CN107474403B - Composite rubber tube inner and outer rubber material and preparation method and application thereof - Google Patents
Composite rubber tube inner and outer rubber material and preparation method and application thereof Download PDFInfo
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- CN107474403B CN107474403B CN201710788216.2A CN201710788216A CN107474403B CN 107474403 B CN107474403 B CN 107474403B CN 201710788216 A CN201710788216 A CN 201710788216A CN 107474403 B CN107474403 B CN 107474403B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C69/00—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore
- B29C69/02—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore of moulding techniques only
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/002—Methods
- B29B7/005—Methods for mixing in batches
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2023/00—Tubular articles
- B29L2023/22—Tubes or pipes, i.e. rigid
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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
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
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- C—CHEMISTRY; METALLURGY
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- 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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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
- 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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- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
Abstract
The invention relates to a composite rubber tube inner and outer rubber material and a preparation method and application thereof, wherein the composite rubber tube inner and outer rubber material comprises the following raw materials in parts by weight: 100 parts of ethylene propylene rubber, 2-5 parts of adhesive, 40-50 parts of plasticizer, 6-9 parts of vulcanizing agent, 2-5 parts of coupling agent, 100-150 parts of filler, 6-10 parts of activator and 3-5 parts of anti-aging agent. The knitted rubber pipe prepared from the inner rubber material and the outer rubber material of the composite rubber pipe has the peel strength of more than 5N/mm, the pulse experiment of the rubber pipe reaches more than 250h, the tensile strength change rate of the rubber pipe after aging at 150 ℃ for 72h is less than or equal to 10, the hardness change rate is less than or equal to 10, and the performances of elongation, compression permanent deformation and the like meet the standard requirements of automobile water pipes. The rubber tube has long service life and reduces the production cost of users.
Description
Technical Field
The invention relates to a composite rubber pipe inner and outer rubber material and a preparation method and application thereof, and belongs to the technical field of rubber pipes.
Background
The composite rubber pipe is generally composed of a multilayer structure and comprises an inner rubber layer, a framework layer and an outer cross layer, wherein the inner rubber layer generally has air tightness and tolerance for conveying media, the framework layer generally needs to bear certain internal pressure, and the outer cross layer has the functions of protecting the integrity of the rubber pipe and resisting the corrosion of the environment to the rubber pipe. The more typical multilayer rubber pipe is a knitted rubber pipe, the inner layer and the outer layer of the rubber pipe are made of rubber, and the production process mainly adopts a knitting method to lay framework materials outside the inner rubber layer and inside the outer rubber layer. The framework layer of the knitted rubber tube is knitted, the material is mainly fiber thread, the knitted rubber tube has elasticity when the tube blank is bent, the knitted structure is stable, the stress tends to be balanced, and the shape of the rubber tube under internal pressure is basically stable.
The automobile rubber tube is one of the most basic parts which are used in a large number in the automobile manufacturing process, and the knitted rubber tube has excellent use performance and is generally applied to the field of automobile manufacturing, for example, the water supply and drainage rubber tube of an automobile engine and the rubber tube for air inlet and outlet are knitted rubber tubes.
The inner and outer rubber materials of the knitted rubber tube mostly adopt ethylene propylene rubber, the ethylene propylene rubber is synthetic rubber taking ethylene and propylene as main monomers, and the knitted rubber tube is divided into ethylene propylene rubber and ethylene propylene diene rubber according to different monomer compositions in a molecular chain, the former is a copolymer of ethylene and propylene and is expressed by EPM, and the latter is a copolymer of ethylene, propylene and a small amount of third non-conjugated diene monomer and is expressed by EPDM. Both are commonly referred to as ethylene propylene rubber, Ethylene Propylene Rubber (EPR). The high-strength high-toughness heat-resistant rubber tube is widely applied to automobile parts, waterproof materials for buildings, wire and cable sheaths, heat-resistant rubber tubes, adhesive tapes, automobile sealing parts, lubricating oil additives and other products.
At present, the bonding process of the inner glue and the outer glue of the composite rubber pipe, especially the knitted rubber pipe, is mainly finished by spraying dimethylbenzene or gasoline on the inner glue, and the peel strength is lower than 3.5N/mm. The solvent sprayed between the inner glue and the outer glue only plays a role in physical bonding or partial-S-S-bond connection, the strength of the-S-S-is low, and the-S-S-is easy to break by heating, so that the inner glue and the outer glue are easy to separate from the framework layer to form a layered structure. And the pulse resistance, the bursting pressure, the high-temperature aging resistance, the compression permanent deformation resistance and the like of the composite rubber pipe can not meet the requirements of the automobile performance, so that cooling water and pipe explosion and the like of an automobile engine are caused to leak, the service time of the automobile is shortened, and the maintenance cost is increased.
Chinese patent document CN103009597A (application number: 201310000359.4) discloses a production process of a knitted rubber tube, which comprises the steps of extruding an inner rubber layer, paving a reinforcing layer on the peripheral side of the inner rubber layer, coating an outer rubber layer on the peripheral side of the reinforcing layer, vulcanizing and the like, wherein burrs of the reinforcing layer are subjected to melting elimination through infrared heating before the step of coating the outer rubber layer on the peripheral side of the reinforcing layer; and then the outer surface layer of the inner rubber layer is plasticized by heating with hot air. However, the inner and outer layer rubber materials of the knitted rubber hose are all conventional rubber, and are still bonded by physical melting, the inner and outer rubber materials are not improved, and the bonding effect still needs to be further improved. The adhesive force of the inner layer adhesive and the outer layer adhesive is increased by adjusting the formula, but the adhesion of the inner layer adhesive and the outer layer adhesive and the fiber of the strong layer can not be achieved, so that an effective inner adhesive and outer adhesive material is found to effectively adhere the inner layer adhesive and the outer layer adhesive and the strong layer together, the performance of the rubber pipe is improved, and the service life of the rubber pipe is prolonged, and the problem to be solved is urgently needed.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a composite rubber tube inner and outer rubber material and a preparation method and application thereof.
The technical scheme of the invention is as follows:
the composite rubber pipe inner and outer rubber material comprises the following raw materials in parts by weight:
100 parts of ethylene propylene rubber, 2-5 parts of adhesive, 40-50 parts of plasticizer, 6-9 parts of vulcanizing agent, 2-5 parts of coupling agent, 100-150 parts of filler, 6-10 parts of activator and 3-5 parts of anti-aging agent.
According to the invention, the ethylene-propylene rubber is preferably ethylene-propylene-diene rubber EPM or/and ethylene-propylene-diene rubber EPDM, and the ethylene-propylene-diene rubber EPDM is further preferably selected.
According to the present invention, preferably, the coupling agent is maleic anhydrified butadiene (MLPB).
According to the invention, preferably, the adhesive is 769 resin or chloroprene rubber A90.
According to the invention, the plasticizer is coumarone (2, 3-benzofuran) and/or paraffin oil, and a mixture of coumarone and paraffin oil in a mass ratio of 1 (6-7) is further preferable.
According to the present invention, preferably, the active agent is zinc oxide, magnesium oxide or/and stearic acid, and further preferably, the ratio of zinc oxide, magnesium oxide and stearic acid is 5: 2: 2 mass ratio of the mixture.
According to the present invention, the antioxidant is preferably antioxidant RD (2,2, 4-trimethyl-1, 2-dihydroquinoline polymer) or/and antioxidant MB (2-mercaptobenzimidazole), and more preferably a mixture of antioxidant RD and antioxidant MB in a mass ratio of 1: 1.
According to the invention, the filler is preferably N550 carbon black, calcium bicarbonate and/or china clay.
According to the invention, preferably, the vulcanizing agent comprises dicumyl peroxide (DCP) or/and triacrylate isocyanurate (TAIC);
further preferably, the vulcanizing agent further comprises 0.5-0.8 part of sulfur. The vulcanization of the peroxide and the addition of a small amount of sulfur can accelerate the vulcanization speed and improve the tensile strength, the tearing strength and the like of the vulcanized rubber.
More preferably, the vulcanizing agent further comprises 0.2-0.5 part of an accelerator TRA (dipentamethylenethiuram tetrasulfide). The TRA is a vulcanizing agent in the invention, and replaces part of sulfur to improve the heat-resisting aging resistance of the rubber tube.
According to the invention, the composite rubber tube inner and outer rubber material comprises the following components in parts by weight:
100 parts of EPDM, 3 parts of 769 resin as a binder, 6 parts of coumarone, 40 parts of paraffin oil, 4 parts of dicumyl peroxide, 2 parts of triallyl isocyanurate TAIC, 2 parts of an anti-aging agent RD, 2 parts of an anti-aging agent MB, 6 parts of zinc oxide, 2 parts of magnesium oxide, 1.5 parts of stearic acid, 100 parts of N550 carbon black, 30 parts of pottery clay, 0.3 part of an accelerator TRA, 0.6 part of sulfur and 2-3 parts of a coupling agent MLPB.
According to the invention, the preparation method of the composite rubber tube inner and outer rubber materials comprises the following steps:
(1) plasticating: plasticating the ethylene propylene rubber at 70-90 ℃ for 3-7 min, standing at normal temperature for 8-24 h to recover the stress of the rubber material so as to facilitate the dispersion of the material during mixing;
(2) mixing: adding plasticated ethylene propylene rubber, 769 resin serving as an adhesive, MLPB serving as a coupling agent, coumarone, paraffin oil, an antioxidant RD, an antioxidant MB, zinc oxide, magnesium oxide, stearic acid, N550 carbon black and clay into an internal mixer, discharging rubber when the temperature reaches 110-120 ℃, and cooling to below 60 ℃ on an open mill to obtain mixed masterbatch; the lower piece is placed and the master batch is mixed so as to be convenient for the full dispersion of the materials;
(3) extruding: standing the mixed master batch for more than 24 hours, adding a vulcanizing agent, carrying out open milling, carrying out thin passing for 3-5 times by using a roller distance of 0.6-0.8 mm, carrying out rubber smashing for 3-5 min by using a roller distance of 7-9 mm, and then carrying out strip cutting and cooling to obtain the composite rubber tube inner and outer rubber materials.
According to the invention, the method also comprises a step (4) of extruding the composite hose:
extruding the glue material inside and outside the composite rubber pipe to form the pipe blank, and standing the pipe blank for more than 24 hours to obtain the composite rubber pipe.
According to the invention, preferably, the extruded tube blank in the step (4) is sleeved on a mold core and vulcanized in a vulcanizing tank at 150-155 ℃ for 30-35 min.
According to the invention, the composite rubber pipe inner and outer rubber materials are used for preparing composite rubber pipes, preferably for preparing knitted intersecting pipes.
The coupling agent is added into the rubber material in a certain part, so that the bonding strength between the inner rubber and the outer rubber and the framework layer is increased, the tensile strength of vulcanized rubber can be improved by more than 20% by adding the coupling agent, the viscosity and mutual viscosity of the rubber material and the activity of the vulcanized rubber are improved, and the tearing strength and the elastic modulus between the inner rubber and the outer rubber and the framework layer are improved. The peel strength of the inner and outer rubber of the rubber tube prepared by adding the coupling agent can be improved by more than 50 percent.
According to the invention, the vulcanizing agent is added into the rubber material in a certain part, so that the heat-resistant aging performance of the rubber tube can be effectively improved, the heat-resistant temperature of the rubber tube vulcanized by peroxide can reach more than 150 ℃, and the heat-resistant temperature of the rubber tube vulcanized by sulfur is below 130 ℃.
The invention adds a certain part of adhesive in the rubber material, increases the adhesion between the inner rubber and the outer rubber, can make the inner rubber and the outer rubber of the rubber tube be better adhered by adding the adhesive, is not easy to delaminate, and changes the technical performance of the ethylene propylene rubber. Waste products such as foaming and delamination caused by process problems are reduced.
The invention has the beneficial effects that:
1. the knitted rubber tube made of the inner and outer rubber materials of the composite rubber tube has the advantages of high bonding strength between the inner rubber and the outer rubber, good thermal aging resistance, high tensile strength, long service life and elongation and compression permanent deformation performance meeting the standard requirements of automobile rubber tubes.
2. The composite rubber pipe inner and outer rubber material has low raw material cost, reduces the production cost of the rubber pipe, and meets the production requirements of enterprises.
3. The knitted rubber pipe prepared from the inner rubber material and the outer rubber material of the composite rubber pipe has the peel strength of more than 5N/mm, the pulse experiment of the rubber pipe reaches more than 250h, the tensile strength change rate of the rubber pipe after aging at 150 ℃ for 72h is less than or equal to 10, the hardness change rate is less than or equal to 10, and the performances of elongation, compression permanent deformation and the like meet the standard requirements of automobile water pipes. The rubber tube has long service life and reduces the production cost of users.
Drawings
Fig. 1 is a schematic view of the main structure of the composite intersection pipe of the present invention.
Wherein: 1. inner glue layer, 2, framework layer, 3, outer glue layer.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following specific examples.
The raw materials used in the examples are all conventional commercial products, and the equipment used is conventional equipment.
Example 1
The composite rubber pipe inner and outer rubber material comprises the following raw materials in parts by weight:
100 parts of EPDM, 3 parts of 769 parts of adhesive resin, 3 parts of coupling agent, 6 parts of coumarone, 40 parts of paraffin oil, 4 parts of dicumyl peroxide, 2 parts of TAIC, 2 parts of anti-aging agent RD, 2 parts of anti-aging agent MB, 6 parts of zinc oxide, 2 parts of magnesium oxide, 1.5 parts of stearic acid, 100 parts of N550 carbon black and 30 parts of argil. 0.3 part of accelerator TRA and 0.6 part of sulfur.
The preparation method comprises the following steps:
(1) plasticating; in order to meet the process requirement and reduce the Mooney viscosity, the EPDM rubber is plasticated in an internal mixer at 80 ℃ for 5min and then placed on a stand for 10h, and the stress of the rubber material is recovered so as to facilitate the dispersion of the material during mixing.
(2) Mixing; mixing 769 resin serving as an adhesive, MLPB serving as a coupling agent, coumarone, paraffin oil, an antioxidant RD, an antioxidant MB, zinc oxide, magnesium oxide, stearic acid, N550 carbon black, clay and EPDM (ethylene-propylene-diene monomer) subjected to plastication treatment in the step (1) in an internal mixer for 6-9 min, discharging the rubber compound on a roller of a milling machine to be cooled to below 60 ℃ when the temperature reaches 110-120 ℃ to obtain a mixing master batch, and placing the mixing master batch on a lower piece to facilitate the material to be fully dispersed;
(3) pressing out; standing the mixed masterbatch for 24 hours, adding a vulcanizing agent on an open mill, thoroughly heating the mixed masterbatch on the open mill, wrapping the rubber material on a roller at a roll distance of 10mm, slowly pouring the vulcanizing agent, adding the vulcanizing agent, thinly passing the rubber material for 3 times at a roll distance of 0.6-0.8 mm, tamping the rubber material on a rubber turnover machine at a roll distance of 7-9 mm for 3min, then discharging, cooling, standing, waiting for the qualified inspection result,
(4) extruding: extruding a tube blank in a 120 extruder according to the process requirements of the product, placing the tube blank for more than 24 times, and sleeving the tube blank on a mold core for vulcanization. And vulcanizing in a vulcanizing tank at 150-155 ℃ for 30-35 min to obtain the composite rubber pipe.
Example 2
The composite rubber pipe inner and outer rubber material comprises the following raw materials in parts by weight:
100 parts of EPDM, 2 parts of 769 parts of adhesive resin, 5 parts of coumarone, 40 parts of paraffin oil, 4 parts of dicumyl peroxide, 2 parts of TAIC, 2 parts of anti-aging agent RD, 2 parts of anti-aging agent MB, 6 parts of zinc oxide, 2 parts of magnesium oxide, 1.5 parts of stearic acid, 100 parts of N550 carbon black, 20 parts of argil and 2 parts of coupling agent.
The preparation method comprises the following steps:
(1) plasticating; in order to meet the process requirement and reduce the Mooney viscosity, the EPDM is plasticated in an internal mixer at 90 ℃ for 5min and then placed on a stand for 12h, and the stress of the rubber material is recovered so as to facilitate the dispersion of the material during mixing.
(2) Mixing; mixing 769 resin serving as an adhesive, MLPB serving as a coupling agent, coumarone, paraffin oil, an antioxidant RD, an antioxidant MB, zinc oxide, magnesium oxide, stearic acid, N550 carbon black, clay and EPDM subjected to plastication treatment in the step (1) in an internal mixer for 6-9 min, discharging the rubber compound on a roller of a milling machine to be cooled to below 60 ℃ when the temperature reaches 110-120 ℃ to obtain a mixing master batch, and placing the lower piece of the mixing master batch for the purpose of fully dispersing the materials;
(3) pressing out; standing the mixed masterbatch for 24 hours, adding a vulcanizing agent on an open mill, thoroughly heating the mixed masterbatch on the open mill, wrapping the rubber material on a roller at a roll distance of 10mm, slowly pouring the vulcanizing agent, adding the vulcanizing agent, thinly passing the rubber material for 3 times at a roll distance of 0.6-0.8 mm, tamping the rubber material on a rubber turnover machine at a roll distance of 7-9 mm for 3min, then discharging, cooling, standing, waiting for the qualified inspection result,
(4) extruding: extruding a tube blank by a 120-degree extruder according to the process requirements of the product, placing the tube blank for more than 24 degrees, and sleeving the tube blank on a mold core for vulcanization. And vulcanizing in a vulcanizing tank at 150-155 ℃ for 30-35 min.
Example 3
The composite rubber pipe inner and outer rubber material comprises the following raw materials in parts by weight:
100 parts of EPDM, 4 parts of 769 resin serving as a binder, 5 parts of coupling agent MLPB, 5 parts of coumarone, 35 parts of paraffin oil, 4 parts of dicumyl peroxide, 2 parts of TAIC, 2 parts of anti-aging agent RD, 2 parts of anti-aging agent MB, 6 parts of zinc oxide, 2 parts of magnesium oxide, 1.5 parts of stearic acid, 100 parts of N550 carbon black and 35 parts of argil. 0.3 part of accelerator TRA and 0.6 part of sulfur.
The preparation method comprises the following steps:
(1) plasticating; in order to meet the process requirement and reduce the Mooney viscosity, the EPDM rubber is plasticated in an internal mixer at 70 ℃ for 7min and then placed on a stand for 20h, and the stress of the rubber material is recovered so as to facilitate the dispersion of the material during mixing.
(2) Mixing; mixing 769 resin serving as an adhesive, MLPB serving as a coupling agent, coumarone, paraffin oil, an antioxidant RD, an antioxidant MB, zinc oxide, magnesium oxide, stearic acid, N550 carbon black, clay and EPDM (ethylene-propylene-diene monomer) subjected to plastication treatment in the step (1) in an internal mixer for 6-9 min, discharging the rubber compound on a roller of a milling machine to be cooled to below 60 ℃ when the temperature reaches 110-120 ℃ to obtain a mixing master batch, and placing the mixing master batch on a lower piece to facilitate the material to be fully dispersed;
(3) pressing out; standing the mixed masterbatch for 24 hours, adding a vulcanizing agent on an open mill, thoroughly heating the mixed masterbatch on the open mill, wrapping the rubber material on a roller at a roll distance of 10mm, slowly pouring the vulcanizing agent, adding the vulcanizing agent, thinly passing the rubber material for 3 times at a roll distance of 0.6-0.8 mm, tamping the rubber material on a rubber turnover machine at a roll distance of 7-9 mm for 3min, then discharging, cooling, standing, waiting for the qualified inspection result,
(4) extruding: extruding a tube blank by a 120-degree extruder according to the process requirements of the product, placing the tube blank for more than 24 degrees, and sleeving the tube blank on a mold core for vulcanization. And vulcanizing in a vulcanizing tank at 150-155 ℃ for 30-35 min.
Example 4
The composite rubber pipe inner and outer rubber material comprises the following raw materials in parts by weight:
100 parts of EPDM, 5 parts of 769 parts of adhesive resin, 3 parts of coupling agent MLPB, 6 parts of coumarone, 42 parts of paraffin oil, 4 parts of dicumyl peroxide, 4 parts of TAIC, 2 parts of anti-aging agent RD, 2 parts of anti-aging agent MB, 6 parts of zinc oxide, 2 parts of magnesium oxide, 1.5 parts of stearic acid, 100 parts of N550 carbon black and 40 parts of argil.
The preparation method comprises the following steps:
(1) plasticating; in order to meet the process requirement and reduce the Mooney viscosity, the EPDM rubber is plasticated in an internal mixer at 80 ℃ for 5min and then placed on a stand for 16h, and the stress of the rubber material is recovered so as to facilitate the dispersion of the material during mixing.
(2) Mixing; mixing 769 resin serving as an adhesive, MLPB serving as a coupling agent, coumarone, paraffin oil, RD serving as an anti-aging agent, MB serving as an anti-aging agent, zinc oxide, magnesium oxide, stearic acid, N550 carbon black, clay and EPDM (ethylene-propylene-diene monomer) subjected to plastication treatment in the step (1) in an internal mixer for 6-9 min, discharging the rubber compound on a roller of a open mill to cool to below 60 ℃ when the temperature reaches 110-120 ℃ to obtain a mixing master batch, and placing the mixing master batch on a lower piece to facilitate full dispersion of materials;
(3) pressing out; standing the mixed masterbatch for 24 hours, adding a vulcanizing agent on an open mill, thoroughly heating the mixed masterbatch on the open mill, wrapping the rubber material on a roller at a roll distance of 10mm, slowly pouring the vulcanizing agent, adding the vulcanizing agent, thinly passing the rubber material for 3 times at a roll distance of 0.6-0.8 mm, tamping the rubber material on a rubber turnover machine at a roll distance of 7-9 mm for 3min, then discharging, cooling, standing, waiting for the qualified inspection result,
(4) extruding: extruding a tube blank by a 120-degree extruder according to the process requirements of the product, placing the tube blank for more than 24 degrees, and sleeving the tube blank on a mold core for vulcanization. And vulcanizing in a vulcanizing tank at 150-155 ℃ for 30-35 min.
Example 5
The composite rubber pipe inner and outer rubber material comprises the following raw materials in parts by weight:
100 parts of EPDM, 2 parts of 769 parts of adhesive resin, 7 parts of coumarone, 42 parts of paraffin oil, 4 parts of dicumyl peroxide, 2 parts of TAIC (polyethylene terephthalate) 2 parts of antioxidant RD 2 parts of antioxidant MB 2 parts, 6 parts of zinc oxide, 2 parts of magnesium oxide, 1.5 parts of stearic acid, 110 parts of N550 carbon black and 30 parts of argil. 0.3 part of accelerator TRA and 0.6 part of sulfur.
The preparation method comprises the following steps:
(1) plasticating; in order to meet the process requirement and reduce the Mooney viscosity, the EPDM rubber is plasticated in an internal mixer at 80 ℃ for 5min, and then placed on a stand for 12h to recover the stress of the rubber material so as to facilitate the dispersion of the material during mixing.
(2) Mixing; mixing 769 resin serving as an adhesive, MLPB serving as a coupling agent, coumarone, paraffin oil, an antioxidant RD, an antioxidant MB, zinc oxide, magnesium oxide, stearic acid, N550 carbon black, clay and EPDM subjected to plastication treatment in the step (1) in an internal mixer for 6-9 min, discharging the rubber compound on a roller of a milling machine to be cooled to below 60 ℃ when the temperature reaches 110-120 ℃ to obtain a mixing master batch, and placing the lower piece of the mixing master batch for the purpose of fully dispersing the materials;
(3) pressing out; standing the mixed masterbatch for 24 hours, adding a vulcanizing agent on an open mill, thoroughly heating the mixed masterbatch on the open mill, wrapping the rubber material on a roller at a roll distance of 10mm, slowly pouring the vulcanizing agent, adding the vulcanizing agent, thinly passing the rubber material for 3 times at a roll distance of 0.6-0.8 mm, tamping the rubber material on a rubber turnover machine at a roll distance of 7-9 mm for 3min, then discharging, cooling, standing, waiting for the qualified inspection result,
(4) extruding: extruding a tube blank by a 120-degree extruder according to the process requirements of the product, placing the tube blank for more than 24 degrees, and sleeving the tube blank on a mold core for vulcanization. And vulcanizing in a vulcanizing tank at 150-155 ℃ for 30-35 min.
Comparative example 1
As described in example 1, except that: 1 part of coupling agent is added.
The performance of the formula is not greatly increased without adding a coupling agent.
Comparative example 2
As described in example 1, except that:
no coupling agent was added.
Comparative example 3
As described in example 1, except that: 8 parts of a coupling agent is added.
The addition of the coupling agent is excessive, the cost is greatly increased, and the performance is not greatly improved.
Comparative example 4
As described in example 1, except that:
3 parts of coupling agent and 5 parts of TAIC are added. Too much TAIC is added, the cost is increased, and the performance is not changed greatly.
Comparative example 5
As described in example 1, except that:
no coupling agent was added, 2 parts of binder 769 resin was added.
Test example 1 testing of Peel Strength and compression set Properties
The knitted intersecting tubes prepared in example 1 and comparative examples 1 to 5 were subjected to peel strength and compression set property tests, and the results are shown in table 1.
TABLE 1
Test example 2 physical Properties
Physical properties of example 1 and comparative example 5 were measured, and the results are shown in table 2.
TABLE 2
As can be seen from Table 1, the peel strength of example 1 of the present invention is greatly improved as compared with comparative example 2 without adding a coupling agent; compared with comparative example 5, the peel strength is also greatly improved, the peel strength is improved from 3.56N/mm to more than 5.2N/mm, and the pressure change is increased from 54.13 to 47.46. The improvement of the peel strength of the rubber tube by 40 percent is very important for the service performance of the automobile rubber tube, and the service life and the overload safety coefficient of the rubber tube can be prolonged.
As can be seen from Table 2, the aging resistance of the present invention is also significantly improved. The EPDM rubber tube of the invention can completely meet the performance requirements of the knitted rubber tube for automobiles.
Claims (7)
1. The composite rubber pipe inner and outer rubber material is characterized by comprising the following raw materials in parts by weight:
100 parts of ethylene propylene rubber, 2-5 parts of adhesive, 40-50 parts of plasticizer, 6-9 parts of vulcanizing agent, 2-5 parts of coupling agent, 100-150 parts of filler, 6-10 parts of activator and 3-5 parts of anti-aging agent;
the coupling agent is maleic anhydride butadiene (MLPB), the adhesive is 769 resin or chloroprene rubber A90, the plasticizer is a mixture of coumarone and paraffin oil in a mass ratio of 1 (6-7), the active agent is zinc oxide, magnesium oxide or/and stearic acid, the anti-aging agent is an anti-aging agent RD (2,2, 4-trimethyl-1, 2-dihydroquinoline polymer) or/and an anti-aging agent MB (2-mercaptobenzimidazole), and the filler is N550 carbon black, calcium bicarbonate and/or argil;
the vulcanizing agent comprises dicumyl peroxide (DCP) or/and triacrylate isocyanurate (TAIC), 0.5-0.8 part of sulfur and 0.2-0.5 part of accelerator TRA (dipentamethylenethiuram tetrasulfide).
2. The composite rubber pipe inner and outer rubber material as claimed in claim 1, wherein the ethylene propylene rubber is ethylene propylene diene rubber (EPM) or/and ethylene propylene diene rubber (EPDM).
3. The preparation method of the composite rubber pipe inner and outer rubber material as claimed in any one of claims 1-2, comprising the steps of:
(1) plasticating: plasticating the ethylene propylene rubber at 70-90 ℃ for 3-7 min, standing at normal temperature for 8-24 h to recover the stress of the rubber material so as to facilitate the dispersion of the material during mixing;
(2) mixing: adding plasticated ethylene propylene rubber, 769 resin serving as an adhesive, MLPB serving as a coupling agent, coumarone, paraffin oil, an antioxidant RD, an antioxidant MB, zinc oxide, magnesium oxide, stearic acid, N550 carbon black and clay into an internal mixer, discharging rubber when the temperature reaches 110-120 ℃, and cooling to below 60 ℃ on an open mill to obtain mixed masterbatch; the lower piece is placed and the master batch is mixed so as to be convenient for the full dispersion of the materials;
(3) extruding: standing the mixed master batch for more than 24 hours, adding a vulcanizing agent, carrying out open milling, carrying out thin passing for 3-5 times at a roll spacing of 0.6-0.8 mm, then smashing the rubber for 3-5 min at a roll spacing of 7-9 mm, and then carrying out strip cooling to obtain the composite rubber tube inner and outer rubber materials.
4. The method for preparing the rubber hose according to claim 3, further comprising a step (4) of extruding the composite rubber hose:
extruding the glue material inside and outside the composite rubber pipe to form the pipe blank, and standing the pipe blank for more than 24 hours to obtain the composite rubber pipe.
5. The preparation method according to claim 4, wherein the extruded tube blank in the step (4) is sleeved on a mold core and vulcanized in a vulcanizing tank at 150-155 ℃ for 30-35 min.
6. The use of the composite hose inner and outer rubber material according to any one of claims 1-2 for the preparation of composite hoses.
7. The use of the composite hose inner and outer rubber material according to any one of claims 1-2 for the preparation of a knitted hose.
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| CN111333963A (en) * | 2020-03-17 | 2020-06-26 | 一汽解放汽车有限公司 | High-pressure-resistance rubber pipe and preparation method and application thereof |
| CN112477213B (en) * | 2020-11-11 | 2023-01-31 | 四川文诚管业有限公司 | Production process of steel wire mesh framework polyethylene composite pipe and composite pipe prepared by production process |
| CN112976728B (en) * | 2021-02-07 | 2023-09-26 | 河南绿色快车橡塑制品有限公司 | Rubber sleeve for composite charging roller, preparation method of rubber sleeve and composite charging roller |
| CN113444323A (en) * | 2021-06-18 | 2021-09-28 | 扬州尚翔汽车零部件有限公司 | Preparation method of novel rubber composition for automobile water pipe |
| CN113669513B (en) * | 2021-07-06 | 2022-10-21 | 中裕软管科技股份有限公司 | Water absorption device with variable pipe diameter |
| CN114593282B (en) * | 2022-03-10 | 2024-03-19 | 一汽解放汽车有限公司 | Low-compression permanent deformation rubber tube and preparation method and application thereof |
| CN114957864A (en) * | 2022-04-18 | 2022-08-30 | 浙江丰茂科技股份有限公司 | High-pressure and high-temperature resistant rubber for high-resistance cooling pipeline |
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