CN117024897B - Oil-resistant sealing element for transformer and preparation process thereof - Google Patents

Oil-resistant sealing element for transformer and preparation process thereof Download PDF

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CN117024897B
CN117024897B CN202310844480.9A CN202310844480A CN117024897B CN 117024897 B CN117024897 B CN 117024897B CN 202310844480 A CN202310844480 A CN 202310844480A CN 117024897 B CN117024897 B CN 117024897B
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oil
mixing
resistant sealing
weight
sealing member
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CN117024897A (en
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龙伍云
易水连
李红玉
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Zhuhai Youyi Electronic Technology Co ltd
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Zhuhai Youyi Electronic Technology Co ltd
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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
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/81—Unsaturated isocyanates or isothiocyanates
    • C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
    • C08G18/8116—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group

Abstract

The invention relates to the field of rubber materials, in particular to an oil-resistant sealing element for a transformer and a preparation process thereof. According to the invention, the acrylate rubber with oil resistance is selected as a base material, and is blended and modified with the thermoplastic polyurethane elastomer to prepare the oil-resistant sealing element; in order to further improve the modification effect of polyurethane on acrylate rubber, ethylene diamine tetraacetic acid, polyethylene glycol and isocyanate ethyl acrylate are used for preparing a modification auxiliary agent, the modification auxiliary agent not only can improve the strength of the polyurethane, but also can introduce acrylate groups into the polyurethane to improve the oil resistance and enhance the compatibility of the polyurethane and the acrylate rubber, so that the crosslinking density of the polyurethane and the acrylate rubber is improved, the diffusion rate of oil products in the rubber is inhibited, the swelling of the rubber is delayed, and the service life is prolonged.

Description

Oil-resistant sealing element for transformer and preparation process thereof
Technical Field
The invention relates to the technical field of rubber materials, in particular to an oil-resistant sealing member for a transformer and a preparation process thereof.
Background
A transformer is a common electrical device, and its working principle is a device for realizing alternating current voltage change by electromagnetic induction. The transformer is generally divided into a dry type transformer and an oil immersed type transformer, wherein the oil immersed type transformer usually takes specific oil products as media, and the oil immersed type transformer can provide good insulating environment and play a role in heat dissipation due to good insulating property and large specific heat capacity of oil, so that the transformer is prevented from being burnt out due to high temperature, and safe and stable operation of the transformer is ensured.
In the use process of an oil immersed transformer, oil leakage and oil seepage are common problems. The leaked oil not only can pollute the surface of the transformer and corrode the shell of the transformer, but also can increase the possibility of creepage; the long-term oil leakage and oil seepage also have potential safety hazards such as fire disaster. At present, the oil immersed transformer is mainly sealed by organic polymer materials such as sealing elements, so that the preparation of the sealing elements with oil resistance is very significant.
Disclosure of Invention
The invention aims to provide an oil-resistant sealing element for a transformer and a preparation process thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: an oil-resistant sealing element for a transformer and a preparation process thereof comprise the following steps:
step 1: mixing ethylenediamine tetraacetic acid and polyethylene glycol, adding p-toluenesulfonic acid and toluene, heating, refluxing for reaction, cooling, adding isocyanate ethyl acrylate, stirring for reaction, continuously adding polyethylene glycol for reaction, and removing toluene and water to obtain a modified auxiliary agent;
step 2:
s1: mixing polyethylene glycol, polytetrahydrofuran glycol, antioxidant 1010 and dibutyl tin dilaurate, and dehydrating to obtain a material A;
s2: mixing diphenylmethane diisocyanate and isophorone diisocyanate to obtain a material B;
s3: mixing the material A, the material B, the modifying additive and propylene glycol for reaction, stirring, extruding and crushing to obtain polyurethane powder;
step 3:
mixing polyurethane powder, acrylate rubber, carbon black, an anti-aging agent 4020, an antioxidant 1010, zinc oxide, stearic acid and sodium stearate, and mixing to obtain a rubber compound; adding sulfur and a promoter CZ into a rubber compound roller, standing and then performing one-stage vulcanization to obtain a vulcanized sealing member; and (3) performing two-stage vulcanization on the sealing element to obtain the oil-resistant sealing element for the transformer.
Further, in the step 1, the specific preparation method of the modifying auxiliary agent comprises the following steps: mixing 1 part of ethylenediamine tetraacetic acid and 0.5-1 part of polyethylene glycol according to the molar parts, adding p-toluenesulfonic acid and toluene, heating to 140-150 ℃, carrying out reflux reaction for 20-24 hours, and cooling; adding 0.5-1 part of isocyanate ethyl acrylate for 2-3 times, stirring and reacting for 30-60 min at 40-50 ℃, continuously adding 3.5-4 parts of polyethylene glycol, reacting for 10-12 h at 140-150 ℃, and evaporating toluene and water under reduced pressure.
Further, in S1, the material A comprises, by weight, 47.5-49% of polyethylene glycol, 47.5-49% of polytetrahydrofuran glycol, 0.1-4.5% of antioxidant 1010 and 0.3-0.5% of dibutyltin dilaurate.
In S1, the dehydration temperature is 100-120 ℃ and the dehydration time is 1-2 h.
In the S2, the mass ratio of the diphenylmethane diisocyanate to the isophorone diisocyanate in the material B is 1 (1-1.2).
Further, in S3, the amount of each component in the polyurethane powder is calculated by weight percent, namely 30 to 40 percent of material A, 40 to 60 percent of material B, 5 to 15 percent of modifying auxiliary agent and 5 to 10 percent of propylene glycol.
In S3, the reaction temperature is 50-80 ℃ and the reaction time is 30-60 min.
Further, in step 3, the amounts of the components in the sealing member are, by weight, 20 to 30 parts of polyurethane powder, 100 parts of acrylate rubber, 50 to 60 parts of carbon black, 2 to 4 parts of anti-aging agent 4020, 1 to 2 parts of antioxidant 1010, 5 to 8 parts of zinc oxide, 1 to 2 parts of stearic acid, 0.8 to 1.2 parts of sodium stearate, 1.6 to 2.2 parts of sulfur, and 0.9 to 1.1 parts of accelerator CZ.
In the step 3, the mixing temperature is 70-90 ℃ and the mixing time is 5-8 min.
Further, in the step 3, the one-stage vulcanization temperature is 150-180 ℃ and the time is 6-10 min.
In the step 3, the second-stage vulcanization temperature is 150-180 ℃ and the time is 3-4 h.
Compared with the prior art, the invention has the following beneficial effects: according to the invention, acrylate rubber with excellent oil resistance is selected as a base material, and a thermoplastic polyurethane elastomer is added to modify the base material, so that an oil-resistant sealing element is prepared; in order to further improve the modification effect of polyurethane on acrylate rubber, ethylene diamine tetraacetic acid, polyethylene glycol and isocyanate ethyl acrylate are used for preparing a modification auxiliary agent, the modification auxiliary agent not only can improve the strength of the polyurethane, but also can introduce acrylate groups into the polyurethane to enhance the oil resistance of the polyurethane, and simultaneously improve the compatibility with the acrylate rubber; after modification, the crosslinking density of the modified rubber and the modified oil is improved, so that the speed of the oil penetrating into the rubber material and the diffusion rate of the oil in the rubber material can be effectively inhibited, the swelling of the rubber is delayed, and the service life is prolonged.
It should be noted that, in preparing the modifying assistant, the present invention also takes into consideration the following points:
for the problem of the dosage of reactants, because the esterification reaction of ethylenediamine tetraacetic acid and polyethylene glycol is carried out and the reverse reaction exists, one reactant needs to be excessive in order to improve the conversion rate of the product; considering that polyethylene glycol can participate in the subsequent polyurethane synthesis reaction, the polyethylene glycol is more economical in excess from the viewpoint of process cost.
In the reaction, polyethylene glycol needs to be added step by step: firstly, ethylene diamine tetraacetic acid and polyethylene glycol are mixed according to a mole ratio of 1: (0.5-1), wherein the excessive ethylenediamine tetraacetic acid is generated, the polyethylene glycol is fully reacted, and hydroxyl groups are introduced; and adding isocyanate ethyl acrylate for reaction, introducing an acrylic ester group, and finally adding the rest polyethylene glycol to enable ethylenediamine tetraacetic acid to fully react, and removing water and toluene through reduced pressure evaporation, so that a small amount of unreacted polyethylene glycol in the system can directly participate in polyurethane synthesis. If excessive polyethylene glycol is added at one time, the residual polyethylene glycol in the reaction system can react with isocyanate ethyl acrylate to generate impurities due to the fact that the polyethylene glycol has a high boiling point and is difficult to remove, so that the polyurethane performance is affected, the modification effect of the polyurethane on the acrylate rubber is reduced, and the performance of the finally obtained sealing piece is poor.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The materials used in the invention and the sources thereof: polyethylene glycol is from the company Chenxin blue Star science and technology, model PEG2000; polytetrahydrofurandiol is available from Shandong Hua Zhuo biotechnology Co., ltd., product number 20220369; antioxidant 1010 is from the friend chemical industry; promoter CZ is from tribute nylon chemical company, inc; the anti-aging agent 4020 is from Jinan Jun Teng chemical Co., ltd; acrylic rubber is from Duwei technology, cat No. ACM-2012; carbon black was from the universal day, cat No. N660.
Example 1
Step 1: mixing 1mol of ethylenediamine tetraacetic acid and 1mol of polyethylene glycol, adding 0.05mol of p-toluenesulfonic acid and 1.5mol of toluene, heating to 140 ℃, carrying out reflux reaction for 24 hours, cooling, adding 0.5mol of isocyanate ethyl acrylate for 3 times, stirring at 40 ℃ for 30 minutes, continuously adding 3.5mol of polyethylene glycol, carrying out reaction at 140 ℃ for 12 hours, and carrying out reduced pressure distillation to remove toluene and water to obtain a modified auxiliary agent;
step 2:
s1: according to weight percentage, 47.5 percent of polyethylene glycol, 47.5 percent of polytetrahydrofuran glycol, 4.5 percent of antioxidant 1010 and 0.5 percent of dibutyl tin dilaurate are mixed, and dehydrated for 1 hour at 120 ℃ to obtain a material A;
s2: mixing diphenylmethane diisocyanate and isophorone diisocyanate according to a mass ratio of 1:1 to obtain a material B;
s3: mixing 40% of a material A, 50% of a material B, 5% of a modifying additive and 5% of propylene glycol according to weight percentage, reacting for 60min at 50 ℃, stirring, extruding and crushing to obtain polyurethane powder;
step 3: mixing 20kg of polyurethane powder, 100kg of acrylate rubber, 50kg of carbon black, 2kg of anti-aging agent 4020, 1kg of antioxidant 1010, 4kg of zinc oxide, 1.8kg of stearic acid and 1.2kg of sodium stearate, and mixing at 70 ℃ for 5min to obtain a mixed rubber; wrapping the rubber compound with a roll at 100 ℃ for 3min, adding 2kg of sulfur and 1kg of accelerator CZ, standing for 10h, and vulcanizing at 150 ℃ for 10min to obtain a vulcanized sealing member; and then carrying out secondary vulcanization on the sealing element at 150 ℃ for 4 hours to obtain the oil-resistant sealing element for the transformer.
Example 2
Step 1: mixing 1mol of ethylenediamine tetraacetic acid and 1mol of polyethylene glycol, adding 0.05mol of p-toluenesulfonic acid and 1.5mol of toluene, heating to 145 ℃, carrying out reflux reaction for 22 hours, cooling, adding 0.5mol of isocyanate ethyl acrylate for 3 times, stirring at 45 ℃ for reaction for 40 minutes, continuously adding 3.5mol of polyethylene glycol, carrying out reaction at 145 ℃ for 11 hours, and carrying out reduced pressure distillation to remove toluene and water to obtain a modified auxiliary agent;
step 2:
s1: according to weight percentage, 47.5 percent of polyethylene glycol, 47.5 percent of polytetrahydrofuran glycol, 4.5 percent of antioxidant 1010 and 0.5 percent of dibutyl tin dilaurate are mixed, and dehydrated for 1.5 hours at 110 ℃ to obtain a material A;
s2: mixing diphenylmethane diisocyanate and isophorone diisocyanate according to a mass ratio of 1:1 to obtain a material B;
s3: mixing 40% of a material A, 50% of a material B, 5% of a modifying additive and 5% of propylene glycol according to weight percentage, reacting for 45min at 60 ℃, stirring, extruding and crushing to obtain polyurethane powder;
step 3: mixing 20kg of polyurethane powder, 100kg of acrylate rubber, 50kg of carbon black, 2kg of anti-aging agent 4020, 1kg of antioxidant 1010, 4kg of zinc oxide, 1.8kg of stearic acid and 1.2kg of sodium stearate, and mixing at 80 ℃ for 7min to obtain a rubber compound; rolling the mixed rubber for 4min at 80 ℃, adding 2kg of sulfur and 1kg of promoter CZ, standing for 11h, and vulcanizing at 170 ℃ for 8min to obtain a vulcanized sealing member; and then carrying out secondary vulcanization on the sealing element at 170 ℃ for 3.5 hours to obtain the oil-resistant sealing element for the transformer.
Example 3
Step 1: mixing 1mol of ethylene diamine tetraacetic acid and 1mol of polyethylene glycol, adding 0.05mol of p-toluenesulfonic acid and 1.5mol of toluene, heating to 150 ℃, carrying out reflux reaction for 20 hours, cooling, adding 0.5mol of isocyanate ethyl acrylate for 3 times, stirring and reacting for 30 minutes at 50 ℃, continuously adding 4mol of polyethylene glycol, carrying out reaction for 10 hours at 150 ℃, and carrying out reduced pressure distillation to remove toluene and water to obtain a modified auxiliary agent;
step 2:
s1: according to weight percentage, 47.5 percent of polyethylene glycol, 47.5 percent of polytetrahydrofuran glycol, 4.5 percent of antioxidant 1010 and 0.5 percent of dibutyl tin dilaurate are mixed, and dehydrated for 2 hours at 100 ℃ to obtain a material A;
s2: mixing diphenylmethane diisocyanate and isophorone diisocyanate according to a mass ratio of 1:1 to obtain a material B;
s3: mixing 40% of a material A, 50% of a material B, 5% of a modifying additive and 5% of propylene glycol according to weight percentage, reacting for 30min at 80 ℃, stirring, extruding and crushing to obtain polyurethane powder;
step 3: mixing 20kg of polyurethane powder, 100kg of acrylate rubber, 50kg of carbon black, 2kg of anti-aging agent 4020, 1kg of antioxidant 1010, 4kg of zinc oxide, 1.8kg of stearic acid and 1.2kg of sodium stearate, and mixing at 90 ℃ for 5min to obtain a mixed rubber; at 60 ℃, wrapping a rubber compound roller for 5min, adding 2kg of sulfur and 1kg of accelerator CZ, standing for 12h, and vulcanizing at 180 ℃ for 6min to obtain a vulcanized sealing member; and then, carrying out secondary vulcanization on the sealing element at 180 ℃ for 3 hours to obtain the oil-resistant sealing element for the transformer.
Example 4
Step 1: mixing 1mol of ethylene diamine tetraacetic acid and 1mol of polyethylene glycol, adding 0.05mol of p-toluenesulfonic acid and 1.5mol of toluene, heating to 140 ℃, carrying out reflux reaction for 20 hours, cooling, adding 0.5mol of isocyanate ethyl acrylate for 2 times, stirring and reacting for 30 minutes at 40 ℃, continuously adding 4mol of polyethylene glycol, carrying out reaction for 10 hours at 140 ℃, and carrying out reduced pressure distillation to remove toluene and water to obtain a modified auxiliary agent;
step 2:
s1: according to weight percentage, 47.5 percent of polyethylene glycol, 47.5 percent of polytetrahydrofuran glycol, 4.5 percent of antioxidant 1010 and 0.5 percent of dibutyl tin dilaurate are mixed, and dehydrated for 1 hour at 100 ℃ to obtain a material A;
s2: mixing diphenylmethane diisocyanate and isophorone diisocyanate according to a mass ratio of 1:1 to obtain a material B;
s3: mixing 40% of a material A, 50% of a material B, 5% of a modifying additive and 5% of propylene glycol according to weight percentage, reacting for 30min at 50 ℃, stirring, extruding and crushing to obtain polyurethane powder;
step 3: mixing 20kg of polyurethane powder, 100kg of acrylate rubber, 50kg of carbon black, 2kg of anti-aging agent 4020, 1kg of antioxidant 1010, 4kg of zinc oxide, 1.8kg of stearic acid and 1.2kg of sodium stearate, and mixing at 70 ℃ for 5min to obtain a mixed rubber; wrapping the rubber compound with a roller for 3min at 60 ℃, adding 2kg of sulfur and 1kg of accelerator CZ, standing for 10h, and vulcanizing at 150 ℃ for 6min to obtain a vulcanized sealing member; and then carrying out secondary vulcanization on the sealing element at 160 ℃ for 3 hours to obtain the oil-resistant sealing element for the transformer.
Example 5
Step 1: mixing 1mol of ethylene diamine tetraacetic acid and 1mol of polyethylene glycol, adding 0.05mol of p-toluenesulfonic acid and 1.5mol of toluene, heating to 145 ℃, carrying out reflux reaction for 20 hours, cooling, adding 0.5mol of isocyanate ethyl acrylate for 2 times, stirring at 45 ℃ for 30 minutes, continuously adding 4mol of polyethylene glycol, carrying out reaction at 140 ℃ for 10 hours, and carrying out reduced pressure distillation to remove toluene and water to obtain a modified auxiliary agent;
step 2:
s1: according to weight percentage, 47.5 percent of polyethylene glycol, 47.5 percent of polytetrahydrofuran glycol, 4.5 percent of antioxidant 1010 and 0.5 percent of dibutyl tin dilaurate are mixed, and dehydrated for 1 hour at 110 ℃ to obtain a material A;
s2: mixing diphenylmethane diisocyanate and isophorone diisocyanate according to a mass ratio of 1:1 to obtain a material B;
s3: mixing 40% of a material A, 50% of a material B, 5% of a modifying additive and 5% of propylene glycol according to weight percentage, reacting for 40min at 50 ℃, stirring, extruding and crushing to obtain polyurethane powder;
step 3: mixing 20kg of polyurethane powder, 100kg of acrylate rubber, 50kg of carbon black, 2kg of anti-aging agent 4020, 1kg of antioxidant 1010, 4kg of zinc oxide, 1.8kg of stearic acid and 1.2kg of sodium stearate, and mixing at 70 ℃ for 6min to obtain a mixed rubber; rolling the mixed rubber for 5min at 80 ℃, adding 2kg of sulfur and 1kg of promoter CZ, standing for 12h, and vulcanizing at 150 ℃ for 8min to obtain a vulcanized sealing member; and then carrying out secondary vulcanization on the sealing element at 170 ℃ for 3 hours to obtain the oil-resistant sealing element for the transformer.
Example 6
Step 1: mixing 1mol of ethylene diamine tetraacetic acid and 1mol of polyethylene glycol, adding 0.05mol of p-toluenesulfonic acid and 1.5mol of toluene, heating to 150 ℃, carrying out reflux reaction for 24 hours, cooling, adding 0.5mol of isocyanate ethyl acrylate for 2 times, stirring at 50 ℃ for reaction for 60 minutes, continuously adding 4mol of polyethylene glycol, carrying out reaction for 12 hours at 150 ℃, and carrying out reduced pressure distillation to remove toluene and water to obtain a modified auxiliary agent;
step 2:
s1: according to weight percentage, 47.5 percent of polyethylene glycol, 47.5 percent of polytetrahydrofuran glycol, 4.5 percent of antioxidant 1010 and 0.5 percent of dibutyl tin dilaurate are mixed, and dehydrated for 2 hours at 120 ℃ to obtain a material A;
s2: mixing diphenylmethane diisocyanate and isophorone diisocyanate according to a mass ratio of 1:1 to obtain a material B;
s3: mixing 40% of a material A, 50% of a material B, 5% of a modifying additive and 5% of propylene glycol according to weight percentage, reacting for 60min at 80 ℃, stirring, extruding and crushing to obtain polyurethane powder;
step 3: mixing 20kg of polyurethane powder, 100kg of acrylate rubber, 50kg of carbon black, 2kg of anti-aging agent 4020, 1kg of antioxidant 1010, 4kg of zinc oxide, 1.8kg of stearic acid and 1.2kg of sodium stearate, and mixing at 90 ℃ for 8min to obtain a rubber compound; at 100 ℃, wrapping a rubber compound roller for 5min, adding 2kg of sulfur and 1kg of accelerator CZ, standing for 12h, and vulcanizing at 180 ℃ for 10min to obtain a vulcanized sealing member; and then, carrying out secondary vulcanization on the sealing element at 180 ℃ for 4 hours to obtain the oil-resistant sealing element for the transformer.
Comparative example 1
Polyurethane powder was prepared without adding a modifying auxiliary and physically blended with the acrylate rubber, the remaining parameters being the same as in example 1.
Step 1:
s1: according to weight percentage, 47.5 percent of polyethylene glycol, 47.5 percent of polytetrahydrofuran glycol, 4.5 percent of antioxidant 1010 and 0.5 percent of dibutyl tin dilaurate are mixed, and dehydrated for 1 hour at 120 ℃ to obtain a material A;
s2: mixing diphenylmethane diisocyanate and isophorone diisocyanate according to a mass ratio of 1:1 to obtain a material B;
s3: mixing 40% of material A, 50% of material B and 10% of propylene glycol according to weight percentage, reacting for 60min at 50 ℃, stirring, extruding and crushing to obtain polyurethane powder;
step 2:
mixing 20kg of polyurethane powder, 100kg of acrylate rubber, 50kg of carbon black, 2kg of anti-aging agent 4020, 1kg of antioxidant 1010, 4kg of zinc oxide, 1.8kg of stearic acid and 1.2kg of sodium stearate, and mixing at 70 ℃ for 5min to obtain a mixed rubber; wrapping the rubber compound with a roll at 100 ℃ for 3min, adding 2kg of sulfur and 1kg of accelerator CZ, standing for 10h, and vulcanizing at 150 ℃ for 10min to obtain a vulcanized sealing member; and then carrying out secondary vulcanization on the sealing element at 150 ℃ for 4 hours to obtain the oil-resistant sealing element for the transformer.
Comparative example 2
In the step 1, after polyethylene glycol reacts with ethylene diamine tetraacetic acid at one time, isocyanate ethyl acrylate is added.
Step 1: mixing 1mol of ethylenediamine tetraacetic acid and 4.5mol of polyethylene glycol, adding 0.05mol of p-toluenesulfonic acid and 1.5mol of toluene, heating to 145 ℃, carrying out reflux reaction for 22 hours, cooling, adding 0.5mol of isocyanate ethyl acrylate for 3 times, stirring and reacting for 40 minutes at 45 ℃, and carrying out reduced pressure distillation to remove toluene and water to obtain a modified auxiliary agent;
step 2:
s1: according to weight percentage, 47.5 percent of polyethylene glycol, 47.5 percent of polytetrahydrofuran glycol, 4.5 percent of antioxidant 1010 and 0.5 percent of dibutyl tin dilaurate are mixed, and dehydrated for 1.5 hours at 110 ℃ to obtain a material A;
s2: mixing diphenylmethane diisocyanate and isophorone diisocyanate according to a mass ratio of 1:1 to obtain a material B;
s3: mixing 40% of a material A, 50% of a material B, 5% of a modifying additive and 5% of propylene glycol according to weight percentage, reacting for 45min at 60 ℃, stirring, extruding and crushing to obtain polyurethane powder;
step 3: mixing 20kg of polyurethane powder, 100kg of acrylate rubber, 50kg of carbon black, 2kg of anti-aging agent 4020, 1kg of antioxidant 1010, 4kg of zinc oxide, 1.8kg of stearic acid and 1.2kg of sodium stearate, and mixing at 80 ℃ for 7min to obtain a rubber compound; rolling the mixed rubber for 4min at 80 ℃, adding 2kg of sulfur and 1kg of promoter CZ, standing for 11h, and vulcanizing at 170 ℃ for 8min to obtain a vulcanized sealing member; and then carrying out secondary vulcanization on the sealing element at 170 ℃ for 3.5 hours to obtain the oil-resistant sealing element for the transformer.
Experiment: the vulcanizates in examples 1 to 6 and comparative examples 1 to 2 were subjected to performance tests. The experimental results are shown in the following table, in which:
mechanical property test: testing the tensile strength of the sample by referring to the method for testing the annular pattern in GB/T528-2009;
oil resistance test: the sample was immersed in IRM903# oil at 150℃for 70 hours, taken out, and tested for tensile strength by referring to the method for testing a ring-shaped pattern in GB/T528-2009.
Project Tensile Strength/MPa Tensile strength/MPa after oil immersion
Example 1 14.6 14.2
Example 2 14.8 14.3
Example 3 14.9 14.3
Example 4 14.5 14.2
Example 5 14.3 14.0
Example 6 14.2 13.8
Comparative example 1 12.7 12.2
Comparative example 2 11.6 10.5
Conclusion: the data of examples 1-6 show that the sealing element prepared by the invention has higher mechanical strength and better oil resistance compared with the conventional acrylate rubber, and can be used as a sealing material for transformers. The data of the example 1 and the comparative example 1 show that compared with the direct blending of polyurethane powder and acrylate rubber, the modified auxiliary agent is added in the example 1, so that the oil resistance and the compatibility of the modified auxiliary agent and the acrylate rubber are improved by introducing the acrylate group into the polyurethane, and the crosslinking density of the modified auxiliary agent and the acrylate rubber is improved after melt blending and vulcanization; the higher crosslinking density can effectively inhibit the diffusion rate of oil products in the rubber material while improving the mechanical property of the rubber material, so that the swelling speed of the rubber material is slowed down, and the service life of the rubber sealing piece is prolonged. The data of example 2 and comparative example 2 show that in the preparation process, after excessive polyethylene glycol is added at one time to react with ethylenediamine tetraacetic acid, and then isocyanate ethyl acrylate is added, part of isocyanate ethyl acrylate is consumed by the residual polyethylene glycol in the system, the generation rate of a target product is affected, and impurities are generated, so that the synthesis of polyurethane is affected, and finally, the performance of a sealing element prepared after blending is reduced.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (9)

1. The preparation process of the oil-resistant sealing element for the transformer is characterized by comprising the following steps of: the method comprises the following steps:
step 1: mixing 1 part of ethylenediamine tetraacetic acid and 0.5-1 part of polyethylene glycol according to the molar parts, mixing the ethylenediamine tetraacetic acid and the polyethylene glycol, adding p-toluenesulfonic acid and toluene, heating to 140-150 ℃, carrying out reflux reaction for 20-24 hours, and cooling; adding isocyanate ethyl acrylate for 2-3 times, stirring at 40-50 ℃ for reaction for 30-60 min, continuously adding polyethylene glycol, reacting at 140-150 ℃ for 10-12 h, and reducing pressure and steaming to remove toluene and water to obtain a modified auxiliary agent;
step 2:
s1: mixing polyethylene glycol, polytetrahydrofuran glycol, antioxidant 1010 and dibutyl tin dilaurate, and dehydrating to obtain a material A;
s2: mixing diphenylmethane diisocyanate and isophorone diisocyanate to obtain a material B;
s3: mixing the material A, the material B, the modifying additive and propylene glycol for reaction, stirring, extruding and crushing to obtain polyurethane powder;
step 3:
mixing polyurethane powder, acrylate rubber, carbon black, an anti-aging agent 4020, an antioxidant 1010, zinc oxide, stearic acid and sodium stearate, and mixing to obtain a rubber compound; adding sulfur and a promoter CZ into a rubber compound roller, standing and then performing one-stage vulcanization to obtain a vulcanized sealing member; and (3) performing two-stage vulcanization on the sealing element to obtain the oil-resistant sealing element for the transformer.
2. The process for preparing an oil-resistant sealing member for a transformer according to claim 1, wherein: in S1, the material A comprises, by weight, 47.5-49% of polyethylene glycol, 47.5-49% of polytetrahydrofuran glycol, 0.1-4.5% of antioxidant 1010 and 0.3-0.5% of dibutyl tin dilaurate.
3. The process for preparing an oil-resistant sealing member for a transformer according to claim 1, wherein: in the S1, the dehydration temperature is 100-120 ℃ and the dehydration time is 1-2 h.
4. The process for preparing an oil-resistant sealing member for a transformer according to claim 1, wherein: in S2, in the material B, the mass ratio of the diphenylmethane diisocyanate to the isophorone diisocyanate is 1 (1-1.2).
5. The process for preparing an oil-resistant sealing member for a transformer according to claim 1, wherein: and S3, the dosages of all components in the polyurethane powder are calculated according to the weight percentage, namely 30-40% of material A, 40-60% of material B, 5-15% of modifying auxiliary agent and 5-10% of propylene glycol.
6. The process for preparing an oil-resistant sealing member for a transformer according to claim 1, wherein: and S3, the reaction temperature is 50-80 ℃, and the reaction time is 30-60 min.
7. The process for preparing an oil-resistant sealing member for a transformer according to claim 1, wherein: in the step 3, the usage amount of each component in the sealing member is 20-30 parts by weight of polyurethane powder, 100 parts by weight of acrylate rubber, 50-60 parts by weight of carbon black, 2-4 parts by weight of anti-aging agent 4020, 1-2 parts by weight of antioxidant 1010, 5-8 parts by weight of zinc oxide, 1-2 parts by weight of stearic acid, 0.8-1.2 parts by weight of sodium stearate, 1.6-2.2 parts by weight of sulfur and 0.9-1.1 parts by weight of accelerator CZ.
8. The process for preparing an oil-resistant sealing member for a transformer according to claim 1, wherein: in the step 3, the mixing temperature is 70-90 ℃ and the mixing time is 5-8 min; the vulcanization temperature is 150-180 ℃ and the time is 6-10 min; the second-stage vulcanization temperature is 150-180 ℃ and the time is 3-4 hours.
9. The oil-resistant sealing member for a transformer, which is prepared by the preparation process of the oil-resistant sealing member for a transformer according to any one of claims 1 to 8.
CN202310844480.9A 2023-07-11 2023-07-11 Oil-resistant sealing element for transformer and preparation process thereof Active CN117024897B (en)

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