CN101225196B - Silicon-aluminium binary hybrid modified glue powder nano composite material and preparation method thereof - Google Patents
Silicon-aluminium binary hybrid modified glue powder nano composite material and preparation method thereof Download PDFInfo
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- CN101225196B CN101225196B CN2007100325272A CN200710032527A CN101225196B CN 101225196 B CN101225196 B CN 101225196B CN 2007100325272 A CN2007100325272 A CN 2007100325272A CN 200710032527 A CN200710032527 A CN 200710032527A CN 101225196 B CN101225196 B CN 101225196B
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Abstract
The invention discloses a silicon aluminum binary hybrid modified rubber powder nanocomposite and a preparation method of the nanocomposite, which is characterized in that: firstly, water, anhydrous alcohol and a precursor containing silicon are added into a vessel, ammonia is also added into the vessel to regulate the pH value in the range of 7.0 to 9.0 and the solution are agitated for 0.5 to 2 hours at 30 to 60 degrees; secondly, rubber powder is added into the vessel and agitated for 2 to 10 hours at 30 to 60 hours; thirdly, a precursor containing aluminum is added into the vessel, hydrochloric acid is added to regulate the pH value to be 7.0, and then the solution are agitated for 2 to 10 hours at 30 to 60 degrees; at last, pumping filtration and drying are carried out till the constant weight of the product is obtained. The silicon aluminum binary hybrid modified rubber powder nanocomposite has the advantages that: the preparation method has s simple technique, mild conditions and easy practice, and the materials can be molecularly dispersed in a short time, the obtained modified rubber powder can be carried out a further modeling processing to be applied in various situations; meanwhile, the rubber powder nanocomposite realizes the molecule level interpenetration of the nanometer silicon dioxide, nanometer alumina and the rubber powder network.
Description
Technical field
The present invention relates to a kind of nano composite material and preparation method thereof, specifically is a kind of silicon-aluminium binary hybrid modified glue powder nano composite material and preparation method thereof.
Background technology
Along with developing rapidly of global rubber industry, caused the accumulation of a large amount of waste rubbers, constituted serious " black pollution ".Produce the main path that rubber powder has become the normal at present processing of adopting and recycled waste rubber.But because rubber powder is the incomplete ruined polymer network of a crosslinking structure, limited the motion of surface molecular chain to a certain extent, and contain less reactive group, insoluble, melting powder not with certain network structure, in the Rubber processing process, be difficult to form Chemical bond, rubber powder is as directly mixing in rubber or plastics, and the interface is difficult to form bonding preferably, thereby causes the decline significantly of composite materials property.
In recent years, utilize the silicon-aluminium binary hybrid material of sol-gel preparation because it has the performance of many excellences, as high-melting-point, good creep-resistant property, high heat resistance, high corrosion resistance energy, high shear modulus, low-k, low dielectric loss and characteristics such as light transmission preferably, and by extensive concern, and become a class type material of progressively researching and developing.Before, the rubber powder hybrid modification technology of inventor's application is to adopt sol-gel method, utilizes siliceous presoma, generates silica hybrid inorganic-organic network in the vulcanized rubber powder transition layer; Simultaneously,, can select polarity, group such as nonpolar, functional as required for use, thereby improve the consistency of modified glue powder nano composite material and matrix by end-group structure is controlled.
Summary of the invention
The purpose of this invention is to provide a kind of silicon-aluminium binary hybrid modified glue powder nano composite material and preparation method thereof.
The preparation method of silicon-aluminium binary hybrid modified glue powder nano composite material of the present invention comprises the steps:
(1) water, dehydrated alcohol and siliceous presoma are added in the container, regulate pH value 7.0-9.0 with ammoniacal liquor, 30-60 ℃ is stirred 0.5-2h down; Add rubber powder again, 30-60 ℃ is stirred 2-10h down; Add aluminiferous presoma again, with salt acid for adjusting pH value to 7.0,30-60 ℃ is stirred 2-10h down;
(2) suction filtration is dried to constant weight.
Above-mentioned raw materials weight part consumption is as follows:
Rubber powder 100
Siliceous presoma 1～80
Aluminiferous presoma 0.5～80
Organo-siloxane 0～30
Water 2～25
Solvent 100～1000
Catalyzer 0～0.35
Preferred version is as follows:
Rubber powder 100
Siliceous presoma 5～40
Aluminiferous presoma 5～40
Organo-siloxane 0～30
Water 5～25
Solvent 200～500
Catalyzer 0.05～0.30
Described rubber powder is 20 orders～200 order shoddies.
Described solvent is a dehydrated alcohol.
Described siliceous presoma is tetraethoxy or water glass.
Described aluminiferous presoma is Tai-Ace S 150, aluminum nitrate or aluminum chloride.
Described catalyzer is ammoniacal liquor, hydrochloric acid.
Described organo-siloxane is RSiX3, in the formula R be non-hydrolysis, can with high molecular polymer bonded organo-functional group, as methyl, vinyl, amino, epoxy group(ing), sulfydryl, acryloyl-oxy propyl group etc.; X is a hydrolysable group, and the typical X group has alkoxyl group, aryloxy, acyl group, chloro etc.; The most frequently used then is methoxyl group and oxyethyl group.Common organo-siloxane comprises γ-(methacryloxy) propyl trimethoxy silicane, vinyltriethoxysilane, vinyltrimethoxy silane, γ-An Bingjisanyiyangjiguiwan, N-β (aminoethyl)-γ-An Bingjisanjiayangjiguiwan, N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane, γ-glycidoxypropyltrime,hoxysilane, γ-mercaptopropyl trimethoxysilane, γ-thiopropyl triethoxyl silane, γ-chloropropyl triethoxysilane or chain alkyl Trimethoxy silane.
To be waste old pulverize or grind the powder mass of making through mechanical means the rubber powder that the present invention adopts, and has certain elasticity and intensity.It is had these characteristics of favorable elasticity is applied in the cement concrete, toughness reinforcing to normal concrete, the handling problem that can solve waste rubber again in a large number simultaneously, form a kind of novel " rubber powder-concrete " matrix material, may be used on places such as road, bridge, urban elevated road, motorway, railroad sleeper, airfield runway.It is reported, though the waste Crumb rubber-concrete composite material of preparation can effectively improve concrete elasticity to a certain extent at present, have better shock resistance and damping sound-proofing properties, but, cause concrete strength obviously to reduce because rubber powder combines relatively poorly with concrete interface.
The present invention compared with prior art has following advantage:
1, method of the present invention generates the nano-particle network structure of silica and alumina owing to introduce siliceous and contain the aluminum binary reactive precursor in the surface depletion layer of rubber powder, and links to each other with chemical bond between rubber powder; On the one hand, the network structure of nano silicon oxide and nano aluminium oxide can be given material better physical mechanical property, thermal characteristics etc., on the other hand, can be by end-group structure be controlled, group can be selected polarity, nonpolar or functional groups etc. as required for use, improve the consistency of rubber powder and matrix, make it and in different matrixes, to use, and show better comprehensive performance.
2, method of the present invention has that technology is simple, mild condition, can reach that the molecule rank is disperseed, easy advantages such as enforcement at short notice, and the modified glue powder that obtains is forming process further, is applied to various occasions.
3, modified glue powder nano composite material of the present invention can be realized nano silicon, nano aluminium oxide and rubber powder network molecule level IPN.
Embodiment
Embodiment 1
Table 1 is the composition of raw materials (mass fraction) that the present invention prepares modified glue powder nano composite material
Table 1
| ?1# | 2# | 3# | 4# | 5# | 6# | 7# | 8# | 9# | 10# | |
| Rubber powder | 100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 |
| Tetraethoxy | 1 | ?10 | ?20 | ?40 | ?80 | ?0 | ?0 | ?0 | ?0 | ?0 |
| Water glass | 0 | ?0 | ?0 | ?0 | ?0 | ?20 | ?40 | ?20 | ?40 | ?80 |
| Tai-Ace S 150 | 0.5 | ?5 | ?10 | ?20 | ?40 | ?0 | ?0 | ?0 | ?0 | ?0 |
| Aluminum nitrate | 0 | ?0 | ?0 | ?0 | ?0 | ?10 | ?20 | ?0 | ?0 | ?0 |
| Aluminum chloride | 0 | ?0 | ?0 | ?0 | ?0 | ?0 | ?0 | ?20 | ?40 | ?80 |
| Water | 2 | ?25 | ?30 | ?40 | ?40 | ?0 | ?0 | ?0 | ?0 | ?0 |
| Ammoniacal liquor | 0.10 | ?0.15 | ?0.20 | ?0.25 | ?0.35 | ?0.20 | ?0.25 | ?0.20 | ?0.25 | ?0.35 |
| Ethanol | 200 | ?200 | ?300 | ?400 | ?400 | ?300 | ?400 | ?300 | ?400 | ?400 |
| Hydrochloric acid | In right amount * | In right amount | In right amount | In right amount | In right amount | In right amount | In right amount | In right amount | In right amount | In right amount |
| Organo-siloxane | 0 | ?0 | ?0 | ?0 | ?0 | ?0 | ?0 | ?0 | ?0 | ?0 |
*It is 7.0 to get final product that an amount of expression of hydrochloric acid is adjusted to the pH value.
Water, dehydrated alcohol and siliceous presoma are added in the container by prescription in the table, add ammoniacal liquor and regulate pH value and stir 1h down for 7.0,60 ℃, add 20 purpose shoddies again, 60 ℃ are stirred 4h down, add various aluminiferous presomas again, with hydrochloric acid conciliation pH value 7.0; 60 ℃ are stirred 4h down; Condensation reaction is hydrolyzed; Suction filtration after reacting completely is dried to constant weight.
The modified glue powder that obtains is added in the concrete, and cement is 42.5 ordinary Portland cements of conch factory, and sand is standard sand; The weight of cement and sand is respectively 450g and 1350g, and water cement ratio is 0.5, and the rubber powder addition is 3% of a cement, and the mechanical property of gained sees Table 2:
Table 2
| Rubber powder | The anti-folding of 3d (MPa) | 3d resistance to compression (MPa) | The anti-folding of 28d (MPa) | 28d resistance to compression (MPa) | Degree of mobilization (mm) |
| ?0# | 4.0 | ?16.8 | ?5.8 | ?25.9 | ?147 |
| ?1# | 4.2 | ?17.9 | ?5.8 | ?29.8 | ?157 |
| ?2# | 4.8 | ?23.0 | ?7.1 | ?37.9 | ?172 |
| ?3# | 4.6 | ?23.6 | ?7.1 | ?39.6 | ?170 |
| ?4# | 5.1 | ?25.0 | ?7.3 | ?41.5 | ?190 |
| ?5# | 5.2 | ?25.9 | ?7.4 | ?43.4 | ?193 |
| ?6# | 4.2 | ?16.9 | ?6.5 | ?30.2 | ?165 |
| ?7# | 4.4 | ?20.2 | ?6.3 | ?33.4 | ?180 |
| ?8# | 4.8 | ?23.8 | ?6.8 | ?38.8 | ?180 |
| ?9# | 5.0 | ?24.1 | ?7.5 | ?41.8 | ?174 |
| ?10# | 4.7 | ?22.2 | ?7.6 | ?38.0 | ?158 |
In the table 2, the 0# rubber powder is represented unmodified rubber powder, and 1#～10# rubber powder is respectively the modified glue powder nano composite material that 1# in the table 1～the 10# raw material obtains, and mixes in the concrete; As can be seen from Table 2, through after hybrid modified glue powder of the present invention mixes in the concrete, no matter be 3 days ultimate compression strength, folding strength, still 28 days ultimate compression strength, folding strength, corresponding unmodified rubber powder is incorporated in the concrete, and raising is in various degree all arranged.Rubber powder was owing to have nano level silica and alumina structure in the surface depletion layer after modification was described, with alumina, the silica similar in the hydrated reaction of cement, has consistency preferably, good dispersity, degree of mobilization also improves thereupon, it is stronger to make that concrete and rubber powder interact, thereby shows mechanical property preferably.
Embodiment 2
Table 3 is composition of raw materials (mass fraction) that the present invention prepares modified glue powder nano composite material
Table 3
| ?1# | 2# | 3# | 4# | 5# | 6# | 7# | 8# | |
| Rubber powder | 100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 |
| Tetraethoxy | 10 | ?20 | ?40 | ?80 | ?0 | ?0 | ?0 | ?0 |
| Water glass | 0 | ?0 | ?0 | ?0 | ?20 | ?40 | ?80 | ?40 |
| Tai-Ace S 150 | 5 | ?10 | ?20 | ?40 | ?0 | ?0 | ?0 | ?0 |
| Aluminum nitrate | 0 | ?0 | ?0 | ?0 | ?0 | ?0 | ?0 | ?20 |
| Aluminum chloride | 0 | ?0 | ?0 | ?0 | ?20 | ?40 | ?80 | ?0 |
| Water | 25 | ?30 | ?40 | ?40 | ?0 | ?0 | ?0 | ?0 |
| Ammoniacal liquor | 0.15 | ?0.20 | ?0.25 | ?0.35 | ?0.20 | ?0.25 | ?0.35 | ?0.25 |
| Ethanol | 200 | ?300 | ?400 | ?400 | ?300 | ?400 | ?400 | ?400 |
| KH570 | 2 | ?0 | ?0 | ?0 | ?0 | ?0 | ?0 | ?0 |
| KH550 | 0 | ?2 | ?0 | ?0 | ?0 | ?0 | ?0 | ?0 |
| KH560 | 0 | ?0 | ?2 | ?0 | ?0 | ?0 | ?0 | ?0 |
| A151 | 0 | ?0 | ?0 | ?2 | ?0 | ?0 | ?0 | ?0 |
| KH602 | 0 | ?0 | ?0 | ?0 | ?2 | ?0 | ?0 | ?0 |
| γ-thiopropyl Trimethoxy silane | 0 | ?0 | ?0 | ?0 | ?0 | ?2 | ?0 | ?0 |
| γ-chloropropyl triethoxysilane | 0 | ?0 | ?0 | ?0 | ?0 | ?0 | ?2 | ?0 |
| The dodecyl Trimethoxy silane | 0 | ?0 | ?0 | ?0 | ?0 | ?0 | ?0 | ?2 |
| Hydrochloric acid | In right amount * | In right amount | In right amount | In right amount | In right amount | In right amount | In right amount | In right amount |
*It is 7.0 to get final product that an amount of expression of hydrochloric acid is adjusted to the pH value.
Water, dehydrated alcohol, ammoniacal liquor and siliceous presoma are added in the container by prescription in the table, and adding ammoniacal liquor is regulated the pH value and is stirred 2h down for 8.0,30 ℃, add 200 purpose shoddies again, 30 ℃ are stirred 10h down, add various aluminiferous presomas again, reconcile the pH value with hydrochloric acid and stir 10h down for 7.0,30 ℃; Condensation reaction is hydrolyzed; Suction filtration after reacting completely is dried to constant weight.
The modified glue powder that obtains is added in the concrete, and cement is 42.5 ordinary Portland cements of conch factory, and sand is standard sand; The weight of cement and sand is respectively 450g and 1350g, and water cement ratio is 0.5, and the rubber powder addition is 7% of a cement, and the mechanical property of gained sees Table 4:
Table 4
| Rubber powder | The anti-folding of 3d (MPa) | 3d resistance to compression (MPa) | The anti-folding of 28d (MPa) | 28d resistance to compression (MPa) | Degree of mobilization (mm) |
| 1# | 5.2 | ?26.4 | ?7.8 | ?43.5 | ?187 |
| ?2# | 5.0 | ?25.7 | ?7.4 | ?42.4 | ?185 |
| ?3# | 5.2 | ?27.1 | ?7.9 | ?46.4 | ?193 |
| ?4# | 5.4 | ?27.2 | ?7.3 | ?43.4 | ?186 |
| ?5# | 4.8 | ?23.8 | ?6.8 | ?38.8 | ?180 |
| ?6# | 5.2 | ?25.9 | ?7.4 | ?43.4 | ?183 |
| ?7# | 5.0 | ?22.4 | ?7.3 | ?39.3 | ?181 |
| ?8# | 4.3 | ?21.2 | ?6.9 | ?35.0 | ?180 |
In the table 4,1#～8# rubber powder is respectively the modified glue powder nano composite material that 1# in the table 3～the 8# raw material obtains, and mixes in the concrete; As can be seen from Table 4, after having added various organo-siloxanes,, so make concrete 3 days ultimate compression strength, folding strength because organo-siloxane can increase rubber powder and concrete consistency, and 28 days ultimate compression strength, folding strength, raising is in various degree all arranged.Rubber powder was owing to added the organo-siloxane that contains different functional groups after modification was described, make and further improved and concrete consistency, some in addition can participate in the hydrated reaction of cement, as the KH560 in the 3# prescription, because its epoxide group that contains can participate in hydrated reaction of cement, make not only good dispersity in concrete of rubber powder, degree of mobilization also makes moderate progress, and has also strengthened the interaction between concrete and rubber powder interface simultaneously, thereby shows mechanical property preferably.
Embodiment 3
Table 5 is composition of raw materials (mass fraction) that the present invention prepares modified glue powder nano composite material
Table 5
| ?1# | 2# | 3# | 4# | 5# | 6# | 7# | 8# | |
| Rubber powder | 100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 | ?100 |
| Tetraethoxy | 40 | ?40 | ?40 | ?40 | ?40 | ?40 | ?40 | ?40 |
| Tai-Ace S 150 | 40 | ?20 | ?20 | ?20 | ?20 | ?20 | ?20 | ?20 |
| Water | 40 | ?40 | ?40 | ?40 | ?40 | ?40 | ?40 | ?40 |
| Ammoniacal liquor | 0.25 | ?0.25 | ?0.25 | ?0.25 | ?0.25 | ?0.25 | ?0.25 | ?0.25 |
| Ethanol | 400 | ?400 | ?400 | ?400 | ?400 | ?400 | ?400 | ?400 |
| KH570 | 1 | ?2 | ?3 | ?0 | ?0 | ?0 | ?0 | ?0 |
| KH550 | 0 | ?0 | ?0 | ?1 | ?2 | ?3 | ?0 | ?0 |
| KH560 | 0 | ?0 | ?0 | ?0 | ?0 | ?0 | ?1 | ?2 |
| Hydrochloric acid | In right amount | In right amount | In right amount | In right amount | In right amount | In right amount | In right amount | In right amount |
*It is 7.0 to get final product that an amount of expression of hydrochloric acid is adjusted to the pH value.
Water, dehydrated alcohol and siliceous presoma are added in the container by prescription in the table, and adding ammoniacal liquor is regulated the pH value and is stirred 1h down for 9.0,50 ℃, add 100 purpose shoddies again, 50 ℃ are stirred 5h down, add various aluminiferous presomas again, reconcile the pH value with hydrochloric acid and stir 6h down for 7.0,50 ℃; Condensation reaction is hydrolyzed; Suction filtration after reacting completely is dried to constant weight.
The modified glue powder that obtains is added in the concrete, and cement is 42.5 ordinary Portland cements of conch factory, and sand is standard sand; The weight of cement and sand is respectively 450g and 1350g, and water cement ratio is 0.5, and the rubber powder addition is 7% of a cement, and the mechanical property of gained sees Table 6:
Table 6
| Rubber powder | The anti-folding of 3d (MPa) | 3d resistance to compression (MPa) | The anti-folding of 28d (MPa) | 28d resistance to compression (MPa) | Degree of mobilization (mm) |
| ?1# | 4.8 | ?25.2 | ?7.3 | ?43.5 | ?183 |
| ?2# | 5.0 | ?26.1 | ?7.9 | ?45.4 | ?186 |
| ?3# | 4.2 | ?24.3 | ?7.5 | ?44.6 | ?181 |
| ?4# | 4.6 | ?24.7 | ?7.4 | ?43.4 | ?183 |
| ?5# | 4.8 | ?25.8 | ?7.8 | ?43.8 | ?185 |
| ?6# | 5.0 | ?25.9 | ?7.9 | ?45.4 | ?190 |
| ?7# | 5.0 | ?26.4 | ?7.6 | ?45.3 | ?190 |
| ?8# | 5.2 | ?27.1 | ?7.9 | ?46.4 | ?193 |
In the table 6,1#～8# rubber powder is respectively the modified glue powder nano composite material that 1# in the table 6～the 8# raw material obtains, and mixes in the concrete; As can be seen from Table 6, the addition of various organo-siloxanes is to concrete 3 days ultimate compression strength, folding strength, and 28 days ultimate compression strength, folding strength, and raising is in various degree all arranged.This is because the addition of different organo-siloxanes makes that the interaction strength that produces between rubber powder and the concrete is different, the modified glue powder of 8# prescription good dispersity in concrete not only wherein, and degree of mobilization is also higher, and mechanical property is also better.
Claims (4)
1. the preparation method of a binary hybrid modified glue powder nano composite material is characterized in that, comprises the steps:
(1) water, dehydrated alcohol and siliceous presoma are added in the container, regulate pH value 7.0-9.0 with ammoniacal liquor, 30-60 ℃ is stirred 0.5-2h down, add rubber powder again, 30-60 ℃ is stirred 2-10h down, adds aluminiferous presoma again, with salt acid for adjusting pH value to 7.0,30-60 ℃ is stirred 2-10h down;
(2) with the product suction filtration of step (1), be dried to constant weight;
Wherein, the weight part of each raw material is as follows:
Rubber powder 100
Siliceous presoma 1～80
Aluminiferous presoma 0.5～80
Organo-siloxane 0～30
Water 2～25
Dehydrated alcohol 100～1000
Ammoniacal liquor and hydrochloric acid 0～0.35;
Described siliceous presoma is tetraethoxy or water glass;
Described aluminiferous presoma is Tai-Ace S 150, aluminum nitrate or aluminum chloride.
2. preparation method according to claim 1 is characterized in that, the weight part of described each raw material can also for:
Rubber powder 100
Siliceous presoma 5～40
Aluminiferous presoma 5～40
Organo-siloxane 0～30
Water 5～25
Dehydrated alcohol 200～500
Ammoniacal liquor and hydrochloric acid 0.05～0.30.
3. preparation method according to claim 1 and 2 is characterized in that, described rubber powder is 20 orders～200 order shoddies.
4. preparation method according to claim 1 and 2, it is characterized in that described organo-siloxane is γ-(methacryloxy) propyl trimethoxy silicane, vinyltriethoxysilane, vinyltrimethoxy silane, γ-An Bingjisanyiyangjiguiwan, N-β (aminoethyl)-γ-An Bingjisanjiayangjiguiwan, N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane, γ-glycidoxypropyltrime,hoxysilane, γ-mercaptopropyl trimethoxysilane, γ-thiopropyl triethoxyl silane or γ-chloropropyl triethoxysilane.
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| CN102838310B (en) * | 2012-09-21 | 2014-08-06 | 广东省建筑材料研究院 | Multifunctional premix mortar thickening material and preparation method thereof |
| CN104031292B (en) * | 2014-05-12 | 2015-05-13 | 谷屿 | Modified nanometer titanium dioxide with improved ultraviolet-ray shielding property and preparation method thereof |
| CN106601983B (en) * | 2016-12-14 | 2019-02-22 | 上海电力学院 | A kind of preparation method of high-cooling property back electrode material |
| CN110993241B (en) * | 2019-10-30 | 2021-11-19 | 安徽朗基新材料科技有限公司 | Soft magnetic ferrite material prepared based on nanoparticles and preparation method thereof |
| CN115652649A (en) * | 2022-11-15 | 2023-01-31 | 福建佳来户外服装有限公司 | Preparation method of water pressure resistant down jacket fabric |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US6878759B2 (en) * | 2001-10-18 | 2005-04-12 | Degussa Ag | Rubber pellets comprising silicatic and oxidic fillers |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6878759B2 (en) * | 2001-10-18 | 2005-04-12 | Degussa Ag | Rubber pellets comprising silicatic and oxidic fillers |
Non-Patent Citations (2)
| Title |
|---|
| 刘岚，罗远芳，贾德民.橡胶纳米复合材料的制备与性能.特种橡胶制品23 3.2002,23(3),8-11. |
| 刘岚,罗远芳,贾德民.橡胶纳米复合材料的制备与性能.特种橡胶制品23 3.2002,23(3),8-11. * |
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