CN107793538A - A kind of preparation method and application of polycarboxylate water-reducer - Google Patents
A kind of preparation method and application of polycarboxylate water-reducer Download PDFInfo
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- CN107793538A CN107793538A CN201710999062.1A CN201710999062A CN107793538A CN 107793538 A CN107793538 A CN 107793538A CN 201710999062 A CN201710999062 A CN 201710999062A CN 107793538 A CN107793538 A CN 107793538A
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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
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2605—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing polyether side chains
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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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
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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
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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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Structural Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a kind of preparation method of polycarboxylate water-reducer, it is characterised in that this method has following processing step：Using polymerizable chain transfer agents：0.5% 1%, citric acid：1% 2.5%, acrylic acid：21% 23%, deionized water：74% 76%, stirring and dissolving, it is well mixed, obtains solution A；Using high price manganese salt or manganese dioxide：0.2% 1%, unsaturated polyether：47% 51%, deionized water：48% 52%, stirring dissolves unsaturated polyether, is well mixed, obtains B solution；40 65 DEG C, it is added dropwise solution A under constant temperature, stirring condition, rate of addition is 5 20 drops/min, and the volume ratio of solution A and B solution is 4:15, the h of isothermal reaction 3 3.5, reaction finish again after being added dropwise, and after being cooled to room temperature, adjust pH to 67 with liquid caustic soda, both obtain polycarboxylate water-reducer.The water reducer water-reducing rate is high, slump retaining is good, steady quality, and using effect is good, and low to mud sensitivity.
Description
Technical field
The invention belongs to technical field of concrete additives, more particularly to a kind of preparation method of polycarboxylate water-reducer.
Background technology
Polycarboxylate water-reducer is a kind of by the unsaturated monomer containing carboxyl and the unsaturated monomer containing other functional groups
The polymer formed by Raolical polymerizable copolymerization, is a kind of random copolymer, its molecular structure is in comb shape, has diminishing
Rate compared with it is high, slump rheological parameters' change with time is small, with different types of well adapting to property of cement the features such as.
Water reducer is a kind of important concrete admixture, is one of staple product of building material pillar industry.Efficiently
Water reducer not only substantially increases the mechanical property of high-strength concrete, and provides easy-to-use construction technology.Rely on
The development and application of high efficiency water reducing agent, various concrete materials and and modernization construction technology developed rapidly.
Although the research and production application of domestic high performance water reducing agent of polyocarboxy acid are obtained for very big development, current city
High-efficiency water-reducing agent of poly-carboxylic acid synthesis is mainly H on field2O2- Vc is used as initiation system.H2O2Hydrogen peroxide is a kind of oxidation of liquid
Agent, transport and storage industrially is all relatively difficult, among the process of transport, fills the equipment temperature of hydrogen peroxide no more than
40 degrees Celsius, and it can not can not be heated by hydrogen peroxide under the sun during storage.Vc is held high due to price
It is expensive so that the cost increase of practical application.
Patent CN103396031A（Publication date 2013.11.20）Report a kind of high-efficiency water-reducing agent of poly-carboxylic acid and its preparation
Method.This method is with H2O2- Vc prepares water reducer as initiation system by Raolical polymerizable.Although invention reaction temperature
Spend low but used H2O2It is a kind of oxidant of liquid, transport and storage industrially is all relatively difficult, and Vc prices are held high
It is expensive.
The initiation system of the high-efficiency water-reducing agent of poly-carboxylic acid of report synthesis at present, the present invention are triggered using high price manganese salt-citric acid
System, reaction activity is low, and transports and store conveniently, and cost is low, and product water-reducing rate height, the slump retaining of synthesis are good, can be obvious
Improve concrete flowability, and it is low to mud sensitivity.It can solve the problem that high-efficiency water-reducing agent of poly-carboxylic acid to coagulation to a certain extent
In soil soil it is more sensitive and because soil exists and the problem of hydraulic performance decline.
The content of the invention
An object of the present invention is to provide a kind of preparation method of polycarboxylate water-reducer, and the polycarboxylate water-reducer of acquisition exists
Application in concrete.
The purpose of the present invention is achieved through the following technical solutions.
A kind of preparation method of polycarboxylate water-reducer, it is characterised in that this method has following processing step：
（1）Solution A configures：In the reactor, added by mass percentage concentration, polymerizable chain transfer agents：0.5%-1%, citric acid：
1%-2.5%, acrylic acid：21%-23%, deionized water：74%-76%, each group point are combined into absolutely, stirring and dissolving, and mixing is equal
It is even, obtain solution A；
（2）B solution configures：In the reactor, add by mass percentage, high price manganese salt or manganese dioxide：0.2%-1%, insatiable hunger
And polyethers：47%-51%, deionized water：48%-52%, being combined into absolutely for each group point, is uniformly mixed, obtains B solution；
（3）B solution is added in the reactor, and temperature rises to 40-65 DEG C, and solution A is added dropwise under constant temperature, stirring condition, and speed is added dropwise
Spend for 5-20 drops/min, the volume ratio of solution A and B solution is 4:15, isothermal reaction 3-3.5 h again after being added dropwise, react
Finish, after being cooled to room temperature, adjust pH to 6-7 with liquid caustic soda, both obtain polycarboxylate water-reducer.
Step（1）The chain-transferring agent is TGA or mercaptopropionic acid；
Step（2）The unsaturated polyether is allyl polyethenoxy base ether（HPEG）Or prenol polyoxyethylene ether
（TPEG）, molecular weight 2400；
Citric acid described above is 1 with the mass ratio of high price manganese salt or manganese dioxide：0.5-1.
Beneficial effects of the present invention：
（1）The present invention prepares the high-efficiency water-reducing agent of poly-carboxylic acid with comb shaped structure using redox radical polymerization technique.From
Molecular Design sets out, and promotes citric acid to produce free radical by redox reaction, then triggers unsaturated monomer to gather again
Close, chain terminal group carries carboxyl, and molecular structure and molecular weight are clear and definite, controllable, and it is efficient can fundamentally to disclose polycarboxylic acids
The molecular structure of water reducer and the relation of its performance.
（2）High with water-reducing rate, slump retaining is good, it is low to mud sensitivity the features such as.
（3）Artificial synthesized citric acid is prepared by fermentation with granulated sugar, molasses, starch, grape etc. containing sugar substance, to obtain
Mode is simple and cost is cheap.
Embodiment
That specific implementation method of the present invention is more stated in detail below, it is therefore intended that illustrate the present invention design and
Feature, it is not intended to limit the scope of the present invention.Any equivalent change or modification in accordance with the spirit of the invention,
It should all be included within the scope of the present invention.
Embodiment 1
（1）Solution A configures：In the reactor, 0.19 g TGAs, 0.48 g citric acids, 4.2 g acrylic acid, 15 g are added
Deionized water, stirring and dissolving, it is well mixed, obtains solution A；
（2）B solution configures：In the reactor, 0.2 g manganese dioxide, 30 g TPEG2400,30 g deionized waters, stirring are added
Dissolve TPEG2400, solution is well mixed, and obtains B solution；
（3）B solution is added in the reactor, and temperature rises to 40-65 DEG C, and solution A is added dropwise under constant temperature, stirring condition, and speed is added dropwise
Spend for 6 drops/min, the h of isothermal reaction 2.5, reaction are finished again after being added dropwise, and after being cooled to room temperature, pH to 6- is adjusted with liquid caustic soda
7, both obtain polycarboxylate water-reducer.
Embodiment 2
（1）Solution A configures：In the reactor, add 0.19 g TGAs, 0.35 g citric acids, 4.2g olefin(e) acids, 15 g go from
Sub- water, stirring and dissolving, it is well mixed, obtains solution A；
（2）B solution configures：In the reactor, 0.25 g manganese dioxide is added, 30 g TPEG2400,30 g deionized waters, is stirred
Mixing dissolves TPEG2400, and solution is well mixed, and obtains B solution；
（3）B solution is added in the reactor, and temperature rises to 40-65 DEG C, and solution A is added dropwise under constant temperature, stirring condition, and speed is added dropwise
Spend for 6 drops/min, the h of isothermal reaction 2.5, reaction are finished again after being added dropwise, and after being cooled to room temperature, pH to 6- is adjusted with liquid caustic soda
7, both obtain polycarboxylate water-reducer.
Comparative example 1
75.053 g TPEG2400 are added into reactor, 85.617 g water, opens and stirs and be warming up to 60 DEG C, treat polymeric monomer
After being completely dissolved, the hydrogenperoxide steam generators of 1.893 g 30% are added, while 10.146 g concentration are added dropwise into reactor as 80% the third
The solution of the olefin(e) acid aqueous solution and 0.130 g Vc and 0.289 g TGAs and 16.467 g water composition；3 h are added dropwise in the former,
3.5 h are added dropwise in the latter, and band continues to react 1 h after being added dropwise to complete, adjusts pH to 6-7 at the end of question response, it is efficient that polycarboxylic acids is made
Water reducer.Labeled as PC3.
Comparative example 2
Commercially available high-efficiency water-reducing agent of poly-carboxylic acid.Labeled as PC4.
Performance test
1. flowing degree of net paste of cement
Measurement results of the high-efficiency water-reducing agent of poly-carboxylic acid PC1-PC3 of table 1 to flowing degree of net paste of cement
From table 1 it follows that the high-efficiency water-reducing agent of poly-carboxylic acid of the inventive method synthesis and tradition side in the case of same acids ether ratio
The comb shape high-efficiency water-reducing agent of poly-carboxylic acid and commercially available comb shape high-efficiency water-reducing agent of poly-carboxylic acid of method synthesis compare, and show more excellent
Different dispersibility and function of slump protection,
2. water reducer hinders mud ability
Identical fluidity is issued to and there is situation in clay in experiment measure（260±5 mm）When water reducer volume, and with not
Compared when mixing clay.Water reducer and existing commercially available traditional comb shape polycarboxylic-acid from the traditional comb shaped structure newly synthesized
Water reducer（Comparative example）It is as a comparison sample.
Non-clay test：300 g cement, 87 g water, adjusting the dosage of water reducer makes paste flowing degree be reached in 10 min
To 260 ± 5 mm；1% clay is tested：297 g cement, 87 g water, 3 g clays, adjusting the dosage of water reducer makes paste flowing degree
Reach 260 ± 5 mm in 10 min.
Result of the test is shown in Table 2.
The water reducer of table 2 hinders mud ability Contrast on effect table
From Table 2, it can be seen that the high-efficiency water-reducing agent of poly-carboxylic acid of the inventive method synthesis is compared with the poly- carboxylic that traditional preparation methods obtain
Sour high efficiency water reducing agent and commercially available comb shape high-efficiency water-reducing agent of poly-carboxylic acid show excellent anti-mud effect.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not limited by embodiment
System, it is other it is any without departing from the present invention Spirit Essences with made under principle change, modification, combine, replacement, simplification should be
Equivalence replacement mode, is included within protection scope of the present invention.
Claims (5)
1. a kind of preparation method of polycarboxylate water-reducer, it is characterised in that this method has following processing step：
(1) solution A configures：In the reactor, added by mass percentage concentration, polymerizable chain transfer agents：0.5%-1%, citric acid：
1%-2.5%, acrylic acid：21%-23%, deionized water：74%-76%, each group point are combined into absolutely, stirring and dissolving,
It is well mixed, obtain solution A；
(2) B solution configures：In the reactor, add by mass percentage, high price manganese salt or manganese dioxide：0.2%-1%, no
Saturation polyethers：47%-51%, deionized water：48%-52%, being combined into absolutely for each group point, is uniformly mixed, obtains B
Solution；
(3) B solution is added in the reactor, and temperature rises to 40-65 DEG C, and solution A is added dropwise under constant temperature, stirring condition, and speed is added dropwise
Spend for 5-20 drops/min, the volume ratio of solution A and B solution is 4:15, isothermal reaction 3-3.5h again after being added dropwise, react
Finish, after being cooled to room temperature, adjust pH to 6-7 with liquid caustic soda, both obtain polycarboxylate water-reducer.
2. the preparation method of a kind of polycarboxylate water-reducer according to claim 1, it is characterised in that it is characterized in that structure
Formula is as follows：
A kind of 3. preparation method of polycarboxylate water-reducer according to claim 1, it is characterised in that step (1) described chain
Transfer agent is TGA or mercaptopropionic acid.
4. the preparation method of a kind of polycarboxylate water-reducer according to claim 1, it is characterised in that step (2) is described not
Saturation polyethers is that polyethers is allyl polyethenoxy base ether (HPEG) or prenol polyoxyethylene ether (TPEG), molecular weight are
2400。
A kind of 5. preparation method of polycarboxylate water-reducer according to claim 1, it is characterised in that step (2) described lemon
Lemon acid is 1 with high price manganese salt or manganese dioxide mass ratio：0.5-1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109053965A (en) * | 2018-09-17 | 2018-12-21 | 山西康力建材有限公司 | A kind of polycarboxylate water-reducer and preparation method thereof modified with high thermal stability |
| CN109593167A (en) * | 2018-12-04 | 2019-04-09 | 贵州铁建恒发新材料科技股份有限公司 | A kind of citric acid-modified polycarboxylate water-reducer of sorbierite acrylate and preparation method thereof |
| CN109880030A (en) * | 2019-01-28 | 2019-06-14 | 济南大学 | One-step method prepares the high-efficiency water-reducing agent of poly-carboxylic acid of three arm branched structures |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106277899A (en) * | 2016-08-22 | 2017-01-04 | 山西大学 | A kind of polycarboxylate water-reducer and preparation method thereof |
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- 2017-10-24 CN CN201710999062.1A patent/CN107793538A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106277899A (en) * | 2016-08-22 | 2017-01-04 | 山西大学 | A kind of polycarboxylate water-reducer and preparation method thereof |
Non-Patent Citations (1)
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| 王文平等: "柠檬酸改性聚羧酸减水剂的合成", 《新型建筑材料》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109053965A (en) * | 2018-09-17 | 2018-12-21 | 山西康力建材有限公司 | A kind of polycarboxylate water-reducer and preparation method thereof modified with high thermal stability |
| CN109593167A (en) * | 2018-12-04 | 2019-04-09 | 贵州铁建恒发新材料科技股份有限公司 | A kind of citric acid-modified polycarboxylate water-reducer of sorbierite acrylate and preparation method thereof |
| CN109880030A (en) * | 2019-01-28 | 2019-06-14 | 济南大学 | One-step method prepares the high-efficiency water-reducing agent of poly-carboxylic acid of three arm branched structures |
| CN109880030B (en) * | 2019-01-28 | 2021-11-02 | 济南大学 | One-step method for preparing polycarboxylic acid high-efficiency water reducing agent with three-arm branched structure |
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