CN110128047A - Viscosity reduction type polycarboxylate water-reducer and its high efficiency preparation method - Google Patents
Viscosity reduction type polycarboxylate water-reducer and its high efficiency preparation method Download PDFInfo
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- CN110128047A CN110128047A CN201910503140.3A CN201910503140A CN110128047A CN 110128047 A CN110128047 A CN 110128047A CN 201910503140 A CN201910503140 A CN 201910503140A CN 110128047 A CN110128047 A CN 110128047A
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- polycarboxylate water
- reducer
- viscosity reduction
- reduction type
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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
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/32—Polyethers, e.g. alkylphenol polyglycolether
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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
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/40—Redox systems
-
- 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
- C04B2103/302—Water reducers
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention belongs to construction materials, especially concrete admixture field, and in particular to viscosity reduction type polycarboxylate water-reducer and its high efficiency preparation method；Viscosity reduction type polycarboxylate water-reducer, is prepared by following raw material: glycol divinyl ether polyoxyethylene ether polymeric monomer, unsaturated carboxylic acid minor comonomer, allyl phenyl ether or propenylbenzene ethylether minor comonomer, oxidant, reducing agent, chain-transferring agent, sodium hydroxide.This method obtains terpolymer by free radical polymerization with glycol divinyl ether polyoxyethylene ether polymeric monomer (EPEG), unsaturated carboxylic acid minor comonomer, allyl phenyl ether or propenylbenzene ethylether minor comonomer, and controls its weight average molecular weight no more than 40000.
Description
Technical field
The invention belongs to construction materials, especially concrete admixture field, and in particular to viscosity reduction type polycarboxylate water-reducer
And its high efficiency preparation method.
Background technique
With the fast development of Building technology, building is increasingly intended to high stratification, enlargement, complicates development, high
Performance concrete is just widely adopted with the small unique advantage of intensity height, good integrity, self weight, large-scale especially in science of bridge building
A large amount of application has been obtained in super high-rise building.Simultaneously energy saving, environmental protection, and sustainable development, environmental condition in terms of
There is obvious benefit, high performance concrete becomes the inexorable trend of contemporary concrete technology development.
High performance concrete reduces the water in concrete unit volume compared with low water binder ratio, and the solid particles volume such as cement increases
The effects of adding, leading to smaller grain spacing, particle friction reinforcement, macroscopically shows as that concrete viscosity is big, and flowing velocity is slow, no
Easily pumping pours and is not easy closely knit, seriously constrains application of the high performance concrete in super high-rise pumping.Simultaneously as building
The continuous exploitation of material, building sand is more and more deficienter, and Machine-made Sand just gradually replaces natural river sand, and Machine-made Sand powder content is higher,
Grain shape does not have that natural river sand is mellow and full, and it is big that this results in concrete viscosity, poor fluidity.These factors seriously restrict high-performance
The popularization and application of concrete, the main method for reducing high performance concrete viscosity at present is some good fine coal of gradation of incorporation
The mineral admixtures such as ash, microballon, silicon ash, but this kind of material prevailing price is expensive, economy is poor, develops a kind of with viscosity reduction
The water-reducing agent of function has a very important significance.
Polycarboxylate water-reducer is the concrete admixture of latest generation, and there is excellent water-reducing rate, good cement to adapt to
Property the features such as, meanwhile, in the production process of polycarboxylate water-reducer without craftsmanship waste water generate, belong to environmental type material.It is poly-
Carboxylic acid water reducer has been widely used in high performance concrete.But common polycarboxylate water-reducer is to concrete viscosity
Improve limited, some even will increase concrete viscosity, therefore need to develop a kind of poly- carboxylic that can be substantially reduced concrete viscosity
Sour water-reducing agent.The synthesis of viscosity reduction type polycarboxylic acids at this stage is usually phosphate group to be introduced in its molecular structure or using modified big
Monomer, the introducing of phosphate group, which needs to synthesize by multi-section, to be just able to achieve, and the modification of polymeric monomer is also complex, causes viscosity reduction poly-
The synthesis technology of carboxylic acid is complicated.On the other hand, the generated time of polycarboxylate water-reducer is longer at this stage, generally 3-4h, synthesis
Complex process shortens the generated time of polycarboxylic acids, and improving production efficiency is also the target that polycarboxylic acids manufacturer is pursued.
Summary of the invention
The purpose of the present invention is to provide a kind of viscosity reduction type polycarboxylate water-reducer and its high efficiency preparation methods, solve above-mentioned skill
The problem in art.This method glycol divinyl ether polyoxyethylene ether polymeric monomer (EPEG), unsaturated carboxylic acid minor comonomer,
Allyl phenyl ether or propenylbenzene ethylether minor comonomer obtain terpolymer by free radical polymerization, and control its and heavy divide equally
Son amount is no more than 40000.
The present invention solves the above problems the scheme of use are as follows:
A kind of viscosity reduction type polycarboxylate water-reducer, is prepared by following raw material: glycol divinyl ether polyoxyethylene ether is big
Monomer, unsaturated carboxylic acid minor comonomer, allyl phenyl ether or propenylbenzene ethylether minor comonomer, oxidant, reducing agent, chain tra nsfer
Agent, sodium hydroxide.
Further, the component that raw material includes following mass fraction: the big list of glycol divinyl ether polyoxyethylene ether is prepared
400-450 parts of body, 30-70 parts of unsaturated carboxylic acid minor comonomer, 25-55 parts of allyl phenyl ether class minor comonomer, 3-5 parts of oxidant,
0.5-1.5 parts of reducing agent, 3-5 parts of chain-transferring agent, 15-35 parts of sodium hydroxide.
Further, the ethylene glycol polyoxyethylene ether molecular weight is 2000-4000.
Further, the unsaturated carboxylic acid minor comonomer is acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, itaconic acid
One or more of.
Further, affiliated oxidant is one or more of hydrogen peroxide, ammonium persulfate, potassium peroxydisulfate.
Further, the reducing agent is Victoria C, sodium bisulphite formaldehyde, sodium thiosulfate, sodium hydrogensulfite, ferrous sulfate
One or more of.
Further, the chain-transferring agent is one or more of mercaptopropionic acid, thioacetic acid, mercaprol.
Further, the polycarboxylate water-reducer weight average molecular weight of synthesis is no more than 40000.
A kind of high efficiency preparation method of viscosity reduction type polycarboxylate water-reducer, including the following steps:
Step 1) prepares A liquid and B liquid, and A liquid is unsaturated carboxylic acid aqueous solution, and B liquid is reducing agent and chain-transferring agent mixing water
Solution；
Reaction kettle, stirring and dissolving is added with mass ratio 1.1:1-1.5:1 in unsaturated polyether polymeric monomer and water by step 2)；
Reaction kettle is added in the A liquid of allyl phenyl ether or propenylbenzene ethylether and 10% by step 3)；
Step 4) controls polyether solutions temperature at 5 DEG C -25 DEG C, and oxidant is added to reaction kettle；
After oxidant 3-5min is added in step 5), while remaining 90%A liquid and B liquid is added dropwise, A drop adds 30-60min, B liquid
10min more than time for adding ratio A liquid；Entire reaction process water-bath temperature control, temperature are no more than 35 DEG C；
Step 6) drips curing 20min, and sodium hydroxide is added, and adjusts pH.
The present invention utilizes unique point of glycol divinyl ether polyoxyethylene ether monomer for the present invention beneficial having the technical effect that
Minor structure, joined allyl phenyl ether monomer or allyl benzene ethyl monomer reduces the hydrophily of polycarboxylic acids, and uses chain tra nsfer
Agent controls its molecular weight and has obtained a kind of polycarboxylic acids molecule for being substantially reduced concrete viscosity no more than 40000.In preparation process
Using the high activity of monomer, adjusts each material amounts and obtained a kind of method for rapidly and efficiently synthesizing the polycarboxylic acids, it is entire to synthesize
Process only needs 1-1.5h, and without heating, synthetic method is simple and efficient.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
Embodiment 1
30g acrylic acid and 60g water are mixed to get A liquid.0.6g Victoria C and 4g mercaptopropionic acid and 75.4g water are mixed to get B
Liquid.It is molten by being stirred in the glycol divinyl ether polyoxyethylene ether 450g and 300g water addition four-hole bottle reaction kettle of molecular weight 2400
The A liquid of 30g allyl phenyl ether and 9g is added in solution, by the control of polyether solutions temperature within 25 DEG C.4g is added into reaction kettle
The hydrogen peroxide that mass fraction is 30%.Remaining A liquid and B liquid is added dropwise simultaneously, A drop adds 30min, and B drop adds 40min, was added dropwise
Journey water-bath temperature control is no more than 35 DEG C.Post curing 20min is added dropwise, 15g sodium hydroxide is added later and adjusts PH, water is added and adjusts
Solid content to get arrive a kind of polycarboxylate water-reducer with good viscosity reducing effect of weight average molecular weight 35000 or so.
Embodiment 2
50g maleic anhydride and 40g water are mixed to get A liquid, by 1.0g sodium bisulphite formaldehyde, 3.0g thioacetic acid with
76g water is mixed to get B liquid.Four-hole bottle is added in glycol divinyl ether polyoxyethylene ether 430g and the 370g water of molecular weight 3000
The A liquid of 50g allyl benzene ethylether and 9g is added in stirring and dissolving in reaction kettle, by the control of polyether solutions temperature within 25 DEG C.
3g ammonium persulfate is added into reaction kettle.Remaining A liquid and B liquid is added dropwise simultaneously, A drop adds 60min, and B drop adds 70min, is added dropwise
Process water-bath temperature control is no more than 35 DEG C.Post curing 20min is added dropwise, 20g sodium hydroxide is added later and adjusts PH, water tune is added
Solid content is saved to get a kind of polycarboxylate water-reducer with good viscosity reducing effect of weight average molecular weight 32000 or so is arrived.
Embodiment 3
70g itaconic acid and 20g water are mixed to get A liquid, 0.8g sodium thiosulfate, 3g mercaptoethanol and 76.2g water are mixed
Conjunction obtains B liquid.Four-hole bottle reaction kettle is added in glycol divinyl ether polyoxyethylene ether 400g and the 350g water of molecular weight 3500
The A liquid of 35g allyl phenyl ether and 9g is added in middle stirring and dissolving, by the control of polyether solutions temperature within 25 DEG C.To reaction kettle
Middle addition 3g potassium peroxydisulfate.Remaining A liquid and B liquid are added dropwise simultaneously, A drop adds 60min, and B drop adds 70min, and process water-bath is added dropwise
Temperature control is no more than 35 DEG C.Post curing 20min is added dropwise, 25g sodium hydroxide is added later and adjusts PH, water adjusting is added and contains admittedly
It measures to get a kind of polycarboxylate water-reducer with good viscosity reducing effect of weight average molecular weight 35000 or so is arrived.
Comparative example 1
Polymeric monomer glycol divinyl ether polyoxyethylene ether in embodiment 1 is substituted for isobutene alcohol polyoxy second by comparative example 1
Alkene ether, other conditions are constant.
Comparative example 2
Minor comonomer allyl benzene ethylether in embodiment 1 is substituted for the hydroxy-ethyl acrylate of good hydrophilic property by comparative example 2,
Its condition is constant.
Comparative example 3
Mercaptoethanol dosage in embodiment 1 is reduced to 2.5g by comparative example 3, and other conditions are constant, the polycarboxylic acids synthesized
Weight average molecular weight is 44000.
Commercially available polycarboxylic-acid similar in the viscosity reduction type polycarboxylate water-reducer sample and water-reducing property that embodiment is synthesized
Water-reducing agent and the polycarboxylate water-reducer of comparative example synthesis carry out performance detection, according to GB8076-2008 " concrete admixture "
With JGJ281-2012 " high-strength concrete application technology regulation ", detect its concrete initial extension degree and through when divergence, and
Measurement lift from slump bucket reach the time T500 of 500mm up to divergence, hold slump bucket emptying time and through when fall
Mention slump bucket emptying time, concrete sand slurry viscosity.Concrete mix are as follows: P.O42.5 cement 448kg/m3, II grades of fine coal
Grey 56kg/m3, S75 miberal powder 56kg/m3, sand 685kg/m3, stone 1000kg/m3, water 165kg/m3, acquired results are as shown in table 1.
1 concrete test tables of data of table
Test result shows that the polycarboxylic acids that embodiment 1 synthesizes has better viscosity reduction to imitate than the polycarboxylic acids that comparative example synthesizes
Fruit, it was demonstrated that technical goal of the invention is achieved；The polycarboxylate water-reducer that embodiment 1 and embodiment 2 synthesize is more common than commercially available
Water-reducing agent has good viscosity reducing effect.
The present invention is not limited by examples detailed above, describes the principle of the present invention and operation side in examples detailed above and specification
Method, various changes and improvements may be made to the invention, these changes and improvements will be fallen into scope of the claimed invention.
Claims (9)
1. a kind of viscosity reduction type polycarboxylate water-reducer, which is characterized in that the polycarboxylate water-reducer is prepared by following raw material: ethylene
Ethyl glycol ether polyoxyethylene ether polymeric monomer, unsaturated carboxylic acid minor comonomer, allyl phenyl ether or the small list of propenylbenzene ethylether
Body, oxidant, reducing agent, chain-transferring agent, sodium hydroxide.
2. a kind of viscosity reduction type polycarboxylic acids as described in claim 1, which is characterized in that it includes following mass fraction that it, which prepares raw material,
Component: 400-450 parts of glycol divinyl ether polyoxyethylene ether polymeric monomer, 30-70 parts of unsaturated carboxylic acid minor comonomer, allyl
25-55 parts of phenyl ethers minor comonomer, 3-5 parts of oxidant, 0.5-1.5 parts of reducing agent, 3-5 parts of chain-transferring agent, sodium hydroxide 15-35
Part.
3. viscosity reduction type polycarboxylate water-reducer according to claim 1, it is characterised in that: the ethylene glycol polyoxy second
Alkene ether molecular weight is 2000-4000.
4. viscosity reduction type polycarboxylate water-reducer according to claim 1, it is characterised in that: the unsaturated carboxylic acid minor comonomer is
One or more of acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, itaconic acid.
5. viscosity reduction type polycarboxylate water-reducer according to claim 1, it is characterised in that: the oxidant be hydrogen peroxide,
One or more of ammonium persulfate, potassium peroxydisulfate.
6. viscosity reduction type polycarboxylate water-reducer according to claim 1, it is characterised in that: the reducing agent is Victoria C, sulphoxylic acid
One or more of hydrogen sodium formaldehyde, sodium thiosulfate, sodium hydrogensulfite, ferrous sulfate.
7. viscosity reduction type polycarboxylate water-reducer according to claim 1, it is characterised in that: the chain-transferring agent is sulfydryl third
One or more of acid, thioacetic acid, mercaprol.
8. viscosity reduction type polycarboxylate water-reducer according to claim 1, it is characterised in that: the polycarboxylate water-reducer weight of synthesis is equal
Molecular weight is no more than 40000.
9. the high efficiency preparation method of viscosity reduction type polycarboxylate water-reducer, characterized in that it comprises the following steps:
Step 1) prepares A liquid and B liquid, and A liquid is unsaturated carboxylic acid monomer aqueous solution, and B liquid is reducing agent and chain-transferring agent mixing water
Solution；
Reaction kettle, stirring and dissolving is added with mass ratio 1.1:1-1.5:1 in unsaturated polyether polymeric monomer and water by step 2)；
Reaction kettle is added in the A liquid of allyl phenyl ether or propenylbenzene ethylether and 10% by step 3)；
Step 4) controls polyether solutions temperature at 5 DEG C -25 DEG C, and oxidant is added to reaction kettle；
After oxidant 3-5min is added in step 5), while remaining 90%A liquid and B liquid is added dropwise, A drop adds 30-60min, and B drop adds
10min more than time ratio A liquid；Entire reaction process water-bath temperature control, temperature are no more than 35 DEG C,
Step 6) drips curing 20min, and sodium hydroxide is added, and adjusts pH.
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Cited By (2)
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| CN112390921A (en) * | 2020-11-05 | 2021-02-23 | 云南建投高分子材料有限公司 | Synthetic viscosity-reducing polycarboxylate superplasticizer and preparation method thereof |
| CN112920344A (en) * | 2021-02-09 | 2021-06-08 | 武汉理工大学 | Small molecule polymer for viscosity reduction of high-grade concrete and preparation method thereof |
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| CN112390921A (en) * | 2020-11-05 | 2021-02-23 | 云南建投高分子材料有限公司 | Synthetic viscosity-reducing polycarboxylate superplasticizer and preparation method thereof |
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