Preparation method of photocuring resin and application thereof

Abstract

The application discloses a preparation method of a photocuring resin and application thereof, and belongs to the technical field of photocuring resin. The photocuring resin is prepared by mixing organic silicon polyol, isocyanate and a second catalyst, and then performing a reaction to obtain a base resin; and the base resin, an end-capping agent and an optional polymerization inhibitor are mixed and then reacted to obtain the photocuring resin. The photocuring resin can be used as a UV material for protecting a battery shell, and the photocuring resin overcomes the defects of a blue film, such as softness, bubbles, poor temperature resistance, shortened battery life and fire accidents. The photocuring resin has good flame-retardant performance without adding a flame retardant, and has excellent flame-retardant performance, temperature resistance, flexibility and insulation performance, and can realize automatic production.

Description

Technical Field

[0001] This invention belongs to the field of UV material technology, and specifically relates to a method for preparing a photocurable resin and its application. Background Technology

[0002] In 2023, a total of 14.2 million new energy vehicles were delivered, representing an increase of over 35%. Among these, the installed capacity of power batteries reached 705.5 GWh. The increased demand for new energy vehicles has also brought certain safety hazards. According to fire data released by the emergency management department, over 3,000 fires involving new energy vehicles occurred throughout 2021, and the spontaneous combustion rate increased by 32% in the first quarter of 2023, averaging eight new energy vehicles experiencing fires (including spontaneous combustion) every day. Insulation, heat insulation, flame retardancy, and fire prevention of the "three electrics" (battery, motor, and electronic control system) of new energy vehicles are crucial aspects of their safety.

[0003] Currently, the insulation function of battery cells is achieved through "blue film" bonding. Its main drawbacks are: its softness makes it prone to surface damage, leading to leakage and potential fires during vehicle use; the tendency to generate air bubbles during bonding, affecting battery life; and the adhesive used in the bonding area, which can be susceptible to localized short-term high temperatures that cause film malfunctions. Patent CN 117229744 A provides a UV adhesive that combines high reliability (insulation, pressure resistance, water resistance, salt spray resistance, etc.) with high bonding strength and rapid curing; however, the coating solution in this patent lacks flame retardancy. Therefore, existing UV adhesives have significantly insufficient insulation pass rate, heat insulation, and flame retardant properties, and their bonding methods cannot be automated, failing to meet the rapidly growing demands of the new energy vehicle market.

[0004] Therefore, it is necessary to develop a photocurable resin with good temperature resistance, excellent flame retardant and insulating properties, its preparation method and its application. Summary of the Invention

[0005] The purpose of this invention is to provide a method for preparing a photocurable resin, which has excellent flame retardancy, temperature resistance, flexibility and insulation properties, and can better insulate and protect the battery cell.

[0006] Another objective of this invention is to provide applications of the aforementioned photocurable resin.

[0007] To achieve the above-mentioned objectives, the technical solution adopted by the present invention is as follows:

[0008] In a first aspect, the present invention provides a method for preparing a photocurable resin, comprising the following steps:

[0009] 1) Synthesis of organosilicon polyols:

[0010] Hydrogen-terminated polydimethylsiloxane, a compound containing both hydroxyl and (methyl)allyl groups, and a first catalyst are mixed and heated to react, yielding a dihydroxy-terminated compound. The dihydroxy-terminated compound, a phosphoric acid-containing compound, a solvent, and an acid-binding agent are mixed and heated to react, and the product is washed and dried to obtain an organosilicon polyol.

[0011] 2) Synthesis of photocurable resin: The organosilicon polyol, isocyanate and second catalyst prepared in step 1) are mixed and reacted to obtain the matrix resin; the prepared matrix resin, end-capping agent and optional polymerization inhibitor are mixed and reacted to obtain the photocurable resin.

[0012] Preferably, the hydrogen content of the hydrogen-capped polydimethylsiloxane is 0.05% to 0.3%, more preferably 0.1% to 0.2%; wherein, the hydrogen content is the mass content of hydrogen in the hydrogen-capped polydimethylsiloxane.

[0013] Preferably, the compound containing both hydroxyl and (methyl)allyl groups is selected from one or more of eugenol, (methyl)allyl ethylene glycol, methyl allyl alcohol, 4-hydroxybutyl (methyl) vinyl ether and their homologues, and more preferably one or more of eugenol and allyl ethylene glycol.

[0014] Preferably, the first catalyst is selected from platinum catalysts, which can be homogeneous or heterogeneous catalysts. Homogeneous catalysts include, but are not limited to, Speier catalysts and Castells catalysts; heterogeneous catalysts include catalysts formed by adsorbing platinum metal onto inorganic particles such as carbon black or alumina; more preferably, they are Castells catalysts.

[0015] Preferably, the phosphorus-containing compound is selected from one or more of phenylphosphine dichloride, 4-nitrophenyl dichloride, 2-chlorophenyl dichloride, p-chlorophenyl dichloride, and m-chlorophenyl dichloride, and more preferably one or more of phenylphosphine dichloride, p-chlorophenyl dichloride, m-chlorophenyl dichloride, and 4-nitrophenyl dichloride.

[0016] Preferably, the molar ratio of the active hydrogen in the hydrogen-terminated polydimethylsiloxane to the (methyl)allyl group in the compound containing both hydroxyl and (methyl)allyl groups is 1:1 to 1:1.1, more preferably 1:1.02 to 1:1.06. The active hydrogen in the hydrogen-terminated polydimethylsiloxane refers to the hydrogen in the Si-H group, which can react with the C=C double bond under platinum catalysis.

[0017] Preferably, the amount of platinum in the first catalyst is 3 to 15 ppm of the total mass of the hydrogen-terminated polydimethylsiloxane and the compound containing both hydroxyl and (methyl)allyl groups, more preferably 5 to 10 ppm.

[0018] Preferably, the molar ratio of the phosphoryl chloride compound to the compound containing both hydroxyl and (methyl)allyl groups is 0.95:4 to 1.1:4, more preferably 1.02:4 to 1.06:4.

[0019] Preferably, the acid-binding agent is pyridine, triethylamine, N,N-diisopropylethylamine (DIEA), sodium carbonate, potassium carbonate, or sodium acetate, more preferably one or more of triethylamine and potassium carbonate, and more preferably one or more of triethylamine, potassium carbonate, and sodium carbonate.

[0020] Preferably, the molar ratio of the acid-binding agent to reactive chlorine is 1:0.9 to 1:1, more preferably 1:0.95 to 1:0.98.

[0021] Preferably, the reaction temperature of the hydrogen-terminated polydimethylsiloxane and the compound containing both hydroxyl and (methyl)allyl groups is 75–85°C.

[0022] Preferably, the reaction temperature of the dihydroxy-terminated compound with the phosphoric acid chloride compound is 20-30°C. Preferably, the molar ratio of the organosilicon polyol to the isocyanate is 1.0:1.9-1.0:2.15, more preferably 1.0:2.0-1.0:2.1.

[0023] Preferably, the amount of the second catalyst added is 0.01 to 0.1% of the total mass of the raw materials, more preferably 0.02 to 0.06%;

[0024] Preferably, the amount of the polymerization inhibitor added is 0 to 0.10% of the total mass of the raw materials, more preferably 0.03 to 0.08%;

[0025] Preferably, the capping agent is a hydroxy acrylate, and more preferably one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate.

[0026] Preferably, the molar ratio of isocyanate to capping agent is 1:1 to 1:1.05, more preferably 1:1.01 to 1:1.03.

[0027] In this invention, the second catalyst is an organotin catalyst, preferably any one or more of dibutyltin dilaurate, dioctyltin dilaurate, stannous octoate, di(dodecyl sulfide)dibutyltin, and dibutyltin diacetate, and preferably any one or more of dibutyltin dilaurate, stannous octoate, and dioctyltin dilaurate.

[0028] In this invention, the polymerization inhibitor is a phenolic compound, preferably selected from any one or more of hydroquinone, 4-methoxyphenol, 2,6-di-tert-butyl-p-cresol, 2,5-di-tert-butyl-p-quinone, and 2-tert-butyl-p-quinone, and more preferably from any one or more of hydroquinone and 4-methoxyphenol.

[0029] Secondly, the present invention provides an application of a photocurable resin prepared by the above method, wherein the photocurable resin can be used in the field of batteries, especially for battery casing protection, and can be used to prepare UV materials for use as battery casing protection.

[0030] A UV material used for battery casing protection comprises the following raw materials in parts by weight:

[0031] UV-curable resin: 30-70 parts;

[0032] Reactive diluent: 30-70 parts;

[0033] Photoinitiator: 0.5–5 parts;

[0034] Additives: 0.5 to 3 parts.

[0035] The photocurable resin is the photocurable resin described in this invention.

[0036] The reactive diluent is an acrylate reactive diluent, preferably one or more of the following: tripropylene glycol diacrylate, hexanediol diacrylate, bisphenol A diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, polyethylene glycol diacrylate, hydroxyethyl methacrylate, cyclotrimethylolpropane methyl acetal acrylate, isobornyl methacrylate, tetrahydrofuran acrylate, neopentyl glycol acrylate, tri(2-hydroxyethyl)isocyanurate triacrylate, and pentaerythritol triacrylate.

[0037] The photoinitiator is one or more of benzophenone and its derivatives, thioxanthones, anthraquinones, and arylalkyl ketones, preferably one or more of benzoin dimethyl ether, benzophenone, 1-hydroxycyclohexylbenzophenone, 2-methyl-1-(4-methylmercaptophenyl)-2-morpholino-1-propanone, 2-hydroxy-2-methyl-phenylpropanone-1, 2,4,6,-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6,-trimethylbenzoyl)phenylphosphine oxide, and 2,4-diethylthioxanthone.

[0038] The additive is one or more of the following: leveling agent, defoamer, or wetting and dispersing agent.

[0039] The photocurable resin described in this invention can be used in the field of new energy vehicles, and is especially suitable for the protection of battery casings in new energy vehicles.

[0040] Compared with the prior art, the beneficial effects of the technical solution of the present invention are as follows:

[0041] The photocurable resin of this invention has self-flame retardant properties. UV materials for the protective casing of new energy batteries prepared using this photocurable resin do not require the addition of flame retardants, thus enabling the coating to have excellent flame-retardant properties. Simultaneously, the organosilicon structure in this invention gives the coating excellent aging resistance, allowing it to maintain good performance under harsh conditions such as thermal shock, high temperature, and high humidity. Furthermore, the organosilicon structure described in this invention has excellent flexibility, making the coating less prone to damage from external impacts that could lead to battery combustion. Compared to traditional blue films, in addition to its excellent protective performance, this material can also achieve automated continuous production, improving production efficiency and reducing production costs. Detailed Implementation

[0042] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. The specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0043] The main equipment used in the various embodiments and comparative examples of this invention is as follows:

[0044] Stirred reaction equipment: RW20 digital, IKA;

[0045] Mixing equipment: DAC600.2 VAC-LR, SpeedMixer;

[0046] UV Curing Lamp: UV-LED-2, Guangdong Gaoqiong Optoelectronic Equipment Co., Ltd.;

[0047] Multi-purpose tensile testing machine: GT-AI-3000, GOTECH;

[0048] Viscometer: HB, BROOKFIELD;

[0049] Adhesion tester: Airipu Instruments Co., Ltd.

[0050] Impact testing equipment: Shenzhen Wright Instrument Equipment Co., Ltd.

[0051] The main raw materials used in the various embodiments and comparative examples of this invention are sourced as follows. Unless otherwise specified, other raw materials and reagents were obtained through commercially available channels:

[0052] Hydrogen-terminated polydimethylsiloxane: RH-H6 (0.11% hydrogen content), RH-H518 (0.18% hydrogen content), Ningbo Runhe Advanced Materials Technology Co., Ltd.

[0053] Polyether polyol: PTMEG3000, BASF

[0054] Flame-retardant polyol: PF-2014, Zibo Ruinuo New Material Co., Ltd.

[0055] Isocyanate: IPDI, Wanhua Chemical

[0056] Catalysts: dibutyltin dilaurate, dioctyltin dilaurate, stannous octoate, Aladdin reagent;

[0057] Polymerization inhibitors: 4-methoxyphenol, hydroquinone, Aladdin reagent;

[0058] Photoinitiator: TPO, 651, Qiaorun New Materials.

[0059] Reactive diluents: THEICTA, THFA, Qiaorun New Materials

[0060] End-capping agents: Hydroxyethyl acrylate (HEA), Hydroxypropyl acrylate (HPA), Hydroxyethyl methacrylate (HEMA), Hydroxypropyl methacrylate (HPMA), Qiaorun New Materials

[0061] Leveling agent: BYK3505, BYK Chemicals

[0062] Defoamer: BYK1788, BYK Chemicals

[0063] Castel platinum catalyst (platinum content 5000ppm): Betterley New Materials Co., Ltd.

[0064] Hydroxyl-terminated silicone oil with dihydroxyl groups: 107 silicone oil (molecular weight 4000), Shenzhen Jipeng Silicone & Fluorine Materials Co., Ltd.

[0065] Others: Eugenol, Allyl Ethylene Glycol, Methallyl Alcohol, Benzophosphonodichloro, 4-Nitrophenyl Dichlorophosphine, 2-Chlorophenyl Dichlorophosphine, p-Chlorophenyl Dichlorophosphate, m-Chlorophenyl Dichlorophosphate, Triethylamine, Potassium Carbonate, Sodium Carbonate, Acetonitrile, Ethyl Acetate, Aladdin Reagent

[0066] Example 1

[0067] The steps for preparing the self-flame-retardant photocurable resin PUA-1 are as follows:

[0068] 1) In a three-necked flask, add 910g of RH-H6 (0.11% hydrogen content, molecular weight 1818, 0.5mol) and 167g of eugenol (1mol), mix and stir until homogeneous. Add 1.2g (5.57ppm) of platinum catalyst, heat to 75℃, and react for 3 hours to obtain a dihydroxy-terminated compound. Add 48.8g (0.25mol) of phenylphosphonic dichloride and stir until homogeneous. Add a mixed solvent of triethylamine (55.3g) / acetonitrile (1200ml), and react at 25℃ for 5 hours. After the reaction, wash the product with ethyl acetate and then dry under vacuum at 60℃ for 8 hours to obtain a self-flame-retardant organosilicon polyol FA1 (molecular weight 4400).

[0069] 2) In a three-necked flask, add 220g of organosilicon polyol FA1 (0.05mol) and 22.7g of IPDI (0.102mol), mix and stir until homogeneous. Add 0.12g of dibutyltin dilaurate (0.05%), heat to 70℃, and react for 2 hours. After the reaction is complete, add 0.12g of 4-methoxyphenol (0.05%) and 12g of HEA (0.103mol), start stirring, heat to 75℃, and react for 2 hours to obtain self-flame-retardant photocurable resin PUA-1.

[0070] Example 2

[0071] The steps for preparing the self-flame-retardant polyurethane acrylate resin PUA-2 are as follows:

[0072] 1) In a three-necked flask, add 556g of RH-H518 (0.18% hydrogen content, molecular weight 1111, 0.5mol) and 106g of allyl ethylene glycol (1.04mol), mix and stir until homogeneous. Add 1.2g (9ppm) of platinum catalyst, heat to 85℃, and react for 3 hours to obtain a dihydroxy-terminated compound. Add 69.2g (0.27mol) of 4-nitrobenzene phosphorus dichloride, mix and stir until homogeneous. Add a mixed solvent of potassium carbonate 77.3g / acetonitrile (1200ml), and react at 20℃ for 5 hours. After the reaction, wash the product with ethyl acetate, and then dry under vacuum at 60℃ for 8 hours to obtain a self-flame-retardant organosilicon polyol FA2 (molecular weight 2800).

[0073] 2) In a three-necked flask, add 140g of organosilicon polyol FA2 (0.05mol) and 22.92g of IPDI (0.103mol), mix and stir until homogeneous. Add 0.1g of stannous octoate (0.06%), heat to 75℃, and react for 2 hours. After the reaction is complete, add 0.1g of 4-methoxyphenol (0.06%) and 13.8g of HPA (0.106mol), start stirring, heat to 75℃, and react for 2 hours to obtain self-flame-retardant photocurable resin PUA-2.

[0074] Example 3

[0075] The steps for preparing the self-flame-retardant polyurethane acrylate resin PUA-3 are as follows:

[0076] 1) In a three-necked flask, add 556g of RH-H518 (0.18% hydrogen content, molecular weight 1111, 0.5mol) and 72g of allyl methyl alcohol (1.06mol), mix and stir until homogeneous. Add 0.9g (7ppm) of platinum catalyst, heat to 75℃, and react for 3 hours to obtain a dihydroxy-terminated compound. Add 68.6g (0.28mol) of 2-chlorophenyldichlorophosphine and stir until homogeneous. Add a mixed solvent of 60.6g sodium carbonate / acetonitrile (1200ml), and react at 25℃ for 5 hours. After the reaction, wash the product with ethyl acetate and then dry under vacuum at 60℃ for 8 hours to obtain a self-flame-retardant organosilicon polyol FA3 (molecular weight 2800).

[0077] 2) In a three-necked flask, add 140g of organosilicon polyol FA3 (0.05mol) and 23.14g of IPDI (0.104mol), mix and stir until homogeneous. Add 0.05g of dioctyltin dilaurate (0.03%), heat to 75℃, and react for 2 hours. After the reaction is complete, add 0.05g of 4-methoxyphenol (0.03%) and 15.4g of HPMA (0.107mol), start stirring, heat to 75℃, and react for 2 hours to obtain self-flame-retardant photocurable resin PUA-3.

[0078] Example 4

[0079] The steps for preparing the self-flame-retardant polyurethane acrylate resin PUA-4 are as follows:

[0080] 1) In a three-necked flask, add 556g of RH-H518 (0.18% hydrogen content, molecular weight 1111, 0.5mol) and 76g of methyl allyl alcohol (1.06mol), mix and stir until homogeneous. Add 0.9g (7ppm) of platinum catalyst, heat to 85℃, and react for 3 hours to obtain a dihydroxy-terminated compound. Add 34.3g each of p-chlorophenyl dichlorophosphate and p-chlorophenyl dichlorophosphate, mix and stir until homogeneous. Add a mixed solvent of 57.57g triethylamine / 1200ml acetonitrile, and react at 25℃ for 5 hours. After the reaction, wash the product with ethyl acetate and then dry under vacuum at 60℃ for 8 hours to obtain a self-flame-retardant organosilicon polyol FA4 (molecular weight 2800).

[0081] 2) In a three-necked flask, add 140g of organosilicon polyol FA4 (0.05mol) and 23.14g of IPDI (0.104mol), mix and stir until homogeneous. Add 0.05g of dioctyltin dilaurate (0.03%), heat to 75℃, and react for 2 hours. After the reaction is complete, add 0.05g of hydroquinone (0.03%) and 13.9g of HEMA (0.107mol), start stirring, heat to 80℃, and react for 2 hours to obtain the self-flame-retardant photocurable resin PUA-4.

[0082] Examples 5-8

[0083] According to the raw material ratio in Table 1 below, the self-flame-retardant UV-curable resins prepared in Examples 1 to 4 are mixed and stirred evenly with additives, photoinitiators, and reactive diluents in a sealed container not exceeding 40°C to obtain self-flame-retardant UV materials.

[0084] Comparative Example 1

[0085] The steps for preparing the photocurable resin PUA-5 are as follows:

[0086] 1) Add 2000g of 107 silicone oil (0.5mol) and 227g of IPDI (1.02mol) to a three-necked flask, mix and stir until homogeneous, then add 1.1g of dibutyltin dilaurate (0.05%), heat to 70℃, and react for 2 hours. After the reaction is complete, add 1.1g of 4-methoxyphenol (0.05%) and 116g of HEA (1.03mol), start stirring, heat to 75℃, and react for 2 hours to obtain the photocurable resin PUA-5.

[0087] Comparative Example 2

[0088] The steps for preparing polyurethane acrylate resin PUA-6 are as follows:

[0089] 1) Add 1500g PTMEG3000 (0.5mol) and 231g IPDI (1.04mol) to a three-necked flask, mix and stir until homogeneous, then add 0.52g (0.03%) of dibutyltin dilaurate, heat to 75℃, and react for 2 hours. After the reaction is complete, add 0.52g (0.03%) of 4-methoxyphenol and 139g HEMA (1.07mol), start stirring, heat to 80℃, and react for 2 hours to obtain the photocurable resin PUA-6.

[0090] Comparative Example 3

[0091] The steps for preparing polyurethane acrylate resin PUA-7 are as follows:

[0092] 1) Add 300g of PF-2014 (0.5mol) and 231g of IPDI (1.04mol) to a three-necked flask, mix and stir until homogeneous. Add 0.52g of dioctyltin dilaurate (0.03%), heat to 75℃, and react for 2 hours. After the reaction is complete, add 0.52g of 4-methoxyphenol (0.03%) and 139g of HEMA (1.07mol), start stirring, heat to 80℃, and react for 2 hours to obtain the photocurable resin PUA-7.

[0093] Comparative Examples 4-7

[0094] According to the raw material ratio in Table 1 below, the photocurable resins prepared in Comparative Examples 1 to 3 were mixed and stirred evenly with additives, photoinitiators, and reactive diluents in a sealed container not exceeding 40°C to obtain UV materials without self-flame retardancy.

[0095] The main testing and characterization methods used in the various embodiments and comparative examples of this invention are as follows, and the results are shown in Table 1:

[0096] Adhesion: Cross-cut adhesion test, test standard GB / T 9286-2021;

[0097] Flame retardancy: UL94

[0098] Bond strength: GB / T33334-016, substrate PC, aluminum 6061;

[0099] Impact strength: GB / T 1732-2020

[0100] Hardness / Shore A: GB / T 39693.7-2022.

[0101] Table 1. Formulations and test results of Examples 5-8 and Comparative Examples 4-7 (the amount of each raw material added is in parts by mass):

[0102]

[0103]

[0104]

[0105] Compared with Comparative Example 4, Example 6, Example 7, and Example 8, Example 5 and Comparative Example 7 all showed good adhesion, bonding strength, and impact resistance, indicating that they had good mechanical properties. In addition, the flame retardant properties of the examples were all better than those of the comparative examples, indicating that the examples had better self-flame retardancy, and that the synthesized flame-retardant polyol was beneficial to improving the flame retardant properties of UV materials.

[0106] After thermal shock aging, the bonding strength of the embodiments changed less than that of the comparative examples, and the adhesion of the embodiments did not change. Comparative examples 4 and 7 contained a large amount of organosilicon components, and their adhesion was grade 0, which did not change. Comparative examples 5 and 6 contained no or a small amount of organosilicon components, and their adhesion became grade 1, indicating that organosilicon components are beneficial to improving the coating's resistance to thermal shock. After thermal shock aging, the impact strength of the embodiments did not change, while the impact strength of the comparative examples decreased, indicating that the embodiments have good resistance to thermal shock.

[0107] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a photocurable resin, characterized in that, Includes the following steps: 1) Synthesis of organosilicon polyols: Hydrogen-terminated polydimethylsiloxane, a compound containing both hydroxyl and (methyl)allyl groups, and a first catalyst are mixed and heated to react, yielding a dihydroxy-terminated compound; the dihydroxy-terminated compound, a phosphoric acid-containing compound, a solvent, and an acid-binding agent are mixed and heated to react, and the product is washed and dried to obtain an organosilicon polyol. 2) Synthesis of photocurable resin: The organosilicon polyol, isocyanate and second catalyst prepared in step 1) are mixed and reacted to obtain the matrix resin; the prepared matrix resin, end-capping agent and optional polymerization inhibitor are mixed and reacted to obtain the photocurable resin. The hydrogen content of the hydrogen-capped polydimethylsiloxane is 0.05%~0.3%, and the hydrogen content is the mass content of hydrogen in the hydrogen-capped polydimethylsiloxane. The molar ratio of the active hydrogen in the hydrogen-capped polydimethylsiloxane to the (methyl)allyl group in the compound containing both hydroxyl and (methyl)allyl groups is 1:1 to 1:1.

1. The molar ratio of the phosphoryl chloride compound to the compound containing both hydroxyl and (methyl)allyl groups is 0.95:4 to 1.1:

4. The molar ratio of the acid-binding agent to reactive chlorine is 1:0.9 to 1:1; The molar ratio of the organosilicon polyol to the isocyanate is 1.0:1.9 to 1.0:2.15; The molar ratio of isocyanate to capping agent is 1:1 to 1:1.05; The capping agent is a hydroxy acrylate.

2. The preparation method according to claim 1, characterized in that, The hydrogen content of the hydrogen-capped polydimethylsiloxane is 0.1% to 0.2%; wherein, the hydrogen content is the mass content of hydrogen in the hydrogen-capped polydimethylsiloxane.

3. The preparation method according to claim 1, characterized in that, The compound containing both hydroxyl and (methyl)allyl groups is selected from one or more of eugenol, (methyl)allyl glycol, methyl allyl alcohol, and 4-hydroxybutyl (methyl) vinyl ether.

4. The preparation method according to claim 3, characterized in that, The compound containing both hydroxyl and (methyl)allyl groups is selected from one or more of eugenol and allyl glycol.

5. The preparation method according to claim 1, characterized in that, The first catalyst is selected from platinum catalysts.

6. The preparation method according to claim 5, characterized in that, The first catalyst is a homogeneous catalyst or a heterogeneous catalyst. Homogeneous catalysts include, but are not limited to, Speier catalysts and Castells catalysts; heterogeneous catalysts include catalysts formed by adsorbing platinum metal onto carbon black or alumina.

7. The preparation method according to claim 6, characterized in that, The first catalyst is a cassiterite catalyst.

8. The preparation method according to claim 1, characterized in that, The phosphorus-containing chloride compound is selected from one or more of phenylphosphine dichloride, 4-nitrophenyl dichloride, 2-chlorophenyl dichlorophosphine, p-chlorophenyl dichlorophosphate, and m-chlorophenyl dichlorophosphate.

9. The preparation method according to claim 8, characterized in that, The phosphorus-containing chloride compound is selected from one or more of phenylphosphodichloro, p-chlorophenyl dichlorophosphate, m-chlorophenyl dichlorophosphate, and 4-nitrophenyl dichlorophosphate.

10. The preparation method according to claim 1, characterized in that, The molar ratio of the active hydrogen in the hydrogen-capped polydimethylsiloxane to the (methyl)allyl group in the compound containing both hydroxyl and (methyl)allyl groups is 1:1.02 to 1:1.

06.

11. The preparation method according to claim 1, characterized in that, The amount of platinum in the first catalyst is 3 to 15 ppm of the total mass of the hydrogen-terminated polydimethylsiloxane and the compound containing both hydroxyl and (methyl)allyl groups.

12. The preparation method according to claim 11, characterized in that, The amount of platinum in the first catalyst is 5 to 10 ppm of the total mass of the hydrogen-terminated polydimethylsiloxane and the compound containing both hydroxyl and (methyl)allyl groups.

13. The preparation method according to claim 1, characterized in that, The molar ratio of the phosphoryl chloride compound to the compound containing both hydroxyl and (methyl)allyl groups is 1.02:4 to 1.06:

4.

14. The preparation method according to claim 1, characterized in that, The acid-binding agent is pyridine, triethylamine, N,N-diisopropylethylamine, sodium carbonate, potassium carbonate, or sodium acetate.

15. The preparation method according to claim 14, characterized in that, The acid-binding agent is one or more of triethylamine, potassium carbonate, and sodium carbonate.

16. The preparation method according to claim 1, characterized in that, The molar ratio of the acid-binding agent to the reactive chlorine is 1:0.95 to 1:0.

98.

17. The preparation method according to claim 1, characterized in that, The reaction temperature for hydrogen-terminated polydimethylsiloxanes and compounds containing both hydroxyl and (methyl)allyl groups is 75-85°C.

18. The preparation method according to claim 1, characterized in that, The reaction temperature of the dihydroxy-terminated compound with the phosphoric acid chloride compound is 20~30℃.

19. The preparation method according to claim 1, characterized in that, The molar ratio of the organosilicon polyol to the isocyanate is 1.0:2.0 to 1.0:2.

1.

20. The preparation method according to claim 1, characterized in that, The amount of the second catalyst added is 0.01 to 0.1% of the total mass of the raw materials.

21. The preparation method according to claim 20, characterized in that, The amount of the second catalyst added is 0.02~0.06% of the total mass of the raw materials.

22. The preparation method according to claim 1, characterized in that, The amount of the polymerization inhibitor added is 0 to 0.10% of the total mass of the raw materials.

23. The preparation method according to claim 22, characterized in that, The amount of the polymerization inhibitor added is 0.03~0.08% of the total mass of the raw materials.

24. The preparation method according to claim 1, characterized in that, The capping agent is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, and hydroxypropyl methacrylate.

25. The preparation method according to claim 1, characterized in that, The molar ratio of isocyanate to capping agent is 1:1.01 to 1:1.

03.

26. The preparation method according to claim 1, characterized in that, The second catalyst is an organotin catalyst.

27. The preparation method according to claim 26, characterized in that, The second catalyst is any one or more of dibutyltin dilaurate, dioctyltin dilaurate, stannous octoate, di(dodecyl sulfide)dibutyltin, and dibutyltin diacetate.

28. The preparation method according to claim 27, characterized in that, The second catalyst is any one or more of dibutyltin dilaurate, stannous octoate, and dioctyltin dilaurate.

29. The preparation method according to claim 1, characterized in that, The polymerization inhibitor is a phenolic compound.

30. The preparation method according to claim 29, characterized in that, The polymerization inhibitor is selected from any one or more of hydroquinone, 4-methoxyphenol, 2,6-di-tert-butyl-p-cresol, 2,5-di-tert-butylhydroquinone, and 2-tert-butylhydroquinone.

31. The preparation method according to claim 30, characterized in that, The polymerization inhibitor is any one or more of hydroquinone and 4-methoxyphenol.

32. An application of a photocurable resin prepared by the preparation method according to any one of claims 1-31, wherein the photocurable resin is used in the field of batteries.

33. The application of the photocurable resin according to claim 32, wherein the photocurable resin is suitable for battery casing protection.

34. The application of the photocurable resin according to claim 33, wherein the photocurable resin is used to prepare a UV material for use as a battery casing protector.

35. A UV material used for battery casing protection, comprising the following raw materials in parts by weight: UV-curable resin: 30-70 parts; Reactive diluent: 30-70 parts; Photoinitiator: 0.5~5 parts; Additives: 0.5-3 parts; The photocurable resin is a photocurable resin prepared by the preparation method according to any one of claims 1-31.

36. The UV material according to claim 35, characterized in that, The reactive diluent is an acrylate reactive diluent. And / or, the photoinitiator is one or more of the following photoinitiators: benzophenone, thioxanthone, anthraquinone, and arylalkyl ketone compounds; And / or, the additive is one or more of a leveling agent, defoamer, or wetting and dispersing agent.

37. The UV material according to claim 36, characterized in that, The active diluent is one or more of the following: tripropylene glycol diacrylate, hexanediol diacrylate, bisphenol A diacrylate, tetraethylene glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, polyethylene glycol diacrylate, hydroxyethyl methacrylate, cyclotrimethylolpropane methyl acetal acrylate, isobornyl methacrylate, tetrahydrofuran acrylate, neopentyl glycol diacrylate, and tri(2-hydroxyethyl)isocyanurate triacrylate. And / or, the photoinitiator is one or more of the following: benzoin dimethyl ether, benzophenone, 1-hydroxycyclohexylbenzophenone, 2-methyl-1-(4-methylmercaptophenyl)-2-morpholino-1-propanone, 2-hydroxy-2-methyl-phenylpropanone-1, 2,4,6,-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6,-trimethylbenzoyl)phenylphosphine oxide, and 2,4-diethylthioxanthrone.

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