CN102351449B - Nonionic surfactant-modified machine-made sand and preparation method thereof - Google Patents
Nonionic surfactant-modified machine-made sand and preparation method thereof Download PDFInfo
- Publication number
- CN102351449B CN102351449B CN 201110179554 CN201110179554A CN102351449B CN 102351449 B CN102351449 B CN 102351449B CN 201110179554 CN201110179554 CN 201110179554 CN 201110179554 A CN201110179554 A CN 201110179554A CN 102351449 B CN102351449 B CN 102351449B
- Authority
- CN
- China
- Prior art keywords
- made sand
- machine
- coupling agent
- nonionic surfactant
- modified machine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- AWGHNBZIYLQVNE-UHFFFAOYSA-N CC(C(OCCC[N](OC)(OC)OC1CCCCCCCC1)=O)=C Chemical compound CC(C(OCCC[N](OC)(OC)OC1CCCCCCCC1)=O)=C AWGHNBZIYLQVNE-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention discloses nonionic surfactant-modified machine-made sand and a preparation method thereof. The preparation method of the nonionic surfactant-modified machine-made sand comprises that 1, machine-made sand is subjected to surface hydroxylation treatment to form hydroxylated machine-made sand; and 2, the hydroxylated machine-made sand is modified by a coupling agent; and through a grafting reaction, the surface of the coupling agent-modified hydroxylated machine-made sand is grafted with a nonionic surfactant to form the nonionic surfactant-modified machine-made sand. The nonionic surfactant-modified machine-made sand can be widely utilized for the building fields of bridges, roads, railways and the like.
Description
One, technical field
The present invention relates to a kind of material of construction and preparation method thereof, exactly is a kind of nonionic surfactant-modified machine-made sand and preparation method thereof.
Two, background technology
Machine-made Sand is to make particle diameter less than the particle of 5mm by rock through explosion and crushing, Mechanical Crushing, screening.Machine-made Sand is rich in corner angle, and is cleaner, and it both had been different from natural sand, is different from again general aggregate chips, is a kind of desirable concrete fine aggregate.The most yellow ground that adopt of China's preparation normal concrete only just can adopt Machine-made Sand when lacking qualified yellow ground.But external concrete also adopts Machine-made Sand simultaneously except using yellow ground.China since nineteen ninety-four, by having carried out experimental study and engineering is used to the physicals of Machine-made Sand and mineral composition with the concrete crushing strength of Machine-made Sand preparation, tensile splitting strength, Young's modulus, folding strength, shrinkage and creep etc., practice show Machine-made Sand substitute the natural sand concrete batching be technically feasible, be rational economically.
The Machine-made Sand particle is coarse, and content of stone powder is high, and this certainly will weaken concrete flowability, increases water requirement, under identical condition, prepare the concrete of the identical slump, Machine-made Sand increases 5-10kg/m3 than natural sand water requirement, causes newly mixing mixed earth cohesiveness, poor water retention property is easily emanated bleeding.And solve such problem in engineering, and add high efficiency water reducing agent in the concrete the inside, add high efficiency water reducing agent and increased cost, if some active groups on the Machine-made Sand surface grafting, Machine-made Sand itself just becomes water reducer, improves simultaneously concrete quality, has reduced again cost.At present, the domestic temporary transient not achievement in research of relevant synthesis technique aspect.
Three, summary of the invention
The present invention aims to provide a kind of nonionic surfactant-modified machine-made sand and preparation method thereof.Technical problem to be solved is the surface that nonionic surface active agent is grafted on Machine-made Sand.
Technical solution problem of the present invention adopts following technical scheme:
The characteristics of a kind of nonionic surfactant-modified machine-made sand of the present invention are: described nonionic surfactant-modified machine-made sand is at first the hydroxylation processing to be carried out on the surface of Machine-made Sand to obtain the hydroxylation Machine-made Sand, subsequently by coupling agent modified hydroxylation Machine-made Sand and by the graft reaction nonionic surfactant-modified machine-made sand that nonionic surface active agent obtains on the surface grafting of coupling agent modified Machine-made Sand.
Nonionic surfactant-modified machine-made sand of the present invention is characterized in that: described nonionic surface active agent is polyalkylene glycol acrylate monomethyl ether ester (MPA).
The preparation method's of nonionic surfactant-modified machine-made sand of the present invention characteristics are to operate according to the following steps:
The preparation of a, hydroxylation Machine-made Sand
Machine-made Sand is placed the vitriol oil of mass concentration 98%, then the hydrogen peroxide solution that adds mass concentration 30%, stirring reaction 15 minutes, add deionized water after the centrifugal desolventizing and left standstill 15-20 minute, successively after filtration, obtain the hydroxylation Machine-made Sand behind the deionized water wash, centrifugal, vacuum-drying;
The volume ratio of the described vitriol oil and hydrogen peroxide solution is 6: 4-7: 3;
The preparation of b, coupling agent modified Machine-made Sand
Step a gained hydroxylation Machine-made Sand 8-10g, coupling agent 8-10mL, hydroquinone of polymerization retarder 0.5g are added in the flask, at 80-90 ℃ of stirring reaction 24-36 hour, reaction was finished by obtaining coupling agent modified Machine-made Sand after centrifugal, deionized water supersound washing and the vacuum-drying take toluene as solvent;
The preparation of c, nonionic surfactant-modified machine-made sand
The coupling agent modified Machine-made Sand 3-5g of step b gained, nonionic surface active agent 1-2g, initiator A IBN 0.05g mixed and take toluene as solvent, in 90-95 ℃ of stirring reaction 8-10 hour, reaction was finished by obtaining nonionic surfactant-modified machine-made sand after centrifugal, deionized water supersound washing and the vacuum-drying.
The preparation method's of nonionic surfactant-modified machine-made sand of the present invention characteristics also are: described nonionic surface active agent is polyalkylene glycol acrylate monomethyl ether ester.
The preparation method's of nonionic surfactant-modified machine-made sand of the present invention characteristics also are: described coupling agent is silane coupling agent.
The preparation method's of nonionic surfactant-modified machine-made sand of the present invention characteristics also are: described coupling agent is 3-(methacryloxypropyl) propyl trimethoxy silicane (KH570).
Reaction by Piranha solution and Machine-made Sand in the inventive method prepares the hydroxylation Machine-made Sand.Piranha solution is the mixing solutions of the hydrogen peroxide of the vitriol oil of mass concentration 98% and mass concentration 30%, and the volume ratio of the general vitriol oil and hydrogen peroxide solution is 6: 4-7: 3.Work as H
2SO
4With H
2O
2Mix, generate permonosulphuric acid, can same H
2O
2Reaction obtains OH and HSO
4Reactive group.These groups can make SiO
2The Si-O-Si bond rupture, then generate Si-O-H, finish the hydroxylation on Machine-made Sand surface by this reaction.
Take coupling agent KH570 as example, the synthetic route of the coupling agent modified Machine-made Sand of the present invention and nonionic surfactant-modified machine-made sand is as follows:
N represents the polymerization degree of poly glycol monomethyl ether in the formula, and m, k represent respectively the polymerization degree of Machine-made Sand and polyalkylene glycol acrylate monomethyl ether ester after the coupling.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, matrix material of the present invention with Machine-made Sand as reactant, wide material sources, use cost is low, has advantages of economy;
2, use the mixed solution treatment mechanism sand surface of hydrogen peroxide and the vitriol oil among the preparation method of the present invention, the Machine-made Sand behind the surface hydroxylation can react with organism;
3, the polymkeric substance of the synthetic and large monomer of graft acrylic acid poly glycol monomethyl ether ester of the Machine-made Sand of coupling described in the inventive method, temperature of reaction is low, mild condition;
4, preparation method's of the present invention aftertreatment is simple, and temperature of reaction is low, and the industrialization cost is little.
5, it is coarse that the present invention adopts the particle of Machine-made Sand, and this must weaken concrete flowability, and nonionogenic tenside on the Machine-made Sand surface grafting improves Machine-made Sand mobile, has reduced concrete water consumption.
Four, description of drawings
Fig. 1 is the infrared contrast spectrogram of silane coupler modified Machine-made Sand and nonionic surfactant-modified machine-made sand.A is silane coupler modified Machine-made Sand among the figure, and B is nonionic surfactant-modified machine-made sand.The infrared principal character peak of nonionic surface active agent polyalkylene glycol acrylate monomethyl ether ester is the carboxyl peak, in the drawings among the A at 1640cm
-1Go out to have the carbon-carbon double bond peak, B is at 1720cm in the drawings
-1The obvious carboxyl peak that gets appears in the place, shows that the rear carbon-carbon double bond of reaction disappears, and the carboxyl peak occurs.A and the contrast of B infrared data show that nonionic surface active agent polyalkylene glycol acrylate monomethyl ether ester successfully is grafted to the Machine-made Sand surface.
Fig. 2 is the TG comparison diagram of unmodified Machine-made Sand and nonionic surfactant-modified machine-made sand.A is unmodified Machine-made Sand among the figure, and B is nonionic surfactant-modified machine-made sand.Weightlessness is arranged twice, and A there is not obvious weightless peak in B.Be the fracture of ester group key the first time of B about 300 ℃, when 750 ℃ of left and right sides, be the Si-O bond rupture for the second time, weight-loss curve from figure, can find out the temperature range weightlessness 10% in room temperature to 500 ℃, illustrate that nonionic surface active agent polyalkylene glycol acrylate monomethyl ether ester is grafted to the Machine-made Sand surface.
Fig. 3 is the XPS spectrum figure of nonionic surfactant-modified machine-made sand.Figure is that the swarming of C1s is processed, 284.8ev wherein, 286.3ev, 288.5ev belong to respectively C-H/C-C, C-O, O-C=O, and do not have the Machine-made Sand surface of grafting the peak of C1s can not occur, the existence of these keys has proved that also nonionic surface active agent polyalkylene glycol acrylate monomethyl ether ester successfully is grafted to the Machine-made Sand surface.
Five, embodiment
Non-limiting examples of the present invention is described below:
1, polyalkylene glycol acrylate monomethyl ether ester synthesis
In the there-necked flask that thermometer, agitator, water-and-oil separator are housed, add vinylformic acid, poly glycol monomethyl ether (molecular weight 1000), tosic acid and Resorcinol, take benzene as solvent, be warming up to 95-100 ℃ of reaction 9h after stirring, desolventizing and unreacted monomer obtain polyalkylene glycol acrylate monomethyl ether ester (MPA), and be for subsequent use;
Wherein the mol ratio of vinylformic acid and poly glycol monomethyl ether is 2.5: 1; The addition of tosic acid is 2.5% of vinylformic acid and poly glycol monomethyl ether quality; The addition of Resorcinol is 2% of vinylformic acid quality.
Reaction formula is as follows:
HO(CH
2CH
2O)nCH
3+CH
3CH
2COOH→CH
3CH
2COO(CH
2CH
2O)nCH
3+H
2O
2, the preparation of hydroxylation Machine-made Sand
The 15gd Machine-made Sand is placed the vitriol oil of 20-30mL mass concentration 98%, then the hydrogen peroxide solution that slowly adds 15-20mL mass concentration 30%, stirring reaction 15 minutes, adding deionized water after the centrifugal desolventizing left standstill 15-20 minute, successively after filtration, deionized water wash and centrifugal treating, repeat filtration, washing and centrifugal three final vacuum dryings and obtain the hydroxylation Machine-made Sand;
3, the preparation of coupling agent modified Machine-made Sand
Hydroxylation Machine-made Sand 8-10g, KH570 8-10mL, hydroquinone of polymerization retarder 0.5g are added in the flask, take toluene as solvent at 80-90 ℃ of stirring reaction 24-36 hour, reaction is finished by centrifugal and deionized water supersound washing, and repeated centrifugation, three final vacuum dryings of washing obtain coupling agent modified Machine-made Sand;
4, the preparation of nonionic surfactant-modified machine-made sand
Coupling agent modified Machine-made Sand 3-5g, polyalkylene glycol acrylate monomethyl ether ester 1-2g, initiator A IBN 0.05g mixed and take toluene as solvent, in 90-95 ℃ of stirring reaction 8-10 hour, reaction is finished by centrifugal, deionized water supersound washing, and repeated centrifugation, three final vacuum dryings of washing obtain nonionic surfactant-modified machine-made sand.
With cement and the poly carboxylic acid series water reducer of the quality such as nonionic surfactant-modified machine-made sand replacement of the present invention preparation, only starch the flowing property test result and see Table 1.The pulp flowage performance test is pressed cement and is the reference cement of " GB8076-2008 concrete admixture " standard code, and mixing water is tap water.The water reducer volume be the water reducer solid account for cement quality 0.2%, water cement ratio is 0.29.Flowing degree of net paste of cement and measure with reference to " GB 8077-2000 Methods for testing uniformity of concrete admixture " through time loss and to test.As can be seen from Table 1, along with the continuous increase of nonionic surfactant-modified machine-made sand addition, the flowing degree of net paste of cement that obtains is increasing, disperses the successful of cement to improve.
The pulp flowage performance of the poly carboxylic acid series water reducer of the quality cement such as the nonionic surfactant-modified machine-made sand replacement of table 1, different addition quantity and 0.2% volume
Claims (3)
1. nonionic surfactant-modified machine-made sand, it is characterized in that: described nonionic surfactant-modified machine-made sand is at first the hydroxylation processing to be carried out on the surface of Machine-made Sand to obtain the hydroxylation Machine-made Sand, subsequently by coupling agent modified hydroxylation Machine-made Sand and by the graft reaction nonionic surfactant-modified machine-made sand that nonionic surface active agent obtains on the surface grafting of coupling agent modified Machine-made Sand;
Described nonionic surface active agent is polyalkylene glycol acrylate monomethyl ether ester;
Described nonionic surfactant-modified machine-made sand is the modification mechanism sand for preparing by the following method:
The preparation of a, hydroxylation Machine-made Sand
Machine-made Sand is placed the vitriol oil of mass concentration 98%, then the hydrogen peroxide solution that adds mass concentration 30%, stirring reaction 15 minutes adds deionized water and left standstill 15-20 minute after the centrifugal desolventizing, successively after filtration, obtain the hydroxylation Machine-made Sand behind the deionized water wash, centrifugal, vacuum-drying;
The preparation of b, coupling agent modified Machine-made Sand
Step a gained hydroxylation Machine-made Sand 8-10g, coupling agent 8-10mL, hydroquinone of polymerization retarder 0.5g are added in the flask, at 80-90 ℃ of stirring reaction 24-36 hour, reaction was finished by obtaining coupling agent modified Machine-made Sand after centrifugal, deionized water supersound washing and the vacuum-drying take toluene as solvent;
The preparation of c, nonionic surfactant-modified machine-made sand
The coupling agent modified Machine-made Sand 3-5g of step b gained, nonionic surface active agent 1-2g, initiator A IBN 0.05g mixed and take toluene as solvent, in 90-95 ℃ of stirring reaction 8-10 hour, reaction was finished by obtaining nonionic surfactant-modified machine-made sand after centrifugal, deionized water supersound washing and the vacuum-drying.
2. the preparation method of a nonionic surfactant-modified machine-made sand as claimed in claim 1 is characterized in that operating according to the following steps:
The preparation of a, hydroxylation Machine-made Sand
Machine-made Sand is placed the vitriol oil of mass concentration 98%, then the hydrogen peroxide solution that adds mass concentration 30%, stirring reaction 15 minutes adds deionized water and left standstill 15-20 minute after the centrifugal desolventizing, successively after filtration, obtain the hydroxylation Machine-made Sand behind the deionized water wash, centrifugal, vacuum-drying;
The preparation of b, coupling agent modified Machine-made Sand
Step a gained hydroxylation Machine-made Sand 8-10g, coupling agent 8-10mL, hydroquinone of polymerization retarder 0.5g are added in the flask, at 80-90 ℃ of stirring reaction 24-36 hour, reaction was finished by obtaining coupling agent modified Machine-made Sand after centrifugal, deionized water supersound washing and the vacuum-drying take toluene as solvent; Described coupling agent is silane coupling agent;
The preparation of c, nonionic surfactant-modified machine-made sand
The coupling agent modified Machine-made Sand 3-5g of step b gained, nonionic surface active agent 1-2g, initiator A IBN 0.05g mixed and take toluene as solvent, in 90-95 ℃ of stirring reaction 8-10 hour, reaction was finished by obtaining nonionic surfactant-modified machine-made sand after centrifugal, deionized water supersound washing and the vacuum-drying;
Described nonionic surface active agent is polyalkylene glycol acrylate monomethyl ether ester;
Described coupling agent is silane coupling agent.
3. preparation method according to claim 2, it is characterized in that: described coupling agent is 3-(methacryloxypropyl) propyl trimethoxy silicane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110179554 CN102351449B (en) | 2011-06-29 | 2011-06-29 | Nonionic surfactant-modified machine-made sand and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110179554 CN102351449B (en) | 2011-06-29 | 2011-06-29 | Nonionic surfactant-modified machine-made sand and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102351449A CN102351449A (en) | 2012-02-15 |
| CN102351449B true CN102351449B (en) | 2013-01-09 |
Family
ID=45575129
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110179554 Expired - Fee Related CN102351449B (en) | 2011-06-29 | 2011-06-29 | Nonionic surfactant-modified machine-made sand and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102351449B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304175B (en) * | 2013-06-14 | 2014-10-08 | 合肥工业大学 | Preparation method of cationic surfactant modified fly ash |
| CN103304177B (en) * | 2013-06-14 | 2014-10-08 | 合肥工业大学 | Preparation method of modified silicon powder |
| CN103588404B (en) * | 2013-10-18 | 2015-05-20 | 北京新奥混凝土集团有限公司 | Method for processing recycled aggregate and method for preparing high performance concrete using same |
| CN105312484B (en) * | 2014-06-16 | 2017-09-29 | 彰武县联信铸造硅砂有限公司 | A kind of silica sand surface pre-treating process and its application |
| CN104446043A (en) * | 2014-11-17 | 2015-03-25 | 合肥工业大学 | Method for preparing high-performance modified mountain powder |
| CN104446073B (en) * | 2014-11-28 | 2016-08-31 | 合肥工业大学 | A kind of preparation method of water soluble polymer surface graft modification Machine-made Sand |
| CN110272219A (en) * | 2019-08-08 | 2019-09-24 | 德庆县九市镇德鑫石矿有限公司 | It is a kind of for substituting the manufacturing method of the Machine-made Sand of natural sand |
| CN110467366B (en) * | 2019-08-23 | 2022-01-04 | 广东中南建设有限公司 | Energy-saving and environment-friendly machine-made sand for building construction |
| CN112125608B (en) * | 2020-09-18 | 2021-07-13 | 台州远巢新型建材有限公司 | High-strength anti-permeability concrete and preparation method thereof |
| CN112430042A (en) * | 2020-12-11 | 2021-03-02 | 保利长大工程有限公司 | Low-rubber high-flow-state high-performance concrete and preparation method thereof |
| CN113152777B (en) * | 2021-04-23 | 2022-05-24 | 安徽省建筑科学研究设计院 | Fabricated concrete brick based on machine-made sand material and preparation method thereof |
| CN113683353B (en) * | 2021-09-11 | 2022-06-17 | 杭州三中新型建材科技有限公司 | Ultrahigh pumping concrete applying machine-made sand and preparation method thereof |
| CN114230271A (en) * | 2021-12-09 | 2022-03-25 | 科之杰新材料集团(广东)有限公司 | Masonry mortar and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6750276B2 (en) * | 1996-08-05 | 2004-06-15 | Arch Chemicals, Inc. | Waterborne soft-feeling coating composition with high gloss |
| CN1986043A (en) * | 2005-12-20 | 2007-06-27 | 中国科学院兰州化学物理研究所 | Preparing process of liquid chromatography stuffing |
| CN101885592B (en) * | 2010-06-10 | 2012-11-21 | 武汉大学 | Mold material and preparation method and application thereof |
-
2011
- 2011-06-29 CN CN 201110179554 patent/CN102351449B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN102351449A (en) | 2012-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102351449B (en) | Nonionic surfactant-modified machine-made sand and preparation method thereof | |
| CN100595173C (en) | Early strength polycarboxylic acid high performance dehydragent and method for preparing same | |
| CN107285707B (en) | coarse aggregate-containing C220 strength grade ultrahigh-performance fiber concrete and preparation method thereof | |
| CN102532435B (en) | Polycarboxylene high-performance water reducing agent and preparation method thereof | |
| CN105418013B (en) | A kind of technique for producing green concrete with latter admixing method | |
| CN109574582B (en) | Pervious concrete with heavy metal ion adsorption capacity and preparation method thereof | |
| CN103980433B (en) | Generating vinyl carboxylate base co-polymer concrete thickening material and preparation method thereof | |
| CN109133692A (en) | A kind of composite modified Machine-made Sand and preparation method thereof | |
| CN102351450B (en) | Amphiphilic mechanism sand and preparation method thereof | |
| CN112430001A (en) | Artificial granite waste residue based cement mortar reinforcing agent and preparation method thereof | |
| CN108558309B (en) | Curb prepared by processing solid waste blast furnace slag and fly ash | |
| CN106810101B (en) | The preparation method of graphene oxide enhanced cement grinding aid | |
| CN112679142B (en) | High-strength epoxy mortar and preparation method thereof | |
| CN102690093A (en) | High-strength water resistance phosphogypsum steam-cured brick and preparation method thereof | |
| CN104479085B (en) | Modified polycarboxylate water-reducer of a kind of sodium sulfanilate and preparation method thereof | |
| CN116253543B (en) | Concrete containing recycled concrete aggregate and wood fiber aggregate | |
| CN114292042B (en) | Preparation method of high-hydrophilicity comb-shaped polymer grafting machine-made sand | |
| JP2017178739A (en) | Method for manufacturing rapid hardening concrete | |
| CN108585671B (en) | Engineering cement-based composite material and preparation method thereof | |
| Deng et al. | Study on the Preparation and Performance of Hexa-carbon Polycarboxylate Superplasticizer with High Workability | |
| CN109251269A (en) | The preparation method of modified natural chitin biology base high-performance polycarboxylic acids water reducing agent | |
| CN111646724A (en) | Water reducing agent for high-strength concrete and preparation method thereof | |
| CN112573865A (en) | High-strength high-impermeability few-layer graphene concrete and preparation method thereof | |
| CN114014992B (en) | Mutually exclusive/associative polycarboxylate superplasticizer and preparation method and application thereof | |
| CN112266433A (en) | Soil sacrificial agent for polycarboxylate superplasticizer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130109 Termination date: 20200629 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |