CN103980620B - 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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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C08J3/00—Processes of treating or compounding macromolecular substances
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- C08J3/246—Intercrosslinking of at least two polymers
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- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—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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- C08J2323/26—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
- C08J2323/28—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 by reaction with halogens or halogen-containing compounds
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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
- C08J2423/02—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
- C08J2423/16—Ethene-propene or ethene-propene-diene copolymers
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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
- C08J2423/28—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 by reaction with halogens or halogen-containing compounds
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- C08L2201/02—Flame or fire retardant/resistant
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08L2201/22—Halogen free composition
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C08L2312/00—Crosslinking
- C08L2312/04—Crosslinking with phenolic resin
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 is and in particular to a kind of include modified nano concave good soil/EPDM
Rubber/brombutyl is combined high temperature resistant, the fire retardant conveyor belt covering rubber of the component such as rubber master batch, white carbon black, halogen-free flame retardants
Glue composite.
Technical background
The structure of conveyer belt includes upper and lower rubber covering layer, casing play and three major parts of rubber adhesive layer, wherein covers
The performance of cap rock rubber is the key determining conveyer belt service life, so improving the thermostability of cover layer rubber, anti-flammability pair
Seem particularly significant in industries such as metallurgy, building materials.The slag of particularly metallurgy industry many blast furnaces is placed directly on conveyer belt, temperature
Degree very high simultaneously with Mars, have a strong impact on the service life of conveyer belt.
The resistance to elevated temperatures improving conveyer belt mainly adopts resistant to elevated temperatures rubber for matrix, typically used below at 180 DEG C
The rubber cover of t4 type heat resistance conveyor belt more than using epdm or with other rubber such as halogenated butyl rubber, silicone rubber, polyolefin
The blend compounds of the compositions such as elastomer.The reinforcing agent commonly used adopts the part such as white carbon, calcinated argil, phyllosilicate to substitute charcoal
Black to improve its resistance to elevated temperatures.Improve the fire resistance aspect of conveyer belt, mainly adopt halogen-free flame retardants to substitute halogen system fire-retardant
Agent, with the shortcoming that when reducing halogenated flame retardant burning, the amount of being fuming is big, discharge a large amount of toxic and harmfuls.Have simultaneously high temperature resistant,
The conveyor belt covering sizing material of fire resistance, the fire retardant that it adds is mainly based on inorganic hydroxide.Its advantage is burning
When non-volatile, the amount of being fuming is few, do not produce toxic gas, but the addition of inorganic combustion inhibitor is excessive and phase with polymer matrix
Capacitive is not good, the physical and mechanical propertiess of impact conveyer belt coating rubber.
Nano-attapulgite is a kind of fibrillar silicate, has the advantages that abundant raw material source, cheap.Certain proportion
The addition of nano-attapulgite, can improve mechanical property, resistance to elevated temperatures and the fire resistance of composite.
Therefore when using halogen-free flame retardants, reduce its consumption, the compatibility improving fire retardant with polymer matrix is no
The emphasis of halogen fire proofing research.
Content of the invention
The task of the present invention is exactly to provide novel fire resistant, flame retardant conveyor belt to cover layer sizing, the high-temperature resistant rubber of selection
Matrix and various auxiliary agents compatible therewith can have excellent high temperature resistant, fire retardant, bond propertiess, improve the use of conveyer belt
Life-span.
The technical scheme that the present invention solves the above problems is as follows:
A kind of high temperature resistant, fire retardant conveyor belt covering sizing material, sizing material includes base rubber and various auxiliary agent, with mass parts
In number meter sizing material, each component is: 50～90 parts of ethylene propylene diene rubber, 10～50 parts of brombutyl, modified nano concave good soil
5～40 parts, 20～35 parts of white carbon black, 50～80 parts of halogen-free flame retardants, 3～5.5 parts of vulcanizing agent, 3～5 parts of age resistor, zinc oxide 3～
5 parts, 1～3 part of stearic acid, 5～15 parts of coumarone.
Above-mentioned modified nano concave good soil is silane coupler modified nano-attapulgite, and nano-attapulgite has raw material
Abundance, cheap the advantages of.The addition of certain proportion nano-attapulgite, can improve composite mechanical property,
Resistance to elevated temperatures and fire resistance.In addition, the addition of nano-attapulgite also can improve the fire resistance of composite, nanometer is recessed
The main component of convex rod soil includes silicon dioxide, also can form siliceous protective layer on system surface, plays adiabatic and shields dual
Effect.
Above-mentioned white carbon black is one or more of n234, n220, n330 mixing composition, intermediate super abrasion furnace black (n234,
) and high wear-resistant carbon black (n330) ensure that composite has good mechanical property and anti-wear performance n220.
Above-mentioned halogen-free flame retardants is APP, Tri-isopropylphenyl phosphate, tripolycyanamide, three kinds in tetramethylolmethane or
Four kinds of any weight ratios mix.Use the high polymerization degree APP after Overheating Treatment (degree of polymerization is 1500),
Its heat stability is good, and fire resistance is lasting, and nontoxic suppression cigarette belongs to phosphorus flame retardant.Tri-isopropylphenyl phosphate is commonly used for polychlorostyrene
The flame-retardant plasticizer of ethylene, is also applied for the fire-retardant plasticising of rubber conveyer belt sizing material, belongs to phosphorus flame retardant.Tripolycyanamide is one
Plant conventional nitrogenated flame retardant, nitrogenous flame ratardant is subject to the non-flammable compressive gases such as heat release carbon dioxide, nitrogen, ammonia, this based flame retardant
Also act as the synergist of other fire retardants such as phosphorus flame retardant, as foaming agent in phosphorus-nitrogen collaboration system.Tetramethylolmethane
Add, expansion type flame retardant can be formed with phosphorus system, nitrogenated flame retardant.Can be in table during the polymer combustion of interpolation expansion type flame retardant
One layer of uniform carbonaceous froth bed is formed on face, this layer of charcoal can play heat-insulated, oxygen barrier, suppression cigarette and anti-molten drop work in condensed phase
With.
Above-mentioned vulcanizing agent is peroxide and resin curing agent mixes.Peroxide-based curing dose uses
Cumyl peroxide (dcp), resin curing agent is bromination Octylphenol aldehyde curing resin (201 resin), dcp's
Co-crosslinker is iso-cyanuric acid triallyl ester (taic) or n, a n '-penylene BMI (hva-2).dcp
Ethylene propylene diene rubber and brombutyl sulfuration all can be made with 201 resins, form the cross-bond of excellent heat resistance.The present invention adopts
Vulcanizing system can make ethylene propylene diene rubber and brombutyl sulfuration, forms the cross-bond of excellent heat resistance.
Above-mentioned age resistor is quinoline type antioxidant and p phenylenediamine type antioxidant mixes.Quinoline type antioxidant is chemistry
Composition is 2,2,4- trimethyl -1,2- dihyaroquinoline polymeric age resistor rd and age resistor fr, compared to age resistor rd, prevents
The amine content of old agent fr is relatively low, affects very little to peroxide cross-linking agent.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) p-phenylenediamine (age resistor
4030).
The preparation method of above-mentioned high temperature resistant, fire retardant conveyor belt covering sizing material is it is characterised in that comprise the following steps:
First nano-attapulgite is modified processing, silane coupler is dissolved in dehydrated alcohol and makes finite concentration
Solution, add nano-attapulgite to stir and heat, after fully reacting, be cooled to room temperature, high speed centrifugation, washing, drying, powder
Modified sample is obtained final product after broken.Make certain density solution as being dissolved in silane coupler (si69) in dehydrated alcohol, add suitable
The nano-attapulgite of amount stirs and heats, and is cooled to room temperature, high speed centrifugation, washing, drying, after pulverizing after fully reacting
Obtain modified nano concave good soil.
Next carries out rubber master batch preparation, adjusts two-roll mill roll spacing to 2mm, adds ethylene propylene diene rubber and butyl rubber bromide
Glue, mixing uniformly add afterwards state attapulgite modified kneaded, finally roll spacing is adjusted to 0.1mm, thin logical 5～8 preparations are female
Glue.
Finally carry out sizing material preparation, adjust two-roll mill roll spacing to 2mm, above-mentioned rubber master batch is carried out in two-roll mill
Plasticate, then sequentially add zinc oxide, stearic acid, coumarone, age resistor, fire retardant are kneaded, subsequently add white carbon black and enter
Row mixing, is eventually adding vulcanizing agent mixing, then roll spacing is adjusted to 0.1mm, thin logical prepares ethylene propylene diene rubber composite wood 5～8 times
Material.
Above-mentioned prepared glue stuff compounding vulcanizes at 160～180 DEG C and can get rubber composite, such as high temperature resistant, difficult
The conveyor belt covering of combustion.After sulfuration, properties of product are shown in table 1 in embodiment.
The method have the advantages that
The present invention applies modified nano concave good soil in heat resistance conveyor belt cover layer, and uses merely carbon black filler
Conveyor belt covering sizing material is compared, and low cost, pollution are little, and the addition of modified nano concave good soil can also improve the resistance to height of sizing material
Warm nature energy.Halogen-free flame-retardant system of the present invention, overall consumption is relatively low, and the compatibility with rubber matrix is preferable, anti-flammability
Can be good.Vulcanizing system of the present invention can make ethylene propylene diene rubber and brombutyl sulfuration, forms thermostability excellent
Good cross-bond.
Specific embodiment
Embodiment 1:
Silane coupler (si69) is dissolved in the solution making 5% in dehydrated alcohol, adds appropriate nano-attapulgite
Stir and heat, temperature is 80 DEG C, fully reaction was cooled to room temperature after 4 hours, and high speed centrifugation, washing, drying, after pulverizing
Obtain modified nano concave good soil.
Embodiment 2:
Adjust two-roll mill roll spacing to 2mm, add 90 parts of (weight portion, similarly hereinafter) ethylene propylene diene rubbers and 10 parts of bromination fourths
Base rubber, mixing uniformly adds 10 parts of above-mentioned modified nano concave good soils to be kneaded afterwards again, finally roll spacing is adjusted to 0.1mm,
Thin logical prepare rubber master batch 5～8 times.
Embodiment 3:
Adjust two-roll mill roll spacing to 2mm, above-mentioned for 110g rubber master batch is plasticated in two-roll mill, then adds
5g zinc oxide, 2g stearic acid, 10g coumarone, 2g age resistor rd and 2g antioxidant 4020,50g APP, 10g tripolycyanamide,
10g tetramethylolmethane is kneaded, then add 15gn234 and 15gn330 kneaded, be eventually adding 2gdcp, 0.5gtaic and
2g201 resin kneads, and finally roll spacing is adjusted to 0.1mm, thin logical prepares elastomeric compound 5～8 times.
Embodiment 4:
Adjust two-roll mill roll spacing to 2mm, add 75g ethylene propylene diene rubber and 25g brombutyl, mixing is uniformly
Add afterwards 20g above-mentioned attapulgite modified kneaded again, finally roll spacing is adjusted to 0.1mm, thin logical prepares rubber master batch 5～8 times.
Adjust two-roll mill roll spacing to 2mm, 120g rubber master batch is plasticated in two-roll mill, then add 5g oxygen
Change zinc, 2g stearic acid, 10g coumarone, 2g age resistor rd and 2g antioxidant 4020,40g APP, 16g tripolycyanamide, 10g
Tetramethylolmethane add mixing, then add 15gn220 and 15gn330 kneaded, be eventually adding 2gdcp, 0.5gtaic and
2g201 resin kneads, and finally roll spacing is adjusted to 0.1mm, thin logical prepares elastomeric compound 5～8 times.
Embodiment 5:
Adjust two-roll mill roll spacing to 2mm, add 50g ethylene propylene diene rubber and 50g brombutyl, mixing is uniformly
Add afterwards 20g above-mentioned attapulgite modified kneaded again, finally roll spacing is adjusted to 0.1mm, thin logical prepares rubber master batch 5～8 times.
Adjust two-roll mill roll spacing to 2mm, 120g rubber master batch is plasticated in two-roll mill, then add 5g oxygen
Change zinc, 2g stearic acid, 10g coumarone, 2g age resistor rd and 2g antioxidant 4020,35g APP, 16g tripolycyanamide, 10g
Tetramethylolmethane, 5g Tri-isopropylphenyl phosphate add mixing, then add 15gn234 and 15gn330 to be kneaded, are eventually adding
2gdcp, 0.5gtaic and 3g201 resin kneads, and finally roll spacing is adjusted to 0.1mm, thin logical prepares elastomeric compound 5～8 times.
Embodiment 6:
The elastomeric compound that above-described embodiment 3-5 is obtained vulcanizes at 170 DEG C, obtains rubber composite and carries out aging examination
Test detection, before and after it is aging, the testing result of performance is shown in Table 1.
High temperature resistant, the fire retardant conveyor belt covering sizing material coherent detection data of table 1
Knowable to table 1 performance, high temperature resistant, flame retardant conveyor belt prepared by the present invention cover the aging forward and backward power of layer sizing
Learn functional, all can reach the basic demand of high temperature-resistance conveyor belt use, there is good fire resistance simultaneously.
Claims (6)
1. a kind of high temperature resistant, fire retardant conveyor belt covering sizing material, sizing material includes base rubber and various auxiliary agent, and its feature exists
In in sizing material in terms of mass fraction, each component is: 50 ~ 90 parts of ethylene propylene diene rubber, 10 ~ 50 parts of brombutyl, modification are received
5 ~ 40 parts of attapulgite of rice, 20 ~ 35 parts of white carbon black, 50 ~ 80 parts of halogen-free flame retardants, 3 ~ 5.5 parts of vulcanizing agent, 3 ~ 5 parts of age resistor, oxidation
3 ~ 5 parts of zinc, 1 ~ 3 part of stearic acid, 5 ~ 15 parts of coumarone；
Described halogen-free flame retardants is APP, Tri-isopropylphenyl phosphate, tripolycyanamide, wantonly three kinds in tetramethylolmethane or
Four kinds are mixed with its any weight ratio；
Described vulcanizing agent is peroxide and resin curing agent any weight ratio mixes；
Described peroxide-based curing dose is cumyl peroxide；
Described resin curing agent is bromination Octylphenol aldehyde curing resin.
2. high temperature resistant, fire retardant conveyor belt covering sizing material according to claim 1 it is characterised in that: described modification is received
Rice attapulgite is silane coupler modified nano-attapulgite.
3. high temperature resistant, fire retardant conveyor belt covering sizing material according to claim 1 it is characterised in that: described white carbon black
Mix composition for one or more of n234, n220, n330.
4. high temperature resistant, fire retardant conveyor belt covering sizing material according to claim 1 it is characterised in that: described poly- phosphorus
Sour ammonium is the high polymerization degree APP after Overheating Treatment, and the degree of polymerization of described APP is 1500.
5. high temperature resistant, fire retardant conveyor belt covering sizing material according to claim 1 it is characterised in that: described is anti-
Old agent is quinoline type antioxidant and p phenylenediamine type antioxidant any weight ratio mixes.
6. a kind of preparation method of high temperature resistant as claimed in claim 1, fire retardant conveyor belt covering sizing material, its feature exists
In: comprise the following steps:
First nano-attapulgite is modified processing, silane coupler is dissolved in the solution making 5% in dehydrated alcohol, plus
Enter nano-attapulgite and be stirred and heated to 80 DEG C, fully reaction is cooled to room temperature after 4 hours, high speed centrifugation, washing, drying,
Modified sample is obtained final product after pulverizing；
Next carries out rubber master batch preparation, adjusts two-roll mill roll spacing to 2mm, adds ethylene propylene diene rubber and brombutyl,
Mixing uniformly adds that stating modified nano concave good soil is kneaded, and is finally adjusted to 0.1mm by roll spacing afterwards, and thin logical 5 ~ 8 preparations are female
Glue；
Finally carry out sizing material preparation, adjust two-roll mill roll spacing to 2mm, above-mentioned rubber master batch is moulded in two-roll mill
Refining, then sequentially adds zinc oxide, stearic acid, coumarone, age resistor, fire retardant are kneaded, subsequently adds white carbon black and carry out
Mixing, is eventually adding vulcanizing agent mixing, then roll spacing is adjusted to 0.1mm, thin logical prepares ternary ethlene propyene rubbercompound material 5 ~ 8 times.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
| CN112321952B (en) * | 2020-11-03 | 2022-12-20 | 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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| CN102275712A (en) * | 2011-05-23 | 2011-12-14 | 兖矿集团有限公司 | High-temperature resistant conveyer belt |
| CN102718016A (en) * | 2012-07-11 | 2012-10-10 | 安徽中意胶带有限责任公司 | High temperature resistant wire rope core flame-retardant conveying belt |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63139807A (en) * | 1986-11-28 | 1988-06-11 | Yokohama Rubber Co Ltd:The | Manufacture of rough top conveyer belt |
| JP2001335667A (en) * | 2000-05-30 | 2001-12-04 | Bando Chem Ind Ltd | Rubber composition and conveyer belt |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102275712A (en) * | 2011-05-23 | 2011-12-14 | 兖矿集团有限公司 | High-temperature resistant conveyer belt |
| CN102718016A (en) * | 2012-07-11 | 2012-10-10 | 安徽中意胶带有限责任公司 | High temperature resistant wire rope core flame-retardant conveying belt |
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Effective date of registration: 20180822 Address after: 053000 north of Jingxian County Development Zone and Jing Kai street, Hengshui, Hebei. Patentee after: Dexin adhesive tape Technology Co., Ltd. Address before: 221000 Xuzhou City, Xuzhou, Jiangsu, No. 1 Xiangwang Road Patentee before: Xuzhou Institute of Industry Technology |
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