Efficient and green cross-linking agent BIPB and preparation method thereof

Abstract

The invention belongs to the technical field of cross-linking agent synthesis, and particularly relates to an efficient and green cross-linking agent BIPB and a preparation method thereof. The efficient and green cross-linking agent BIPB is prepared from the following raw materials: tert-butyl hydroperoxide, 2-hydroxyisopropyl benzene, a perchloric acid solution, epoxy acrylate, reinforced ethylene glycol vinyl ether, 2-hydroxy-2-methyl-1-phenylacetone, a surfactant and petroleum ether. A photocuring system is constructed in the preparation process of a cross-linking agent BIPB, firstly, acrylate groups are grafted on the surface of the cross-linking agent BIPB to achieve efficient absorption of light energy, meanwhile, reinforced ethylene glycol vinyl ether is introduced, in the cross-linking process, dispersion of the cross-linking agent BIPB is improved, aggregation is avoided, and in order to ensure that the photocuring system can achieve reaction, the photocuring system is prepared. The prepared BIPB crystal is subjected to surface treatment through a surfactant, and then 2-hydroxy-2-methyl-1-phenylacetone is adsorbed on the surface of the BIPB crystal, so that efficient and green crosslinking is realized.

Description

Technical Field

[0001] The present invention belongs to the technical field of cross-linking agent synthesis, and specifically relates to an efficient and green cross-linking agent BIPB and a preparation method thereof. Background Art

[0002] In the field of modern materials science and industrial production, cross-linking technology plays a vital role. As the key substance to initiate and promote cross-linking reactions, the performance of cross-linking agents directly affects the quality and application effect of the final product.

[0003] BIPB is a green cross-linking agent. During its synthesis and use, it does not produce harmful gases like organic halides. The decomposition products are relatively simple and non-toxic, and will not cause persistent pollution to the environment. Although the cross-linking agent BIPB has many advantages, it requires external heat energy to decompose during actual use. The decomposition process is long, and there may be problems such as uneven curing dispersion, unstable curing performance, and severe aging after curing.

[0004] In view of the technical problems of the existing cross-linker BIPB, there is an urgent need to develop an efficient and green cross-linker BIPB to meet industrial needs. Summary of the Invention

[0005] In response to the defects of the prior art, the present invention discloses an efficient and green crosslinker BIPB. A photocuring system is constructed during the entire crosslinker preparation process. In order to ensure that the photocuring system can achieve an orderly reaction, the prepared BIPB crystals are surface activated by a surfactant to form an adsorption film. Then, the photoinitiator 2-hydroxy-2-methyl-1-phenylpropanone is adsorbed on the surface of the BIPB crystals, and acrylate groups are grafted on the surface of the crosslinker BIPB to achieve efficient absorption of light energy and reduce the activation energy of the entire crosslinking process. At the same time, reinforcing ethylene glycol vinyl ether is introduced to improve the dispersion of the crosslinker BIPB during the entire crosslinking process, avoid the aggregation of the crosslinker BIPB, and affect the crosslinking effect. Efficient and green crosslinking is achieved by replacing the external heat energy of the prior art with light energy.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is a highly efficient and green crosslinking agent BIPB, which includes the following raw materials: tert-butyl hydroperoxide, 2-hydroxyisopropylbenzene, perchloric acid solution, epoxy acrylate, reinforced ethylene glycol vinyl ether, 2-hydroxy-2-methyl-1-phenylacetone, surfactant and petroleum ether;

[0007] Furthermore, the preparation method of the reinforced ethylene glycol vinyl ether comprises the following steps:

[0008] (1) Weigh ethylene glycol vinyl ether, aminoformamide, phosphorus pentachloride, dichloromethane, tetrahydrofuran, and triethylamine in the following proportions: 1.5-3 ml: 1.2-2.5 g: 3.5-6 g: 13 ml: 5-8 ml: 2.5-4.5 ml;

[0009] (2) adding the carbamamide weighed in step (1) to dichloromethane, stirring for 30 min at a power of 0.5 kW to obtain a uniform organic solution I, slowly adding the phosphorus pentachloride weighed in step (1) to the uniform organic solution I, stirring at a power of 0.5 kW, controlling the temperature at 2-6°C, and reacting for 2 h to obtain a carbamoyl chloride reaction solution;

[0010] (3) distilling the carbamoyl chloride reaction solution obtained in step (2) under normal pressure at a distillation temperature of 45° C. for a distillation time of 0.5-1.5 h to obtain carbamoyl chloride;

[0011] (4) Add the carbamoyl chloride obtained in step (3) to tetrahydrofuran, stir at a power of 0.5 kW for 30 min to obtain a uniform organic liquid II, then slowly dropwise add ethylene glycol vinyl ether and triethylamine to the uniform organic liquid II, stir under an argon flow rate of 50 ml / min, control the temperature at -10-0°C, react for 4 h, and naturally cool to room temperature to obtain a fortified ethylene glycol vinyl ether reaction solution;

[0012] (5) The enhanced ethylene glycol vinyl ether reaction solution obtained in step (4) is distilled at a pressure of 4-8 kPa, a distillation temperature of 70° C., and a distillation time of 1-2 h to obtain enhanced ethylene glycol vinyl ether.

[0013] The present invention also provides a method for preparing an efficient and green crosslinking agent BIPB, comprising the following steps:

[0014] Step 1: Weigh tert-butyl hydroperoxide, 2-hydroxyisopropylbenzene, perchloric acid solution, epoxy acrylate, fortified ethylene glycol vinyl ether, and petroleum ether in the ratio of 3-5 ml: 1.2-2.2 ml: 0.8-1.4 ml: 1-1.5 ml: 0.6-1.2 ml: 15 ml;

[0015] Step 2: Weigh tert-butyl hydroperoxide and 2-hydroxyisopropylbenzene in step 1 and add them to petroleum ether in sequence, stir and mix under a power of 0.5 kW to obtain a pre-reaction liquid, slowly dropwise add the perchloric acid solution measured in step 1 to the pre-reaction liquid, wherein the concentration of the perchloric acid solution is 70%, stir and raise the temperature to 40-55° C., react for 1-1.5 hours, then add epoxy acrylate, continue to react for 3-4 hours, then add fortified ethylene glycol vinyl ether, react for another 2 hours, and then cool to room temperature to obtain a crude reaction liquid;

[0016] Step 3: adding ice to the crude reaction solution, wherein the ratio of the crude reaction solution to ice is 1 ml: 1.5-2.5 g, stirring at a power of 0.5 kW for 30 min, and separating to obtain an organic phase of the crude reaction solution;

[0017] Step 4: Add sodium carbonate solution to the organic phase of the crude reaction solution obtained in step 3 to adjust the pH to neutral to obtain a neutral organic phase, and continue to add sodium chloride solution to the neutral organic phase, wherein the ratio of the neutral organic phase to the sodium chloride solution is 1 ml:0.8-1.3 ml, and stir at a power of 0.5 kW for 1 h, perform separation, and obtain a BIPB crude phase;

[0018] Step 5: Add anhydrous sodium sulfate to the BIPB crude phase obtained in step 4, wherein the ratio of BIPB crude phase to anhydrous sodium sulfate is 1 ml: 0.3-0.7 g, stir at a power of 0.5 kW for 1 hour, and filter to obtain the BIPB organic phase;

[0019] Step 6: The BIPB organic phase obtained in step 5 is subjected to vacuum distillation at a pressure of 5-15 kPa, a temperature of 40-60° C., and a distillation time of 1.5-3 h to obtain concentrated BIPB;

[0020] Step 7: The concentrated BIPB obtained in step 6 is subjected to low-temperature treatment at a temperature of -30 to -10°C, and filtered to obtain BIPB crystals;

[0021] Step 8: Dissolve the BIPB crystals obtained in anhydrous ethanol and stir evenly, weigh a surfactant and add it to stir to obtain a BIPB active agent, weigh 2-hydroxy-2-methyl-1-phenylpropanone and add it to the BIPB active agent, wherein the ratio of BIPB crystals, 2-hydroxy-2-methyl-1-phenylpropanone, surfactant and anhydrous ethanol is 2-4g:0.3-0.5ml:0.5-1.2g:10ml, perform ultrasonic treatment at a power of 20-40kHz for 30min, and oscillate at a frequency of 200-400bpm for 30min to obtain a highly efficient and green cross-linking agent BIPB precursor;

[0022] Step 9: The highly efficient and green crosslinking agent BIPB precursor obtained in step 8 is subjected to reduced pressure distillation at a pressure of 2-6 kPa and room temperature, and then dried at a drying temperature of 55° C. and a drying time of 24 h to obtain a highly efficient and green crosslinking agent BIPB.

[0023] The beneficial effects achieved by the present invention are as follows:

[0024] The highly efficient and green crosslinking agent BIPB prepared by the present invention introduces a photosensitized acrylate material for the first time. When exposed to light under the action of a photoinitiator, the photosensitizer absorbs photon energy and transitions from a ground state to an excited state, thereby reducing the activation energy of the entire reaction. The photosensitizer in the excited state breaks bonds and generates free radicals. After the addition of reinforced ethylene glycol vinyl ether, the crosslinking agent BIPB and the acrylate material can be dispersed more quickly and evenly between the rubber molecular chains, so that when a crosslinking reaction is subsequently initiated by light, it can proceed evenly in all parts of the rubber, which is conducive to forming a crosslinked network structure with consistent overall performance.

[0025] The efficient and green crosslinking agent BIPB prepared by the present invention, the synergistic effect of the photosensitized acrylate material and the reinforced ethylene glycol vinyl ether helps to form a more uniform and dense crosslinked network structure. During the photocuring process, the uniformly dispersed acrylate material and the crosslinking agent BIPB can orderly construct crosslinking points with the help of the "bridge" effect of the reinforced ethylene glycol vinyl ether, avoiding the situation where the local crosslinking density is too large or too small, realizing the efficient reaction of the light-induced crosslinking agent BIPB and the synergistic diluent to promote the polymerization, crosslinking and other reactions of the curable components to achieve the curing process.

[0026] The efficient and green crosslinker BIPB prepared by the present invention takes reaction efficiency and green energy saving as the key considerations for the first time. During the crosslinking process, energy can be provided solely by light, without the need for traditional thermal or chemical initiation methods, which greatly reduces energy use. In addition, light-induced crosslinking has the advantages of being fast, efficient, and highly controllable, and can better meet the needs of efficient and green production. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 A diagram showing a preparation method according to an embodiment of the present invention;

[0028] Figure 2 This is a comparison chart of aging data according to an embodiment of the present invention;

[0029] The accompanying drawings are used to provide further understanding of the present invention and constitute a part of the specification. They are used to explain the present invention together with the embodiments of the present invention and do not constitute a limitation of the present invention. DETAILED DESCRIPTION

[0030] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all the embodiments; based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0031] Unless otherwise defined, all technical and scientific terms used herein have the same meanings as those familiar to those skilled in the art. Furthermore, any methods and materials similar or equivalent to those described herein can be applied to the present invention. The preferred embodiments and materials described herein are for illustrative purposes only and are not intended to limit the scope of this application.

[0032] The preparation methods in the following examples are described in detail in Figure 1 Unless otherwise specified, all methods are conventional. The materials used in the following examples, unless otherwise specified, and the saturated solutions of the present invention are solutions prepared at 25°C with the corresponding solubility of the materials, in which Span 40 is selected as a surfactant.

[0033] Example 1: An efficient and green crosslinking agent BIPB, comprising the following raw materials: tert-butyl hydroperoxide, 2-hydroxyisopropylbenzene, perchloric acid solution, epoxy acrylate, reinforced ethylene glycol vinyl ether, 2-hydroxy-2-methyl-1-phenylpropanone, Span 40, and petroleum ether;

[0034] The preparation method of reinforced ethylene glycol vinyl ether comprises the following steps:

[0035] (1) Weigh 1.2 g of carbamamide and add it to 13 ml of dichloromethane. Stir it for 30 min at a power of 0.5 kW to obtain a uniform organic solution I. Weigh 3.5 g of phosphorus pentachloride and slowly add it to the uniform organic solution I. Stir it at a power of 0.5 kW. Control the temperature at 2 ° C. and react for 2 h to obtain a carbamoyl chloride reaction solution.

[0036] (2) distilling the carbamoyl chloride reaction solution obtained in step (1) at atmospheric pressure at 45° C. for 0.5 h to obtain carbamoyl chloride;

[0037] (3) Add the carbamoyl chloride obtained in step (2) to 5 ml of tetrahydrofuran, stir at a power of 0.5 kW for 30 min to obtain a uniform organic liquid II, then slowly and simultaneously add 1.5 ml of ethylene glycol vinyl ether and 2.5 ml of triethylamine to the uniform organic liquid II, stir under an argon flow rate of 50 ml / min, control the temperature at -10 ° C, react for 4 h, and then naturally cool to room temperature to obtain a fortified ethylene glycol vinyl ether reaction solution;

[0038] (4) The enhanced ethylene glycol vinyl ether reaction solution obtained in step (3) was distilled at a pressure of 4 kPa for 1 hour and a distillation temperature of 70° C. to obtain enhanced ethylene glycol vinyl ether.

[0039] This embodiment also provides a method for preparing an efficient and green cross-linking agent BIPB, comprising the following steps:

[0040] Step 1: Weigh 3 ml of tert-butyl hydroperoxide and 1.2 ml of 2-hydroxyisopropylbenzene, add them to 15 ml of petroleum ether in sequence, stir and mix at a power of 0.5 kW to obtain a pre-reaction solution, weigh 0.8 ml of a 70% perchloric acid solution, slowly dropwise add it to the pre-reaction solution, stir and raise the temperature to 40°C, react for 1 hour, add 1 ml of epoxy acrylate, continue to react for 3 hours, add 0.6 ml of fortified ethylene glycol vinyl ether, react for another 2 hours, and then cool to room temperature to obtain a crude reaction solution;

[0041] Step 2: adding ice to the crude reaction solution, wherein the ratio of the crude reaction solution to ice is 1 ml:1.5 g, stirring at a power of 0.5 kW for 30 min, and separating to obtain an organic phase of the crude reaction solution;

[0042] Step 3: Add saturated sodium carbonate solution to the organic phase of the crude reaction liquid obtained in step 2 to adjust the pH to neutral to obtain a neutral organic phase, and continue to add saturated sodium chloride solution to the neutral organic phase, wherein the ratio of the neutral organic phase to the saturated sodium chloride solution is 1 ml:0.8 ml, and stir for 1 hour at a power of 0.5 kW, and separate to obtain a BIPB crude phase;

[0043] Step 4: Add anhydrous sodium sulfate to the BIPB crude phase obtained in step 3, wherein the ratio of BIPB crude phase to anhydrous sodium sulfate is 1 ml and 0.3 g, stir at a power of 0.5 kW for 1 hour, and filter to obtain a BIPB organic phase;

[0044] Step 5: The BIPB organic phase obtained in step 5 is subjected to reduced pressure distillation at a pressure of 5 kPa for 1.5 h at a temperature of 40° C. to obtain concentrated BIPB;

[0045] Step 6: The concentrated BIPB obtained in step 5 is subjected to a low-temperature treatment at a temperature of -30°C and filtered to obtain BIPB crystals;

[0046] Step 7: Dissolve 2 g of BIPB crystals in 10 ml of anhydrous ethanol and stir evenly. Weigh 0.5 g of Span 40 and add the mixture with stirring to obtain the BIPB active agent. Weigh 0.3 ml of 2-hydroxy-2-methyl-1-phenylpropanone and add the BIPB active agent. Ultrasonicate at a power of 20 kHz for 30 minutes and oscillate at a frequency of 200 bpm for 30 minutes to obtain the highly efficient and green crosslinker BIPB precursor.

[0047] Step 8: The highly efficient and green cross-linking agent BIPB precursor is subjected to reduced pressure distillation at a pressure of 2 kPa and a temperature of room temperature, and then dried at a drying temperature of 55° C. and a drying time of 24 h to obtain a highly efficient and green cross-linking agent BIPB.

[0048] Example 2: An efficient and green crosslinking agent BIPB, comprising the following raw materials: tert-butyl hydroperoxide, 2-hydroxyisopropylbenzene, perchloric acid solution, epoxy acrylate, reinforced ethylene glycol vinyl ether, 2-hydroxy-2-methyl-1-phenylpropanone, Span 40, and petroleum ether;

[0049] The preparation method of reinforced ethylene glycol vinyl ether comprises the following steps:

[0050] (1) Weigh 1.8 g of carbamamide and add it to 13 ml of dichloromethane. Stir it for 30 min at a power of 0.5 kW to obtain a uniform organic solution I. Weigh 4.8 g of phosphorus pentachloride and slowly add it to the uniform organic solution I. Stir it at a power of 0.5 kW. Control the temperature at 4 ° C. and react for 2 h to obtain a carbamoyl chloride reaction solution.

[0051] (2) distilling the carbamoyl chloride reaction solution obtained in step (1) at atmospheric pressure at 45° C. for 1 h to obtain carbamoyl chloride;

[0052] (3) The carbamoyl chloride obtained in step (2) was added to 6.5 ml of tetrahydrofuran, and stirred at a power of 0.5 kW for 30 min to obtain a uniform organic liquid II. Subsequently, 2.3 ml of ethylene glycol vinyl ether and 3.5 ml of triethylamine were slowly and simultaneously added dropwise to the uniform organic liquid II, and stirred under an argon flow rate of 50 ml / min. The temperature was controlled at -5 ° C. and the reaction was carried out under temperature control for 4 h. After that, the mixture was naturally cooled to room temperature to obtain a fortified ethylene glycol vinyl ether reaction liquid;

[0053] (4) The enhanced ethylene glycol vinyl ether reaction solution obtained in step (3) was distilled at a pressure of 6 kPa for 1.5 h and a distillation temperature of 70° C. to obtain enhanced ethylene glycol vinyl ether.

[0054] This embodiment also provides a method for preparing an efficient and green cross-linking agent BIPB, comprising the following steps:

[0055] Step 1: Weigh 4 ml of tert-butyl hydroperoxide and 1.7 ml of 2-hydroxyisopropylbenzene, add them to 15 ml of petroleum ether in sequence, stir and mix under a power of 0.5 kW to obtain a pre-reaction solution, weigh 1.1 ml of a 70% perchloric acid solution, slowly dropwise add it to the pre-reaction solution, stir and raise the temperature to 48°C, react for 1.3 h, add 1.3 ml of epoxy acrylate, continue to react for 3.5 h, add 0.9 ml of fortified ethylene glycol vinyl ether, react for another 2 h, and then cool to room temperature to obtain a crude reaction solution;

[0056] Step 2: adding ice to the crude reaction solution, wherein the ratio of the crude reaction solution to ice is 1 ml:2 g, stirring at a power of 0.5 kW for 30 min, and separating to obtain an organic phase of the crude reaction solution;

[0057] Step 3: Add saturated sodium carbonate solution to the organic phase of the crude reaction liquid obtained in step 2 to adjust the pH to neutral to obtain a neutral organic phase, and continue to add saturated sodium chloride solution to the neutral organic phase, wherein the ratio of the neutral organic phase to the saturated sodium chloride solution is 1 ml:1.1 ml, and stir for 1 hour at a power of 0.5 kW, and separate to obtain a BIPB crude phase;

[0058] Step 4: Add anhydrous sodium sulfate to the BIPB crude phase obtained in step 3, wherein the ratio of BIPB crude phase to anhydrous sodium sulfate is 1 ml and 0.5 g, stir at a power of 0.5 kW for 1 hour, and filter to obtain a BIPB organic phase;

[0059] Step 5: The BIPB organic phase obtained in step 5 is subjected to reduced pressure distillation at a pressure of 10 kPa for 2.3 hours at a temperature of 50° C. to obtain concentrated BIPB;

[0060] Step 6: The concentrated BIPB obtained in step 5 is subjected to a low-temperature treatment at a temperature of -20°C and filtered to obtain BIPB crystals;

[0061] Step 7: Dissolve 3 g of BIPB crystals in 10 ml of anhydrous ethanol and stir evenly. Weigh 0.9 g of Span 40 and add the mixture with stirring to obtain a BIPB active agent. Weigh 0.4 ml of 2-hydroxy-2-methyl-1-phenylpropanone and add the BIPB active agent. Ultrasonicate at 30 kHz for 30 minutes and oscillate at 300 bpm for 30 minutes to obtain a highly efficient, green crosslinker BIPB precursor.

[0062] Step 8: The highly efficient and green cross-linking agent BIPB precursor is subjected to reduced pressure distillation at a pressure of 4 kPa and a temperature of room temperature, and then dried at a drying temperature of 55° C. and a drying time of 24 h to obtain a highly efficient and green cross-linking agent BIPB.

[0063] Example 3: An efficient and green crosslinking agent BIPB, comprising the following raw materials: tert-butyl hydroperoxide, 2-hydroxyisopropylbenzene, perchloric acid solution, epoxy acrylate, reinforced ethylene glycol vinyl ether, 2-hydroxy-2-methyl-1-phenylpropanone, Span 40, and petroleum ether;

[0064] The preparation method of reinforced ethylene glycol vinyl ether comprises the following steps:

[0065] (1) Weigh 2.5 g of carbamamide and add it to 13 ml of dichloromethane. Stir it for 30 min at a power of 0.5 kW to obtain a uniform organic solution I. Weigh 6 g of phosphorus pentachloride and slowly add it to the uniform organic solution I. Stir it at a power of 0.5 kW. Control the temperature at 6 ° C. and react for 2 h to obtain a carbamoyl chloride reaction solution.

[0066] (2) distilling the carbamoyl chloride reaction solution obtained in step (1) at atmospheric pressure at 45° C. for 1.5 h to obtain carbamoyl chloride;

[0067] (3) The carbamoyl chloride obtained in step (2) was added to 6.5 ml of tetrahydrofuran, and stirred at a power of 0.5 kW for 30 min to obtain a uniform organic liquid II. Subsequently, 3 ml of ethylene glycol vinyl ether and 4.5 ml of triethylamine were slowly and simultaneously added dropwise to the uniform organic liquid II, and stirred under an argon flow rate of 50 ml / min. The temperature was controlled at 0°C, and the reaction was carried out under temperature control for 4 h. The mixture was then naturally cooled to room temperature to obtain a fortified ethylene glycol vinyl ether reaction solution.

[0068] (4) The enhanced ethylene glycol vinyl ether reaction solution obtained in step (3) was distilled at a pressure of 8 kPa for 2 h and a distillation temperature of 70° C. to obtain enhanced ethylene glycol vinyl ether.

[0069] This embodiment also provides a method for preparing an efficient and green cross-linking agent BIPB, comprising the following steps:

[0070] Step 1: Weigh 5 ml of tert-butyl hydroperoxide and 2.2 ml of 2-hydroxyisopropylbenzene, add them to 15 ml of petroleum ether in sequence, stir and mix under a power of 0.5 kW to obtain a pre-reaction liquid, weigh 1.4 ml of a 70% perchloric acid solution, slowly add dropwise to the pre-reaction liquid, stir and raise the temperature to 55°C, react for 1.5 hours, add 1.3 ml of epoxy acrylate, continue to react for 4 hours, add 1.2 ml of fortified ethylene glycol vinyl ether, react for another 2 hours, and then cool to room temperature to obtain a crude reaction liquid;

[0071] Step 2: adding ice to the crude reaction solution, wherein the ratio of the crude reaction solution to ice is 1 ml:2.5 g, stirring at a power of 0.5 kW for 30 min, and separating to obtain an organic phase of the crude reaction solution;

[0072] Step 3: Add saturated sodium carbonate solution to the organic phase of the crude reaction liquid obtained in step 2 to adjust the pH to neutral to obtain a neutral organic phase, and continue to add saturated sodium chloride solution to the neutral organic phase, wherein the ratio of the neutral organic phase to the saturated sodium chloride solution is 1 ml:1.3 ml, and stir for 1 hour at a power of 0.5 kW, and separate to obtain a BIPB crude phase;

[0073] Step 4: Add anhydrous sodium sulfate to the BIPB crude phase obtained in step 3, wherein the ratio of BIPB crude phase to anhydrous sodium sulfate is 1 ml and 0.7 g, stir at a power of 0.5 kW for 1 hour, and filter to obtain a BIPB organic phase;

[0074] Step 5: The BIPB organic phase obtained in step 5 is subjected to reduced pressure distillation at a pressure of 15 kPa for 3 hours at a temperature of 60° C. to obtain concentrated BIPB;

[0075] Step 6: The concentrated BIPB obtained in step 5 is subjected to a low-temperature treatment at a temperature of -10°C and filtered to obtain BIPB crystals;

[0076] Step 7: Dissolve 4 g of BIPB crystals in 10 ml of anhydrous ethanol and stir evenly. Weigh 1.2 g of Span 40 and add the mixture with stirring to obtain the BIPB active agent. Weigh 0.5 ml of 2-hydroxy-2-methyl-1-phenylpropanone and add the BIPB active agent. Ultrasonicate at 40 kHz for 30 minutes and oscillate at 400 bpm for 30 minutes to obtain the highly efficient and green crosslinker BIPB precursor.

[0077] Step 8: The highly efficient and green cross-linking agent BIPB precursor is subjected to reduced pressure distillation at a pressure of 6 kPa and a temperature of room temperature, and then dried at a drying temperature of 55° C. and a drying time of 24 h to obtain a highly efficient and green cross-linking agent BIPB.

[0078] Comparative Example:

[0079] The difference between Comparative Example 1 and Example 2 is that no epoxy acrylate is added, and the rest is the same as Example 2;

[0080] The difference between Comparative Example 2 and Example 2 is that ethylene glycol vinyl ether is not reinforced, and the rest of the components are the same as Example 2;

[0081] The difference between Comparative Example 3 and Example 2 is that 2-hydroxy-2-methyl-1-phenylpropanone is not added, and the rest is the same as Example 2;

[0082] According to the following formula, weigh 55g natural rubber, 2.5g efficient green crosslinking agent BIPB, 0.8g vulcanization accelerator CBS, 4.5g active agent, and BHT antioxidant. 0.3g, placed in a clean and dry container for later use, add natural rubber to the open mill, and then preheat the open mill rollers. The preheating temperature is 50℃ and the preheating time is about 10min. Put the natural rubber between the preheated rollers and adjust the roller distance to 6mm to make the rubber roll form a film. Add the activator and mix for 10min. During the mixing process, adjust the roller distance appropriately to maintain the appropriate shear force to ensure that the activator can be fully dispersed in the rubber. The dispersion effect can be judged by observing whether the appearance of the film is uniform and whether there is agglomeration. Then add the antioxidant BHT and mix for 10min. Pay attention to the state of the film to ensure that the antioxidant is evenly mixed into the rubber system. Then add the vulcanization accelerator CBS and mix for 5min. Pay attention to controlling the speed when adding so that the vulcanization accelerator is evenly dispersed in the rubber to avoid agglomeration caused by adding too quickly and affecting the subsequent cross-linking reaction. Then add the high-efficiency green light-curing cross-linking agent BIPB and mix for 10 minutes. Observe the appearance of the rubber film to make it more delicate and uniform in color. It shows that the crosslinking agent has been well mixed into the rubber. After completing the addition and mixing of the above-mentioned additives, the roller spacing is narrowed to 2mm, and a thin-pass operation is performed, with the number of thin-passes being 5, to further improve the uniformity of each component in the rubber. After the thin-pass operation is completed, the roller spacing is adjusted to 2mm, and the mixed rubber film is removed from the open mill to form a film with a size of approximately 30mm·30mm·2mm in length, width and thickness for standby use. During the light curing operation, a xenon lamp with a light intensity of 1500mW / cm² is used for illumination. The distance between the light source and the material is kept at 30cm. The prepared rubber film is placed in a stable illumination area of ​​the light curing equipment and the illumination time is maintained for 5 minutes. During the illumination process, the photoinitiator produces active species such as free radicals under the action of light, which triggers the crosslinker to participate in the crosslinking reaction between the rubber molecular chains, gradually forming a three-dimensional network structure, completing the light curing crosslinking process, and obtaining a crosslinked film, after which subsequent performance tests can be carried out. For the aging test, the crosslinked film is aged at 70°C for 200h.

[0083] Table 1 shows the performance data of the cross-linked films prepared in Example;

[0084]

[0085] From the results in Table 1 above, it can be seen that the prepared efficient and green crosslinking agent BIPB plays a vital role in the crosslinking process of the film. The crosslinked film prepared by Example 2 has the lowest aging rate, indicating the best crosslinking property. At the same time, it reflects the high efficiency of the crosslinking agent BIPB. With regard to the photocuring performance, according to the conditions of Example 2, without adding light, the final aging rate is 30.4%, which is 5.7 times the aging multiple of Example 2, indicating that the photocuring system has a certain promoting effect on the crosslinking process and improves the crosslinking property.

[0086] Table 2 shows the performance data of the cross-linked film prepared in the comparative example, wherein the process of preparing the cross-linked film in the comparative example is the same as that in Example 2;

[0087]

[0088] It can be seen from Table 2 that the overall tensile strength of the cross-linked film prepared in the comparative example is lower than that in the example, and the aging rate of the comparative example is higher than that of the example.

[0089] pass Figure 2 The aging rate and aging time of the prepared cross-linked films were compared. It can be seen that with the increase of aging time, the aging rate of the cross-linked film prepared in the embodiment changes little. For the cross-linked film obtained without adding light, it can be seen that the aging rate increases. For the comparative example, the aging rate of the obtained cross-linked film continues to increase with the increase of aging time, indicating that it is not conducive to the preparation of cross-linked film according to the comparative example and without adding light.

[0090] Obviously, the above comparative examples and embodiments are only a part of the comparative examples and embodiments of the present invention, and they and the comparative examples and embodiments based on such references are all within the scope of protection of this invention.

[0091] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

[0092] The present invention and its embodiments are described above. Such description is not restrictive. The drawings show only one embodiment of the present invention, and actual applications are not limited thereto. In short, if a person skilled in the art is inspired by the above, and does not deviate from the purpose of the present invention, any method and embodiment similar to the technical solution without creative design shall fall within the scope of protection of the present invention.

Claims

1. An efficient and green crosslinking agent BIPB, characterized in that: The method comprises the following raw materials in the following proportions: tert-butyl hydroperoxide: 2-hydroxyisopropylbenzene: perchloric acid solution: epoxy acrylate: reinforced ethylene glycol vinyl ether: 2-hydroxy-2-methyl-1-phenylacetone: surfactant and petroleum ether = 3-5 ml: 1.2-2.2 ml: 0.8-1.4 ml: 1-1.5 ml: 0.6-1.2 ml: 0.3-0.5 ml: 0.5-1.2 g: 15 ml; The reinforced ethylene glycol vinyl ether raw material includes the following materials in the following proportions: ethylene glycol vinyl ether, aminoformamide, phosphorus pentachloride, dichloromethane, tetrahydrofuran and triethylamine = 1.5-3 ml: 1.2-2.5 g: 3.5-6 g: 13 ml: 5-8 ml: 2.5-4.5 ml.

2. The efficient and green crosslinking agent BIPB according to claim 1, characterized in that: The preparation method of the reinforced ethylene glycol vinyl ether comprises the following steps: (1) Weighing carbamamide and adding it to dichloromethane, stirring to obtain a uniform organic solution I; weighing phosphorus pentachloride and adding it to the uniform organic solution I, stirring and controlling the temperature to obtain a carbamoyl chloride reaction solution; (2) distilling the carbamoyl chloride reaction solution to obtain carbamoyl chloride; (3) Add carbamoyl chloride to tetrahydrofuran and stir to obtain a uniform organic solution II, weigh ethylene glycol vinyl ether and triethylamine and add them to the uniform organic solution II, stir and control the temperature, and cool to obtain a fortified ethylene glycol vinyl ether reaction solution; (4) The reaction liquid of the fortified ethylene glycol vinyl ether is distilled to obtain the fortified ethylene glycol vinyl ether.

3. A method for preparing an efficient and green crosslinking agent BIPB according to any one of claims 1 to 2, characterized in that: The steps include: Step 1: Weigh tert-butyl hydroperoxide and 2-hydroxyisopropylbenzene, add them to petroleum ether in sequence, stir to obtain a pre-reaction liquid, weigh perchloric acid solution, add it to the pre-reaction liquid, stir and heat, and add epoxy acrylate and fortified ethylene glycol vinyl ether in sequence to obtain a crude reaction liquid; Step 2: treating the crude reaction solution to obtain BIPB crystals; Step 3: Dissolve BIPB crystals in ethanol and stir, weigh a surfactant and add it, stir to obtain BIPB active agent, weigh 2-hydroxy-2-methyl-1-phenylacetone and add it to the BIPB active agent, sonicate and oscillate to obtain a highly efficient and green cross-linking agent BIPB precursor; Step 4: distill and dry the precursor of the highly efficient and green cross-linking agent BIPB to obtain the highly efficient and green cross-linking agent BIPB.

4. The method for preparing a highly efficient and green crosslinking agent BIPB according to claim 3, characterized in that: The ratio of the BIPB crystals, 2-hydroxy-2-methyl-1-phenylpropanone, surfactant and ethanol used in step 3 is 2-4 g: 0.3-0.5 ml: 0.5-1.2 g: 10 ml.

5. The method for preparing a highly efficient and green crosslinking agent BIPB according to claim 3, characterized in that: Step 2 treatment includes the following materials: sodium carbonate solution, sodium chloride solution and anhydrous sodium sulfate; The processing steps are as follows: (a) adding ice to the crude reaction solution, stirring and separating to obtain an organic phase of the crude reaction solution; (b) adding sodium carbonate solution to the organic phase of the crude reaction solution to adjust the pH to obtain a neutral organic phase, adding sodium chloride solution to the neutral organic phase, stirring and separating to obtain a BIPB crude phase; (c) Weigh anhydrous sodium sulfate and add it to the BIPB crude phase, stir, and filter to obtain the BIPB organic phase; (d) distilling the BIPB organic phase to obtain concentrated BIPB; (e) The concentrated BIPB is treated at low temperature and filtered to obtain BIPB crystals.

6. The method for preparing a highly efficient and green crosslinking agent BIPB according to claim 5, characterized in that: The ratio of the reaction crude solution and ice in step (a) is 1 ml: 1.5-2.5 g, the ratio of the neutral organic phase and sodium chloride solution in step (b) is 1 ml: 0.8-1.3 ml, and the ratio of the BIPB crude phase and anhydrous sodium sulfate in step (c) is 1 ml: 0.3-0.7 g.

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