CN116239844B - High-temperature-resistant rubber water stop and preparation method and application thereof - Google Patents
High-temperature-resistant rubber water stop and preparation method and application thereof Download PDFInfo
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- CN116239844B CN116239844B CN202310537388.8A CN202310537388A CN116239844B CN 116239844 B CN116239844 B CN 116239844B CN 202310537388 A CN202310537388 A CN 202310537388A CN 116239844 B CN116239844 B CN 116239844B
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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
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
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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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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
- E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
- E04B1/62—Insulation or other protection; Elements or use of specified material therefor
- E04B1/66—Sealings
- E04B1/68—Sealings of joints, e.g. expansion joints
- E04B1/6806—Waterstops
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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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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/011—Nanostructured additives
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
The invention provides a high-temperature-resistant rubber water stop and a preparation method and application thereof, and belongs to the field of water stops. The invention provides a high-temperature-resistant rubber water stop which is prepared from the following components in parts by weight: 50-70 parts of polyisobutylene, 30-50 parts of ethylene propylene rubber, 4-10 parts of zinc oxide, 2-6 parts of stearic acid, 1.2-2 parts of an anti-aging agent, 40-60 parts of carbon black, 20-30 parts of modified sepiolite, 10-20 parts of nano magnesium oxide, 8-15 parts of activated carbon fiber, 5-10 parts of plasticizer, 2-3 parts of vulcanizing agent and 1-3 parts of trimethylolpropane triacrylate, wherein the viscosity average molecular weight of the polyisobutylene is 50-500 ten thousand. The high-temperature-resistant rubber water stop belt provided by the invention has good high-temperature aging resistance and is suitable for high-geothermal areas.
Description
Technical Field
The invention relates to the technical field of water stops, in particular to a high-temperature-resistant rubber water stop and a preparation method and application thereof.
Background
The rubber water stop is mainly used at the joint of concrete building components to prevent water seepage and water leakage at the joint of the building and ensure the weight of the building. However, the rubber can be aged gradually in the long-term use process, the higher the working environment is, the faster the aging speed is, along with the construction of railways and highways, the construction of traffic infrastructures in western plateau areas is accelerated gradually, a plurality of high geothermal environments exist in plateau areas, the stratum temperature of the areas is over 60 ℃ throughout the year, the geothermal temperature of part of the areas is even up to 90 ℃, and the high temperature can aggravate the thermal aging of a rubber water stop belt, so that the sealing is invalid and the tunnel water seepage is caused. The hot air aging condition in the design standard of the existing water stop is 70 ℃ multiplied by 168 hours, and the water stop under the standard obviously cannot be used as a water stop for concrete buildings such as tunnels in high geothermal areas.
Disclosure of Invention
In view of the above, the invention aims to provide a high-temperature-resistant rubber water stop strip, and a preparation method and application thereof. The high-temperature-resistant rubber water stop belt provided by the invention has good high-temperature aging resistance and is suitable for high-geothermal areas.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a high-temperature-resistant rubber water stop which is prepared from the following components in parts by weight: 50-70 parts of polyisobutylene, 30-50 parts of ethylene propylene rubber, 4-10 parts of zinc oxide, 2-6 parts of stearic acid, 1.2-2 parts of an anti-aging agent, 40-60 parts of carbon black, 20-30 parts of modified sepiolite, 10-20 parts of nano magnesium oxide, 8-15 parts of activated carbon fiber, 5-10 parts of plasticizer, 2-3 parts of vulcanizing agent and 1-3 parts of trimethylolpropane triacrylate, wherein the viscosity average molecular weight of the polyisobutylene is 50-500 ten thousand.
Preferably, the polyisobutene comprises a high molecular weight series polyisobutene product or an ultra-high molecular weight series polyisobutene product, wherein the viscosity average molecular weight of the high molecular weight series polyisobutene product is 50-60 ten thousand, and the viscosity average molecular weight of the ultra-high molecular weight series polyisobutene product is 76-500 ten thousand.
Preferably, the ethylene propylene rubber is ethylene propylene diene rubber or ethylene propylene diene rubber, the ethylene propylene diene rubber is prepared from monomers, the monomers comprise ethylene, propylene and dicyclopentadiene, and the content of the dicyclopentadiene in the monomers is less than 6wt%.
Preferably, the anti-aging agent comprises one or more of an anti-aging agent MB, an anti-aging agent MBZ, and an anti-aging agent ZMTI.
Preferably, the carbon black comprises carbon black N330 and carbon black N550, and the mass ratio of the carbon black N330 to the carbon black N550 in the carbon black is 1:1-1:2.
Preferably, the modified sepiolite is prepared by modifying sepiolite with a coupling agent, the dosage of the coupling agent is 2% -5% of the mass of the sepiolite, and the coupling agent comprises a silane coupling agent and/or a titanate coupling agent.
Preferably, the activated carbon fiber is obtained by carrying out hot air oxidation treatment on the carbon fiber, wherein the temperature of the hot air oxidation treatment is 500-600 ℃ and the time is 1-1.5 h.
Preferably, the sulfiding agent comprises one or more of dicumyl peroxide, di (t-butylperoxyisopropyl) benzene and 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane.
The invention also provides a preparation method of the high-temperature-resistant rubber water stop belt, which comprises the following steps:
firstly mixing polyisobutylene, a plasticizer and ethylene propylene rubber to obtain a first mixed rubber;
carrying out second mixing on the first mixed rubber, zinc oxide, stearic acid, an anti-aging agent, carbon black, modified sepiolite, nano magnesium oxide and active carbon fibers to obtain a second mixed rubber;
carrying out open mixing on the second rubber compound, and then carrying out third mixing on the second rubber compound, a vulcanizing agent and trimethylolpropane triacrylate to obtain a third rubber compound;
and vulcanizing and molding the third rubber compound to obtain the high-temperature-resistant rubber water stop belt.
The invention also provides the application of the high-temperature-resistant rubber water stop belt prepared by the technical scheme or the preparation method of the technical scheme in a high geothermal environment, wherein the temperature of the high geothermal environment is higher than 60 ℃.
The invention provides a high-temperature-resistant rubber water stop which is prepared from the following components in parts by weight: 50-70 parts of polyisobutylene, 30-50 parts of ethylene propylene rubber, 4-10 parts of zinc oxide, 2-6 parts of stearic acid, 1.2-2 parts of an anti-aging agent, 40-60 parts of carbon black, 20-30 parts of modified sepiolite, 10-20 parts of nano magnesium oxide, 8-15 parts of activated carbon fiber, 5-10 parts of plasticizer, 2-3 parts of vulcanizing agent and 1-3 parts of trimethylolpropane triacrylate, wherein the viscosity average molecular weight of the polyisobutylene is 50-500 ten thousand.
Compared with the prior art, the invention has the following beneficial effects:
the polyisobutene is ultrahigh molecular weight polyisobutene (HMPIB), the polyisobutene and the ethylene propylene rubber are used as rubber matrixes and mainly comprise the polyisobutene, the ultrahigh molecular weight polyisobutene is a typical saturated linear rubbery polymer, the molecular chain of the polyisobutene does not contain double bonds, the polyisobutene has good high-temperature aging resistance and ozone aging resistance, but the ultrahigh molecular weight polyisobutene has higher toughness and rebound resilience, the polyisobutene and the plasticizer are used together, the toughness of the HMPIB can be reduced, and the processability of the ultrahigh molecular weight polyisobutene is further improved by blending the polyisobutene with the ethylene propylene rubber; the ultrahigh molecular weight polyisobutylene and the ethylene propylene rubber are vulcanized by adopting a vulcanizing agent and the trimethylolpropane triacrylate, and the generated crosslinking bond is a carbon-carbon bond with higher bond energy, so that the rubber water stop has good high temperature resistance, and the trimethylolpropane triacrylate can further improve the crosslinking degree of the rubber matrix, so that the rubber water stop has higher physical and mechanical properties and elasticity.
Further, the selected antioxidant is one or more of MB, MBZ and ZMTI, and belongs to the antioxidant for benzimidazole rubber, so that the antioxidant has excellent heat resistance, has the effect of decomposing peroxide, and does not catch free radicals generated during decomposition of a vulcanizing agent, thereby not affecting the crosslinking of a peroxide vulcanization system and the physical and mechanical properties of a vulcanized rubber matrix;
further, the sepiolite fiber is a natural mineral fiber, the sepiolite has better heat resistance, the sepiolite is obtained by modifying by a silane coupling agent or a titanate coupling agent, can be uniformly dispersed in a rubber matrix to reinforce the rubber matrix, has a special lamellar or needle-shaped structure, can effectively inhibit permeation of oxygen molecules in the oxidation process, and has good barrier effect on heat and oxygen; the sepiolite has strong adsorptivity and inhibits the chain reaction, so that the sepiolite can effectively improve the thermal oxygen stability of the composite rubber, and test data show that the tensile strength and the elongation at break of the rubber water stop prepared by equivalently replacing the common white carbon black in the rubber water stop after hot air aging (120 ℃ multiplied by 168 h) are 1.08 times and more than 1.04 times of the rubber performance prepared by the original formula; the nanometer magnesia can be uniformly dispersed in the rubber matrix, the heat insulation effect of the magnesia can effectively block the damage of thermal oxygen to a rubber molecular chain, the thermal-oxidative aging resistance of rubber is improved, and test data show that the tensile strength and the elongation at break of the rubber water stop prepared by equivalently replacing the common white carbon black in the rubber water stop after thermal air aging (120 ℃ multiplied by 168 h) are 1.06 times and more than 1.05 times of the rubber performance prepared by the original formula; the activated carbon fiber is fibrous, micropores are distributed on the fiber, a large number of rubber matrixes can be adsorbed, the damage of thermal oxygen to a rubber macromolecular chain is prevented, the heat resistance of the rubber material is improved, and the activated carbon fiber has a good reinforcing effect on the rubber matrixes and can effectively improve the physical and mechanical properties of the rubber material; test data show that the addition of the activated carbon fiber in the rubber formula of the common rubber water stop belt can improve the tensile strength of the rubber material by 10% -15%, and the retention rate of the tensile strength and the elongation at break can be improved by 8% after hot air aging (120 ℃ for 168 hours). Under the synergistic effect of the modified sepiolite, the nano magnesium oxide and the activated carbon fiber, the rubber matrix can be reinforced, the mechanical property of the rubber matrix is improved, the thermal oxygen can be isolated, and the thermal oxidative aging resistance of the rubber material is improved.
Detailed Description
The invention provides a high-temperature-resistant rubber water stop which is prepared from the following components in parts by weight: 50-70 parts of polyisobutylene, 30-50 parts of ethylene propylene rubber, 4-10 parts of zinc oxide, 2-6 parts of stearic acid, 1.2-2 parts of an anti-aging agent, 40-60 parts of carbon black, 20-30 parts of modified sepiolite, 10-20 parts of nano magnesium oxide, 8-15 parts of activated carbon fiber, 5-10 parts of plasticizer, 2-3 parts of vulcanizing agent and 1-3 parts of trimethylolpropane triacrylate, wherein the viscosity average molecular weight of the polyisobutylene is 50-500 ten thousand.
In the present invention, all materials used are commercial products in the art unless otherwise specified.
The weight part of polyisobutene in the raw material of the high-temperature-resistant rubber water stop belt is preferably 58-66 parts, and more preferably 65 parts.
In the present invention, the polyisobutylene preferably includes a high molecular weight series polyisobutylene product or an ultra-high molecular weight series polyisobutylene product, the high molecular weight series polyisobutylene product preferably has a viscosity average molecular weight of 50 to 60 tens of thousands, more preferably 55 tens of thousands, and the ultra-high molecular weight series polyisobutylene product preferably has a viscosity average molecular weight of 76 to 500 tens of thousands, more preferably 120 to 370 tens of thousands, and most preferably 180 tens of thousands.
Based on the weight parts of polyisobutylene, the weight parts of ethylene propylene rubber in the raw materials of the high-temperature-resistant rubber water stop belt are preferably 34-42 parts, and more preferably 35 parts.
In the present invention, the ethylene propylene rubber is preferably ethylene propylene diene rubber or ethylene propylene diene rubber, the ethylene propylene diene rubber is preferably prepared from monomers, the monomers preferably comprise ethylene, propylene and dicyclopentadiene, and the content of dicyclopentadiene in the monomers is preferably less than 6wt%.
Based on the mass parts of polyisobutylene, the weight parts of the anti-aging agent in the raw materials of the high-temperature-resistant rubber water stop belt are preferably 1.5-1.6 parts.
In the present invention, the antioxidant preferably includes one or more of an antioxidant MB, an antioxidant MBZ, and an antioxidant ZMTI. When the antioxidant is preferably a mixture, the mass ratio of each substance in the mixture is not particularly limited, and any mixture of any mass ratio may be used. The selected antioxidant belongs to the antioxidant for benzimidazole rubber, has excellent heat resistance, has the effect of decomposing peroxide, and can not catch free radicals generated during decomposition of the vulcanizing agent, so that the crosslinking of a peroxide vulcanization system is not influenced, and the physical and mechanical properties of a vulcanized rubber matrix are not influenced.
Based on the mass parts of polyisobutylene, the weight parts of carbon black in the raw materials of the high-temperature-resistant rubber water stop belt are preferably 45-53 parts.
In the invention, the carbon black preferably comprises carbon black N330 and carbon black N550, and the mass ratio of the carbon black N330 to the carbon black N550 in the carbon black is preferably 1:1-1:2.
Based on the mass parts of polyisobutylene, the weight parts of the modified sepiolite in the raw materials of the high-temperature-resistant rubber water stop belt are preferably 22-28 parts, and more preferably 25-26 parts.
In the invention, the purity of the modified sepiolite is preferably not less than 97wt%, and the particle size is preferably 20-300 nm.
In the invention, the modified sepiolite is preferably prepared by modifying sepiolite with a coupling agent, the dosage of the coupling agent is preferably 2% -5% of the mass of the sepiolite, and the coupling agent preferably comprises a silane coupling agent and/or a titanate coupling agent. The sepiolite fiber is a natural mineral fiber, the sepiolite has better heat resistance, the selected modified sepiolite is obtained by modifying by a silane coupling agent or a titanate coupling agent, can be uniformly dispersed in a rubber matrix to reinforce the rubber matrix, has a special lamellar or needle-shaped structure, can effectively inhibit permeation of oxygen molecules in the oxidation process, has good barrier effect on heat and oxygen, and has an inhibition effect on chain reaction due to stronger adsorptivity of the sepiolite, so that the sepiolite can effectively improve the thermal oxygen stability of the composite rubber.
Based on the parts by weight of polyisobutylene, the weight of zinc oxide in the raw materials of the high-temperature-resistant rubber water stop belt is preferably 6-8 parts.
Based on the mass parts of polyisobutylene, the weight parts of stearic acid in the raw materials of the high-temperature-resistant rubber water stop belt provided by the invention are preferably 3-5 parts.
Based on the mass portion of polyisobutylene, the weight portion of the nano magnesium oxide in the raw material of the high-temperature-resistant rubber water stop belt is preferably 12-17 parts, more preferably 14-16 parts, the nano magnesium oxide can be uniformly dispersed in a rubber matrix, the heat insulation effect of the magnesium oxide can effectively prevent the damage of thermal oxygen to a rubber molecular chain, and the thermal-oxidative aging resistance of rubber is improved.
In the invention, the particle size of the nano magnesium oxide is preferably 30-50 nm, and the dry content of the magnesium oxide is preferably not less than 99.5wt%.
Based on the parts by weight of polyisobutylene, the weight of the active carbon fiber in the raw material of the high-temperature-resistant rubber water stop belt is preferably 9-12 parts, more preferably 10-11 parts.
In the invention, the carbon content of the activated carbon fiber is preferably not less than 96wt%, and the diameter of a monofilament is preferably 5-8 mu m.
In the invention, the activated carbon fiber is preferably obtained by carrying out hot air oxidation treatment on the carbon fiber, the temperature of the hot air oxidation treatment is preferably 500-600 ℃ and the time is preferably 1-1.5 h, the activated carbon fiber is fibrous, micropores are fully distributed on the fiber, a large number of rubber matrixes can be adsorbed, the damage of hot oxygen to rubber macromolecular chains is prevented, the heat resistance of the rubber materials is improved, and the activated carbon fiber has a good reinforcing effect on the rubber matrixes and can effectively improve the physical and mechanical properties of the rubber materials.
Under the synergistic effect of the modified sepiolite, the nano magnesium oxide and the activated carbon fiber, the invention not only can strengthen the rubber matrix and improve the mechanical property of the rubber matrix, but also can play a role in isolating hot oxygen and improve the thermo-oxidative aging resistance of the rubber material.
Based on the mass parts of polyisobutylene, the weight parts of the vulcanizing agent in the raw materials of the high-temperature-resistant rubber water stop belt are preferably 2.2-2.6 parts, and more preferably 2.5 parts.
In the present invention, the vulcanizing agent preferably includes one or more of dicumyl peroxide, di (t-butylperoxyisopropyl) benzene, and 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexane. When the vulcanizing agent is preferably a mixture, the mass ratio of each substance in the mixture is not particularly limited, and any mixture of any mass ratio may be used.
Based on the weight parts of polyisobutylene, the weight parts of the plasticizer in the raw materials of the high-temperature-resistant rubber water stop belt are preferably 8 parts.
In the present invention, the plasticizer preferably includes one or more of tricresyl phosphate, toluene diphenyl phosphate, and triphenyl phosphate. When the plasticizer is preferably a mixture, the mass ratio of each substance in the mixture is not particularly limited in the present invention, and any mass ratio of the mixture may be used.
Based on the parts by weight of polyisobutylene, the weight part of trimethylolpropane triacrylate in the raw material of the high-temperature-resistant rubber water stop belt is preferably 1.4-2 parts, and more preferably 1.5 parts.
In the invention, the ultrahigh molecular weight polyisobutylene and the ethylene propylene rubber are vulcanized by adopting a vulcanizing agent and matched with the trimethylolpropane triacrylate, and the generated crosslinking bond is a carbon-carbon bond with higher bond energy, so that the rubber water stop has good high temperature resistance, and the trimethylolpropane triacrylate can further improve the crosslinking degree of a rubber matrix, so that the rubber water stop has higher physical and mechanical properties and elasticity.
The invention also provides a preparation method of the high-temperature-resistant rubber water stop belt, which comprises the following steps:
firstly mixing polyisobutylene, a plasticizer and ethylene propylene rubber to obtain a first mixed rubber;
carrying out second mixing on the first mixed rubber, zinc oxide, stearic acid, an anti-aging agent, carbon black, modified sepiolite, nano magnesium oxide and active carbon fibers to obtain a second mixed rubber;
carrying out open mixing on the second rubber compound, and then carrying out third mixing on the second rubber compound, a vulcanizing agent and trimethylolpropane triacrylate to obtain a third rubber compound;
and vulcanizing and molding the third rubber compound to obtain the high-temperature-resistant rubber water stop belt.
The invention carries out first mixing on polyisobutylene, plasticizer and ethylene propylene rubber to obtain first mixed rubber.
According to the invention, the polyisobutene and the plasticizer are preferably added into an internal mixer, mixed for 40-80 seconds, then the ethylene propylene rubber is added, and mixed for 55-85 seconds.
After the first rubber compound is obtained, the first rubber compound, zinc oxide, stearic acid, an anti-aging agent, carbon black, modified sepiolite, nano magnesium oxide and activated carbon fiber are subjected to second mixing to obtain a second rubber compound.
According to the invention, the zinc oxide, the stearic acid and the anti-aging agent are preferably added into the first rubber compound, the carbon black, the modified sepiolite, the nano magnesium oxide and the activated carbon fiber are added after the first rubber compound is mixed for 40-60 seconds, and the rubber compound is discharged after the mixing temperature is between 90 and 15 seconds or the mixing temperature is between 160 ℃.
In the invention, the rubber discharging is preferably carried out on an open mill, and the second rubber compound is subjected to open mill and then is subjected to third mixing with a vulcanizing agent and trimethylolpropane triacrylate to obtain a third rubber compound.
In the invention, the open mill is preferably carried out on an open mill, the roll gap of the open mill is preferably 1-3 mm, the open mill is preferably thin-passed for 3-5 times, then the vulcanizing agent and the trimethylolpropane triacrylate are added, and the mixture is uniformly mixed and then discharged for standby.
After the third rubber compound is obtained, the third rubber compound is vulcanized and molded to obtain the high-temperature-resistant rubber water stop belt.
In the present invention, the vulcanization molding is preferably an extrusion process or a compression molding process.
In the invention, the vulcanization temperature of the die pressing process is preferably 165-180 ℃, more preferably 170-175 ℃, the vulcanization pressure is preferably 10-15 MPa, more preferably 12-14 MPa, the vulcanization time is preferably 15-40 min, more preferably 18-20 min.
In the present invention, the extrusion process preferably includes the steps of: the third rubber compound is extruded by an extruder and then vulcanized and formed by a vulcanizing box, the vulcanizing box preferably comprises an infrared heating section, a microwave heating section and a hot air heating section, the length of the infrared heating section is preferably 3-6 m, the length of the microwave heating section is preferably 7-12 m, the length of the hot air heating section is preferably 15-22 m, the temperature of a screw and a machine barrel is preferably 60-80 ℃, the temperature of the infrared heating section is preferably 200-240 ℃, the temperature of the microwave heating section is preferably 170-190 ℃, the microwave power is preferably 1-5 kW, the temperature of the hot air heating section is preferably 200-240 ℃, and the traction speed of vulcanizing and forming of the vulcanizing box is preferably 1-2 m/min.
The invention also provides the application of the high-temperature-resistant rubber water stop belt prepared by the technical scheme or the preparation method of the technical scheme in a high geothermal environment, wherein the temperature of the high geothermal environment is higher than 60 ℃.
The specific mode of the application of the present invention is not particularly limited, and modes well known to those skilled in the art can be adopted.
In order to further illustrate the present invention, the following examples are provided to describe the high temperature resistant rubber waterstop of the present invention in detail, and the preparation method and application thereof, but they should not be construed as limiting the scope of the present invention.
The raw materials used in the embodiment of the invention are as follows:
the ethylene propylene rubber is ethylene propylene rubber;
the modified sepiolite is obtained by modifying a silane coupling agent, and the use amount of the coupling agent is 2wt% of the use amount of the sepiolite; the purity of the modified sepiolite is not less than 97wt percent, and the particle size distribution is 20-300 nm;
the particle size of the nano magnesium oxide is 30-50 nm, and the dry basis content of the magnesium oxide is not less than 99.5wt%;
the activated carbon fiber is carbon fiber subjected to hot air oxidation treatment, the carbon content is not less than 96wt%, the diameter of a monofilament is 5-8 mu m, the temperature of the hot air oxidation treatment is 500 ℃, and the heat treatment time is 1h;
example 1
Firstly, 50 parts by mass of ultra-high molecular weight polyisobutene with 120 ten thousand viscosity average molecular weight and 5 parts by mass of plasticizer tricresyl phosphate are added into an internal mixer, 50 parts by mass of ethylene propylene rubber is added after mixing for 45 seconds, mixing is carried out for 60 seconds, then 4 parts by mass of zinc oxide, 2 parts by mass of stearic acid and 1.2 parts by mass of antioxidant MBZ are added, 20 parts by mass of carbon black N330 and 30 parts by mass of carbon black N550 are added after mixing for 40 seconds, 25 parts by mass of modified sepiolite, 12 parts by mass of nano magnesium oxide and 10 parts by mass of active carbon fiber are mixed for 95 seconds, rubber is discharged onto an open mill, the roll spacing of the open mill is 1.2 mm, 2.2 parts by mass of 2, 5-dimethyl-2, 5-bis (tertiary butyl peroxy) hexane and 1.5 parts by mass of trimethylolpropane triacrylate are added after thinning for 4 times, and the sheet is discharged for standby after mixing evenly.
Vulcanization molding
And adopting a mould pressing vulcanization process, wherein the thickness of the water stop belt is 6 mm, the vulcanization temperature is 170 ℃, the vulcanization pressure is 12MPa, and the vulcanization time is 18min, so that the high-temperature-resistant rubber water stop belt is obtained.
Example 2
Firstly, 58 parts by mass of high molecular weight polyisobutene with the viscosity average molecular weight of 55 ten thousand and 8 parts by mass of plasticizer tricresyl phosphate are added into an internal mixer, after mixing for 55 seconds, 42 parts by mass of ethylene propylene rubber is added, mixing for 70 seconds, then 6 parts by mass of zinc oxide, 3 parts by mass of stearic acid and 1.5 parts by mass of antioxidant MB are added, after mixing for 50 seconds, 25 parts by mass of carbon black N330 and 25 parts by mass of carbon black N550, 22 parts by mass of modified sepiolite, 14 parts by mass of nano magnesium oxide and 9 parts by mass of active carbon fiber are added, after mixing for 95 seconds, rubber is discharged onto an open mill, the roll spacing of the open mill is 1.5 mm, after passing through the mixer for 5 times, 2.5 parts by mass of 2, 5-dimethyl-2, 5-bis (tertiary butyl peroxy) hexane and 2 parts by mass of trimethylolpropane triacrylate are added, and after mixing evenly, the mixture is discharged for standby.
Vulcanization molding
Adopting a mould pressing extrusion process, wherein the thickness of the water stop belt is 6 mm;
the mixed sizing material is extruded by an extruder and then vulcanized and molded by a vulcanizing box, the vulcanizing box is divided into an infrared heating section, a microwave heating section and a hot air heating section, the length of each section is respectively 3 meters, 8 meters and 19 meters, the temperature of a screw rod and a machine barrel is set to 65 ℃, the set temperature of the infrared heating section is 220 ℃, the set temperature of the microwave heating section is 185 ℃, the microwave power is set to 2kW, the temperature of the hot air heating section is set to 210 ℃, and the traction speed is 1.5m/min.
Example 3
Firstly, 65 parts by mass of ultra-high molecular weight polyisobutene with 180 ten thousand viscosity average molecular weight and 10 parts by mass of plasticizer tricresyl phosphate are added into an internal mixer, after 70 seconds of mixing, 35 parts by mass of ethylene propylene rubber is added, after 70 seconds of mixing, 8 parts by mass of zinc oxide, 3 parts by mass of stearic acid and 1.6 parts by mass of antioxidant ZMTI are added, after 50 seconds of mixing, 20 parts by mass of carbon black N330 and 40 parts by mass of carbon black N550, 26 parts by mass of modified sepiolite, 17 parts by mass of nano magnesium oxide and 11 parts by mass of active carbon fiber are added, after 100 seconds of mixing, the mixture is discharged into an open mill, the roll gap of the open mill is 1.0 millimeter, after 3 times of thin pass, 3 parts by mass of 2, 5-dimethyl-2, 5-bis (tertiary butyl peroxy) hexane and 1.5 parts by mass of trimethylolpropane triacrylate are added, and after even mixing, the mixture is discharged into a sheet for standby.
Vulcanization molding
And adopting a mould pressing vulcanization process, wherein the thickness of the water stop belt is 8 mm, the vulcanization temperature is 175 ℃, the vulcanization pressure is 14MPa, and the vulcanization time is 20min, so that the high-temperature-resistant rubber water stop belt is obtained.
Example 4
Firstly, 70 parts by mass of ultra-high molecular weight polyisobutene with the viscosity average molecular weight of 370 ten thousand and 10 parts by mass of plasticizer tricresyl phosphate are added into an internal mixer, 30 parts by mass of ethylene propylene rubber is added after 80 seconds of mixing, then 10 parts by mass of zinc oxide, 5 parts by mass of stearic acid and 2 parts by mass of antioxidant ZMTI are added, 15 parts by mass of carbon black N330 and 30 parts by mass of carbon black N550 are added after 60 seconds of mixing, 30 parts by mass of modified sepiolite, 20 parts by mass of nano magnesium oxide and 15 parts by mass of active carbon fiber are added, after 110 seconds of mixing, rubber is discharged onto an open mill, the roll distance of the open mill is 2 millimeters, 3 parts by mass of dicumyl peroxide and 2 parts by mass of trimethylolpropane triacrylate are added after 5 times of thin pass, and the mixture is uniformly mixed and then discharged for standby.
Vulcanization molding
Adopting a mould pressing extrusion process, wherein the thickness of the water stop belt is 8 mm;
the mixed sizing material is extruded by an extruder and then vulcanized and molded by a vulcanizing box, the vulcanizing box is divided into an infrared heating section, a microwave heating section and a hot air heating section, the length of each section is 5 meters, 10 meters and 20 meters, the temperature of a screw rod and a machine barrel are respectively set to 60 ℃, the set temperature of the infrared heating section is 210 ℃, the set temperature of the microwave heating section is 180 ℃, the microwave power is set to 3kW, the temperature of the hot air heating section is set to 200 ℃, and the traction speed is 1.3m/min.
Example 5
Firstly, 66 parts by mass of ultra-high molecular weight polyisobutene with viscosity average molecular weight of 500 ten thousand and 10 parts by mass of plasticizer tricresyl phosphate are added into an internal mixer, after 75 seconds of mixing, 34 parts by mass of ethylene propylene rubber, 85 seconds of mixing, then 8 parts by mass of zinc oxide, 6 parts by mass of stearic acid and 2 parts by mass of antioxidant MB are added, after 55 seconds of mixing, 18 parts by mass of carbon black N330 and 35 parts by mass of carbon black N550, 28 parts by mass of modified sepiolite, 16 parts by mass of nano magnesium oxide and 12 parts by mass of active carbon fiber are added, after 105 seconds of mixing, the mixture is discharged onto an open mill, the roll distance of the open mill is 1 millimeter, after 4 times of thin pass, 2.6 parts by mass of di (tert-butyl isopropyl peroxide) benzene and 1.4 parts by mass of trimethylolpropane triacrylate are added, and after even mixing, the mixture is discharged for standby.
Vulcanization molding
Adopting a mould pressing extrusion process, wherein the thickness of the water stop belt is 8 mm;
the mixed sizing material is extruded by an extruder and then vulcanized and molded by a vulcanizing box, the vulcanizing box is divided into an infrared heating section, a microwave heating section and a hot air heating section, the lengths of each section are respectively 6 meters, 12 meters and 22 meters, the temperature of a screw rod and a machine barrel are set to 75 ℃, the set temperature of the infrared heating section is 240 ℃, the set temperature of the microwave heating section is 190 ℃, the microwave power is set to 3kW, the temperature of the hot air heating section is set to 230 ℃, and the traction speed is 1.2m/min.
Comparative example 1
(1) The raw materials in parts by weight are as follows: ethylene propylene diene monomer 100, stearic acid 3, zinc oxide 5, carbon black 50, white carbon black 18, sulfur 1 and vulcanization accelerator di (tert-butyl isopropyl peroxide) benzene 1;
(2) Mixing ethylene propylene rubber in an internal mixer for 2min, sequentially adding carbon black, white carbon black, zinc oxide and stearic acid into the internal mixer, continuously mixing for 2min, discharging sizing material from the internal mixer, thinning for 2 times on an open mill, packaging for 2 times, discharging tablets, standing at room temperature for 8 hours,
(3) Putting the sizing material, sulfur and a vulcanization accelerator into an internal mixer again, mixing for 1min, discharging the sizing material from the internal mixer, carrying out thinning 2 times on an open mill, packing 2 times, discharging tablets, and placing for 4 hours at room temperature, and then adding the sizing material into an extruder at the temperature of: the screw and barrel temperatures were set at 75 ℃, and then extrusion molding was performed: shaping at 180 ℃ at one stage, vulcanizing at 180 ℃ at 600W at two stages, heating and vulcanizing at 170 ℃ at three stages by hot air, and obtaining the high-temperature aging-resistant rubber water stop belt after vulcanizing.
Comparative example 2
(1) The weight portions of the raw materials are as follows: ethylene propylene rubber 80, polyisobutylene (viscosity average molecular weight 76000) 20, stearic acid 2, zinc oxide 4, carbon black 40, white carbon black 15, sulfur 1.1 and vulcanization accelerator di (tert-butyl isopropyl peroxide) benzene 1.2;
(2) Mixing ethylene propylene rubber and polyisobutylene in an internal mixer for 1.5min, sequentially adding carbon black, white carbon black, zinc oxide and stearic acid into the internal mixer, continuously mixing for 3min, discharging sizing materials from the internal mixer, thinning for 3 times on an open mill, packaging for 2 times, discharging tablets, and standing at room temperature for 8 hours;
(3) Putting the sizing material, sulfur and a vulcanization accelerator into an internal mixer again, mixing for 1.5min, discharging the sizing material from the internal mixer, carrying out thinning 2 times on an open mill, packing 3 times, discharging tablets, and placing for 5 hours at room temperature, and then adding the sizing material into an extruder at the following temperature: the screw and barrel temperatures were set at 70 ℃, and then extrusion molding was performed: and (3) heating and vulcanizing the first section at 190 ℃, shaping, second section at 800W microwave vulcanization at 180 ℃ and third section at 180 ℃ by hot air, and obtaining the high-temperature aging-resistant rubber water stop belt after vulcanization.
The performance of the finished product is detected in Table 1, and the detection method refers to the related standard cited in GB18173.2-2014 "high molecular waterproof Material 2 nd part waterstop", and the difference is that the test temperatures of part of the performances are different. As can be seen from Table 1, compared with the rubber water stop of the comparative example, the high-temperature resistant rubber water stop of the invention can still maintain higher mechanical properties at high temperature, the tensile strength is more than 16MPa, and the elongation at break is more than 460%; after hot air aging (120 ℃ multiplied by 168 hours), the retention rates of tensile strength and elongation at break are respectively maintained to be above 95% and 90%, which shows that the high-temperature-resistant rubber water stop belt for the high-geothermal environment can be suitable for the high-geothermal environment.
Table 1 results of Performance test of rubber Water stops obtained in examples and comparative examples
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be comprehended within the scope of the present invention.
Claims (3)
1. The high-temperature-resistant rubber water stop belt is characterized by being prepared from the following components in parts by weight: 58 parts of polyisobutylene, 42 parts of ethylene propylene rubber, 6 parts of zinc oxide, 3 parts of stearic acid, 1.5 parts of an anti-aging agent, 330 parts of carbon black N, 550 parts of carbon black N, 22 parts of modified sepiolite, 14 parts of nano magnesium oxide, 9 parts of activated carbon fiber, 8 parts of plasticizer, 2-3 parts of vulcanizing agent and 2 parts of trimethylolpropane triacrylate, wherein the viscosity average molecular weight of the polyisobutylene is 55 ten thousand, the plasticizer is tricresyl phosphate, the anti-aging agent is an anti-aging agent MB, the modified sepiolite is obtained by modifying the silane coupling agent, the coupling agent is 2wt% of the sepiolite, the purity of the modified sepiolite is not less than 97wt%, and the particle size distribution is 20-300 nm; the vulcanizing agent is 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane.
2. The method for preparing the high temperature resistant rubber water stop belt as claimed in claim 1, comprising the steps of:
firstly mixing polyisobutylene, a plasticizer and ethylene propylene rubber to obtain a first mixed rubber;
carrying out second mixing on the first mixed rubber, zinc oxide, stearic acid, an anti-aging agent, carbon black, modified sepiolite, nano magnesium oxide and active carbon fibers to obtain a second mixed rubber;
carrying out open mixing on the second rubber compound, and then carrying out third mixing on the second rubber compound, a vulcanizing agent and trimethylolpropane triacrylate to obtain a third rubber compound;
and vulcanizing and molding the third rubber compound to obtain the high-temperature-resistant rubber water stop belt.
3. The use of the high temperature resistant rubber water stop of claim 1 or the high temperature resistant rubber water stop prepared by the preparation method of claim 2 in a high geothermal environment, wherein the temperature of the high geothermal environment is greater than 60 ℃.
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| US4601935A (en) * | 1985-05-06 | 1986-07-22 | Gencorp Inc. | EPDM laminate |
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| CN105153551A (en) * | 2015-09-17 | 2015-12-16 | 沈阳化工大学 | High-temperature-resistant EPDM (ethylene-propylene-diene monomer) sealing material |
| CN109942964A (en) * | 2019-03-22 | 2019-06-28 | 衡水中铁建工程橡胶有限责任公司 | It is a kind of suitable for the highly thermally heat resistant rubber waterstop in area |
| CN112251154B (en) * | 2019-07-22 | 2022-12-20 | 深圳科创新源新材料股份有限公司 | Waterproof insulating adhesive tape with low-temperature operation performance and preparation method and application thereof |
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| CN112126166B (en) * | 2020-09-29 | 2023-04-04 | 一汽解放汽车有限公司 | Ethylene propylene diene monomer composition, rubber tube, and preparation method and application thereof |
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