CN103435877A - High-abrasion-resistance rubber/phyllosilicate nano composite material flame-retardant steel cord conveyer belt cover rubber and preparation method thereof - Google Patents

High-abrasion-resistance rubber/phyllosilicate nano composite material flame-retardant steel cord conveyer belt cover rubber and preparation method thereof Download PDF

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CN103435877A
CN103435877A CN2013104089607A CN201310408960A CN103435877A CN 103435877 A CN103435877 A CN 103435877A CN 2013104089607 A CN2013104089607 A CN 2013104089607A CN 201310408960 A CN201310408960 A CN 201310408960A CN 103435877 A CN103435877 A CN 103435877A
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rubber
composite material
steel cord
fire
conveyor belt
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CN103435877B (en
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陈林
宋国君
马培瑜
李培耀
李明霞
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Qingdao Huaxia Rubber Industry Co Ltd
Qingdao University
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Qingdao Huaxia Rubber Industry Co Ltd
Qingdao University
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Abstract

The invention discloses a high-abrasion-resistance rubber/phyllosilicate nano composite material flame-retardant steel cord conveyer belt cover rubber and a preparation method thereof. The preparation method comprises the following steps: selecting high-flame-retardancy chloroprene rubber and high-elasticity cis-1,4-polybutadiene rubber as main raw materials, preparing nano phyllosilicate by an intercalation process, and intensely mixing the nano phyllosilicate with the rubbers and a compounding agent thereof by a mechanical blending process to prepare the rubber/phyllosilicate nano composite material cover rubber. Since the phyllosilicate in the prepared composite material is uniformly dispersed in the system in a nano lamina mode; and the phyllosilicate has favorable binding force with the rubber base, thereby greatly synchronously enhancing the abrasion resistance, tearing strength, aging resistance, dielectric resistance, heat resistance, flame retardancy and the like of the composite material and the conveyer belt, and prolonging the service life of the conveyer belt. The conveyer belt cover rubber disclosed by the invention has the advantages of long service life and high cost performance. The invention has important application value.

Description

Fire-retardant Steel Cord Conveyor Belt rubber cover of a kind of high wear-resistant rubber/laminated nm-silicate composite material and preparation method thereof
Technical field
The invention belongs to technical field of polymer materials, be specifically related to fire-retardant Steel Cord Conveyor Belt rubber cover of a kind of high wear-resistant rubber/laminated nm-silicate composite material and preparation method thereof.
Background technology
Rubber conveyer belt is a kind of important rubber product, it is the important means that modern industry material and product are carried, be widely used in each department of the national economy such as colliery, electric power, cement, iron and steel, chemical industry, harbour, its consumption is very big, in rubber product only time and tire.Be that the conveying belt industry is put forward high-quality most important research direction the work-ing life of improving conveying belt, is also that the scientific worker is devoted to the sixty-four dollar question solved always.And affect at present in the factor in conveying belt life-span, more than 95%, be that conveyer belt coating rubber wears away, expose framework material and lose practical value.Other is mainly improper use and cause destroying.The wear resisting property quality of conveyer belt coating rubber just becomes that to affect the most important of work-ing life be also the factor of most critical.Therefore, how improving the conveyer belt coating rubber wear resisting property is current raising conveying belt quality, the most important problem increased the service life.
Affect rubber cover actual wear resisting property be a composite factor, except the wear resisting property of the rubber cover of lab investigation itself, in actual the use also with tear resistance (in actual the use, because of rib shape thing incised wound rubber cover, accelerating abrasion), ageing-resistant performance (actual use in because of the aging wear resisting property that reduces rubber cover), the performances such as medium-resistance (because of the environment greasy dirt, the contact rubber covers such as soda acid cause rubber cover swelling etc. and reduced the wear resisting property of rubber cover) are closely related.
For a long time, the method that improves the wear resisting property of conveyer belt coating rubber is mainly to add the strengthening agents such as carbon black and white carbon black, yet need to adding in a large number, these strengthening agents just can significantly improve wear resisting property (and severe contamination), and in rubber matrix, add to when a certain amount of, the comprehensive physical mechanical property has reached the limit, continue to improve that addition can cause that the sizing material processing performance is poor, product hardness is high on the contrary, causes the material early damage in flexibility decrease, use procedure.Therefore how to improve the wear resisting property of rubber cover, and then be a serious bottleneck problem work-ing life of raising conveying belt always.The strengthening agent (being mainly wear-resisting) of finding a kind of excellent combination property is the important topic that the scientific worker is devoted to research for a long time always.
The wear resisting property that the research of rubber/lamellar silicate nanometer composite material is conveying belt provides a new opportunity.Layered silicate is a kind of natural mineral, itself is exactly the nanoscale structures of stratiform, and it is by diameter 100 nanometers, and thickness is the lamella of 1 nanometer approximately, by the Van der Waals force formation that is superimposed.By effective means, layered silicate is carried out to chemical treatment, then, with rubber combined, can under shearing action, make layered silicate realize splitting, and then be dispersed in rubber matrix with the form of nanoscale twins.Research shows, adds the seldom layered silicate of amount (3wt% weight part), can make the over-all propertieies such as tensile strength, wear resisting property, tear resistance, ageing-resistant performance and medium-resistance of rubber significantly improve, and processing performance is constant.
For a long time, people never are interrupted the exploration to this problem.Chinese patent " clay-rubber nm-class composite material and preparation method thereof for a kind of used for conveyer belt tectum " (application number 201110404103.0, publication number CN102516610A) a kind of latex coprecipitation method that first adopts is disclosed, directly add the natural rubber latex Ruzhong to be condensed clay (layered silicate), prepare the coprecipitated glue of natural rubber/layered silicate and make rubber master batch, and then carry out compoundly with synthetic rubber and Synergist S-421 95 thereof, prepare clay-rubber nm-class composite material as conveyor belt covering.Can only prepare by this method take the clay-rubber nm-class composite material conveyor belt covering that natural rubber is basic glue, and need to be first coprecipitated compound with nature rubber latex and clay, and the production process complexity is time-consuming.But technique scheme preparation method is more loaded down with trivial details, and have not improved significantly the performance of conveying belt.
Summary of the invention
In prior art, the present invention proposes fire-retardant Steel Cord Conveyor Belt rubber cover of a kind of high-wear-resistance long-service-life rubber/lamellar silicate nanometer composite material and preparation method thereof.
For achieving the above object, the present invention adopts following technical proposals to be achieved:
The fire-retardant Steel Cord Conveyor Belt rubber cover of a kind of high-wear-resistance long-service-life rubber/lamellar silicate nanometer composite material, it comprises following component: have than the chloroprene rubber of high flame retardant wireline ageing-resistant performance and cis-1,4-polybutadiene rubber and with rubber totally 100 weight parts, organic modified sheet silicate 1-50 weight part, vulcanizing agent 1-8 weight part, packing strengthening agent 1-80 weight part, anti-aging agent 1-5 weight part and tenderizer 1-50 weight part, the part by weight of described chloroprene rubber and cis-1,4-polybutadiene rubber is 70-90:30-10.
The present invention also provides the preparation method of the fire-retardant Steel Cord Conveyor Belt rubber cover of described high-wear-resistance long-service-life rubber/lamellar silicate nanometer composite material, it comprises the following steps: the chloroprene rubber of the described consumption of weighing and the cis-1,4-polybutadiene rubber of good springiness, organic modified sheet silicate, vulcanizing agent, packing strengthening agent, anti-aging agent and tenderizer prepare the fire-retardant Steel Cord Conveyor Belt rubber cover of rubber/lamellar silicate nanometer composite material by mechanically mixing, mixing step.
Compared with prior art, advantage of the present invention and positively effect are: the invention discloses fire-retardant Steel Cord Conveyor Belt rubber cover of a kind of high wear-resistant rubber/laminated nm-silicate composite material and preparation method thereof.At first selecting chloroprene rubber that flame retardant properties is good and the cis-1,4-polybutadiene rubber of good springiness is body material, utilize graft process to prepare nano layered silicate, then by the mechanical blending method by itself and rubber and Synergist S-421 95 powerful mixing thereof, prepare rubber/lamellar silicate nanometer composite material rubber cover, again that this matrix material and framework material is compound, prepare the fire-retardant Steel Cord Conveyor Belt of high-wear-resistance long-service-life.
Superiority of the present invention is: (1) chloroprene rubber and cis-1,4-polybutadiene rubber also is used as basic glue, two kinds of rubber performances are learnt from other's strong points to offset one's weaknesses, bring out the best in each other, both brought into play the ageing-resistant characteristic of fire-retardant wireline of chloroprene rubber, the good characteristics of cis-1,4-polybutadiene rubber wear resisting property have been brought into play again, for fire-retardant Steel Cord Conveyor Belt has been accomplished fluently basis substantially; (2) add a small amount of organic modified sheet silicate, because the form of prepared matrix material laminate silicate with nanoscale twins is dispersed in system, and there is good bonding force with rubber matrix, synchronously improve significantly the wear resisting property, tear strength of matrix material and conveying belt, ageing-resistant, media-resistant, heat-resisting and flame retardant properties etc., improved the work-ing life of conveying belt, the product cost performance is high; (3) the method method by mechanical blending prepares conveyer belt coating rubber, can carry out the production of rubber cover and conveying belt under the prerequisite that does not change existing conveying belt refining glue and production technique, and technique is simple, and production cost is low, easily realizes industrialization.
The present invention can carry out the production of novel high-performance conveying belt under the prerequisite that does not change existing rubber conveyer belt basic production technique, and technique is simple.Prepared conveying belt long service life, cost performance is high.There is important using value.
After reading the specific embodiment of the present invention, it is clearer that the other features and advantages of the invention will become.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is described in further detail.
Embodiment 1
The preparation method of the fire-retardant Steel Cord Conveyor Belt rubber cover of high wear-resistant rubber/laminated nm-silicate composite material of the present invention comprises the following steps:
1, starting material component
Component (A) is rubber, component (B) is organic modified sheet silicate (referring to the preparation of organic modified sheet silicate), and component (C) is vulcanizing agent and vulcanization aid, and component (D) is packing strengthening agent, component (E) is anti-aging agent, and component (F) is tenderizer.
2, the preparation of organic modified sheet silicate (B component)
The laminar silicic acid salt mine, after the removal of impurity, desanding, the means such as sieve are carried out purifying, drying, is ground layered silicate with ball mill, and by 325 purpose sieve, the ion exchange capacity of the layered silicate obtained is 96.4meq/100g.The 0.01M HCL that the 1.8g amino dodecane is dissolved in to the 1000ml of 60 ℃ makes solution, the 10g layered silicate adds in this solution gradually, the suspension concuss 3h obtained, with deionized water, repeatedly wash again, filtered residue, at 80 ℃ of lower vacuum-drying 12h, is regrinded and carefully through 325 purpose sieve, is just obtained organic modified sheet silicate.
3, the preparation of rubber/lamellar silicate nanometer composite material
Adopt variable ratio frequency changer speed governing internal rubber mixer, at first add chloroprene rubber and cis-1,4-polybutadiene rubber, organic modified sheet silicate, packing strengthening agent, anti-aging agent, tenderizer and vulcanization aid, under 30 rev/mins of rotating speeds mixing 10 minutes, then being adjusted to rotating speed is 50 rev/mins, mixing 15 minutes, sheet under discharging.After sizing material is placed and is cooled to normal temperature, then add vulcanizing agent (sulphur etc.) on opening rubber mixing machine, refine glue after three minutes, thin-pass 3-5 time under the roll spacing of 2-3 millimeter, lower is stand-by.
The preparation method of described organic modified sheet silicate is as follows: by the layered silicate removal of impurities, grind, sieve, then with intercalator, dispersion medium or tensio-active agent, by ion exchange treatment, obtain the layered silicate of modification.Described layered silicate is one or more in clay, swelling, native polynite, carclazyte, terre verte, talcum powder, beidellite, hectorite, silica, halloysite, montmorillonite or Meccah stone.Described intercalator is lauryl amine, octadecylamine, thanomin, diethanolamine, trolamine, lauric acid amine, hexanolactam, hexanediamine, trimethylammonium ammonia chloride, quaternary amine, one or more in phenyl-ethyl amine or Ursol D.Described tensio-active agent is linear alkyl benzene sulphonic acid class, branched-chain alkyl phenyl Sulfonates, alkylsurfuric acid salt, sylvic acid salt, alkyl polyvinyl ether Sulfates or quaternary ammonium salt.Described dispersion medium can be water, ethanol, ethylene glycol, 1,3-propyl alcohol, BDO, one or more in acetone or chaff ketone.
Described packing strengthening agent is carbon black, white carbon black, calcium carbonate or potter's clay.
Described anti-aging agent is 4010N or ODA.
Described tenderizer is aromatic hydrocarbon oil, process oil, naphthenic oil, dibutyl phthalate or vegetables oil and modification derivant thereof.
Embodiment 2
Take chloroprene rubber/cis-1,4-polybutadiene rubber (part by weight is 70:30) and with glue as the main raw material conveyer belt coating rubber is example, preparation method and the performance (experimental group 1-3 and comparative group) of the fire-retardant Steel Cord Conveyor Belt rubber cover of rubber/lamellar silicate nanometer composite material of the present invention is described.
1, starting material component
Component (A) is rubber, and component (B) is organic modified sheet silicate (referring to the preparation of organic modified sheet silicate); Component (C) is vulcanizing agent and vulcanization aid, and component (D) is packing strengthening agent, and component (E) is anti-aging agent, and component (F) is tenderizer.
2, the preparation of organic modified sheet silicate
The laminar silicic acid salt mine, after the removal of impurity, desanding, the means such as sieve are carried out purifying, drying, is ground layered silicate with ball mill, and by 325 purpose sieve, the ion exchange capacity of the layered silicate obtained is 96.4meq/100g.The 0.01M HCL that the 1.8g amino dodecane is dissolved in to the 1000ml of 60 ℃ makes solution, the 10g layered silicate adds in this solution gradually, the suspension concuss 3h obtained, with deionized water, repeatedly wash again, filtered residue is at 80 ℃ of lower vacuum-drying 12h, regrind and carefully through 325 purpose sieve, just obtain organic modified sheet silicate, stand-by.
3, the preparation of rubber/lamellar silicate nanometer composite material
On the internal rubber mixer of 55 liter variable ratio frequency changer speed governing, at first add chloroprene rubber and cis-1,4-polybutadiene rubber, organic modified sheet silicate, packing strengthening agent, anti-aging agent, tenderizer and vulcanization aid, under 30 rev/mins of rotating speeds mixing 10 minutes, then being adjusted to rotating speed is 50 rev/mins, mixing 15 minutes, sheet under discharging.After sizing material is placed and is cooled to normal temperature, then add vulcanizing agent (sulphur etc.) on 12 inches opening rubber mixing machines, refine glue after three minutes, thin-pass 3-5 time under the roll spacing of 2-3 millimeter, lower is stand-by.Composition of raw materials is as table 1.
The composition of raw materials of table 1 experimental group and comparative group (weight part)
Example Experimental group 1 Experimental group 2 Experimental group 3 Comparative group
Chloroprene rubber 70 70 70 70
Cis-1,4-polybutadiene rubber 30 30 30 30
Linking agent 9 9 9 9
Vulcanizing agent 4 4 4 4
Altax 0.3 0.3 0.3 0.3
Stearic acid 0.3 0.3 0.3 0.3
Flame-retardant system 1.5 1.5 1.5 1.5
Silicon six or nine 32.5 32.5 32.5 32.5
Hard(carbon)black 7 7 7 7
Graphitized carbon black 2.5 2.5 2.5 2.5
White carbon black 2 2 2 2
Antioxidant 4010NA 2 2 2 2
Phosphoric acid ester 3 3 3 3
Organic modified sheet silicate 10 10 10 10
4, the fire-retardant Steel Cord Conveyor Belt rubber cover of rubber/lamellar silicate nanometer composite material service check
Test piece sulfuration: on 25 tons of vulcanizing presses, under 151 ℃, vulcanize 35min.
Performance test: carry out according to GB.
The gained assay is as shown in table 2.
The test-results of table 2 experimental group and comparative group
Figure BDA0000379873040000071
From table 2, with Comparative Examples, compare, add in the embodiment after organic modified sheet silicate, the properties of matrix material all improves a lot, the organic modified sheet silicate that wherein adds 5wt%, tensile strength improves 20%, and tear strength improves 36.9%, abrasion reduce by 18.7%, and hardness and elongation change are little.The raising of these performances all extremely is conducive to the conveyer belt coating rubber prolongation in work-ing life.
Above embodiment is only in order to technical scheme of the present invention to be described, but not is limited; Although with reference to previous embodiment, the present invention is had been described in detail, for the person of ordinary skill of the art, the technical scheme that still can put down in writing previous embodiment is modified, or part technical characterictic wherein is equal to replacement; And these modifications or replacement do not make the essence of appropriate technical solution break away from the spirit and scope of the present invention's technical scheme required for protection.

Claims (10)

1. the fire-retardant Steel Cord Conveyor Belt rubber cover of high-wear-resistance long-service-life rubber/lamellar silicate nanometer composite material, it is characterized in that it comprises following component: have than the chloroprene rubber of high flame retardant wireline ageing-resistant performance and cis-1,4-polybutadiene rubber and with rubber totally 100 weight parts, organic modified sheet silicate 1-50 weight part, vulcanizing agent 1-8 weight part, packing strengthening agent 1-80 weight part, anti-aging agent 1-5 weight part and tenderizer 1-50 weight part, the part by weight of described chloroprene rubber and cis-1,4-polybutadiene rubber is 70-90:30-10.
2. the fire-retardant Steel Cord Conveyor Belt rubber cover of high-wear-resistance long-service-life rubber/lamellar silicate nanometer composite material according to claim 1, it is characterized in that: the preparation method of wherein said organic modified sheet silicate is as follows: by the layered silicate removal of impurities, grind, sieve, then with intercalator, dispersion medium or tensio-active agent, by ion exchange treatment, obtain the layered silicate of modification.
3. the fire-retardant Steel Cord Conveyor Belt rubber cover of high-wear-resistance long-service-life rubber/lamellar silicate nanometer composite material according to claim 2, it is characterized in that: described layered silicate is one or more in clay, swelling, native polynite, carclazyte, terre verte, talcum powder, beidellite, hectorite, silica, halloysite, montmorillonite or Meccah stone.
4. the fire-retardant Steel Cord Conveyor Belt rubber cover of high-wear-resistance long-service-life rubber/lamellar silicate nanometer composite material according to claim 2, it is characterized in that: described intercalator is lauryl amine, octadecylamine, thanomin, diethanolamine, trolamine, lauric acid amine, hexanolactam, hexanediamine, the trimethylammonium ammonia chloride, quaternary amine, one or more in phenyl-ethyl amine or Ursol D.
5. the fire-retardant Steel Cord Conveyor Belt rubber cover of high-wear-resistance long-service-life rubber/lamellar silicate nanometer composite material according to claim 2, it is characterized in that: described tensio-active agent is linear alkyl benzene sulphonic acid class, branched-chain alkyl phenyl Sulfonates, alkylsurfuric acid salt, sylvic acid salt, alkyl polyvinyl ether Sulfates or quaternary ammonium salt.
6. the fire-retardant Steel Cord Conveyor Belt rubber cover of high-wear-resistance long-service-life rubber/lamellar silicate nanometer composite material according to claim 2, it is characterized in that: described dispersion medium can be water, ethanol, ethylene glycol, 1,3-propyl alcohol, BDO, one or more in acetone or chaff ketone.
7. the fire-retardant Steel Cord Conveyor Belt rubber cover of high-wear-resistance long-service-life rubber/lamellar silicate nanometer composite material according to claim 1, it is characterized in that: described packing strengthening agent is carbon black, white carbon black, calcium carbonate or potter's clay.
8. the fire-retardant Steel Cord Conveyor Belt rubber cover of high-wear-resistance long-service-life rubber/lamellar silicate nanometer composite material according to claim 1, it is characterized in that: described anti-aging agent is 4010N or ODA.
9. the fire-retardant Steel Cord Conveyor Belt rubber cover of high-wear-resistance long-service-life rubber/lamellar silicate nanometer composite material according to claim 1, it is characterized in that: described tenderizer is aromatic hydrocarbon oil, process oil, naphthenic oil, dibutyl phthalate or vegetables oil and modification derivant thereof.
10. according to the preparation method of the fire-retardant Steel Cord Conveyor Belt rubber cover of claim 1-9 any one described high-wear-resistance long-service-life rubber/lamellar silicate nanometer composite material, it is characterized in that it comprises the following steps: the chloroprene rubber of the described consumption of weighing and the cis-1,4-polybutadiene rubber of good springiness, organic modified sheet silicate, vulcanizing agent, packing strengthening agent, anti-aging agent and tenderizer prepare the fire-retardant Steel Cord Conveyor Belt rubber cover of rubber/lamellar silicate nanometer composite material by mechanically mixing, mixing step.
CN201310408960.7A 2013-09-10 2013-09-10 Fire-retardant Steel Cord Conveyor Belt rubber cover of a kind of high wear-resistant rubber/laminated nm-silicate composite material and preparation method thereof Active CN103435877B (en)

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CN104558768A (en) * 2014-12-23 2015-04-29 贾纬民 Preparation method of environment-friendly reducing clean ecotype foaming material, prepared foaming material and terminal product
CN104910472A (en) * 2015-06-26 2015-09-16 无锡宝通带业股份有限公司 High-strength wear-resistant flame-retardant conveying belt cover rubber for coal mine and preparation method thereof
CN106241436A (en) * 2016-08-19 2016-12-21 苏州毕诺佳医药技术有限公司 A kind of transfer robot of medical artificial plate incrustation paper
CN106322931A (en) * 2016-08-19 2017-01-11 苏州毕诺佳医药技术有限公司 Medical equipment accessory drying robot

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104558768A (en) * 2014-12-23 2015-04-29 贾纬民 Preparation method of environment-friendly reducing clean ecotype foaming material, prepared foaming material and terminal product
CN104910472A (en) * 2015-06-26 2015-09-16 无锡宝通带业股份有限公司 High-strength wear-resistant flame-retardant conveying belt cover rubber for coal mine and preparation method thereof
CN106241436A (en) * 2016-08-19 2016-12-21 苏州毕诺佳医药技术有限公司 A kind of transfer robot of medical artificial plate incrustation paper
CN106322931A (en) * 2016-08-19 2017-01-11 苏州毕诺佳医药技术有限公司 Medical equipment accessory drying robot
CN106241436B (en) * 2016-08-19 2018-07-03 苏州毕诺佳医药技术有限公司 A kind of transfer robot of medical artificial plate surface facing paper

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