CN106496438B - A kind of amidation graphene oxide modified polycarboxylic acid water-reducing agent and preparation method thereof - Google Patents
A kind of amidation graphene oxide modified polycarboxylic acid water-reducing agent and preparation method thereof Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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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
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Abstract
The invention discloses a kind of amidation graphene oxide modified polycarboxylic acid water-reducing agent, 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 that allyl amine and graphene oxide are first prepared to the graphene oxide of 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, polymerisation occurs under the initiation of Oxidizing and Reducing Agents, to obtain amidation graphene oxide modified polycarboxylic acid water-reducing agent.The present invention's mainly utilizes the amidation process between allyl amine and graphene oxide, graphene oxide two-dimensional nano-lamellar structure is combined closely with polycarboxylate water-reducer molecule, to preferably disperse when graphene oxide being enable to be applied in concrete, the water-reducing agent properties of product of synthesis are more stablized.
Description
Technical field
The present invention relates to a kind of amidation graphene oxide modified polycarboxylic acid water-reducing agents and preparation method thereof, belong to chemical engineering of materials
Field.
Background technology
Water-reducing agent is a kind of high molecular polymer being applied in the cementitious materials such as concrete, can be polymerize by various of monomer and be made
.Obtain more closely knit so as to improve the working performance of concrete since it contains many active groups, mechanical property is more
Good concrete.By the development of several generations water-reducing agent, poly carboxylic acid series water reducer, which has been substituted naphthalene water reducer, to be become in concrete
In most widely used product.
Graphene oxide is two-dimensional nano lamella structure, itself has the elasticity modulus of superelevation, is 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 plays the role of stronger Van der Waals force due to dimensional effect between lamellar structure, therefore is applied to pass through one in concrete
The section time can reunite the performance for influencing concrete between nanoscale twins.
Invention content
The technical problem to be solved by the present invention is to provide a kind of amidation in view of the deficiency of the prior art
Graphene oxide modified polycarboxylic acid water-reducing agent and preparation method thereof improves dispersibility of the graphene oxide in concrete, to
Dosage of the graphene oxide in concrete application is reduced, and improves the mechanical property and durability of concrete.
The present invention be solve the problems, such as it is set forth above used by technical solution be：
A kind of amidation graphene oxide modified polycarboxylic acid water-reducing agent, 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, above-mentioned amidation graphene oxide modified polycarboxylic acid water-reducing agent, primary raw material component press quality hundred
Divide as follows than counting：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%.
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, initiation 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 hydrogensulfite.
Preferably, amidation condensing agent of the present invention is 1- ethyls-(3- dimethylaminopropyls) phosphinylidyne diimmonium salt
Hydrochlorate EDC.HCL, activator are n-hydroxysuccinimide NHS.
The preparation method of amidation graphene oxide modified polycarboxylic acid water-reducing agent of the present invention：By said ratio, first will
Allyl amine prepares allyl amine modification under the action of condensing agent and activator with graphene oxide by amidation process
Graphene oxide, the graphene oxide for then modifying gained allyl amine and methyl allyl polyoxyethylene ether, acrylic acid with
And maleic anhydride mixing, polymerisation occurs under the initiation of Oxidizing and Reducing Agents, stone is aoxidized to obtain amidation
Black alkene modified polycarboxylic acid water-reducing agent.More specifically steps are as follows for it：
(1) raw material specification and proportioning are pressed, each raw material component is weighed；And by methyl allyl polyoxyethylene ether, acrylic acid and
Maleic anhydride, reducing agent and graphene oxide are configured to aqueous solution respectively；
(2) after condensing agent and activator being dissolved in water, it is configured to activated carboxylic liquid；By gained activated carboxylic liquid and oxidation stone
The graphene oxide water solution of activated carboxylic is made in black alkene solution hybrid reaction；
(3) allyl amine is added to the graphene oxide solution of activated carboxylic obtained by step (2), allyl amine is obtained by the reaction
The graphene oxide of modification；
(4) it is 75~80 DEG C to stir methyl allyl polyoxyethylene ether aqueous solution and be warming up to temperature, is then added dropwise third
The graphene oxide solution and go back that allyl amine obtained by olefin(e) acid aqueous solution, maleic anhydride aqueous solution and step (3) is modified
Former agent aqueous solution, time for adding are 3~4 hours；
(5) after being added dropwise in step (4), by gained reaction system in 75~85 DEG C of heat preservation 1.5~2.5h of curing, so
Postcooling to room temperature mend lye to pH be neutral to get to amidation graphene oxide modified polycarboxylic acid water-reducing agent.
By said program, the molar ratio in the activated carboxylic liquid of the step (2) between condensing agent and activator, water is 1:
1:8000~10000.
By said program, in the step (4), the time for adding of reducing agent aqueous solution is later than other and 1~5 point of component is added dropwise
Clock.
By said program, in the step (4), the time for adding of reducing agent sodium hydrogensulfite is required than acrylic acid, Malaysia
The time for adding of acid anhydrides and the graphene oxide of allyl amine modification is slightly long.Acrylic acid aqueous solution, maleic anhydride aqueous solution, alkene
It is 2~3 hours that the amine-modified graphene oxide solution of propyl, which is added dropwise the duration, reducing agent solution time for adding continues 3.2~
3.5 hour.
By said program, in the step (5), pH adjusting agent is lye, commonly uses the sodium hydroxide that mass concentration is 10%
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 reducing agent solution is 0.5%~1%.
Preferably, the mass concentration of the graphene oxide solution is 0.2%~2%.
Water-reducing agent of the present invention is by methyl allyl polyoxyethylene ether polymeric monomer and acrylic acid and allyl amine
And pass through the poly- of the pectination for polymerizeing main chain and side chain of the formation with certain length of double bond between four kinds of monomers of maleic anhydride
Close object；Meanwhile by the backbone of graphene oxide layer structural integrity to polycarboxylate water-reducer, and its approach is to pass through
It is realized by amidation process between amino related on related carboxyl and allyl amine on graphene oxide.The present invention is logical
It crosses in the molecular structure that this mode is formed, bonding action is stronger between the diminishing agent molecule of graphene oxide and pectinate texture,
It 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 amide occur between allyl amine
Change reaction.In order to reduce the generation of the reaction, the present invention solves with the following method：Using first by allyl amine and graphite oxide
Alkene reaction simultaneously keeps reaction abundant as possible, reduces allyl amine in reaction system, makes the more graphene oxide allyl amines of generation
Compound, the product after in addition reacting remove catalyst EDC hydrochlorides in reaction system by washing；In addition, charging when
It waits to use and acrylic acid solution is first added dropwise, then the graphene oxide solution and reducing agent of the allyl amine modification being prepared is added dropwise
Solution can reduce the probability that amidation process occurs between allyl amine and acrylic acid in this way.Moreover, reducing agent sodium hydrogensulfite
Time for adding require the time for adding for the graphene oxide modified than acrylic acid minor comonomer and allyl amine slightly long.This be by
It is gradually to be added dropwise to enter reaction system in minor comonomer acrylic acid solution, therefore it is required that there is initiation in reaction system from beginning to end
Agent；If the time for adding of reducing agent is shorter than the time for adding of minor comonomer, the minor comonomer being added afterwards may be because of not causing
The initiation of agent and polymerisation can not be completed.
Compared with prior art, the beneficial effects of the invention are as follows：
1, the method is mainly characterized in that using the amidation process between allyl amine and graphene oxide, stone will be aoxidized
Black alkene two-dimensional nano lamella structure is combined closely with polycarboxylate water-reducer molecule, to make graphene oxide answering in concrete
Used time can preferably disperse, and the water-reducing agent properties of product of synthesis are more stablized.
2, water-reducing agent of the present invention so that graphene oxide is evenly dispersed during concrete optimum, on the one hand applies
Durability, the mechanical property of concrete are significantly improved in concrete；On the other hand since the dispersion of graphene oxide is more equal
It is even, compared to the method for being mixed with water-reducing agent, being used for concrete after ultrasound, oxygen in heretofore described modified polycarboxylic acid water-reducing agent
The dosage of graphite alkene is relatively less.
3, the amidation graphene oxide modified polycarboxylic acid water-reducing agent volume that the present invention synthesizes is low, good product performance, diminishing
Rate is high, better than commercially available water-reducing agent water-reducing effect under same volume, and the loss after 0.5 hour is also smaller.
4, the mechanical property for the amidation graphene oxide modified polycarboxylic acid Water-reducing Admixtures To Cements glue sand that the present invention synthesizes carries
Liter is very big, and comparing can further be promoted with existing technology, compression strength.
5, product synthesis technology of the present invention is simple, and selected synthesis material is all safe and non-toxic, and production process is also without harmful
Substance release, safety and environmental protection.
Specific implementation mode
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, 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 amidation graphene oxide modified polycarboxylic acid water-reducing agent, raw material components are as follows as mass fraction：Oxidation
Graphene 0.141% (0.1g), methyl allyl polyoxyethylene ether 16.908% (12g), acrylic acid 1.014% (1.08g), horse
Come acid anhydrides 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 hydrochlorides 0.006% (0.0045g), NHS 0.004%
(0.003g)。
The preparation method of above-mentioned amidation graphene oxide modified polycarboxylic acid water-reducing agent, specific steps are as follows：
(1) 4.5mgEDC.HCL is weighed in 25ml beakers, 5ml water is added thereto and is sufficiently stirred, then to mixing
3mgNHS is added in solution, ultrasound obtains activated carboxylic liquid in 10 minutes after stirring fully；
(2) it takes the graphene oxide water solution that 34.48g mass fractions are 0.29% in reactor, is added while stirring
Gained activated carboxylic liquid in step (1), is added 0.1425g allyl amines after mixing, after reacting 4 hours, obtains allyl
Amine-modified graphene oxide solution, centrifugation, washing save backup after removing activating solution；
(3) it is 50% solution to take 12g methyl allyl polyoxyethylene ether compound concentrations, and 0.19g oxidant mistakes are added
Ammonium sulfate；It is 50% solution to take 0.72g acrylic acid compound concentrations；Take 0.735 maleic anhydride be configured to a concentration of 50% it is molten
Liquid is simultaneously mixed into minor comonomer solution with acrylic acid solution；Take 0.042g sodium hydrogensulfites be configured to a concentration of 1% reducing agent it is molten
Liquid；
(4) methyl allyl polyoxyethylene ether solution is added in reactor, it is 80 DEG C to stir and be warming up to temperature；Then
Minor comonomer solution, the allyl amine being prepared in beginning a dropping step (2) after one minute modification are slowly added dropwise into reactor
Graphene oxide solution and reducing agent solution；When the graphene oxide solution of allyl amine modification is added dropwise with minor comonomer solution
Between be 3 hours, reducing agent time for adding be 3.5 hours；
(5) after being added dropwise in step (4), by gained reaction system in 80 DEG C temperature curing 2 hours, after complete reaction
It is cooled to room temperature and adjusts its pH to 7 with 10% sodium hydroxide solution and subtract to get to amidation graphene oxide modified polycarboxylic acid
Aqua.
Embodiment 2
A kind of amidation graphene oxide modified polycarboxylic acid water-reducing agent, raw material components are as follows as mass fraction：Oxidation
Graphene 0.181% (0.2g), methyl allyl polyoxyethylene ether 10.861% (12g), acrylic acid 0.652% (0.72g), horse
Come acid anhydrides 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 hydrochlorides 0.016% (0.018g), NHS0.011%
(0.012g)。
The preparation method of above-mentioned amidation graphene oxide modified polycarboxylic acid water-reducing agent, specific steps are as follows：
(1) it weighs 18mgEDC.HCL and 20ml water in 25ml beakers, is added thereto and is sufficiently stirred, then to mixing
12mgNHS is added in solution, ultrasound obtains activated carboxylic liquid in 10 minutes after stirring fully；
(2) it takes the graphene oxide water solution that 68.96g mass fractions are 0.29% in reactor, is added while stirring
Gained activated carboxylic liquid in step (1), is added 0.1425g allyl amines after mixing, after reacting 4 hours, obtains allyl
Amine-modified graphene oxide solution, centrifugation, washing save backup after removing activating solution；
(3) it is 50% solution to take 12g methyl allyl polyoxyethylene ether compound concentrations, and 0.19g oxidant mistakes are added
Ammonium sulfate；It is 50% solution to take 0.72g acrylic acid compound concentrations；Take 0.735 maleic anhydride be configured to a concentration of 50% it is molten
Liquid is simultaneously mixed into minor comonomer solution with acrylic acid solution；Take 0.042g sodium hydrogensulfites be configured to a concentration of 1% reducing agent it is molten
Liquid；
(4) methyl allyl polyoxyethylene ether solution is added in reactor, it is 80 DEG C to stir and be warming up to temperature；Then
Minor comonomer solution, the allyl amine being prepared in beginning a dropping step (2) after one minute modification are slowly added dropwise into reactor
Graphene oxide solution and reducing agent solution；When the graphene oxide solution of allyl amine modification is added dropwise with minor comonomer solution
Between be 3 hours, reducing agent time for adding be 3.5 hours；
(5) after being added dropwise in step (4), by gained reaction system in 80 DEG C temperature curing 2 hours, after complete reaction
It is cooled to room temperature and adjusts its pH to 7 with 10% sodium hydroxide solution and subtract to get to amidation graphene oxide modified polycarboxylic acid
Aqua.
Embodiment 3
A kind of amidation graphene oxide modified polycarboxylic acid water-reducing agent, raw material components are as follows as mass fraction：Oxidation
Graphene 0.142% (0.1g), methyl allyl polyoxyethylene ether 16.991% (12g), acrylic acid 1.019% (0.72g), horse
Come acid anhydrides 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 hydrochlorides 0.006% (0.0045g), NHS0.004%
(0.003g)。
The preparation method of above-mentioned amidation graphene oxide modified polycarboxylic acid water-reducing agent, specific steps are as follows：
(1) it weighs 4.5mgEDC.HCL and 20ml water in 25ml beakers, is added thereto and is sufficiently stirred, then to mixing
3mgNHS is added in solution, ultrasound obtains activated carboxylic liquid in 10 minutes after stirring fully；
(2) it takes the graphene oxide water solution that 34.48g mass fractions are 0.29% in reactor, is added while stirring
Gained activated carboxylic liquid in step (1), is added 0.285g allyl amines after mixing, after reacting 4 hours, obtains allyl amine
The graphene oxide solution of modification, centrifugation, washing save backup after removing activating solution；
(3) it is 50% solution to take 12g methyl allyl polyoxyethylene ether compound concentrations, and 0.19g oxidant mistakes are added
Ammonium sulfate；It is 50% solution to take 0.72g acrylic acid compound concentrations；0.49 maleic anhydride is taken to be configured to a concentration of 50% solution
And it is mixed into minor comonomer solution with acrylic acid solution；0.042g sodium hydrogensulfites are taken to be configured to a concentration of 1% reducing agent solution；
(4) methyl allyl polyoxyethylene ether solution is added in reactor, it is 80 DEG C to stir and be warming up to temperature；Then
Minor comonomer solution, the allyl amine being prepared in beginning a dropping step (2) after one minute modification are slowly added dropwise into reactor
Graphene oxide solution and reducing agent solution；When the graphene oxide solution of allyl amine modification is added dropwise with minor comonomer solution
Between be 3 hours, reducing agent time for adding be 3.5 hours；
(5) after being added dropwise in step (4), by gained reaction system in 80 DEG C temperature curing 2 hours, after complete reaction
It is cooled to room temperature and adjusts its pH to 7 with 10% sodium hydroxide solution and subtract to get to amidation graphene oxide modified polycarboxylic acid
Aqua.
Embodiment 4
A kind of amidation graphene oxide modified polycarboxylic acid water-reducing agent, raw material components are as follows as mass fraction：Oxidation
Graphene 0.182% (0.2g), methyl allyl polyoxyethylene ether 10.896% (12g), acrylic acid 0.654% (0.72g), horse
Come acid anhydrides 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 hydrochlorides 0.016% (0.018g), NHS 0.011% (0.012g).
The preparation method of above-mentioned amidation graphene oxide modified polycarboxylic acid water-reducing agent, specific steps are as follows：
(1) it weighs 18mgEDC.HCL and 20ml water in 25ml beakers, is added thereto and is sufficiently stirred, then to mixing
12mgNHS is added in solution, ultrasound obtains activated carboxylic liquid in 10 minutes after stirring fully；
(2) it takes the graphene oxide water solution that 68.96g mass fractions are 0.29% in reactor, is added while stirring
Gained activated carboxylic liquid in step (1), is added 0.285g allyl amines after mixing, after reacting 4 hours, obtains allyl amine
The graphene oxide solution of modification, centrifugation, washing save backup after removing activating solution；
(3) it is 50% solution to take 12g methyl allyl polyoxyethylene ether compound concentrations, and 0.19g oxidant mistakes are added
Ammonium sulfate；It is 50% solution to take 0.72g acrylic acid compound concentrations；0.49 maleic anhydride is taken to be configured to a concentration of 50% solution
And it is mixed into minor comonomer solution with acrylic acid solution；0.042g sodium hydrogensulfites are taken to be configured to a concentration of 1% reducing agent solution；
(4) methyl allyl polyoxyethylene ether solution is added in reactor, it is 80 DEG C to stir and be warming up to temperature；Then
Minor comonomer solution, the allyl amine being prepared in beginning a dropping step (2) after one minute modification are slowly added dropwise into reactor
Graphene oxide solution and reducing agent solution；When the graphene oxide solution of allyl amine modification is added dropwise with minor comonomer solution
Between be 3 hours, reducing agent time for adding be 3.5 hours；
(5) after being added dropwise in step (4), by gained reaction system in 80 DEG C temperature curing 2 hours, after complete reaction
It is cooled to room temperature and adjusts its pH to 7 with 10% sodium hydroxide solution and subtract to get to amidation graphene oxide modified polycarboxylic acid
Aqua.
In order to prove the performance of the compound polycarboxylate water-reducer of graphene oxide of the present invention, in above-described embodiment
The water-reducing agent of synthesis is according to GBT 8077-2012《Methods for testing uniformity of concrete admixture》It is real to carry out flowing degree of net paste of cement
It tests.Test result is as shown in table 1.Comparative example 1 is using being not added with synthesized polycarboxylic acids in the case of graphene oxide in experiment
The result measured when water-reducing agent.
1 flowing degree of net paste of cement test result of table
As seen from the results in Table 1：The amidation graphene oxide modified polycarboxylic acid water-reducing agent volume that the present invention synthesizes is low, on an equal basis
It is better than commercially available water-reducing agent water-reducing effect under volume, and the loss after 0.5 hour is also smaller.Since embodiment 1,2 is allyl
Base amine 1/4 replaces maleic anhydride, and carboxyl quantity is reduced in long-chain molecule, embodiment 1,2 paste flowing degree knots under same volume
Fruit is almost equal with comparative example；When allyl amine 1/2 replaces maleic anhydride (embodiment 3,4), carboxyl on product long-chain molecule
Quantity is further reduced, and paste flowing degree is reduced 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-reducing agent synthesized in above-described embodiment according to GB/T17671-1999《Test method for strength of hydraulic cement mortar》Carry out power
Learn performance test.Test result is as shown in table 2.Wherein, cement used is new 42.5 grade cement of China, the ratio of mud 0.3；Diminishing
Agent volume is 1.2%；Comparative example 2 is using the result obtained by general water-reducing agent；Comparative example 3 is using general water-reducing agent and to mix
Graphene oxide experimental results.
2 cement mortar intensity test result of table
As seen from the results in Table 2：The amidation graphene oxide modified polycarboxylic acid Water-reducing Admixtures To Cements glue sand that the present invention synthesizes
Mechanical property promoted it is very big, comparing can further be promoted with existing technology, compression strength.When the dosage of graphene oxide is
The 0.0021% of cement quality, it is maximum to the performance boost of cement mortar when allyl amine replaces maleic anhydride to be 1/2.Embodiment
2 show that the dosage of allyl amine is bigger when graphene oxide alkene dosage is identical with embodiment 4, to the pressure resistance of cement mortar
Degree promotion is bigger, illustrates that distribution of the graphene oxide in cement mortar is more uniform.Although comparative example 3 can reach almost same
Strength enhancing effect, but graphene oxide dosage is really many more than embodiment.
The above is only a preferred embodiment of the present invention, it is noted that come for those of ordinary skill in the art
It says, without departing from the concept of the premise of the invention, several modifications and variations can also be made, these belong to the present invention's
Protection domain.
Claims (8)
1. a kind of preparation method of amidation graphene oxide modified polycarboxylic acid water-reducing agent, it is characterised in that press 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 and graphene oxide in condensing agent and activator
Under the action of by amidation process prepare allyl amine modification graphene oxide, the oxygen for then modifying gained allyl amine
Graphite alkene is mixed with methyl allyl polyoxyethylene ether, acrylic acid and maleic anhydride, in the initiation of Oxidizing and Reducing Agents
Effect is lower to occur polymerisation, to obtain amidation graphene oxide modified polycarboxylic acid water-reducing agent.
2. a kind of preparation method of amidation graphene oxide modified polycarboxylic acid water-reducing agent according to claim 1, special
Sign is that a diameter of 400~800nm of the graphene oxide layer, thickness are 1~8 layer；The methacrylic polyoxyethylene
Ether molecular weight is 2200~2600g/mol.
3. a kind of preparation method of amidation graphene oxide modified polycarboxylic acid water-reducing agent according to claim 1, special
Sign is that the condensing agent is carbodiimide hydrochloride class condensing agent, and activator is n-hydroxysuccinimide.
4. a kind of preparation method of amidation graphene oxide modified polycarboxylic acid water-reducing agent, it is characterised in that specific step is such as
Under：
（1）It is by primary raw material constituent 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%, reduction
Agent 0.03%~0.06%, condensing agent 0.005%~0.02% and activator 0.002%~0.02% weigh each raw material component；And it will
Methyl allyl polyoxyethylene ether, acrylic acid, maleic anhydride, reducing agent and graphene oxide are configured to aqueous solution respectively；
（2）After condensing agent and activator are dissolved in water, it is configured to activated carboxylic liquid；By gained activated carboxylic liquid and graphene oxide
The graphene oxide water solution of activated carboxylic is made in solution hybrid reaction；
（3）Step is added in allyl amine（2）Allyl amine modification is obtained by the reaction in the graphene oxide solution of gained activated carboxylic
Graphene oxide；
（4）It is 75~80 DEG C that methyl allyl polyoxyethylene ether aqueous solution, which is stirred, and is warming up to temperature, and acrylic acid is then added dropwise
Aqueous solution, maleic anhydride aqueous solution and step（3）The graphene oxide solution and reducing agent of the allyl amine modification of gained
Aqueous solution, time for adding are 3~4 hours；
（5）Wait for step（4）In be added dropwise after, by gained reaction system in 75~85 DEG C heat preservation curing 1.5~2.5h, it is then cold
But to room temperature mend lye to PH be neutral to get to amidation graphene oxide modified polycarboxylic acid water-reducing agent.
5. a kind of preparation method of amidation graphene oxide modified polycarboxylic acid water-reducing agent according to claim 4, special
Sign is the step（2）Activated carboxylic liquid in molar ratio between condensing agent and activator, water be 1:1:8000~
10000。
6. a kind of preparation method of amidation graphene oxide modified polycarboxylic acid water-reducing agent according to claim 4, special
Sign is the step（4）In, the time for adding of reducing agent aqueous solution is later than other components solution 1~5 minute, when being added dropwise lasting
Between it is 30~60 minutes longer than other components solution.
7. a kind of preparation method of amidation graphene oxide modified polycarboxylic acid water-reducing agent according to claim 4, special
Sign is step（1）The methyl allyl polyoxyethylene ether concentration of polymer solution is 30%~50%, the quality of acrylic acid solution
A concentration of 30%~50%；The mass concentration of maleic anhydride solution is 30%~50%.
8. a kind of preparation method of amidation graphene oxide modified polycarboxylic acid water-reducing agent according to claim 4, special
Sign is a concentration of the 0.29%~1% of graphene oxide solution.
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