CN109503775A - A kind of synthetic method of the polycarboxylate water-reducer for refractory material - Google Patents
A kind of synthetic method of the polycarboxylate water-reducer for refractory material Download PDFInfo
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- CN109503775A CN109503775A CN201811463511.1A CN201811463511A CN109503775A CN 109503775 A CN109503775 A CN 109503775A CN 201811463511 A CN201811463511 A CN 201811463511A CN 109503775 A CN109503775 A CN 109503775A
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- Prior art keywords
- refractory material
- polycarboxylate water
- reducer
- synthetic method
- acrylate
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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
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/165—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
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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
- C04B2103/302—Water reducers
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses a kind of synthetic methods of polycarboxylate water-reducer for refractory material, including step are as follows: (1) reacts polyethylene glycol and methyl acrylate to obtain polyalkylene glycol acrylate macromonomer；(2) using polyalkylene glycol acrylate macromonomer made from acrylic acid, Sodium Allyl Sulfonate, hydroxy-ethyl acrylate, maleic anhydride, acrylamide and step (1) as raw material, it heats in aqueous solution and passes through initiator and cause copolymerization, isothermal reaction obtains the polycarboxylate water-reducer for refractory material.Through the above way, the present invention, which passes through, determines polycarboxylate water-reducer branch lengths, greatly improve its dispersibility, polycarboxylate water-reducer obtained can use in the high refractory material of ultra micro powder content, play an important role to the market of extension Unshaped Casting Refractories.
Description
Technical field
The present invention relates to the field of building materials, more particularly to a kind of synthesis of polycarboxylate water-reducer for refractory material
Method.
Background technique
Refractory material is used as the puzzle joint material of refractory product masonry, by material can be divided into clay matter, High-Alumina, it is siliceous and
Magnesite refractory etc..During producing refractory material, be added additive can greatly improve the masonry performance of refractory wass with
And the cohesive force of the refractoriness of adjustment material and raising material.Polycarboxylate water-reducer has ultra-dispersed performance, applied widely, energy
Meet the requirement of various cement base building materials.But Unshaped Casting Refractories are directed to, applicable performance is with regard to poor, especially
It is for the castable refractory system containing silicon ash, when silicon ash mass content is more than 5% or more, often dispersion performance is very poor even
There is no dispersion performance, using effect is bad.
Summary of the invention
The invention mainly solves the technical problem of providing a kind of synthesis sides of polycarboxylate water-reducer for refractory material
Method, polycarboxylate water-reducer using effect obtained are good.
In order to solve the above technical problems, one technical scheme adopted by the invention is that: it provides a kind of for refractory material
The synthetic method of polycarboxylate water-reducer, including step are as follows: (1) react polyethylene glycol and methyl acrylate to obtain the poly- second of acrylic acid
Glycol macromonomer；(2) with acrylic acid, Sodium Allyl Sulfonate, hydroxy-ethyl acrylate, maleic anhydride, acrylamide
It is raw material with polyalkylene glycol acrylate macromonomer made from step (1), heats and drawn by initiator in aqueous solution
Hair copolymerization, isothermal reaction obtain the polycarboxylate water-reducer for refractory material.
In a preferred embodiment of the present invention, polyethylene glycol described in step (1) is quantitative, the methyl acrylate
It is excessive.
In a preferred embodiment of the present invention, reaction described in step (1) is heating in the presence of a catalyst
It is warming up to 80 DEG C~90 DEG C, the reaction time 3 hours~6 hours.
In a preferred embodiment of the present invention, it is evaporated under reduced pressure after being reacted described in step (1), removes extra acrylic acid
Methyl esters and extra methanol.
In a preferred embodiment of the present invention, acrylic acid described in step (2), the Sodium Allyl Sulfonate, described third
Olefin(e) acid hydroxyl ethyl ester, the maleic anhydride, the acrylamide and the polyalkylene glycol acrylate macromonomer rub
You are than being 1:0-1.5:0.2-1:0.8-1:0.1-1:0.5-1.
In a preferred embodiment of the present invention, initiator described in step (2) is potassium peroxydisulfate.
In a preferred embodiment of the present invention, isothermal reaction described in step (2) is that constant temperature is anti-at 70 DEG C~95 DEG C
It answers 3~6 hours.
The beneficial effects of the present invention are: the synthetic method of the polycarboxylate water-reducer for refractory material of the invention, passes through
It determines polycarboxylate water-reducer branch lengths, greatly improves its dispersibility, polycarboxylate water-reducer obtained can contain in Ultramicro-powder
It measures and is used in high refractory material, the market of extension Unshaped Casting Refractories is played an important role.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiments of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's all other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment one:
A kind of synthetic method of polycarboxylate water-reducer for refractory material, including step are provided are as follows:
(1) first quantitative polyethylene glycol and excessive methyl acrylate are added in four-hole boiling flask, catalyst, heat temperature raising is added
It to 85 DEG C, the reaction time 5 hours, is then evaporated under reduced pressure, removes extra methyl acrylate and extra methanol, obtain acrylic acid
Polyethylene glycol macromonomer；
(2) with 0.15mol acrylic acid, 0.15mol Sodium Allyl Sulfonate, 0.01 mol hydroxy-ethyl acrylate, 0.15mol maleic
0.08mol polyalkylene glycol acrylate macromonomer made from dicarboxylic anhydride, 0.17mol acrylamide and step (1) is raw material,
It heats and is caused by potassium peroxydisulfate in aqueous solution and is copolymerized, isothermal reaction 4 hours, obtain for refractory material at 85 DEG C
Polycarboxylate water-reducer.
Embodiment two:
A kind of synthetic method of polycarboxylate water-reducer for refractory material, including step are provided are as follows:
(1) first quantitative polyethylene glycol and excessive methyl acrylate are added in four-hole boiling flask, catalyst, heat temperature raising is added
It to 80 DEG C, the reaction time 6 hours, is then evaporated under reduced pressure, removes extra methyl acrylate and extra methanol, obtain acrylic acid
Polyethylene glycol macromonomer；
(2) with 0.05mol acrylic acid, 0.10mol Sodium Allyl Sulfonate, 0.05 mol hydroxy-ethyl acrylate, 0.03mol maleic
0.04mol polyalkylene glycol acrylate macromonomer made from dicarboxylic anhydride, 0.09mol acrylamide and step (1) is raw material,
It heats and is caused by potassium peroxydisulfate in aqueous solution and is copolymerized, isothermal reaction 5 hours, obtain for refractory material at 80 DEG C
Polycarboxylate water-reducer.
Embodiment three:
A kind of synthetic method of polycarboxylate water-reducer for refractory material, including step are provided are as follows:
(1) first quantitative polyethylene glycol and excessive methyl acrylate are added in four-hole boiling flask, catalyst, heat temperature raising is added
It to 90 DEG C, the reaction time 3 hours, is then evaporated under reduced pressure, removes extra methyl acrylate and extra methanol, obtain acrylic acid
Polyethylene glycol macromonomer；
(2) with 0.20mol acrylic acid, 0.05mol Sodium Allyl Sulfonate, 0.03 mol hydroxy-ethyl acrylate, 0.18mol maleic
0.10mol polyalkylene glycol acrylate macromonomer made from dicarboxylic anhydride, 0.17mol acrylamide and step (1) is raw material,
It heats and is caused by potassium peroxydisulfate in aqueous solution and is copolymerized, isothermal reaction 3 hours, obtain for refractory material at 95 DEG C
Polycarboxylate water-reducer.
Example IV:
A kind of synthetic method of polycarboxylate water-reducer for refractory material, including step are provided are as follows:
(1) first quantitative polyethylene glycol and excessive methyl acrylate are added in four-hole boiling flask, catalyst, heat temperature raising is added
It to 85 DEG C, the reaction time 4 hours, is then evaporated under reduced pressure, removes extra methyl acrylate and extra methanol, obtain acrylic acid
Polyethylene glycol macromonomer；
(2) with 0.10mol acrylic acid, 0.04 mol hydroxy-ethyl acrylate, 0.12mol maleic anhydride, 0.02mol acryloyl
0.06mol polyalkylene glycol acrylate macromonomer made from amine and step (1) is raw material, heats and passes through in aqueous solution
Potassium peroxydisulfate causes copolymerization, and isothermal reaction 6 hours at 70 DEG C obtain the polycarboxylate water-reducer for refractory material.
In Unshaped Casting Refractories, needs to disperse or the object of diminishing is Ultramicro-powder.Ultramicro-powder includes ultra-fine oxygen
Change aluminium powder, SILICA FUME, bauxite, magnesia, carbon black etc., most of is all some inertia powders, is with polycarboxylate water-reducer effect
Using steric hindrance effect or intermolecular force, to obtain water-reducing effect.The present invention passes through to polycarboxylate water-reducer
MOLECULE DESIGN, and had an impact, be made in refractory material using performance of the various reaction monomers to co-poly carboxylic acid
Polycarboxylate water-reducer.The present invention is to determine acrylic acid, maleic anhydride, acrylamide, propylene according to molecular design theory
Sour hydroxyl ethyl ester, polyalkylene glycol acrylate ester, Sodium Allyl Sulfonate are as reaction monomers.Synthetic method of the invention utilizes acrylic acid
Polymeric monomer is prepared with methyl acrylate exchange reaction, then carries out the free-radical polymerized object system of reacting with polymeric monomer with each vinyl monomer
Standby co-poly carboxylic acid, determines optimum reaction condition by orthogonal test.
The branch that the present invention is grafted different length on main chain forms co-poly carboxylic acid, while passing through test branch copolymerization
The performance of object, it is determined that influence of the branch lengths difference to co-poly carboxylic acid performance, especially the length of branch is to polycarboxylic acids
The dispersibility of water-reducing agent has larger impact, and polycarboxylate water-reducer is enable to be used in castable refractory.
The above description is only an embodiment of the present invention, is not intended to limit the scope of the invention, all to utilize this hair
Equivalent structure or equivalent flow shift made by bright description is applied directly or indirectly in other relevant technology necks
Domain is included within the scope of the present invention.
Claims (7)
1. a kind of synthetic method of the polycarboxylate water-reducer for refractory material, which is characterized in that including step are as follows: (1) will gather
Ethylene glycol and methyl acrylate react to obtain polyalkylene glycol acrylate macromonomer；(2) with acrylic acid, allyl sulphonic acid
Polyalkylene glycol acrylate ester large molecule list made from sodium, hydroxy-ethyl acrylate, maleic anhydride, acrylamide and step (1)
Body is raw material, heats in aqueous solution and causes copolymerization by initiator, and isothermal reaction obtains the polycarboxylic acids for refractory material
Water-reducing agent.
2. the synthetic method of the polycarboxylate water-reducer according to claim 1 for refractory material, which is characterized in that step
(1) polyethylene glycol described in be it is quantitative, the methyl acrylate is excessive.
3. the synthetic method of the polycarboxylate water-reducer according to claim 1 for refractory material, which is characterized in that step
(1) reaction is in the presence of a catalyst, to heat to 80 DEG C~90 DEG C, the reaction time 3 hours~6 is small described in
When.
4. the synthetic method of the polycarboxylate water-reducer according to claim 1 for refractory material, which is characterized in that step
(1) it is evaporated under reduced pressure after being reacted described in, removes extra methyl acrylate and extra methanol.
5. the synthetic method of the polycarboxylate water-reducer according to claim 1 for refractory material, which is characterized in that step
(2) acrylic acid described in, the Sodium Allyl Sulfonate, the hydroxy-ethyl acrylate, the maleic anhydride, the acryloyl
Amine, the polyalkylene glycol acrylate macromonomer molar ratio be 1:0-1.5:0.2-1:0.8-1:0.1-1:0.5-1.
6. the synthetic method of the polycarboxylate water-reducer according to claim 1 for refractory material, which is characterized in that step
(2) initiator described in is potassium peroxydisulfate.
7. the synthetic method of the polycarboxylate water-reducer according to claim 1 for refractory material, which is characterized in that step
(2) isothermal reaction described in is isothermal reaction 3~6 hours at 70 DEG C~95 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811463511.1A CN109503775A (en) | 2018-12-03 | 2018-12-03 | A kind of synthetic method of the polycarboxylate water-reducer for refractory material |
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| CN201811463511.1A CN109503775A (en) | 2018-12-03 | 2018-12-03 | A kind of synthetic method of the polycarboxylate water-reducer for refractory material |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735411A (en) * | 2010-01-08 | 2010-06-16 | 北京工业大学 | Method for preparing sustained-release polycarboxylic water reducer |
| CN102815882A (en) * | 2012-08-03 | 2012-12-12 | 山西科腾环保科技有限公司 | High-performance water reducer of polycarboxylic acid, and preparation method thereof |
-
2018
- 2018-12-03 CN CN201811463511.1A patent/CN109503775A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735411A (en) * | 2010-01-08 | 2010-06-16 | 北京工业大学 | Method for preparing sustained-release polycarboxylic water reducer |
| CN102815882A (en) * | 2012-08-03 | 2012-12-12 | 山西科腾环保科技有限公司 | High-performance water reducer of polycarboxylic acid, and preparation method thereof |
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