CN108929414A - A kind of preparation and application of hyperbranched type modified starch water-reducing agent - Google Patents
A kind of preparation and application of hyperbranched type modified starch water-reducing agent Download PDFInfo
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- CN108929414A CN108929414A CN201811023858.4A CN201811023858A CN108929414A CN 108929414 A CN108929414 A CN 108929414A CN 201811023858 A CN201811023858 A CN 201811023858A CN 108929414 A CN108929414 A CN 108929414A
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- reducing agent
- hyperbranched
- base water
- hyperbranched type
- starch base
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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
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/04—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters
- C08F299/0485—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters from polyesters with side or terminal unsaturations
- C08F299/0492—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters from polyesters with side or terminal unsaturations the unsaturation being in acrylic or methacrylic groups
-
- 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
-
- 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 present invention relates to the technical field of retarding-type superplasticizer, the hyperbranched type starch base water-reducing agent of more specifically to a kind of superbrnaching end-hydroxy polyester is improving the application in concrete flowability energy.Starch is pre-processed first, then has synthesized a kind of Hyperbranched Polymer with Terminal Hydroxyl, then hyper-branched polyester is grafted to and synthesizes a kind of new hyperbranched type starch base water-reducing agent on pre-gelatinized starch.The hyperbranched type starch base water-reducing agent is applied into high efficiency water reducing agent field, concrete flowability energy can be improved well, synthesis technology is easy, easily industrializes, is a kind of retarding-type superplasticizer of function admirable.
Description
Technical field
The present invention relates to modified starch water-reducing agent technical fields, in particular to high, fluidity good for water-reducing rate, while can improve
A kind of retarding-type superplasticizer of the mobility of concrete and each age strength, further relates 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 table
Face makes like charges on cement granules band, generates electrostatic repulsion, wetting and lubricating action is generated to cement granules, so that cement
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.
Current water-reducing agent will be largely solved by the research and development of the starch water-reducing agent of raw material and application of natural polymer
The problem of market, it is also the application of natural macromolecular material that only additive sustainable development, which does not provide strength guarantee,
New field is started.
The invention patent is intended to introduce the hyperbranched resin for containing a large amount of hydroxyl telechelic polyesters, in its original molecular structure
Access have compared with strong fix effect-OH ,-COOH etc., improve its retarding time, keep 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 soil flow
Dynamic property, delays the preparation method of the hyperbranched modified starch water-reducing agent of its setting time.
The present invention is achieved by the following measures:
(1) to starch carry out pre-gelatinized processing, synthesize a kind of dissaving polymer, obtain to end be hydroxyl dissaving polymer
It polymerize to obtain hyperbranched type modified starch with pre-gelatinized starch；
(2) hyperbranched modified starch is evaporated under reduced pressure again, using filter, drying, broken obtains hyperbranched type starch base water-reducing agent
Finished product.
The hyperbranched type starch base water-reducing agent reacts to obtain AB with trimesic acid and trimethylolpropane2Type monomer, with
Propenyl makees core molecule, AB2Type monomer is reacted with core molecule, then utilizes divergent method, controls core molecule and AB2Type monomer rubs
That ratio, obtains the superbrnaching end-hydroxy polyester of different algebra, then polymerize itself and modified starch to obtain hyperbranched type shallow lake
Powder base water-reducing agent, then be evaporated under reduced pressure using filter, drying, broken obtains the finished product of hyperbranched type starch base water-reducing agent.
The hyperbranched type starch base water-reducing agent carries out pre-gelatinized to starch first, using ammonium persulfate as initiator, with
Methacrylic acid is monomer, is grafted on starch structure.
The hyperbranched type starch base water-reducing agent, the core molecule and AB of superbrnaching end-hydroxy polyester2Monomer according to 1:4 or
First generation carboxyl end group polyamides that 1:16 molar ratio reaction respectively obtains, second generation carboxyl end group polyamides.
The hyperbranched type starch base water-reducing agent, hyperbranched polyester and pre-gelatinized starch are according to 1:12,1:24 or 1:
The hyperbranched type starch base water-reducing agent of the first generation that 48 molar ratio reactions respectively obtain, the hyperbranched type starch base water-reducing agent of the second generation and
The hyperbranched type starch base water-reducing agent of the third generation.
The AB2Monomer is to be synthesized by trimesic acid and trimethylolpropane according to molar ratio for 1:2.
The hyperbranched type starch base water-reducing agent, the additive amount of preferred hyperbranched type starch base water-reducing agent are concrete
The 0.03~0.1% of additive gross mass.
The specific synthetic method of hyperbranched type starch base water-reducing agent:
1. the pre-gelatinized of starch
The graft modification of starch:
(1) starch and methacrylic acid graft copolymerization:
2. the synthesis of dissaving polymer
⑴AB2The synthesis of monomer
1 mole of trimesic acid and the reaction of 2 moles of trimethylolpropane:
(2) the synthesis of hydroxyl dissaving polymer
1. molecule: propenyl
2. molecule and AB2Monomer polymerization:
(2) the synthesis of first generation hyper-branched polymer compound:
(3) the synthesis of second generation hyper-branched polymer compound
3. pre-gelatinized starch is polymerize with dissaving polymer:
Beneficial effects of the present invention:
1, the present invention is that AB is made with reactions such as trimesic acid and trimethylolpropanes2Monomer, the length and density of side chain can have
Effect improves the electrostatic force and repulsive force between concrete particle, to improve its water-reducing rate to varying degrees, retarding performance draws
Gas performance etc. meets the requirement of various aspects.
2, pass through selection preparation AB2The raw material of monomer, synthesis of super branched type starch base water-reducing agent promote water-reducing agent in slow setting
Duration in the process；And the compatibility of relatively large molecular weight and high molecular material can improve.
3, it is all by the substance reaction system of polyacid and hydroxyl that the end used in the present invention, which is the dissaving polymer of hydroxyl,
Obtain and starch reaction synthesizes a kind of hyperbranched type starch base water-reducing agent, can preferably promote the diminishing efficiency of water-reducing agent, mention
High 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) 32.00g(0.1mol is weighed) starch 150.00g(0.4mol) water, starch and water are added have magnetic agitation first
In the four-hole boiling flask of device, adds appropriate ammonium persulfate 8.00g and make it dissolve, add 8.00g methacrylic acid, be warming up to 40
DEG C, synthesis under normal pressure 6h both obtains pre-gelatinized starch.
(2) esterification is utilized, under the action of catalyst p-methyl benzenesulfonic acid, using benzene as solution, propenyl and three hydroxyl first
Base propane, trimesic acid are monomer, and condensation reaction is carried out at 80 DEG C, 12~48h are reacted, by the way that AB is added repeatedly2Monomer comes
Hyperbranched algebra is controlled, a generation, two generation dissaving polymers are synthesized.A certain amount of dissaving polymer and pre-gelatinized is taken to form sediment
Powder, mixing are added in there-necked flask, and a certain amount of initiator is added, and stirring is warming up to 65 DEG C, 8h is stirred to react, then with 40%
Sodium hydroxide solution adjusts pH=7~7.5, then is evaporated under reduced pressure, and using filter, drying, broken obtains hyperbranched type starch base diminishing
The finished product of agent.
(3) 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) 32.00g(0.1mol is weighed) starch 150.00g(0.4mol) water, starch and water are added have magnetic agitation first
In the four-hole boiling flask of device, adds appropriate ammonium persulfate 8.00g and make it dissolve, add 8.00g methacrylic acid, be warming up to 40
DEG C, synthesis under normal pressure 6h；It is cooled to room temperature, both obtains pre-gelatinized starch.
(2) esterification is utilized, under the action of catalyst p-methyl benzenesulfonic acid, using benzene as solution, propenyl and three hydroxyl first
Base propane, trimesic acid are monomer, and condensation reaction is carried out at 80 DEG C, 12~48h are reacted, by the way that AB is added repeatedly2Monomer comes
Hyperbranched algebra is controlled, a generation, two generation dissaving polymers are synthesized.A certain amount of dissaving polymer and pre-gelatinized is taken to form sediment
Powder, mixing are added in there-necked flask, and a certain amount of initiator is added, and stirring is warming up to 65 DEG C, 8h is stirred to react, then with 40%
Sodium hydroxide solution adjusts pH=7~7.5, then is evaporated under reduced pressure, and using filter, drying, broken obtains hyperbranched type starch base diminishing
The finished product of agent.
(3) 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) 32.00g(0.1mol is weighed) starch 150.00g(0.4mol) water, starch and water are added have magnetic agitation first
In the four-hole boiling flask of device, adds appropriate ammonium persulfate 8.00g and make it dissolve, add 8.00g methacrylic acid, be warming up to 40
DEG C, synthesis under normal pressure 6h；It is cooled to room temperature, both obtains pre-gelatinized starch.
(2) esterification is utilized, under the action of catalyst p-methyl benzenesulfonic acid, with benzene position solution, propenyl and three hydroxyl first
Base propane, trimesic acid are monomer, and condensation reaction is carried out at 80 DEG C, 12~48h are reacted, by the way that AB is added repeatedly2Monomer comes
Hyperbranched algebra is controlled, a generation, two generation dissaving polymers are synthesized.A certain amount of dissaving polymer and pre-gelatinized is taken to form sediment
Powder, mixing are added in there-necked flask, and a certain amount of initiator is added, and stirring is warming up to 65 DEG C, 8h is stirred to react, then with 40%
Sodium hydroxide solution adjusts pH=7~7.5, then is evaporated under reduced pressure, and using filter, drying, broken obtains hyperbranched type starch base diminishing
The finished product of agent.
(3) 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) 32.00g(0.1mol is weighed) starch 150.00g(0.4mol) water, starch and water are added have magnetic agitation first
In the four-hole boiling flask of device, adds appropriate ammonium persulfate 8.00g and make it dissolve, add 8.00g methacrylic acid, be warming up to 40
DEG C, synthesis under normal pressure 6h；It is cooled to room temperature, both obtains pre-gelatinized starch.
(2) esterification is utilized, under the action of catalyst p-methyl benzenesulfonic acid, using benzene as solution, propenyl and three hydroxyl first
Base propane, trimesic acid are monomer, and condensation reaction is carried out at 80 DEG C, 12~48h are reacted, by the way that AB is added repeatedly2Monomer comes
Hyperbranched algebra is controlled, a generation, two generation dissaving polymers are synthesized.A certain amount of dissaving polymer and pre-gelatinized is taken to form sediment
Powder, mixing are added in there-necked flask, and a certain amount of initiator is added, and stirring is warming up to 65 DEG C, 8h is stirred to react, then with 40%
Sodium hydroxide solution adjusts pH=7~7.5, then is evaporated under reduced pressure, and using filter, drying, broken obtains hyperbranched type starch base diminishing
The finished product of 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
It is below exactly to subtract hyperbranched type starch base obtained in implementation method of the present invention in order to illustrate actual effect of the invention
The test of aqua progress 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 hyperbranched type starch base water-reducing agent of terminal hydroxy group base and uncommon retarding water reducer of this experiment synthesis
There is apparent improvement compared to resistance to mobility.Starch used in this experiment is raw material, and green non-pollution is from a wealth of sources, substantially reduces
The dosage of concrete admixture, has 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 (8)
1. a kind of hyperbranched type starch base water-reducing agent by following steps it is characterized in that obtained:
Methacrylic acid is grafted on starch；
2. synthesizing AB with trimesic acid and trimethylolpropane2Monomer；
3. with core molecule and AB2Monomer polymerization synthesis of super branched polymer；
4. dissaving structure is grafted on pre-gelatinized starch；
5. graft polymers is evaporated under reduced pressure again, using filter, drying, it is broken obtain hyperbranched type starch base water-reducing agent at
Product.
2. a kind of hyperbranched type starch base water-reducing agent, it is characterised in that a large amount of hydroxyl in end increases between cement granules
Steric hindrance improves its mobile performance.
3. according to claim 1, it is characterised in that hyperbranched type starch base water-reducing agent is as concrete admixture addition content
It is the 0.03%~0.1% of concrete gross mass.
4. according to claim 1, it is characterised in that core molecule and AB2Monomer mole ratio is 1:4,1:16, respectively obtains first
For Hyperbranched Polymer with Terminal Hydroxyl, second generation Hyperbranched Polymer with Terminal Hydroxyl.
5. hyperbranched type starch base water-reducing agent according to claim 1, it is characterised in that the core molecule is propenyl.
6. according to claim 1, it is characterised in that starch is modified with monomer methacrylic acid.
7. according to claim 1, it is characterised in that the hyperbranched type starch base water-reducing agent, hyperbranched polyester and pre-
Gelatinized starch is according to the hyperbranched type starch base water-reducing agent of the first generation that 1:12,1:24 or 1:48 molar ratio reaction respectively obtain,
Two generations hyperbranched type starch base water-reducing agent and the hyperbranched type starch base water-reducing agent of the third generation.
8. according to claim 1, it is characterized in that the AB of the dissaving polymer2Monomer is by trimesic acid and three hydroxyl first
Base propane is synthesized according to molar ratio 1:2.
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| CN201811023858.4A CN108929414A (en) | 2018-09-04 | 2018-09-04 | A kind of preparation and application of hyperbranched type modified starch water-reducing agent |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007149045A1 (en) * | 2006-06-23 | 2007-12-27 | Swetree Technologies Ab | Copolymer, modified polymer carbohydrate material, modified buld polymer, composite material, and methods of preparation |
| CN108084447A (en) * | 2016-11-22 | 2018-05-29 | 武汉超支化树脂科技有限公司 | End carboxyl super branched polymer and its application in the preparation of high performance plastics composite material |
| CN108440762A (en) * | 2018-03-19 | 2018-08-24 | 济南大学 | A kind of preparation of hyperbranched type starch base water-reducing agent |
-
2018
- 2018-09-04 CN CN201811023858.4A patent/CN108929414A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007149045A1 (en) * | 2006-06-23 | 2007-12-27 | Swetree Technologies Ab | Copolymer, modified polymer carbohydrate material, modified buld polymer, composite material, and methods of preparation |
| CN108084447A (en) * | 2016-11-22 | 2018-05-29 | 武汉超支化树脂科技有限公司 | End carboxyl super branched polymer and its application in the preparation of high performance plastics composite material |
| CN108440762A (en) * | 2018-03-19 | 2018-08-24 | 济南大学 | A kind of preparation of hyperbranched type starch base water-reducing agent |
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Application publication date: 20181204 |