阅读说明：本技术 一种耐高温低蠕变密封板及其制备工艺 (High-temperature-resistant low-creep sealing plate and preparation process thereof ) 是由 叶声波 冷钢 封婷婷 于 2020-12-21 设计创作，主要内容包括：本发明公开了一种耐高温低蠕变密封板及其制备工艺。包括改性金属基材和涂覆在改性金属基材上下两面的橡胶层,所述橡胶层是由橡胶混合料经过晾干得到。本发明制备的密封板结合了金属基材的高强度和橡胶层的高弹性和可压缩性,质量轻、密封性好、抗热氧化性能优异,金属基材与橡胶层之间结合力强,长时间在高温环境下工作也不会发生起皮剥落的问题,蠕变松弛率低,应用范围广,非常具有实用性。(The invention discloses a high-temperature-resistant low-creep sealing plate and a preparation process thereof. The rubber layer is prepared by airing a rubber mixture. The sealing plate prepared by the invention combines the high strength of the metal base material and the high elasticity and compressibility of the rubber layer, has light weight, good sealing performance, excellent thermal oxidation resistance, strong bonding force between the metal base material and the rubber layer, low creep relaxation rate, wide application range and high practicability, and can not cause the problem of peeling off even in a high-temperature environment for long-time work.)

1. A high temperature resistant low creep seal plate characterized in that: the rubber layer is prepared by attaching a rubber mixture to the modified metal base material and heating the rubber layer through a drying channel.

2. The high temperature resistant low creep seal plate of claim 1, wherein: the modified metal substrate comprises the following raw material components: 80-100 parts of metal base material and 30-50 parts of silane coupling agent.

3. The high temperature resistant low creep seal plate of claim 1, wherein: the rubber mixture comprises the following raw material components: by weight, 80-100 parts of polymerization liquid, 30-40 parts of filler, 120 parts of natural rubber, 150 parts of ethylene propylene diene monomer, 150 parts of nitrile rubber, 20-30 parts of paraffin, 40-80 parts of sulfur, 20-30 parts of accelerator, 40-80 parts of stearic acid and 70-80 parts of EDOT.

4. The high temperature resistant low creep seal plate of claim 3, wherein: the polymerization liquid mainly comprises: 80-100 parts of 2, 7-dibromopyrene-4, 5,9, 10-tetraone, 40-60 parts of bis (1, 5-cyclooctadiene) nickel (0), 50-70 parts of 1, 5-cyclooctadiene, and 30-50 parts of 4, 4-diamino-2, 2-bipyridine.

5. The high temperature resistant low creep seal plate of claim 3, wherein: the filler comprises the following raw material components: 60-70 parts of polyethyleneimine, 10-20 parts of nano zinc oxide, 10-20 parts of nano magnesium oxide, 8-16 parts of carbon black and 20-30 parts of carbon nano tube.

6. The high temperature resistant low creep seal plate of claim 2, wherein: the silane coupling agent is one or more of carboxyl silane coupling agent and epoxy hydrocarbyl silane coupling agent.

7. The preparation process of the high-temperature-resistant low-creep sealing plate is characterized by comprising the following steps of:

s1, preparing a modified metal base material;

s2, preparing a polymerization solution;

s3, preparing a filler;

s4, preparing a rubber mixture;

and S5, synthesizing a sealing plate.

8. The process for preparing a high temperature resistant low creep seal plate of claim 7, wherein: the method specifically comprises the following steps:

s1, preparing a modified metal base material:

A. polishing the metal base material by using abrasive paper, then washing, derusting, degreasing, and drying to obtain a metal base material A;

B. placing a silane coupling agent in an ethanol solution, stirring and dispersing, adding the metal substrate A under the constant temperature condition of 40-60 ℃, ultrasonically dispersing for 5-8h, and taking out to obtain a modified metal substrate;

s2, preparing a polymerization solution: placing 2, 7-dibromopyrene-4, 5,9, 10-tetraketone in N, N-dimethylformamide solution, stirring and dissolving, sequentially adding bis (1, 5-cyclooctadiene) nickel (0) and 1, 5-cyclooctadiene, stirring and reacting for 10-20min, sequentially adding 4, 4-diamino-2, 2-bipyridine and a modified metal substrate, ultrasonically dispersing for 10-20h at the constant temperature of 50-60 ℃, taking out the modified metal substrate for later use, and collecting the rest solution to obtain a polymerization solution;

s3, preparing a filler: under the condition of low pressure, putting polyethyleneimine into an ethanol solution, stirring and dispersing, sequentially adding nano zinc oxide, nano magnesium oxide, carbon black and carbon nano tubes, ultrasonically dispersing for 2-4h, and performing suction filtration and drying to obtain a filler;

s4, preparing a rubber mixture: placing natural rubber into an internal mixer for plasticating, sequentially adding ethylene propylene diene monomer and nitrile rubber for mixing, sequentially adding filler, polymerization liquid, paraffin, sulfur, accelerator, stearic acid and EDOT, stirring for reaction for 1-2h, stirring for 30-50min at the rotating speed of 500r/min with 200 plus materials, and discharging rubber to obtain a rubber mixture;

s5, synthesizing a sealing plate: and adhering the rubber mixture to the modified metal base material in a roller coating, spraying, curtain coating or dipping mode, heating the rubber mixture through a drying tunnel to form a rubber layer on the modified metal base material, transferring the rubber layer into a drying oven for high-temperature vulcanization treatment, and taking out the rubber layer to obtain the sealing plate.

9. The process for preparing a high temperature resistant low creep seal plate of claim 8, wherein: the step S2 needs to be performed under a nitrogen atmosphere.

10. The process for preparing a high temperature resistant low creep seal plate of claim 8, wherein: the low pressure condition of the step S3 is 0.01-0.03 MPa.

Technical Field

The invention relates to the technical field of sealing plates, in particular to a high-temperature-resistant low-creep sealing plate and a preparation process thereof.

Background

The sealing plate is mainly made of metal materials and non-metal materials, the metal materials are generally used as rigid frameworks to support the non-metal materials on the surface of the metal materials, and the non-metal materials generally have strong flexibility and elasticity, so that the sealing effect of the sealing plate is realized. The non-metallic materials used for preparing the sealing plate mainly comprise plastics, rubber, asbestos and the like, and the plastic materials have poor weather resistance, large brittleness and easy aging; the asbestos material is easy to be damaged, has insufficient sealing performance and short service life. Rubber materials have certain advantages compared with plastic and asbestos materials.

However, the interface bonding force between the metal substrate and the non-metal material of the sealing plate on the market at present is insufficient, and the metal material and the non-metal material of the sealing plate are easy to peel and age under high temperature and hot oxygen environment, which will cause the non-uniform pressure of the sealing plate, so that the sealing effect is reduced or disappeared, and the leakage of substances is easy to cause by not being processed in time, which causes serious accidents and difficult-to-recover loss. The creep rate of a common sealing plate is high, the stability and the durability of the sealing plate are poor, the potential safety hazard is large when the sealing plate is applied to actual production, frequent replacement is needed, the cost of later maintenance and replacement is high, and the development of the sealing plate is limited.

Therefore, a sealing plate with high temperature resistance, low creep, good sealing effect and long service life and a preparation process thereof are needed to solve the problems in the background.

Disclosure of Invention

The invention aims to provide a high-temperature-resistant low-creep sealing plate and a preparation process thereof, so as to solve the problems in the background technology.

The high-temperature-resistant low-creep sealing plate comprises a modified metal base material and a rubber layer attached to one side or two sides of the modified metal base material, wherein the rubber layer is obtained by attaching a rubber mixture to the modified metal base material and heating the rubber layer through a drying channel.

Further, the modified metal substrate comprises the following raw material components: 80-100 parts of metal base material and 30-50 parts of silane coupling agent.

Further, the rubber mixture comprises the following raw material components: by weight, 80-100 parts of polymerization liquid, 30-40 parts of filler, 120 parts of natural rubber, 150 parts of ethylene propylene diene monomer, 150 parts of nitrile rubber, 20-30 parts of paraffin, 40-80 parts of sulfur, 20-30 parts of accelerator, 40-80 parts of stearic acid and 70-80 parts of EDOT.

Further, the polymerization liquid mainly comprises: 80-100 parts of 2, 7-dibromopyrene-4, 5,9, 10-tetraone, 40-60 parts of bis (1, 5-cyclooctadiene) nickel (0), 50-70 parts of 1, 5-cyclooctadiene, and 30-50 parts of 4, 4-diamino-2, 2-bipyridine.

Further, the filler comprises the following raw material components: 60-70 parts of polyethyleneimine, 10-20 parts of nano zinc oxide, 10-20 parts of nano magnesium oxide, 8-16 parts of carbon black and 20-30 parts of carbon nano tube.

Further, the silane coupling agent is one or more of carboxyl silane coupling agent and epoxy hydrocarbon silane coupling agent.

The method comprises the following steps:

s1, preparing a modified metal base material;

s2, preparing a polymerization solution;

s3, preparing a filler;

s4, preparing a rubber mixture;

and S5, synthesizing a sealing plate.

The method specifically comprises the following steps:

s1, preparing a modified metal base material:

A. polishing the metal base material by using abrasive paper, then washing, derusting, degreasing, and drying to obtain a metal base material A;

B. placing a silane coupling agent in an ethanol solution, stirring and dispersing, adding the metal substrate A under the constant temperature condition of 40-60 ℃, ultrasonically dispersing for 5-8h, and taking out to obtain a modified metal substrate;

s2, preparing a polymerization solution: placing 2, 7-dibromopyrene-4, 5,9, 10-tetraketone in N, N-dimethylformamide solution, stirring and dissolving, sequentially adding bis (1, 5-cyclooctadiene) nickel (0) and 1, 5-cyclooctadiene, stirring and reacting for 10-20min, sequentially adding 4, 4-diamino-2, 2-bipyridyl and a modified metal substrate, and ultrasonically dispersing for 10-20h at the constant temperature of 50-60 ℃, wherein the molecular chain movement rate can be accelerated by proper heating, and the reaction time can be shortened; taking out the modified metal base material for later use, and collecting the rest solution to obtain a polymerization solution;

s3, preparing a filler: under the condition of low pressure, putting polyethyleneimine into an ethanol solution, stirring and dispersing, sequentially adding nano zinc oxide, nano magnesium oxide, carbon black and carbon nano tubes, ultrasonically dispersing for 2-4h, and performing suction filtration and drying to obtain a filler;

s4, preparing a rubber mixture: placing natural rubber into an internal mixer for plasticating, sequentially adding ethylene propylene diene monomer and nitrile rubber for mixing, sequentially adding filler, polymerization liquid, paraffin, sulfur, accelerator, stearic acid and EDOT, stirring for reaction for 1-2h, stirring for 30-50min at the rotating speed of 500r/min with 200 plus materials, and discharging rubber to obtain a rubber mixture;

s5, synthesizing a sealing plate: and adhering the rubber mixture to the modified metal base material in a roller coating, spraying, curtain coating or dipping mode, heating the rubber mixture through a drying tunnel to form a rubber layer on the modified metal base material, transferring the rubber layer into a drying oven for high-temperature vulcanization treatment, and taking out the rubber layer to obtain the sealing plate.

Further, the step S2 needs to be performed under a nitrogen atmosphere; attention is paid to exhaust at the same time; because 1, 5-cyclooctadiene has certain toxicity and can explode under oxygen and high-temperature environments, the polymerization solution needs to be carried out under the nitrogen atmosphere, the exhaust is noticed, and the reaction temperature needs to be controlled between 50 ℃ and 60 ℃ to avoid explosion caused by heat accumulation;

further, the low pressure condition of the step S3 is 0.01-0.03 MPa; the low-pressure condition is favorable for the molecular chain of the polyethyleneimine solution to expand towards the interior of nano zinc oxide, nano magnesium oxide, carbon black and carbon nano tube particles, and the loading capacity of the polyethyleneimine in the interior of filler particles is increased.

According to the invention, firstly, abrasive paper is used for carrying out rough treatment on the surface of the metal base material, the friction force of the surface of the metal base material after being polished by the abrasive paper is large, and mechanical occlusion can be formed between the metal base material and the rubber layer at the later stage, so that the rubber layer is prevented from falling off; the mechanical polishing by using abrasive paper can expose more active sites on the surface of the metal substrate, thereby being beneficial to the modification of the silane coupling agent on the surface; the silane coupling agent used in the invention is one of an epoxy hydrocarbyl silane coupling agent and a carboxyl silane coupling agent; in the invention, silicon hydroxyl in the silane coupling agent and hydroxyl on the surface of the metal substrate are subjected to hydrogen bonding, so that the silane coupling agent is successfully modified on the surface of the metal substrate; the modification of the silane coupling agent introduces a large amount of epoxy groups and carboxyl groups into the metal substrate, and the epoxy groups and the carboxyl groups react with amino groups on the 4, 4-diamino-2, 2-bipyridyl at the later stage, so that part of the 4, 4-diamino-2, 2-bipyridyl in the polymerization solution can be modified on the surface of the metal substrate. 4, 4-diamino-2, 2-bipyridyl participates in the polymerization reaction between 2, 7-dibromopyrene-4, 5,9, 10-tetraone, bis (1, 5-cyclooctadiene) nickel (0) and 1, 5-cyclooctadiene in the polymerization solution, the polymerization reaction generates a large amount of conjugated carbonyl polymer in the polymerization solution, and a polymer network can be formed in the rubber mixture through the conjugated carbonyl polymer at the later stage. Because the silane coupling agent on the modified metal base material is chemically combined with the 4, 4-diamino-2, 2-bipyridyl, part of conjugated carbonyl polymer is also generated on the modified metal base material in the polymerization process, and the compatibility between the modified metal base material and the rubber mixture can be effectively improved by modifying the conjugated carbonyl polymer on the modified metal base material; the conjugated carbonyl polymer can react with the filler in the rubber mixture at the later stage, so that the compatibility between the modified metal base material and the rubber mixture is further improved, the metal base material and the rubber layer are effectively combined, and the phenomena of layering and stripping of the metal base material and the rubber layer in a severe environment are avoided, so that the sealing plate is not stressed uniformly, and the sealing performance and the service life of the sealing plate are influenced.

The method comprises the steps of polymerizing 2, 7-dibromopyrene-4, 5,9, 10-tetrone, bis (1, 5-cyclooctadiene) nickel (0) and 1, 5-cyclooctadiene under the action of 4, 4-diamino-2, 2-bipyridyl to generate poly (pyrene-4, 5,9, 10-tetrone), namely polymerization liquid in the method; according to the invention, the polymerization liquid is mixed into the rubber mixture, because the polymerization liquid contains a large amount of carbonyl groups, the carbonyl groups can perform nucleophilic addition reaction with primary amine on the filler, and pi-pi bonding can also occur between the poly (pyrene-4, 5,9, 10-tetraone) and the carbon nano tube, and because the filler is uniformly dispersed, the poly (pyrene-4, 5,9, 10-tetraone) molecular chain can extend and expand around the rubber mixture and is combined with the filler, so that a stable polymer network structure is formed in the rubber mixture, and the polymer network structure has a rigid conjugated structure and has a prominent effect on improvement of the stability and the creep property of the rubber layer; the poly (pyrene-4, 5,9, 10-tetraone) molecular chain can be entangled with rubber molecules and PEDOT molecular chains in the stirring process, the compactness of a polymer network is further enhanced, the compatibility among natural rubber, ethylene propylene diene monomer and nitrile rubber is effectively improved, and the impact resistance and the thermal oxidation aging resistance of the sealing plate are improved.

According to the invention, nano zinc oxide, nano magnesium oxide, carbon black and carbon nano tubes are firstly placed in polyethyleneimine for impregnation treatment, polyethyleneimine molecular chains are loaded on the surface and in pores of the filler treated by the polyethyleneimine, and the dispersibility of the filler in the rubber mixture A is obviously improved due to the charge interaction because the polyethyleneimine contains a large amount of amino groups.

The addition of the polyethyleneimine can increase the viscosity of the rubber mixture, improve the physical binding force between the rubber mixture and the modified metal base material, improve the binding property between the rubber mixture and the modified metal base material, and simultaneously improve the creep resistance of the rubber layer; the polyethyleneimine is introduced to nano zinc oxide, nano magnesium oxide, carbon black and carbon nano tube particles, so that on one hand, the compatibility between the filler and the rubber layer can be improved, and on the other hand, the modification of the polyethyleneimine also introduces a large amount of tertiary amine and primary amine to the filler; the primary amine on the filler can perform nucleophilic addition reaction with carbonyl on a polymer network in the rubber layer, and then the primary amine is effectively fixed in the rubber layer, so that the filler cannot be peeled from the rubber layer at high temperature, the bonding force between the filler and the rubber layer is further enhanced, and the creep resistance of the prepared sealing plate is obviously improved.

The interfacial bonding force between the rubber mixture and the modified metal base material is generated under the synergistic action of mechanical occlusion, physical bonding and chemical bond bonding, the interfacial bonding force between the modified metal base material and the rubber mixture is strong, the prepared sealing plate is not easy to peel and delaminate in a high-temperature environment, the use of a bonding agent can be effectively reduced, and the production cost is reduced.

The filler in the invention is beneficial to the occurrence of vulcanization and the improvement of the stability of the sealing plate, and can be used as a bonding site of a polymer network in the rubber layer to enhance the mechanical property of the sealing plate, further reduce the creep rate of the sealing plate, improve the sealing property of the sealing plate and prolong the service life.

In order to obtain a rubber layer with better comprehensive performance, a rubber mixture obtained by mixing natural rubber, hydrogenated nitrile rubber and ethylene propylene diene monomer is used as a main raw material of the rubber layer. The natural rubber has excellent flexibility and flexibility, the sealing performance is obvious, the anti-seismic performance is good, but the high-temperature resistance of the natural rubber is insufficient, the problem of thermal oxidation aging is easy to occur, the development of the service life and the application field of the natural rubber is influenced, in order to make up for the insufficiency of the natural rubber, hydrogenated nitrile rubber is added, the high-temperature resistance, oxidation resistance and chemical resistance of the nitrile rubber are more outstanding, the high-temperature resistance of the natural rubber can be obviously improved by mixing the nitrile rubber with the natural rubber, the excellent weather resistance and electric insulation property can be endowed to a rubber mixture by adding the ethylene propylene diene monomer, and the safety performance of the sealing plate can be effectively improved. The sealing plate obtained by mixing the three rubbers combines the advantages of the three rubber materials, and has the advantages of good high-temperature resistance, lower creep property, more excellent comprehensive performance and wider application range.

The problem that compatibility among rubber components is insufficient easily caused by directly mixing three kinds of rubber, performance of the sealing plate in the actual use process is affected, and the rubber layer needs to be modified to improve compatibility of the rubber components and improve comprehensive performance of the sealing plate.

In the invention, the EDOT added in particular can be polymerized to form PEDOT polymer in the rubber mixing process, and PEDOT molecular chain is further entangled with poly (pyrene-4, 5,9, 10-tetraketone) molecular chain and rubber molecular chain, so that the polymer network in the rubber mixture is more compact, and the comprehensive performance of the sealing plate is further improved.

Compared with the prior art, the invention has the following beneficial effects:

the modified metal base material and the rubber layer have good compatibility, the phenomena of layering and stripping of the modified metal base material and the rubber layer in a severe environment can be effectively avoided, the sealing property is greatly improved, and the service life is greatly prolonged.

The polymerization liquid contains a large amount of carbonyl groups, nucleophilic addition reaction can be carried out on the carbonyl groups and primary amine on the filler, and pi-pi bonding can be also carried out between the polymerization liquid and the carbon nano tube, so that a molecular chain of the polymerization liquid can extend around the rubber mixture and form a stable polymer network structure, the stability of the sealing plate is effectively improved, and the creep relaxation rate of the sealing plate is reduced.

Under the action of polyethyleneimine, filler particles contain a large amount of amino groups, and the dispersibility of the filler in the rubber mixture A is remarkably improved due to charge interaction; the added polyethyleneimine can obviously improve the viscosity of the rubber mixture and improve the creep resistance of the rubber layer; the polyethyleneimine can improve the compatibility between the filler and the rubber layer, strengthen the interfacial bonding force between the polymer network and the filler, improve the compatibility of the filler in a rubber mixture and effectively reduce the creep relaxation rate of the sealing plate.

The filler in the invention is beneficial to the occurrence of vulcanization and the improvement of the stability of the sealing plate, and can be used as a bonding site of a polymer network in the rubber layer to enhance the mechanical property of the sealing plate, further reduce the creep rate of the sealing plate, improve the sealing property of the sealing plate and prolong the service life.

The sealing plate prepared by the invention combines the advantages of three rubber materials, and has the advantages of good high-temperature resistance, lower creep property, more excellent comprehensive performance and wider application range.

In the invention, the EDOT added in particular can be polymerized to form PEDOT polymer in the rubber mixing process, and PEDOT molecular chain is further entangled with poly (pyrene-4, 5,9, 10-tetraketone) molecular chain and rubber molecular chain, so that the polymer network in the rubber mixture is more compact, and the comprehensive performance of the sealing plate is further improved.

The sealing plate prepared by the invention combines the high strength of the metal base material and the high elasticity and compressibility of the rubber layer, has light weight, good sealing performance, excellent thermal oxidation resistance, strong bonding force between the metal base material and the rubber layer, low creep relaxation rate, wide application range and high practicability, and can not cause the problem of peeling off even in a high-temperature environment for long-time work.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

The high-temperature-resistant low-creep sealing plate comprises a modified metal base material and rubber layers coated on the upper surface and the lower surface of the modified metal base material, wherein the rubber layers are obtained by airing a rubber mixture.

The modified metal substrate comprises the following raw material components: the adhesive comprises, by weight, 80 parts of a metal base material, 30 parts of a silane coupling agent, and 30 parts of 4, 4-diamino-2, 2-bipyridine.

The rubber mixture comprises the following raw material components: the rubber material comprises, by weight, 80 parts of a polymerization liquid, 30 parts of a filler, 100 parts of natural rubber, 120 parts of ethylene propylene diene monomer, 120 parts of nitrile rubber, 20 parts of paraffin, 40 parts of sulfur, 20 parts of an accelerator, 40 parts of stearic acid and 70 parts of EDOT.

The polymerization liquid mainly comprises: 80 parts of 2, 7-dibromopyrene-4, 5,9, 10-tetrone, 40 parts of bis (1, 5-cyclooctadiene) nickel (0) and 50 parts of 1, 5-cyclooctadiene; the polymerization solution needs to be accelerated by the modified metal substrate.

The filler comprises the following raw material components: 60 parts of polyethyleneimine, 10 parts of nano zinc oxide, 10 parts of nano magnesium oxide, 8 parts of carbon black and 20 parts of carbon nanotubes.

S1, preparing a modified metal base material:

A. polishing the metal base material by using abrasive paper, then washing, derusting, degreasing, and drying to obtain a metal base material A;

B. placing a silane coupling agent in an ethanol solution, stirring and dispersing, adding the metal substrate A under the constant temperature condition of 40 ℃, ultrasonically dispersing for 5 hours, and taking out to obtain a modified metal substrate;

s2, preparing a polymerization solution: placing 2, 7-dibromopyrene-4, 5,9, 10-tetraketone in N, N-dimethylformamide solution, stirring and dissolving, sequentially adding bis (1, 5-cyclooctadiene) nickel (0) and 1, 5-cyclooctadiene, stirring and reacting for 10min, sequentially adding 4, 4-diamino-2, 2-bipyridine and a modified metal substrate, performing ultrasonic dispersion for 10h at the constant temperature of 50 ℃, taking out the modified metal substrate for later use, and collecting the rest solution to obtain a polymerization solution;

s3, preparing a filler: under the condition of low pressure of 0.01MPa, putting polyethyleneimine into an ethanol solution, stirring and dispersing, sequentially adding nano zinc oxide, nano magnesium oxide, carbon black and carbon nano tubes, ultrasonically dispersing for 2 hours, and performing suction filtration and drying to obtain a filler;

s4, preparing a rubber mixture: plasticating natural rubber in an internal mixer, sequentially adding ethylene propylene diene monomer and nitrile rubber for mixing, sequentially adding filler, polymerization liquid, paraffin, sulfur, accelerator, stearic acid and EDOT, stirring for reaction for 1-2h, stirring for 30min at the rotating speed of 200r/min, and discharging rubber to obtain a rubber mixture;

s5, synthesizing a sealing plate: and adhering the rubber mixture to the modified metal base material in a roller coating, spraying, curtain coating or dipping mode, heating the rubber mixture through a drying tunnel to form a rubber layer on the modified metal base material, transferring the rubber layer into a drying oven for high-temperature vulcanization treatment, and taking out the rubber layer to obtain the sealing plate.

Step S2 needs to be performed under a nitrogen atmosphere while taking care to evacuate.

Example 2

The high-temperature-resistant low-creep sealing plate comprises a modified metal base material and rubber layers coated on the upper surface and the lower surface of the modified metal base material, wherein the rubber layers are obtained by airing a rubber mixture.

The modified metal substrate comprises the following raw material components: the adhesive comprises, by weight, 90 parts of a metal base material, 40 parts of a silane coupling agent, and 40 parts of 4, 4-diamino-2, 2-bipyridine.

The rubber mixture comprises the following raw material components: the rubber material comprises, by weight, 90 parts of a polymerization solution, 35 parts of a filler, 110 parts of natural rubber, 135 parts of ethylene propylene diene monomer, 135 parts of nitrile rubber, 25 parts of paraffin, 65 parts of sulfur, 25 parts of an accelerator, 60 parts of stearic acid and 75 parts of EDOT.

The polymerization liquid mainly comprises: 90 parts of 2, 7-dibromopyrene-4, 5,9, 10-tetrone, 50 parts of bis (1, 5-cyclooctadiene) nickel (0) and 60 parts of 1, 5-cyclooctadiene; the polymerization solution needs to be accelerated by the modified metal substrate.

The filler comprises the following raw material components: 65 parts of polyethyleneimine, 15 parts of nano zinc oxide, 15 parts of nano magnesium oxide, 13 parts of carbon black and 25 parts of carbon nano tube.

S1, preparing a modified metal base material:

A. polishing the metal base material by using abrasive paper, then washing, derusting, degreasing, and drying to obtain a metal base material A;

B. placing a silane coupling agent in an ethanol solution, stirring and dispersing, adding the metal substrate A under the constant temperature condition of 50 ℃, ultrasonically dispersing for 6.5 hours, and taking out to obtain a modified metal substrate; (ii) a

S2, preparing a polymerization solution: placing 2, 7-dibromopyrene-4, 5,9, 10-tetraketone in N, N-dimethylformamide solution, stirring and dissolving, sequentially adding bis (1, 5-cyclooctadiene) nickel (0) and 1, 5-cyclooctadiene, stirring and reacting for 15min, sequentially adding 4, 4-diamino-2, 2-bipyridine and a modified metal substrate, performing ultrasonic dispersion for 15h at the constant temperature of 55 ℃, taking out the modified metal substrate for later use, and collecting the rest solution to obtain a polymerization solution;

s3, preparing a filler: under the condition of low pressure of 0.02MPa, putting polyethyleneimine into an ethanol solution, stirring and dispersing, sequentially adding nano zinc oxide, nano magnesium oxide, carbon black and carbon nanotubes, ultrasonically dispersing for 3 hours, and performing suction filtration and drying to obtain a filler;

s4, preparing a rubber mixture: placing natural rubber into an internal mixer for plasticating, sequentially adding ethylene propylene diene monomer and nitrile rubber for mixing, sequentially adding filler, polymerization liquid, paraffin, sulfur, accelerator, stearic acid and EDOT, stirring for reaction for 1.5h, stirring for 40min at the rotating speed of 350r/min, and discharging rubber to obtain a rubber mixture;

s5, synthesizing a sealing plate: and adhering the rubber mixture to the modified metal base material in a roller coating, spraying, curtain coating or dipping mode, heating the rubber mixture through a drying tunnel to form a rubber layer on the modified metal base material, transferring the rubber layer into a drying oven for high-temperature vulcanization treatment, and taking out the rubber layer to obtain the sealing plate. .

Step S2 needs to be performed under a nitrogen atmosphere while taking care to evacuate.

Example 3

The high-temperature-resistant low-creep sealing plate comprises a modified metal base material and rubber layers coated on the upper surface and the lower surface of the modified metal base material, wherein the rubber layers are obtained by airing a rubber mixture.

The modified metal substrate comprises the following raw material components: the adhesive comprises, by weight, 100 parts of a metal base material, 50 parts of a silane coupling agent, and 50 parts of 4, 4-diamino-2, 2-bipyridine.

The rubber mixture comprises the following raw material components: 100 parts of polymerization liquid, 40 parts of filler, 120 parts of natural rubber, 150 parts of ethylene propylene diene monomer, 150 parts of nitrile rubber, 30 parts of paraffin, 80 parts of sulfur, 30 parts of accelerator, 80 parts of stearic acid and 80 parts of EDOT.

The polymerization liquid mainly comprises: 100 parts of 2, 7-dibromopyrene-4, 5,9, 10-tetrone, 60 parts of bis (1, 5-cyclooctadiene) nickel (0) and 70 parts of 1, 5-cyclooctadiene; the polymerization solution needs to be accelerated by the modified metal substrate.

The filler comprises the following raw material components: 70 parts of polyethyleneimine, 20 parts of nano zinc oxide, 20 parts of nano magnesium oxide, 16 parts of carbon black and 30 parts of carbon nano tube.

S1, preparing a modified metal base material:

A. polishing the metal base material by using abrasive paper, then washing, derusting, degreasing, and drying to obtain a metal base material A;

B. placing a silane coupling agent in an ethanol solution, stirring and dispersing, adding the metal substrate A under the constant temperature condition of 60 ℃, ultrasonically dispersing for 8 hours, and taking out to obtain a modified metal substrate; (ii) a

S2, preparing a polymerization solution: placing 2, 7-dibromopyrene-4, 5,9, 10-tetraketone in N, N-dimethylformamide solution, stirring and dissolving, sequentially adding bis (1, 5-cyclooctadiene) nickel (0) and 1, 5-cyclooctadiene, stirring and reacting for 20min, sequentially adding 4, 4-diamino-2, 2-bipyridine and a modified metal substrate, performing ultrasonic dispersion for 20h at a constant temperature of 60 ℃, taking out the modified metal substrate for later use, and collecting the rest solution to obtain a polymerization solution;

s3, preparing a filler: under the condition of low pressure of 0.03MPa, putting polyethyleneimine into an ethanol solution, stirring and dispersing, sequentially adding nano zinc oxide, nano magnesium oxide, carbon black and carbon nanotubes, ultrasonically dispersing for 4 hours, and performing suction filtration and drying to obtain a filler;

s4, preparing a rubber mixture: placing natural rubber into an internal mixer for plasticating, sequentially adding ethylene propylene diene monomer and nitrile rubber for mixing, sequentially adding filler, polymerization liquid, paraffin, sulfur, accelerator, stearic acid and EDOT, stirring for reaction for 2h, stirring at the rotating speed of 500r/min for 50min, and discharging rubber to obtain a rubber mixture;

s5, synthesizing a sealing plate: and adhering the rubber mixture to the modified metal base material in a roller coating, spraying, curtain coating or dipping mode, heating the rubber mixture through a drying tunnel to form a rubber layer on the modified metal base material, transferring the rubber layer into a drying oven for high-temperature vulcanization treatment, and taking out the rubber layer to obtain the sealing plate. .

Step S2 needs to be performed under a nitrogen atmosphere while taking care to evacuate.

Experiment:

thermal oxygen aging test: after the sealing plate samples were exposed to heat in air at 230 ℃ for 180 hours, they were subjected to a bending resistance test (using a mandrel bar having a diameter of 4 mm) in accordance with ASTM D3111-99(2004) el according to JIS-K5600-5-1, and evaluated in accordance with the following evaluation standards:

5: the rubber layer has no cracks and peeling phenomena;

4: small cracks and partial falling phenomena appear on the end surface of the rubber layer;

3: cracks exist on the whole rubber layer, and about half of the cracks fall off;

2: cracks are formed on the whole rubber layer, and most of the cracks fall off;

1: the rubber layer was completely peeled off.

And (3) testing heat resistance: the sealing plate samples prepared in the examples and comparative examples were left at a temperature of 120 ℃ for 24 hours, and the weight increase rate and the thickness increase rate change thereof were measured; the weight increase rate and thickness increase rate change tests are tested according to the standard ASTMF146-2012 Standard test method for the gasket Material to resist fluid action; the larger the rate of increase in weight and the rate of increase in thickness of the seal plate sample are, the more unstable the state of the seal plate at high temperature is, and the worse the high temperature resistance is.

Creep relaxation rate test: the creep relaxation rate was measured by subjecting the gasket to 100 ℃ for 22 hours according to ASTM F38-2000, Standard test method for creep relaxation of gasket materials.

And (3) testing the sealing property: testing is carried out according to standard of standard test method for sealing performance of gasket materials of ASTMF 37-2000; and (3) testing conditions are as follows: gasket stress: 25.0 MPa; medium: 99 percent; nitrogen pressure: 0.2 MPa.

As can be seen from the data in the table, the sealing plate samples prepared in examples 1 to 3 have excellent thermo-oxidative aging resistance, the weight increase rate and the thickness increase rate under a high-temperature environment are far lower than those of the comparative example, the state under a high temperature is relatively stable, the high-temperature resistance is excellent, meanwhile, the creep relaxation rate is also kept below 5.0%, the creep rate is relatively low, the sealing performance is excellent, the comprehensive performance is more outstanding than that of the comparative example, and the sealing plate samples have very high practicability.

Example 4

The difference from example 3 is that the metal substrate is not modified by using a silane coupling agent, 4-diamino-2, 2-bipyridine cannot be introduced on the surface of the metal substrate due to lack of modification of the silane coupling agent, and poly (pyrene-4, 5,9, 10-tetraketone) generated in a polymerization solution has a small loading amount on the surface of the metal substrate, so that the compatibility between the metal substrate and a rubber layer is poor, a delamination phenomenon occurs between the rubber layer and the metal substrate in a thermo-oxidative aging test, and the sealing performance is also reduced.

Example 5

The difference from the embodiment 3 is that no polymer liquid is added, as less polymer liquid forms a polymer network in the rubber mixture, the interface bonding force among the natural rubber, the ethylene propylene diene monomer and the nitrile rubber is insufficient, the interface bonding force between the filler particles and the rubber mixture is reduced, and the prepared sealing plate has poor high-temperature resistance, high creep rate in a high-temperature environment and insufficient sealing performance.

Example 6

The difference from the embodiment 3 is that the nano magnesium oxide, the nano zinc oxide, the carbon black and the carbon nano tube are not impregnated by using polyethyleneimine, the filler is lack of modification of the polyethyleneimine, the agglomeration phenomenon among the fillers is obvious, the dispersibility of the filler in the rubber mixture is poor, meanwhile, the poly (pyrene-4, 5,9, 10-tetraone) molecular chain cannot be dispersed in the rubber mixture in time and forms a compact network structure, and the prepared sealing plate has the defects of poor high-temperature resistance and thermal-oxidative aging resistance, high creep rate and poor comprehensive performance.

Comparative example: a rubber-metal matrix composite sealing plate is randomly purchased in the market.

From the above data and experiments, we can conclude that: the modified metal base material and the rubber layer have good compatibility, the phenomena of layering and stripping of the modified metal base material and the rubber layer in a severe environment can be effectively avoided, the sealing property is greatly improved, and the service life is greatly prolonged.

The polymerization liquid contains a large amount of carbonyl groups, nucleophilic addition reaction can be carried out on the carbonyl groups and primary amine on the filler, and pi-pi bonding can be also carried out between the polymerization liquid and the carbon nano tube, so that a molecular chain of the polymerization liquid can extend around the rubber mixture and form a stable polymer network structure, the stability of the sealing plate is effectively improved, and the creep relaxation rate of the sealing plate is reduced.

Under the action of polyethyleneimine, filler particles contain a large amount of amino groups, and the dispersibility of the filler in the rubber mixture A is remarkably improved due to charge interaction.

The added polyethyleneimine can obviously improve the viscosity of the rubber mixture and improve the creep resistance of the rubber layer; the polyethyleneimine can improve the compatibility between the filler and the rubber layer, strengthen the interfacial bonding force between the polymer network and the filler, improve the compatibility of the filler in a rubber mixture and effectively reduce the creep relaxation rate of the sealing plate.

The filler in the invention is beneficial to the occurrence of vulcanization and the improvement of the stability of the sealing plate, and can be used as a bonding site of a polymer network in the rubber layer to enhance the mechanical property of the sealing plate, further reduce the creep rate of the sealing plate, improve the sealing property of the sealing plate and prolong the service life.

The sealing plate prepared by the invention combines the advantages of three rubber materials, and has the advantages of good high-temperature resistance, lower creep property, more excellent comprehensive performance and wider application range.

In the invention, the EDOT added in particular can be polymerized to form PEDOT polymer in the rubber mixing process, and PEDOT molecular chain is further entangled with poly (pyrene-4, 5,9, 10-tetraketone) molecular chain and rubber molecular chain, so that the polymer network in the rubber mixture is more compact, and the comprehensive performance of the sealing plate is further improved.

The sealing plate prepared by the invention combines the high strength of the metal base material and the high elasticity and compressibility of the rubber layer, has light weight, good sealing performance, excellent thermal oxidation resistance, strong bonding force between the metal base material and the rubber layer, low creep relaxation rate, wide application range and high practicability, and can not cause the problem of peeling off even in a high-temperature environment for long-time work.

Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.