CN101955593A - Method for improving surface hydrophilicity of waste rubber powder - Google Patents
Method for improving surface hydrophilicity of waste rubber powder Download PDFInfo
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- CN101955593A CN101955593A CN 201010167618 CN201010167618A CN101955593A CN 101955593 A CN101955593 A CN 101955593A CN 201010167618 CN201010167618 CN 201010167618 CN 201010167618 A CN201010167618 A CN 201010167618A CN 101955593 A CN101955593 A CN 101955593A
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Abstract
The invention discloses a method for improving surface hydrophilicity of waste rubber powder, which is characterized by comprising the following steps of: putting 10 to 100 weight parts of the waste rubber powder into a plasma processing device; and jetting plasma to the surface of the waste rubber powder in an open environment with room temperature and atmospheric pressure to ensure that the waste rubber powder moves and is processed in a plasma atmosphere, wherein the power for processing the waste rubber powder is 10 to 5,000 W, and the time is 2.0 to 300 s. After the plasma processing, the surface polarity of the waste rubber powder is increased, the surface oxygen and nitrogen are increased, and the surface hydrophilicity is significantly improved. The method is a one-step method, which improves the surface property, the structure and the shape of the waste rubber powder and improves the added amount in a polymer. The method has the advantages of simple process, strong controllability, simple and convenient operation and high efficiency, needs no organic solvent and is environmentally-friendly.
Description
Technical field
The present invention relates to a kind of method of improving the waste rubber powder surface hydrophilicity, belong to waste rubber powder surface modification field.
Background technology
Along with the fast development of automotive industry, the backlog of the junked tire in the world has reached 3,000,000,000, and increases sharply with annual 1000000000 amount, so the handling problem of junked tire also becomes increasingly serious.Junked tire is also referred to as " black pollution ".Method such as landfill and burning is because take resource and secondary pollution is eliminated gradually, and except renovation and original shape utilization, most of junked tires are made into rubber powder.Waste-tyre rubber-powder is through removing the rubber grain with certain particle size that obtains after crushed behind steel wire, the cord thread by waste and used rubber tyre, be a kind of mixture of forming by multiple materials such as natural rubber, cis-1,4-polybutadiene rubber, strengthening agent (carbon black), lubricant, sulphur and vulcanization accelerators that contains crosslinking structure, be used for fields such as asphalt modification, waterproof roll, rubber brick and tire weighting material.
In recent years, along with the development of polymer composite and the improvement of rubber powder production technology, especially the application development of modified glue powder in polymer composite is very fast for rubber powder.Waste rubber powder be can be applicable in rubber, plastics and the material of construction by modification, not only can reduce the production cost of material, can also improve some physical and chemical performance of material, as in rubber, improving flexible resistance, improving processing characteristics; Mixing in plastics can toughened plastics; In material of construction, can improve damping, shock-absorbing capacity etc.It is introduced, the doping level of the rubber powder of non-modified (fine glue powder) in sizing material is generally below 10%, and handle through modification, doping level can be brought up to 25%-50%, doping level in plastics is then bigger, can reach 100%, and the surface bonding power of rubber powder and other polymkeric substance (as thermoplastics, rubber etc.) is stronger, mechanical property is better, the surface modification of rubber powder to the application of expanding rubber powder, improve its added value and have important practical and be worth.
Because waste rubber powder still has cross-linked structure, its surface is inertia, and this also is a great problem that rubber powder is recycled.It is difficult to produce the good interface consistency with material of main part, can on purpose change the physicochemical property of vulcanized rubber powder according to application need, as surface tissue and functional group, surface energy, surface wettability and surface adsorption etc., to satisfy the needs of modern novel material, novel process and development of new techniques.At present, the waste rubber powder main methods of modification has physics method, chemical method, mechanical process and biological process etc.Wherein especially with physical method efficient height, pollute little and praised highly.But utilize room temperature, atmospheric dielectric barrier plasma that waste rubber powder surface-treated modification technology be yet there are no report.
Summary of the invention
A kind of method of improving the waste rubber powder surface hydrophilicity of providing at the deficiencies in the prior art is provided, be characterized in that under room temperature, atmospheric opening condition using plasma is handled the waste rubber powder that waste rubber powder obtains surface modification.
Purpose of the present invention is realized that by following technical measures the umber of wherein said raw material is parts by weight except that specified otherwise.
The method of improving the waste rubber powder surface hydrophilicity may further comprise the steps:
Waste rubber powder 10-100 part is placed plasma processing apparatus, under room temperature, atmospheric open environment, plasma jet is arrived the waste rubber powder surface, make waste rubber powder motion process in plasma atmosphere, the power of handling waste rubber powder is 10W-5000W, time is 2.0s-300s, generates waste rubber powder plasma modification powder.
Waste rubber powder is waste-tyre rubber-powder, waste and old viton rubber powder or waste and old moistureproof cushion rubber powder.
Plasma body is at least a in nitrogen, air and the functional gas, wherein the purity of nitrogen is 99.99%, the gas mole ratio of nitrogen and air is 0.1-1, the mol ratio of functional gas and nitrogen or air is 0.001-0.3, and the plasma body of flowing through simultaneously forms the district and forms plasma atmosphere.
Functional gas is at least a in oxygen, sulfurous gas, siloxane gas and vinylformic acid, methacrylic acid, methyl acrylate and the methyl methacrylate steam.
The waste rubber powder of the surface hydrophilic property improvement for preparing as stated above.
The waste rubber powder of surface hydrophilic property improvement is used for the modification of thermoplastic macromolecule material, the modification of high polymer elastic composite material.
Performance test
1. waste-tyre rubber-powder hydrophilic variation before and after Cement Composite Treated by Plasma
As shown in Figure 2, waste-tyre rubber-powder has hydrophobicity before without Cement Composite Treated by Plasma, and rubber powder floats on the surface of water fully; Have very strong wetting ability through after the Cement Composite Treated by Plasma, be suspended in the water equably.
2. waste-tyre rubber-powder water contact angle changing conditions
Test result shows when plasma treatment time is 120s, only need the power of 30W, the water contact angle of waste-tyre rubber-powder is just reduced to 39.4 ° by untreated 124.7 °, increase power again to 40W, water contact angle is zero, show that this moment, waste-tyre rubber-powder changed wetting ability into by hydrophobicity, detailed being shown in Table 1.
3. the waste-tyre rubber-powder water contact angle is with the changing conditions of plasma treatment time
Experimental result shows that when Cement Composite Treated by Plasma power was 80W, the treatment time only was 10s, and the water contact angle of waste-tyre rubber-powder is just reduced to 0 ° by 124.7 °, shows Cement Composite Treated by Plasma under suitable power condition, and its processing efficiency is very high, detailed being shown in Table 2.
4. the x-ray photoelectron spectroscopy analysis of vulcanized rubber powder element before and after the Cement Composite Treated by Plasma
Learn that by table 3 data 8.12% before vulcanized rubber powder oxygen element content is by Cement Composite Treated by Plasma increases to 12.54%, nitrogen element content increases to 1.2% by 0.63%.Vulcanized rubber powder oxy radical that the present invention obtains and nitrogen-containing group all increase than having to a certain degree before handling, and analytical results shows that Cement Composite Treated by Plasma can obtain the chemically active rubber powder of having of functionalisation of surfaces.
5. the plasma surface modification waste rubber powder is to the influence of composite materials property.
Test result shows, GTR behind plasma surface modification can make the mechanical property of matrix material significantly improve, when waste-tyre rubber-powder (GTR) substitutes styrene-butadiene rubber(SBR) (NBR) 20 weight parts, the tensile strength of the GTR/NBR matrix material of non-modified is 2.4MPa, through the tensile strength 3.4MPa of the GTR/NBR of modification of the present invention matrix material, improved about 42%; Tear strength is increased to 19.1KN/m by the 15.0KN/m before unmodified; 100% stress at definite elongation is increased to 1.9MPa by 1.7MPa, sees Fig. 3, Fig. 4 and shown in Figure 5 for details.This is because after surface modification, and the GTR surface is wetting ability, and the consistency of itself and NBR matrix is improved, and has improved the comprehensive mechanical property of matrix material.Unmodified GTR is because the nonpolar feature on its surface causes GTR to be difficult to disperse in polar polymer NBR matrix, and prepared composite materials property is poor.
The present invention has following advantage:
(1) technical process is short, technology is simple, controllability is strong, need not aftertreatment, level of automation height, energy consumption are low, pollution-free, easily realize continuous operation.
(2) waste rubber powder surface produces the same sex effect of repelling each other, and prevents that effectively powder from reuniting in the blend matrix, obtains the polymer composites of waste rubber powder even size distribution.
(3) whippy structure of waste rubber powder rubber powder inside can not change, its even particle distribution, narrow distribution range, the excellent combination property with corresponding polymer after compound.
(4) the present invention adopts medium barrier plasma discharge that waste rubber powder is carried out surface modification, the efficient height, and speed is fast, helps suitability for industrialized production, for the higher value application of waste Crumb rubber provides new technological line.
Description of drawings
Fig. 1 is waste rubber powder modification low-temperature plasma generating unit structural representation
1. electrode, 2. plasma generator, 3. waste rubber powder, 4 220V voltages, 5 transformers, 6 plasma electrical sources.
Fig. 2 is that the waste rubber powder experiment that suspends in water contrasts before and after the atmospheric pressure at room Cement Composite Treated by Plasma
The former GTR B of A plasma modification GTR
Fig. 3 be under room temperature, the normal atmosphere plasma modification to the influence of GTR/NBR matrix material tensile strength
Fig. 4 be under room temperature, the normal atmosphere plasma modification to the influence of GTR/NBR matrix material tear strength
Fig. 5 be under room temperature, the normal atmosphere plasma modification to the influence of GTR/NBR matrix material 100% stress at definite elongation
Embodiment
Below by embodiment the present invention is carried out concrete description; be necessary to be pointed out that at this following examples only are used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Waste-tyre rubber-powder is placed plasma processing apparatus for 10 parts.(or install the plasma body transmitting device additional as shown in Figure 1, realize continuous production), this container or carrier place the below of room temperature, atmospheric-pressure plasma jet, apart from top quartz plate distance is 2mm, it is in the quartz glass ware of 70mm that waste rubber powder is tiled in the below diameter, and the tiling mean thickness of rubber powder is about 1mm.Open plasma apparatus, carry out Cement Composite Treated by Plasma in room temperature, air atmosphere, the treatment time is 300s, and power is 10W.
Waste and old viton powder is placed the Cement Composite Treated by Plasma specific equipment for 100 parts.(or install the plasma body transmitting device additional as shown in Figure 1, realize continuous production), this container or carrier place the below of room temperature, atmospheric-pressure plasma jet, apart from top quartz plate distance is 2mm, it is in the quartz glass ware of 70mm that waste rubber powder is tiled in the below diameter, and the tiling mean thickness of rubber powder is 1mm.Open plasma apparatus, carry out Cement Composite Treated by Plasma in room temperature, nitrogen atmosphere, the treatment time is 2s, and power is 5000W.
Waste and old moistureproof cushion rubber powder is placed the Cement Composite Treated by Plasma specific equipment for 60 parts.As shown in Figure 1, this container or carrier place the below of normal pressure, room-temperature plasma jet apparatus, are 2mm apart from top quartz plate distance, and it is in the quartz glass ware of 70mm that waste rubber powder is tiled in the below diameter, and the tiling mean thickness of rubber powder is 1mm.Opening plasma apparatus, is 1 in the mol ratio of air and nitrogen, and vinylformic acid steam and nitrogen mol ratio are to carry out Cement Composite Treated by Plasma in 0.1 the atmosphere, and the treatment time is 120s, and power is 80W.
Table 1 waste rubber powder water contact angle is with the variation (waste-tyre rubber-powder, the treatment time is 120s) of Cement Composite Treated by Plasma power
Table 2 waste rubber powder water contact angle is with the variation of plasma treatment time
The surface light electronic spectrum ultimate analysis of waste tyre rubber powder before and after table 3 plasma modification
Claims (6)
1. method of improving the waste rubber powder surface hydrophilicity is characterized in that this method may further comprise the steps:
Waste rubber powder 10-100 weight part is placed plasma processing apparatus, under room temperature, atmospheric open environment, plasma jet is arrived the waste rubber powder surface, make waste rubber powder motion process in plasma atmosphere, the power of handling waste rubber powder is 10W-5000W, time is 2.0s-300s, generates waste rubber powder plasma modification powder.
2. improve the method for waste rubber powder surface hydrophilicity according to claim 1, it is characterized in that waste rubber powder is any in waste-tyre rubber-powder, waste and old viton rubber powder or the waste and old moistureproof cushion rubber powder.
3. improve the method for waste rubber powder surface hydrophilicity according to claim 1, it is characterized in that plasma body is at least a in nitrogen, air and the functional gas, wherein the purity of nitrogen is 99.99%, the gas mole ratio of nitrogen and air is 0.1-1, the mol ratio of functional gas and nitrogen or air is 0.001-0.3, and the plasma body of flowing through simultaneously forms the district and forms plasma atmosphere.
4. press plasma modification processing method as waste rubber powder surface air as described in claim 1 or 3, it is characterized in that described functional gas is at least a in oxygen, sulfurous gas, siloxane gas and vinylformic acid, methacrylic acid, methyl acrylate and the methyl methacrylate steam.
5. the waste rubber powder of the surface hydrophilic property improvement for preparing as method as described in one of claim 1-4.
6. the waste rubber powder as surface hydrophilic property improvement as described in the claim 5 is used for the modification of thermoplastic macromolecule material, the modification of high polymer elastic composite material.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103305197A (en) * | 2013-06-08 | 2013-09-18 | 西南石油大学 | Cement paste toughening agent and application of cement paste toughening agent in preparation of cementing flexible cement paste |
| CN104311865A (en) * | 2014-10-13 | 2015-01-28 | 重庆交通大学 | Rubber surface modification method |
| CN106079012A (en) * | 2016-06-21 | 2016-11-09 | 南京林业大学 | A kind of method utilizing steam dielectric barrier discharge plasma to strengthen agricultural crop straw glue performance |
| CN108822734A (en) * | 2018-06-22 | 2018-11-16 | 安徽快来防水防腐有限公司 | A kind of high temperature resistant, the preparation method of the SBS of resistance to ultralow temperature modified asphalt waterproof coiled material |
| CN109121277A (en) * | 2018-08-23 | 2019-01-01 | 国网天津市电力公司电力科学研究院 | A kind of dielectric barrier discharge system and method improving rubber surface hydrophilicity |
| CN109503865A (en) * | 2018-12-18 | 2019-03-22 | 广西远景资源再生有限公司 | A kind of technique that rubber powder surface is modified |
| CN111621058A (en) * | 2020-05-15 | 2020-09-04 | 大连理工大学 | Method and device for regenerating waste rubber by low-temperature plasma desulfurization |
| CN112830723A (en) * | 2021-02-26 | 2021-05-25 | 西南石油大学 | High-temperature-resistant elastic and tough cement paste system for shale oil-gas well |
| CN113461866A (en) * | 2021-07-28 | 2021-10-01 | 四川大学 | Hydrophilic waste rubber powder, high-strength composite hydrogel and preparation method and application thereof |
| CN114350003A (en) * | 2022-01-18 | 2022-04-15 | 库博标准投资有限公司 | Method for changing surface activity of rubber material |
Citations (1)
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| CN1858091A (en) * | 2006-04-25 | 2006-11-08 | 扬州大学 | Method for treating fluoro rubber by vacuum radio frequency plasma polarization |
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Patent Citations (1)
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| CN1858091A (en) * | 2006-04-25 | 2006-11-08 | 扬州大学 | Method for treating fluoro rubber by vacuum radio frequency plasma polarization |
Non-Patent Citations (1)
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103305197A (en) * | 2013-06-08 | 2013-09-18 | 西南石油大学 | Cement paste toughening agent and application of cement paste toughening agent in preparation of cementing flexible cement paste |
| CN103305197B (en) * | 2013-06-08 | 2015-06-10 | 西南石油大学 | Cement paste toughening agent and application of cement paste toughening agent in preparation of cementing flexible cement paste |
| CN104311865A (en) * | 2014-10-13 | 2015-01-28 | 重庆交通大学 | Rubber surface modification method |
| CN104311865B (en) * | 2014-10-13 | 2017-04-05 | 重庆交通大学 | A kind of rubber surface method of modifying |
| CN106079012A (en) * | 2016-06-21 | 2016-11-09 | 南京林业大学 | A kind of method utilizing steam dielectric barrier discharge plasma to strengthen agricultural crop straw glue performance |
| CN108822734A (en) * | 2018-06-22 | 2018-11-16 | 安徽快来防水防腐有限公司 | A kind of high temperature resistant, the preparation method of the SBS of resistance to ultralow temperature modified asphalt waterproof coiled material |
| CN109121277A (en) * | 2018-08-23 | 2019-01-01 | 国网天津市电力公司电力科学研究院 | A kind of dielectric barrier discharge system and method improving rubber surface hydrophilicity |
| CN109503865A (en) * | 2018-12-18 | 2019-03-22 | 广西远景资源再生有限公司 | A kind of technique that rubber powder surface is modified |
| CN111621058A (en) * | 2020-05-15 | 2020-09-04 | 大连理工大学 | Method and device for regenerating waste rubber by low-temperature plasma desulfurization |
| CN112830723A (en) * | 2021-02-26 | 2021-05-25 | 西南石油大学 | High-temperature-resistant elastic and tough cement paste system for shale oil-gas well |
| CN113461866A (en) * | 2021-07-28 | 2021-10-01 | 四川大学 | Hydrophilic waste rubber powder, high-strength composite hydrogel and preparation method and application thereof |
| CN114350003A (en) * | 2022-01-18 | 2022-04-15 | 库博标准投资有限公司 | Method for changing surface activity of rubber material |
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Open date: 20110126 |