CN106496438A - A kind of amidatioon graphene oxide modified polycarboxylic acid water reducer and preparation method thereof - Google Patents
A kind of amidatioon graphene oxide modified polycarboxylic acid water reducer and preparation method thereof Download PDFInfo
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- 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
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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
- C04B24/40—Compounds containing silicon, titanium or zirconium or other organo-metallic compounds; Organo-clays; Organo-inorganic complexes
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
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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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Abstract
The invention discloses a kind of amidatioon graphene oxide modified polycarboxylic acid water reducer, primary raw material component is as follows：Graphene oxide, methyl allyl polyoxyethylene ether, acrylic acid, allyl amine, maleic anhydride, water, oxidant and reducing agent and condensing agent and activator.Main method is the graphene oxide that allyl amine and graphene oxide are first prepared allyl amine modification by amidation process, then the graphene oxide that gained allyl amine is modified is mixed with methyl allyl polyoxyethylene ether, acrylic acid and maleic anhydride, there is polyreaction under the initiation of Oxidizing and Reducing Agents, so as to obtain amidatioon graphene oxide modified polycarboxylic acid water reducer.The amidation process mainly used between allyl amine and graphene oxide of the present invention, graphene oxide two-dimensional nano-lamellar structure and polycarboxylate water-reducer molecule are combined closely, so that graphene oxide preferably can disperse when applying in concrete, the water reducer properties of product of synthesis are more stable.
Description
Technical field
The present invention relates to a kind of amidatioon graphene oxide modified polycarboxylic acid water reducer and preparation method thereof, belongs to chemical engineering of materials
Field.
Background technology
Water reducer is a kind of high molecular polymer being applied in the Binder Materials such as concrete, can be by various of monomer polymerization system
?.Obtain more closely knit as which contains service behaviour of a lot of active groups so as to improve concrete, mechanical property is more
Good concrete.Through the development of several generations water reducer, poly carboxylic acid series water reducer has been substituted naphthalene water reducer to be become in concrete
In most widely used product.
Graphene oxide is two-dimensional nano lamellar structure, itself there is the elastic modelling quantity of superelevation, be applied to coagulation
The performance of concrete can be improved in soil, but graphene oxide is easy to reunite.This is because graphene oxide is two-dimensional nano
Material, due to dimensional effect, plays the role of stronger Van der Waals force, is therefore applied in concrete through one between lamellar structure
The section time, can reunite between nanoscale twins so as to affecting the performance of concrete.
Content of the invention
The technical problem to be solved is the deficiency and a kind of amidatioon of offer existed for above-mentioned prior art
Graphene oxide modified polycarboxylic acid water reducer and preparation method thereof, improves dispersibility of the graphene oxide in concrete, so as to
Consumption of the graphene oxide in concrete application is reduced, and improves the mechanical property and durability of concrete.
The present invention by solve the problems, such as the technical scheme for adopting set forth above for：
A kind of amidatioon graphene oxide modified polycarboxylic acid water reducer, its primary raw material component are as follows：Graphene oxide, first
Base allyl polyethenoxy ether, acrylic acid, allyl amine, water and small amounts agent and reducing agent.
Further, quality hundred pressed by above-mentioned amidatioon graphene oxide modified polycarboxylic acid water reducer, its primary raw material component
Divide as follows than meter：Graphene oxide 0.1%～0.3%, methyl allyl polyoxyethylene ether 10%～18%, acrylic acid 0.5%
～1.5%, allyl amine 0.1%～0.4%, water 80%～89%, oxidant 0.1%～0.3%, reducing agent 0.03%～
0.06%th, condensing agent 0.005%～0.02% and activator 0.002%～0.02%.
Preferably, the graphene oxide is prepared by improved hummer methods, a diameter of 400～800nm of lamella, and thickness is
1～8 layer.
Preferably, the methyl allyl polyoxyethylene ether molecular weight is 2200～2600g/mol.
Preferably, initiator system selected by the present invention is redox system, and oxidant is Ammonium persulfate. or potassium peroxydisulfate etc.
Persulfate, reducing agent are the sulphite such as sodium sulfite.
Preferably, amidatioon condensing agent of the present invention is 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt
Hydrochlorate EDC.HCL, activator are N-hydroxy-succinamide NHS.
The preparation method of amidatioon graphene oxide modified polycarboxylic acid water reducer of the present invention：Said ratio is pressed, first will
Allyl amine prepares allyl amine modification by amidation process with graphene oxide in the presence of condensing agent and activator
Graphene oxide, graphene oxide and the methyl allyl polyoxyethylene ether that then gained allyl amine is modified, acrylic acid with
And maleic anhydride mixing, there is polyreaction under the initiation of Oxidizing and Reducing Agents, so as to obtain amidatioon oxidation stone
Black alkene modified polycarboxylic acid water reducer.Its specifically the step of as follows：
(1) by raw material specification and proportioning, each raw material components are weighed；And by methyl allyl polyoxyethylene ether, acrylic acid and
Maleic anhydride, reducing agent and graphene oxide are configured to aqueous solution respectively；
(2) condensing agent and activator are dissolved in after water, are configured to activated carboxylic liquid；By gained activated carboxylic liquid and oxidation stone
Black alkene solution hybrid reaction, is obtained the graphene oxide water solution of activated carboxylic；
(3) allyl amine is added the graphene oxide solution of step (2) gained activated carboxylic, reaction to obtain allyl amine
The graphene oxide of modification；
(4) methyl allyl polyoxyethylene ether aqueous solution is stirred and temperature is warming up to for 75～80 DEG C, then Deca third
Graphene oxide solution and go back that the allyl amine of olefin(e) acid aqueous solution, maleic anhydride aqueous solution and step (3) gained is modified
Former agent aqueous solution, time for adding are 3～4 hours；
(5) after completion of dropping in step (4), gained reaction system is incubated 1.5～2.5h of ripening in 75～85 DEG C, so
After be cooled to room temperature mend alkali liquor to pH for neutrality, that is, obtain amidatioon graphene oxide modified polycarboxylic acid water reducer.
Such scheme is pressed, the mol ratio in the activated carboxylic liquid of step (2) between condensing agent and activator, water is 1:
1:8000～10000.
Such scheme is pressed, in step (4), the time for adding of reducing agent aqueous solution is later than 1～5 point of other Deca components
Clock.
Such scheme is pressed, in step (4), the time for adding of reducing agent sodium sulfite is required than acrylic acid, Malaysia
The time for adding of the graphene oxide of anhydride and allyl amine modification is slightly long.Acrylic acid aqueous solution, maleic anhydride aqueous solution, alkene
The propyl group amine-modified graphene oxide solution Deca persistent period is 2～3 hours, reductant solution time for adding continues 3.2～
3.5 hour.
Such scheme is pressed, in step (5), pH adjusting agent is alkali liquor, conventional mass concentration is 10% sodium hydroxide
Solution.
Preferably, the methyl allyl polyoxyethylene ether concentration of polymer solution is 30%～50%, acrylic acid solution
Mass concentration is 30%～50%, and maleic anhydride solution concentration is 30%～50%.
Preferably, the mass concentration of the reductant solution is 0.5%～1%.
Preferably, the mass concentration of the graphene oxide solution is 0.2%～2%.
Water reducer of the present invention is by methyl allyl polyoxyethylene ether polymeric monomer and acrylic acid and allyl amine
And the pectination of the main chain and side chain between four kinds of monomers of maleic anhydride by the polymerization formation of double bond with certain length is poly-
Compound；Meanwhile, in the middle of the backbone of graphene oxide layer structural integrity to polycarboxylate water-reducer, and its approach is to pass through
Realized by amidation process between related amino on related carboxyl and allyl amine on graphene oxide.The present invention is logical
Cross in the molecular structure that this mode is formed, between the diminishing agent molecule of graphene oxide and pectinate texture, bonding action is higher,
Can the more stable polycarboxylate water-reducer of forming properties.
Due to being also connected with carboxyl on acrylic acid minor comonomer in the monomer of synthesis, it is possible to which amide occurs between allyl amine
Change reaction.In order to reduce the generation of the reaction, the present invention is adopted and is solved with the following method：Using first by allyl amine and graphite oxide
Alkene reaction simultaneously makes reaction as far as possible fully, reduces allyl amine in reaction system, makes the more graphene oxide allyl amines of generation
Complex, the product after in addition reacting remove catalyst EDC hydrochlorates in reaction system by washing；Additionally, charging when
Wait using first Deca acrylic acid solution, then the graphene oxide solution of allyl amine modification for preparing of Deca and reducing agent
Solution, can so reduce the probability that amidation process occurs between allyl amine and acrylic acid.And, reducing agent sodium sulfite
Time for adding require that the time for adding of the graphene oxide that modifies than acrylic acid minor comonomer and allyl amine is slightly long.This be by
It is that progressively Deca enters reaction system in minor comonomer acrylic acid solution, therefore it is required that there is initiation in reaction system from start to finish
Agent；If the time for adding of reducing agent is shorter than the time for adding of minor comonomer, the minor comonomer for adding afterwards may be because of not initiation
The initiation of agent and polyreaction cannot be completed.
Compared with prior art, the invention has the beneficial effects as follows：
1 the method is mainly characterized in that using the amidation process between allyl amine and graphene oxide, will aoxidize stone
Black alkene two-dimensional nano lamellar structure is combined closely with polycarboxylate water-reducer molecule, so that graphene oxide answering in concrete
Used time preferably can disperse, and the water reducer properties of product of synthesis are more stable.
2nd, water reducer of the present invention causes graphene oxide dispersed during concrete optimum, on the one hand applies
Durability, the mechanical property of concrete is significantly improved in concrete；On the other hand as the dispersion of graphene oxide is more equal
Even, compared to mixing with water reducer, after ultrasound for concrete method, oxygen in heretofore described modified polycarboxylic acid water reducer
The consumption of graphite alkene is relatively less.
3rd, the amidatioon graphene oxide modified polycarboxylic acid water reducer volume of present invention synthesis is low, good product performance, diminishing
Rate is high, better than commercially available water reducer water-reducing effect under equal volume, and the loss after 0.5 hour is also smaller.
4th, the mechanical property of the amidatioon graphene oxide modified polycarboxylic acid Water-reducing Admixtures To Cements glue sand of present invention synthesis is carried
Rise very greatly, compare and existing technology, comprcssive strength further can be lifted.
5th, product synthesis technique of the present invention is simple, selected synthesis material all safety non-toxics, and production process is also without harmful
Substance release, safety and environmental protection.
Specific embodiment
For a better understanding of the present invention, present disclosure is further elucidated with reference to embodiment, but the present invention is not
It is limited only to the following examples.
In following embodiments, the graphene oxide is prepared by improved hummer methods, a diameter of 400～800nm of lamella,
Thickness is 1～8 layer；The methyl allyl polyoxyethylene ether molecular weight is 2200～2600g/mol.
Embodiment 1
A kind of amidatioon graphene oxide modified polycarboxylic acid water reducer, its raw material components are as follows in parts by weight：Oxidation
Graphene 0.141% (0.1g), methyl allyl polyoxyethylene ether 16.908% (12g), acrylic acid 1.014% (1.08g), horse
Come anhydride 1.036% (0.735g), allyl amine 0.201% (0.1425g), water 80.306% (57.305g), oxidant
0.268% (0.19g), reducing agent 0.059% (0.042g), EDC hydrochlorates 0.006% (0.0045g), NHS 0.004%
(0.003g).
The preparation method of above-mentioned amidatioon graphene oxide modified polycarboxylic acid water reducer, concrete step are as follows：
(1) 4.5mgEDC.HCL is weighed in 25ml beakers, be added thereto to 5ml water and be sufficiently stirred for, then to mixing
3mgNHS is added in solution, and after stirring fully, ultrasound obtains activated carboxylic liquid in 10 minutes；
(2) graphene oxide water solution that 34.48g mass fractions are 0.29% is taken in reactor, add while stirring
Gained activated carboxylic liquid in step (1), adds 0.1425g allyl amines after mix homogeneously, after reacting 4 hours, obtains pi-allyl
Amine-modified graphene oxide solution, centrifugation, washing are saved backup after removing activating solution；
(3) solution that 12g methyl allyl polyoxyethylene ether compound concentrations are 50% is taken, and adds 0.19g oxidant mistakes
Ammonium sulfate；Take the solution that 0.72g acrylic acid compound concentrations are 50%；Take 0.735 maleic anhydride be configured to concentration be 50% molten
Liquid is simultaneously mixed into minor comonomer solution with acrylic acid solution；Taking 0.042g sodium sulfitees, to be configured to the reducing agent that concentration is 1% molten
Liquid；
(4) methyl allyl polyoxyethylene ether solution is added in reactor, temperature is stirred and be warming up to for 80 DEG C；Then
The allyl amine for be slowly added dropwise minor comonomer solution in reactor, starting to prepare after one minute in Deca step (2) is modified
Graphene oxide solution and reductant solution；When the graphene oxide solution of allyl amine modification is with minor comonomer solution Deca
Between be 3 hours, reducing agent time for adding be 3.5 hours；
(5) after completion of dropping in step (4), by gained reaction system in 80 DEG C of warm ripenings 2 hours, after question response is complete
Be cooled to room temperature and its pH to 7 adjusted with 10% sodium hydroxide solution, that is, obtain amidatioon graphene oxide modified polycarboxylic acid and subtract
Water preparation.
Embodiment 2
A kind of amidatioon graphene oxide modified polycarboxylic acid water reducer, its raw material components are as follows in parts by weight：Oxidation
Graphene 0.181% (0.2g), methyl allyl polyoxyethylene ether 10.861% (12g), acrylic acid 0.652% (0.72g), horse
Come anhydride 0.665% (0.735g), allyl amine 0.129% (0.1425g), water 87.275% (96.425g), oxidant
0.172% (0.19g), reducing agent 0.038% (0.042g), EDC hydrochlorates 0.016% (0.018g), NHS0.011%
(0.012g).
The preparation method of above-mentioned amidatioon graphene oxide modified polycarboxylic acid water reducer, concrete step are as follows：
(1) weigh in 18mgEDC.HCL and 25ml beakers, be added thereto to 20ml water and be sufficiently stirred for, then to mixing
12mgNHS is added in solution, and after stirring fully, ultrasound obtains activated carboxylic liquid in 10 minutes；
(2) graphene oxide water solution that 68.96g mass fractions are 0.29% is taken in reactor, add while stirring
Gained activated carboxylic liquid in step (1), adds 0.1425g allyl amines after mix homogeneously, after reacting 4 hours, obtains pi-allyl
Amine-modified graphene oxide solution, centrifugation, washing are saved backup after removing activating solution；
(3) solution that 12g methyl allyl polyoxyethylene ether compound concentrations are 50% is taken, and adds 0.19g oxidant mistakes
Ammonium sulfate；Take the solution that 0.72g acrylic acid compound concentrations are 50%；Take 0.735 maleic anhydride be configured to concentration be 50% molten
Liquid is simultaneously mixed into minor comonomer solution with acrylic acid solution；Taking 0.042g sodium sulfitees, to be configured to the reducing agent that concentration is 1% molten
Liquid；
(4) methyl allyl polyoxyethylene ether solution is added in reactor, temperature is stirred and be warming up to for 80 DEG C；Then
The allyl amine for be slowly added dropwise minor comonomer solution in reactor, starting to prepare after one minute in Deca step (2) is modified
Graphene oxide solution and reductant solution；When the graphene oxide solution of allyl amine modification is with minor comonomer solution Deca
Between be 3 hours, reducing agent time for adding be 3.5 hours；
(5) after completion of dropping in step (4), by gained reaction system in 80 DEG C of warm ripenings 2 hours, after question response is complete
Be cooled to room temperature and its pH to 7 adjusted with 10% sodium hydroxide solution, that is, obtain amidatioon graphene oxide modified polycarboxylic acid and subtract
Water preparation.
Embodiment 3
A kind of amidatioon graphene oxide modified polycarboxylic acid water reducer, its raw material components are as follows in parts by weight：Oxidation
Graphene 0.142% (0.1g), methyl allyl polyoxyethylene ether 16.991% (12g), acrylic acid 1.019% (0.72g), horse
Come anhydride 0.694% (0.49g), allyl amine 0.404% (0.1425g), water 80.411% (56.79g), oxidant
0.269% (0.19g), reducing agent 0.059% (0.042g), EDC hydrochlorates 0.006% (0.0045g), NHS0.004%
(0.003g).
The preparation method of above-mentioned amidatioon graphene oxide modified polycarboxylic acid water reducer, concrete step are as follows：
(1) weigh in 4.5mgEDC.HCL and 25ml beakers, be added thereto to 20ml water and be sufficiently stirred for, then to mixing
3mgNHS is added in solution, and after stirring fully, ultrasound obtains activated carboxylic liquid in 10 minutes；
(2) graphene oxide water solution that 34.48g mass fractions are 0.29% is taken in reactor, add while stirring
Gained activated carboxylic liquid in step (1), adds 0.285g allyl amines after mix homogeneously, after reacting 4 hours, obtains allyl amine
The graphene oxide solution of modification, centrifugation, washing are saved backup after removing activating solution；
(3) solution that 12g methyl allyl polyoxyethylene ether compound concentrations are 50% is taken, and adds 0.19g oxidant mistakes
Ammonium sulfate；Take the solution that 0.72g acrylic acid compound concentrations are 50%；Take 0.49 maleic anhydride and be configured to the solution that concentration is 50%
And minor comonomer solution is mixed into acrylic acid solution；Take 0.042g sodium sulfitees and be configured to the reductant solution that concentration is 1%；
(4) methyl allyl polyoxyethylene ether solution is added in reactor, temperature is stirred and be warming up to for 80 DEG C；Then
The allyl amine for be slowly added dropwise minor comonomer solution in reactor, starting to prepare after one minute in Deca step (2) is modified
Graphene oxide solution and reductant solution；When the graphene oxide solution of allyl amine modification is with minor comonomer solution Deca
Between be 3 hours, reducing agent time for adding be 3.5 hours；
(5) after completion of dropping in step (4), by gained reaction system in 80 DEG C of warm ripenings 2 hours, after question response is complete
Be cooled to room temperature and its pH to 7 adjusted with 10% sodium hydroxide solution, that is, obtain amidatioon graphene oxide modified polycarboxylic acid and subtract
Water preparation.
Embodiment 4
A kind of amidatioon graphene oxide modified polycarboxylic acid water reducer, its raw material components are as follows in parts by weight：Oxidation
Graphene 0.182% (0.2g), methyl allyl polyoxyethylene ether 10.896% (12g), acrylic acid 0.654% (0.72g), horse
Come anhydride 0.445% (0.49g), allyl amine 0.259% (0.285g), water 87.328% (96.18g), oxidant 0.173%
(0.19g), reducing agent 0.038% (0.042g), EDC hydrochlorates 0.016% (0.018g), NHS 0.011% (0.012g).
The preparation method of above-mentioned amidatioon graphene oxide modified polycarboxylic acid water reducer, concrete step are as follows：
(1) weigh in 18mgEDC.HCL and 25ml beakers, be added thereto to 20ml water and be sufficiently stirred for, then to mixing
12mgNHS is added in solution, and after stirring fully, ultrasound obtains activated carboxylic liquid in 10 minutes；
(2) graphene oxide water solution that 68.96g mass fractions are 0.29% is taken in reactor, add while stirring
Gained activated carboxylic liquid in step (1), adds 0.285g allyl amines after mix homogeneously, after reacting 4 hours, obtains allyl amine
The graphene oxide solution of modification, centrifugation, washing are saved backup after removing activating solution；
(3) solution that 12g methyl allyl polyoxyethylene ether compound concentrations are 50% is taken, and adds 0.19g oxidant mistakes
Ammonium sulfate；Take the solution that 0.72g acrylic acid compound concentrations are 50%；Take 0.49 maleic anhydride and be configured to the solution that concentration is 50%
And minor comonomer solution is mixed into acrylic acid solution；Take 0.042g sodium sulfitees and be configured to the reductant solution that concentration is 1%；
(4) methyl allyl polyoxyethylene ether solution is added in reactor, temperature is stirred and be warming up to for 80 DEG C；Then
The allyl amine for be slowly added dropwise minor comonomer solution in reactor, starting to prepare after one minute in Deca step (2) is modified
Graphene oxide solution and reductant solution；When the graphene oxide solution of allyl amine modification is with minor comonomer solution Deca
Between be 3 hours, reducing agent time for adding be 3.5 hours；
(5) after completion of dropping in step (4), by gained reaction system in 80 DEG C of warm ripenings 2 hours, after question response is complete
Be cooled to room temperature and its pH to 7 adjusted with 10% sodium hydroxide solution, that is, obtain amidatioon graphene oxide modified polycarboxylic acid and subtract
Water preparation.
In order to prove the performance of the compound polycarboxylate water-reducer of graphene oxide of the present invention, with above-described embodiment
The water reducer of synthesis is according to GBT 8077-2012《Methods for testing uniformity of concrete admixture》Carry out flowing degree of net paste of cement reality
Test.Result of the test is as shown in table 1.In experiment, comparative example 1 is using being not added with synthesized polycarboxylic acids in the case of graphene oxide
The result measured during water reducer.
1 flowing degree of net paste of cement test result of table
As seen from the results in Table 1：The amidatioon graphene oxide modified polycarboxylic acid water reducer volume of present invention synthesis is low, on an equal basis
Better than commercially available water reducer water-reducing effect under volume, and the loss after 0.5 hour is also smaller.As embodiment 1,2 is allyl
1/4 replacement maleic anhydride of base amine, in long-chain molecule, carboxyl quantity is reduced, embodiment 1,2 paste flowing degrees knot under equal volume
Fruit is almost equal with comparative example；(embodiment 3,4), carboxyl on product long-chain molecule when 1/2 replacement maleic anhydride of allyl amine
Quantity is further reduced, and paste flowing degree reduces relative to comparative example.
In order to prove the compound polycarboxylate water-reducer of graphene oxide of the present invention to cement mortar mechanical property
Effect, with the water reducer synthesized in above-described embodiment according to GB/T17671-1999《Test method for strength of hydraulic cement mortar》Carry out power
Learn performance test.Result of the test is as shown in table 2.Wherein, cement used is new 42.5 grade cement of China, and the ratio of mud is 0.3；Diminishing
Agent volume is 1.2%；Comparative example 2 is the result using general water reducer gained；Comparative example 3 is using general water reducer and to mix
Graphene oxide experimental results.
2 cement mortar intensity test result of table
As seen from the results in Table 2：The amidatioon graphene oxide modified polycarboxylic acid Water-reducing Admixtures To Cements glue sand of present invention synthesis
Mechanical property lifted very big, compare and existing technology, comprcssive strength further can be lifted.When the consumption of graphene oxide is
The 0.0021% of cement quality, allyl amine replacement maleic anhydride are maximum to the performance boost of cement mortar when being 1/2.Embodiment
With embodiment 4,2 show that the consumption of allyl amine is bigger, the pressure resistance to cement mortar when graphene oxide alkene consumption is identical
Degree lifting is bigger, illustrates that distribution of the graphene oxide in cement mortar is more uniform.Although comparative example 3 can reach almost equal
Strength enhancing effect, but graphene oxide consumption is really a lot of more than embodiment.
The above is only the preferred embodiment of the present invention, it is noted that for one of ordinary skill in the art comes
Say, without departing from the concept of the premise of the invention, some modifications and variations can also be made, these belong to the present invention's
Protection domain.
Claims (10)
1. a kind of amidatioon graphene oxide modified polycarboxylic acid water reducer, it is characterised in that primary raw material component is as follows：Oxidation stone
Black alkene, methyl allyl polyoxyethylene ether, acrylic acid, allyl amine, condensing agent and activating agent, water and oxidant and reduction
Agent.
2. a kind of amidatioon graphene oxide modified polycarboxylic acid water reducer according to claim 1, it is characterised in that described
Primary raw material component is as follows by mass percentage：Graphene oxide 0.1%～0.3%, methyl allyl polyoxyethylene ether
10%～18%, acrylic acid 0.5%～1.5%, allyl amine 0.1%～0.4%, water 80%～89%, oxidant 0.1%～
0.3%th, reducing agent 0.03%～0.06%, condensing agent 0.005%～0.02% and activator 0.002%～0.02%.
3. a kind of amidatioon graphene oxide modified polycarboxylic acid water reducer according to claim 1, it is characterised in that described
A diameter of 400～the 800nm of graphene oxide layer, thickness are 1～8 layer；The methyl allyl polyoxyethylene ether molecular weight is
2200～2600g/mol.
4. a kind of amidatioon graphene oxide modified polycarboxylic acid water reducer according to claim 1, it is characterised in that described
Condensing agent is carbodiimide hydrochloride class condensing agent, and activator is N-hydroxy-succinamide.
5. a kind of preparation method of amidatioon graphene oxide modified polycarboxylic acid water reducer, it is characterised in that by primary raw material component
Mass percent is as follows：Graphene oxide 0.1%～0.3%, methyl allyl polyoxyethylene ether 10%～18%, acrylic acid
0.5%～1.5%, allyl amine 0.1%～0.4%, water 80%～89%, oxidant 0.1%～0.3%, reducing agent
0.03%～0.06%, condensing agent 0.005%～0.02% and activator 0.002%～0.02%, first by allyl amine with
Graphene oxide prepares the graphene oxide of allyl amine modification in the presence of condensing agent and activator by amidation process,
Then the graphene oxide that gained allyl amine is modified is mixed with methyl allyl polyoxyethylene ether, acrylic acid and maleic anhydride
Close, polyreaction occurs under the initiation of Oxidizing and Reducing Agents, so as to obtain the modified poly- carboxylic of amidatioon graphene oxide
Sour water reducer.
6. a kind of preparation method of amidatioon graphene oxide modified polycarboxylic acid water reducer, it is characterised in that concrete step is such as
Under：
(1) by primary raw material constituent mass percentage ratio it is：Graphene oxide 0.1%～0.3%, methyl allyl polyoxyethylene ether
10%～18%, acrylic acid 0.5%～1.5%, allyl amine 0.1%～0.4%, water 80%～89%, oxidant 0.1%～
0.3%th, reducing agent 0.03%～0.06%, condensing agent 0.005%～0.02% and activator 0.002%～0.02% are weighed
Each raw material components；And methyl allyl polyoxyethylene ether, acrylic acid, maleic anhydride, reducing agent and graphene oxide are matched somebody with somebody respectively
Make aqueous solution；
(2) condensing agent and activator are dissolved in after water, are configured to activated carboxylic liquid；By gained activated carboxylic liquid and graphene oxide
Solution hybrid reaction, is obtained the graphene oxide water solution of activated carboxylic；
(3) allyl amine is added the graphene oxide solution of step (2) gained activated carboxylic, reaction to obtain allyl amine modification
Graphene oxide；
(4) methyl allyl polyoxyethylene ether aqueous solution is stirred and temperature is warming up to for 75～80 DEG C, then Deca acrylic acid
The graphene oxide solution of the allyl amine modification of aqueous solution, maleic anhydride aqueous solution and step (3) gained and reducing agent
Aqueous solution, time for adding are 3～4 hours；
(5) after completion of dropping in step (4), gained reaction system is incubated 1.5～2.5h of ripening, Ran Houleng in 75～85 DEG C
But it is neutrality to mend alkali liquor to PH to room temperature, that is, obtain amidatioon graphene oxide modified polycarboxylic acid water reducer.
7. the preparation method of a kind of amidatioon graphene oxide modified polycarboxylic acid water reducer according to claim 6, its are special
It is 1 to levy the mol ratio in the activated carboxylic liquid for be the step (2) between condensing agent and activator, water:1:8000～
10000.
8. the preparation method of a kind of amidatioon graphene oxide modified polycarboxylic acid water reducer according to claim 6, its are special
Levy and be in the step (4), the time for adding of reducing agent aqueous solution is later than other components solution 1～5 minute, when Deca continues
Between longer than other components solution 30～60 minutes.
9. the preparation method of a kind of amidatioon graphene oxide modified polycarboxylic acid water reducer according to claim 6, its are special
Levy and be that step (1) the methyl allyl polyoxyethylene ether concentration of polymer solution is 30%～50%, the matter of acrylic acid solution
Amount concentration is 30%～50%；The mass concentration of maleic anhydride solution is 30%～50%.
10. the preparation method of a kind of amidatioon graphene oxide modified polycarboxylic acid water reducer according to claim 6, its are special
Levy be graphene oxide solution concentration be 0.29%～1%.
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