CN109206041A - A kind of preparation and application of hyperbranched type water-reducing agent - Google Patents
A kind of preparation and application of hyperbranched type water-reducing agent Download PDFInfo
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- CN109206041A CN109206041A CN201811023851.2A CN201811023851A CN109206041A CN 109206041 A CN109206041 A CN 109206041A CN 201811023851 A CN201811023851 A CN 201811023851A CN 109206041 A CN109206041 A CN 109206041A
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- Prior art keywords
- reducing agent
- type water
- hyperbranched
- hyperbranched type
- polymer
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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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
- C04B24/283—Polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- 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
Landscapes
- 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)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The present invention relates to the technical field of retarding-type superplasticizer, the hyperbranched type water-reducing agent of more specifically to a kind of end carboxyl super branched polyester is improving the application in concrete flowability energy.A kind of end carboxyl super branched polymer has been synthesized first, which is applied into high efficiency water reducing agent field, can improve concrete flowability energy well, and synthesis technology is easy, easily industrializes, is a kind of retarding-type superplasticizer of function admirable.
Description
Technical field
The present invention relates to water-reducing agent technical fields, in particular to high, fluidity good for water-reducing rate, while can improve coagulation
The mobility of soil and a kind of retarding-type superplasticizer of each age strength, further relate to preparation method.
Background technique
After water-reducing agent mixes concrete batching system, the anion seeking group on diminishing agent molecule is adsorbed on cement granules
Surface makes like charges on cement granules band, generates electrostatic repulsion, wetting and lubricating action is generated to cement granules, so that water
Mud particle more disperses, and hydration efficiency improves, and mixing water amount is reduced, and the working performance of concrete improves.
With the fast development of highway, railway, construction industry, water-reducing agent application market is gradually expanded, both at home and abroad for diminishing
The mechanism study of agent is more and more.As the non-renewable and petroleum resources of petroleum constantly consume, oil shortage will limit with
Petroleum is the development in the water-reducing agent market of raw material.The application of petroleum resources brings the increasingly exacerbation of environmental pollution, green, environmental protection,
Free of contamination material and technology are gradually paid attention to.
The invention patent is intended to introduce the hyperbranched resin for containing a large amount of Amino End Group polyester, in its original molecular structure
Access have compared with strong fix effect-NH2,-COOH etc. improves its retarding time, keeps its mobility.
Dissaving polymer has 3 D stereo reticular structure, and active site is more, and viscosity is small, good with matrix amalgamation, tool
Have broad application prospects, is all shown in fields such as photoelectric material, coating, adhesive, nanosecond science and technology, drug carriers at present
Huge application value.
Summary of the invention
Long in order to solve water-reducing agent retarding time, the problems such as poor fluidity, the present invention provides one kind for improving coagulation
Native mobility delays the preparation method of the hyperbranched type water-reducing agent of its setting time.
The present invention is achieved by the following measures:
(1) design a kind of dissaving polymer, obtain to end be carboxyl dissaving polymer；
(2) using dissaving polymer as concrete admixture.
The hyperbranched type starch base water-reducing agent is to polyalcohols such as glycerine, trimethylolpropane, isoprene and right
The polyacids such as phthalic acid, trimesic acid react to obtain AB2Type monomer, using the monohydric alcohols such as citric acid, malic acid polyacid as core point
Son, AB2Type monomer is reacted with core molecule, then utilizes divergent method, controls core molecule and AB2The molar ratio of type monomer, obtains difference
The amine-terminated hyperbrancedization polyester of algebra.
The hyperbranched type water-reducing agent, the core molecule and AB of end carboxyl super branched polyester2Monomer rubs according to 1:3 or 1:12
You are than reacting the first generation terminal carboxyl polyester, the second generation terminal carboxyl polyester that respectively obtain.
The AB2Monomer be by glycerine, trimethylolpropane, isoprene and terephthalic acids, trimesic acid according to
Molar ratio is the synthesis such as 1:2,1:1.
The hyperbranched type water-reducing agent, the additive amount of preferred hyperbranched type water-reducing agent are concrete admixture gross mass
0.03~0.1%.
The specific synthetic method of hyperbranched type water-reducing agent: (by taking glycerine and terephthalic acids as an example)
1. the synthesis of dissaving polymer
(1) AB2The synthesis of monomer
1 mole of glycerine and the reaction of 2 moles of terephthalic acid (TPA):
(2) synthesis of amino dissaving polymer
Core molecule: by taking citric acid as an example
(3) synthesis of first generation hyper-branched polymer compound:
(4) synthesis of second generation hyper-branched polymer compound
Beneficial effects of the present invention:
1, the present invention is to the polyalcohols such as glycerine, trimethylolpropane, isoprene and terephthalic acid (TPA), trimesic acid etc.
AB is made in the reactions such as polyacid2Monomer, the length and density of side chain can effectively improve electrostatic force and row between concrete particle
Repulsion, to improve its water-reducing rate to varying degrees, retarding performance, bleed performance etc. meets the requirement of various aspects.
2, pass through selection preparation AB2The raw material of monomer, synthesis of super branched type water-reducing agent promote water-reducing agent during slow setting
Duration；And the compatibility of relatively large molecular weight and high molecular material can improve.
3, it is all the substance reaction by polyacid and polyacid that the end used in the present invention, which is the dissaving polymer of carboxyl,
It is obtained, the diminishing efficiency of water-reducing agent can be preferably promoted, improves retarding performance, and reduce additive amount.
Specific embodiment
More to be stated in detail to specific implementation method of the present invention below, it is therefore intended that illustrate design of the invention 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 be covered by the protection scope of the present invention.
Implementation method one
(1) esterification is utilized, under the action of catalyst p-methyl benzenesulfonic acid, using benzene as solution, citric acid and glycerine, to benzene
Diacid is monomer, and condensation reaction is carried out at 80 DEG C, 12~48h is reacted, by the way that AB is added repeatedly2Monomer, it is hyperbranched to control
Algebra, synthesize a generation, two generation dissaving polymers.It is evaporated under reduced pressure again, obtains the finished product of hyperbranched type water-reducing agent.
(2) it weighs 300g cement to pour into agitated kettle, 0.5% hyperbranched type starch base water-reducing agent and 87g water is added, stand
(quick 120s) is stirred, the net slurry being stirred is injected rapidly in the mould of truncated cone garden, with doctor blade, truncated cone garden mould is pressed vertical
Direction lifts, and starts simultaneously at manual time-keeping, and cement paste is appointed to flow on a glass, until 30s, it is mutual to measure trickling part with ruler
The maximum gauge of perpendicular both direction, is averaged as flowing degree of net paste of cement.
Implementation method two
(1) esterification is utilized, under the action of catalyst p-methyl benzenesulfonic acid, using benzene as solution, citric acid and terephthalic acid (TPA),
Glycerine is monomer, and condensation reaction is carried out at 80 DEG C, 12~48h is reacted, by the way that AB is added repeatedly2Monomer, to control over-expense
The algebra of change synthesizes a generation, two generation dissaving polymers.It is evaporated under reduced pressure again, obtains the finished product of hyperbranched type water-reducing agent.
(2) it weighs 300g cement to pour into agitated kettle, 0.6% hyperbranched type starch base water-reducing agent and 87g water is added, stand
(quick 120s) is stirred, the net slurry being stirred is injected rapidly in the mould of truncated cone garden, with doctor blade, truncated cone garden mould is pressed vertical
Direction lifts, and starts simultaneously at manual time-keeping, and cement paste is appointed to flow on a glass, until 30s, it is mutual to measure trickling part with ruler
The maximum gauge of perpendicular both direction, is averaged as flowing degree of net paste of cement.
Implementation method three
(1) esterification is utilized, under the action of catalyst p-methyl benzenesulfonic acid, with benzene position solution, citric acid and terephthalic acid (TPA),
Glycerine is monomer, and condensation reaction is carried out at 80 DEG C, 12~48h is reacted, by the way that AB is added repeatedly2Monomer, to control over-expense
The algebra of change synthesizes a generation, two generation dissaving polymers.It is evaporated under reduced pressure again, obtains the finished product of hyperbranched type water-reducing agent.
(2) it weighs 300g cement to pour into agitated kettle, 0.8% hyperbranched type starch base water-reducing agent and 87g water is added, stand
(quick 120s) is stirred, the net slurry being stirred is injected rapidly in the mould of truncated cone garden, with doctor blade, truncated cone garden mould is pressed vertical
Direction lifts, and starts simultaneously at manual time-keeping, and cement paste is appointed to flow on a glass, until 30s, it is mutual to measure trickling part with ruler
The maximum gauge of perpendicular both direction, is averaged as flowing degree of net paste of cement.
Implementation method four
(1) esterification is utilized, under the action of catalyst p-methyl benzenesulfonic acid, using benzene as solution, citric acid and terephthalic acid (TPA),
Glycerine is monomer, and condensation reaction is carried out at 80 DEG C, 12~48h is reacted, by the way that AB is added repeatedly2Monomer, to control over-expense
The algebra of change synthesizes a generation, two generation dissaving polymers.It is evaporated under reduced pressure again, obtains the finished product of hyperbranched type water-reducing agent.
(3) it weighs 300g cement to pour into agitated kettle, 1% hyperbranched type starch base water-reducing agent and 87g water is added, immediately
It stirs (quick 120s), the net slurry being stirred is injected rapidly in the mould of truncated cone garden, with doctor blade, truncated cone garden mould is pressed into Vertical Square
To lifting, manual time-keeping is started simultaneously at, cement paste is appointed to flow on a glass, until 30s, it is mutual to measure trickling part with ruler
The maximum gauge of vertical both direction, is averaged as flowing degree of net paste of cement.
Comparison is implemented
It weighs 300g cement to pour into agitated kettle, 1% ordinary water-reducing agent and 87g water is added, stir (quick 120s) immediately, it will
The net slurry being stirred is injected rapidly in the mould of truncated cone garden, with doctor blade, truncated cone garden mould is lifted in a vertical direction, starts simultaneously at the second
When meter, cement paste is appointed to flow on a glass, until 30s, measures trickling part two mutually perpendicular directions with ruler
Maximum gauge is averaged as flowing degree of net paste of cement.
Performance test
In order to illustrate actual effect of the invention, be exactly below by hyperbranched type water-reducing agent obtained in implementation method of the present invention into
The test of row flowing degree of net paste of cement.
Test performance is respectively such as the following table 1.
The flowing degree of net paste of cement of 1. retarding water reducer of table
| Hyperbranched resin | Flowing degree of net paste of cement/mm |
| Comparison is implemented | 180 |
| Implementation method one (0.5%) | 185 |
| Implementation method two (0.6%) | 215 |
| Implementation method three (0.8%) | 240 |
| Implementation method four (1%) | 260 |
As shown in Table 1, the end carboxyl super branched type water-reducing agent of this experiment synthesis is resistant to flow compared with uncommon retarding water reducer
Dynamic property has apparent improvement.This experiment is raw materials used, green non-pollution, from a wealth of sources, greatly reduces concrete admixture
Dosage, saved cost.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by the limit of embodiment
System, other any changes made without departing from the spirit and principles of the present invention, modification, combination, substitution, simplification should be
Equivalence replacement mode, is included within the scope of the present invention.
Claims (6)
1. a kind of hyperbranched type water-reducing agent by following steps it is characterized in that obtained:
The polyalcohols such as the polyacids such as terephthalic acid (TPA), trimesic acid and glycerine, trimethylolpropane, isoprene synthesize AB2It is single
Body；
With core molecule and AB2Monomer polymerization synthesis of super branched polymer；
Polymer is evaporated under reduced pressure again, obtains the finished product of hyperbranched type water-reducing agent.
2. a kind of hyperbranched type water-reducing agent, it is characterised in that a large amount of carboxyl in end increases the space bit between cement granules
Resistance, improves its mobile performance.
3. according to claim 1, it is characterised in that hyperbranched type water-reducing agent is coagulation as concrete admixture addition content
The 0.03%~0.1% of native gross mass.
4. according to claim 1, it is characterised in that core molecule and AB2Monomer mole ratio is 1:3,1:10, respectively obtains first
For Hyperbranched Polymer with Terminal Hydroxyl, second generation Hyperbranched Polymer with Terminal Hydroxyl.
5. hyperbranched type water-reducing agent according to claim 1, it is characterised in that the core molecule citric acid.
6. according to claim 1, it is characterized in that the AB of the dissaving polymer2Monomer is by terephthalic acid (TPA) and the third three
Alcohol is synthesized according to molar ratio 2:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811023851.2A CN109206041A (en) | 2018-09-04 | 2018-09-04 | A kind of preparation and application of hyperbranched type water-reducing agent |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811023851.2A CN109206041A (en) | 2018-09-04 | 2018-09-04 | A kind of preparation and application of hyperbranched type water-reducing agent |
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| CN109206041A true CN109206041A (en) | 2019-01-15 |
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| CN201811023851.2A Withdrawn CN109206041A (en) | 2018-09-04 | 2018-09-04 | A kind of preparation and application of hyperbranched type water-reducing agent |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115611564A (en) * | 2022-11-14 | 2023-01-17 | 江苏双龙集团有限公司 | Concrete for slip form process and preparation method thereof |
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