CN101020765A - Process of preparing natural rubber filler with solid waste oil shale - Google Patents
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Abstract
The present invention relates to natural rubber filler, and is especially process of preparing natural rubber filler with solid waste oil shale. The process includes the following steps: 1. crushing and grinding solid waste oil shale to obtain solid waste oil shale powder; 2. surface modifying the solid waste oil shale powder with surface modifier in the amount of 0.8-3 wt% of the solid waste oil shale powder at 80-200 deg.c for 15-30 min to obtain modified solid waste oil shale powder; and 3. mixing the modified solid waste oil shale powder and anti-ageing agent in the weight ratio of 10-60 to 2-4 to obtain the natural rubber filler product. The anti-ageing agent contains at least one component capable of deactivating heavy metal elements. The present invention has simple preparation process and low cost.
Description
Technical field
The present invention relates to a kind of preparation method of natural rubber filler, be specifically related to a kind of method of utilizing solid waste oil shale to prepare natural rubber filler.
Technical background
Resinous shale is the organic rock of formation of deposits simultaneously by fine mineral chip and lower animal and plant residue decomposition, form by organic and inorganic mineral two portions, organic matter is formed through gelification by unicellular lower eukaryote remains such as algae, inorganic mineral is formed and to be comprised various mineral, and wherein the most common have quartz, clay mineral, carbonate, vitriol, sulfide, ironic hydroxide and a salt etc.The exploitation of resinous shale has for many years formed a large amount of solid waste oil shales, and the stacking of these solid waste has taken a large amount of soils.And solid waste oil shale contains a large amount of toxicity or genotoxic potential material, as heavy metal element, trace-level activity element, carcinogenic substance etc., through water source, soil and the biology around rainwater leaching or the diffusion back severe contamination, destroy agriculture production, make that the soil poisons, acidifying, destroy soil throughput, thus the harm residents ' health.In addition, the environment around the bulk deposition of waste has had a strong impact on, its pollution range often surpass the several times of shared land area, havoc ecotope.
At present, the integrated application of solid waste oil shale has: as cement filler; The preparation haydite; As the light cinder brick material; For the high resinous shale of kaolinite content, remaining lime-ash is handled after shale oil is extracted in destructive distillation, can obtain the high-quality calcined kaolin; Raw material as white carbon black; Through high-temperature calcination, the kerosene shale ash that has formed loose porous structure is as the weighting agent of rubber and plastics etc.
Most widely used particulate filler mainly is carbon black, white carbon black and light calcium carbonate etc. in the rubber industry.This class filler is also high because of production cost high price, along with a large amount of uses of rubber and the continuous increase of consumption thereof, the demand of filler also increases thereupon, therefore, seeking cheap surrogate has become the core of current exploitation rubber with weighting agent with the cost that reduces rubber item, and people begin natural mineral and mining industry waste are done the applied research of loading material of rubber surrogate and pay attention to greatly.To carry out as the resinous shale of solid waste making an addition in the natural rubber after the deep processing, both can reduce the cost of rubber item, can effectively utilize solid waste oil shale again, reduce the pollution of ecotope.
Patent related to the present invention has Chinese patent publication number CN1098117, this patent is a kind of oil shale ash-polyolefin loading, it is to be mixed in the high-speed mixer high speed by a certain percentage by kerosene shale ash, coupling agent, dispersion agent, lubricant, resin, be cut into required particle again, as the filler of plastics or rubber.
Bibliographical information is arranged under the synergy of potassium acetate and KOH, the crystalline structure of oil shale is become the filler of amorphous structure as natural rubber, but this oil shale treatment process is complicated.
Directly make an addition in the rubber as filler after also having bibliographical information with oil shale waste pulverizing or surface modification, but the solid waste oil shale of windrow composting is formed more complicated, and the composition of different layers position, different location, different states sample is also different, the resinous shale generating is not only arranged or directly be used as the burning slag of fuel and the oil shale wastes such as destructive distillation slag that refine shale oil, also have the resinous shale that oil length is low, oil refining value is little, and rock mud and the country rock followed in the recovery process.Through chemical composition analysis, these solid waste contain some heavy metal elements such as Mn, Cu, Fe, and the aging of natural rubber quickened in their existence, makes rubber item lose actual use value.
Summary of the invention
The object of the present invention is to provide a kind of method of utilizing solid waste oil shale to prepare natural rubber filler, this method technology is simple, cost is low.
To achieve these goals, technical scheme of the present invention is: a kind of method of utilizing solid waste oil shale to prepare natural rubber filler is characterized in that it comprises the steps:
1), with solid waste oil shale pulverize, levigate, the solid waste oil shale superfine powder;
2), above-mentioned solid waste oil shale superfine powder is obtained the modification solid waste oil shale after the surface-modifying agent modification, the add-on of surface-modifying agent is 0.8～3% of a solid waste oil shale superfine powder quality, 80～200 ℃ of modification temperatures, modification time 15～30 minutes;
3), the mass ratio by modification solid waste oil shale and anti-aging agent is: choose modification solid waste oil shale and anti-aging agent at 10～60: 2～4, product [the modification solid waste oil shale mix with anti-aging agent product, mix respectively when perhaps modification solid waste oil shale and anti-aging agent are used as natural rubber filler]; Wherein, contain a kind of anti-aging agent that makes the heavy metal element passivation in the anti-aging agent at least, anti-aging agent is when (containing two kinds) more than two kinds, to be any proportioning.
Described solid waste oil shale is any one or any mixture that (contains two kinds) more than two kinds in resinous shale, oil shale waste, country rock, the rock mud, and any is any proportioning when (containing two kinds) more than two kinds and mixing.The main component of solid waste oil shale is kaolinite and quartz, contains a small amount of illite.
The granularity of described solid waste oil shale superfine powder is 3～15 μ m.
Described surface-modifying agent is silane coupling agent KH-570, stearic acid, calcium stearate or aluminic acid ester etc.Can improve the performance of cross-linked rubber through the solid waste oil shale of surface-modifying agent modification.
Described anti-aging agent is antioxidant A, antioxidant D, anti-aging agent RD, antioxidant 4010, antioxidant 4010NA etc.; Wherein antioxidant 4010, antioxidant 4010NA are the anti-aging agent that makes the heavy metal element passivation.
The application of the product of the present invention's preparation: the prescription of natural rubber vulcanized rubber is: 100 parts of natural rubbers, 1.5～3 parts in sulphur, 0.5～1.5 part of vulkacit D, 0.5～2.5 part of captax, 0.5～3 part of stearic acid, 3～5 parts in zinc oxide, 0.5～2.5 part in softening agent, 12～64 parts of natural rubber fillers (10～60 parts of modification solid waste oil shales, 2～4 parts in anti-aging agent).
The invention has the beneficial effects as follows:
1, the present invention utilizes solid waste oil shale to prepare natural rubber filler, and solid waste oil shale is mainly the low resinous shale of oil length, oil shale waste, rock mud, country rock or their mixture, thereby raw materials cost is low, and can reduce environmental pollution.
2, the filling effect of the solid waste oil shale filling natural rubber of surface modification is suitable with general carbon black, thereby solid waste oil shale can be used for substituting the filler of general carbon black as rubber.
3, at containing some heavy metal elements such as the Mn, the Cu that quicken ageing of rubber, Fe in the solid waste oil shale, add the anti-aging agent that makes the heavy metal element passivation in the solid waste oil shale, make the aging resistance of natural rubber vulcanized rubber obtain very big improvement, improve the ageing-resistant performance of natural rubber.
4, preparation technology of the present invention is simple, and solid waste oil shale is easy to mix with natural rubber, and maximum loading level can reach more than 60 parts.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
Comparative example 1:
The prescription of selecting following (mass ratio): natural rubber 100, sulphur 2.5, vulkacit D 1.0, captax 1.5, stearic acid 2.0, zinc oxide 5.0, anti-aging agent RD 1.0, antioxidant 4010NA 1.5, dibutyl phthalate 1.5, general carbon black 50.
The preparation method of cross-linked rubber is as follows: natural rubber is plasticated on opening rubber mixing machine, by above-mentioned prescription mixing back slice on opening rubber mixing machine, under 150 ℃ of curing temperatures, sulfide stress 15MPa, vulcanize then, make cross-linked rubber, the performance of test cross-linked rubber.The performance of its cross-linked rubber sees Table 1.
Comparative example 2:
Resinous shale, oil shale waste, country rock, rock mud were by 10: 50: 20: 20 mass ratio makes up oil behind the shale mixture, oven dry, ground for 10 seconds in vibration mill, ground 15 minutes in speed muller then, obtaining granularity is the resinous shale mixture powder of 3～15 μ m.The resinous shale mixture powder is put into high-speed mixer, the calcium stearate that adds resinous shale mixture powder quality 1% carries out surface modification under 170 ℃, modification time 20 minutes obtains the active resinous shale mixture powder (be called for short modified oil shale mixture) of calcium stearate surface modification.By the mass ratio of modified oil shale mixture and anti-aging agent is to choose modified oil shale mixture and anti-aging agent at 50: 1.0, natural rubber filler; Wherein, anti-aging agent is an antioxidant A.
The application of above-mentioned natural rubber filler: the prescription of cross-linked rubber is as follows: natural rubber 100, sulphur 2.5, vulkacit D 1.0, captax 1.5, stearic acid 2.0, zinc oxide 5.0, dibutyl phthalate 1.5, natural rubber filler (modified oil shale mixture 50, antioxidant A 1.0) 51.0.
The preparation method of cross-linked rubber is as follows: natural rubber is plasticated on opening rubber mixing machine, by above-mentioned prescription mixing back slice on opening rubber mixing machine, under 150 ℃ of curing temperatures, sulfide stress 15MPa, vulcanize then, make cross-linked rubber, the performance of test cross-linked rubber.The performance of its cross-linked rubber sees Table 1.
Embodiment 1:
A kind of method of utilizing solid waste oil shale to prepare natural rubber filler, it comprises the steps: that resinous shale, oil shale waste, country rock, rock mud were in 10: 50: 20: 20 ratio makes up oil behind the shale solid mixture, oven dry, in vibration mill, ground for 10 seconds, ground 15 minutes in speed muller then, making granularity is the resinous shale mixture powder of 3～15 μ m.The resinous shale mixture powder is put into high-speed mixer, and the calcium stearate that adds resinous shale mixture powder quality 1% carries out surface modification under 170 ℃, and modification time 20 minutes obtains modified oil shale mixture powder.By the mass ratio of modified oil shale mixture powder and anti-aging agent is to choose modified oil shale mixture powder and anti-aging agent at 50: 2.5, natural rubber filler; Wherein, anti-aging agent is antioxidant 4010NA and anti-aging agent RD, antioxidant 4010NA 1.5, anti-aging agent RD 1.0.
The application of above-mentioned natural rubber filler: the prescription of cross-linked rubber following (mass ratio): natural rubber 100, sulphur 2.5, vulkacit D 1.0, captax 1.5, stearic acid 2.0, zinc oxide 5.0, dibutyl phthalate 1.5, natural rubber filler (modified oil shale mixture 50, antioxidant 4010NA 1.5, anti-aging agent RD 1.0) 52.5.
The preparation method of cross-linked rubber is as follows: natural rubber is plasticated on opening rubber mixing machine, by above-mentioned prescription mixing back slice on opening rubber mixing machine, under 150 ℃ of curing temperatures, sulfide stress 15MPa, vulcanize then, make cross-linked rubber, the performance of test cross-linked rubber.The performance of its cross-linked rubber sees Table 1.
Embodiment 2:
A kind of method of utilizing solid waste oil shale to prepare natural rubber filler, it comprises the steps: that resinous shale, oil shale waste, country rock, rock mud were in 10: 50: 20: 20 ratio makes up oil behind the shale solid mixture, oven dry, in vibration mill, ground for 10 seconds, ground 15 minutes in speed muller then, making granularity is the resinous shale mixture powder of 3～15 μ m.The resinous shale mixture powder is put into high-speed mixer, and the calcium stearate that adds resinous shale mixture powder quality 1% carries out surface modification under 170 ℃, and modification time 20 minutes obtains modified oil shale mixture powder.By the mass ratio of modified oil shale mixture powder and anti-aging agent is to choose modified oil shale mixture powder and anti-aging agent at 60: 2.5, natural rubber filler; Wherein, anti-aging agent is antioxidant 4010NA and anti-aging agent RD, antioxidant 4010NA 1.5, anti-aging agent RD 1.0.
The application of above-mentioned natural rubber filler: the prescription of cross-linked rubber is as follows: natural rubber 100, sulphur 2.5, vulkacit D 1.0, captax 1.5, stearic acid 2.0, zinc oxide 5.0, dibutyl phthalate 1.5, natural rubber filler (the resinous shale mixture 60 of calcium stearate modification, antioxidant 4010NA 1.5, anti-aging agent RD 1.0) 62.5.
The preparation method of cross-linked rubber is as follows: natural rubber is plasticated on opening rubber mixing machine, by above-mentioned prescription mixing back slice on opening rubber mixing machine, under 150 ℃ of curing temperatures, sulfide stress 15MPa, vulcanize then, make cross-linked rubber, the performance of test cross-linked rubber.The performance of its cross-linked rubber sees Table 1.
Embodiment 3:
A kind of method of utilizing solid waste oil shale to prepare natural rubber filler, it comprises the steps: oil shale waste oven dry earlier, ground for 10 seconds in vibration mill, ground 15 minutes in speed muller then, making granularity is the oil shale waste powder of 3～15 μ m.The oil shale waste powder is put into high-speed mixer, and the calcium stearate that adds oil shale waste powder quality 1% carries out surface modification under 170 ℃, and modification time 20 minutes obtains modified oil shale ground-slag body.By the mass ratio of modified oil shale ground-slag body and anti-aging agent is to choose modified oil shale ground-slag body and anti-aging agent at 50: 2.5, natural rubber filler; Wherein, anti-aging agent is antioxidant 4010NA and anti-aging agent RD, antioxidant 4010NA 1.5, anti-aging agent RD 1.0.
The application of above-mentioned natural rubber filler: the prescription of cross-linked rubber is as follows: natural rubber 100, sulphur 2.5, vulkacit D 1.0, captax 1.5, stearic acid 2.0, zinc oxide 5.0, dibutyl phthalate 1.5, natural rubber filler (modified oil shale ground-slag body 50, antioxidant 4010NA 1.5, anti-aging agent RD 1.0) 52.5.
The preparation method of cross-linked rubber is as follows: natural rubber is plasticated on opening rubber mixing machine, by above-mentioned prescription mixing back slice on opening rubber mixing machine, under 150 ℃ of curing temperatures, sulfide stress 15MPa, vulcanize then, make cross-linked rubber, the performance of test cross-linked rubber.The performance of its cross-linked rubber sees Table 1.
Embodiment 4:
A kind of method of utilizing solid waste oil shale to prepare natural rubber filler, it comprises the steps: oil shale waste oven dry earlier, ground for 10 seconds in vibration mill, ground 15 minutes in speed muller then, making granularity is the oil shale waste powder of 3～15 μ m.The oil shale waste powder is put into high-speed mixer, and the calcium stearate that adds oil shale waste powder quality 1% carries out surface modification under 170 ℃, and modification time 20 minutes obtains modified oil shale ground-slag body.By the mass ratio of modified oil shale ground-slag body and anti-aging agent is to choose modified oil shale ground-slag body and anti-aging agent at 60: 2.5, natural rubber filler; Wherein, anti-aging agent is antioxidant 4010NA and anti-aging agent RD, antioxidant 4010NA 1.5, anti-aging agent RD 1.0.
The application of above-mentioned natural rubber filler: the prescription of cross-linked rubber is as follows: natural rubber 100, sulphur 2.5, vulkacit D 1.0, captax 1.5, stearic acid 2.0, zinc oxide 5.0, dibutyl phthalate 1.5, natural rubber filler (modified oil shale ground-slag body 60, antioxidant 4010NA 1.5, anti-aging agent RD 1.0) 62.5.
The preparation method of cross-linked rubber is as follows: natural rubber is plasticated on opening rubber mixing machine, by above-mentioned prescription mixing back slice on opening rubber mixing machine, under 150 ℃ of curing temperatures, sulfide stress 15MPa, vulcanize then, make cross-linked rubber, the performance of test cross-linked rubber.The performance of its cross-linked rubber sees Table 1.
Embodiment 5:
A kind of method of utilizing solid waste oil shale to prepare natural rubber filler, it comprises the steps: oil shale waste oven dry earlier, ground for 10 seconds in vibration mill, ground 15 minutes in speed muller then, making granularity is the oil shale waste powder of 3～15 μ m.The oil shale waste powder is put into high-speed mixer, and the silane coupling agent KH-570 that adds oil shale waste powder quality 1% carries out surface modification under 120 ℃, and modification time 30 minutes obtains modified oil shale ground-slag body.By the mass ratio of modified oil shale ground-slag body and anti-aging agent is to choose modified oil shale ground-slag body and anti-aging agent at 60: 2.5, natural rubber filler; Wherein, anti-aging agent is antioxidant 4010NA and anti-aging agent RD, antioxidant 4010NA 1.5, anti-aging agent RD 1.0.
The application of above-mentioned natural rubber filler: the prescription of cross-linked rubber is as follows: natural rubber 100, sulphur 2.5, vulkacit D 1.0, captax 1.5, stearic acid 2.0, zinc oxide 5.0, dibutyl phthalate 1.5, natural rubber filler (modified oil shale ground-slag body 60, antioxidant 4010NA 1.5, anti-aging agent RD 1.0) 62.5.
The preparation method of cross-linked rubber is as follows: natural rubber is plasticated on opening rubber mixing machine, by above-mentioned prescription mixing back slice on opening rubber mixing machine, under 150 ℃ of curing temperatures, sulfide stress 15MPa, vulcanize then, make cross-linked rubber, the performance of test cross-linked rubber.The performance of its cross-linked rubber sees Table 1.
Embodiment 6:
A kind of method of utilizing solid waste oil shale to prepare natural rubber filler, it comprises the steps: oil shale waste oven dry earlier, ground for 10 seconds in vibration mill, ground 15 minutes in speed muller then, making granularity is the oil shale waste powder of 3～15 μ m.The oil shale waste powder is put into high-speed mixer, and the stearic acid that adds oil shale waste powder quality 0.8% carries out surface modification under 90 ℃, and modification time 15 minutes obtains modified oil shale ground-slag body.By the mass ratio of modified oil shale ground-slag body and anti-aging agent is to choose modified oil shale ground-slag body and anti-aging agent at 60: 2.5, natural rubber filler; Wherein, anti-aging agent is antioxidant 4010NA and anti-aging agent RD, antioxidant 4010NA 1.5, anti-aging agent RD 1.0.
The application of above-mentioned natural rubber filler: the prescription of cross-linked rubber is as follows: natural rubber 100, sulphur 2.5, vulkacit D 1.0, captax 1.5, stearic acid 2.0, zinc oxide 5.0, dibutyl phthalate 1.5, natural rubber filler (modified oil shale ground-slag body 60, antioxidant 4010NA 1.5, anti-aging agent RD 1.0) 62.5.
The preparation method of cross-linked rubber is as follows: natural rubber is plasticated on opening rubber mixing machine, by above-mentioned prescription mixing back slice on opening rubber mixing machine, under 150 ℃ of curing temperatures, sulfide stress 15MPa, vulcanize then, make cross-linked rubber, the performance of test cross-linked rubber.The performance of its cross-linked rubber sees Table 1.
Embodiment 7:
A kind of method of utilizing solid waste oil shale to prepare natural rubber filler, it comprises the steps:
1), with solid waste oil shale pulverize, levigate, granularity be the solid waste oil shale superfine powder of 3～15 μ m; Described solid waste oil shale is a resinous shale;
2), above-mentioned solid waste oil shale superfine powder is obtained the modification solid waste oil shale after the surface-modifying agent modification, the add-on of surface-modifying agent is 1.0% of a solid waste oil shale superfine powder quality, 90 ℃ of modification temperatures, modification time 20 minutes; Described surface-modifying agent is the aluminic acid ester;
3), the mass ratio by modification solid waste oil shale and anti-aging agent is: choose modification solid waste oil shale and anti-aging agent, get natural rubber filler at 10: 2; Wherein, anti-aging agent is antioxidant A and antioxidant 4010NA, and the mass ratio of antioxidant A is 1, and the mass ratio of antioxidant 4010NA is 1.
The application of above-mentioned natural rubber filler: the prescription of natural rubber vulcanized rubber is: 100 parts of natural rubbers, 2.5 parts in sulphur, 1.0 parts of vulkacit Ds, 1.5 parts of captaxs, 1 part of stearic acid, 5 parts in zinc oxide, 0.5 part in softening agent, 12 parts of natural rubber fillers (10 parts of modification solid waste oil shales, 1 part of antioxidant A, 1 part of antioxidant 4010NA).
Embodiment 8:
A kind of method of utilizing solid waste oil shale to prepare natural rubber filler is characterized in that it comprises the steps:
1), with solid waste oil shale pulverize, levigate, granularity be the solid waste oil shale superfine powder of 3～15 μ m; Described solid waste oil shale is a country rock;
2), above-mentioned solid waste oil shale superfine powder is obtained the modification solid waste oil shale after the surface-modifying agent modification, the add-on of surface-modifying agent is 1% of a solid waste oil shale superfine powder quality, 120 ℃ of modification temperatures, modification time 30 minutes; Described surface-modifying agent is silane coupling agent KH-570;
3), the mass ratio by modification solid waste oil shale and anti-aging agent is: choose modification solid waste oil shale and anti-aging agent, get natural rubber filler at 60: 4; Described anti-aging agent is antioxidant A and antioxidant 4010, and the mass ratio of antioxidant A is 2, and the mass ratio of antioxidant 4010 is 2.
The application of above-mentioned natural rubber filler: the prescription of natural rubber vulcanized rubber is: 100 parts of natural rubbers, 2.5 parts in sulphur, 1.0 parts of vulkacit Ds, 1.5 parts of captaxs, 1.5 parts of stearic acid, 5 parts in zinc oxide, 1.5 parts in softening agent, 64 parts of natural rubber fillers (the modification solid waste oil shale is that 60 parts, antioxidant A are 2 parts, and antioxidant 4010 is 2 parts).
Discarded mixture of table 1 resinous shale and general carbon black cured properties
| Example | Filling kind | The surface-modifying agent kind | Carbon black or resinous shale umber/phr | Tensile strength/MPa | 300% stress at definite elongation/MPa | Tensile yield/% | Tear strength/kN m -1 | Hardness (Shao Er A)/degree | 70 ℃ * 72h of hot air aging | ||
| Tensile strength velocity of variation/% | Tensile yield velocity of variation/% | Changes in hardness/degree | |||||||||
| Comparative example 1 | General carbon black | 50 | ?16.4 | ?4.0 | ?596 | ?28.2 | ?50 | -6 | -6 | ?1 | |
| Comparative example 2 | The resinous shale mixture | Calcium stearate | 50 | ?16.6 | ?5.7 | ?512 | ?33.1 | ?61 | -69 | -48 | ?0 |
| Embodiment 1 | The resinous shale mixture | Calcium stearate | 50 | ?16.0 | ?5.7 | ?568 | ?25.9 | ?50 | -4 | -17 | ?1 |
| Embodiment 2 | The resinous shale mixture | Calcium stearate | 60 | ?14.3 | ?5.9 | ?530 | ?24.7 | ?52 | -5 | -16 | ?2 |
| Embodiment 3 | Oil shale waste | Calcium stearate | 50 | ?18.5 | ?5.1 | ?540 | ?32.4 | ?61 | -4 | -13 | ?1 |
| Embodiment 4 | Oil shale waste | Calcium stearate | 60 | ?16.3 | ?5.4 | ?510 | ?29.3 | ?62 | -6 | -14 | ?3 |
| Embodiment 5 | Oil shale waste | KH-5 70 | ?60 | ?13.9 | ?4.8 | ?520 | ?30.0 | ?58 | -5 | -8 | ?2 |
| Embodiment 6 | Oil shale waste | Stearic acid | 60 | ?14.0 | ?4.8 | ?540 | ?28.7 | ?57 | -6 | -9 | ?1 |
Annotate: the anti-aging agent of comparative example 2 is 1 part of antioxidant A in the table 1.Remaining example anti-aging agent is 1.5 parts of antioxidant 4010NAs and 1.0 parts of anti-aging agent RDs and uses.
Table 1 has illustrated: contain trace metal ions such as copper, iron, manganese in the solid waste oil shale, and the oxidising process of their strong catalysis rubber, the oxidation of quickening rubber destroys.Comparative example 2 anti-aging agent have only 1 part, and addition and does not add the anti-aging agent that makes metal passivation very little, are not enough to prevent the aging of cross-linked rubber, and ageing-resistant performance is very poor, and cross-linked rubber loses actual use value.The anti-aging agent addition is 2.5 parts among the embodiment 1～6, and the anti-aging agent addition is many, and a part is consumed in trace metal ion passivation such as being used for copper, iron, manganese in the solid waste oil shale, and another part is used for conventional the aging of cross-linked rubber that prevent.Under same filler umber, the over-all properties of modification solid waste oil shale rubbery system is better than general black rubber system.
The upper limit of modification temperature, lower limit can both be realized the present invention, do not enumerate embodiment one by one at this.
Claims (5)
1. a method of utilizing solid waste oil shale to prepare natural rubber filler is characterized in that it comprises the steps:
1), with solid waste oil shale pulverize, levigate, the solid waste oil shale superfine powder;
2), above-mentioned solid waste oil shale superfine powder is obtained the modification solid waste oil shale after the surface-modifying agent modification, the add-on of surface-modifying agent is 0.8～3% of a solid waste oil shale superfine powder quality, 80～200 ℃ of modification temperatures, modification time 15～30 minutes;
3), the mass ratio by modification solid waste oil shale and anti-aging agent is: choose modification solid waste oil shale and anti-aging agent at 10～60: 2～4, gets product; Wherein, contain a kind of anti-aging agent that makes the heavy metal element passivation in the anti-aging agent at least, anti-aging agent is more than two kinds the time, is any proportioning.
2. a kind of method of utilizing solid waste oil shale to prepare natural rubber filler according to claim 1, it is characterized in that: described solid waste oil shale is any one or any mixture more than two kinds in resinous shale, oil shale waste, country rock, the rock mud, and any is any proportioning when mixing more than two kinds.
3. a kind of method of utilizing solid waste oil shale to prepare natural rubber filler according to claim 1 is characterized in that: the granularity of described solid waste oil shale superfine powder is 3～15 μ m.
4. a kind of method of utilizing solid waste oil shale to prepare natural rubber filler according to claim 1 is characterized in that: described surface-modifying agent is silane coupling agent KH-570, stearic acid, calcium stearate or aluminic acid ester.
5. a kind of method of utilizing solid waste oil shale to prepare natural rubber filler according to claim 1 is characterized in that: described to make the anti-aging agent of heavy metal element passivation be that antioxidant 4010 is or/and antioxidant 4010NA.
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| CN107939881A (en) * | 2017-12-31 | 2018-04-20 | 三橡股份有限公司 | A kind of compartment damping rubber pad and preparation method thereof |
| CN110054812A (en) * | 2019-04-08 | 2019-07-26 | 沈阳化工大学 | It is a kind of using oil shale as the method for preparing rubber of filler |
| CN110330698A (en) * | 2019-04-04 | 2019-10-15 | 沈阳化工大学 | A kind of shale ashes modified natural rubber and preparation method thereof |
| CN110922649A (en) * | 2019-12-06 | 2020-03-27 | 桂林电子科技大学 | Rubber composite material and preparation method thereof |
| WO2022226863A1 (en) * | 2021-04-29 | 2022-11-03 | 德州学院 | Method for preparing, by using oil sand tailing, composite pigment and filler for coating |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1052128A (en) * | 1989-11-27 | 1991-06-12 | 湖南省煤炭科学研究所 | A kind of industrial filler that constitutes by slag |
| CN1042545C (en) * | 1993-07-29 | 1999-03-17 | 中国石化总公司茂名石油化工公司 | Oil shale ash-polyolefin loading and preparing process thereof |
-
2007
- 2007-03-16 CN CNB2007100516848A patent/CN100434461C/en not_active Expired - Fee Related
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| CN106220906A (en) * | 2016-08-14 | 2016-12-14 | 王法军 | A kind of preparation method of natural rubber/foundry waste composite |
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| CN106566291A (en) * | 2016-11-09 | 2017-04-19 | 中国神华能源股份有限公司 | Preparation method of filler, filler, as well as polyethylene composite material and preparation method thereof |
| CN106590066A (en) * | 2016-11-09 | 2017-04-26 | 中国神华能源股份有限公司 | Rubber packing preparation method, rubber packing and compound rubber |
| CN106566291B (en) * | 2016-11-09 | 2018-10-12 | 中国神华能源股份有限公司 | The preparation method of filler, filler, composite polyethylene material and preparation method thereof |
| CN106867065A (en) * | 2017-03-08 | 2017-06-20 | 吉林大学 | A kind of method that utilization modified oil shale semicoke prepares gum filler |
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| CN107939881A (en) * | 2017-12-31 | 2018-04-20 | 三橡股份有限公司 | A kind of compartment damping rubber pad and preparation method thereof |
| CN110330698A (en) * | 2019-04-04 | 2019-10-15 | 沈阳化工大学 | A kind of shale ashes modified natural rubber and preparation method thereof |
| CN110054812A (en) * | 2019-04-08 | 2019-07-26 | 沈阳化工大学 | It is a kind of using oil shale as the method for preparing rubber of filler |
| CN110922649A (en) * | 2019-12-06 | 2020-03-27 | 桂林电子科技大学 | Rubber composite material and preparation method thereof |
| CN110922649B (en) * | 2019-12-06 | 2022-02-08 | 桂林电子科技大学 | Rubber composite material and preparation method thereof |
| WO2022226863A1 (en) * | 2021-04-29 | 2022-11-03 | 德州学院 | Method for preparing, by using oil sand tailing, composite pigment and filler for coating |
| CN115443314A (en) * | 2021-04-29 | 2022-12-06 | 德州学院 | Method for preparing composite pigment and filler for paint by using oil sand tailings |
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