CN109942221A - Silane-modified graphene oxide chemical modification type polycarboxylate water-reducer and preparation method thereof - Google Patents
Silane-modified graphene oxide chemical modification type polycarboxylate water-reducer and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of silane-modified graphene oxide modification type polycarboxylate water-reducers and preparation method thereof, and the water-reducing agent is prepared by the following method: γ-methacryloxypropyl trimethoxy silane is uniformly mixed to complete hydrolysis with the ethanol solution of 50% concentration into silanol groups；Graphene oxide, ultrasonic disperse to evenly dispersed and heating water bath is added；To but to room temperature, be filtered by vacuum pump to it and pass through ethanol solution and washed to it；Prepared silane-modified graphene oxide and isobutene alcohol polyoxyethylene ether are subjected to aqueous free radical polymerization reaction, obtain silane-modified graphene oxide chemical modification type polycarboxylate water-reducer.Compared with prior art, the present invention has many advantages, such as strong to cement-based material peptizaiton is newly mixed, significant to hardening cement base material reinforcing effect, and preparation process is simple, and raw material is easy to get, low in cost, is suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of polycarboxylate water-reducers and preparation method thereof, more particularly, to a kind of silane-modified graphite oxide
Alkene chemical modification type polycarboxylate water-reducer and preparation method thereof.
Background technique
Graphene oxide has the characteristics that extra specific surface area and aperture is small and lamella on containing there are many functional groups, work as incorporation
When cement-based material, the gap of cement granules can be filled, reduce porosity fixed Free water simultaneously.And graphene oxide layer
On oxygen-containing functional group provide active site, controllable hydrated product and aggregated structure for hydrated cementitious crystal growth, make it
Shape and aggregate structure tend to regular orderly microstructure, lack to control the crack generated in cement matrix, hole etc.
Fall into structure and infiltration and caused by cracking phenomena, effectively improve the mechanical property and durability of cement-based material.However, at present
The problem is that graphene oxide is interfered since size is small and there is stronger Van der Waals force and hydrogen bond agglomeration easily occurs
Graphene oxide is evenly dispersed with lamella in cement matrix, and cement-based material is caused to generate defect, and the big aggregation formed
Body reduces its specific surface area, influences its effect in cement-based material.
In order to solve the problems, such as that graphene oxide is evenly dispersed in cement-based material, it is necessary to pass through the side of chemical modification
Formula prepares few lamella, small size and evenly dispersed graphene oxide dispersion, fundamentally reaches graphene oxide in water
Evenly dispersed effect in mud matrix.
Chinese patent 201310192111.2 discloses a kind of silane-modified graphene oxide chemical modification type polycarboxylic acids and subtracts
The preparation method of aqua.Specific step is as follows: first pre-oxidizing graphite, prepares graphene oxide, then by graphene oxide
Solution and polycarboxylate water-reducer pass through ultrasonication after mixing evenly and obtain graphene oxide modified polycarboxylic acid water-reducing agent.The party
Graphene oxide modified polycarboxylic acid water-reducing agent prepared by method is physical modification, and being likely encountered under different solutions ambient condition can lead
Cause graphene oxide and polycarboxylate water-reducer interaction are failed, to influence graphene oxide uniformly dividing in cement-based material
Scattered and useful effect.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of silane-modified oxidations
Graphene chemical modification type polycarboxylate water-reducer and preparation method thereof.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method of silane-modified graphene oxide chemical modification type polycarboxylate water-reducer, comprising the following steps:
(1) γ-methacryloxypropyl trimethoxy silane is uniformly mixed with the ethanol solution of 50% concentration,
Magnetic agitation 1h under 30~40 DEG C of water baths, until methoxy silane in γ-methacryloxypropyl trimethoxy silane
Complete hydrolysis is at silanol groups；
(2) graphene oxide is added in the mixed solution in step (1), ultrasonic disperse 1h to graphene oxide uniformly divides
It dissipates.
(3) magnetic agitation and heating water bath carried out to mixed liquor in step (2), 80 DEG C of heating temperature, time 5h.
(4) mixed solution in step (3) is cooled to room temperature, it is filtered by vacuum pump and passes through 50% ethanol solution
It is washed 6 times.
(5) silane-modified graphene oxide in step (4) is mixed with deionized water, passes through ultrasonic disperse 1h；
(6) pre- solvent isobutene alcohol polyoxyethylene ether is added in step (5) reaction system, then put into ammonium persulfate with
Hydrogen peroxide is mixed evenly；
(7) reaction system obtained to step (6) heats, while by pre- solvent methacrylic acid, L- Vitamin C
Acid and mercaptopropionic acid are added dropwise in reaction system respectively；
(4) after being added dropwise to complete, reaction system is sufficiently stirred, adds and neutralizes alkali neutralization to pH=6-7 to get to purpose
Product；
Isobutene alcohol polyoxyethylene ether is with 100 parts by weight timing, and the additive amount of other raw material components is specific as follows: γ-first
10~15 parts of base acryloyloxypropyltrimethoxysilane, 3~5 parts of graphene oxide, 0.2-2 parts of ammonium persulfate, hydrogen peroxide
0.5-1.2 parts, 0.3-1.0 parts of L-AA, 0.5-1.5 parts of mercaptopropionic acid；
The rate of addition of pre- solvent methacrylic acid, L-AA and chain-transferring agent meets in step (7):
Methacrylic acid control is added dropwise to complete in 1-2h；L-AA and chain-transferring agent are after methacrylic acid drips
It is added dropwise to complete in half an hour；
Pre- solvent methacrylic acid, L-AA and chain-transferring agent are aqueous solution, mass concentration in step (7)
It is 1-5%.
Preferably, methacrylic acid control is added dropwise to complete in 1-2h；L-AA and chain-transferring agent are in methacrylic acid
It drips in half an hour after and is added dropwise to complete；
Preferably, isobutene alcohol polyoxyethylene ether is with 100 parts by weight timing, and the additive amount of other raw material components is specifically such as
Under: 12~15 parts of γ-methacryloxypropyl trimethoxy silane, 4~5 parts of graphene oxide, ammonium persulfate 0.5-2
Part, 1.0-1.2 parts of hydrogen peroxide, 0.5-1.0 parts of L-AA, 0.8-1.5 parts of mercaptopropionic acid.
Preferably, one in the potassium hydroxide for neutralizing the sodium hydroxide that alkali is 30% concentration or 30% mass concentration
Kind or two kinds.
Compared with prior art, the invention has the following advantages that
(1) by introducing the siloxanes that there is chemical condensation reagentia with graphene oxide and successfully connecing siloxanes
Branch on graphene oxide, forming the graphene oxide for being rich in activity double key, and by with methacrylic acid monomer and isobutene
The copolyreaction of alcohol polyoxyethylene ether, synthesizing silane modified graphene oxide type polycarboxylate water-reducer fundamentally improve oxidation
Dispersibility of the graphene in cement-based material improves graphene oxide for newly mixing the negative shadow of cement-based material workability
It rings, improves graphene oxide to cement-based material enhancing and effect of optimization.
(2) preparation process is simple, and raw material is easy to get, low in cost, is suitable for industrialized production, and production process is simple, and nothing has
Malicious discharge of poisonous waste.
(3) silane-modified graphene oxide chemical modification type polycarboxylate water-reducer of the invention has both superpower absorption-point
It dissipates property and to hydrolysis product of cement microstructure Optimum Regulation effect, can make fresh concrete Workable, good fluidity,
Hardening cement base material even pore distribution simultaneously, overall porosity is low, and hardening cement base material density is high, and mechanical strength is high,
Durability is good.
Specific embodiment
The present invention is described in detail for specific embodiment below.
Embodiment 1
A kind of silane-modified graphene oxide chemical modification type polycarboxylate water-reducer, by the component system of following parts by weight
At: 100 parts of isobutene alcohol polyoxyethylene ether, 12 parts of γ-methacryloxypropyl trimethoxy silane, graphene oxide 5
Part, 2 parts of ammonium persulfate, 1.0 parts of hydrogen peroxide, 0.5 part of L-AA, 0.8 part of mercaptopropionic acid.
Above-mentioned water-reducing agent specific the preparation method is as follows:
γ-methacryloxypropyl trimethoxy silane is uniformly mixed with the ethanol solution of 50% concentration, 30
Magnetic agitation 1h under~40 DEG C of water baths, until methoxy silane is complete in γ-methacryloxypropyl trimethoxy silane
All-hydrolytic is at silanol groups；Graphene oxide is added into mixed solution, ultrasonic disperse 1h is evenly dispersed to graphene oxide；It is right
Mixed solution progress magnetic agitation and heating water bath, 80 DEG C of heating temperature, time 5h；Solution to be mixed is cooled to room temperature, and is led to
It crosses vacuum pump it is filtered and passes through 50% ethanol solution and it is washed 6 times；By the silane-modified graphene oxide of gained and go from
Sub- water mixing, passes through ultrasonic disperse 1h；Pre- solvent isobutene alcohol polyoxyethylene ether is added, then puts into ammonium persulfate and dioxygen
Water is mixed evenly；Reaction system is heated (80 DEG C) by water-bath, while by pre- solvent methacrylic acid, L-
Ascorbic acid and mercaptopropionic acid are added dropwise in reaction system respectively；Wherein, methacrylic acid control is added dropwise to complete in 2h；L- is anti-bad
Hematic acid and chain-transferring agent drip in half an hour after in methacrylic acid to be added dropwise to complete；It is abundant to reaction system after being added dropwise to complete
Stirring adds neutralization 30%NaOH solution and is neutralized to pH=6.5 to get purpose production is arrived when reaction system is cooled to room temperature
Object.
Embodiment 2
A kind of silane-modified polycarboxylate water-reducer of sulfate resistance competitive Adsorption type, is made of the component of following parts by weight:
100 parts of isobutene alcohol polyoxyethylene ether, 15 parts of γ-methacryloxypropyl trimethoxy silane, 4 parts of graphene oxide,
0.5 part of ammonium persulfate, 1.2 parts of hydrogen peroxide, 1.0 parts of L-AA, 0.8 part of mercaptopropionic acid.
Above-mentioned water-reducing agent specific the preparation method is as follows:
γ-methacryloxypropyl trimethoxy silane is uniformly mixed with the ethanol solution of 50% concentration, 30
Magnetic agitation 1h under~40 DEG C of water baths, until methoxy silane is complete in γ-methacryloxypropyl trimethoxy silane
All-hydrolytic is at silanol groups；Graphene oxide is added into mixed solution, ultrasonic disperse 1h is evenly dispersed to graphene oxide；It is right
Mixed solution progress magnetic agitation and heating water bath, 80 DEG C of heating temperature, time 5h；Solution to be mixed is cooled to room temperature, and is led to
It crosses vacuum pump it is filtered and passes through 50% ethanol solution and it is washed 6 times；By the silane-modified graphene oxide of gained and go from
Sub- water mixing, passes through ultrasonic disperse 1h；Pre- solvent isobutene alcohol polyoxyethylene ether is added, then puts into ammonium persulfate and dioxygen
Water is mixed evenly；Reaction system is heated (80 DEG C) by water-bath, while by pre- solvent methacrylic acid, L-
Ascorbic acid and mercaptopropionic acid are added dropwise in reaction system respectively；Wherein, methacrylic acid control is added dropwise to complete in 1.5h；L- is anti-
Bad hematic acid and chain-transferring agent drip in half an hour after in methacrylic acid to be added dropwise to complete；After being added dropwise to complete, reaction system is filled
Divide stirring, when reaction system is cooled to room temperature, adds neutralization 30%NaOH solution and be neutralized to pH=7 to get purpose production is arrived
Object.
Embodiment 3
A kind of silane-modified polycarboxylate water-reducer of sulfate resistance competitive Adsorption type, is made of the component of following parts by weight:
Isobutene alcohol polyoxyethylene ether is with 100 parts, 14 parts of γ-methacryloxypropyl trimethoxy silane, graphene oxide 4.5
Part, 1.0 parts of ammonium persulfate, 1.1 parts of hydrogen peroxide, 0.9 part of L-AA, 1.3 parts of mercaptopropionic acid.
Above-mentioned water-reducing agent specific the preparation method is as follows:
γ-methacryloxypropyl trimethoxy silane is uniformly mixed with the ethanol solution of 50% concentration, 30
Magnetic agitation 1h under~40 DEG C of water baths, until methoxy silane is complete in γ-methacryloxypropyl trimethoxy silane
All-hydrolytic is at silanol groups；Graphene oxide is added into mixed solution, ultrasonic disperse 1h is evenly dispersed to graphene oxide；It is right
Mixed solution progress magnetic agitation and heating water bath, 80 DEG C of heating temperature, time 5h；Solution to be mixed is cooled to room temperature, and is led to
It crosses vacuum pump it is filtered and passes through 50% ethanol solution and it is washed 6 times；By the silane-modified graphene oxide of gained and go from
Sub- water mixing, passes through ultrasonic disperse 1h；Pre- solvent isobutene alcohol polyoxyethylene ether is added, then puts into ammonium persulfate and dioxygen
Water is mixed evenly；Reaction system is heated (80 DEG C) by water-bath, while by pre- solvent methacrylic acid, L-
Ascorbic acid and mercaptopropionic acid are added dropwise in reaction system respectively；Wherein, methacrylic acid control is added dropwise to complete in 1h；L- is anti-bad
Hematic acid and chain-transferring agent are added dropwise to complete in 0.5h after methacrylic acid drips；After being added dropwise to complete, reaction system is sufficiently stirred
It mixes, when reaction system is cooled to room temperature, adds neutralization 30%NaOH solution and be neutralized to pH=6 to get purpose product is arrived.
Embodiment 4
By water-reducing agent made from above-described embodiment 1-3, according to GB/T8077-2000, " concrete admixture homogeneity is tested
Method " respectively measure cement paste through when fluidity, the results are shown in Table 1.And water is had detected according to GB/T50080-2002
The anti-folding of earth rubber sand, compression strength, the results are shown in Table 2.
Table 1: mix polycarboxylate water-reducer cement slurry fluidity and through when fluidity
Table 2 mixes the cement mortar mechanical strength of polycarboxylate water-reducer
In polycarboxylate water-reducer incorporation cement slurry prepared by embodiment 1-3, cement slurry fluidity and through Shi Liudong
Degree is shown in Table 1.As shown in Table 1, embodiment 1-3, which prepares polycarboxylate water-reducer, has preferable dispersion performance to cement slurry and through the time-division
Retention property is dissipated, it can negative effect of the graphene oxide to cement slurry workability very well.In addition, prepared by embodiment 1-3
Polycarboxylate water-reducer incorporation cement mortar in, the anti-folding of cement mortar 3d and 28d and compression strength are shown in Table 2. as shown in Table 2, real
The silane-modified graphene oxide chemical modification type polycarboxylate water-reducer for applying 1-3 preparation, which has cement-based material, to be significantly increased
Effect.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (3)
1. a kind of preparation method of silane-modified graphene oxide chemical modification type polycarboxylate water-reducer, which is characterized in that described
Polycarboxylate water-reducer is made up of following steps:
(1) γ-methacryloxypropyl trimethoxy silane is uniformly mixed with the ethanol solution of 50% concentration, 30~
Magnetic agitation 1h under 40 DEG C of water baths, until methoxy silane is complete in γ-methacryloxypropyl trimethoxy silane
It is hydrolyzed into silanol groups；
(2) graphene oxide is added in the mixed solution in step (1), ultrasonic disperse 1h is evenly dispersed to graphene oxide.
(3) magnetic agitation and heating water bath carried out to mixed liquor in step (2), 80 DEG C of heating temperature, time 5h.
(4) mixed solution in step (3) is cooled to room temperature, it is filtered by vacuum pump and passes through 50% ethanol solution to it
Washing 6 times.
(5) silane-modified graphene oxide in step (4) is mixed with deionized water, passes through ultrasonic disperse 1h；
(6) pre- solvent isobutene alcohol polyoxyethylene ether is added in step (5) reaction system, then puts into ammonium persulfate and dioxygen
Water is mixed evenly；
(7) reaction system obtained to step (6) heats, at the same by pre- solvent methacrylic acid, L-AA and
Mercaptopropionic acid is added dropwise in reaction system respectively；
(4) after being added dropwise to complete, reaction system is sufficiently stirred, neutralization alkali neutralization is added and is produced to pH=6-7 to get to purpose
Object；
Isobutene alcohol polyoxyethylene ether is with 100 parts by weight timing, and the additive amount of other raw material components is specific as follows: γ-methyl-prop
10~15 parts of alkene acryloxypropylethoxysilane trimethoxy silane, 3~5 parts of graphene oxide, 0.2-2 parts of ammonium persulfate, hydrogen peroxide 0.5-
1.2 parts, 0.3-1.0 parts of L-AA, 0.5-1.5 parts of mercaptopropionic acid；
The rate of addition of pre- solvent methacrylic acid, L-AA and chain-transferring agent meets in step (7):
Methacrylic acid control is added dropwise to complete in 1-2h；L-AA and chain-transferring agent drip later half small in methacrylic acid
When interior be added dropwise to complete；
Pre- solvent methacrylic acid, L-AA and chain-transferring agent are aqueous solution in step (7), and mass concentration is
1-5%.
2. a kind of preparation side of silane-modified graphene oxide chemical modification type polycarboxylate water-reducer according to claim 1
Method, which is characterized in that for isobutene alcohol polyoxyethylene ether with 100 parts by weight timing, the additive amount of other raw material components is specific as follows:
It is 12~15 parts of γ-methacryloxypropyl trimethoxy silane, 4~5 parts of graphene oxide, 0.5-2 parts of ammonium persulfate, double
1.0-1.2 parts of oxygen water, 0.5-1.0 parts of L-AA, 0.8-1.5 parts of mercaptopropionic acid.
3. the system of any a kind of silane-modified graphene oxide chemical modification type polycarboxylate water-reducer according to claim 1
Preparation Method, which is characterized in that the neutralization alkali is one or more of sodium hydroxide or potassium hydroxide.
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| CN111363138A (en) * | 2020-05-18 | 2020-07-03 | 天津冶建特种材料有限公司 | Novel polyether and preparation method and application thereof |
| CN111978010A (en) * | 2020-09-09 | 2020-11-24 | 西安市质量与标准化研究院 | Silicon-containing graphene oxide magnetic polycarboxylate water reducer containing allyl alcohol polyoxyethylene ether |
| CN112062912A (en) * | 2020-09-14 | 2020-12-11 | 西安市质量与标准化研究院 | Silicon-containing magnetic polycarboxylate water reducer containing isobutenol polyoxyethylene ether |
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| CN112939498A (en) * | 2021-01-29 | 2021-06-11 | 南京工业大学 | Preparation method and application of modified graphene oxide |
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| CN111978010A (en) * | 2020-09-09 | 2020-11-24 | 西安市质量与标准化研究院 | Silicon-containing graphene oxide magnetic polycarboxylate water reducer containing allyl alcohol polyoxyethylene ether |
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| CN112062912A (en) * | 2020-09-14 | 2020-12-11 | 西安市质量与标准化研究院 | Silicon-containing magnetic polycarboxylate water reducer containing isobutenol polyoxyethylene ether |
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| CN112707668A (en) * | 2020-09-15 | 2021-04-27 | 科之杰新材料集团有限公司 | Modified polyol acrylate, shrinkage-reducing polycarboxylate superplasticizer and preparation method thereof |
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| CN112062913A (en) * | 2020-09-16 | 2020-12-11 | 西安市质量与标准化研究院 | Silicon-containing graphene oxide magnetic polycarboxylate water reducer containing prenyl polyoxyethylene ether |
| CN112939498A (en) * | 2021-01-29 | 2021-06-11 | 南京工业大学 | Preparation method and application of modified graphene oxide |
| CN113248661B (en) * | 2021-06-02 | 2022-06-24 | 甘肃新纪元建材有限公司 | Corrosion inhibition type polycarboxylate superplasticizer and preparation method thereof |
| CN113248661A (en) * | 2021-06-02 | 2021-08-13 | 甘肃新纪元建材有限公司 | Corrosion inhibition type polycarboxylate superplasticizer and preparation method thereof |
| CN113896453A (en) * | 2021-10-27 | 2022-01-07 | 北京石墨烯技术研究院有限公司 | Modified graphene composite material and preparation method thereof, cement reinforcing agent and application thereof |
| CN115073100A (en) * | 2022-07-12 | 2022-09-20 | 江西省萍乡市华东出口电瓷有限公司 | High-strength durable porcelain insulator cement adhesive and preparation method thereof |
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Application publication date: 20190628 |