Insulating pressure-resistant light-cured resin and preparation method thereof

Abstract

The invention relates to the technical field of light-cured resin, in particular to insulating pressure-resistant light-cured resin and a preparation method thereof.The preparation method comprises the steps that toluene-2, 4-diisocyanate, polypropylene glycol and butyltin dilaurate are evenly mixed and react to obtain a prepolymer; adding hydroxyethyl acrylate, butanol and hydroquinone into the prepolymer, and reacting to obtain an end-capped prepolymer; and adding a diluent and modified nanoparticles into the end-capped prepolymer, and carrying out ultrasonic dispersion to prepare the insulating pressure-resistant light-cured resin. According to the invention, the adopted nanoparticles are modified by methyl methacrylate, and the surfaces of the nanoparticles contain acrylate groups, so that the photocuring reaction is further carried out, and the reaction degree is increased; moreover, the groups can also generate adsorption and bonding effects with a resin matrix, so that the high-strength property of the nanoparticles can be combined with the resin matrix, and the insulativity and the pressure resistance of the light-cured resin are improved.

Description

Technical Field

[0001] The present invention relates to the technical field of photocurable resins, and specifically relates to an insulating and voltage-resistant photocurable resin and a preparation method thereof. Background Technique

[0002] With the development of industrialization and the increasing attention to environmental protection, the application fields of chemical materials such as coatings and adhesives have gradually expanded. Among them, photocurable resins have become one of the widely used materials due to their rapid curing, high efficiency, low energy consumption, and environmental protection characteristics. Photocurable resins can be used to make inks for inkjet printing on the outer layer of power batteries for packaging and protection.

[0003] For the traditional PET blue film packaging on the outer layer of the battery core, due to the limitations of the glue performance and construction process, it is difficult to achieve a complete fit with the outer layer of the battery core. Compared with using PET blue film, inkjet printing can achieve a tight fit with the surface of the outer layer of the battery core, providing more comprehensive protection for the battery, and there is a trend to replace PET blue film. However, the resins used in existing photocurable inks generally have poor voltage resistance and insulation performance, and the film layers formed by inkjet printing are easily damaged by external forces such as friction and scratching, resulting in a risk of electric leakage. Based on this, an insulating and voltage-resistant photocurable resin and a preparation method thereof are proposed. Summary of the Invention

[0004] Aiming at the deficiencies of the prior art, the present invention provides an insulating and voltage-resistant photocurable resin and a preparation method thereof. By modifying the nanoparticles, the high-strength properties of the nanoparticles themselves are combined with the resin matrix, improving the insulation and voltage resistance of the photocurable resin.

[0005] To achieve the above object, the present invention provides the following technical solution: An insulating and voltage-resistant photocurable resin, comprising the following raw materials in parts by weight: 40-50 parts of toluene-2,4-diisocyanate, 30-40 parts of polypropylene glycol, 10-15 parts of butanol, 20-30 parts of hydroxyethyl acrylate, 10-15 parts of diluent, 0.1-0.5 part of dibutyltin dilaurate, 0.5-1 part of hydroquinone, and 5-8 parts of modified nanoparticles.

[0006] Preferably, the diluent is selected from dipentaerythritol hexaacrylate and dipropylene glycol diacrylate.

[0007] Preferably, the preparation method of the modified nanoparticles is as follows: S1. Mix 90 wt% sodium dodecylbenzenesulfonate aqueous solution and toluene to obtain a mixture; S2. Add nanoparticles to the mixture, stir at room temperature, then add azobisisobutyronitrile and methyl methacrylate and continue to stir, heat up and react; S3. After the reaction is completed, filter, wash, dry and grind to obtain modified nanoparticles.

[0008] Preferably, in step S1, the mass ratio of the sodium dodecylbenzenesulfonate aqueous solution to toluene is 1:1.

[0009] Preferably, in step S2, the nanoparticles are selected from nano-magnesium oxide, nano-silica, and nano-mica powder.

[0010] Preferably, in step S2, the material-liquid ratio of the nanoparticles to the mixture is 1:(20 - 25) g / mL; the material-liquid ratio of azobisisobutyronitrile to the mixture is 1:200 g / mL; the volume ratio of methyl methacrylate to the mixture is 1:(4 - 6) mL / mL.

[0011] Preferably, in step S2, stir at room temperature for 60 - 90 min, then heat up to 60 - 65 °C and react for 8 - 10 h.

[0012] The present invention also provides a preparation method of an insulating and voltage-resistant photocurable resin, comprising the following steps:

[0013] (1) Uniformly mix toluene - 2,4 - diisocyanate, polypropylene glycol, and dibutyltin dilaurate, and react at 80 - 90 °C for 1 - 1.5 h to obtain a prepolymer;

[0014] (2) Add hydroxyethyl acrylate, butanol, and hydroquinone to the prepolymer, and react at 40 - 50 °C for 5 - 6 h to obtain a capped prepolymer;

[0015] (3) Add a diluent and modified nanoparticles to the capped prepolymer, and ultrasonically disperse for 1 - 3 h to prepare the insulating and voltage-resistant photocurable resin.

[0016] The present invention provides an insulating and voltage-resistant photocurable resin and its preparation method, which has the following beneficial effects compared with the prior art:

[0017] The nanoparticles used in the present invention are modified with methyl methacrylate, and their surfaces contain acrylate groups, which enables the photocuring reaction to proceed further and increases the reaction degree; moreover, such groups can also have adsorption and bonding effects with the resin matrix, enabling the high strength properties of the nanoparticles themselves to be combined with the resin matrix, thereby improving the insulation and voltage resistance of the photocurable resin.

[0018] By modifying the surface of the nanoparticles, the present invention also facilitates the uniform dispersion and filling of the nanoparticles on the resin matrix, avoiding agglomeration between the nanoparticles, and thus improving the overall performance of the photocurable resin. Detailed Embodiments

[0019] The following examples are used to illustrate the implementation manners of the present application in detail, so as to fully understand how the present application uses technical means to solve technical problems and achieve the realization process of technical effects and implement accordingly.

[0020] Example 1

[0021] The preparation method of modified nano-silica is as follows:

[0022] S1. Mix the 90wt% sodium dodecylbenzenesulfonate aqueous solution and toluene according to a mass ratio of 1:1 to obtain a mixture;

[0023] S2. Add nano-silica to the mixture, stir at room temperature for 60 min, then add azobisisobutyronitrile and methyl methacrylate and continue stirring, heat up to 60 °C and react for 8 h;

[0024] The material-liquid ratio of the above nano-silica to the mixture is 1:20 g / mL; the material-liquid ratio of azobisisobutyronitrile to the mixture is 1:200 g / mL; the volume ratio of methyl methacrylate to the mixture is 1:4 mL / mL.

[0025] S3. After the reaction is completed, filter, wash, dry and grind to obtain modified nano-silica.

[0026] Example 2

[0027] The preparation method of modified nano-mica powder is as follows:

[0028] S1. Mix the 90wt% sodium dodecylbenzenesulfonate aqueous solution and toluene according to a mass ratio of 1:1 to obtain a mixture;

[0029] S2. Add nano-mica powder to the mixture, stir at room temperature for 90 min, then add azobisisobutyronitrile and methyl methacrylate and continue stirring, heat up to 65 °C and react for 8 h;

[0030] The material-liquid ratio of the above nano-mica powder to the mixture is 1:25 g / mL; the material-liquid ratio of azobisisobutyronitrile to the mixture is 1:200 g / mL; the volume ratio of methyl methacrylate to the mixture is 1:6 mL / mL.

[0031] S3. After the reaction is completed, filter, wash, dry and grind to obtain modified nano-mica powder.

[0032] Example 3

[0033] The preparation method of modified nano-magnesium oxide is as follows:

[0034] S1. Mix the 90wt% sodium dodecylbenzenesulfonate aqueous solution and toluene according to a mass ratio of 1:1 to obtain a mixture;

[0035] S2. Add nano-magnesium oxide to the mixture, stir at room temperature for 70 min, then add azobisisobutyronitrile and methyl methacrylate and continue stirring, heat up to 60 °C and react for 9 h;

[0036] The material-liquid ratio of the above-mentioned nano-magnesium oxide to the mixture is 1:22 g / mL; the material-liquid ratio of azobisisobutyronitrile to the mixture is 1:200 g / mL; the volume ratio of methyl methacrylate to the mixture is 1:5 mL / mL.

[0037] S3. After the reaction is completed, the modified nano-magnesium oxide is obtained through filtration, washing, drying and grinding.

[0038] Example 4

[0039] The preparation method of the modified nano-magnesium oxide is as follows:

[0040] S1. Mix an aqueous solution of 90 wt% sodium dodecylbenzenesulfonate and toluene according to a mass ratio of 1:1 to obtain a mixture.

[0041] S2. Add nano-magnesium oxide to the mixture, stir at room temperature for 80 min, then add azobisisobutyronitrile and methyl methacrylate and continue stirring, heat up to 65 °C and react for 8 h.

[0042] The material-liquid ratio of the above-mentioned nano-magnesium oxide to the mixture is 1:20 g / mL; the material-liquid ratio of azobisisobutyronitrile to the mixture is 1:200 g / mL; the volume ratio of methyl methacrylate to the mixture is 1:4 mL / mL.

[0043] S3. After the reaction is completed, the modified nano-magnesium oxide is obtained through filtration, washing, drying and grinding.

[0044] Example 5

[0045] An insulating and voltage-resistant photocurable resin, comprising the following raw materials in parts by weight: 50 parts of toluene-2,4-diisocyanate, 30 parts of polypropylene glycol, 15 parts of butanol, 20 parts of hydroxyethyl acrylate, 15 parts of dipentaerythritol hexaacrylate diluent, 0.1 part of dibutyltin dilaurate, 1 part of hydroquinone, and 5 parts of the modified nano-magnesium oxide in Example 3.

[0046] The preparation method of the above-mentioned insulating and voltage-resistant photocurable resin comprises the following steps:

[0047] (1) Uniformly mix toluene-2,4-diisocyanate, polypropylene glycol and dibutyltin dilaurate, and react at 90 °C for 1 h to obtain a prepolymer.

[0048] (2) Add hydroxyethyl acrylate, butanol and hydroquinone to the prepolymer, and react at 50 °C for 5 h to obtain a blocked prepolymer.

[0049] (3) Add dipentaerythritol hexaacrylate diluent and the modified nano-magnesium oxide in Example 3 to the blocked prepolymer, and perform ultrasonic dispersion for 1 h to obtain the insulating and voltage-resistant photocurable resin.

[0050] Example 6

[0051] An insulating and voltage-resistant photocurable resin, comprising the following raw materials in parts by weight: 40 parts of toluene-2,4-diisocyanate, 40 parts of polypropylene glycol, 10 parts of butanol, 30 parts of hydroxyethyl acrylate, 10 parts of dipropylene glycol diacrylate diluent, 0.5 part of dibutyltin dilaurate, 0.5 part of hydroquinone, and 8 parts of the modified nano-magnesium oxide in Example 4.

[0052] The preparation method of the above-mentioned insulating and voltage-resistant photocurable resin comprises the following steps:

[0053] (1) Uniformly mix toluene-2,4-diisocyanate, polypropylene glycol and dibutyltin dilaurate, and react at 80 °C for 1.5 h to obtain a prepolymer;

[0054] (2) Add hydroxyethyl acrylate, butanol and hydroquinone to the prepolymer, and react at 40 °C for 6 h to obtain a blocked prepolymer;

[0055] (3) Add dipropylene glycol diacrylate diluent and the modified nano-magnesium oxide in Example 4 to the blocked prepolymer, and ultrasonically disperse for 3 h to prepare the insulating and voltage-resistant photocurable resin.

[0056] Example 7

[0057] An insulating and voltage-resistant photocurable resin, comprising the following raw materials in parts by weight: 45 parts of toluene-2,4-diisocyanate, 35 parts of polypropylene glycol, 12 parts of butanol, 25 parts of hydroxyethyl acrylate, 13 parts of dipentaerythritol hexaacrylate diluent, 0.3 part of dibutyltin dilaurate, 0.8 part of hydroquinone, and 7 parts of the modified nano-magnesium oxide in Example 4.

[0058] The preparation method of the above-mentioned insulating and voltage-resistant photocurable resin comprises the following steps:

[0059] (1) Uniformly mix toluene-2,4-diisocyanate, polypropylene glycol and dibutyltin dilaurate, and react at 85 °C for 1.2 h to obtain a prepolymer;

[0060] (2) Add hydroxyethyl acrylate, butanol and hydroquinone to the prepolymer, and react at 40 °C for 5.5 h to obtain a blocked prepolymer;

[0061] (3) Add dipentaerythritol hexaacrylate diluent and the modified nano-magnesium oxide in Example 4 to the blocked prepolymer, and ultrasonically disperse for 2 h to prepare the insulating and voltage-resistant photocurable resin.

[0062] Comparative Example 1

[0063] An insulating and voltage-resistant photocurable resin, comprising the following raw materials in parts by weight: 45 parts of toluene-2,4-diisocyanate, 35 parts of polypropylene glycol, 12 parts of butanol, 25 parts of hydroxyethyl acrylate, 13 parts of dipentaerythritol hexaacrylate diluent, 0.3 part of dibutyltin dilaurate, and 0.8 part of hydroquinone.

[0064] The preparation method of the above-mentioned insulating and voltage-resistant photocurable resin comprises the following steps:

[0065] (1) Uniformly mix toluene-2,4-diisocyanate, polypropylene glycol and dibutyltin dilaurate, and react at 85 °C for 1.2 h to obtain a prepolymer;

[0066] (2) Add hydroxyethyl acrylate, butanol and hydroquinone to the prepolymer, and react at 40 °C for 5.5 h to obtain a blocked prepolymer;

[0067] (3) Add dipentaerythritol hexaacrylate diluent to the blocked prepolymer, and ultrasonically disperse for 2 h to obtain the insulating and voltage-resistant photocurable resin.

[0068] Comparative Example 2

[0069] An insulating and voltage-resistant photocurable resin, comprising the following raw materials in parts by weight: 45 parts of toluene-2,4-diisocyanate, 35 parts of polypropylene glycol, 12 parts of butanol, 25 parts of hydroxyethyl acrylate, 13 parts of dipentaerythritol hexaacrylate diluent, 0.3 part of dibutyltin dilaurate, 0.8 part of hydroquinone, and 7 parts of nano-magnesium oxide.

[0070] The preparation method of the above-mentioned insulating and voltage-resistant photocurable resin comprises the following steps:

[0071] (1) Uniformly mix toluene-2,4-diisocyanate, polypropylene glycol and dibutyltin dilaurate, and react at 85 °C for 1.2 h to obtain a prepolymer;

[0072] (2) Add hydroxyethyl acrylate, butanol and hydroquinone to the prepolymer, and react at 40 °C for 5.5 h to obtain a blocked prepolymer;

[0073] (3) Add dipentaerythritol hexaacrylate diluent and nano-magnesium oxide to the blocked prepolymer, and ultrasonically disperse for 2 h to obtain the insulating and voltage-resistant photocurable resin.

[0074] Comparative Example 3

[0075] It is basically the same as Example 7, the difference being: the preparation method of the modified nano-magnesium oxide is different. The preparation method of the modified nano-magnesium oxide in this comparative example is: surface modification of nano-magnesium oxide with silane coupling agent KH-560 to obtain modified nano-magnesium oxide.

[0076] Comparative Example 4

[0077] It is basically the same as Example 7, except that: in Example 4, the modified nano-magnesium oxide is 15 parts. The volume resistivity of the obtained insulating and voltage-resistant photocurable resin is 3.52×10 15 Ω·m.

[0078] Quality inspection

[0079] 1. Volume resistivity test: After the resin is photocured, it is tested according to the standard of GB / T 1410. The instrument used is the ZST-121 volume and surface resistivity tester. Keep the experimental environment temperature at 23±2°C and the humidity not higher than 80%. The specific test results are shown in the following table.

[0080] Table 1 Volume resistivity

[0081] Category Volume Resistivity (Ω·m) Example 5 <![CDATA[5.18×10 15 > Example 6 <![CDATA[5.15×10 15 <!-- 4 -->]]> Example 7 <![CDATA[5.23×10 15 > Comparative Example 1 <![CDATA[2.16×10 15 > Comparative Example 2 <![CDATA[4.14×10 15 > Comparative Example 3 <![CDATA[4.88×10 15 >

[0082] 2. Flexural strength test: After the resin is photocured, it is tested according to the standard of GB / T 9341-2000, and the compression rate is controlled at 0.5 mm / min. The specific test results are shown in the following table.

[0083] Table 2 Flexural strength

[0084]

[0085]

[0086] As can be seen from Table 1 and Table 2 above: Compared with Example 7, the volume resistivity and compressive properties of the insulating and voltage-resistant photocurable resins in Comparative Examples 1, 2, and 3 are inferior to those of Example 7, indicating that the modified nano-magnesium oxide used in Example 7 has the best modification effect on the resin matrix, and the obtained photocurable resin has excellent insulating and voltage-resistant properties.

[0087] Although the embodiments of the present invention have been shown and described, for those of ordinary skill in the art, it can be understood that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. An insulating voltage-resistant photocurable resin, characterized in that, It comprises the following raw materials in parts by weight: 40-50 parts of toluene-2,4-diisocyanate, 30-40 parts of polypropylene glycol, 10-15 parts of butanol, 20-30 parts of hydroxyethyl acrylate, 10-15 parts of diluent, 0.1-0.5 part of dibutyltin dilaurate, 0.5-1 part of hydroquinone, and 5-8 parts of modified nanoparticles.

2. The insulating and voltage-resistant photocurable resin according to claim 1, characterized in that The diluent is selected from dipentaerythritol hexaacrylate and dipropylene glycol diacrylate.

3. The insulating and voltage-resistant photocurable resin according to claim 1, characterized in that, The preparation method of the modified nanoparticles is as follows: S1. Mix an aqueous solution of 90 wt% sodium dodecylbenzenesulfonate and toluene to obtain a mixture. S2. Add nanoparticles to the mixture, stir at room temperature, then add azobisisobutyronitrile and methyl methacrylate and continue stirring, heat up and react. S3. After the reaction is completed, filter, wash, dry and grind to obtain the modified nanoparticles.

4. The insulating and voltage-resistant photocurable resin according to claim 3, wherein, In step S1, the mass ratio of the aqueous sodium dodecylbenzenesulfonate solution to toluene is 1:

1.

5. The insulating and voltage-resistant photocurable resin according to claim 3, characterized in that, In step S2, the nanoparticles are selected from nano magnesium oxide, nano silicon dioxide and nano mica powder.

6. The insulating voltage-resistant photocurable resin according to claim 3, characterized in that, In step S2, the material ratio of the nanoparticles to the mixture is 1:(20-25) g / mL; the material ratio of azobisisobutyronitrile to the mixture is 1:200 g / mL; the volume ratio of methyl methacrylate to the mixture is 1:(4-6) mL / mL.

7. The insulating and voltage-resistant photocurable resin according to claim 1, wherein, In step S2, stir at room temperature for 60-90 min, heat up to 60-65 °C and react for 8-10 h.

8. The preparation method of the insulating and voltage-resistant photocurable resin according to any one of claims 1-7, characterized in that, It comprises the following steps: (1) Uniformly mix toluene-2,4-diisocyanate, polypropylene glycol and dibutyltin dilaurate, react at 80-90 °C for 1-1.5 h to obtain a prepolymer. (2) Add hydroxyethyl acrylate, butanol and hydroquinone to the prepolymer, react at 40-50 °C for 5-6 h to obtain a blocked prepolymer. (3) Add a diluent and modified nanoparticles to the blocked prepolymer, ultrasonically disperse for 1-3 h to obtain an insulating and voltage-resistant photocurable resin.

Images