CN107759748A - A kind of solid high early strength poly-carboxylic water reducer and preparation method thereof - Google Patents
A kind of solid high early strength poly-carboxylic water reducer and preparation method thereof Download PDFInfo
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- CN107759748A CN107759748A CN201711084353.4A CN201711084353A CN107759748A CN 107759748 A CN107759748 A CN 107759748A CN 201711084353 A CN201711084353 A CN 201711084353A CN 107759748 A CN107759748 A CN 107759748A
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- early strength
- water reducer
- solid high
- high early
- unsaturated
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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
- C04B24/16—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
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses a kind of solid high early strength poly-carboxylic water reducer and preparation method thereof, the solid high early strength poly-carboxylic water reducer is to be prepared by unsaturated APEO, acrylic acid, esters of unsaturated carboxylic acids and unsaturated sulfonic acid ester by polymerisation.Solid high early strength poly-carboxylic water reducer disclosed by the invention, early strength is high, and workability is good, function admirable.
Description
Technical field
The invention belongs to build additive technical field, it is related to a kind of solid high early strength poly-carboxylic based on cement-based material
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
Build additive, but the product of mainly 40% or 50% strength of fluid.Although easy to use, cost of transportation is added, particularly
In the transport supply of long range, the profit of logistics cost Eroded product.In addition, the popularization in dry powder and mortar market improves
The market demand of solid polycarboxylic acid water reducing agent, some enterprises prepare powder polycarboxylic acids water reducing agent using spray drying, but spray
Drying process needs high temperature dehydration, increases energy consumption, cost is higher, and for the ease of adding interleaving agent into powder, virtually reduces
Effective content.Polycarboxylate water-reducer can be prepared by polymerisation in bulk in itself, as CN106749966A discloses one
The preparation method of kind solid polycarboxylic acids early strength agent, but organic solvent is employed to dissolve initiator and chain-transferring agent, it is necessary to pass through
Later stage vacuumize process removes solvent, has both added cost or has brought certain problem of environmental pollution.
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
There is the solid high early strength poly-carboxylic water reducer of good early epistasis energy, the object of the present invention is achieved like this：
A kind of solid high early strength poly-carboxylic water reducer, feature are them by unsaturated APEO, acrylic acid, 3- allyloxys -2-
Hydroxyl -1- propane sulfonic acids sodium and esters of unsaturated carboxylic acids pass through at 50 DEG C -80 DEG C under the conditions of initiator and chain-transferring agent are existing
Polymerisation in bulk prepares, unsaturated APEO：Acrylic acid：3- allyloxy -2- hydroxyl -1- propane sulfonic acid sodium：Insatiable hunger
Monomer mole ratio with carboxylate is 1:2~5:0.1~1.2:0.1~2；Wherein, unsaturated APEO is methallyl
One or more in alcohol APEO, isobutene alcohol APEO or isoamyl alcohol polyoxyethylene ether；Unsaturated carboxylic acid
Ester is one kind in hydroxy-ethyl acrylate, hydroxypropyl acrylate or β-propyloic acrylic ester.
The initiator is ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, azodiisobutyronitrile, ABVN, azo
Two isobutyl dimethyl phthalates, azo-bis-isobutyl cyanide base formamide, the isobutyl imidazoline hydrochloride of azo two, dibenzoyl peroxide, mistake
The one or more in t-butyl perbenzoate or di-isopropyl peroxydicarbonate are aoxidized, initiator amount is monomer gross mass
0.2%-1.5%。
The chain-transferring agent is mercaptoethanol, mercaprol, TGA, mercaptopropionic acid, lauryl mercaptan or mercaptopropionic acid
The one or more of different monooctyl ester, chain-transferring agent dosage are the 0.3%-2% of monomer gross mass.
The unsaturated APEO molecular weight is 4000-5000.
A kind of preparation method of solid high early strength poly-carboxylic water reducer, this method step are as follows：
Unsaturated APEO is placed in reactor, 3- allyloxy -2- hydroxyls -1- is sequentially added into after heating melting
Propane sulfonic acid sodium and initiator, then beginning to dropwise addition acrylic acid, esters of unsaturated carboxylic acids and chain-transferring agent mixed liquor, time for adding is
1.5-4 hours, after completion of dropwise addition in the molten state continue be incubated 1.5-3 hours make bulk polymerization complete, by liquid
Polymerizate enters slicer cooling section by pipeline, and crushing obtains solid high early strength poly-carboxylic water reducer；
Solid high early strength poly-carboxylic water reducer disclosed by the invention, does not use organic solvent, and preparation process is simple, product solid content
100%, the solid early strength water-reducing agent performance prepared not transfusion fluid product.
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 1200g molecular weight is 4000 is put into reactor, added respectively after 70 degree of heating meltings
Enter 13g 3- allyloxys -2- hydroxyls -1- propane sulfonic acids sodium and 7g ammonium persulfates, start to be added dropwise after stirring by 86.4g third
The mixed liquor of olefin(e) acid, 43.2g β-propyloic acrylic ester and 12g isooctyl mercaptopropionates composition, is added dropwise 150min, completion of dropwise addition
Insulation reaction 120min makes polymerisation complete afterwards, then cools down section and crushes to obtain solid high early strength poly-carboxylic water reducer RPC-1.
Embodiment 2
The isoamyl alcohol polyoxyethylene ether that 1200g molecular weight is 4000 is put into reactor, added respectively after 75 degree of heating meltings
Enter 26g 3- allyloxys -2- hydroxyls -1- propane sulfonic acids sodium and 7g ammonium persulfates, start to be added dropwise after stirring by 97.2g third
The mixed liquor of olefin(e) acid, 34.8g hydroxy-ethyl acrylates and 11g isooctyl mercaptopropionates composition, is added dropwise 120min, is protected after completion of dropwise addition
Temperature reaction 120min makes polymerisation complete, then cools down section and crushes to obtain solid high early strength poly-carboxylic water reducer RPC-2.
Embodiment 3
The methyl enol APEO that 1200g molecular weight is 4000 is put into reactor, added respectively after 80 degree of heating meltings
Enter 6.5g 3- allyloxys -2- hydroxyls -1- propane sulfonic acids sodium and 9g azodiisobutyronitriles, start after stirring be added dropwise by
The mixed liquor of 108g acrylic acid, 19.5g hydroxypropyl acrylates and 12g lauryl mercaptans composition, is added dropwise 120min, is protected after completion of dropwise addition
Temperature reaction 120min makes polymerisation complete, then cools down section and crushes to obtain solid high early strength poly-carboxylic water reducer RPC-3.
Embodiment 4
The methyl enol APEO that 1200g molecular weight is 4000 is put into reactor, added respectively after 70 degree of heating meltings
Enter 32.5g 3- allyloxy -2- hydroxyl -1- propane sulfonic acids sodium, 5g ammonium persulfates and 3g azodiisobutyronitriles, after stirring
Start that the mixed liquor being made up of 108g acrylic acid, 17.4g hydroxy-ethyl acrylates and 10g isooctyl mercaptopropionates is added dropwise, be added dropwise
180min, insulation reaction 120min makes polymerisation complete after completion of dropwise addition, then cools down section and crushes to obtain the early strong poly- carboxylic of solid
Sour water reducer RPC-4.
Application examples
By the sample and comparative sample in embodiment 1-4（Common polycarboxylate water-reducer, the auspicious commercially available VIVID-500 in Shanghai three gather
Carboxylic acid water reducer）According to GB8076-2008《Concrete admixture》Slump and each age strength are tested in standard, using cement
For southern P.O42.5, river sand modulus of fineness 2.7, cobble-stone diameter is 5~25mm continuous grading rubbles.Match ratio is：Cement
360kg/m3, sand 837kg/m3, stone 10.01kg/m3, experimental result is shown in Table 1.
The different embodiment concrete experiments results of table 1
| Sample | Initial slump degree mm | 1d compression strength Mpa | 3d compression strength Mpa | 7d compression strength Mpa | 28d compression strength Mpa |
| RPC-1 | 180 | 17.8 | 24.1 | 32.3 | 41.5 |
| RPC-2 | 180 | 18.4 | 26.3 | 35.7 | 44.2 |
| RPC-3 | 180 | 18.9 | 27.4 | 39.4 | 48.4 |
| RPC-4 | 180 | 18.1 | 25.7 | 34.9 | 45.3 |
| Control sample | 180 | 12.8 | 18.6 | 29.2 | 41.6 |
Experimental result illustrates the early strong intensity of 4 Early-strength polycarboxylate superplasticizers of the present embodiment than commercially available plain edition polycarboxylic acids diminishing
Agent is high, function admirable.
Claims (5)
1. a kind of solid high early strength poly-carboxylic water reducer, it is characterised in that it is by unsaturated APEO, acrylic acid, 3- allyl oxygen
Base -2- hydroxyls -1- propane sulfonic acids sodium and esters of unsaturated carboxylic acids are at 50 DEG C -80 DEG C, condition existing for initiator and chain-transferring agent
Prepared by polymerisation in bulk down, unsaturated APEO:Acrylic acid:3- allyloxy -2- hydroxyl -1- propane sulfonic acids
Sodium:The monomer mole ratio of esters of unsaturated carboxylic acids is 1:2~5:0.1~1.2:0.1~2；Wherein, unsaturated APEO is first
One or more in base allyl alcohol polyethenoxy ether, isobutene alcohol APEO or isoamyl alcohol polyoxyethylene ether；Insatiable hunger
It is one kind in hydroxy-ethyl acrylate, hydroxypropyl acrylate or β-propyloic acrylic ester with carboxylate.
2. solid high early strength poly-carboxylic water reducer according to claim 1, it is characterised in that initiator is ammonium persulfate, over cure
Sour potassium, sodium peroxydisulfate, azodiisobutyronitrile, ABVN, azo-bis-iso-dimethyl, azo-bis-isobutyl cyanide base formyl
Amine, the isobutyl imidazoline hydrochloride of azo two, dibenzoyl peroxide, peroxidized t-butyl perbenzoate or dicetyl peroxydicarbonate two are different
One or more in propyl ester, initiator amount are the 0.2%-1.5% of monomer gross mass.
3. solid high early strength poly-carboxylic water reducer according to claim 1, it is characterised in that chain-transferring agent is mercaptoethanol, mercapto
Base propyl alcohol, TGA, mercaptopropionic acid, the one or more of lauryl mercaptan or isooctyl mercaptopropionate, chain-transferring agent dosage are
The 0.3%-2% of monomer gross mass.
4. solid high early strength poly-carboxylic water reducer according to claim 1, it is characterised in that unsaturated APEO molecule
Measure as 4000-5000.
5. a kind of preparation method of solid high early strength poly-carboxylic water reducer, it is characterised in that step is as follows：
Unsaturated APEO is placed in reactor, 3- allyloxy -2- hydroxyls -1- is sequentially added into after heating melting
Propane sulfonic acid sodium and initiator, then beginning to dropwise addition acrylic acid, esters of unsaturated carboxylic acids and chain-transferring agent mixed liquor, time for adding is
1.5-4 hours, after completion of dropwise addition in the molten state continue be incubated 1.5-3 hours make bulk polymerization complete, by liquid
Polymerizate enters slicer cooling section by pipeline, and crushing obtains solid high early strength poly-carboxylic water reducer.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711084353.4A CN107759748A (en) | 2017-11-07 | 2017-11-07 | A kind of solid high early strength poly-carboxylic water reducer and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109437644A (en) * | 2018-12-03 | 2019-03-08 | 苏州市兴邦化学建材有限公司 | A kind of synthetic method improving polycarboxylate water-reducer cement adaptability |
| 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 |
| CN109721690A (en) * | 2019-01-25 | 2019-05-07 | 中建西部建设西南有限公司 | A kind of viscosity reduction type polycarboxylic acids high efficiency solid water-reducing agent and its preparation and application |
| CN109836541A (en) * | 2019-02-01 | 2019-06-04 | 抚顺东科精细化工有限公司 | A method of preparing pure solid polycarboxylic acid slump retaining agent |
| CN111808240A (en) * | 2020-07-13 | 2020-10-23 | 山东华迪建筑科技有限公司 | Plastic-retaining polycarboxylic acid water reducing agent and preparation 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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| CN102993387A (en) * | 2012-09-13 | 2013-03-27 | 北京工业大学 | Method for directly synthesizing pure solid high-performance polycarboxylate water-reducer in one step |
| CN105199054A (en) * | 2015-09-17 | 2015-12-30 | 河北三楷深发科技股份有限公司 | Synthetic technology of slump-retaining polycarboxylic type water reducer |
| CN106866894A (en) * | 2017-03-14 | 2017-06-20 | 重庆石博士新材料有限公司 | A kind of solid polycarboxylic acid water reducing agent and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102993387A (en) * | 2012-09-13 | 2013-03-27 | 北京工业大学 | Method for directly synthesizing pure solid high-performance polycarboxylate water-reducer in one step |
| CN105199054A (en) * | 2015-09-17 | 2015-12-30 | 河北三楷深发科技股份有限公司 | Synthetic technology of slump-retaining polycarboxylic type water reducer |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109437644A (en) * | 2018-12-03 | 2019-03-08 | 苏州市兴邦化学建材有限公司 | A kind of synthetic method improving polycarboxylate water-reducer cement adaptability |
| 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 |
| CN109721690A (en) * | 2019-01-25 | 2019-05-07 | 中建西部建设西南有限公司 | A kind of viscosity reduction type polycarboxylic acids high efficiency solid water-reducing agent and its preparation and application |
| CN109721690B (en) * | 2019-01-25 | 2021-06-18 | 中建西部建设西南有限公司 | Viscosity-reduction type polycarboxylic acid high-efficiency solid water reducer and preparation and application thereof |
| CN109836541A (en) * | 2019-02-01 | 2019-06-04 | 抚顺东科精细化工有限公司 | A method of preparing pure solid polycarboxylic acid slump retaining agent |
| CN111808240A (en) * | 2020-07-13 | 2020-10-23 | 山东华迪建筑科技有限公司 | Plastic-retaining polycarboxylic acid water reducing agent and preparation 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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Application publication date: 20180306 |