CN110878161A - High-temperature-resistant energy-saving adhesive layer rubber for conveyer belt - Google Patents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to a high-temperature-resistant energy-saving adhesive layer rubber for a conveyor belt, belonging to the technical field of rubber modification. The high-temperature-resistant energy-saving bonding layer rubber for the conveying belt is prepared by taking high-vinyl polybutadiene rubber (HVPBR) as a raw material and cashew nut shell oil as an anti-aging agent to prepare oil-filled rubber, and then taking polyisoprene rubber (LIR) as a plasticizer, mixing and vulcanizing Ethylene Propylene Diene Monomer (EPDM) and the oil-filled rubber. The invention solves the problem of the adhesiveness between the adhesive layer rubber and the covering rubber and the polyvinyl acetate canvas, improves the heat resistance and aging resistance of the adhesive material, and enables the conveyor belt to have the functions of light weight, energy conservation, environmental protection and long service life.
Description
Technical Field
The invention relates to a high-temperature-resistant energy-saving adhesive layer rubber for a conveyor belt, belonging to the technical field of rubber modification.
Background
The conveying belt industry is an important industry second to the tire industry in the rubber industry, the high-temperature-resistant conveying belt is mainly applied to conveying of various high-temperature materials, the temperature of the materials is generally higher than 200 ℃, and Ethylene Propylene Diene Monomer (EPDM) is mainly selected as covering rubber for the high-temperature-resistant conveying belt at home and abroad in order to enable the conveying belt body to have excellent heat resistance and aging resistance. The high-temperature resistant conveying belt consists of three parts, namely covering rubber, bonding layer rubber and framework material, the determining factor of the performance of the high-temperature resistant conveying belt is the heat resistance of the covering rubber, the molecular chain of the ethylene propylene diene monomer rubber is basically saturated, and the ethylene propylene diene monomer rubber can be used in a high-temperature environment for a long time and keeps good performance by using a peroxide vulcanization system, but the ethylene propylene diene monomer rubber has poor self-adhesion and mutual adhesion and is difficult to be directly bonded with the framework material polyvinyl canvas, so that the bonding layer rubber is formed. The high-temperature resistant conveying belt is prepared by using natural rubber, styrene-butadiene rubber and ethylene propylene diene monomer rubber together, and the combined system is used as bonding rubber which can be bonded with ethylene propylene diene monomer rubber covering rubber and also can be bonded with polyvinyl acetate canvas. Although the ethylene propylene diene monomer/natural rubber/styrene butadiene rubber combined bonding system can solve the bonding problem of the high-temperature resistant conveying belt, the natural rubber and the styrene butadiene rubber in the system are gradually aged and hardened in a high-temperature environment for a long time, so that the bonding performance is reduced, and the high-temperature resistant conveying belt is delaminated in severe cases.
Therefore, the ethylene propylene diene monomer rubber composite material with high bonding performance is developed, not only can the bonding between bonding rubber and covering rubber and the polyester canvas be solved, but also the heat resistance and aging resistance of the bonding material can be greatly improved.
Disclosure of Invention
The invention aims to provide a high-temperature-resistant energy-saving bonding layer rubber for a conveying belt, which solves the problem of bonding with covering rubber and polyvinyl acetate canvas, improves the heat-resistant and aging-resistant performance of a bonding material, and enables the conveying belt to have the functions of light weight, energy conservation, environmental protection and long service life.
The high-temperature-resistant energy-saving bonding layer rubber for the conveying belt is prepared by taking high-vinyl polybutadiene rubber (HVPBR) as a raw material and cashew nut shell oil as an anti-aging agent to prepare oil-filled rubber, and then taking liquid polyisoprene rubber (LIR) as a plasticizer to mix and vulcanize Ethylene Propylene Diene Monomer (EPDM) and the oil-filled rubber.
The high-temperature-resistant energy-saving adhesive layer rubber for the conveying belt is prepared by the following steps:
(1) preparing the oil-extended rubber:
preheating 15-35 parts by weight of cashew shell oil to 40 ℃, adding the cashew shell oil into 100 parts by weight of high vinyl polybutadiene rubber solution, mechanically stirring at the rotating speed of 400rpm for 40min, condensing by using steam, removing monomers and solvent, and drying to obtain the oil-extended rubber. Wherein the HVPBR vinyl content is more than 80%, and the Mooney viscosity ML100 ℃ 1+4 is 70-90.
(2) Mixing and banburying 30-50 parts by weight of oil-extended rubber and 50-70 parts by weight of EPDM in an internal mixer, adding 5-15 parts by weight of LIR, and banburying a certain amount of carbon black and an auxiliary agent for 10-15min to obtain the mixed composite rubber, and vulcanizing. Wherein the third monomer Ethylidene Norbornene (ENB) content of the EPDM is 8% -11%, and the Mn of the LIR is 4-5 ten thousand.
(3) The vulcanization formula of the oil-extended rubber is as follows, and the oil-extended rubber is measured by weight parts:
(4) sample preparation:
the rubber material mixing is carried out in 3 sections:
one-stage mixing is carried out in an internal mixer, the initial temperature of an internal mixing chamber is 60 ℃, the rotating speed of a rotor is 40rpm, and the feeding sequence is as follows: oil extended HVPBR and EPDM → LIR → carbon black and adjuvant → exhaust (105 ℃) → binder removal (120 ℃).
The two-stage mixing is carried out on an open mill, and the mixing process comprises the following steps: one rubber batch → 2 times of thinpass → 3 times of left and right rubber tapping → 10 times of rubber pouring → lower piece → parking.
The final mixing was carried out in an internal mixer with an initial temperature of 50 ℃ and a rotor speed of 40 rpm. The feeding sequence is as follows: 1/2 second batch → vulcanizing agent and accelerator → the rest 1/2 second batch → exhaust → rubber discharge (80 ℃).
The process conditions are as follows:
and (3) rubber vulcanization: placing for over 24 hours for vulcanization after the piece feeding, wherein the vulcanization condition is 145 ℃, 45min, the vulcanization press pressure is 15MPa, the preheating and pressure maintaining time is 5 minutes respectively, the middle exhaust is carried out for 5 times, and the size of a vulcanization sample piece is as follows: the length, width and thickness are 15mm, 15mm and 2mm, and the amount of the mixed rubber is 62 g.
The high vinyl polybutadiene rubber (HVPBR) selected by the invention has high heat aging resistance due to the small quantity of double bonds on the HVPBR main chain and the small quantity of active hydrogen. The molecular chain of Ethylene Propylene Diene Monomer (EPDM) is basically saturated, the structure ensures that the EPDM has good heat-resistant and ageing-resistant performance, and the two rubbers with closer unsaturation degree can balance the vulcanization crosslinking speed of the two rubbers by using the compounding of HVPBR and EPDM. The addition of the plasticizing softener can greatly improve the self-adhesion and the elongation at break of rubber, and some plasticizing softeners can be evaporated and pumped out at a higher temperature, so that the rubber material becomes hard and the aging resistance of the rubber material is also influenced. For the traditional rubber material for the high-temperature resistant conveying belt, paraffin oil, naphthenic oil and the like are used as plasticizers. The plasticizer has a low flash point, and once the plasticizer is used at an excessively high temperature, the plasticizer volatilizes and migrates after being used for a long time, so that the performance of the rubber composite material is seriously influenced. Compared with common plasticizers, the reactive liquid rubber used as the plasticizer not only can endow the rubber with good processability, but also can participate in crosslinking reaction to form a component of a crosslinking network during vulcanization due to the chain structure which is the same as or similar to that of the main material, so that the vulcanized rubber has excellent physical properties and chemical stability. The liquid polyisoprene rubber (LIR) is a viscous transparent substance which is nontoxic, tasteless and colorless, and has the performance of a common elastomer after being vulcanized. LIR is a reactive plasticizer that can be used with sulfur or peroxide and has high self-tack. Due to the influence of the hydroxyl of cardanol in the cashew nut shell oil, the cashew nut shell oil plays a role of a reactive anti-aging agent, and therefore the thermal-oxidative aging resistance of vulcanized rubber is improved.
The invention has the following beneficial effects:
the invention solves the problem of the adhesiveness between the adhesive layer rubber and the covering rubber and the polyvinyl acetate canvas, improves the heat resistance and aging resistance of the adhesive material, and enables the conveyor belt to have the functions of light weight, energy conservation, environmental protection and long service life.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the practice of the invention.
The preparation process of the oil-extended HVPBR rubber is as follows:
preheating 15-35 parts by weight of cashew nut shell oil to 40 ℃, adding the cashew nut shell oil into high vinyl polybutadiene rubber liquid in parts by weight, mechanically stirring at the rotating speed of 400rpm for 40min, condensing by using steam, removing monomers and solvent, and drying to obtain the oil-filled HVPBR rubber. Wherein the HVPBR vinyl content is more than 80%, and the Mooney viscosity ML100 ℃ 1+4 is 70-90.
The rubber material mixing is carried out in 3 sections:
one-stage mixing is carried out in an internal mixer, the initial temperature of an internal mixing chamber is 60 ℃, the rotating speed of a rotor is 40rpm, and the feeding sequence is as follows: oil extended HVPBR and EPDM → LIR → carbon black and adjuvant → exhaust (105 ℃) → binder removal (120 ℃).
The two-stage mixing is carried out on an open mill, and the mixing process comprises the following steps: one rubber batch → 2 times of thinpass → 3 times of left and right rubber tapping → 10 times of rubber pouring → lower piece → parking.
The final mixing was carried out in an internal mixer with an initial temperature of 50 ℃ and a rotor speed of 40 rpm. The feeding sequence is as follows: 1/2 second batch → vulcanizing agent and accelerator → the rest 1/2 second batch → exhaust → rubber discharge (80 ℃).
Example 1
30 parts of oil-extended HVPBR rubber and 70 parts of EPDM rubber are weighed and mixed for 3min,10 parts of LIR is mixed for 2min, and 10 parts of white carbon black and a certain amount of auxiliary agents in the vulcanization formula of the oil-extended rubber are mixed in an internal mixer for 10min and then vulcanized to obtain the rubber composite material.
Example 2
Weighing 40 parts of oil-extended HVPBR rubber and 60 parts of EPDM rubber, banburying for 3min, banburying for 10 parts of LIR for 2min, and mixing 10 parts of white carbon black and a certain amount of auxiliary agents in a vulcanization formula of the oil-extended rubber in a banbury mixer for 10min and then vulcanizing to obtain the rubber composite material.
Example 3
50 parts of oil-extended HVPBR rubber and 50 parts of EPDM rubber are weighed and mixed for 3min,10 parts of LIR is mixed for 2min, and 10 parts of white carbon black and a certain amount of auxiliary agents in the vulcanization formula of the oil-extended rubber are mixed in an internal mixer for 10min and then vulcanized to prepare the rubber composite material.
Comparative example 1
30 parts of oil-extended HVPBR rubber and 70 parts of EPDM rubber are weighed and mixed for 3min,5 parts of LIR is mixed for 2min,10 parts of white carbon black and a certain amount of auxiliary agents in the vulcanization formula of the oil-extended rubber are mixed in an internal mixer for 10min and then vulcanized to prepare the rubber composite material.
Comparative example 2
30 parts of oil-extended HVPBR rubber and 70 parts of EPDM rubber are weighed and mixed for 3min,15 parts of LIR is mixed for 2min,10 parts of white carbon black and a certain amount of auxiliary agents in the vulcanization formula of the oil-extended rubber are mixed in an internal mixer for 10min and then vulcanized to prepare the rubber composite material.
Comparative example 3
100 parts of EPDM rubber is plasticized in an internal mixer, 10 parts of LIR is mixed for 2min, and 10 parts of white carbon black and a certain amount of auxiliary agents in the vulcanization formula of the oil-extended rubber are mixed in the internal mixer for 10min and vulcanized to prepare the rubber composite material.
Comparative example 4
30 parts of HVPBR rubber and 70 parts of EPDM rubber are weighed and mixed for 3min,15 parts of LIR is mixed for 2min,10 parts of white carbon black and a certain amount of auxiliary agents in the vulcanization formula of the oil-extended rubber are mixed for 10min in an internal mixer and vulcanized to prepare the rubber composite material.
After the rubber composite materials prepared in examples 1 to 3 and comparative examples 1 to 4 were subjected to two-stage kneading and three-stage kneading in this order, they were left to stand for 24 hours or more after sheet feeding for vulcanization:
the vulcanization condition is 145 ℃, 45min, the vulcanization press pressure is 15MPa, the preheating and pressure maintaining time is 5min respectively, the middle exhaust is carried out for 5 times, and the size of the vulcanized sample piece is as follows: the length, width and thickness are 15mm, 15mm and 2mm, and the amount of the mixed rubber is 62 g.
TABLE 1
Note: 1. aging conditions 1: 175 ℃/96 h; aging at 235 deg.C/4 h; high temperature test conditions: 175 ℃/1 h.
As can be seen from Table 1, the oil-filled HVPBR/EPDM (ethylene-propylene-diene monomer copolymer) composite material is used as the adhesive glue of the high-temperature resistant conveying belt, the performances are superior to those of the EPDM, and the density of the composite material is 1.05g/cm3The conveyer belt has the functions of light weight, energy saving, environmental protection and long service life.
Claims (10)
1. The utility model provides a high temperature resistant energy-saving adhesive layer rubber for conveyer belt which characterized in that: high vinyl polybutadiene rubber is used as a raw material, cashew shell oil is used as an anti-aging agent to prepare oil-extended rubber, and then polyisoprene rubber is used as a plasticizer to mix and vulcanize ethylene propylene diene monomer and the oil-extended rubber to prepare the high-temperature-resistant energy-saving adhesive layer rubber for the conveyer belt.
2. The high-temperature-resistant energy-saving adhesive layer rubber for a conveyor belt according to claim 1, characterized in that: the dosage of the high vinyl polybutadiene rubber solution is 100 weight portions, and the dosage of the cashew nut shell oil is 15-35 weight portions.
3. The high-temperature-resistant energy-saving adhesive layer rubber for a conveyor belt according to claim 1, characterized in that: the dosage of the oil-extended rubber is 30-50 parts by weight, the dosage of the ethylene propylene diene monomer is 50-70 parts by weight, and the dosage of the polyisoprene rubber is 5-15 parts by weight.
4. The high-temperature-resistant energy-saving adhesive layer rubber for a conveyor belt according to claim 1, characterized in that: the preparation method of the oil extended rubber comprises the following steps:
preheating cashew nut shell oil to 40 ℃, adding the cashew nut shell oil into high vinyl polybutadiene rubber liquid, mechanically stirring at the rotating speed of 400rpm for 40min, condensing by using steam, removing monomers and a solvent, and drying to obtain the oil-extended rubber.
5. The high-temperature-resistant energy-saving adhesive layer rubber for a conveyor belt according to claim 1, characterized in that: the vulcanization formula of the oil-extended rubber is as follows, and the oil-extended rubber is measured by weight parts:
6. the high-temperature-resistant energy-saving adhesive layer rubber for a conveyor belt according to claim 1, characterized in that: the mixing process is divided into three sections, wherein one section of mixing is carried out in an internal mixer, the temperature of an internal mixing chamber is 60 ℃, and the rotating speed of a rotor is 40 rpm; the two-stage mixing is carried out on an open mill; the three-stage mixing is carried out in an internal mixer, the initial temperature of an internal mixing chamber is 50 ℃, and the rotating speed of a rotor is 40 rpm.
7. The high-temperature-resistant energy-saving adhesive layer rubber for a conveyor belt according to claim 6, wherein: the first-stage mixing process comprises the following steps: firstly adding oil-extended rubber and ethylene propylene diene monomer rubber, mixing and banburying, then adding polyisoprene rubber, banburying, adding carbon black, exhausting at 105 ℃, and discharging rubber at 120 ℃.
8. The high-temperature-resistant energy-saving adhesive layer rubber for a conveyor belt according to claim 6, wherein: the two-stage mixing process comprises the following steps: and (3) thinly passing the first-stage rubber compound for 2 times, then tapping for 3 times, pouring for 10 times, and finally discharging and standing.
9. The high-temperature-resistant energy-saving adhesive layer rubber for a conveyor belt according to claim 6, wherein: the three-stage mixing process comprises the following steps: and taking one half of the second-stage rubber compound, adding a vulcanizing machine and an accelerator for mixing and banburying, adding the other half of the second-stage rubber compound for banburying, then exhausting, and carrying out rubber discharge at 80 ℃.
10. The high-temperature-resistant energy-saving adhesive layer rubber for a conveyor belt according to claim 1, characterized in that: the vulcanization condition is 145 ℃ and 45 min; the pressure of the vulcanizing press is 15MPa, the preheating and pressure maintaining time is respectively 5 minutes, and the middle exhaust is carried out for 5 times.
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