CN103980620A - High-temperature resistant and flame-retardant convey belt coating layer rubber material and preparation method thereof - Google Patents
High-temperature resistant and flame-retardant convey belt coating layer rubber material and preparation method thereof Download PDFInfo
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- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
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- C08L2201/02—Flame or fire retardant/resistant
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Abstract
The invention discloses a high-temperature resistant and flame-retardant convey belt coating layer rubber material and a preparation method thereof. The rubber material comprises the following raw materials in parts by weight: 50 to 90 parts of ethylene-propylene-diene-terpolymer rubber, 10 to 50 parts of bromated butyl rubber, 5 to 40 parts of modified nano attapulgite, 20 to 35 parts of carbon black, 50 to 80 parts of halogen-free fire retardant, 3 to 5.5 parts of vulcanizer, 3 to 5 parts of anti-aging agent, 3 to 5 parts of zinc oxide, 1 to 3 parts of stearic acid, and 5 to 15 parts of coumarone. The preparation method comprises the following steps: carrying out a modification treatment on nano attapulgite by using a silane coupling agent, then using ethylene-propylene-diene-terpolymer rubber, bromated butyl rubber, and modified nano attapulgite to prepare master batch, finally smelting the master batch on a double-roller open mill, adding zinc oxide, stearic acid, coumarone, an anti-aging agent, a fire retardant, carbon black, and a vulcanizer into the master batch, and blending so as to obtain the rubber material. The rubber material meets or even exceeds the national standards of processing performance, high temperature resistant property, and fire retardant property. The product and technology have very good social and economic profits, and thus have a promotion and application prospect.
Description
Technical field
The invention belongs to rubber product technical field, be specifically related to a kind of high temperature resistant, difficult conveyor belt covering rubber composite firing that comprises the components such as the compound rubber master batch of modified Nano attapulgite/terpolymer EP rubber/brominated butyl rubber, carbon black, halogen-free flame retardants.
Technical background
The structure of conveying belt comprises upper and lower rubber covering layer, casing ply and three major portion of rubber adhesion layer, wherein the performance of tectum rubber is to determine the conveying belt key in work-ing life, so improve thermotolerance, the flame retardant resistance of tectum rubber, for industries such as metallurgy, building materials, seems very important.Particularly the slag of the many blast furnaces of metallurgy industry is placed directly on conveying belt, and the very high while of temperature has a strong impact on the work-ing life of conveying belt with Mars.
It is matrix that the resistance to elevated temperatures that improves conveying belt mainly adopts resistant to elevated temperatures rubber, generally the rubber cover of 180 ℃ of following T4 type heat resistance conveyor belts that use adopt more EPDM or with other rubber as the compositions such as halogenated butyl rubber, silicon rubber, polyolefin elastomer and use glue.Conventional strengthening agent adopts the part alternative carbon black such as white carbon black, calcinated argil, layered silicate to improve its resistance to elevated temperatures.The flame retardant properties aspect that improves conveying belt, mainly adopts halogen-free flame retardants to substitute halogenated flame retardant, when reducing halogenated flame retardant burning the amount of being fuming greatly, discharge the shortcoming of a large amount of toxic and harmfuls.Have conveyor belt covering sizing material high temperature resistant, flame retardant properties, the fire retardant of its interpolation mainly be take inorganic hydroxide as main simultaneously.Its advantage is that when burning is non-volatile, the amount of being fuming is few, do not produce toxic gas, but the addition of inorganic combustion inhibitor is excessive and not good with the consistency of polymer matrix, affects the physical and mechanical properties of conveyer belt coating rubber.
Nano-attapulgite is a kind of fibrillar silicate, has the advantages such as raw material sources are abundant, cheap.Adding of certain proportion nano-attapulgite, can improve mechanical property, resistance to elevated temperatures and the flame retardant properties of matrix material.
Therefore when adopting halogen-free flame retardants, reduce its consumption, the consistency that improves fire retardant and polymer matrix is the emphasis of bittern-free flame-proof material research.
Summary of the invention
Task of the present invention is just to provide novel fire resistant, flame retardant conveyor belt tectum sizing material, and the high-temperature resistant rubber matrix of selecting and with it compatible various auxiliary agents can have excellent high temperature resistant, difficult combustion, bond properties, the work-ing life of improving conveying belt.
The technical scheme that the present invention addresses the above problem is as follows:
A kind of high temperature resistant, difficult conveyor belt covering sizing material firing, sizing material comprises base rubber and various auxiliary agent, take in mass fraction sizing material each component as 50～90 parts of terpolymer EP rubbers, 10～50 parts of brominated butyl rubbers, 5～40 parts of modified Nano attapulgites, 20～35 parts of carbon blacks, 50～80 parts of halogen-free flame retardantss, 3～5.5 parts of vulcanizing agents, 3～5 parts, anti-aging agent, 3～5 parts, zinc oxide, 1～3 part of stearic acid, 5～15 parts of coumarones.
Above-mentioned modified Nano attapulgite is silane coupler modified nano-attapulgite, and nano-attapulgite has the advantages such as raw material sources are abundant, cheap.Adding of certain proportion nano-attapulgite, can improve mechanical property, resistance to elevated temperatures and the flame retardant properties of matrix material.In addition, nano-attapulgite add the flame retardant properties that also can improve matrix material, the main component of nano-attapulgite comprises silicon-dioxide, also can form siliceous protective layer on system surface, play adiabatic and shielding dual function.
Above-mentioned carbon black is that one or more mixing in N234, N220, N330 form, and intermediate super abrasion furnace black (N234, N220) and high wear-resistant carbon black (N330) can guarantee that matrix material has good mechanical property and wear resisting property.
Above-mentioned halogen-free flame retardants is that in ammonium polyphosphate, Tri-isopropylphenyl phosphate, trimeric cyanamide, tetramethylolmethane three kinds or four kinds of any weight ratios mix.What adopt is the high polymerization degree APP (polymerization degree is 1500) after Overheating Treatment, its Heat stability is good, and flame retardant properties is lasting, and the nontoxic cigarette that presses down, belongs to phosphorus flame retardant.Tri-isopropylphenyl phosphate is commonly used for the flame-retardant plasticizer of polyvinyl chloride, is also applicable to the fire-retardant plasticising of rubber conveyer belt sizing material, belongs to phosphorus flame retardant.Trimeric cyanamide is a kind of conventional nitrogenated flame retardant, and containing the nitrogen combustion inhibitor non-flammable gases such as emitting carbonic acid gas, nitrogen, ammonia that is heated, this based flame retardant also can be used as other fire retardant as the synergist of phosphorus flame retardant, in phosphorus-nitrogen collaboration system as whipping agent.Adding of tetramethylolmethane, can form expansion type flame retardant with phosphorus system, nitrogenated flame retardant.Add expansion type flame retardant polymer combustion time can form from the teeth outwards the uniform carbonaceous foam layer of one deck, the effect that this charcoal layer is on good terms and is played heat insulation, oxygen barrier, presses down cigarette and anti-molten drop in cohesion.
Above-mentioned vulcanizing agent is that peroxide and resin curing agent mix.That peroxide vulcanizing agent adopts is dicumyl peroxide (DCP), what resin curing agent was used is bromination Octylphenol aldehyde sulfuration resin (201 resin), that the co-crosslinker of DCP is used is iso-cyanuric acid triallyl ester (TAIC) or N, a N '-penylene bismaleimides (HVA-2).DCP and 201 resins all can make terpolymer EP rubber and brominated butyl rubber sulfuration, form the cross-link bond of excellent heat resistance.The vulcanization system that the present invention adopts can make terpolymer EP rubber and brominated butyl rubber sulfuration, forms the cross-link bond of excellent heat resistance.
Above-mentioned anti-aging agent is that quinoline type antioxidant and p phenylenediamine type antioxidant mix.Quinoline type antioxidant is that chemical composition is 2,2,4-trimethylammonium-1, the polymeric anti-aging agent RD of 2-dihyaroquinoline and aging inhibitor FR, and than anti-aging agent RD, the amine content of aging inhibitor FR is lower, very little on peroxide cross-linking agent impact.P phenylenediamine type antioxidant is N-(1,3-dimethyl) butyl-N'-diphenyl-para-phenylene diamine (antioxidant 4020) and N, N '-bis-(Isosorbide-5-Nitrae-dimethyl amyl group) Ursol D (anti-aging agent 4030).
The preparation method of the conveyor belt covering sizing material of above-mentioned high temperature resistant, difficult combustion, is characterized in that comprising the following steps:
First nano-attapulgite is carried out to modification, silane coupling agent is dissolved in dehydrated alcohol and makes certain density solution, add nano-attapulgite to stir and heat, fully after reaction, be cooled to room temperature, high speed centrifugation, washing, oven dry, obtain modified sample after pulverizing.As being dissolved in, silane coupling agent (Si69) makes certain density solution in dehydrated alcohol, add appropriate nano-attapulgite stir and heat, fully after reaction, be cooled to room temperature, high speed centrifugation, washing, oven dry, get final product to obtain modified Nano attapulgite after pulverizing.
Next carries out rubber master batch preparation, regulates two roller mill roll spacings to 2mm, adds terpolymer EP rubber and brominated butyl rubber, and mixing adding after evenly above-mentionedly attapulgite modifiedly carries out mixingly, finally roll spacing is adjusted to 0.1mm, and thin-pass is prepared rubber master batch 5～8 times.
Finally carry out sizing material preparation, regulate two roller mill roll spacings to 2mm, above-mentioned rubber master batch is plasticated in two roller mills, then add successively zinc oxide, stearic acid, coumarone, anti-aging agent, fire retardant to carry out mixing, add again carbon black to carry out subsequently mixing, finally add vulcanizing agent mixing, then roll spacing is adjusted to 0.1mm, thin-pass is prepared ternary ethlene propyene rubbercompound material 5～8 times.
The above-mentioned glue stuff compounding making vulcanizes and can obtain rubber composite at 160～180 ℃, as conveyor belt covering high temperature resistant, difficult combustion.After sulfuration, product performance are shown in table 1 in embodiment.
The present invention has following beneficial effect:
The present invention is applied in modified Nano attapulgite in heat resistance conveyor belt tectum, compares with the conveyor belt covering sizing material of simple use carbon black filler, and cost is low, it is little to pollute, modified Nano attapulgite add the resistance to elevated temperatures that can also improve sizing material.Halogen-free flame-retardant system of the present invention, overall consumption is lower, and better with the consistency of rubber matrix, flame retardant properties is good.Vulcanization system of the present invention can make terpolymer EP rubber and brominated butyl rubber sulfuration, forms the cross-link bond of excellent heat resistance.
Embodiment
Embodiment 1:
Silane coupling agent (Si69) is dissolved in to the solution of making 5% in dehydrated alcohol, add appropriate nano-attapulgite stir and heat, temperature is 80 ℃, fully reacts after 4 hours and is cooled to room temperature, high speed centrifugation, washing, oven dry, get final product to obtain modified Nano attapulgite after pulverizing.
Embodiment 2:
Regulate two roller mill roll spacings to 2mm, add 90 parts of (weight part, lower with) terpolymer EP rubber and 10 parts of brominated butyl rubbers, mixingly add 10 parts of above-mentioned modified Nano attapulgites to carry out again mixing after evenly, finally roll spacing is adjusted to 0.1mm, thin-pass prepares rubber master batch 5～8 times.
Embodiment 3:
Regulate two roller mill roll spacings to 2mm, the above-mentioned rubber master batch of 110g is plasticated in two roller mills, then add 5g zinc oxide, 2g stearic acid, 10g coumarone, 2g anti-aging agent RD and 2g antioxidant 4020,50g ammonium polyphosphate, 10g trimeric cyanamide, 10g tetramethylolmethane to carry out mixing, then add 15gN234 and 15gN330 to carry out mixing, finally add 2gDCP, 0.5gTAIC and 2g201 resin mixing, finally roll spacing is adjusted to 0.1mm, thin-pass is prepared rubber unvulcanizate 5～8 times.
Embodiment 4:
Regulate two roller mill roll spacings to 2mm, add 75g terpolymer EP rubber and 25g brominated butyl rubber, mixingly add that 20g is above-mentioned attapulgite modifiedly to carry out mixingly again after evenly, finally roll spacing is adjusted to 0.1mm, thin-pass is prepared rubber master batch 5～8 times.
Regulate two roller mill roll spacings to 2mm, 120g rubber master batch is plasticated in two roller mills, then add 5g zinc oxide, 2g stearic acid, 10g coumarone, 2g anti-aging agent RD and 2g antioxidant 4020,40g ammonium polyphosphate, 16g trimeric cyanamide, 10g tetramethylolmethane to add mixing, then add 15gN220 and 15gN330 to carry out mixing, finally add 2gDCP, 0.5gTAIC and 2g201 resin mixing, finally roll spacing is adjusted to 0.1mm, thin-pass is prepared rubber unvulcanizate 5～8 times.
Embodiment 5:
Regulate two roller mill roll spacings to 2mm, add 50g terpolymer EP rubber and 50g brominated butyl rubber, mixingly add that 20g is above-mentioned attapulgite modifiedly to carry out mixingly again after evenly, finally roll spacing is adjusted to 0.1mm, thin-pass is prepared rubber master batch 5～8 times.
Regulate two roller mill roll spacings to 2mm, 120g rubber master batch is plasticated in two roller mills, then add 5g zinc oxide, 2g stearic acid, 10g coumarone, 2g anti-aging agent RD and 2g antioxidant 4020,35g ammonium polyphosphate, 16g trimeric cyanamide, 10g tetramethylolmethane, 5g Tri-isopropylphenyl phosphate to add mixing, then add 15gN234 and 15gN330 to carry out mixing, finally add 2gDCP, 0.5gTAIC and 3g201 resin mixing, finally roll spacing is adjusted to 0.1mm, thin-pass is prepared rubber unvulcanizate 5～8 times.
Embodiment 6:
The rubber unvulcanizate that above-described embodiment 3-5 is obtained vulcanizes at 170 ℃, obtains rubber composite and carries out weathering test detection, and the detected result of its aging front and back performance is in Table 1.
Table 1 is high temperature resistant, the conveyor belt covering sizing material correlation detection data of difficult combustion
From table 1 performance, the aging forward and backward good mechanical properties of high temperature resistant, the flame retardant conveyor belt tectum sizing material that the present invention is prepared, all can reach the basic demand that high temperature-resistance conveyor belt is used, and has good flame retardant properties simultaneously.
Claims (10)
1. the conveyor belt covering sizing material of high temperature resistant, a difficult combustion, sizing material comprises base rubber and various auxiliary agent, it is characterized in that, take in mass fraction sizing material each component as 50～90 parts of terpolymer EP rubbers, 10～50 parts of brominated butyl rubbers, 5～40 parts of modified Nano attapulgites, 20～35 parts of carbon blacks, 50～80 parts of halogen-free flame retardantss, 3～5.5 parts of vulcanizing agents, 3～5 parts, anti-aging agent, 3～5 parts, zinc oxide, 1～3 part of stearic acid, 5～15 parts of coumarones.
2. high temperature resistant, the difficult conveyor belt covering sizing material firing according to claim 1, is characterized in that described modified Nano attapulgite is silane coupler modified nano-attapulgite.
3. high temperature resistant, the difficult conveyor belt covering sizing material firing according to claim 1, is characterized in that described carbon black is one or more mixing compositions in N234, N220, N330.
4. the conveyor belt covering sizing material of high temperature resistant, difficult combustion according to claim 1, is characterized in that described halogen-free flame retardants is that in ammonium polyphosphate, Tri-isopropylphenyl phosphate, trimeric cyanamide, tetramethylolmethane wantonly three kinds or four kinds mix with its any weight ratio.
5. high temperature resistant, the difficult conveyor belt covering sizing material firing according to claim 4, is characterized in that described ammonium polyphosphate is the high polymerization degree APP after Overheating Treatment, and the polymerization degree of described ammonium polyphosphate is 1500.
6. the conveyor belt covering sizing material of high temperature resistant, difficult combustion according to claim 1, described vulcanizing agent is that peroxide and any weight ratio of resin curing agent mix.
7. the conveyor belt covering sizing material of high temperature resistant, difficult combustion according to claim 6, described peroxide vulcanizing agent is dicumyl peroxide.
8. the conveyor belt covering sizing material of high temperature resistant, difficult combustion according to claim 6, described resin curing agent is bromination Octylphenol aldehyde sulfuration resin.
9. the conveyor belt covering sizing material of high temperature resistant, difficult combustion according to claim 1, described anti-aging agent is that quinoline type antioxidant and any weight ratio of p phenylenediamine type antioxidant mix.
10. a method of preparing the conveyor belt covering sizing material of high temperature resistant, difficult combustion claimed in claim 1, is characterized in that comprising the following steps:
First nano-attapulgite is carried out to modification, silane coupling agent is dissolved in to the solution of making 5% in dehydrated alcohol, adds nano-attapulgite to stir and be heated to 80 ℃, fully react after 4 hours and be cooled to room temperature, high speed centrifugation, washing, oven dry, obtain modified sample after pulverizing;
Next carries out rubber master batch preparation, regulates two roller mill roll spacings to 2mm, adds terpolymer EP rubber and brominated butyl rubber, mixingly adds above-mentioned modified Nano attapulgite after evenly and carries out mixingly, finally roll spacing is adjusted to 0.1mm, and thin-pass is prepared rubber master batch 5～8 times;
Finally carry out sizing material preparation, regulate two roller mill roll spacings to 2mm, above-mentioned rubber master batch is plasticated in two roller mills, then add successively zinc oxide, stearic acid, coumarone, anti-aging agent, fire retardant to carry out mixing, add again carbon black to carry out subsequently mixing, finally add vulcanizing agent mixing, then roll spacing is adjusted to 0.1mm, thin-pass is prepared ternary ethlene propyene rubbercompound material 5～8 times.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105419124A (en) * | 2015-12-31 | 2016-03-23 | 张桂华 | Novel anti-compression rubber formula and preparation method |
| CN105968588A (en) * | 2016-05-25 | 2016-09-28 | 浙江三维橡胶制品股份有限公司 | Special conveyer belt for chemical fertilizer granulation tank |
| CN109666221A (en) * | 2018-11-22 | 2019-04-23 | 三力士股份有限公司 | A kind of infantees band vulcanization dedicated vulcanization offset plate and preparation method thereof |
| CN109749175A (en) * | 2017-11-01 | 2019-05-14 | 丹阳西联生物技术有限公司 | A kind of Wear-resistant, high-temperature resistant rubber |
| CN111944231A (en) * | 2020-08-24 | 2020-11-17 | 安徽省康利亚股份有限公司 | Low-smoke halogen-free flame-retardant super-flexible oil-resistant cable material |
| CN112321952A (en) * | 2020-11-03 | 2021-02-05 | 中物院成都科学技术发展中心 | Ethylene propylene diene monomer composite rubber material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105419124A (en) * | 2015-12-31 | 2016-03-23 | 张桂华 | Novel anti-compression rubber formula and preparation method |
| CN105968588A (en) * | 2016-05-25 | 2016-09-28 | 浙江三维橡胶制品股份有限公司 | Special conveyer belt for chemical fertilizer granulation tank |
| CN109749175A (en) * | 2017-11-01 | 2019-05-14 | 丹阳西联生物技术有限公司 | A kind of Wear-resistant, high-temperature resistant rubber |
| CN109666221A (en) * | 2018-11-22 | 2019-04-23 | 三力士股份有限公司 | A kind of infantees band vulcanization dedicated vulcanization offset plate and preparation method thereof |
| CN111944231A (en) * | 2020-08-24 | 2020-11-17 | 安徽省康利亚股份有限公司 | Low-smoke halogen-free flame-retardant super-flexible oil-resistant cable material |
| CN111944231B (en) * | 2020-08-24 | 2024-04-12 | 安徽省康利亚股份有限公司 | Low-smoke halogen-free flame-retardant super-flexible oil-resistant cable material |
| CN112321952A (en) * | 2020-11-03 | 2021-02-05 | 中物院成都科学技术发展中心 | Ethylene propylene diene monomer composite rubber material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103980620B (en) | 2017-01-18 |
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