CN102351450A - Amphiphilic mechanism sand and preparation method thereof - Google Patents
Amphiphilic mechanism sand and preparation method thereof Download PDFInfo
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- CN102351450A CN102351450A CN2011101849731A CN201110184973A CN102351450A CN 102351450 A CN102351450 A CN 102351450A CN 2011101849731 A CN2011101849731 A CN 2011101849731A CN 201110184973 A CN201110184973 A CN 201110184973A CN 102351450 A CN102351450 A CN 102351450A
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Abstract
The invention discloses amphiphilic mechanism sand and a preparation method thereof. The amphiphilic mechanism sand is prepared according to the following steps that: firstly, the surface of the mechanism sand is hydroxylated to obtain the hydroxylation mechanism sand, then, the hydroxylated mechanism sand is modified through coupling agents to obtain the coupling agent modified mechanism sand, next, the coupling agent modified mechanism sand is grafted and polymerized with dimethylamino ethyl methacrylate to obtain poly dimethylamino ethyl methacrylate grafted mechanism sand, and finally, the amphiphilic mechanism sand is obtained through quaterisation. The amphiphilic mechanism sand has the advantages that amphiphilic active agents are grafted on the surface of the mechanism sand, the flowability of the mechanism sand is improved, and the water consumption of concrete is reduced. The preparation method has the advantages that the reaction temperature is low, the condition is mild, the post treatment is simple, and the industrial cost is low.
Description
One, technical field
The present invention relates to modification mechanism sand and preparation method thereof, exactly is amphipathic machine-processed sand and preparation method thereof.
Two, background technology
Mechanism sand is processed by Mechanical Crushing, screening; Particle diameter is less than the rock particles of 4.75mm; With advantages such as its wide material sources, production cost are low, replace natural sands in a lot of areas at present and obtain using comparatively widely, solve the non-renewable shortcoming with long-distance transportation of natural sand resource.At present, the research of composite organic-inorganic material has obtained very big progress, and is widely used in fields such as optics, electricity, magnetics, biology, a lot of inorganic material such as SiO
2, TiO
2, carbon nanotube, silicon chip etc. all can be used to prepare composite organic-inorganic material.Yet in composite organic-inorganic material, the performance of inorganic substance directly influences the use of matrix material with originating.
Mechanism sand particle is coarse, and content of stone powder is high, and this certainly will weaken concrete flowability, increases water requirement, under identical condition, prepares the concrete of the identical slump, and machine-processed sand increases (5-10) kg/m than natural sand water requirement
3, causing newly mixing and mix the earth cohesiveness, poor water retention property is prone to segregation, bleeding.And on engineering, solve such problem, 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 machine-processed sand surface grafting; Mechanism sand itself just becomes water reducer, improves quality of concrete simultaneously, has reduced cost again.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 amphipathic machine-processed sand and preparation method thereof, to improve the flowability of machine-processed sand, reduces concrete water consumption.Technical problem to be solved is an amphipathic group on the surface grafting of machine-processed sand.
Technical solution problem of the present invention adopts following technical scheme:
The characteristics of the amphipathic machine-processed sand of the present invention are: said amphipathic machine-processed sand is at first the hydroxylation processing to be carried out on the surface of machine-processed sand to obtain hydroxylation mechanism sand; Obtain coupling agent modified machine-processed sand through coupling agent modified hydroxylation mechanism sand subsequently; Make coupling agent modified machine-processed sand and Dimethylaminoethyl Methacrylate graft polymerization obtain polymethyl acrylic acid dimethylin ethyl ester grafting mechanism sand through graft polymerization reaction again, after quaterisation obtains amphipathic machine-processed sand.
The preparing method's of the amphipathic machine-processed sand of the present invention characteristics are to operate according to the following steps:
The preparation of a, hydroxylation mechanism sand
Under the ice-water bath condition, the hydrogen peroxide solution of mass concentration 30% joined in the vitriol oil of mass concentration 98% mixed solution; Liquid to be mixed after being cooled to room temperature joins in the mixed solution machine-processed sand in 50 ℃ of heating 5 minutes; Filtration washing then, dry hydroxylation mechanism sand under 50 ℃ of nitrogen protections;
The volume ratio of the said vitriol oil and hydrogen peroxide solution is 6: 4-7: 3;
The preparation of b, coupling agent modified machine-processed sand
Step a gained hydroxylation mechanism sand 1-3g, coupling agent 1-3g and hydroquinone of polymerization retarder 0.5-1.5g are added in the flask; With 50mL toluene be solvent at 50-80 ℃ of stirring reaction 5-10 hour, reaction is accomplished after obtain coupling agent modified machine-processed sand after centrifugal, deionized water supersound washing and the room temperature vacuum-drying;
The preparation of c, polymethyl acrylic acid dimethylin ethyl ester grafting mechanism sand
In 50mL toluene, add 0.03-0.09g initiator benzoyl peroxide and the coupling agent modified machine-processed sand of 1-3g; Dispersed with stirring evenly and feed nitrogen; Drip the 10-30mL dimethylaminoethyl methacrylate; Control reaction temperature 80-110 ℃ of stirring reaction 12 hours will react products therefrom centrifugation, washing and vacuum-drying and obtain polymethyl acrylic acid dimethylin ethyl ester grafting mechanism sand;
The preparation of d, amphipathic machine-processed sand
In the 50mL tetrahydrofuran (THF), add hexyl bromide 1 bromohexane 1.5-4.5mL and polymethyl acrylic acid dimethylin ethyl ester grafting mechanism sand 0.5-1.5g; Reacted 12-18 hour down in 20-50 ℃; Reaction finishes that the back is separated, washing and under vacuum condition drying at room temperature 24 hours, obtain amphipathic machine-processed sand.
The preparing method's of the amphipathic machine-processed sand of the present invention characteristics also are: said coupling agent is a silane coupling agent.
The preparing method's of the amphipathic machine-processed sand of the present invention characteristics also are: said coupling agent is 3-(methacryloxypropyl) propyl trimethoxy silicane.
Amphipathic machine-processed sand among the present invention has hydrophilic preferably and lipophilicity, can be compatible to water-based material and oily material preferably, and the reaction product separate easily has wide range of applications.
Pass through the prepared in reaction hydroxylation mechanism sand of Piranha solution and machine-processed sand in the inventive method.Piranha solution is the mixing solutions of ydrogen peroxide 50 of the vitriol oil and the mass concentration 30% of mass concentration 98%, 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, generate Si-O-H then, accomplish the hydroxylation on machine-processed sand surface through this reaction.
With coupling agent KH570 is example, and the synthetic route of coupling agent modified machine-processed sand of the present invention and polymethyl acrylic acid dimethylin ethyl ester grafting mechanism sand is following:
N representes the polymerization degree of polymethyl acrylic acid dimethylaminoethyl in the formula, and m representes the polymerization degree of coupling agent modified machine-processed sand.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, the raw material sources of the amphipathic machine-processed sand of the present invention are extensive, and use cost is low, have the advantage of economy.
2, preparing method's temperature of reaction of the present invention is low, mild condition, and aftertreatment is simple, and the industrialization cost is little.
3, the amphipathic machine-processed sand of the present invention amphipathic promoting agent on machine-processed sand surface grafting, it is mobile to improve machine-processed sand, has reduced concrete water consumption.
Four, description of drawings
Fig. 1 is the infrared contrast spectrogram that amphipathic machine-processed sand prepares each step products in the process.Curve a is unmodified machine-processed sand among the figure, and curve b is coupling agent modified machine-processed sand, and curve c is a polymethyl acrylic acid dimethylin ethyl ester grafting mechanism sand, and curve d is amphipathic machine-processed sand.Can find out 1000-1250cm from Fig. 1 a
-1Near strong absorption peak is arranged, similar with the stretching vibration peak of Si-O-Si, this is at all SiO
2Can see in the sample, can judge roughly in the machine-processed sand that is adopted in this experiment and contain SiO
2Composition.From Fig. 1 b, can see, 2856 and 2935cm
-1Near absorption peak is arranged, this is because the introducing of coupling agent kh-570; At 1727cm
-1There is a weak absorption peak at the place, because the absorption peak here is the characteristic absorbance peak position of C=O, so can illustrate in the machine-processed sand sample article of graft modification and contain the C=O key.Can find out from Fig. 1 c, 2935 and 1466cm
-1Near tangible absorption peak is arranged, and 1727cm
-1The absorption peak at place obviously increases, this all with the DMAEMA structure of matter in carbochain relevant with the C=O key, illustrate DMAEMA with the coupling agent kh-570 structure in C=C pair key polymerization reaction take places, polyreaction successfully realizes.Can find out 2856 and 2935cm from Fig. 1 d
-1Near absorption peak increase clearly, 1466 and 1727cm
-1The absorption peak at place also exists simultaneously, illustrates that quaterisation introduced long carbochain in the structure of matrix material, thereby the charateristic avsorption band of C-C key and c h bond is significantly increased.Amphipathic molecule successfully is grafted to machine-processed sand surface in sum.
Fig. 2 is the TG comparison diagram that amphipathic machine-processed sand prepares each step products of process.Curve a is unmodified machine-processed sand among the figure, and curve b is coupling agent modified machine-processed sand, and curve c is a polymethyl acrylic acid dimethylin ethyl ester grafting mechanism sand, and curve d is amphipathic machine-processed sand.From Fig. 2 a, can find out, be about 2.1% at the thermal weight loss of sample below 120 ℃, this possibly be to be produced by the thermosteresis that machine-processed sand surface adsorption water and other volatile components cause; Along with the rising of temperature, the thermal weight loss trend of sample is slow, and when temperature was increased to 800 ℃, the thermal weight loss of sample was 7%.Can find out that from Fig. 2 b when temperature was increased to 800 ℃, coupling mechanism sand had part weightless, is about 7.8%, with unmodified machine-processed sand facies than (7%), the thermal weight loss difference is 0.8%.Can find out among Fig. 2 c; When temperature is elevated to 800 ℃; The thermal weight loss of polymethyl acrylic acid dimethylin ethyl ester grafting mechanism sand is about 11.4%; The thermal weight loss of product is compared with previous stage; 3.6% difference is arranged, we can say that from above-mentioned difference express contract has 3.6% polymethyl acrylic acid dimethylin ethyl ester to be grafted on machine-processed sand surface.Can find out that from Fig. 2 d when temperature was increased to 800 ℃, sample had 13% thermal weight loss approximately, promptly have 1.6% organism to be introduced in the structure of matrix material through quaterisation.In sum, through series of chemical, there is 10% organism approximately on the surface of machine-processed sand.
Fig. 3 is the XPS spectrum figure of the amphipathic machine-processed sand for preparing of the present invention.As can be seen from the figure, wherein have respectively: silicon (152eV, Si (2s); 102eV, Si (2p)), oxygen (531eV, O (1s)), carbon (284eV, C (1s)), nitrogen (401eV, N (1s)), bromine (169eV, Br (3p); 66eV, Br (3d)) several elements, and this conclusion is consistent with description before.Fig. 4 is two swarming figure of N 1s, respectively 339.3 and 401.7eV near two swarmings appear, represent N
+With the C-N key; Fig. 5 is the swarming figure of C 1s, and as can be seen from the figure it has four swarmings, 284.4,285.6,286.7, near the 288.4eV, represents C-Si respectively, C-H/C-C, C-O/C-N, C=O key.Wherein, N among Fig. 4
+Appearance with C-Si, C-Br/C-N, C=O among the existence of C-N key and Fig. 5 is illustrated in the amphipathic machine-processed sand of synthetic surface and has above-mentioned chemical combination key, illustrates that the amphipathic machine-processed sand of target product has prepared success.
Five, embodiment
Embodiment 1:
1, under the ice-water bath condition, the hydrogen peroxide solution of 4mL mass concentration 30% joined in the vitriol oil of 6mL mass concentration 98% mixed solution; Liquid to be mixed after being cooled to room temperature joins in the mixed solution machine-processed sand 2g in 50 ℃ of heating 5 minutes; Filtration washing then, dry hydroxylation mechanism sand under 50 ℃ of nitrogen protections.
2,1g hydroxylation mechanism sand, 1g3-(methacryloxypropyl) propyl trimethoxy silicane (KH-570) and hydroquinone of polymerization retarder 0.5g are dissolved in the 50mL toluene; 80 ℃ were reacted 5 hours down; The washing of centrifugation afterwards, vacuum-drying obtained coupling agent modified machine-processed sand in 24 hours under the room temperature.
3, in the 50mL toluene solvant, add coupling agent modified machine-processed sand of 1g and 0.03g initiator benzoyl peroxide; Back feeding nitrogen is uniformly dispersed; Drip the 10mL dimethylaminoethyl methacrylate; Controlled temperature is 80 ℃ of reactions 12 hours, and reaction finishes back centrifugation, washing and vacuum-drying and obtains polymethyl acrylic acid dimethylin ethyl ester grafting mechanism sand.
4, hexyl bromide 1 bromohexane and the 0.5g polymethyl acrylic acid dimethylin ethyl ester grafting mechanism sand with 1.5mL joins in the 50mL tetrahydrofuran (THF); 20 ℃ were reacted 18 hours down; Reaction finishes the back centrifugation and washs for several times with tetrahydrofuran (THF); Drying at room temperature is 24 hours under vacuum condition, obtains amphipathic machine-processed sand buff powder at last.
Embodiment 2:
1, under the ice-water bath condition, the hydrogen peroxide solution of 8mL mass concentration 30% joined in the vitriol oil of 12mL mass concentration 98% mixed solution; Liquid to be mixed after being cooled to room temperature joins in the mixed solution machine-processed sand 4g in 50 ℃ of heating 5 minutes; Filtration washing then, dry hydroxylation mechanism sand under 50 ℃ of nitrogen protections.
2,2g hydroxylation mechanism sand, 2g3-(methacryloxypropyl) propyl trimethoxy silicane (KH-570) and hydroquinone of polymerization retarder 1g are dissolved in the 50mL toluene; 70 ℃ were reacted 6 hours down; The washing of centrifugation afterwards, vacuum-drying obtained coupling agent modified machine-processed sand in 24 hours under the room temperature.
3, in the 50mL toluene solvant, add coupling agent modified machine-processed sand of 2g and 0.06g initiator benzoyl peroxide; Back feeding nitrogen is uniformly dispersed; Drip the 20mL dimethylaminoethyl methacrylate; Controlled temperature is 110 ℃ of reactions 12 hours, and reaction finishes back centrifugation, washing and vacuum-drying and obtains polymethyl acrylic acid dimethylin ethyl ester grafting mechanism sand.
4, hexyl bromide 1 bromohexane and the 1g polymethyl acrylic acid dimethylin ethyl ester grafting mechanism sand with 3mL joins in the 50mL tetrahydrofuran (THF); 50 ℃ were reacted 12 hours down; Reaction finishes the back centrifugation and washs for several times with tetrahydrofuran (THF); Drying at room temperature is 24 hours under vacuum condition, obtains amphipathic machine-processed sand buff powder at last.
Embodiment 3:
1, under the ice-water bath condition, the hydrogen peroxide solution of 12mL mass concentration 30% joined in the vitriol oil of 18mL mass concentration 98% mixed solution; Liquid to be mixed after being cooled to room temperature joins in the mixed solution machine-processed sand 6g in 50 ℃ of heating 5 minutes; Filtration washing then, dry hydroxylation mechanism sand under 50 ℃ of nitrogen protections.
2,3g hydroxylation mechanism sand, 3g3-(methacryloxypropyl) propyl trimethoxy silicane (KH-570) and hydroquinone of polymerization retarder 1.5g are dissolved in the 50mL toluene; 60 ℃ were reacted 5 hours down; The washing of centrifugation afterwards, vacuum-drying obtained coupling agent modified machine-processed sand in 24 hours under the room temperature.
3, in the 50mL toluene solvant, add coupling agent modified machine-processed sand of 3g and 0.09g initiator benzoyl peroxide; Back feeding nitrogen is uniformly dispersed; Drip the 10mL dimethylaminoethyl methacrylate; Controlled temperature is 90 ℃ of reactions 12 hours, and reaction finishes back centrifugation, washing and vacuum-drying and obtains polymethyl acrylic acid dimethylin ethyl ester grafting mechanism sand.
4, hexyl bromide 1 bromohexane and the 1.5g polymethyl acrylic acid dimethylin ethyl ester grafting mechanism sand with 4.5mL joins in the 50mL tetrahydrofuran (THF); 50 ℃ were reacted 12 hours down; Reaction finishes the back centrifugation and washs for several times with tetrahydrofuran (THF); Drying at room temperature is 24 hours under vacuum condition, obtains amphipathic machine-processed sand buff powder at last.
With the cement and the poly carboxylic acid series water reducer of the quality such as amphipathic machine-processed sand replacement of the present invention preparation, starch the flowing property test result only and see table 1.The reference cement of cement for " GB8076-2008 concrete admixture " standard code pressed in the test of cement paste flowing property, and mixing water is a tap water.The water reducer volume accounts for 0.2% of cement quality for the water reducer solid, and 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.Can find out that by table 1 along with the continuous increase of amphipathic machine-processed sand addition, the flowing degree of net paste of cement that obtains is increasing, disperse the effect of cement obviously to improve.
The cement paste flowing property of the poly carboxylic acid series water reducer of quality cement such as the amphipathic machine-processed sand replacement of table 1, different volumes and 0.2% volume
| Amphipathic machine-processed sand consumption/g | Cement consumption/g | Consumptive use of water normal consistence/g | Clean slurry degree of mobilization/ |
| 0 | 300 | 87 | 290×290 |
| 6 | 294 | 87 | 292×292 |
| 12 | 288 | 87 | 295×295 |
| 18 | 282 | 87 | 298×298 |
| 24 | 276 | 87 | 300×300 |
| 30 | 270 | 87 | 302×302 |
Claims (4)
1. amphipathic machine-processed sand; It is characterized in that: said amphipathic machine-processed sand is at first the hydroxylation processing to be carried out on the surface of machine-processed sand to obtain hydroxylation mechanism sand; Obtain coupling agent modified machine-processed sand through coupling agent modified hydroxylation mechanism sand subsequently; Make coupling agent modified machine-processed sand and Dimethylaminoethyl Methacrylate graft polymerization obtain polymethyl acrylic acid dimethylin ethyl ester grafting mechanism sand through graft polymerization reaction again, after quaterisation obtains amphipathic machine-processed sand.
2. the preparation method of an amphipathic machine-processed sand as claimed in claim 1 is characterized in that operating according to the following steps:
The preparation of a, hydroxylation mechanism sand
Under the ice-water bath condition, the hydrogen peroxide solution of mass concentration 30% joined in the vitriol oil of mass concentration 98% mixed solution; Liquid to be mixed after being cooled to room temperature joins in the mixed solution machine-processed sand in 50 ℃ of heating 5 minutes; Filtration washing then, dry hydroxylation mechanism sand under 50 ℃ of nitrogen protections;
The volume ratio of the said vitriol oil and hydrogen peroxide solution is 6: 4-7: 3;
The preparation of b, coupling agent modified machine-processed sand
Step a gained hydroxylation mechanism sand 1-3g, coupling agent 1-3g and hydroquinone of polymerization retarder 0.5-1.5g are added in the flask; With 50mL toluene be solvent at 50-80 ℃ of stirring reaction 5-10 hour, reaction is accomplished after obtain coupling agent modified machine-processed sand after centrifugal, deionized water supersound washing and the room temperature vacuum-drying;
The preparation of c, polymethyl acrylic acid dimethylin ethyl ester grafting mechanism sand
In 50mL toluene, add 0.03-0.09g initiator benzoyl peroxide and the coupling agent modified machine-processed sand of 1-3g; Dispersed with stirring evenly and feed nitrogen; Drip the 10-30mL dimethylaminoethyl methacrylate; Control reaction temperature 80-110 ℃ of stirring reaction 12 hours will react products therefrom centrifugation, washing and vacuum-drying and obtain polymethyl acrylic acid dimethylin ethyl ester grafting mechanism sand;
The preparation of d, amphipathic machine-processed sand
In the 50mL tetrahydrofuran (THF), add hexyl bromide 1 bromohexane 1.5-4.5mL and polymethyl acrylic acid dimethylin ethyl ester grafting mechanism sand 0.5-1.5g; Reacted 12-18 hour down in 20-50 ℃; Reaction finishes that the back is separated, washing and under vacuum condition drying at room temperature 24 hours, obtain amphipathic machine-processed sand.
3. preparation method according to claim 2 is characterized in that: said coupling agent is a silane coupling agent.
4. preparation method according to claim 3 is characterized in that: said coupling agent is 3-(methacryloxypropyl) propyl trimethoxy silicane.
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Cited By (5)
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| CN104446073A (en) * | 2014-11-28 | 2015-03-25 | 合肥工业大学 | Preparation method of water-soluble macromolecular surface-grafted modified machine-made sand |
| CN107469463A (en) * | 2017-08-11 | 2017-12-15 | 河北工程大学 | A kind of preparation method of compound hydrophilic modifying quartz sand filter media |
| CN112979197A (en) * | 2021-02-21 | 2021-06-18 | 谢真 | Machine-made sand and preparation method thereof |
| CN113979663A (en) * | 2021-12-06 | 2022-01-28 | 广东浪淘砂新型材料有限公司 | Sandstone regulator and preparation method and application thereof |
| CN116496027A (en) * | 2023-06-26 | 2023-07-28 | 河北福威建材科技有限公司 | Application of tailing water washing machine-made sand in concrete |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104446073A (en) * | 2014-11-28 | 2015-03-25 | 合肥工业大学 | Preparation method of water-soluble macromolecular surface-grafted modified machine-made sand |
| CN107469463A (en) * | 2017-08-11 | 2017-12-15 | 河北工程大学 | A kind of preparation method of compound hydrophilic modifying quartz sand filter media |
| CN107469463B (en) * | 2017-08-11 | 2021-09-17 | 河北工程大学 | Preparation method of composite hydrophilic modified quartz sand filter material |
| CN112979197A (en) * | 2021-02-21 | 2021-06-18 | 谢真 | Machine-made sand and preparation method thereof |
| CN113979663A (en) * | 2021-12-06 | 2022-01-28 | 广东浪淘砂新型材料有限公司 | Sandstone regulator and preparation method and application thereof |
| CN113979663B (en) * | 2021-12-06 | 2022-06-24 | 广东浪淘砂新型材料有限公司 | Sandstone regulator and preparation method and application thereof |
| CN116496027A (en) * | 2023-06-26 | 2023-07-28 | 河北福威建材科技有限公司 | Application of tailing water washing machine-made sand in concrete |
| CN116496027B (en) * | 2023-06-26 | 2023-09-05 | 河北福威建材科技有限公司 | Application of tailing water washing machine-made sand in concrete |
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