CN107739424A - A kind of solid protects the polycarboxylate water-reducer and preparation method thereof that collapses - Google Patents
A kind of solid protects the polycarboxylate water-reducer and preparation method thereof that collapses Download PDFInfo
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- CN107739424A CN107739424A CN201711084074.8A CN201711084074A CN107739424A CN 107739424 A CN107739424 A CN 107739424A CN 201711084074 A CN201711084074 A CN 201711084074A CN 107739424 A CN107739424 A CN 107739424A
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- Prior art keywords
- collapses
- reducer
- water
- protects
- maleate
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Classifications
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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
-
- 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
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a kind of solid to protect the polycarboxylate water-reducer and preparation method thereof that collapses, and it is to be prepared by isobutene alcohol APEO or isoamyl alcohol polyoxyethylene ether, acrylic acid, β propyloic acrylic esters, maleate-type monomers and the methyl-propyl phosphonic acids of 2 acrylamide 2 by polymerisation that the solid, which protects the polycarboxylate water-reducer that collapses,.Solid disclosed by the invention protects the water reducer that collapses, and slump retaining is good, strong adaptability, and process safety is green.
Description
Technical field
The invention belongs to build additive technical field, it is related to a kind of solid based on cement-based material and protects the polycarboxylic acids that collapses
Water reducer and preparation method thereof.
Background technology
For polycarboxylate water-reducer because its volume is low, performance is good, green, has become building for domestic market dosage maximum
Additive is built, market accounting alreadys exceed 60%.
High-performance polycarboxylic acids water reducing agent on the market is mainly the product of 40% or 50% strength of fluid at present, easy to use,
But cost of transportation is virtually added, particularly in the transport supply of long range, the profit of logistics cost Eroded product.
In order to improve conevying efficiency, some enterprises employ spray drying to prepare powder polycarboxylic acids water reducing agent, but drying process with atomizing
High temperature is needed, increases energy consumption, and safety problem easily occurs in technique.Another solution route is prepared admittedly using polymerisation in bulk
Body polycarboxylate water-reducer, not only safety and environmental protection but also cost was reduced, but existing bulk technique prepares solid polycarboxylic acids diminishing
Agent largely uses oil-soluble initiator and oil-soluble chain-transferring agent, needs to use organic solution to dissolve in preparation process,
Need to remove solvent by later stage vacuumize process, both added cost or brought certain environmental pollution, this outer body gathers
The problems such as reaction temperature is too high, and stirring viscosity is big, local implode also be present in conjunction.
The content of the invention
A kind of technique that the purpose of the present invention is in view of the shortcomings of the prior art and provided is simple, green while have
The solid for having good function of slump protection protects the polycarboxylate water-reducer that collapses, and solvent is made using a small amount of water, reduces local in polymerization process
React the risk of too fast generation implode.
The object of the present invention is achieved like this：
A kind of solid protects the polycarboxylate water-reducer that collapses, and feature is that it includes the raw material of following percentage by weight：
Acrylic acid：1%-15%；
β-propyloic acrylic ester：1%-10%；
2- acrylamide -2- methyl-propyl phosphonic acids：0.05%-2%；
Maleate-type monomers：1%-15%；
Isobutene alcohol APEO or isoamyl alcohol polyoxyethylene ether：65%-80%；
Initiator：0.2%-1%；
Reducing agent：0.01%-0.5%；
Chain-transferring agent：0.2%-1%；
Water：1%-8%；
Piece alkali:0.5%-1.5%；
Wherein, maleate-type monomers are monomethyl maleate, ethyl maleate, the single condensed binaryglycol ester of maleic acid, horse
The one kind come in sour single macrogol ester, dimethyl maleate, diethyl maleate or diisobutyl maleate；
Described solid protects the polycarboxylate water-reducer that collapses, initiator be one kind in ammonium persulfate, potassium peroxydisulfate or sodium peroxydisulfate or
It is several；Reducing agent is the one or more in vitamin C, sodium formaldehyde sulfoxylate, sodium hydrogensulfite or ferrous sulfate；Chain-transferring agent is sulfydryl
Ethanol, TGA, the one or more of mercaptopropionic acid or sodium hypophosphite.
Described solid protects collapse polycarboxylate water-reducer, isobutene alcohol APEO or isoamyl alcohol polyoxyethylene ether molecule
Measure as 1200-5000.
Described solid protects the preparation method for the polycarboxylate water-reducer that collapses, and comprises the following steps：
（1）Isobutene alcohol APEO or isoamyl alcohol polyoxyethylene ether are placed in reactor, heating melting temperature control is 50
℃-70℃；
（2）Maleate-type monomers and initiator solution are disposably separately added on stirring, after stirring respectively
Be added dropwise the first mixed liquor for being made up of acrylic acid, β-propyloic acrylic ester, 2- acrylamides -2- methyl-propyls phosphonic acids and water and
The second mixed liquor being made up of chain-transferring agent, reducing agent and water, wherein 1.5-3 hours, the second mixed liquor is added dropwise in the first mixed liquor
Time for adding adds piece alkali and stirred after 2-3.5 hours, completion of dropwise addition follow-up continuous insulation reaction 1-2 hours；
（3）The polymerizate of liquid is entered into slicer cooling section by pipeline, crushing obtains solid and protects the polycarboxylic acids diminishing that collapses
Agent；
Described solid protects the preparation method method for the polycarboxylate water-reducer that collapses, and water consumption accounts for the 1%- of gross weight in initiator solution
5%。
Solid disclosed by the invention protects the polycarboxylate water-reducer that collapses, and it is raw material to employ β-propyloic acrylic ester monomer, i.e.,
There is diminishing function, water-reduction still can be played after ester linkage hydrolyzing, continuation is good, and maleate-type monomers collapse group for conventional guarantor
Point, 2- acrylamide -2- methyl-propyls phosphonic acids has good scattered and salt resistance effect, and makees solvent using a small amount of water, prepares
The solid gone out protects the water reducer performance not transfusion fluid product that collapses.
Embodiment
Below with reference to specific embodiment, invention is described further, but any restrictions are not caused to invention.
Embodiment 1
The isoamyl alcohol polyoxyethylene ether that 720g molecular weight is 2400 is put into reactor, heating melting 65 DEG C of stirrings of temperature control,
It is separately added into 64.8g ethyl maleates and 37.2g ammonium persulfate aqueous solutions（2.5g ammonium persulfates are dissolved in 34.7g water）, stir
Start that the mixed liquors of 48g first are added dropwise after mixing uniformly（By 10.8g acrylic acid, 21.6g β-propyloic acrylic ester, 12.4g 2- third
Acrylamide -2- methyl-propyls phosphonic acids and 3.2g water composition）With the mixed liquors of 21g second（By 0.3g vitamin Cs, 3.2g mercaptoethanols
It is dissolved in 17.5g water and obtains）, the first mixed liquor dropwise addition 180min, the second mixed liquor dropwise addition 210min, it is incubated after completion of dropwise addition anti-
Answer 120min to make polymerisation complete, then add 9g piece alkali, after cooling section crush solid is protected and collapsed polycarboxylate water-reducer
GWR-1。
Embodiment 2
The isoamyl alcohol polyoxyethylene ether that 720g molecular weight is 2400 is put into reactor, heating melting 65 DEG C of stirrings of temperature control,
It is separately added into 43.2g dimethyl maleates and 47g ammonium persulfate aqueous solutions（2.5g ammonium persulfates are dissolved in 44.5g water）, stirring
Start that the mixed liquors of 57.8g first are added dropwise after uniformly（By 15.1g acrylic acid, 21.6g β-propyloic acrylic ester, 12.4g 2- third
Acrylamide -2- methyl-propyls phosphonic acids and 8.7g water composition）With the mixed liquors of 21g second（By 0.3g vitamin Cs, 3.0g mercaptoethanols
It is dissolved in 17.7g water and obtains）, the first mixed liquor dropwise addition 180min, the second mixed liquor dropwise addition 210min, it is incubated after completion of dropwise addition anti-
Answer 120min to make polymerisation complete, then add 11g piece alkali, after cooling section crush solid is protected and collapsed polycarboxylate water-reducer
GWR-2。
Embodiment 3
The isobutene alcohol APEO that 720g molecular weight is 2400 is put into reactor, heating melting 55 DEG C of stirrings of temperature control,
It is separately added into 51.6g diethyl maleates and 41.4g ammonium persulfate aqueous solutions（2.7g ammonium persulfates are dissolved in 38.7g water）, stir
Start that the mixed liquors of 54g first are added dropwise after mixing uniformly（By 21.6g acrylic acid, 21.6g β-propyloic acrylic ester, 6.2g 2- propylene
Acid amides -2- methyl-propyls phosphonic acids and 4.6g water composition）With the mixed liquors of 21g second（By 0.4g sodium hydrogensulfites, 3.2g sulfydryl second
Alcohol, which is dissolved in 17.5g water, to be obtained）, the first mixed liquor dropwise addition 180min, the second mixed liquor dropwise addition 210min, it is incubated after completion of dropwise addition
Reaction 120min makes polymerisation complete, then adds 12g piece alkali, after cooling section crush solid is protected and collapsed polycarboxylate water-reducer
GWR-3。
Embodiment 4
The isobutene alcohol APEO that 696g molecular weight is 2400 is put into reactor, heating melting 60 DEG C of stirrings of temperature control,
It is separately added into the single condensed binaryglycol ester of 59.1g maleic acids and 31g ammonium persulfate aqueous solutions（3g ammonium persulfates are dissolved in 28g water
In）, start that the mixed liquors of 75g first are added dropwise after stirring（By 20.8g acrylic acid, 29.2g β-propyloic acrylic ester, 18g
2- acrylamides -2- methyl-propyls phosphonic acids and 7g water composition）With the mixed liquors of 21g second（By 0.4g vitamin cs, 3.5g sulfydryl second
Alcohol, which is dissolved in 17.1g water, to be obtained）, the first mixed liquor dropwise addition 180min, the second mixed liquor dropwise addition 210min, it is incubated after completion of dropwise addition
Reaction 120min makes polymerisation complete, then adds 13g piece alkali, after cooling section crush solid is protected and collapsed polycarboxylate water-reducer
GWR-4。
Application examples
According to GB8076-2008《Concrete admixture》The test request of high-performance water reducing agent in standard, it will be synthesized in embodiment
Sample and commercially available certain collapse protective poly-carboxylic acid water reducing agent（Code name PCE）Performance comparison has been carried out, has used cement as south
P.O42.5, river sand modulus of fineness 2.7, cobble-stone diameter are 5~25mm continuous grading rubbles.Experimental result is shown in Table 1.
The different embodiment concrete experiments results of table 1
4 collapse protective poly-carboxylic acid water reducing agents guarantor's plasticity that embodiment is can be seen that from the concrete experiments result of table 1 can be no worse than
Commercially available collapse protective poly-carboxylic acid water reducing agent, there is preferable slump holding capacity, function admirable.
Claims (5)
1. a kind of solid protects the polycarboxylate water-reducer that collapses, it is characterised in that it includes the raw material of following percentage by weight：
Acrylic acid：1%-15%；
β-propyloic acrylic ester：1%-10%；
2- acrylamide -2- methyl-propyl phosphonic acids：0.05%-2%；
Maleate-type monomers：1%-15%；
Isobutene alcohol APEO or isoamyl alcohol polyoxyethylene ether：65%-80%；
Initiator：0.2%-1%；
Reducing agent：0.01%-0.5%；
Chain-transferring agent：0.2%-1%；
Water：1%-8%；
Piece alkali:0.5%-1.5%；
Wherein, maleate-type monomers are monomethyl maleate, ethyl maleate, the single condensed binaryglycol ester of maleic acid, horse
The one kind come in sour single macrogol ester, dimethyl maleate, diethyl maleate or diisobutyl maleate.
2. solid according to claim 1 protects the polycarboxylate water-reducer that collapses, it is characterised in that initiator is ammonium persulfate, over cure
One or more in sour potassium or sodium peroxydisulfate；Reducing agent is in vitamin C, sodium formaldehyde sulfoxylate, sodium hydrogensulfite or ferrous sulfate
It is one or more of；Chain-transferring agent is the one or more of mercaptoethanol, TGA, mercaptopropionic acid or sodium hypophosphite.
3. solid according to claim 1 protects the polycarboxylate water-reducer that collapses, it is characterised in that isobutene alcohol APEO or
Isoamyl alcohol polyoxyethylene ether molecular weight is 1200-5000.
4. a kind of solid protects the preparation method for the polycarboxylate water-reducer that collapses, it is characterised in that comprises the following steps：
（1）Isobutene alcohol APEO or isoamyl alcohol polyoxyethylene ether are placed in reactor, heating melting temperature control is 50
℃-70℃；
（2）Maleate-type monomers and initiator solution are disposably separately added on stirring, after stirring respectively
Be added dropwise the first mixed liquor for being made up of acrylic acid, β-propyloic acrylic ester, 2- acrylamides -2- methyl-propyls phosphonic acids and water and
The second mixed liquor being made up of chain-transferring agent, reducing agent and water, wherein 1.5-3 hours, the second mixed liquor is added dropwise in the first mixed liquor
Time for adding adds piece alkali and stirred after 2-3.5 hours, completion of dropwise addition follow-up continuous insulation reaction 1-2 hours；
（3）The polymerizate of liquid is entered into slicer cooling section by pipeline, crushing obtains solid and protects the polycarboxylic acids diminishing that collapses
Agent.
5. solid according to claim 4 protects the preparation method for the polycarboxylate water-reducer that collapses, it is characterised in that described initiation
Water consumption accounts for the 1%-5% of gross weight in the agent aqueous solution.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711084074.8A CN107739424A (en) | 2017-11-07 | 2017-11-07 | A kind of solid protects the polycarboxylate water-reducer and preparation method thereof that collapses |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711084074.8A CN107739424A (en) | 2017-11-07 | 2017-11-07 | A kind of solid protects the polycarboxylate water-reducer and preparation method thereof that collapses |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109705280A (en) * | 2018-12-24 | 2019-05-03 | 广东科隆智谷新材料股份有限公司 | A kind of preparation method of solid polycarboxylic acid water reducing agent |
| CN111154047A (en) * | 2019-12-31 | 2020-05-15 | 陕西友邦新材料科技有限公司 | Polycarboxylate superplasticizer for lightweight concrete and preparation method thereof |
| CN113416283A (en) * | 2021-08-12 | 2021-09-21 | 福建钟山化工有限公司 | High-dispersibility solid polycarboxylate superplasticizer, and preparation method and application method thereof |
| WO2022095232A1 (en) * | 2020-11-03 | 2022-05-12 | 科之杰新材料集团有限公司 | Ether-type anti-corrosive polycarboxylic acid water reducer and preparation method therefor |
| CN116162211A (en) * | 2022-11-14 | 2023-05-26 | 南京瑞固聚合物有限公司 | beta-CEA/AA/TPEG ternary polymerization high water-reducing polycarboxylate superplasticizer and synthesis process thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109705280A (en) * | 2018-12-24 | 2019-05-03 | 广东科隆智谷新材料股份有限公司 | A kind of preparation method of solid polycarboxylic acid water reducing agent |
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| WO2022095232A1 (en) * | 2020-11-03 | 2022-05-12 | 科之杰新材料集团有限公司 | Ether-type anti-corrosive polycarboxylic acid water reducer and preparation method therefor |
| CN113416283A (en) * | 2021-08-12 | 2021-09-21 | 福建钟山化工有限公司 | High-dispersibility solid polycarboxylate superplasticizer, and preparation method and application method thereof |
| CN116162211A (en) * | 2022-11-14 | 2023-05-26 | 南京瑞固聚合物有限公司 | beta-CEA/AA/TPEG ternary polymerization high water-reducing polycarboxylate superplasticizer and synthesis process thereof |
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