, water-reducing rate is high, the slump keeps
Property the advantage such as big, the environmental protection of good, Molecular Design degree of freedom, become focus and the exploitation of concrete admixture area research
Emphasis.
Along with concrete material application property is required more and more higher, when keeping high performance concrete workability by architectural engineering
Between require the longest, the most effectively control concrete slump loss minimum or do not lose be the most both at home and abroad scientific research institutions and
The problem that water reducer enterprise needs solution badly.
At present, slow-release type polycarboxylate super plasticizer is protected landslide face at diminishing and is had been achieved for certain achievement, as
CN104261719A with unsaturated polyester ether 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, drips 4-6h, insulation 2h and prepares the polycarboxylic acids with phosphate ester structure
Water reducer, but this patent uses heating systems in preparation process, higher to equipment requirements, and generated time is longer, energy consumption is relatively
Greatly, relatively costly.
Patent CN 105367720 A is with prenol polyether monomer, acrylic acid, acrylic acid hydroxy alkyl ester, unsaturated phosphoric acid
Ester, unsaturated alcohol ether are raw material, and with hydrogen peroxide as initiator, sodium formaldehyde sulphoxylate or ascorbic acid are reducing agent, with mercapto
Guanidine-acetic acid is molecular weight regulator, causes radical polymerization at a temperature of 5-40 DEG C, is prepared for a kind of slow-release type polycarboxylate and subtracts
Water preparation.But the unsaturated phosphate ester that this patent uses is 2-methacryloxyethyl phosphate ester or 2-methacryloxy
Propyl phosphate, preparation process wants thermal dehydration, and esterification yield is low, and production process energy consumption and cost are high, are unfavorable for industrialized production,
And addition is less in slow-release type polycarboxylate water reducer preparation process, this water reducer adds in concrete, mixed in control
Solidifying soil later-slump loss aspect is limited, is difficult to meet requirement of engineering.
Summary of the invention
For poly carboxylic acid series super plasticizer now in the unmanageable deficiency of later concrete slump-loss, the present invention carries
Having supplied a kind of sustained-release polycarboxylic super plasticizer, this plasticiser is to contain phosphate-based and unsaturated acyl epoxide unsaturation simultaneously
Ester is raw material, and this 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.
Present invention also offers the preparation method of above-mentioned sustained-release polycarboxylic super plasticizer, the method process safety is simple,
Environmental protection, energy consumption are low.
Sustained-release polycarboxylic super plasticizer of the present invention be unsaturated carboxylic acid, unsaturated polyether and beta-unsaturated esters oxidant,
Carry out what free radicals copolymerization reaction prepared under reducing agent and chain-transferring agent effect, the method process safety is simple, environmental protection, energy
Consuming low, it is good that products obtained therefrom protects water-reducing effect of collapsing, and efficiently solves the thorny problem faced in engineering.Concrete technical scheme is as follows:
Sustained-release polycarboxylic super plasticizer of the present invention, is made up of the raw material of following weight portion: unsaturated carboxylic acid 20～43 parts,
Unsaturated polyether 300～360 parts, beta-unsaturated esters 25～35 parts, oxidant 2.2～5 parts, reducing agent 0.6～1.5 parts, chain tra nsfer
Agent 0.5～2.5 parts.
The raw materials used beta-unsaturated esters of the present invention is the small-molecular-weight beta-unsaturated esters of a kind of new structure, and it has following formula I institute
The structural formula shown:
Wherein, R1And R2Separately represent-H or-(CH2)xCOOH, and R1And R2It is asynchronously-H, R3Represent-H or-OH；x
=0,1 or 2, n=0 or 1.
Beta-unsaturated esters of the present invention is dibasic acid esters, molecular weight, and relative molecular mass is less than 600, belongs to small-molecular-weight insatiable hunger
And ester, under alkaline environment, hydrolysis ability is good, and the raw material as super plasticizer is conducive to the guarantor improving super plasticizer to collapse ability.
Preferably, described beta-unsaturated esters R3For-OH.
Preferably, described beta-unsaturated esters x=0.
In sustained-release polycarboxylic super plasticizer of the present invention, described unsaturated carboxylic acid is acrylic acid, methacrylic acid, Malaysia
One or more in acid, fumaric acid and itaconic acid.
In sustained-release polycarboxylic super plasticizer of the present invention, described unsaturated polyether be relative molecular mass be 1600～4000
Isobutene alcohol polyoxyethylene ether or isopentenol polyoxyethylene ether.
In sustained-release polycarboxylic super plasticizer of the present invention, the oxidant of described free radicals copolymerization reaction is Ammonium persulfate., mistake
One or both in sodium sulfate, potassium peroxydisulfate and hydrogen peroxide.
In sustained-release polycarboxylic super plasticizer of the present invention, the reducing agent of described free radicals copolymerization reaction be sodium sulfite,
One or both in sodium formaldehyde sulphoxylate and ascorbic acid.
In sustained-release polycarboxylic super plasticizer of the present invention, the chain-transferring agent of described free radicals copolymerization reaction be TGA,
Mercaptopropionic acid, sodium hypophosphite or methacrylic sulfonic acids sodium.
The preparation method of sustained-release polycarboxylic super plasticizer of the present invention, comprises the following steps:
(1) unsaturated carboxylic acid is soluble in water, obtain A material, reducing agent is soluble in water with chain-transferring agent, obtain B material；
(2) by soluble in water to unsaturated polyether and beta-unsaturated esters, be subsequently adding oxidant, after stirring, start to drip A material and
B expects, wherein A gob adds 1.5～3 hours, and B gob adds 2～3.5 hours, and A material and B continue room temperature reaction 1 after expecting equal completion of dropwise addition
～2 hours, after reaction, adjustment solids content is to 35-45%, obtains sustained-release polycarboxylic super plasticizer.
When preparing beta-unsaturated esters, hydroxyl in polyhydric alcohol first and phosphorus pentoxide or phosphorus oxychloride reaction, then with unsaturation
Anhydride reaction, forms phosphate ester and two kinds of ester groups of unsaturated acid ester.Beta-unsaturated esters specifically includes following preparation process:
A. there is esterification in phosphorus pentoxide or phosphorus oxychloride and polyhydric alcohol under catalyst action, forms esterification shown in formula II
Product, R in formula3Represent-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, R1And R2
Separately represent-H or-(CH2)xCOOH, and R1And R2It is asynchronously-H, R3Represent-H or-OH；X=0,1 or 2, n=0 or 1；
。
When preparing beta-unsaturated esters, phosphorus pentoxide or phosphorus oxychloride need to enter in the presence of a catalyst in the reaction of polyhydric alcohol
OK, described catalyst is polyoxometallic acid salt catalyst, such as phosphotungstate load type active carbon.
When preparing beta-unsaturated esters, catalyst amount is phosphorus pentoxide or the 2 ~ 5% of phosphorus oxychloride quality, preferably 2-3%.
When preparing beta-unsaturated esters, each parts by weight of raw materials magnitude relation is: phosphorus pentoxide or phosphorus oxychloride 12 ~ 15 parts, many
Unit's alcohol 5 ~ 11 parts, unsaturated acid anhydride 8 ~ 12 parts, it is preferably: phosphorus pentoxide or phosphorus oxychloride 14 ~ 15 parts, polyhydric alcohol 6 ~ 10 parts,
Unsaturated acid anhydride 9 ~ 10 parts.
When preparing beta-unsaturated esters, described polyhydric alcohol is glycerol, 1,3-PD or ethylene glycol, preferably glycerol or second
Glycol.
When preparing beta-unsaturated esters, described unsaturated acid anhydride is preferably maleic anhydride.
When preparing beta-unsaturated esters, above-mentioned steps a and b all react under gas shield.
In above-mentioned steps a, answering temperature to be 55-70 DEG C, the response time is 4-5h；In step b, reaction temperature is 70-80 DEG C,
Response time is 6-8h.
When preparing beta-unsaturated esters, step a reaction terminate after, can be directly added in reactant liquor unsaturated acid anhydride continue into
Row reaction, after the product of step a need not being separated again with unsaturated acids anhydride reactant.
When preparing sustained-release polycarboxylic super plasticizer, each raw material carries out free radicals copolymerization reaction, this reaction without heating,
Can carry 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: unsaturated carboxylic acid 20～43 parts, unsaturated polyether 300～360 parts, beta-unsaturated esters 25
～35 parts, oxidant 2.2～5 parts, reducing agent 0.6～1.5 parts, chain-transferring agent 0.5～2.5 parts；
(2) unsaturated carboxylic acid is dissolved in 50～70 weight parts waters, obtains A material, reducing agent and chain-transferring agent are dissolved in 80～120 weights
In amount part water, obtain B material；
(3) being stirred together to unsaturated polyether, beta-unsaturated esters and 300 weight parts waters dissolve, be subsequently adding oxidant, stirring is all
After even, starting to drip A material and B expects, wherein A material time for adding is 1.5～3 hours, and B material time for adding is 2～3.5 hours, and A expects
Reaction 1～2 hour is continued after expecting equal completion of dropwise addition with B；
(4) after reaction terminates, adjusting solids content with deionized water is 35-45wt%, obtains sustained-release polycarboxylic super plasticizer and produces
Product.
Further, in step (4), preferably adjusting solids content is 39-41wt%.
Preferably, each parts by weight of raw materials consumption is: unsaturated carboxylic acid 22～23 parts, unsaturated polyether 350～360 parts, no
Saturated ester 30～32 parts, oxidant 3.5～4.0 parts, reducing agent 1.0～1.5 parts, chain-transferring agent 1.2～1.5 parts.
The invention have the benefit that
1. the invention provides the beta-unsaturated esters of a kind of relatively small molecular weight, its preparation process is simple, easily-controllable, and productivity is high, without the three wastes
Discharge.This small-molecular-weight beta-unsaturated esters exists two kinds of ester bonds of carboxyl and phosphate group and the hydroxyl formation of polyhydric alcohol, is formed
The ester bond of different gradient hydrolysis abilities under alkaline environment, after making sustained-release polycarboxylic super plasticizer with it as raw material,
The ester bond of this gradient hydrolysis ability has ensured the sustained release of concrete system sustained-release polycarboxylic super plasticizer, makes super plasticized
Effect that agent has a more excellent diminishing and guarantor is collapsed, overcomes that existing unsaturated phosphate ester cost performance is low and unsaturated carboxylic acid monoesters water
Solve limited in one's ability and affect the defect of gained poly carboxylic acid series water reducer performance.
Sustained-release polycarboxylic super plasticizer the most of the present invention is by unsaturated carboxylic acid, unsaturated polyether and small-molecular-weight beta-unsaturated esters
Prepared by free radicals copolymerization reaction under oxidant, reducing agent and chain-transferring agent effect, preparation technology ring safe and simple, green
Protect, need not heat, esterification yield is high, energy consumption is low, low cost, is suitable for industrial scale and produces.The sustained-release polycarboxylic prepared
Super plasticizer in concrete system can sustained release go on a tour from phosphate radical and polyhydric alcohol, extend hydrated cementitious induction period,
Hinder hydrated cementitious；Super plasticizer molecule also can discharge substantial amounts of carboxyl and alcoholic extract hydroxyl group, continue to play scattered effect, make
Super plasticizer is protected the ability of collapsing and is substantially improved, and also has, at later concrete, ability of collapsing of well protecting.
Detailed description of the invention
For making technical scheme and advantage clearer, illustrated by specific embodiment further below,
Following embodiment is only exemplary, is not defined its content.
The structural formula of beta-unsaturated esters of the present invention shown in formula I, R1And R2Separately represent-H or-(CH2)xCOOH, and
R1And R2It is asynchronously-H；R3Represent-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 illustrates.
Embodiment 1
Prepare sustained-release polycarboxylic super plasticizer:
By 14.20g phosphorus pentoxide, 9.21g glycerol and 0.42g phosphate-tungstic acid salt load type active carbon, join three mouthfuls
In flask, carry out nitrogen and replace after three times, start stirring.Control reaction temperature, at 60 ~ 70 DEG C, is incubated 4 hours, adds after reaction
Maleic anhydride 9.8g, and carry out nitrogen and replace after three times, keeping reaction temperature is discharging after 70～80 DEG C of reactions 6 hours, no
Saturated ester, is designated as DT-A.Gained beta-unsaturated esters structural formula as shown in formula I, R1For-H, R2For-COOH, R3For-OH, n=1.
Deionized water 300g, unsaturation is added in the 1000ml four-hole boiling flask being configured with electric mixing device, peristaltic pump
Ester DT-A30g, isopentene group polyoxyethylene ether (relative molecular weight is 3000) 360g, stirring is warming up to be completely dissolved, then
Disposably add the initiation liquid being made into by 3.5g hydrogen peroxide and 15g deionized water, start to drip A material after stirring 5min and B expects, A
Material is made up of 23g acrylic acid, 60g deionized water, at the uniform velocity drips off in 3 hours, and B expects by 1.0g vitamin C, 1.2g mercaptopropionic acid
Form with 85g water, at the uniform velocity dripped off in 3.5 hours.After A material and B material are added dropwise to complete, continue room temperature reaction 2 hours, mend after reaction
Deionized water 160g, stirs 30min, measures solids content through determination of solid content instrument, obtains the spacetabs type that solid content is 39.5wt%
Polycarboxylic acid super-plasticizer, is designated as HPC-A.
Embodiment 2
Prepare sustained-release polycarboxylic super plasticizer:
By 14.20g phosphorus pentoxide, 7.61g1, ammediol and 0.32g phosphate-tungstic acid salt load type active carbon, join
In there-necked flask, carry out nitrogen and replace after three times, start stirring.Control reaction temperature, at 55 ~ 60 DEG C, is incubated 4.5 hours, reaction
Rear addition maleic anhydride 9.80g, and carry out nitrogen and replace after three times, keeping reaction temperature is that 75～80 DEG C of reactions go out after 6 hours
Material, obtain beta-unsaturated esters, be designated as DT-B, gained beta-unsaturated esters structural formula as shown in formula I, wherein R1For-H, R2For-COOH, R3For-
H、n=1。
Deionized water 300g, unsaturation is added in the 1000ml four-hole boiling flask being configured with electric mixing device, peristaltic pump
Ester DT-B32g, isopentene group polyoxyethylene ether (relative molecular weight is 3000) 360g, stirring is warming up to be completely dissolved.Then
Disposably add the initiation liquid being made into by 3.5g hydrogen peroxide and 15g deionized water, start to drip A material after stirring 5min and B expects, A
Material is made up of 22g acrylic acid, 60g deionized water, at the uniform velocity drips off in 3 hours, and B expects by 1.0g vitamin C, 1.3g mercaptopropionic acid
Form with 85g water, at the uniform velocity dripped off in 3.5 hours.After A material and B material are added dropwise to complete, continue room temperature reaction 2 hours, mend after reaction
Deionized water 162g, stirs 30min, measures solids content through determination of solid content instrument, obtains the poly-carboxylic of spacetabs type of solid content 39.2%
Acid super plasticizer, is designated as HPC-B.
Embodiment 3
Prepare sustained-release polycarboxylic super plasticizer:
By 14.20g phosphorus pentoxide, 6.21g ethylene glycol and 0.38g phosphate-tungstic acid salt load type active carbon, join three mouthfuls
In flask, carry out nitrogen and replace after three times, start stirring.Control reaction temperature, at 55 ~ 60 DEG C, is incubated 4.5 hours, adds after reaction
Entering maleic anhydride 9.80g, and carry out after nitrogen replaces three times, keeping reaction temperature is discharging after 75～80 DEG C of reactions 6 hours,
Beta-unsaturated esters, is designated as DT-C, gained beta-unsaturated esters structural formula as shown in formula I, wherein R1For-H, R2For-COOH, n=0.
Preparing sustained-release polycarboxylic super plasticizer according to the method for embodiment 1, except for the difference that beta-unsaturated esters used is DT-C,
Products obtained therefrom solid content is 39.5%, is designated as HPC-C.
Comparative example
Sustained-release polycarboxylic super plasticizer is prepared, except for the difference that: beta-unsaturated esters used is 2-methyl-prop according to the method for embodiment 1
Alkene trimethylammonium phosphate ester.
In order to verify the improvement to super plasticizer performance of the present configuration beta-unsaturated esters, carry out following experiment:
The super plasticizer 1.2g of Example 1, embodiment 2, embodiment 3 and comparative example, experimental water 87g, reference cement 300g,
According to GB/T8077-2012 " concrete admixture homogeneity test method " standard, flowing degree of net paste of cement is measured.Real
Test and the results are shown in Table 1.
As seen from the results in Table 1, compare comparative example, embodiment 1-3 120min, 180min and 240min fluidity through time
Loss aspect is substantially better than comparative example, 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, has a more excellent diminishing and guarantor is collapsed effect.
The above, the only present invention preferably detailed description of the invention, it will be appreciated by those of skill in the art that
In the case of the present inventive concept limited without departing from claims and scope, the present invention can be made various amendment, add
Add and replace.
Claims (10)
1. a sustained-release polycarboxylic super plasticizer, is characterized in that being made up of the raw material of following weight portion: unsaturated carboxylic acid 20～
43 parts, unsaturated polyether 300～360 parts, beta-unsaturated esters 25～35 parts, oxidant 2.2～5 parts, reducing agent 0.6～1.5 parts, chain
Transfer agent 0.5～2.5 parts, described beta-unsaturated esters has a structural formula shown in lower formula I:
Wherein, R1And R2Separately represent-H or-(CH2)xCOOH, and R1And R2It is asynchronously-H, R3Represent-H or-OH；x=
0,1 or 2, n=0 or 1.
Sustained-release polycarboxylic super plasticizer the most according to claim 1, is characterized in that: in formula I, R3For-OH.
Sustained-release polycarboxylic super plasticizer the most according to claim 1, is characterized in that: in formula I, x=0.
Sustained-release polycarboxylic super plasticizer the most according to claim 1, is characterized in that: its solid content is 35-45%.
5. a preparation method for the sustained-release polycarboxylic super plasticizer described in claim 1, is characterized in that comprising the following steps:
(1) unsaturated carboxylic acid is soluble in water, obtain A material, reducing agent is soluble in water with chain-transferring agent, obtain B material；
(2) by soluble in water to unsaturated polyether and beta-unsaturated esters, be subsequently adding oxidant, after stirring, start to drip A material and
B expects, wherein A gob adds 1.5～3 hours, and B gob adds 2～3.5 hours, and A material and B continue room temperature reaction 1 after expecting equal completion of dropwise addition
～2 hours, after reaction, adjustment solids content is to 35-45%, obtains sustained-release polycarboxylic super plasticizer.
Preparation method the most according to claim 5, is characterized in that: described unsaturated carboxylic acid be acrylic acid, methacrylic acid,
One or more in maleic acid, fumaric acid and itaconic acid；Described unsaturated polyether be relative molecular mass be 1600～4000
Isobutene alcohol polyoxyethylene ether or isopentenol polyoxyethylene ether；Described oxidant is Ammonium persulfate., sodium peroxydisulfate, persulfuric acid
One or both in potassium and hydrogen peroxide；Described reducing agent is sodium sulfite, sodium formaldehyde sulphoxylate and ascorbic acid
In one or both；Described chain-transferring agent is TGA, mercaptopropionic acid, sodium hypophosphite or methacrylic sulfonic acids sodium.
Preparation method the most according to claim 5, is characterized in that: described beta-unsaturated esters prepares in accordance with the following methods:
A. there is esterification in phosphorus pentoxide or phosphorus oxychloride and polyhydric alcohol under catalyst action, forms esterification shown in formula II
Product, R in formula3Represent-H or-OH, n=0 or 1；
B. the esterification products of step (1) and unsaturated acid anhydride carry out esterification, obtain the beta-unsaturated esters shown in Formulas I, in formula, R1And R2
Separately represent-H or-(CH2)xCOOH, and R1And R2It is asynchronously-H, R3Represent-H or-OH；X=0,1 or 2, n=0 or 1；
。
Preparation method the most according to claim 7, is characterized in that: when preparing beta-unsaturated esters, described polyhydric alcohol be glycerol,
1,3-PD or ethylene glycol, preferably glycerol or ethylene glycol；Described catalyst is polyoxometallic acid salt catalyst；Described
Unsaturated acid anhydride is maleic anhydride.
Preparation method the most according to claim 1, is characterized in that: when preparing beta-unsaturated esters, and each parts by weight of raw materials consumption is:
Phosphorus pentoxide or phosphorus oxychloride 12 ~ 15 parts, polyhydric alcohol 5 ~ 11 parts, unsaturated acid anhydride 8 ~ 12 parts.
Preparation method the most according to claim 1, is characterized in that: when preparing beta-unsaturated esters, and step a and b all protect at gas
Protect down and react；In step a, reaction temperature is 55-70 DEG C, and the response time is 4-5h；In step b, reaction temperature is 70-80
DEG C, the response time is 6-8h.
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| CN108997151A (en) * | 2018-08-30 | 2018-12-14 | 济南大学 | The preparation method and products obtained therefrom of a kind of beta-unsaturated esters of alcohol-containing amine groups and application |
| CN109354654A (en) * | 2018-08-30 | 2019-02-19 | 济南大学 | A kind of Early-strength polycarboxylate superplasticizer and preparation method thereof |
| CN110642988A (en) * | 2018-06-26 | 2020-01-03 | 科之杰新材料集团有限公司 | Preparation method of early-strength ether polycarboxylate superplasticizer |
| 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 |
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| CN108997151A (en) * | 2018-08-30 | 2018-12-14 | 济南大学 | The preparation method and products obtained therefrom of a kind of beta-unsaturated esters of alcohol-containing amine groups and application |
| CN109354654A (en) * | 2018-08-30 | 2019-02-19 | 济南大学 | A kind of Early-strength polycarboxylate superplasticizer and preparation method thereof |
| CN109354654B (en) * | 2018-08-30 | 2021-09-24 | 济南大学 | Early-strength polycarboxylate superplasticizer and preparation method thereof |
| WO2022000306A1 (en) * | 2020-06-29 | 2022-01-06 | 江苏苏博特新材料股份有限公司 | Multifunctional superplasticizer for ultra-high performance concrete and preparation method therefor |
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| 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 |
| CN113603840A (en) * | 2021-09-06 | 2021-11-05 | 抚顺东科精细化工有限公司 | Preparation method of antirust slow-release polycarboxylic acid superplasticizer |
| 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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