CN102516610B - Clay rubber nanocomposite for conveyor belt covering layer and preparation method thereof - Google Patents
Clay rubber nanocomposite for conveyor belt covering layer and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a clay rubber nano composite material for a conveyor belt covering layer and a preparation method thereof, which can be matched with various large-traffic and long-distance conveyors and can be widely applied to heavy industry such as metallurgy, coal mines, ports and the like. A clay rubber nanometer composite material for a conveyor belt covering layer is prepared by taking nanometer clay and natural rubber, preparing nanometer clay/natural rubber nanometer composite master batch through an emulsion flocculation method, adding synthetic rubber for plastication, sequentially adding zinc oxide, stearic acid, an anti-aging agent, a coupling agent and a reinforcing agent, carrying out primary mixing, adding sulfur and an accelerator, and carrying out secondary mixing to obtain a product; the covering rubber of the conveying belt is made of the clay rubber nano composite material, so that the tensile strength, the tearing strength and the cutting resistance of the covering rubber can be improved, and the service life of the conveying belt is prolonged. In the preparation process, a small amount of nano clay and a large amount of carbon black are used as a filling system, so that the reinforcing effect can be achieved, and the lamellar structure of the nano clay can effectively inhibit the transfer of gas and heat, so that the thermal-oxidative aging resistance of the conveying belt can be improved, and the conveying belt is not easy to age when being used in an open-air environment for a long time.
Description
Technical field
The present invention relates to a kind of conveyor belt covering with clay rubber nano composite material and preparation method thereof, can support the use with all kinds of large conveying quantities, long belt conveyor, be widely used in the heavy industry industries such as metallurgy, colliery, harbour.
Background technology
Along with the raising of whole world expanding economy and industrial automation level, the application surface of conveying belt becomes more and more wider, and demand is increasing, requires also more and more higher.The departments such as mine, building materials, chemical industry, harbour, grain, electric power and coal have proposed Secretary to mass transport: long distance (refers to the unit delivered length, reach most 15000m abroad, the domestic 8984m that reaches most), large conveying quantity (high belt speed and large bandwidth) and high spud angle (＞15 °).In order to satisfy the requirement of high-tenacity, rubber cover generally selects natural rubber as the rubber matrix of rubber cover, yet the chemical structure due to natural rubber, easily produce aging and corrosion in long-term open-air atmosphere, when cold weather (lower than-10 ℃), the easier embrittlement of crystallization is because occuring in natural rubber, thereby shortened the work-ing life of conveying belt.When transporting the sharp-pointed material of hard, out-of-shape, corner angle, although framework material is intact, rubber cover is subject to heavy wear, pierces through and tears and can not use.And at present, domestic manufacturer does not systematically test and evaluates anti-cutting, anti-puncture, anti-flexing fatigue and the aspects such as the growth of cracking resistance line and low-temperature physics mechanical property.Therefore these reasons have limited long range of application apart from conveying belt and work-ing life.
In order to extend long work-ing life apart from conveying belt, should improve following some performance of conveying belt: tear resistance, wear resisting property, counter-bending fatigue property, elasticity, ageing-resistant performance and cutting resistance as far as possible.Niu Honglong has introduced a kind of high abrasion steel cable core conveying belt in [the rubber and plastic utilization of resources, 2007 (6): 7-10], rubber cover adopts natural gum and cis-butadiene cement and use, has obtained tensile strength high (19.5MPa), wear-resistant (wear(ing)value 85mm
3) the high abrasion steel cable core conveying belt.Introduced a kind of anti-tear, antiwear conveying belt in CN200710020742.0, adopt natural rubber, solution polymerized butadiene styrene rubber and cis-1,4-polybutadiene rubber and use, add aramid fiber short fibre in infill system, and set up the belt carcass tension element between working face and non-working surface rubber cover, obtain excellent anti-tear performance, wear resisting property, improved work-ing life.Wang Di brightness etc. has been introduced a kind of cold-resistant difficult combustion steel cable core conveying belt in [China Rubber/plastics Technology and equipment, 2004,30:22-25], utilize natural rubber and cis-1,4-polybutadiene rubber and use, has obtained that under normal temperature, tensile strength is 18MPa, and wear(ing)value is 108mm
3, both can guarantee good physical and mechanical properties at refrigerant latitudes, can significantly improve again the formula of cold tolerance (under 45 ℃, cold-resistant coefficient is 0.6).
For conveyer belt coating rubber, affect the factor in its work-ing life except tensile strength and wear resisting property, also have even more important tear resistance, cutting resistance energy, cracking resistance line to increase performance and anti-flexing fatigue performance.And in above design for rubber formulation, only considered the impact of tensile strength and abrasion, and can't satisfy the high-tenacity conveying belt DIN-X rank standard in German standard DIN22131 T1: tensile strength 〉=25.0MPa, tensile yield 〉=450%, cylinder wear(ing)value≤120mm
3
Summary of the invention
The purpose of this invention is to provide a kind of conveyor belt covering clay rubber nano composite material and preparation method thereof, it comprises rubber matrix and the corresponding auxiliary agent that adds.The synergy of tradition strengthening agent and nanoclay makes rubber cover have high-tenacity, high anti-tear texts; Because nanoclay lamella in rubber disperses, the performances such as the anti-cutting of rubber cover, anti-flexing fatigue, the growth of cracking resistance line have been improved; Laminated structure has certain barrier properties for gases simultaneously, has improved the ageing resistance of rubber cover, thereby has realized the long lifetime of conveying belt.Meanwhile, this product has higher brute force at low temperatures, and can not crack or brittle failure, has overcome the shortcomings such as conveying belt can't use due to low-temperature embrittleness in cold area.
Technical scheme of the present invention: a kind of conveyor belt covering clay rubber nano composite material, get nanoclay and natural rubber and prepare the compound rubber master batch of nanoclay/natural rubber nano by the emulsion flocculence, then adding synthetic rubber plasticates, add successively again after zinc oxide, stearic acid, anti-aging agent, coupling agent, strengthening agent once mixingly, add the mixing product that obtains of secondary after sulphur, promotor;
Concrete component is as follows: natural rubber: 60-100 part, synthetic rubber: 0-40 part, nanoclay: 1-10 part, sulphur: 1.0-2.5 part, zinc oxide: 3-6 part, stearic acid: 1-3 part, promotor: 1.5-2.5 part, strengthening agent: 30-60 part, tenderizer: 0-6 part, anti-aging agent: 1-5 part and coupling agent: 1-10 part.
A kind of conveyor belt covering preparation method of clay rubber nano composite material, step is:
(1) preparation of the compound rubber master batch of nanoclay/natural rubber nano: get nanoclay 1-10 part and be dissolved in 10-100 part water, contain natural rubber 60-100 part, concentration is 41% rubber latex, the suspension of nanoclay and water is mixed with rubber latex, form uniform mixed solution, add the flocculation agent of mixed solution gross weight 1%-5% to flocculate, filtration obtains throw out, obtains nanoclay/natural rubber nano composite material after spraying drying;
(2) one sections mixing: the compound rubber master batch of nanoclay/natural rubber nano and synthetic rubber 0-40 part of adding step (1) preparation in two roller mills, 30-45s plasticates, then add successively zinc oxide 3-6 part, stearic acid 1-3 part, anti-aging agent 1-5 part, coupling agent 1-10 part, strengthening agent 30-60 part, mixing 10-15min parks 12-16h, obtains one section rubber unvulcanizate;
(3) two-stage mixing: add sulphur 1.0-2.5 part in one section rubber unvulcanizate of step (2) gained, promotor 1.5-2.5 part obtains two-stage mixing glue after mixing 2-5min, be product conveyor tectum clay rubber nano composite material again.
Described nanoclay is inorganic polynite and/or organo montmorillonite.
Described synthetic rubber is styrene-butadiene rubber(SBR) or cis-1,4-polybutadiene rubber.
Natural rubber in rubber matrix and nanoclay are to adopt the preparation of emulsion flocculence, are provided by inthe Shanmen area, Siping, Jilin province city Liu house mining industry company limited, add with the form of the compound rubber master batch of nanoclay/natural rubber nano.Than traditional pure carbon black filled system, the lamella of nanoclay in rubber disperses, the effect of existing enhancing, the anti-cutting that also can improve rubber, anti-flexing fatigue, the growth of cracking resistance line, barrier properties for gases and ageing resistance, thus improved long work-ing life apart from conveying belt.And the consumption of nanoclay is unsuitable too high, and the too high wear resistance that can reduce rubber cover of umber reduces work-ing life.Than the ball-like structure of carbon black, the laminated structure of nanoclay uniqueness to a certain extent can passivation branching crack tip, and crackle is deflected, and the cracking resistance line that therefore can improve nano composite material increases performance; Find with the surface that SEM observes after cutting, adding of nanoclay makes the rear section of cutting relatively smooth, there is no obvious cavity and groove, and good belt cutting-resisting property is arranged.
In rubber matrix, synthetic rubber is styrene-butadiene rubber(SBR) and/or cis-1,4-polybutadiene rubber.Styrene-butadiene rubber(SBR) has certain heatproof air aging performance, and the wear resisting property of cis-1,4-polybutadiene rubber and low-temperature performance are all very excellent.
Described promotor is DM:2,2 '-dithio-bis-benzothiazole, DTDM:4,4`-dimorpholinyl disulfide or TMTD: tetramethyl-thiuram disulfide.Promotor is adopted suitable cross-linking system, not only can obtain good coke burning performance and processing characteristics, and good crosslinking structure can also be provided, thereby obtains excellent physical and mechanical properties.
Described strengthening agent is super-high wear-resistant carbon black N115, intermediate super abrasion furnace black N220 or high abrasion furnace carbon black N330.Carbon black in strengthening agent and the synergy of nanoclay can improve intensity and the wear resisting property of rubber cover.
Described anti-aging agent is RD:2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer, the combination of any one in 4010NA:N-sec.-propyl-N`-diphenyl-para-phenylene diamine, 4020:N-(1,3-dimethylbutyl)-N '-diphenyl-para-phenylene diamine or MC:N-(4-anilino phenyl) maleimide or any two kinds.Anti-aging agent has good thermo oxidative aging performance, ozone resistance and ultraviolet aging resistance performance.
Described coupling agent is silane coupling agent, comprises solid silicone coupling agent and/or liquid silane coupling agent.Coupling agent can effectively improve nanoclay is combined with the interface of rubber, thereby reaches high strength, high anti-tear effect.
Described tenderizer is the petroleum softening agent, and coal tar is softening agent, and pine tar is softening agent, the combination of one or both in fatty series softening agent and synthetic softening agent.
Described flocculation agent is calcium chloride or hydrogenchloride.
The high-tenacity conveying belt DIN-X rank that the physical and mechanical properties of product satisfies in German standard DIN22131 T1 requires: tensile strength 〉=25.0MPa, tensile yield 〉=450%, cylinder wear(ing)value≤120mm
3
The invention has the beneficial effects as follows: the present invention adopts the nanoclay rubber nano composite material to make the rubber cover of conveying belt, can improve its tensile strength, tear strength and cutting resistance energy, thereby improves the work-ing life of conveying belt.Adopt a small amount of nanoclay in preparation process with a large amount of carbon blacks and be used as infill system, not only can play the effect of enhancing, and the laminated structure of nanoclay can effectively suppress gas and heat transfer, thereby can carry its heatproof air aging performance, be difficult for aging in the open when making conveying belt use in environment for a long time.Adopting another advantage of nanoclay is the crack tip of passivation branching to a certain extent, and crackle is deflected, and can play the effect that the cracking resistance line increases when transporting the sharp-pointed material of hard, out-of-shape, corner angle.
Embodiment
Embodiment 1
in two rod mills, add and contain 1 part of nanoclay, 40 parts of the nanoclay of 60 parts of natural rubbers/natural rubber rubber master batch (inthe Shanmen area, Siping, Jilin province city Liu house mining industry company limited) and cis-1,4-polybutadiene rubbers (BR9000) are plasticated, then add successively 1 part of 3 parts, zinc oxide and stearic acid, 2, 2, 4-trimethylammonium-1, 1 part of 2-dihyaroquinoline (RD), N-sec.-propyl-1 part of N`-diphenyl-para-phenylene diamine (4010NA), 2 parts of solid silicone coupling agents, 40 parts of carbon black N115, carry out once mixing, after parking 12 hours, add linking agent and additional crosslinker: 1 part, sulphur and 2, 2 '-2 parts of dithio-bis-benzothiazoles (DM), mix 2min and obtain two-stage mixing glue in mill.
Vulcanize on vulcanizing press, 150 ℃ of curing temperatures, sulfide stress are 10MPa.The physical and mechanical properties of its rubber cover sees Table 1.
Embodiment 2
in two rod mills, add and contain 5 parts of nanoclays, the nanoclay of 80 parts of natural rubbers/natural rubber rubber master batch (inthe Shanmen area, Siping, Jilin province city Liu house mining industry company limited), 10 parts of 10 parts, styrene-butadiene rubber(SBR) (SBR1502) and cis-1,4-polybutadiene rubbers (BR9000) are plasticated, then add successively 2 parts of 5 parts, zinc oxide and stearic acid, 2, 2, 4-trimethylammonium-1, 1 part of 2-dihyaroquinoline (RD), 1 part of N-(4-anilino phenyl) maleimide (MC), 3 parts of solid silicone coupling agents, 50 parts of carbon black N220, carry out once mixing, after parking 12 hours, add linking agent and additional crosslinker: 2 parts, sulphur and 4, 2 parts of 4`-dimorpholinyl disulfides (DTDM), mix in mill and obtain two-stage mixing glue.
Vulcanize on vulcanizing press, 150 ℃ of curing temperatures, sulfide stress are 10MPa.The physical and mechanical properties of its rubber cover sees Table 1.
Embodiment 3
in two rod mills, add the nanoclay that contains 8 parts of nanoclays and 100 parts of natural rubbers/natural rubber rubber master batch 380g, 30 parts of 10 parts, styrene-butadiene rubber(SBR) (SBR1502) and cis-1,4-polybutadiene rubbers (BR9000) are plasticated, then add successively 2 parts of 5 parts, zinc oxide and stearic acid, 1 part of N-(4-anilino phenyl) maleimide (MC), N-sec.-propyl-1 part of N`-diphenyl-para-phenylene diamine (4010NA), 3 parts of solid silicone coupling agents, 60 parts of carbon black N330, carry out once mixing, after parking 12 hours, add linking agent and additional crosslinker: 2 parts, sulphur and 4, 2 parts of 4`-dimorpholinyl disulfides (DTDM), mix in mill and obtain two-stage mixing glue.
Vulcanize on vulcanizing press, 150 ℃ of curing temperatures, sulfide stress are 10MPa.The physical and mechanical properties of its rubber cover sees Table 1.
Embodiment 4
in two rod mills, add and contain 8 parts of nanoclays, the nanoclay of 70 parts of natural rubbers/natural rubber rubber master batch, 10 parts of 10 parts, styrene-butadiene rubber(SBR) (SBR1502) and cis-1,4-polybutadiene rubbers (BR9000) are plasticated, then add successively 2 parts of 5 parts, zinc oxide and stearic acid, 2, 2, 4-trimethylammonium-1, 1 part of 2-dihyaroquinoline (RD), N-(1, the 3-dimethylbutyl)-N '-(4020) 1 parts of diphenyl-para-phenylene diamines, 3 parts of solid silicone coupling agents, 40 parts of carbon black N115, carry out once mixing, after parking 12 hours, add linking agent and additional crosslinker: 2 parts of 2 parts, sulphur and tetramethyl-thiuram disulfides (TMTD), mix in mill and obtain two-stage mixing glue.
Vulcanize on vulcanizing press, 150 ℃ of curing temperatures, sulfide stress are 10MPa.The physical and mechanical properties of its rubber cover sees Table 1.
The comparative example 1
In two rod mills, add natural rubber (commercially available 10# standard rubber) 500g to plasticate, then add successively zinc oxide 25g and stearic acid 10g, 2,2,4-trimethylammonium-1,2-dihyaroquinoline (RD) 5g, N-sec.-propyl-N`-diphenyl-para-phenylene diamine (4010NA) 5g, solid silicone coupling agent 15g, carbon black N115200g, carry out once mixing, after parking 12 hours, add linking agent and additional crosslinker: sulphur 9g and 2,2 '-dithio-bis-benzothiazole (DM) 10g mixes in mill and obtains two-stage mixing glue.Vulcanize on vulcanizing press, 150 ℃ of curing temperatures, sulfide stress are 10MPa.The physical and mechanical properties of its rubber cover sees Table 1.
The comparative example 2
in two rod mills, add natural rubber (commercially available 10# standard rubber) 400g, styrene-butadiene rubber(SBR) (SBR1502) 100g plasticates, then add successively zinc oxide 25g and stearic acid 10g, 2, 2, 4-trimethylammonium-1, 2-dihyaroquinoline (RD) 5g, N-sec.-propyl-N`-diphenyl-para-phenylene diamine (4010NA) 5g, solid silicone coupling agent 15g, carbon black N115 200g, carry out once mixing, after parking 12 hours, add linking agent and additional crosslinker: sulphur 9g and 4, 4`-dimorpholinyl disulfide (DTDM) 10g, mix and obtain two-stage mixing glue in mill.Vulcanize on vulcanizing press, 150 ℃ of curing temperatures, sulfide stress are 10MPa.The physical and mechanical properties of its rubber cover sees Table 1.
Table 1: the Performance Ratio of the embodiment of the present invention and Comparative Examples
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative Examples 1 | Comparative Examples 2 | |
| Shao A hardness | 60 | 62 | 60 | 65 | 63 | 63 |
| 300% tensile modulus/MPa | 8.5 | 8.3 | 8.0 | 8.7 | 6.7 | 6.7 |
| Tensile strength/MPa | 28.4 | 27.8 | 27.9 | 28.2 | 23.3 | 22.4 |
| Elongation at break/% | 630 | 647 | 656 | 624 | 676 | 657 |
| Tension set/% | 20 | 24 | 24 | 20 | 28 | 28 |
| Angle tear strength/KN/m | 120 | 107 | 104 | 112 | 90 | 86 |
| Cylinder abrasion/mm 3 | 75 | 68 | 80 | 69 | 93 | 93 |
| -40 ℃ of tensile strength/MPa | 34.0 | 32.7 | 33.5 | 34.3 | 33.7 | 32.5 |
| -40 ℃ of elongation at break/% | 579 | 520 | 546 | 585 | 430 | 358 |
| 70 ℃ of * 7d aging coefficients | 0.84 | 0.85 | 0.87 | 0.89 | 0.62 | 0.64 |
| Anti-cutting quality loss/g | 1.68 | 1.59 | 1.63 | 1.67 | 1.87 | 1.90 |
The physical and mechanical properties testing method of conveyer belt coating rubber is come the mechanical property of test compound material by the ASTMD412 standard.Stretching experiment adopts the wide cut-off knife of 6.00mm dumbbell plate processed without exception, tears experiment and tears sample for perpendicular type.Draw speed is 500mm/min, and probe temperature is 23 ℃.The cryogenic stretching performance test is completed on high low temperature puller system, and the temperature setting of high-low temperature chamber is tested according to the tensile property testing standard after being set to-40 ℃.Cutting resistance can test be to adopt the RCC-I of all things on earth Yifang Technology Co., Ltd. type rubber dynamic machine of anti-cutting test the in Beijing to test, test condition: cutting knife frequency of impact: 2Hz, sample rotating speed: 720rpm.Experimental result represents with the quality loss of sample before and after test.Other performance tests are all completed according to the ASTM standard.
The physical and mechanical properties of the embodiment that surveys is tensile strength 〉=27.0MPa, tensile yield 〉=500%, angle tear strength 〉=100KN/m, cylinder wear(ing)value≤80mm
3, hardness 60-65A (Shao Er).
Comparative example 1 and 2 the general natural rubber of rubber cover, its every physical and mechanical properties all is starkly lower than embodiment.Adopt in the present invention nanoclay/natural rubber rubber master batch, can effectively improve tear strength, in use effectively suppress crack propagation, also can further improve the tensile strength of rubber cover and the work-ing life of conveying belt.
Claims (7)
1. a conveyor belt covering with the preparation method of clay rubber nano composite material, is characterized in that step is:
(1) preparation of the compound rubber master batch of nanoclay/natural rubber nano: get nanoclay 1-10 part and be dissolved in 10-100 part water, contain natural rubber 60-100 part, concentration is 41% rubber latex, the suspension of nanoclay and water is mixed with rubber latex, form uniform mixed solution, add the flocculation agent of mixed solution gross weight 1%-5% to flocculate, filtration obtains throw out, obtains nanoclay/natural rubber nano composite material after spraying drying;
(2) one sections mixing: the compound rubber master batch of nanoclay/natural rubber nano and synthetic rubber 0-40 part of adding step (1) preparation in two roller mills, 30-45s plasticates, then add successively zinc oxide 3-6 part, stearic acid 1-3 part, anti-aging agent 1-5 part, coupling agent 1-10 part, strengthening agent 30-60 part, mixing 10-15min parks 12-16h, obtains one section rubber unvulcanizate;
(3) two-stage mixing: add sulphur 1.0-2.5 part in one section rubber unvulcanizate of step (2) gained, promotor 1.5-2.5 part obtains two-stage mixing glue after mixing 2-5min, be product conveyor tectum clay rubber nano composite material again;
Described synthetic rubber is styrene-butadiene rubber(SBR) and/or cis-1,4-polybutadiene rubber; Described coupling agent is silane coupling agent;
Described nanoclay is inorganic polynite and/or organo montmorillonite.
According to claim 1 conveyor belt covering with the preparation method of clay rubber nano composite material, it is characterized in that: described promotor is DM:2,2'-dithio-bis-benzothiazole, DTDM:4,4`-dimorpholinyl disulfide or TMTD: tetramethyl-thiuram disulfide.
3. conveyor belt covering is with the preparation method of clay rubber nano composite material according to claim 1, and it is characterized in that: described strengthening agent is super abrasion resistant carbon black N115, intermediate super abrasion furnace black N220 or high abrasion furnace carbon black N330.
According to claim 1 conveyor belt covering with the preparation method of clay rubber nano composite material, it is characterized in that: described anti-aging agent is RD:2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer, 4010NA:N-sec.-propyl-N`-diphenyl-para-phenylene diamine, 4020:N-(1,3-dimethylbutyl) any one in-N'-diphenyl-para-phenylene diamine or MC:N-(4-anilino phenyl) maleimide or the wherein combination of two kinds.
5. conveyor belt covering is with the preparation method of clay rubber nano composite material according to claim 1, and it is characterized in that: described silane coupling agent is solid silicone coupling agent and/or liquid silane coupling agent.
According to claim 1 conveyor belt covering with the preparation method of clay rubber nano composite material, it is characterized in that: described tenderizer is the petroleum softening agent, coal tar is softening agent, and pine tar is softening agent, a kind of or wherein combination of two kinds in fatty series softening agent and synthetic softening agent.
7. conveyor belt covering is with the preparation method of clay rubber nano composite material according to claim 1, and it is characterized in that: described flocculation agent is calcium chloride or hydrogenchloride.
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| JP7110551B2 (en) * | 2017-04-05 | 2022-08-02 | 横浜ゴム株式会社 | conveyor belt |
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