UV curing type liquid ethylene propylene diene monomer applied to battery sealant and preparation method of UV curing type liquid ethylene propylene diene monomer

Abstract

The invention relates to the technical field of sealants, in particular to UV (ultraviolet) curing type liquid ethylene propylene diene monomer applied to a battery sealant and a preparation method of the UV curing type liquid ethylene propylene diene monomer, and the UV curing type liquid ethylene propylene diene monomer comprises the following components in parts by weight: 20-30 parts of liquid ethylene propylene diene monomer, 20-30 parts of petroleum ether, 0.2-1 part of sulfydryl-1, 2-propylene glycol, 0.05-0.5 part of an initiator, 20-30 parts of acetone, isocyanate ethyl acrylate and 0.1-0.2 part of a catalyst. And 0.1 to 0.2 part of a polymerization inhibitor. Liquid ethylene propylene diene monomer containing 10% of a third monomer is used as a raw material for modification, and a photocuring group is grafted to a molecular side chain of the liquid ethylene propylene diene monomer through a thiol-ene click reaction and an addition reaction of isocyanate, so that after the battery sealant is prepared, a rapid curing effect can be realized through LED irradiation at a dispensing position, and the service life of the battery sealant is prolonged. Therefore, the production speed is increased and the production cost is reduced.

Description

Technical Field

[0001] The invention relates to the technical field of sealants, and in particular to a UV-curable liquid EPDM rubber used for battery sealants. Background Art

[0002] As a UV-curable hydrogen fuel cell bipolar plate sealant, it must have the characteristics of fast curing, high sealing, high durability, and high and low temperature resistance. Hydrogen fuel cells are stacked with single cells consisting of bipolar plates, sealing rubber rings and membrane electrodes. Sealing rubber rings need to have high gas barrier properties, low moisture permeability, moisture resistance, environmental heat resistance, environmental insulation, rubber elastomer, coolant resistance, and a long service life to meet the needs of hydrogen energy vehicles.

[0003] Common fuel cell sealants are silicone rubber and fluororubber. Silicone rubber has excellent thermal stability and low temperature resistance, as well as good electrical insulation, rubber elasticity, low compression deformation, acid resistance and solvent resistance. However, silicone rubber has a short service life and poor air tightness, and cannot meet the needs of long-term use of hydrogen energy stacks. Although fluororubber has low permanent pressure and high air tightness, it does not work well in low temperature environments. The gas barrier properties, moisture resistance and rubber elasticity of polyisobutylene rubber are better than those of silicone rubber, but its low temperature resistance needs to be improved. EPDM, or ethylene propylene diene monomer rubber, has good low temperature resistance, air tightness and durability, so it can be made into sealants for use in hydrogen fuel cell bipolar plates.

[0004] As a sealing material, EPDM is often used in the solid form of sealing strips and sealing rings in the automotive field. Liquid EPDM is often used as a plasticizer. The patent "An EPDM sealing material for hydrogen fuel cells and its preparation method and application" provides an EPDM sealing material for hydrogen fuel cells, which uses a thermosetting method for curing and molding. However, thermosetting sealants require higher temperatures, large energy losses, and longer curing times, which affect production speed. Summary of the invention

[0005] The purpose of the present invention is to provide a UV-curable liquid EPDM rubber used for battery sealant and a preparation method thereof. After the battery sealant is made, the glue point can be irradiated by LED to achieve a rapid curing effect, thereby increasing the production speed and reducing the production cost.

[0006] In order to achieve the above object, the present invention adopts the following technical solution:

[0007] A UV-curable liquid ethylene propylene diene monomer rubber used for battery sealant comprises the following components by weight: 20-30 parts of liquid ethylene propylene diene monomer rubber, 20-30 parts of petroleum ether, 0.2-1 part of 3-mercapto-1,2-propylene glycol, 0.05-0.5 part of initiator, 20-30 parts of acetone, ethyl isocyanate acrylate, 0.1-0.2 part of catalyst, and 0.1-0.2 part of polymerization inhibitor; the amount of ethyl isocyanate acrylate added is added according to the molar ratio of product 4 weight, and the added molar ratio is product 4 weight: ethyl isocyanate acrylate in the range of 5000:282.24 to 5000:141.12, and the weight of product 4 is the weight of the liquid after the solvent is removed; the product 4 is the impurity-removed product obtained by reacting liquid ethylene propylene diene monomer rubber, petroleum ether, 3-mercapto-1,2-propylene glycol, and initiator.

[0008] Preferably, the initiator is one or more of benzoyl peroxide, diisopropylbenzene peroxide, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and benzoin dimethyl ether; the catalyst is one or more of dibutyltin dilaurate, stannous octoate, and triethylamine; and the inhibitor is one or more of MEHQ, hydroquinone, tetrachlorobenzoquinone, and p-phenylenediamine.

[0009] A method for preparing UV-curable liquid EPDM rubber for battery sealant comprises the following steps:

[0010] A. Add liquid EPDM rubber, petroleum ether, 3-mercapto-1,2-propylene glycol and initiator according to the formula ratio, stir at room temperature to react, irradiate with a 365nm LED lamp during the reaction, and obtain product 1 after the reaction is completed; B. Put the product 1 obtained in step A into a rotary evaporator to remove the petroleum ether to obtain product 2; C. Add acetone to the product 2 obtained in step B according to the formula ratio and mix evenly, let it stand until stratification, remove the upper liquid, and obtain product 3;

[0011] D. putting the product 3 obtained in step C into an oven and drying it to obtain product 4;

[0012] E. Weigh the product 4 obtained in step D, add ethyl isocyanate acrylate in a molar ratio according to the weight of the product 4, then add a catalyst and an inhibitor in a formula ratio to heat and stir the reaction, continue heating after the reaction is completed, and evacuate the mixture to remove impurities while heating to obtain the final product.

[0013] Preferably, in step A, liquid EPDM rubber, petroleum ether, 3-mercapto-1,2-propylene glycol, and benzoin dimethyl ether are added to a three-necked flask according to the formula ratio, and then the three-necked flask is placed in a magnetic oil bath stirrer, a rotor is added to the three-necked flask and stirred at room temperature for 10 minutes, during which time it is irradiated with a 365nm LED lamp, the stirring speed is 100-300r / min, and the reaction is completed to obtain product 1.

[0014] Preferably, the product 1 obtained in step A is placed in a rotary evaporator, the rotary evaporation temperature is controlled at 60 degrees Celsius, the vacuum degree is controlled at 0.08 MPa, and the petroleum ether is removed by rotary evaporation to obtain product 2.

[0015] Preferably, the product 2 obtained in step B is poured into a separatory funnel while hot, acetone is added according to the formula ratio and mixed evenly, and the mixture is allowed to stand until stratification, and the upper layer of liquid is removed to obtain product 3.

[0016] Preferably, the product 3 obtained in step C is placed in an oven at a temperature of 80 degrees Celsius and dried for 6 to 12 hours to remove the residual solvent to obtain the product 4.

[0017] Preferably, the product 4 obtained in step D is taken out of the oven and weighed. After weighing, it is put into a clean three-necked flask, and isocyanate ethyl acrylate is added according to the molar ratio according to the weight of the product 4, and then the catalyst and the inhibitor are added according to the formula ratio. After the feeding is completed, the three-necked flask is placed in a magnetic oil bath stirrer for heating and stirring reaction, the reaction temperature is 75 to 80 degrees Celsius, and the reaction time is 2 to 4 hours; after the reaction is completed, the temperature is continued to be raised to 90 degrees Celsius, and a vacuum pump is used to evacuate for 30 minutes, and the vacuum degree is controlled below 0.08MPa to obtain the final product.

[0018] Preferably, the EPDM rubber in step A is first placed in an oven at 80° C. to soften for 0.5-1 hour before the reaction to obtain the oven-softened EPDM rubber.

[0019] Preferably, the EPDM rubber softened in an oven and petroleum ether are placed in a three-necked flask and mixed at a rate of 100 r / min for 10 minutes; after mixing, 3-mercapto-1,2-propylene glycol and benzoin dimethyl ether are added to the three-necked flask, and the stirring rate is increased to 300 r / min; stirring for 10 minutes, during which time the mixture is irradiated with a 365nm LED lamp, and the reaction is completed to obtain product 1.

[0020] In summary, the present invention utilizes the characteristics of EPDM rubber, modifies it to have photoactive groups, and applies it to the gas path seal of hydrogen fuel cell bipolar plates. By chemical modification, UV-curable liquid EPDM rubber is obtained, which is superior, convenient, and efficient when applied to fuel cell sealants compared to traditional thermosetting sealants.

[0021] The advantages of the present invention are:

[0022] 1. Use liquid EPDM rubber with UV curing function as the raw material of fuel cell bipolar plate sealant, which makes the sealant have the advantages of fast curing and controllable.

[0023] 2. First, a thiol having a mercapto group and a hydroxyl group is used to graft the hydroxyl group with the carbon-carbon double bond of the EPDM rubber side chain, and then a compound having an isocyanate group and an acryloxy group structure is used to graft the isocyanate group with the hydroxyl group of the EPDM rubber side chain, and the acryloxy group is introduced into the EPDM rubber. The EPDM rubber having an acryloxy group on the side chain is obtained, and after the acryloxy group is introduced, the rubber has photocuring activity.

[0024] 3. The mercapto-ene reaction and the addition reaction of isocyanate are applied simultaneously. The above reaction conditions are mild, the reaction rate is fast, and the product yield is high. DETAILED DESCRIPTION

[0025] In order to explain the technical content, achieved objectives and effects of the present invention in detail, the following is an explanation in conjunction with the implementation modes, but it does not constitute a limitation on the protection scope of the present invention.

[0026] The invention adopts liquid EPDM rubber containing 10% of the third monomer as the raw material for modification, and grafts the photocurable group onto the side chain of the liquid EPDM rubber molecule through the mercapto-ene click reaction and the isocyanate addition reaction, so that after the battery sealant is made, the LED irradiation glue point can achieve the effect of rapid curing, thereby improving the production speed and reducing the production cost.

[0027] The reaction route diagram is as follows:

[0028]

[0029] In the above reaction equation: the R group in Formula 2 refers to the long chain of EPDM rubber to which the sulfur group is added in the product structure of Formula 1. There are multiple double bonds in EPDM rubber, all of which have the possibility of reacting with 3-mercapto-1,2-propylene glycol. The hydroxyl group of 3-mercapto-1,2-propylene glycol can react and graft with the isocyanate group of isocyanate ethyl acrylate, so there is at least one acryloyloxy group on the product in Formula 2.

[0030] The invention discloses a UV curable liquid ethylene propylene diene monomer rubber applied to a battery sealant. The UV curable liquid ethylene propylene diene monomer rubber comprises the following components by weight: 20-30 parts of liquid ethylene propylene diene monomer rubber, 20-30 parts of petroleum ether, 0.2-1 parts of mercapto-1,2-propylene glycol, 0.05-0.5 parts of initiator, 20-30 parts of acetone, ethyl isocyanate acrylate, 0.1-0.2 parts of catalyst and 0.1-0.2 parts of polymerization inhibitor; the amount of ethyl isocyanate acrylate added is added according to the molar ratio of the weight of product 4, and the added molar ratio is in the range of 5000:282.24 to 5000:141.12 of the weight of product 4:ethyl isocyanate acrylate; and product 4 is obtained by reacting liquid ethylene propylene diene monomer rubber, petroleum ether, 3-mercapto-1,2-propylene glycol and initiator.

[0031] As a preferred embodiment of the present invention, the initiator is benzoin dimethyl ether, the catalyst is dibutyltin dilaurate, and the inhibitor is MEHQ.

[0032] The present invention provides a method for preparing UV-curable liquid EPDM rubber for battery sealant, comprising the following steps:

[0033] A. In a three-necked flask, add 20-30 g of liquid EPDM rubber, 20-30 g of petroleum ether, 0.2-1 g of 3-mercapto-1,2-propylene glycol, and 0.05-0.5 g of benzoin dimethyl ether, then put the three-necked flask into a magnetic oil bath stirrer, add a rotor to the three-necked flask and stir at room temperature for 10 minutes, during which time it is irradiated with a 365 nm LED lamp, and the stirring speed is 100-300 r / min. The reaction is completed to obtain product 1.

[0034] B. Place the product 1 obtained in step A into a rotary evaporator, control the rotary evaporation temperature at 60 degrees Celsius, and control the vacuum degree at 0.08 MPa to obtain product 2.

[0035] C. Pour the product 2 obtained in step B into a separatory funnel while hot, add 25 g of acetone and mix evenly, let it stand until it separates into layers, remove the upper liquid (at this time, 3-mercapto-1,2-propylene glycol and benzoin dimethyl ether are dissolved in acetone, and the acetone in the upper layer of the separatory funnel is removed) to obtain product 3.

[0036] D. The product 3 obtained in step C is placed in an oven at a temperature of 80 degrees Celsius and dried for 6 to 12 hours to remove the residual solvent to obtain the product 4.

[0037] E. The product 4 obtained in step D is taken out of the oven for weighing, and after weighing, it is put into a clean three-necked flask, and ethyl isocyanate acrylate is added according to the molar ratio according to the weight of the product 4, and then the catalyst and the polymerization inhibitor are added according to the formula ratio. After the feeding is completed, the three-necked flask is placed in a magnetic oil bath agitator for heating and stirring reaction, the reaction temperature is 75 to 80 degrees Celsius, and the reaction time is 2 to 4 hours; after the reaction is completed, the temperature is continued to rise to 90 degrees Celsius, and a vacuum pump is used for 30 minutes, and the vacuum degree is controlled below 0.08MPa, and the residual ethyl isocyanate acrylate is removed to obtain the final product. The reaction product is weighed and added to a clean three-necked flask, and ethyl isocyanate acrylate, dibutyltin dilaurate and MEHQ are added according to a certain ratio according to the weight of the reaction product, and the three-necked flask is placed in a magnetic oil bath agitator and the temperature is controlled at 75 to 80 degrees Celsius and the rotor is magnetically stirred for 2 to 4 hours. The temperature was then continued to rise to 90 degrees Celsius and vacuum was evacuated with a vacuum pump for 30 minutes, with the vacuum degree controlled below 0.08 MPa to obtain the final product.

[0038] The following are specific embodiments of the present invention.

[0039] Example 1

[0040] The main equipment and materials are listed as follows:

[0041]

[0042]

[0043] The preparation method of this embodiment includes the following steps: put EPDM rubber in an oven at 80°C for 30 minutes, take 24.47g of EPDM rubber softened in the oven and 25g of petroleum ether and place them in a 100ml three-necked flask and mix them at a rate of 100r / min for 10 minutes. Add 0.53g of 3-mercapto-1,2-propylene glycol and 0.075g of benzoin dimethyl ether, and increase the stirring rate to 300r / min. After irradiating with a 365nm LED lamp for 10 minutes, turn off the light, put the material in the flask into a rotary evaporator, control the rotary evaporation temperature at 60 degrees Celsius, and control the vacuum degree at 0.08MPa. The purpose is to remove petroleum ether, and continue until the weight difference between the material before and after is less than 0.02g. After removing the petroleum ether, pour it into a separatory funnel while hot, add 25g of acetone and mix evenly, let it stand until stratification, remove the acetone, and then put it into a vacuum drying oven to remove the residual acetone. The dried product was added to a three-necked flask, the weight of the added product was weighed, an equal weight of petroleum ether was added, and ethyl isocyanate acrylate was added according to the molar ratio of 5000:282.24 based on the weight of the product. Dibutyltin dilaurate and MEHQ were added at 0.5% of the product mass. The mixture was kept at 80°C for 2 hours, then heated to 90°C and vacuumed for 30 minutes to remove petroleum ether and residual ethyl isocyanate acrylate to obtain the final product.

[0044] The liquid EPDM rubber battery sealant prepared by the present invention is used, and the preparation method of the UV-curable fuel cell bipolar plate sealant of Example 1 of the present invention comprises the following steps:

[0045] raw material share Final product 63 Isobornyl acrylate 21 1173 3 TPO-L 3 White Carbon Black 10 Adhesion promoter (silane coupling agent KH-570) 0.1 Inhibitor (p-methoxyphenol) 0.05 Anti-aging agent (hydroquinone) 0.1

[0046] Weigh each raw material according to the raw material ratio:

[0047] ① Add 21g of isobornyl acrylate, 3g of 1173, 3g of TPO-L, 10g of white carbon black, and 0.05g of inhibitor (p-methoxyphenol) into a 300ml vacuum mixer and stir for 40min at a stirring speed of 10r / min and a dispersion speed of 15r / min;

[0048] ② Add the product into a vacuum mixer and stir for 50 minutes at a stirring speed of 20 r / min and a dispersion speed of 30 r / min;

[0049] ③ Add 0.1 g adhesion promoter (silane coupling agent KH-570) and 0.1 g antioxidant (hydroquinone) into a vacuum mixer and stir for 50 min at a stirring speed of 20 r / min and a dispersion speed of 30 r / min to obtain a mixture;

[0050] ④Finally, the obtained mixture was vacuumed for 1 hour, and filtered into a container using a 150-200 mesh filter to obtain a sealant.

[0051] Example 2

[0052] The main equipment and materials are listed as follows:

[0053] Materials / Equipment source EPDM American Lion Chemical 3-Mercapto-1,2-propanediol Shanghai Myril Chemical Technology Co., Ltd. Benzoin dimethyl ether Shanghai Myril Chemical Technology Co., Ltd. acetone Sinopharm Chemical Reagent Co., Ltd. Ethyl isocyanate acrylate Shanghai Myril Chemical Technology Co., Ltd. Dibutyltin dilaurate Shanghai Myril Chemical Technology Co., Ltd. MEHQ Shanghai Myril Chemical Technology Co., Ltd. Petroleum ether Shanghai Myril Chemical Technology Co., Ltd. LED Light - 365nm Zhongshan Zigu Lighting Appliance Factory Rotary evaporator Henan Aihua Instrument Equipment Co., Ltd.

[0054] The preparation method of this embodiment includes the following steps: put EPDM rubber in an oven at 80°C for 30 minutes, take 24.47g of EPDM rubber softened in the oven and 25g of petroleum ether and place them in a 100ml three-necked flask and mix them at a rate of 100r / min for 10 minutes. Add 0.53g of 3-mercapto-1,2-propylene glycol and 0.075g of benzoin dimethyl ether, and increase the stirring rate to 300r / min. After irradiating with a 365nm LED lamp for 10 minutes, turn off the light, put the material in the flask into a rotary evaporator, control the rotary evaporation temperature at 60 degrees Celsius, and control the vacuum degree at 0.08MPa. The purpose is to remove petroleum ether, and continue until the weight difference between the material before and after is less than 0.02g. After removing the petroleum ether, pour it into a separatory funnel while hot, add 25g of acetone and mix evenly, let it stand until stratification, remove the acetone, and then put it into a vacuum drying oven to remove the residual acetone. The dried product was added to a three-necked flask, the weight of the added product was weighed, an equal weight of petroleum ether was added, and ethyl isocyanate acrylate was added according to the molar ratio of 5000:141.12 based on the weight of the product. Dibutyltin dilaurate and MEHQ were added at 0.5% of the product mass. The mixture was kept at 80°C for 2 hours, then heated to 90°C and vacuumed for 30 minutes to remove petroleum ether and residual ethyl isocyanate acrylate to obtain the final product.

[0055] The preparation method of the UV-curable fuel cell bipolar plate sealant of Example 2 of the present invention comprises the following steps:

[0056] raw material share Final product 63 Isobornyl acrylate 21 1173 3 TPO-L 3 White Carbon Black 10 Adhesion promoter (silane coupling agent KH-570) 0.1 Inhibitor (p-methoxyphenol) 0.05 Anti-aging agent (hydroquinone) 0.1

[0057] Weigh each raw material according to the raw material ratio:

[0058] ① Add 21g of isobornyl acrylate, 3g of 1173, 3g of TPO-L, 10g of white carbon black, and 0.05g of inhibitor (p-methoxyphenol) into a 300ml vacuum mixer and stir for 40min at a stirring speed of 10r / min and a dispersion speed of 15r / min;

[0059] ② Add the product into a vacuum mixer and stir for 50 minutes at a stirring speed of 20 r / min and a dispersion speed of 30 r / min;

[0060] ③ Add 0.1 g adhesion promoter (silane coupling agent KH-570) and 0.1 g antioxidant (hydroquinone) into a vacuum mixer and stir for 50 min at a stirring speed of 20 r / min and a dispersion speed of 30 r / min to obtain a mixture;

[0061] ④Finally, the obtained mixture was vacuumed for 1 hour, and filtered into a container using a 150-200 mesh filter to obtain a sealant.

[0062] Example 3

[0063] The main equipment and materials are listed as follows:

[0064] Materials / Equipment source EPDM American Lion Chemical 3-Mercapto-1,2-propanediol Shanghai Myril Chemical Technology Co., Ltd. Benzoin dimethyl ether Shanghai Myril Chemical Technology Co., Ltd. acetone Sinopharm Chemical Reagent Co., Ltd. Ethyl isocyanate acrylate Shanghai Myril Chemical Technology Co., Ltd. Dibutyltin dilaurate Shanghai Myril Chemical Technology Co., Ltd. MEHQ Shanghai Myril Chemical Technology Co., Ltd. Petroleum ether Shanghai Myril Chemical Technology Co., Ltd. LED Light - 365nm Zhongshan Zigu Lighting Appliance Factory Rotary evaporator Henan Aihua Instrument Equipment Co., Ltd.

[0065] The preparation method of this embodiment includes the following steps: put EPDM rubber in an oven at 80°C for 30 minutes, take 24.47g of EPDM rubber softened in the oven and 25g of petroleum ether and place them in a 100ml three-necked flask and mix them at a rate of 100r / min for 10 minutes. Add 0.53g of 3-mercapto-1,2-propylene glycol and 0.075g of benzoin dimethyl ether, and increase the stirring rate to 300r / min. After irradiating with a 365nm LED lamp for 120 minutes, turn off the light, put the material in the flask into a rotary evaporator, control the rotary evaporation temperature at 60 degrees Celsius, and control the vacuum degree at 0.08MPa. The purpose is to remove petroleum ether, and continue until the weight difference between the material before and after is less than 0.02g. After removing the petroleum ether, pour it into a separatory funnel while hot, add 25g of acetone and mix evenly, let it stand until stratification, remove the acetone, and then put it into a vacuum drying oven to remove the residual acetone. The dried product was added to a three-necked flask, the weight of the added product was weighed, an equal weight of petroleum ether was added, and ethyl isocyanate acrylate was added according to the molar ratio of 5000:282.24 based on the weight of the product. Dibutyltin dilaurate and MEHQ were added at 0.5% of the product mass. The mixture was kept at 80°C for 2 hours, then heated to 90°C and vacuumed for 30 minutes to remove petroleum ether and residual ethyl isocyanate acrylate to obtain the final product.

[0066] The preparation method of the UV-curable fuel cell bipolar plate sealant of Example 3 of the present invention comprises the following steps:

[0067] raw material share Final product 63 Isobornyl acrylate 21 1173 3 TPO-L 3 White Carbon Black 10 Adhesion promoter (silane coupling agent KH-570) 0.1 Inhibitor (p-methoxyphenol) 0.05 Anti-aging agent (hydroquinone) 0.1

[0068] Weigh each raw material according to the raw material ratio:

[0069] ① Add 21g of isobornyl acrylate, 3g of 1173, 3g of TPO-L, 10g of white carbon black, and 0.05g of inhibitor (p-methoxyphenol) into a 300ml vacuum mixer and stir for 40min at a stirring speed of 10r / min and a dispersion speed of 15r / min;

[0070] ② Add the product into a vacuum mixer and stir for 50 minutes at a stirring speed of 20 r / min and a dispersion speed of 30 r / min;

[0071] ③ Add 0.1 g adhesion promoter (silane coupling agent KH-570) and 0.1 g antioxidant (hydroquinone) into a vacuum mixer and stir for 50 min at a stirring speed of 20 r / min and a dispersion speed of 30 r / min to obtain a mixture;

[0072] ④Finally, the obtained mixture was vacuumed for 1 hour, and filtered into a container using a 150-200 mesh filter to obtain a sealant.

[0073] Example 4

[0074] The main equipment and materials are listed as follows:

[0075] Materials / Equipment source EPDM American Lion Chemical 3-Mercapto-1,2-propanediol Shanghai Myril Chemical Technology Co., Ltd. Benzoin dimethyl ether Shanghai Myril Chemical Technology Co., Ltd. acetone Sinopharm Chemical Reagent Co., Ltd. Ethyl isocyanate acrylate Shanghai Myril Chemical Technology Co., Ltd. Dibutyltin dilaurate Shanghai Myril Chemical Technology Co., Ltd. MEHQ Shanghai Myril Chemical Technology Co., Ltd. Petroleum ether Shanghai Myril Chemical Technology Co., Ltd. LED Light - 365nm Zhongshan Zigu Lighting Appliance Factory Rotary evaporator Henan Aihua Instrument Equipment Co., Ltd.

[0076] The preparation method of this embodiment includes the following steps: put EPDM rubber in an oven at 80°C for 30 minutes, take 24.47g of EPDM rubber softened in the oven and 25g of petroleum ether and place them in a 100ml three-necked flask and mix them at a rate of 100r / min for 10 minutes. Add 0.53g of 3-mercapto-1,2-propylene glycol and 0.15g of benzoin dimethyl ether, and the stirring rate is increased to 300r / min. After irradiating with a 365nm LED lamp for 10 minutes, turn off the light, put the material in the flask into a rotary evaporator, control the rotary evaporation temperature at 60 degrees Celsius, and control the vacuum degree at 0.08MPa. The purpose is to remove petroleum ether, and continue until the weight difference between the material before and after is less than 0.02g. After removing the petroleum ether, pour it into a separatory funnel while hot, add 25g of acetone and mix evenly, let it stand until stratification, remove the acetone, and then put it into a vacuum drying oven to remove the residual acetone. The dried product was added to a three-necked flask, the weight of the added product was weighed, an equal weight of petroleum ether was added, and ethyl isocyanate acrylate was added according to the molar ratio of 5000:282.24 based on the weight of the product. Dibutyltin dilaurate and MEHQ were added at 0.5% of the product mass. The mixture was kept at 80°C for 2 hours, then heated to 90°C and vacuumed for 30 minutes to remove petroleum ether and residual ethyl isocyanate acrylate to obtain the final product.

[0077] The preparation method of the UV-curable fuel cell bipolar plate sealant of Example 4 of the present invention comprises the following steps:

[0078] raw material share Final product 63 Isobornyl acrylate 21 1173 3 TPO-L 3 White Carbon Black 10 Adhesion promoter (silane coupling agent KH-570) 0.1 Inhibitor (p-methoxyphenol) 0.05 Antioxidant (hydroquinone) 0.1

[0079] Weigh each raw material according to the raw material ratio:

[0080] ① Add 21g of isobornyl acrylate, 3g of 1173, 3g of TPO-L, 10g of white carbon black, and 0.05g of inhibitor (p-methoxyphenol) into a 300ml vacuum mixer and stir for 40min at a stirring speed of 10r / min and a dispersion speed of 15r / min;

[0081] ② Add the product into a vacuum mixer and stir for 50 minutes at a stirring speed of 20 r / min and a dispersion speed of 30 r / min;

[0082] ③ Add 0.1 g adhesion promoter (silane coupling agent KH-570) and 0.1 g antioxidant (hydroquinone) into a vacuum mixer and stir for 50 min at a stirring speed of 20 r / min and a dispersion speed of 30 r / min to obtain a mixture;

[0083] ④Finally, the obtained mixture was vacuumed for 1 hour, and filtered into a container using a 150-200 mesh filter to obtain a sealant.

[0084] Example 5

[0085] The main equipment and materials are listed as follows:

[0086] Materials / Equipment source EPDM American Lion Chemical 3-Mercapto-1,2-propanediol Shanghai Myril Chemical Technology Co., Ltd. Benzoin dimethyl ether Shanghai Myril Chemical Technology Co., Ltd. acetone Sinopharm Chemical Reagent Co., Ltd. Ethyl isocyanate acrylate Shanghai Myril Chemical Technology Co., Ltd. Dibutyltin dilaurate Shanghai Myril Chemical Technology Co., Ltd. MEHQ Shanghai Myril Chemical Technology Co., Ltd. Petroleum ether Shanghai Myril Chemical Technology Co., Ltd. LED Light - 365nm Zhongshan Zigu Lighting Appliance Factory Rotary evaporator Henan Aihua Instrument Equipment Co., Ltd.

[0087] The preparation method of this embodiment includes the following steps: put EPDM rubber in an oven at 80°C for 30 minutes, take 24.47g of EPDM rubber softened in the oven and 25g of petroleum ether and place them in a 100ml three-necked flask and mix them at a rate of 100r / min for 10 minutes. Add 0.53g of 3-mercapto-1,2-propylene glycol and 0.075g of benzoin dimethyl ether, and increase the stirring rate to 300r / min. After irradiating with a 365nm LED lamp for 10 minutes, turn off the light, put the material in the flask into a rotary evaporator, control the rotary evaporation temperature at 60 degrees Celsius, and control the vacuum degree at 0.08MPa. The purpose is to remove petroleum ether, and continue until the weight difference between the material before and after is less than 0.02g. After removing the petroleum ether, pour it into a separatory funnel while hot, add 25g of acetone and mix evenly, let it stand until stratification, remove the acetone, and then put it into a vacuum drying oven to remove the residual acetone. The dried product was added to a three-necked flask, the weight of the added product was weighed, an equal weight of petroleum ether was added, and ethyl isocyanate acrylate was added according to the molar ratio of 5000:282.24 based on the weight of the product. Dibutyltin dilaurate and MEHQ were added at 0.5% of the product mass. The mixture was kept at 80°C for 4 hours, then heated to 90°C and vacuumed for 30 minutes to remove petroleum ether and residual ethyl isocyanate acrylate to obtain the final product.

[0088] The preparation method of the UV-curable fuel cell bipolar plate sealant of Example 5 of the present invention comprises the following steps:

[0089]

[0090]

[0091] Weigh each raw material according to the raw material ratio:

[0092] ① Add 21g of isobornyl acrylate, 3g of 1173, 3g of TPO-L, 10g of white carbon black, and 0.05g of inhibitor (p-methoxyphenol) into a 300ml vacuum mixer and stir for 40min at a stirring speed of 10r / min and a dispersion speed of 15r / min;

[0093] ② Add the product into a vacuum mixer and stir for 50 minutes at a stirring speed of 20 r / min and a dispersion speed of 30 r / min;

[0094] ③ Add 0.1 g adhesion promoter (silane coupling agent KH-570) and 0.1 g antioxidant (hydroquinone) into a vacuum mixer and stir for 50 min at a stirring speed of 20 r / min and a dispersion speed of 30 r / min to obtain a mixture;

[0095] ④Finally, the obtained mixture was vacuumed for 1 hour, and filtered into a container using a 150-200 mesh filter to obtain a sealant.

[0096] Comparative Example 1

[0097] Heat-curing silicone sealant. ELASTOSIL RT 624 from Wacker Chemicals.

[0098] Comparative Example 2

[0099] Thermosetting polyolefin sealant. Japan ThreeBond TB1153E.

[0100] Comparative Example 3

[0101] Thermosetting EPDM rubber sealant. The formula is as follows

[0102]

[0103]

[0104] Processing is carried out according to the components and dosages of the formula listed in the table: liquid EPDM rubber, ZnO, ZDMA, paraffin oil and half of the amount of reinforcing agent N990 are added to a planetary mixer and mixed for 10 minutes. Then, filler talcum powder and moisture absorbent CaO are added and mixed for 5 minutes, and then the remaining reinforcing agent N990 is added and mixed for 10 minutes, and then peroxide curing agent TMCH and accelerator TAIC are added and mixed for 5 minutes; the mixed rubber is left for 12 hours, and then vulcanized at 120°C for 2 hours, and a thermosetting EPDM rubber sealant is obtained after vulcanization.

[0105] According to the shape and size specified in GB / T2941-2006, take the sealant sample and cure it in the following way:

[0106] In embodiments 1 to 5, the curing method is to irradiate with a 365 nm ultraviolet lamp for 20 to 40 seconds.

[0107] The curing method of Comparative Example 1 is thermal curing at 120 degrees Celsius for 1.5 hours.

[0108] The curing method of Comparative Example 2 is thermal curing at 130 degrees Celsius for 1.5 hours.

[0109] The curing method of Comparative Example 3 is thermal curing at 130 degrees Celsius for 1.5 hours.

[0110] The cured sealant samples were tested according to the following standards.

[0111]

[0112]

[0113] Data Analysis:

[0114] ① Among Examples 1 to 5, the mechanical properties of Example 2 are significantly reduced. This is because the amount of the key raw material, ethyl isocyanate acrylate, added is reduced, which reduces the functionality of the product. Compared with other examples, the degree of crosslinking in Example 2 is lower, so the mechanical properties are significantly reduced.

[0115] ② It can be seen from the curing conditions of Example 1 and Comparative Examples 1 to 3 that the use of light curing can achieve energy-saving and time-saving effects. Compared with Comparative Example 1, the airtightness of Example 1 is improved by 30%, and the change rates of the four groups of performance parameters of the low-temperature durability test of Example 1 are lower, indicating that the low-temperature durability of Example 1 is better than that of Comparative Example 1.

[0116] ③ Compared with Comparative Example 2, the change rates of the four groups of performance parameters of Example 1 in the low-temperature durability test are lower, indicating that the low-temperature durability of Example 1 is also better than that of Comparative Example 2.

[0117] ④ The overall performance of Example 1 and Comparative Example 3 is similar because the main raw materials are both EPDM rubber. The difference lies in the different curing forms, Example 1 is light curing, and Comparative Example 3 is heat curing. Example 1 introduces light curing groups through modification, and can be cured by irradiating UV light of a certain intensity for 20S, while Comparative Example 3 has no modification and can only be cured by adding a vulcanizing agent and baking at 130 degrees Celsius for 90 minutes to achieve thermal curing.

[0118] The above embodiments only express several implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for those of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A UV-curable liquid EPDM rubber for battery sealant, characterized in that: The following components are included by weight: 20-30 parts of liquid EPDM rubber, 20-30 parts of petroleum ether, 0.2-1 parts of 3-mercapto-1,2-propylene glycol, 0.05-0.5 parts of initiator, 20-30 parts of acetone, ethyl isocyanate acrylate, 0.1-0.2 parts of catalyst, and 0.1-0.2 parts of inhibitor; The amount of the ethyl isocyanate acrylate added is based on the weight of the product 4 according to the molar ratio, and the added molar ratio is the weight of the product 4: ethyl isocyanate acrylate in the range of 5000:282.24 to 5000:141.12, and the weight of the product 4 is the weight of the liquid after the solvent is removed; The product 4 is a product obtained by reacting liquid EPDM rubber, petroleum ether, 3-mercapto-1,2-propylene glycol and an initiator, and the impurity is removed.

2. The UV-curable liquid EPDM rubber for battery sealant according to claim 1, characterized in that: The initiator is one or more of benzoyl peroxide, diisopropylbenzene peroxide, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and benzoin dimethyl ether; the catalyst is one or more of dibutyltin dilaurate, stannous octoate, and triethylamine; and the inhibitor is one or more of MEHQ, hydroquinone, tetrachlorobenzoquinone, and p-phenylenediamine.

3. A method for preparing a UV-curable liquid EPDM rubber for battery sealant as claimed in any one of claims 1 to 2, characterized in that: The following steps are involved: A. Add liquid EPDM rubber, petroleum ether, 3-mercapto-1,2-propylene glycol and initiator according to the formula ratio, stir at room temperature to react, use 365nm LED light to irradiate during the reaction, and the reaction is completed to obtain product 1; B. placing the product 1 obtained in step A into a rotary evaporator to remove petroleum ether to obtain product 2; C. Add acetone to the product 2 obtained in step B according to the formula ratio and mix evenly, let it stand until stratification, remove the upper layer of liquid, and obtain product 3; D. putting the product 3 obtained in step C into an oven and drying it to obtain product 4; E. Weigh the product 4 obtained in step D, add ethyl isocyanate acrylate in a molar ratio according to the weight of the product 4, then add a catalyst and an inhibitor in a formula ratio to heat and stir the reaction, continue heating after the reaction is completed, and evacuate the mixture to remove impurities while heating to obtain the final product.

4. The method for preparing a UV-curable liquid EPDM rubber for battery sealant according to claim 3, characterized in that: In step A, liquid EPDM rubber, petroleum ether, 3-mercapto-1,2-propylene glycol, and benzoin dimethyl ether are added to a three-necked flask according to the formula ratio, and then the three-necked flask is placed in a magnetic oil bath stirrer, a rotor is added to the three-necked flask, and stirring is carried out at room temperature for 10 minutes, during which time it is irradiated with a 365nm LED lamp, and the stirring speed is 100-300r / min. The reaction is completed to obtain product 1.

5. The method for preparing a UV-curable liquid EPDM rubber for battery sealant according to claim 3, characterized in that: The product 1 obtained in step A is placed in a rotary evaporator, the rotary evaporation temperature is controlled at 60 degrees Celsius, the vacuum degree is controlled at 0.08 MPa, and the petroleum ether is removed by rotary evaporation to obtain product 2.

6. The method for preparing a UV-curable liquid EPDM rubber for battery sealant according to claim 3, characterized in that: Pour the product 2 obtained in step B into a separatory funnel while hot, add acetone according to the formula ratio and mix evenly, let it stand until it separates into layers, remove the upper layer of liquid, and obtain product 3.

7. The method for preparing a UV-curable liquid EPDM rubber for battery sealant according to claim 3, characterized in that: The product 3 obtained in step C is placed in an oven at a temperature of 80 degrees Celsius and dried for 6 to 12 hours to remove the residual solvent to obtain the product 4.

8. The method for preparing UV-curable liquid EPDM rubber for battery sealant according to claim 3, characterized in that: The product 4 obtained in step D is taken out of the oven and weighed. After weighing, it is put into a clean three-necked flask, and isocyanate ethyl acrylate is added according to the molar ratio according to the weight of the product 4, and then the catalyst and the inhibitor are added according to the formula ratio. After the feeding is completed, the three-necked flask is placed in a magnetic oil bath stirrer for heating and stirring reaction. The reaction temperature is 75 to 80 degrees Celsius and the reaction time is 2 to 4 hours. After the reaction is completed, the temperature is continued to be raised to 90 degrees Celsius, and a vacuum pump is used to evacuate for 30 minutes, and the vacuum degree is controlled below 0.08MPa to obtain the final product.

9. The method for preparing UV-curable liquid EPDM rubber for battery sealant according to claim 4, characterized in that: The EPDM rubber in step A is first placed in an oven at 80° C. to soften for 0.5-1 hour before the reaction to obtain the oven-softened EPDM rubber.

10. The method for preparing UV-curable liquid EPDM rubber for battery sealant according to claim 9, characterized in that: The EPDM rubber softened in an oven and petroleum ether were placed in a three-necked flask and mixed at a rate of 100 r / min for 10 minutes; after mixing, 3-mercapto-1,2-propanediol and benzoin dimethyl ether were added to the three-necked flask, and the stirring rate was increased to 300 r / min; the mixture was stirred for 10 minutes, during which time it was irradiated with a 365nm LED lamp, and the reaction was completed to obtain product 1.

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