阅读说明：本技术 一种耐高温导电吸波密封材料 (High-temperature-resistant conductive wave-absorbing sealing material ) 是由 斯惠仙 张义忠 吴尤嘉 于 2020-08-16 设计创作，主要内容包括：本发明公开一种耐高温导电吸波密封材料,包括如下步骤：(1)按照质量份数,将液态聚硫橡胶、共聚单体、酰胺化硫醇基纳米管材料、偶联剂、增塑剂、抗氧剂,加入到到反应釜中,2000-3000r/min分散5min以上,然后加入增稠剂,2000-3000r/min分散5min以上,得到A组分；(2)将固化剂、促进剂、增塑剂混合均匀,得到B组分；(3)将A组分和B组分混合均匀,室温固化,得到一种耐高温导电吸波密封材料。本发明得到的导电吸波密封材料,抗撕裂能力强,拥有良好的导电吸波性能及耐高温性能,可以应用在导电、吸收电磁波、防静电等领域。(The invention discloses a high-temperature-resistant conductive wave-absorbing sealing material, which comprises the following steps: (1) adding liquid polysulfide rubber, a comonomer, an amidated thiol group nanotube material, a coupling agent, a plasticizer and an antioxidant into a reaction kettle according to the mass parts, dispersing for more than 5min at 3000r/min for 2000-plus, then adding a thickening agent, and dispersing for more than 5min at 3000r/min for 2000-plus to obtain a component A; (2) uniformly mixing a curing agent, an accelerator and a plasticizer to obtain a component B; (3) and uniformly mixing the component A and the component B, and curing at room temperature to obtain the high-temperature-resistant conductive wave-absorbing sealing material. The conductive wave-absorbing sealing material obtained by the invention has strong tear resistance, good conductive wave-absorbing performance and high temperature resistance, and can be applied to the fields of conductivity, electromagnetic wave absorption, static resistance and the like.)

1. A high-temperature-resistant conductive wave-absorbing sealing material is characterized by comprising the following steps:

(1) adding 100 parts by mass of liquid polysulfide rubber, 10-20 parts by mass of comonomer, 10-15 parts by mass of amidated thiol nanotube material, 1-3 parts by mass of coupling agent, 5-10 parts by mass of plasticizer and 1-3 parts by mass of antioxidant into a reaction kettle, dispersing for more than 5min at 3000r/min of 2000-materials, then adding 1-5 parts by mass of thickener, and dispersing for more than 5min at 3000r/min of 2000-materials to obtain a component A;

(2) uniformly mixing 10-15 parts of curing agent, 0.3-0.9 part of accelerator and 1-5 parts of plasticizer to obtain a component B;

(3) and uniformly mixing the component A and the component B, and curing at room temperature to obtain the high-temperature-resistant conductive wave-absorbing sealing material.

2. The method according to claim 1, wherein the comonomer in step (1) is one or more of ortho-benzenedithiol, para-benzenedithiol, 3, 4-methanedithiol, 4' -biphenyldithiol, 2, 7-naphthalenedithiol, and 1, 8-naphthalenedithiol.

3. The method of claim 1, wherein the amidated thiol group nanotube material of step (1) is prepared by:

dispersing 15-22 parts of carboxylated carbon nanotubes in 200 parts of carbon tetrachloride by mass, adding 3-8 parts of thionyl chloride, controlling the temperature to be 50-70 ℃, stirring for reaction for 2-5h, adding 5-9 parts of 3, 4-diaminobenzenethiol under the protection of nitrogen, stirring and mixing uniformly, carrying out reflux reaction for 15-20h, filtering after the reaction is finished, and drying to obtain the amidated thiol group nanotube material.

4. The method according to claim 1, wherein the coupling agent in step (1) is one or more of a silane coupling agent and a titanate coupling agent.

5. The method according to claim 1, wherein the plasticizer in step (1) is one or more selected from the group consisting of dioctyl adipate, dibutyl phthalate, di-n-butyl adipate, tributyl citrate, trioctyl citrate, tributyl acetyl citrate, trioctyl acetyl citrate, diisopropyl 1, 2-cyclohexane-dicarboxylic acid, and epoxidized soybean oil.

6. The method according to claim 1, wherein the antioxidant in step (1) is one or a combination of several of antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 1520, antioxidant 168, antioxidant BHT and antioxidant 1024.

7. The method according to claim 1, wherein the thickener in step (1) is one or more of fumed silica, polyethylene wax powder, polyamide wax powder and organic bentonite.

8. The method of claim, wherein the curing agent in step (2) is one or more of manganese dioxide and zinc oxide.

9. The method of claim, wherein the accelerator of step (2) is a combination of one or more of sulfur, diphenyl guanidine, and thiuram.

Technical Field

The invention relates to the field of new polymer materials, in particular to a high-temperature-resistant conductive wave-absorbing sealing material.

Background

The polysulfide sealant is an elastic sealing material prepared by taking liquid polysulfide rubber as a base material, and as the molecular network of the polysulfide sealant contains more ether-containing chain segments, the polysulfide sealant has better flexibility and excellent low-temperature resistance, in addition, the polysulfide sealant has excellent oil resistance, solvent resistance, aging resistance and other properties, and compared with polyurethane and silicone sealants, the polysulfide sealant has better water resistance and is widely used in the fields of aerospace, electric appliances, instrument lamps and other lamps.

Because the polysulfide sealant has poor heat resistance and is easy to degrade, the sealant has high density due to the addition of a large amount of fillers, and the application of the polysulfide sealant in the high-temperature resistant fields of aerospace and the like is influenced; the volume resistance of the polysulfide sealant is higher due to the poor compatibility of the molecular structure of the polysulfide sealant and some amidated thiol group nanotube materials; because the polysulfide sealant is a flexible main chain, the performance of the sealant after curing is lower, and the application of the sealant in certain sealing fields needing higher strength cannot be met.

CN201910362120.9 discloses a preparation method of a conductive sealant. In the process of forming the nitrile rubber by copolymerizing acrylonitrile and butadiene, the nano graphite sheet can initiate a cross-linking reaction of rubber due to the existence of active reaction points in the nano graphite sheet layer, so that the mobility of a nitrile rubber chain segment is greatly reduced, the influence of a high-frequency electromagnetic field can be suppressed by filling the high-conductivity nitrile rubber between layers of the conductive sealant, an interference field forms eddy currents in the conductive sealant and generates reflection on the surface of the conductive sealant, the shielding effect is achieved, and the copper powder with high magnetic conductivity is added, so that the electromagnetic shielding effect is improved; the sweet potato powder, the glycerol and the water are mixed and dispersed at a high speed and then are extruded by an extruder to obtain the starch filler, so that the bonding strength of the sealant is improved, and meanwhile, the soybean protein emulsion has good low-temperature flexibility, can have good sealing performance in a low-temperature environment, enhances the elasticity and toughness of the conductive sealant, and has wide application prospect.

CN201710259533.5 discloses an isocyanated carbon black/polyurethane conductive sealant, which is prepared by carrying out surface oxidation treatment on carbon black, functionalizing the isocyanate by using toluene diisocyanate, then participating in the copolymerization reaction of polyol and polyisocyanate to obtain an isocyanated carbon black/polyurethane prepolymer, and then mixing the isocyanate carbon black/polyurethane prepolymer with liquid butyl rubber and the like to prepare the conductive sealant, wherein the conductive sealant has the effect of uniform electric field. The surface of the carbon black is grafted with isocyanate and participates in the reaction of the polyurethane prepolymer, so that the compatibility of the amidation thiol group nanotube material carbon black in the polyurethane sealant is improved, the amidation thiol group nanotube material carbon black is uniformly dispersed in the conductive sealant, the nonuniformity of an electric field in a cable can be effectively reduced, and in addition, the carbon black can be filled in gaps in a polyurethane sealant layer, so that the bonding performance of the conductive sealant is enhanced.

CN201710552508.6 discloses a silane modified polyurethane conductive sealant and a preparation method thereof, wherein the silane modified polyurethane conductive sealant comprises the following components in parts by weight: silane-modified polyurethane prepolymer: 100 parts of (A); initial adhesion promoter: 15-20 parts of a solvent; active diluent: 2-5 parts; plasticizer: 20-30 parts of a solvent; conductive carbon black: 8-15 parts; gas-phase white carbon black: 5-10 parts; thixotropic agent: 1-2 parts; light stabilizer: 1-2 parts; thermal stabilizer: 1-2 parts; water removal agent: 2-3 parts of a solvent; adhesion promoter: 2-4 parts; catalyst: 0.2 to 0.5 portion. The silane modified polyurethane conductive sealant disclosed by the invention is single-component, is cured at room temperature, has excellent conductivity, is high in surface drying speed, is high in initial adhesion formation, does not need to be coated with a base coat during construction, and has good temperature resistance, water resistance, aging resistance and high physical and mechanical properties after being cured.

Disclosure of Invention

The invention provides a high-temperature-resistant antistatic sealing material, and the obtained conductive wave-absorbing sealing material has strong tear resistance, good conductive wave-absorbing performance and high-temperature resistance, and can be applied to the fields of conductivity, electromagnetic wave absorption, static resistance and the like. .

A high-temperature-resistant conductive wave-absorbing sealing material is characterized by comprising the following steps:

(1) adding 100 parts by mass of liquid polysulfide rubber, 10-20 parts by mass of comonomer, 10-15 parts by mass of amidated thiol nanotube material, 1-3 parts by mass of coupling agent, 5-10 parts by mass of plasticizer and 1-3 parts by mass of antioxidant into a reaction kettle, dispersing for more than 5min at 3000r/min of 2000-materials, then adding 1-5 parts by mass of thickener, and dispersing for more than 5min at 3000r/min of 2000-materials to obtain a component A;

(2) uniformly mixing 10-15 parts of curing agent, 0.3-0.9 part of accelerator and 1-5 parts of plasticizer to obtain a component B;

(3) and uniformly mixing the component A and the component B, and curing at room temperature to obtain the high-temperature-resistant conductive wave-absorbing sealing material.

Preferably, the comonomer in step (1) is one or a combination of more of ortho-benzenedithiol, para-benzenedithiol, 3, 4-methanebenzenedithiol, 4' -biphenyldithiol, 2, 7-naphthalenedithiol and 1, 8-naphthalenedithiol;

the preparation method of the amidated thiol group nanotube material in the step (1) comprises the following steps:

dispersing 15-22 parts of carboxylated carbon nanotubes in 200 parts of carbon tetrachloride by mass, adding 3-8 parts of thionyl chloride, controlling the temperature to be 50-70 ℃, stirring for reaction for 2-5h, adding 5-9 parts of 3, 4-diaminobenzenethiol under the protection of nitrogen, stirring and mixing uniformly, carrying out reflux reaction for 15-20h, filtering after the reaction is finished, and drying to obtain the amidated thiol group nanotube material.

Preferably, the coupling agent in the step (1) is one or a combination of silane coupling agent and titanate coupling agent;

preferably, the plasticizer in step (1) is one or a combination of several of dioctyl adipate, dibutyl phthalate, di-n-butyl adipate, tributyl citrate, trioctyl citrate, acetyl tributyl citrate, acetyl trioctyl citrate, 1, 2-cyclohexane dicarboxylic acid diisopropyl ester, and epoxidized soybean oil;

preferably, the antioxidant in the step (1) is one or a combination of several of antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 1520, antioxidant 168, antioxidant BHT and antioxidant 1024;

preferably, the thickener in step (1) is one or a combination of more of fumed silica, polyethylene wax powder, polyamide wax powder and organic bentonite;

preferably, the curing agent in the step (2) is one or a combination of manganese dioxide and zinc oxide;

preferably, the accelerator in step (2) is one or a combination of sulfur, diphenyl guanidine and thiuram.

Part of reaction mechanisms in the preparation process of the high-temperature resistant conductive wave-absorbing sealing material are shown as follows:

compared with the prior art, the invention has the beneficial effects that:

1. the rigidity of the main chain is improved by introducing structures such as benzene rings into the main chain, so that the obtained conductive wave-absorbing sealing material has strong tear resistance and greatly improved tensile strength;

2. rigid structures such as benzene rings and the like are introduced into the main chain, so that the density of ether bonds which are easy to break in the main chain is reduced, the temperature resistance of the main chain is greatly improved, and the thermal decomposition temperature is obviously increased;

3. by adding the amidated thiol group nanotube material into the substrate, the defect that the conductive material is easy to agglomerate is overcome, the compatibility of the amidated thiol group nanotube material and the substrate is improved, a conductive network is formed between the amidated thiol group nanotube material, the volume resistance of the sealant is greatly reduced, the conductivity and the wave-absorbing performance of the material are improved, and the application field of the sealant is expanded.

Drawings

FIG. 1 is a Fourier Infrared Spectroscopy of the product obtained in example 1:

at 1131cm^-1An antisymmetric telescopic absorption peak of ether bond at 2929cm^-1The expansion absorption peak of carbon-hydrogen bond is present nearby and is 727cm^-1An absorption peak of a carbon-sulfur bond exists nearby, which indicates that the liquid polysulfide rubber participates in the reaction; at 1379cm^-1The absorption peak of naphthalene ring exists nearby, which indicates that the 1, 8-naphthalene dithiolParticipates in the reaction; at 466cm^-1An absorption peak of zinc oxide exists nearby, which indicates that the zinc oxide participates in the reaction; at 554cm^-1An absorption peak of iron oxide exists nearby, which indicates that ferrite participates in the reaction; at 1739cm^-1An absorption peak of ester carbonyl exists nearby, which indicates that trioctyl citrate participates in the reaction; at 1080cm^-1An absorption peak of a carbon-nitrogen single bond exists nearby, which indicates that the polyamide wax powder participates in the reaction.

Detailed Description

The raw materials used in the following examples are all commercially available products, the parts are by weight, and the examples are further illustrative of the present invention and do not limit the scope of the present invention;

the performance test methods are as follows:

1. tensile strength, tested according to GB/T528-1998;

2. elongation at break, tested according to GB/T528-1998;

3. volume resistivity, as tested according to GB T15662-1995;

4. the fastest decomposition temperature is tested by adopting TGA;