Organic semiconductor powder-methyl fullerene modified spraying type polyurea material and preparation method thereof

Abstract

The invention provides an organic semiconductor powder-methyl fullerene modified spraying type polyurea material and a preparation method thereof, and relates to the technical field of polyurea materials. The preparation method comprises the following steps: adding a [6, 6]-phenyl-C61-methyl butyrate solution into a polyurea blend, carrying out an ultrasonic reaction, coating a mold with a reaction solution after the reaction is finished, and drying to obtain the organic semiconductor powder-methyl fullerene modified spraying type polyurea material. Compared with a traditional insulating sheath, the prepared spraying type polyurea material has better thermal performance and electrical performance, insulation protection difficulty caused by cross arm appearance difference is effectively eliminated, and the maintenance cost caused by bird damage and foreign matter is reduced. The spraying type polyurea material has the advantages that the curing time is short, dripping and hanging objects cannot be formed to influence the physical properties, meanwhile, the material waste can be effectively reduced, and the spraying type polyurea material has higher economical efficiency and wider application scenes.

Description

Technical Field

[0001] The present invention provides a sprayable polyurea material modified by organic semiconductor powder - methyl fullerenes and a preparation method thereof, belonging to the technical field of polyurea materials. Background Art

[0002] In areas with severe industrial pollution, due to the long - term deposition of pollutants in the atmosphere, the surface pollution density of insulators coated with room temperature vulcanized silicone rubber (RTV) increases significantly, and the probability of flashover accidents also increases greatly. Since the water contact angle of RTV is less than 110° and the rolling angle is relatively large, under conditions such as fog, rain or dew, water droplets are likely to aggregate on the surface of RTV material and are difficult to roll. When the aggregation phenomenon is serious, the water droplets will dissolve the charged particles in the pollutants to form a large - area conductive water film, resulting in the easy occurrence of surface flashover of insulators. In addition, many investigation reports in recent years have shown that under the influence of typical subtropical climates such as strong radiation and high humidity and heat unique to southern regions, the operation of RTV coatings not only has the problem of serious surface fouling caused by environmental pollution, but also faces risks such as peeling, powdering and even falling off due to ultraviolet aging. Long - term ultraviolet radiation will damage the molecular chain of RTV silicone rubber, change its chemical structure, and then cause the RTV coating to lose its hydrophobicity and a serious decrease in the pollution flashover voltage. At present, the application scenario of RTV coatings is mainly insulators, and there is still a gap for the spraying material on the cross - arm side. In addition, the curing time of RTV is relatively long, and it is difficult to form a relatively thick insulating protective layer on the surface.

[0003] Polyurea is a new type of insulating spraying material applied to transmission lines. It is a block polymer prepared by the reaction of an isocyanate - terminated prepolymer (Component A) with an amino - terminated resin and an amino - terminated chain extender (Component B). The reaction process of polyurea mainly has two reaction mechanisms. One is that when a hydroxyl - terminated compound contacts an isocyanate group, the oxygen atom of the hydroxyl group nucleophilically attacks the carbon atom on the isocyanate group and hydrogen transfer occurs to form a urethane bond; the other is that an amino group reacts with an isocyanate through a nucleophilic reaction to form a urea bond. The nucleophilic center on the amino group - the nitrogen atom has a higher electron cloud density and stronger electronegativity, higher reactivity with the isocyanate group, and the formed urea bond has a greater bond energy and is more stable.

[0004] The urethane bonds and urea bonds in the polyurea molecular chain have relatively large cohesive energy and steric volume, and can form hard domains through intermolecular forces; while the long carbon chains have weak polarity and strong flexure, and can entangle with each other to form soft domains. Due to the large difference in polarity and free energy between the hard and soft domains, they are incompatible with each other, resulting in the phenomenon of microphase separation, and the hard domains exist in the form of isolated rods in the non-phase-separated soft domains. The properties of polyurea are closely related to the structure and content of the hard and soft domains: the hard domains can act as rigid reinforcements and interchain connections, affecting the molecular structure stability and mechanical properties of polyurea, and the microphase separation of the hard and soft domains can also improve the tensile strength or elongation rate to varying degrees, especially significantly improving the low-temperature mechanical properties and low-temperature "dewetting" phenomenon.

[0005] The two-component polyurea elastomer spraying technology is a new type of solvent-free and pollution-free green construction technology developed to meet the environmental protection requirements. This technology has the following advantages:

[0006] (1) The material has a fast curing speed, can be spray-formed in one pass on various complex curved surfaces without sagging;

[0007] (2) It is insensitive to moisture and humidity, can be constructed in a cold environment of -28°C and cured normally;

[0008] (3) The solid content of the material can reach 99%, zero VOC, and is environmentally friendly;

[0009] (4) It can be designed into a portable mobile spraying platform, which is convenient for construction and has high construction efficiency; it can be sprayed to the designed thickness in a single pass, overcoming the disadvantages of multi-pass construction of ordinary coatings;

[0010] (5) The material has good physical and chemical properties, such as tensile strength, wear resistance, aging resistance, chemical resistance, corrosion resistance, etc.;

[0011] (6) The material has excellent thermal stability, can be used for a long time at a temperature of 120°C, and can also withstand the impact of a short-term high temperature of 350°C;

[0012] (7) The formula color can be flexibly adjusted, and various pigments and dyes can be added to the coating to meet different requirements;

[0013] (8) There are various types of polyurea materials with a wide range of strengths, ranging from soft rubber (Shore A30) to hard elastomers (Shore D65).

[0014] At present, there is a certain gap in the thermal conductivity of polyurea materials compared with RTV materials. Therefore, further improving the performance of polyurea materials to meet practical applications is a current research hotspot. Summary of the Invention

[0015] In view of this, the object of the present invention is to provide a sprayable polyurea material modified with organic semiconductor powder - methyl fullerenes and a preparation method thereof. The present invention modifies polyurea with organic semiconductor fillers to form a new material suitable for protecting the cross arms of 110 kV line poles and towers.

[0016] The present invention is achieved by the following technical solutions:

[0017] A preparation method of a sprayable polyurea material modified with organic semiconductor powder - methyl fullerenes, comprising the following steps:

[0018] (1) Add 4,4'-diphenylmethane diisocyanate to a reaction kettle and heat it to 60 - 70 °C for melting;

[0019] (2) Disperse diethyltoluene diamine in N-methylpyrrolidone to obtain a diethyltoluene diamine solution;

[0020] (3) Slowly drop the diethyltoluene diamine solution into the reaction kettle, control the reaction temperature at 80 - 90 °C for reaction to obtain a polyurea blend;

[0021] (4) Dissolve [6,6]-phenyl-C61-butyric acid methyl ester in N-methylpyrrolidone to obtain a [6,6]-phenyl-C61-butyric acid methyl ester solution;

[0022] (5) Add the [6,6]-phenyl-C61-butyric acid methyl ester solution to the polyurea blend for ultrasonic reaction for 1 - 3 h. After the reaction, coat the reaction solution on a mold and dry it to obtain a sprayable polyurea material modified with organic semiconductor powder - methyl fullerenes.

[0023] Preferably, the molar ratio of 4,4'-diphenylmethane diisocyanate to diethyltoluene diamine is 1:0.95 - 1.05.

[0024] Preferably, the reaction time in step (3) is 2 - 3 h.

[0025] Preferably, the mass ratio of [6,6]-phenyl-C61-butyric acid methyl ester to 4,4'-diphenylmethane diisocyanate is 0.8 - 3.2:25.

[0026] Preferably, the drying temperature in step (5) is 60 - 90 °C.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] The sprayable polyurea material prepared by the present invention has better thermal and electrical properties compared to traditional insulating sheaths, effectively eliminating the difficulty of insulation protection caused by differences in the shape of cross arms and reducing the maintenance costs caused by bird damage and foreign objects. The sprayable polyurea material of the present invention has a very fast curing time, does not form drips that affect its physical properties, and can effectively reduce material waste, with high economy and a broader application scenario. Description of the Drawings

[0029] Figure 1 It is the test result of the dielectric constant of the sprayable polyurea materials prepared in Examples 1-4 and Comparative Example 1 of the present invention;

[0030] Figure 2 It is the test result of the tangent value of the dielectric loss of the sprayable polyurea materials prepared in Examples 1-4 and Comparative Example 1 of the present invention. Detailed Embodiments

[0031] To make the objectives, technical solutions and advantages of the present invention clearer, the preferred implementation solutions of the present invention will be further described in detail below in conjunction with examples. Based on the examples in the present invention, all other examples obtained by those of ordinary skill in the art without making creative efforts fall within the scope of protection of the present invention.

[0032] Example 1

[0033] Add 2.5 g of 4,4'-diphenylmethane diisocyanate (MDI) to a dry reaction kettle and heat it to 70 °C to melt. Dissolve 1.6 g of diethyltoluenediamine (DETDA) solution in 60 mL of N-methylpyrrolidone (NMP) to obtain a diethyltoluenediamine solution; slowly add the diethyltoluenediamine solution to the reaction kettle, control the temperature at 80 °C, and react for 3 hours to obtain a polyurea blend. Dissolve 80 mg of [6,6]-phenyl-C61-butyric acid methyl ester in 10 ml of NMP to obtain a [6,6]-phenyl-C61-butyric acid methyl ester solution; add the [6,6]-phenyl-C61-butyric acid methyl ester solution to the polyurea blend and carry out ultrasonic stirring reaction for 2 hours. After the reaction, coat the reaction solution on an aluminum plate mold and keep it in a drying oven at 80 °C for 12 hours to remove the solvent, obtaining a 1-mm-thick organic semiconductor powder-methyl fullerene modified sprayable polyurea material.

[0034] Example 2

[0035] Add 2.5 g of 4,4'-diphenylmethane diisocyanate (MDI) to a dry reaction kettle and heat it to 70 °C to melt. Dissolve 1.6 g of diethyltoluenediamine (DETDA) solution in 60 mL of N-methylpyrrolidone (NMP) to obtain a diethyltoluenediamine solution; slowly add the diethyltoluenediamine solution to the reaction kettle, control the temperature at 80 °C, and react for 3 hours to obtain a polyurea blend. Dissolve 160 mg of [6,6]-phenyl-C61-butyric acid methyl ester in 10 ml of NMP to obtain a [6,6]-phenyl-C61-butyric acid methyl ester solution; add the [6,6]-phenyl-C61-butyric acid methyl ester solution to the polyurea blend and carry out ultrasonic stirring reaction for 2 hours. After the reaction, coat the reaction solution on an aluminum plate mold and keep it in a drying oven at 80 °C for 12 hours to remove the solvent, obtaining a sprayable polyurea material modified with organic semiconductor powder-methyl fullerenes with a thickness of 1 mm.

[0036] Example 3

[0037] Add 2.5 g of 4,4'-diphenylmethane diisocyanate (MDI) to a dry reaction kettle and heat it to 70 °C to melt. Dissolve 1.6 g of diethyltoluenediamine (DETDA) solution in 60 mL of N-methylpyrrolidone (NMP) to obtain a diethyltoluenediamine solution; slowly add the diethyltoluenediamine solution to the reaction kettle, control the temperature at 80 °C, and react for 3 hours to obtain a polyurea blend. Dissolve 240 mg of [6,6]-phenyl-C61-butyric acid methyl ester in 10 ml of NMP to obtain a [6,6]-phenyl-C61-butyric acid methyl ester solution; add the [6,6]-phenyl-C61-butyric acid methyl ester solution to the polyurea blend and carry out ultrasonic stirring reaction for 2 hours. After the reaction, coat the reaction solution on an aluminum plate mold and keep it in a drying oven at 80 °C for 12 hours to remove the solvent, obtaining a sprayable polyurea material modified with organic semiconductor powder-methyl fullerenes with a thickness of 1 mm.

[0038] Example 4

[0039] 2.5 g of 4,4'-diphenylmethane diisocyanate (MDI) was added to a dry reaction kettle and heated to 70 °C for melting. 1.6 g of diethyltoluenediamine (DETDA) solution was dissolved in 60 mL of N-methylpyrrolidone (NMP) to obtain a diethyltoluenediamine solution; the diethyltoluenediamine solution was slowly added dropwise to the reaction kettle, the temperature was controlled at 80 °C, and the reaction was carried out for 3 hours to obtain a polyurea blend. 320 mg of [6,6]-phenyl-C61-butyric acid methyl ester was dissolved in 10 mL of NMP to obtain a [6,6]-phenyl-C61-butyric acid methyl ester solution; the [6,6]-phenyl-C61-butyric acid methyl ester solution was added to the polyurea blend and subjected to ultrasonic stirring reaction for 2 hours. After the reaction, the reaction solution was coated on an aluminum plate mold and kept in a drying oven at 80 °C for 12 hours to remove the solvent, obtaining a sprayable polyurea material modified with organic semiconductor powder-methylfullerene with a thickness of 1 mm.

[0040] Comparative Example 1

[0041] 2.5 g of 4,4'-diphenylmethane diisocyanate (MDI) was added to a dry reaction kettle and heated to 70 °C for melting. 1.6 g of diethyltoluenediamine (DETDA) solution was dissolved in 60 mL of N-methylpyrrolidone (NMP) to obtain a diethyltoluenediamine solution; the diethyltoluenediamine solution was slowly added dropwise to the reaction kettle, the temperature was controlled at 80 °C, and the reaction was carried out for 3 hours to obtain a polyurea blend. The polyurea blend was coated on an aluminum plate mold and kept in a drying oven at 80 °C for 12 hours to remove the solvent, obtaining a sprayable polyurea material with a thickness of 1 mm.

[0042] The dielectric constant and dielectric loss tangent values of the sprayable polyurea materials prepared in Examples 1 to 4 and Comparative Example 1 were detected under a 50 Hz alternating electric field, as Figure 1 and Figure 2 shown.

[0043] The described embodiments are part of the embodiments of the present invention, rather than all embodiments. The detailed description of the embodiments of the present invention is not intended to limit the scope of the claimed invention, but merely represents selected embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments in the present invention without creative efforts fall within the scope of protection of the present invention.

Claims

1. A method for preparing a spray-coated polyurea material modified with organic semiconductor powder-methylfullerene, characterized in that: The following steps are involved: (1) adding 4,4'-diphenylmethane diisocyanate into a reaction kettle and heating it to 60-70°C to melt; (2) dispersing diethyltoluenediamine in N-methylpyrrolidone to obtain a diethyltoluenediamine solution; (3) slowly adding the diethyltoluenediamine solution dropwise into the reaction kettle, controlling the reaction temperature to 80-90° C. to react, and obtaining a polyurea blend; (4) dissolving [6,6]-phenyl-C61-butyric acid methyl ester in N-methylpyrrolidone to obtain a [6,6]-phenyl-C61-butyric acid methyl ester solution; (5) adding the [6,6]-phenyl-C61-butyric acid methyl ester solution to the polyurea blend for ultrasonic reaction for 1 to 3 hours, coating the reaction solution on a mold after the reaction is completed, and obtaining an organic semiconductor powder-methylfullerene modified spray-coated polyurea material after drying.

2. The method for preparing the spray-coated polyurea material of organic semiconductor powder-methylfullerene modified according to claim 1, characterized in that: The molar ratio of the 4,4'-diphenylmethane diisocyanate to diethyltoluenediamine is 1:0.95-1.

05.

3. The method for preparing the spray-coated polyurea material of organic semiconductor powder-methylfullerene modified according to claim 1, characterized in that: The reaction time of step (3) is 2 to 3 hours.

4. The method for preparing the spray-coated polyurea material of organic semiconductor powder-methylfullerene modified according to claim 1, characterized in that: The mass ratio of [6,6]-phenyl-C61-butyric acid methyl ester to 4,4'-diphenylmethane diisocyanate is 0.8 to 3.2:

25.

5. The method for preparing the spray-coated polyurea material of organic semiconductor powder-methylfullerene modified according to claim 1, characterized in that: The drying temperature in step (5) is 60-90°C.

6. An organic semiconductor powder-methylfullerene modified spray-coated polyurea material, characterized in that: Prepared by the method according to any one of claims 1 to 5.

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