A method for preparing high viscosity epoxide polymerization product

Abstract

The present invention belongs to the technical field of preparation of epoxide polymerization products, and discloses a method for preparing a high-viscosity epoxide polymerization product. The method for preparing the high-viscosity epoxide polymerization product comprises the following steps: step (1): adding polyepoxide to deionized water, stirring, and ultrasonically dispersing to obtain a polyepoxide solution; step (2): adding composite silicon-cellulose, carbazole-based thermal stabilizer and compatibilizer to deionized water, stirring to obtain a uniformly dispersed mixed solution, and then adding the mixed solution to the polyepoxide solution, stirring while adding, continuing to stir after adding completely, and pouring into a product mold after stirring, and after drying, obtaining a high-viscosity epoxide polymerization product. By adding composite silicon-cellulose and carbazole-based thermal stabilizer to polyepoxide, the viscosity and thermal stability of the product can be effectively improved.

Description

Technical Field

[0001] The invention belongs to the technical field of preparation of epoxide polymerization products, and in particular relates to a preparation method of a high-viscosity epoxide polymerization product. Background Art

[0002] With the continuous development of materials science, the demand for high-performance polymers is also growing. Epoxide is an important polymerization monomer, and its polymerization products have excellent physical and chemical properties.

[0003] When epoxide polymerization products have high viscosity characteristics, they have many advantages. First, due to their viscous texture, high-viscosity epoxide polymerization products can adhere more tightly to the surface of the substrate to form a stable and lasting adhesion layer. When used as adhesives or sealing materials, they can provide better sealing effects and stronger bonding forces to prevent leakage of liquids or gases. High-viscosity polymers usually have higher molecular weights and complex molecular structures, which give them better structural stability and load-bearing capacity, and are not prone to deformation or rupture. Therefore, the excellent performance of high-viscosity epoxide polymerization products gives them a wide range of application prospects.

[0004] The patent with publication number CN113683765A discloses a method for preparing a carbon dioxide-epoxide copolymer, comprising: after mixing a solvent with a catalyst, introducing carbon dioxide, heating and continuously or batchwise adding an epoxide monomer under supercritical conditions to react, and obtaining a carbon dioxide-epoxide copolymer. By adopting a process of adding epoxide monomers in batches or continuously on the basis of supercritical solution polymerization, on the one hand, utilizing the characteristics of strong solubility, low viscosity and high diffusion coefficient of supercritical carbon dioxide, by increasing the polymerization pressure, the carbon dioxide-epoxide mixed solution is in a supercritical state, and under the condition of maintaining a high molecular weight and high carbonate content of the product, by continuously or batchwise feeding process, the epoxy monomer is maintained at a relatively low concentration, the risk of thermal runaway of the reaction can be eliminated, the complexity and investment of the industrial device can be reduced, and on the other hand, the epoxy monomer self-polymerization can be avoided, the ether segment is increased, and the carbon dioxide fixation efficiency is improved. However, the method of continuously or batchwise adding monomers under supercritical conditions to react makes the structural stability and carrying capacity of the product insufficient. Therefore, the composition and process of the epoxide polymerization product need to be improved to improve the viscosity and thermal stability of the epoxide polymerization product. Summary of the invention

[0005] The object of the present invention is to provide a method for preparing a high-viscosity epoxide polymerization product, which is used to solve the technical problem that the composition and process of the epoxide polymerization product prepared in the prior art need to be improved, so as to improve the viscosity and thermal stability of the epoxide polymerization product.

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

[0007] The present invention provides a method for preparing a high-viscosity epoxide polymerization product, comprising the following steps:

[0008] Step (1): adding polyepoxide to deionized water, stirring, and ultrasonically dispersing to obtain a polyepoxide solution;

[0009] Step (2): Add the composite silicon-cellulose, carbazole-based thermal stabilizer and compatibilizer into deionized water and stir to obtain a uniformly dispersed mixed solution. Then add the mixed solution into the polyepoxide solution while stirring. Continue stirring after the addition is complete. After stirring, pour into a product mold and dry to obtain a high-viscosity epoxide polymerization product.

[0010] Preferably, the high viscosity epoxide polymerization product is composed of the following components in parts by weight: 36-52 parts of polyepoxide, 4-8 parts of composite silicon-cellulose, 1-3 parts of carbazole-based heat stabilizer, 1-2 parts of compatibilizer, and 30-50 parts of deionized water.

[0011] Preferably, the preparation method of the polyepoxide comprises the following steps:

[0012] R1: Add 1-ethyl-3-methylimidazolium chloride and phthalic anhydride to a reaction bottle, seal it with a rubber stopper, evacuate it, then add valerolactone, tetrahydrofuran and propylene oxide, react in an oil bath, cool it, and dissolve it with chloroform;

[0013] R2: Then, the product was precipitated with anhydrous methanol, and the operation was repeated, and then the product was dried in a vacuum oven to obtain polyepoxide.

[0014] In the above process, 1-ethyl-3-methylimidazolium chloride is used as a catalyst to synthesize polyepoxide, wherein the reaction mechanism of polyepoxide is as follows:

[0015]

[0016] Preferably, in R1, the dosage ratio of 1-ethyl-3-methylimidazolium chloride, phthalic anhydride, valerolactone, tetrahydrofuran and propylene oxide is (0.1-0.5) g: (3.46-17.3) g: (3.31-16.55) mL: (5-25) mL: (4.77-23.85) mL, the vacuuming time is 30-40 min, the oil bath temperature is 100-110° C., and the oil bath reaction time is 1-3 h; in R2, the operation is repeated 3-5 times, and the drying temperature is 60-70° C.

[0017] Preferably, the preparation method of the composite silicon-cellulose comprises the following steps:

[0018] Q1: Bamboo pulp is placed in a three-necked flask, and then sodium hydroxide solution and ethylene glycol are added, the three-necked flask is immersed in a water bath, stirred, chloroacetic acid is added, the temperature is raised, and an etherification reaction is carried out. After the reaction is completed, the three-necked flask is taken out, cooled, acetic acid solution is added for neutralization, filtered, the filter residue is washed with ethanol, dried, and cooled to obtain carboxymethyl cellulose;

[0019] Q2: Add the Custer catalyst and 4-allyl-2-methoxyphenol to a three-necked flask, and then add toluene. Heat the flask under nitrogen protection, and then slowly add 1,1,3,3-tetramethyldisiloxane to the three-necked flask through a micro-syringe pump. After the reaction is completed, heat and vacuum evaporation is performed to obtain modified silicone.

[0020] Q3: Add carboxymethyl cellulose to the modified silicone, add formic acid at the same time, stir, heat and mix to obtain composite silicone-cellulose.

[0021] In the above process, sodium hydroxide is mixed with bamboo pulp and stirred evenly to fully alkalize the cellulose in the bamboo pulp. Subsequently, chloroacetic acid is mixed with the alkalized cellulose. Chloroacetic acid is first neutralized with sodium hydroxide, and the resulting product undergoes a nucleophilic substitution reaction with alkaline cellulose to form an ether bond to obtain carboxymethyl cellulose; subsequently, 4-allyl-2-methoxyphenol and 1,1,3,3-tetramethyldisiloxane are reacted to obtain modified silicone. Subsequently, the carboxymethyl cellulose and the modified silicone are mixed, and the hydroxyl and carboxyl groups undergo an esterification reaction to form an ester bond. The carboxymethyl cellulose and the modified silicone can also be physically mixed and combined with the molecular chains through entanglement to form a stable composite silicone-cellulose.

[0022] Preferably, in Q1, the particle size of bamboo pulp is 20-40 mesh, the dosage ratio of bamboo pulp, sodium hydroxide, ethylene glycol and chloroacetic acid is (5-7) g: (15-20) mL: (150-200) mL: (11-14) g, the volume fraction of sodium hydroxide is 30 vt%, the stirring time is 1-2 h, the heating temperature is 60-70°C, the etherification reaction time is 2-4 h, and the volume fraction of acetic acid solution is 10 vt%.

[0023] Preferably, in Q2, the amount ratio of Custer catalyst, 4-allyl-2-methoxyphenol, toluene and 1,1,3,3-tetramethyldisiloxane is (0.35-0.44) g: (16-17) g: (18-22) mL: (6.5-6.94) g, the three-necked flask is equipped with a reflux condenser, a nitrogen inlet and outlet and a magnetic stirrer, the heating temperature is 60-70°C, the reaction time is 48-52h, and the heating vacuum rotary evaporation temperature is 70-80°C; in Q3, the amount ratio of carboxymethyl cellulose and modified silicone is (10-20) mg: (40-60) mL, the stirring time is 20-40min, and the heating temperature is 60-70°C.

[0024] Preferably, the method for preparing the carbazole-based thermal stabilizer comprises the following steps:

[0025] S1: Carbazole, 4-tert-butyl-iodobenzene, cuprous iodide, and potassium phosphate are placed in two beakers under a nitrogen atmosphere, the gas is evacuated with a double-row pipe, and N,N-dimethylformamide that has been dehydrated and deoxygenated is injected, and the reaction is heated. After the reaction is completed, the reaction solution is cooled to room temperature, extracted with water, and then extracted with a mixed solution of dichloromethane and saturated brine. The bottom organic solvent is dried with anhydrous sodium sulfate, and then silica gel powder is added, rotary evaporated, and separated by a chromatography column to obtain a white powder substance;

[0026] S2: Stir the white powder, 2,6-difluoro-4-bromoacetophenone, tetrahydrofuran and potassium carbonate aqueous solution under nitrogen protection, then add PdCl2(PPh3)2, continue heating reaction under nitrogen protection, after the reaction is completed, cool to room temperature, add silica gel powder, rotary evaporate, separate by chromatography column, and obtain carbazole-based polymer;

[0027] S3: Dissolve ferric chloride in 1,2-dichloroethane, stir and dissolve to obtain a ferric chloride solution, then dissolve the carbazole-based polymer in 1,2-dichloroethane and add it dropwise to the ferric chloride solution for reaction, then add methanol, stir and filter, wash the filter cake with methanol and water, then place it in a hydrochloric acid solution, stir, filter, wash, extract, and vacuum dry to obtain a carbazole-based thermal stabilizer.

[0028] In the above process, carbazole and 4-tert-butyl-iodobenzene undergo Ullmann reaction under the condition of cuprous iodide and potassium phosphate as catalysts, so that carbazole and benzene ring are connected. Subsequently, the white powder substance undergoes nucleophilic substitution reaction with 2,6-difluoro-4-bromoacetophenone in potassium carbonate aqueous solution and tetrahydrofuran. The nitrogen atom contained in the white powder substance undergoes nucleophilic attack on the ketone carbonyl to form a new carbon-nitrogen bond. After adding PdCl2(PPh3)2, a palladium-catalyzed cross-coupling reaction occurs to obtain a carbazole-based polymer. Finally, the carbazole-based polymer is used as a catalyst to generate a carbazole-based thermal stabilizer. The reaction chemical formula of the carbazole-based thermal stabilizer is as follows:

[0029]

[0030] After mass spectrometry analysis, the mass spectrum results of the white powder substance were: m / z: 299.17 (100.0%), 300.17 (24.0%), 301.17 (2.8%); the mass spectrum results of the carbazole-based polymer were: m / z: 455.21 (100.0%), 456.21 (32.8%), 457.21 (5.4%).

[0031] Preferably, in S1, the amount ratio of carbazole, 4-tert-butyl-iodobenzene, cuprous iodide, potassium phosphate, and N,N-dimethylformamide is (3-3.68) g: (6-6.48) g: (3.49-4.29) g: (5.1-5.53) g: (70-90) mL, the heating reaction temperature is 150-170°C, and the reaction time is 20-24 h; in S2, the amount ratio of white powder, 2,6-difluoro-4-bromoacetophenone, tetrahydrofuran, potassium carbonate, and PdCl2(PPh3)2 is (1.48-1.56) g: (0.78-0.84) g: 20 mL: (10-15) mL: (0.18-0.38) g, and the amount ratio of carbonic acid is (1.48-1.56) g: (0.78-0.84) g: 20 mL: (10-15) mL: (0.18-0.38) g. The concentration of the potassium aqueous solution is 2 mol / L, the temperature of the heating reaction is 70-90°C, and the heating reaction time is 40-50 hours. In the S3, the dosage ratio of ferric chloride to 1,2-dichloroethane is (0.7-0.77) g: 20 mL, the dosage ratio of the carbazole polymer to 1,2-dichloroethane is (0.01-0.21) g: 5 mL, the reaction time is 22-26 hours, the stirring time after adding methanol is 30-45 minutes, the volume fraction of the hydrochloric acid solution is 10vt%, and the stirring time is 1-2 hours. During the extraction process, methanol is first used for extraction for 20-24 hours, and then tetrahydrofuran is used for extraction for 20-24 hours. The vacuum drying temperature is 100-110°C.

[0032] Preferably, in step (1), the temperature during stirring is 60-70°C and the stirring time is 12-14h; in step (2), the stirring time is 7-9h, the stirring time is continued for 12-14h, and the drying temperature is 70-80°C and the time is 16-20h.

[0033] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0034] 1. The present invention firstly uses 1-ethyl-3-methylimidazolium chloride as a catalyst, valerolactone, propylene oxide and phthalic anhydride as raw materials, polymerizes to generate polyepoxide, then uses bamboo pulp to prepare carboxymethyl cellulose, and reacts with modified silicone to obtain a stable composite silicon-cellulose with viscosity; then uses carbazole as a main raw material, reacts with 4-tert-butyl-iodobenzene, and then obtains a carbazole-based thermal stabilizer through polymerization and other reactions, and adds the composite silicon-cellulose, the carbazole-based thermal stabilizer and the compatibilizer into the polyepoxide for compounding, so that the obtained epoxide polymerization product has excellent viscosity and thermal stability.

[0035] 2. The present invention uses 1-ethyl-3-methylimidazolium chloride with excellent solubility and catalytic activity as a catalyst, which can effectively promote the ring-opening polymerization reaction of epoxide and accelerate the polymerization reaction; valerolactone and propylene oxide, as epoxide monomers, have different reactivity and segment structures, and can cooperate with each other in the polymerization process to form a polymer chain with a complex structure and excellent performance; the introduction of phthalic anhydride can increase the rigidity and thermal stability of polyepoxide, so that the obtained polymerization product has excellent thermal stability.

[0036] 3. The present invention obtains a stable composite silicon-cellulose that can increase the viscosity of epoxide polymerization products by compounding carboxymethyl cellulose and modified silicone. The carboxymethyl cellulose and modified silicone in the composite silicon-cellulose both have high molecular weights, and the viscosity of the product is increased by interacting with the polyepoxide molecular chains. The polar groups contained in the composite silicon-cellulose can also form hydrogen bonds with the polyepoxide molecular chains to further increase the viscosity of the product. At the same time, the network structure formed by the composite silicon-cellulose in the solution can disperse stress and improve the tensile strength and toughness of the product. The interaction between the composite silicon-cellulose and the polyepoxide can also enhance the intermolecular binding force. The presence of silicone can also enhance the rigidity and stability of the molecular chain, thereby improving the stability of the product.

[0037] 4. The present invention uses carbazole as a main raw material to prepare a carbazole-based heat stabilizer, and adds the carbazole-based heat stabilizer to an epoxide polymerization product, thereby effectively improving the thermal stability of the product. Under high temperature conditions, the carbazole group can absorb and disperse the heat on the polyepoxide molecular chain, slowing down the thermal degradation process. The carbazole group can also react with free radicals in the molecular chain to terminate the free radical chain reaction, further inhibiting the thermal oxidative degradation of the polyepoxide. The ferric chloride component contained in the carbazole-based heat stabilizer can also interact with the polar groups in the polyepoxide molecular chain to form ionic bonds or coordination bonds, thereby enhancing the interaction force between the molecular chains, and helping to improve the heat resistance and thermal oxidation resistance of the epoxide polymerization product. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0039] Figure 1 The present invention is a flow chart of the preparation method of the high viscosity epoxide polymerization product. DETAILED DESCRIPTION

[0040] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0041] The chemical reagents used in the embodiments and comparative examples are all commercially available products, and the manufacturers and CAS numbers are as follows:

[0042] 1-Ethyl-3-methylimidazolium chloride was purchased from Jinan Henghan Chemical Co., Ltd., CAS No.: 65039-09-0;

[0043] Phthalic anhydride was purchased from Shandong Jinhe Chemical Co., Ltd., CAS No.: 85-44-9;

[0044] Valerolactone was purchased from Xiamen Yudeshun Chemical Products Co., Ltd., CAS number: 524-28-9;

[0045] Tetrahydrofuran was purchased from Jinan Chuangshi Chemical Co., Ltd., CAS number: 109-99-9;

[0046] Propylene oxide was purchased from Jinan Shuangying Chemical Co., Ltd., CAS No.: 75-56-9;

[0047] Chloroform was purchased from Anhui Jinyueguan New Material Technology Co., Ltd., CAS No.: 67-66-3;

[0048] Anhydrous methanol was purchased from Shandong Mingyue Chemical Co., Ltd., CAS No.: 67-56-1;

[0049] Bamboo pulp was purchased from Shanghai Tianzhu Textile Fiber Co., Ltd.;

[0050] Sodium hydroxide was purchased from Hebei Senqiao Chemical Co., Ltd., CAS No.: 1310-73-2;

[0051] Ethylene glycol was purchased from Shandong Junda Chemical Co., Ltd., CAS No.: 107-21-1;

[0052] Chloroacetic acid was purchased from Shandong Xuchen Chemical Technology Co., Ltd., CAS No.: 79-11-8;

[0053] Acetic acid was purchased from Jinan Chengyijia Chemical Technology Co., Ltd., CAS No.: 64-19-7;

[0054] Ethanol was purchased from Jinan Mingxin Chemical Co., Ltd., CAS No.: 64-17-5;

[0055] 4-Allyl-2-methoxyphenol was purchased from Shandong Jinshengtai Chemical Co., Ltd., CAS No.: 97-53-0;

[0056] Toluene was purchased from Nanjing Kaiyan Environmental Protection Technology Co., Ltd., CAS No.: 108-88-3;

[0057] 1,1,3,3-Tetramethyldisiloxane was purchased from Hubei Chengfeng Chemical Co., Ltd., CAS No.: 30110-74-8;

[0058] Formic acid was purchased from Shandong Jinli Chemical Co., Ltd., CAS No.: 64-18-6;

[0059] Carbazole was purchased from Shanghai Jizhi Biochemical Technology Co., Ltd., CAS number: 86-74-8;

[0060] 4-tert-Butyl-iodobenzene was purchased from Hubei Yunmei Technology Co., Ltd., CAS No.: 35779-04-5;

[0061] Cuprous iodide was purchased from Shengguang Recycling Resources Co., Ltd., Congtai District, Handan City, CAS No.: 7681-65-4;

[0062] Potassium phosphate was purchased from Qianyan Chemical Technology (Wuhan) Co., Ltd., CAS number: 7778-53-2;

[0063] N,N-dimethylformamide was purchased from Shandong Changyuan Chemical Co., Ltd., CAS No.: 68-12-2;

[0064] Anhydrous sodium sulfate was purchased from Shandong Haihua Supply Chain Co., Ltd., CAS number: 7757-82-6;

[0065] 2,6-Difluoro-4-bromoacetophenone was purchased from Beijing Solebow Technology Co., Ltd., CAS No.: 746630-34-2;

[0066] Potassium carbonate was purchased from Langfang Qianyao Technology Co., Ltd., CAS No.: 584-08-7;

[0067] Ferric chloride was purchased from Jinan Linsheng Chemical Co., Ltd., CAS number: 7705-08-0;

[0068] Methanol was purchased from Jinan Hongboli Chemical Co., Ltd., CAS No.: 67-56-1;

[0069] Hydrochloric acid was purchased from Guangzhou Zhuohou Environmental Protection Technology Co., Ltd., CAS number: 7647-01-0;

[0070] γ-Aminopropyltriethoxysilane was purchased from Hangzhou Jessica Chemical Co., Ltd., CAS No.: 919-30-2.

[0071] Example 1

[0072] This embodiment discloses a method for preparing a polyepoxide, comprising the following steps:

[0073] R1: Add 0.25 g of 1-ethyl-3-methylimidazolium chloride and 10.28 g of phthalic anhydride to a reaction bottle, seal it with a rubber stopper, evacuate for 30 min, then add 10.01 mL of valerolactone, 20 mL of tetrahydrofuran and 14.17 mL of propylene oxide, react in an oil bath at 100 °C for 3 h, cool it, and dissolve it with chloroform;

[0074] R2: Then, the product was precipitated with anhydrous methanol, and the operation was repeated three times. The product was dried in a vacuum oven at 70° C. to obtain a polyepoxide.

[0075] This embodiment discloses a method for preparing a composite silicon-cellulose, comprising the following steps:

[0076] Q1: 6 g of 40 mesh bamboo pulp was placed in a three-necked flask, and then 17 mL of 30 vt% sodium hydroxide solution and 170 mL of ethylene glycol were added, the three-necked flask was immersed in a water bath, stirred for 2 h, 13 g of chloroacetic acid was added, the temperature was raised to 60 ° C, and the etherification reaction was carried out for 4 h. After the reaction was completed, the three-necked flask was taken out, cooled, and 10 vt% acetic acid solution was added for neutralization, filtered, and the filter residue was washed with ethanol, dried, and cooled to obtain carboxymethyl cellulose;

[0077] Q2: 0.40g of Custer catalyst and 16.5g of 4-allyl-2-methoxyphenol were added to a three-necked flask equipped with a reflux condenser, a nitrogen inlet and outlet, and a magnetic stirrer, and 20mL of toluene was added. Under nitrogen protection, the heating temperature was 70°C, and then 6.74g of 1,1,3,3-tetramethyldisiloxane was slowly added to the three-necked flask through a micro-syringe pump. The reaction was continued for 48h. After the reaction was completed, the mixture was heated to 80°C for vacuum rotary evaporation to obtain modified silicone.

[0078] Q3: Add 15 mg of carboxymethyl cellulose to 50 mL of modified silicone, add formic acid at the same time, stir for 30 minutes, heat to 70°C and mix to obtain composite silicone-cellulose.

[0079] This embodiment discloses a method for preparing a carbazole-based thermal stabilizer, comprising the following steps:

[0080] S1: 3.34 g of carbazole, 6.24 g of 4-tert-butyl-iodobenzene, 3.89 g of cuprous iodide, and 5.25 g of potassium phosphate were placed in two beakers under a nitrogen atmosphere, and the gas was evacuated with a double-row pipe. 80 mL of N,N-dimethylformamide that had been dehydrated and deoxygenated was injected, and the mixture was heated at 160° C. for 24 h. After the reaction was completed, the reaction solution was cooled to room temperature, extracted with water, and then extracted with a mixed solution of dichloromethane and saturated brine. The bottom organic solvent was dried with anhydrous sodium sulfate, and then silica gel powder was added, rotary evaporated, and separated by a chromatography column to obtain a white powder substance;

[0081] S2: 1.52 g of white powder, 0.80 g of 2,6-difluoro-4-bromoacetophenone, 20 mL of tetrahydrofuran and 12.5 mL of 2 mol / L potassium carbonate aqueous solution were stirred for reaction under nitrogen protection, and then 0.28 g of PdCl2(PPh3)2 was added, and the reaction was continued under nitrogen protection at 90°C for 48 h. After the reaction was completed, the reaction was cooled to room temperature, and silica gel powder was added, and the reaction was performed by rotary evaporation and separation by chromatography to obtain a carbazole-based polymer;

[0082] S3: Dissolve 0.75g of ferric chloride in 20mL of 1,2-dichloroethane, stir and dissolve to obtain a ferric chloride solution, then dissolve 0.11g of a carbazole-based polymer in 5mL of 1,2-dichloroethane, and add it dropwise to the ferric chloride solution for reaction for 24h, then add methanol and stir for 45min, filter, wash the filter cake with methanol and water, then place it in a 10vt% hydrochloric acid solution and stir for 2h, filter, wash, and extract. During the extraction process, first use methanol for 24h, then use tetrahydrofuran for 24h, and then vacuum dry at 110°C to obtain a carbazole-based thermal stabilizer.

[0083] This embodiment discloses a high viscosity epoxide polymerization product, which is composed of the following components in parts by weight: 48 parts of polyepoxide, 6 parts of composite silicon-cellulose, 2 parts of carbazole-based thermal stabilizer, 1.5 parts of γ-aminopropyltriethoxysilane, and 40 parts of deionized water.

[0084] See also Figure 1 As shown, this embodiment discloses a method for preparing a high viscosity epoxide polymerization product, comprising the following steps:

[0085] Step (1): add 48 g of polyepoxide to 28 mL of deionized water, stir at 70° C. for 12 h, and ultrasonically disperse to obtain a polyepoxide solution;

[0086] Step (2): 6 g of composite silicon-cellulose, 2 g of carbazole-based thermal stabilizer and 1.5 g of γ-aminopropyltriethoxysilane are added to 12 mL of deionized water and stirred for 9 h to obtain a uniformly dispersed mixed solution. The mixed solution is then added to the polyepoxide solution while stirring. After the addition is complete, stirring is continued for 14 h. After stirring, the mixture is poured into a product mold and dried for 8 h to obtain a high-viscosity epoxide polymerization product.

[0087] Example 2

[0088] This embodiment discloses a method for preparing a polyepoxide, comprising the following steps:

[0089] R1: Add 0.5 g of 1-ethyl-3-methylimidazolium chloride and 17.3 g of phthalic anhydride to a reaction bottle, seal with a rubber stopper, evacuate for 30 min, then add 4.28 mL of valerolactone, 25 mL of tetrahydrofuran and 4.98 mL of propylene oxide, react in an oil bath at 100 °C for 3 h, cool, and dissolve with chloroform;

[0090] R2: Then, the product was precipitated with anhydrous methanol, and the operation was repeated three times. The product was dried in a vacuum oven at 70° C. to obtain a polyepoxide.

[0091] This embodiment discloses a method for preparing a composite silicon-cellulose, comprising the following steps:

[0092] Q1: 5 g of 40 mesh bamboo pulp was placed in a three-necked flask, and then 15 mL of 30 vt% sodium hydroxide solution and 200 mL of ethylene glycol were added. The three-necked flask was immersed in a water bath, stirred for 2 h, and then 12 g of chloroacetic acid was added. The temperature was raised to 60 ° C. and the etherification reaction was carried out for 4 h. After the reaction was completed, the three-necked flask was taken out, cooled, and 10 vt% acetic acid solution was added for neutralization. The filter was filtered, and the filter residue was washed with ethanol, dried, and cooled to obtain carboxymethyl cellulose;

[0093] Q2: 0.35 g of Custer catalyst and 16 g of 4-allyl-2-methoxyphenol were added to a three-necked flask equipped with a reflux condenser, a nitrogen inlet and outlet, and a magnetic stirrer, and 18 mL of toluene was added. Under nitrogen protection, the heating temperature was 70°C, and then 6.52 g of 1,1,3,3-tetramethyldisiloxane was slowly added to the three-necked flask through a micro-syringe pump. The reaction was continued for 48 hours. After the reaction was completed, the reaction was heated to 80°C for vacuum rotary evaporation to obtain modified silicone.

[0094] Q3: Add 10 mg of carboxymethyl cellulose to 40 mL of modified silicone, add formic acid at the same time, stir for 30 minutes, heat to 70°C and mix to obtain composite silicone-cellulose.

[0095] This embodiment discloses a method for preparing a carbazole-based thermal stabilizer, comprising the following steps:

[0096] S1: 3.28 g of carbazole, 6.12 g of 4-tert-butyl-iodobenzene, 3.69 g of cuprous iodide, and 5.15 g of potassium phosphate were placed in two beakers under a nitrogen atmosphere, and the gas was evacuated with a double-row pipe. 70 mL of N,N-dimethylformamide that had been dehydrated and deoxygenated was injected, and the mixture was heated at 160°C for 24 h. After the reaction, the reaction solution was cooled to room temperature, extracted with water, and then extracted with a mixed solution of dichloromethane and saturated brine. The bottom organic solvent was dried with anhydrous sodium sulfate, and then silica gel powder was added, rotary evaporated, and separated by a chromatography column to obtain a white powder substance;

[0097] S2: 1.48 g of white powder, 0.78 g of 2,6-difluoro-4-bromoacetophenone, 20 mL of tetrahydrofuran and 10 mL of 2 mol / L potassium carbonate aqueous solution were stirred for reaction under nitrogen protection, and then 0.18 g of PdCl2(PPh3)2 was added, and the reaction was continued under nitrogen protection at 90°C for 48 h. After the reaction was completed, the reaction was cooled to room temperature, and silica gel powder was added, and the reaction was performed by rotary evaporation and separation by chromatography to obtain a carbazole-based polymer;

[0098] S3: Dissolve 0.73g of ferric chloride in 20mL of 1,2-dichloroethane, stir and dissolve to obtain a ferric chloride solution, then dissolve 0.08g of a carbazole-based polymer in 5mL of 1,2-dichloroethane, and add it dropwise to the ferric chloride solution for reaction for 24h, then add methanol and stir for 45min, filter, wash the filter cake with methanol and water, then place it in a 10vt% hydrochloric acid solution and stir for 2h, filter, wash, and extract. During the extraction process, first use methanol for 24h, then use tetrahydrofuran for 24h, and then vacuum dry at 110°C to obtain a carbazole-based thermal stabilizer.

[0099] This embodiment discloses a high viscosity epoxide polymerization product, which is composed of the following components in parts by weight: 36 parts of polyepoxide, 4 parts of composite silicon-cellulose, 1 part of carbazole-based thermal stabilizer, 1 part of γ-aminopropyltriethoxysilane, and 30 parts of deionized water.

[0100] See also Figure 1 As shown, this embodiment discloses a method for preparing a high viscosity epoxide polymerization product, comprising the following steps:

[0101] Step (1): add 36 g of polyepoxide to 22 mL of deionized water, stir at 70° C. for 12 h, and ultrasonically disperse to obtain a polyepoxide solution;

[0102] Step (2): 4 g of composite silicon-cellulose, 1 g of carbazole-based thermal stabilizer and 1 g of γ-aminopropyltriethoxysilane are added to 8 mL of deionized water and stirred for 9 h to obtain a uniformly dispersed mixed solution. The mixed solution is then added to the polyepoxide solution while stirring. After the addition is complete, stirring is continued for 14 h. After stirring, the mixture is poured into a product mold and dried for 8 h to obtain a high-viscosity epoxide polymerization product.

[0103] Example 3

[0104] This embodiment discloses a method for preparing a polyepoxide, comprising the following steps:

[0105] R1: Add 0.1 g of 1-ethyl-3-methylimidazolium chloride and 3.46 g of phthalic anhydride to a reaction bottle, seal it with a rubber stopper, evacuate for 30 min, then add 14.39 mL of valerolactone, 5 mL of tetrahydrofuran and 22.73 mL of propylene oxide, react in an oil bath at 100 °C for 3 h, cool it, and dissolve it with chloroform;

[0106] R2: Then, the product was precipitated with anhydrous methanol, and the operation was repeated three times. The product was dried in a vacuum oven at 70° C. to obtain a polyepoxide.

[0107] This embodiment discloses a method for preparing a composite silicon-cellulose, comprising the following steps:

[0108] Q1: 7 g of 40 mesh bamboo pulp was placed in a three-necked flask, and then 20 mL of 30 vt% sodium hydroxide solution and 150 mL of ethylene glycol were added, the three-necked flask was immersed in a water bath, stirred for 2 h, 11 g of chloroacetic acid was added, the temperature was raised to 60 ° C, and the etherification reaction was carried out for 4 h. After the reaction was completed, the three-necked flask was taken out, cooled, and 10 vt% acetic acid solution was added for neutralization, filtered, and the filter residue was washed with ethanol, dried, and cooled to obtain carboxymethyl cellulose;

[0109] Q2: 0.44 g of Custer catalyst and 17 g of 4-allyl-2-methoxyphenol were added to a three-necked flask equipped with a reflux condenser, a nitrogen inlet and outlet, and a magnetic stirrer, and 22 mL of toluene was added. Under nitrogen protection, the heating temperature was 70°C, and then 6.94 g of 1,1,3,3-tetramethyldisiloxane was slowly added to the three-necked flask through a micro-syringe pump. The reaction was continued for 48 hours. After the reaction was completed, the mixture was heated to 80°C for vacuum rotary evaporation to obtain modified silicone.

[0110] Q3: Add 20 mg of carboxymethyl cellulose to 60 mL of modified silicone, add formic acid at the same time, stir for 30 minutes, heat to 70°C and mix to obtain composite silicone-cellulose.

[0111] This embodiment discloses a method for preparing a carbazole-based thermal stabilizer, comprising the following steps:

[0112] S1: 3.45 g of carbazole, 6.36 g of 4-tert-butyl-iodobenzene, 4.09 g of cuprous iodide, and 5.53 g of potassium phosphate were placed in two beakers under a nitrogen atmosphere, and the gas was evacuated with a double-row pipe. 90 mL of N,N-dimethylformamide that had been dehydrated and deoxygenated was injected, and the mixture was heated at 160°C for 24 h. After the reaction, the reaction solution was cooled to room temperature, extracted with water, and then extracted with a mixed solution of dichloromethane and saturated brine. The bottom organic solvent was dried with anhydrous sodium sulfate, and then silica gel powder was added, rotary evaporated, and separated by a chromatography column to obtain a white powder substance;

[0113] S2: 1.56 g of white powder, 0.82 g of 2,6-difluoro-4-bromoacetophenone, 20 mL of tetrahydrofuran and 15 mL of 2 mol / L potassium carbonate aqueous solution were stirred for reaction under nitrogen protection, and then 0.38 g of PdCl2(PPh3)2 was added, and the reaction was continued under nitrogen protection at 90°C for 48 h. After the reaction was completed, the reaction was cooled to room temperature, and silica gel powder was added, and the reaction was performed by rotary evaporation and separation by chromatography to obtain a carbazole-based polymer;

[0114] S3: Dissolve 0.74 g of ferric chloride in 20 mL of 1,2-dichloroethane, stir and dissolve to obtain a ferric chloride solution, then dissolve 0.21 g of a carbazole-based polymer in 5 mL of 1,2-dichloroethane, and add it dropwise to the ferric chloride solution for reaction for 24 hours, then add methanol and stir for 45 minutes, filter, wash the filter cake with methanol and water, then place it in a 10vt% hydrochloric acid solution and stir for 2 hours, filter, wash, and extract. During the extraction process, first use methanol for 24 hours, then use tetrahydrofuran for 24 hours, and then vacuum dry at 110°C to obtain a carbazole-based thermal stabilizer.

[0115] This embodiment discloses a high viscosity epoxide polymerization product, which is composed of the following components in parts by weight: 52 parts of polyepoxide, 8 parts of composite silicon-cellulose, 3 parts of carbazole-based thermal stabilizer, 2 parts of γ-aminopropyltriethoxysilane, and 50 parts of deionized water.

[0116] See also Figure 1 As shown, this embodiment discloses a method for preparing a high viscosity epoxide polymerization product, comprising the following steps:

[0117] Step (1): add 52 g of polyepoxide to 35 mL of deionized water, stir at 70° C. for 12 h, and ultrasonically disperse to obtain a polyepoxide solution;

[0118] Step (2): 8 g of composite silicon-cellulose, 3 g of carbazole-based thermal stabilizer and 2 g of γ-aminopropyltriethoxysilane are added to 15 mL of deionized water and stirred for 9 h to obtain a uniformly dispersed mixed solution. The mixed solution is then added to the polyepoxide solution while stirring. After the addition is complete, stirring is continued for 14 h. After stirring, the mixture is poured into a product mold and dried for 8 h to obtain a high-viscosity epoxide polymerization product.

[0119] Example 4

[0120] This embodiment discloses a method for preparing a polyepoxide, comprising the following steps:

[0121] R1: 0.2 g of 1-ethyl-3-methylimidazolium chloride and 5.78 g of phthalic anhydride were added to a reaction bottle, sealed with a rubber stopper, and vacuumed for 30 min. Then, 12.17 mL of valerolactone, 15 mL of tetrahydrofuran, and 12.85 mL of propylene oxide were added. After reacting in an oil bath at 100 °C for 3 h, the mixture was cooled and dissolved with chloroform.

[0122] R2: Then, the product was precipitated with anhydrous methanol, and the operation was repeated three times. The product was dried in a vacuum oven at 70° C. to obtain a polyepoxide.

[0123] This embodiment discloses a method for preparing a composite silicon-cellulose, comprising the following steps:

[0124] Q1: 5.5 g of 40-mesh bamboo pulp was placed in a three-necked flask, and then 18 mL of 30 vt% sodium hydroxide solution and 160 mL of ethylene glycol were added. The three-necked flask was immersed in a water bath, stirred for 2 h, and then 14 g of chloroacetic acid was added. The temperature was raised to 60 ° C. and the etherification reaction was carried out for 4 h. After the reaction was completed, the three-necked flask was taken out, cooled, and 10 vt% acetic acid solution was added for neutralization. The filter was filtered, and the filter residue was washed with ethanol, dried, and cooled to obtain carboxymethyl cellulose;

[0125] Q2: 0.42g of Custer catalyst and 16.2g of 4-allyl-2-methoxyphenol were added to a three-necked flask equipped with a reflux condenser, a nitrogen inlet and outlet, and a magnetic stirrer, and 21mL of toluene was added. Under nitrogen protection, the heating temperature was 70°C, and then 6.83g of 1,1,3,3-tetramethyldisiloxane was slowly added to the three-necked flask through a micro-syringe pump. The reaction was continued for 48h. After the reaction was completed, the mixture was heated to 80°C for vacuum rotary evaporation to obtain modified silicone.

[0126] Q3: Add 13 mg of carboxymethyl cellulose to 45 mL of modified silicone, add formic acid at the same time, stir for 30 minutes, heat to 70°C and mix to obtain composite silicone-cellulose.

[0127] This embodiment discloses a method for preparing a carbazole-based thermal stabilizer, comprising the following steps:

[0128] S1: 3.21 g of carbazole, 6.48 g of 4-tert-butyl-iodobenzene, 3.49 g of cuprous iodide, and 5.37 g of potassium phosphate were placed in two beakers under a nitrogen atmosphere, and the gas was evacuated with a double-row pipe. 75 mL of N,N-dimethylformamide that had been dehydrated and deoxygenated was injected, and the mixture was heated at 160°C for 24 h. After the reaction, the reaction solution was cooled to room temperature, extracted with water, and then extracted with a mixed solution of dichloromethane and saturated brine. The bottom organic solvent was dried with anhydrous sodium sulfate, and then silica gel powder was added, rotary evaporated, and separated by a chromatography column to obtain a white powder substance;

[0129] S2: 1.50 g of white powder, 0.84 g of 2,6-difluoro-4-bromoacetophenone, 20 mL of tetrahydrofuran and 11 mL of 2 mol / L potassium carbonate aqueous solution were stirred for reaction under nitrogen protection, and then 0.24 g of PdCl2(PPh3)2 was added, and the reaction was continued under nitrogen protection at 90°C for 48 h. After the reaction was completed, the reaction was cooled to room temperature, and silica gel powder was added, and the reaction was performed by rotary evaporation and separation by chromatography to obtain a carbazole-based polymer;

[0130] S3: Dissolve 0.7g of ferric chloride in 20mL of 1,2-dichloroethane, stir and dissolve to obtain a ferric chloride solution, then dissolve 0.19g of a carbazole-based polymer in 5mL of 1,2-dichloroethane, and add it dropwise to the ferric chloride solution for reaction for 24h, then add methanol and stir for 45min, filter, wash the filter cake with methanol and water, then place it in a 10vt% hydrochloric acid solution and stir for 2h, filter, wash, and extract. During the extraction process, first use methanol for 24h, then use tetrahydrofuran for 24h, and then vacuum dry at 110°C to obtain a carbazole-based thermal stabilizer.

[0131] This embodiment discloses a high viscosity epoxide polymerization product, which is composed of the following components in parts by weight: 38 parts of polyepoxide, 5 parts of composite silicon-cellulose, 1.5 parts of carbazole-based thermal stabilizer, 1.7 parts of γ-aminopropyltriethoxysilane, and 35 parts of deionized water.

[0132] See also Figure 1 As shown, this embodiment discloses a method for preparing a high viscosity epoxide polymerization product, comprising the following steps:

[0133] Step (1): 38 g of polyepoxide was added to 26 mL of deionized water, stirred at 70° C. for 12 h, and ultrasonically dispersed to obtain a polyepoxide solution;

[0134] Step (2): Add 5 g of composite silicon-cellulose, 1.5 g of carbazole-based thermal stabilizer and 1.7 g of γ-aminopropyltriethoxysilane to 9 mL of deionized water and stir for 9 h to obtain a uniformly dispersed mixed solution. Then add the mixed solution to the polyepoxide solution while stirring. After the addition is complete, continue stirring for 14 h. After stirring, pour into a product mold and dry for 8 h to obtain a high-viscosity epoxide polymerization product.

[0135] Example 5

[0136] This embodiment discloses a method for preparing a polyepoxide, comprising the following steps:

[0137] R1: Add 0.3 g of 1-ethyl-3-methylimidazolium chloride and 9.43 g of phthalic anhydride to a reaction bottle, seal it with a rubber stopper, evacuate for 30 min, then add 5.83 mL of valerolactone, 12.5 mL of tetrahydrofuran and 18.04 mL of propylene oxide, react in an oil bath at 100 °C for 3 h, cool it, and dissolve it with chloroform;

[0138] R2: Then, the product was precipitated with anhydrous methanol, and the operation was repeated three times. The product was dried in a vacuum oven at 70° C. to obtain a polyepoxide.

[0139] This embodiment discloses a method for preparing a composite silicon-cellulose, comprising the following steps:

[0140] Q1: 6.5 g of 40 mesh bamboo pulp was placed in a three-necked flask, and then 19 mL of 30 vt% sodium hydroxide solution and 180 mL of ethylene glycol were added, the three-necked flask was immersed in a water bath, stirred for 2 h, 12.5 g of chloroacetic acid was added, the temperature was raised to 60 ° C, and the etherification reaction was carried out for 4 h. After the reaction was completed, the three-necked flask was taken out, cooled, and 10 vt% acetic acid solution was added for neutralization, filtered, and the filter residue was washed with ethanol, dried, and cooled to obtain carboxymethyl cellulose;

[0141] Q2: 0.37 g of Custer catalyst and 16.8 g of 4-allyl-2-methoxyphenol were added to a three-necked flask equipped with a reflux condenser, a nitrogen inlet and outlet, and a magnetic stirrer, and 19 mL of toluene was added. Under nitrogen protection, the heating temperature was 70°C, and then 6.67 g of 1,1,3,3-tetramethyldisiloxane was slowly added to the three-necked flask through a micro-syringe pump. The reaction was continued for 48 hours. After the reaction was completed, the mixture was heated to 80°C for vacuum rotary evaporation to obtain modified silicone.

[0142] Q3: Add 18 mg of carboxymethyl cellulose to 55 mL of modified silicone, add formic acid at the same time, stir for 30 minutes, heat to 70°C and mix to obtain composite silicone-cellulose.

[0143] This embodiment discloses a method for preparing a carbazole-based thermal stabilizer, comprising the following steps:

[0144] S1: 3.51 g of carbazole, 6.06 g of 4-tert-butyl-iodobenzene, 4.29 g of cuprous iodide, and 5.48 g of potassium phosphate were placed in two beakers under a nitrogen atmosphere, and the gas was evacuated with a double-row pipe. 85 mL of N,N-dimethylformamide that had been dehydrated and deoxygenated was injected, and the mixture was heated at 160°C for 24 h. After the reaction, the reaction solution was cooled to room temperature, extracted with water, and then extracted with a mixed solution of dichloromethane and saturated brine. The bottom organic solvent was dried with anhydrous sodium sulfate, and then silica gel powder was added, rotary evaporated, and separated by a chromatography column to obtain a white powder substance;

[0145] S2: 1.54 g of white powder, 0.83 g of 2,6-difluoro-4-bromoacetophenone, 20 mL of tetrahydrofuran and 13 mL of 2 mol / L potassium carbonate aqueous solution were stirred for reaction under nitrogen protection, and then 0.34 g of PdCl2(PPh3)2 was added, and the reaction was continued under nitrogen protection at 90°C for 48 h. After the reaction was completed, the reaction was cooled to room temperature, and silica gel powder was added, and the reaction was performed by rotary evaporation and separation by chromatography to obtain a carbazole-based polymer;

[0146] S3: Dissolve 0.77g of ferric chloride in 20mL of 1,2-dichloroethane, stir and dissolve to obtain a ferric chloride solution, then dissolve 0.14g of a carbazole-based polymer in 5mL of 1,2-dichloroethane, and add it dropwise to the ferric chloride solution for reaction for 24h, then add methanol and stir for 45min, filter, wash the filter cake with methanol and water, then place it in a 10vt% hydrochloric acid solution and stir for 2h, filter, wash, and extract. During the extraction process, first use methanol for 24h, then use tetrahydrofuran for 24h, and then vacuum dry at 110°C to obtain a carbazole-based thermal stabilizer.

[0147] This embodiment discloses a high viscosity epoxide polymerization product, which is composed of the following components in parts by weight: 45 parts of polyepoxide, 7 parts of composite silicon-cellulose, 2.5 parts of carbazole-based thermal stabilizer, 1.3 parts of γ-aminopropyltriethoxysilane, and 45 parts of deionized water.

[0148] See also Figure 1 As shown, this embodiment discloses a method for preparing a high viscosity epoxide polymerization product, comprising the following steps:

[0149] Step (1): add 45 g of polyepoxide to 32 mL of deionized water, stir at 70° C. for 12 h, and ultrasonically disperse to obtain a polyepoxide solution;

[0150] Step (2): 7 g of composite silicon-cellulose, 2.5 g of carbazole-based thermal stabilizer and 1.3 g of γ-aminopropyltriethoxysilane are added to 13 mL of deionized water and stirred for 9 h to obtain a uniformly dispersed mixed solution. The mixed solution is then added to the polyepoxide solution while stirring. After the addition is complete, stirring is continued for 14 h. After stirring, the mixture is poured into a product mold and dried for 8 h to obtain a high-viscosity epoxide polymerization product.

[0151] Example 6

[0152] This embodiment discloses a method for preparing a polyepoxide, comprising the following steps:

[0153] R1: 0.4 g of 1-ethyl-3-methylimidazolium chloride and 15.21 g of phthalic anhydride were added to a reaction bottle, sealed with a rubber stopper, and vacuumed for 30 min. Then, 7.57 mL of valerolactone, 10 mL of tetrahydrofuran and 15.71 mL of propylene oxide were added, and the mixture was reacted in an oil bath at 100 °C for 3 h, cooled, and dissolved with chloroform;

[0154] R2: Then, the product was precipitated with anhydrous methanol, and the operation was repeated three times. The product was dried in a vacuum oven at 70° C. to obtain a polyepoxide.

[0155] This embodiment discloses a method for preparing a composite silicon-cellulose, comprising the following steps:

[0156] Q1: 5.1 g of 40-mesh bamboo pulp was placed in a three-necked flask, and then 17.5 mL of a 30 vt% sodium hydroxide solution and 175 mL of ethylene glycol were added. The three-necked flask was immersed in a water bath, stirred for 2 h, and then 13.5 g of chloroacetic acid was added. The temperature was raised to 60 ° C. and the etherification reaction was carried out for 4 h. After the reaction was completed, the three-necked flask was taken out, cooled, and a 10 vt% acetic acid solution was added for neutralization. The filter was filtered, and the filter residue was washed with ethanol, dried, and cooled to obtain carboxymethyl cellulose;

[0157] Q2: 0.36 g of Custer catalyst and 16.6 g of 4-allyl-2-methoxyphenol were added to a three-necked flask equipped with a reflux condenser, a nitrogen inlet and outlet, and a magnetic stirrer, and 20 mL of toluene was added. Under nitrogen protection, the heating temperature was 70°C, and then 5.59 g of 1,1,3,3-tetramethyldisiloxane was slowly added to the three-necked flask through a micro-syringe pump. The reaction was continued for 48 hours. After the reaction was completed, the mixture was heated to 80°C for vacuum rotary evaporation to obtain modified silicone.

[0158] Q3: Add 11 mg of carboxymethyl cellulose to 58 mL of modified silicone, add formic acid at the same time, stir for 30 minutes, heat to 70°C and mix to obtain composite silicone-cellulose.

[0159] This embodiment discloses a method for preparing a carbazole-based thermal stabilizer, comprising the following steps:

[0160] S1: 3.63 g of carbazole, 6.32 g of 4-tert-butyl-iodobenzene, 4.11 g of cuprous iodide, and 5.42 g of potassium phosphate were placed in two beakers under a nitrogen atmosphere, and the gas was evacuated with a double-row pipe. 78 mL of N,N-dimethylformamide that had been dehydrated and deoxygenated was injected, and the mixture was heated at 160°C for 24 h. After the reaction, the reaction solution was cooled to room temperature, extracted with water, and then extracted with a mixed solution of dichloromethane and saturated brine. The bottom organic solvent was dried with anhydrous sodium sulfate, and then silica gel powder was added, rotary evaporated, and separated by a chromatography column to obtain a white powder substance;

[0161] S2: 1.53 g of white powder, 0.81 g of 2,6-difluoro-4-bromoacetophenone, 20 mL of tetrahydrofuran and 13.5 mL of 2 mol / L potassium carbonate aqueous solution were stirred for reaction under nitrogen protection, and then 0.32 g of PdCl2(PPh3)2 was added, and the reaction was continued under nitrogen protection at 90°C for 48 h. After the reaction was completed, the reaction was cooled to room temperature, and silica gel powder was added, and the reaction was performed by rotary evaporation and separation by chromatography to obtain a carbazole-based polymer;

[0162] S3: Dissolve 0.72g of ferric chloride in 20mL of 1,2-dichloroethane, stir and dissolve to obtain a ferric chloride solution, then dissolve 0.15g of a carbazole-based polymer in 5mL of 1,2-dichloroethane, and add it dropwise to the ferric chloride solution for reaction for 24h, then add methanol and stir for 45min, filter, wash the filter cake with methanol and water, then place it in a 10vt% hydrochloric acid solution and stir for 2h, filter, wash, and extract. During the extraction process, first use methanol for 24h, then use tetrahydrofuran for 24h, and then vacuum dry at 110°C to obtain a carbazole-based thermal stabilizer.

[0163] This embodiment discloses a high viscosity epoxide polymerization product, which is composed of the following components in parts by weight: 41 parts of polyepoxide, 6.5 parts of composite silicon-cellulose, 2.8 parts of carbazole-based thermal stabilizer, 1.9 parts of γ-aminopropyltriethoxysilane, and 38 parts of deionized water.

[0164] See also Figure 1 As shown, this embodiment discloses a method for preparing a high viscosity epoxide polymerization product, comprising the following steps:

[0165] Step (1): add 41 g of polyepoxide to 30 mL of deionized water, stir at 70° C. for 12 h, and ultrasonically disperse to obtain a polyepoxide solution;

[0166] Step (2): Add 6.5 g of composite silicon-cellulose, 2.8 g of carbazole-based thermal stabilizer and 1.9 g of γ-aminopropyltriethoxysilane to 8 mL of deionized water and stir for 9 h to obtain a uniformly dispersed mixed solution. Then add the mixed solution to the polyepoxide solution while stirring. After the addition is complete, continue stirring for 14 h. After stirring, pour into a product mold and dry for 8 h to obtain a high-viscosity epoxide polymerization product.

[0167] Comparative Example 1

[0168] Comparative Example 1 Compared with Example 1, in the process of preparing the composite silicon-cellulose in Comparative Example 1, 4-allyl-2-methoxyphenol was not added, and other conditions remained unchanged.

[0169] Comparative Example 2

[0170] Comparative Example 2 Compared with Example 1, in the process of preparing the composite silicon-cellulose in Comparative Example 2, no carboxymethyl cellulose was added, and other conditions remained unchanged.

[0171] Comparative Example 3

[0172] Comparative Example 3 Compared with Example 1, in the process of preparing the carbazole-based thermal stabilizer in Comparative Example 3, 2,6-difluoro-4-bromoacetophenone was not added, and other conditions remained unchanged.

[0173] Comparative Example 4

[0174] Comparative Example 4 Compared with Example 1, in the process of preparing the carbazole-based thermal stabilizer in Comparative Example 4, 4-tert-butyl-iodobenzene was not added, and other conditions remained unchanged.

[0175] Comparative Example 5

[0176] Comparative Example 5 Compared with Example 1, in the preparation process of the high-viscosity epoxide polymerization product in Comparative Example 5, no composite silicon-cellulose is added, and other conditions remain unchanged.

[0177] Comparative Example 6

[0178] Comparative Example 6 Compared with Example 1, in the preparation process of the high-viscosity epoxide polymerization product in Comparative Example 6, no carbazole-based thermal stabilizer was added, and other conditions remained unchanged.

[0179] Comparative Example 7

[0180] Comparative Example 7 Compared with Example 1, in the preparation process of polyepoxide in Comparative Example 7, no valerolactone was added, and other conditions remained unchanged.

[0181] The properties of the high viscosity epoxide polymerization products prepared in Examples 1-6 and Comparative Examples 1-7 were tested. The viscosity of the samples was measured according to GB / T 15357-2014, and the thermal stability of the samples was measured according to GB / T 22232-2008. The test results are shown in Table 1:

[0182] Table 1 Performance test results of products prepared in Examples 1-6 and Comparative Examples 1-7

[0183]

[0184] It can be seen from the test results in Table 1 that the preparation method adopted in Examples 1-6 of the present invention enables the epoxide polymerization product to have excellent viscosity and thermal stability. By comparing Comparative Example 1 with Examples 1-6, it can be seen that the addition of 4-allyl-2-methoxyphenol can increase the viscosity of the epoxide polymerization product; by comparing Comparative Example 2 with Examples 1-6, it can be seen that the addition of carboxymethyl cellulose can increase the viscosity of the epoxide polymerization product; by comparing Comparative Example 3 with Examples 1-6, it can be seen that the addition of 2,6-difluoro-4-bromoacetophenone can increase the thermal stability of the epoxide polymerization product; by comparing Comparative Example 4 with Examples 1-6, it can be seen that the addition of 4-tert-butyl-iodobenzene can increase the thermal stability of the epoxide polymerization product; by comparing Comparative Example 5 with Examples 1-6, it can be seen that the addition of composite silicon-cellulose can increase the viscosity of the epoxide polymerization product; by comparing Comparative Example 6 with Examples 1-6, it can be seen that the addition of a carbazole-based thermal stabilizer can increase the thermal stability of the epoxide polymerization product; by comparing Comparative Example 7 with Examples 1-6, it can be seen that the addition of valerolactone can increase the thermal stability of the epoxide polymerization product.

[0185] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

[0186] The preferred embodiments of the present invention disclosed above are only used to help explain the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to only specific implementation methods. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A method for preparing a high viscosity epoxide polymerization product, characterized in that: The following steps are involved: Step (1): adding polyepoxide to deionized water, stirring, and ultrasonically dispersing to obtain a polyepoxide solution; Step (2): adding the composite silicon-cellulose, carbazole-based heat stabilizer and compatibilizer into deionized water, stirring to obtain a uniformly dispersed mixed solution, then adding the mixed solution into the polyepoxide solution, stirring while adding, continuing to stir after the addition is complete, pouring into a product mold after stirring, and drying to obtain a high-viscosity epoxide polymerization product; The preparation method of the polyepoxide comprises the following steps: R1: Add 1-ethyl-3-methylimidazolium chloride and phthalic anhydride to a reaction bottle, seal it with a rubber stopper, evacuate it, then add valerolactone, tetrahydrofuran and propylene oxide, react in an oil bath, cool it, and dissolve it with chloroform; R2: Then, the precipitation is performed with anhydrous methanol, and the operation is repeated, and then the polyepoxide is obtained by drying in a vacuum oven; The preparation method of composite silicon-cellulose comprises the following steps: Q1: Bamboo pulp is placed in a three-necked flask, and then sodium hydroxide solution and ethylene glycol are added, the three-necked flask is immersed in a water bath, stirred, chloroacetic acid is added, the temperature is raised, and an etherification reaction is carried out. After the reaction is completed, the three-necked flask is taken out, cooled, acetic acid solution is added for neutralization, filtered, the filter residue is washed with ethanol, dried, and cooled to obtain carboxymethyl cellulose; Q2: Add the Custer catalyst and 4-allyl-2-methoxyphenol to a three-necked flask, and then add toluene. Heat the flask under nitrogen protection, and then slowly add 1,1,3,3-tetramethyldisiloxane to the three-necked flask through a micro-syringe pump. After the reaction is completed, heat and vacuum evaporation is performed to obtain modified silicone. Q3: Add carboxymethyl cellulose to the modified silicone, add formic acid at the same time, stir, heat and mix to obtain composite silicone-cellulose; The preparation method of the carbazole-based thermal stabilizer comprises the following steps: S1: Carbazole, 4-tert-butyl-iodobenzene, cuprous iodide, and potassium phosphate are placed in two beakers under a nitrogen atmosphere, the gas is evacuated with a double-row pipe, and N,N-dimethylformamide that has been dehydrated and deoxygenated is injected, and the reaction is heated. After the reaction is completed, the reaction solution is cooled to room temperature, extracted with water, and then extracted with a mixed solution of dichloromethane and saturated brine. The bottom organic solvent is dried with anhydrous sodium sulfate, and then silica gel powder is added, rotary evaporated, and separated by a chromatography column to obtain a white powder substance; S2: Stir the white powder, 2,6-difluoro-4-bromoacetophenone, tetrahydrofuran and potassium carbonate aqueous solution under nitrogen protection, then add PdCl2(PPh3)2, continue heating and reacting under nitrogen protection, and after the reaction is completed, cool to room temperature, add silica gel powder, perform rotary evaporation, and separate by chromatography column to obtain a carbazole-based substance; S3: Dissolve ferric chloride in 1,2-dichloroethane, stir and dissolve to obtain a ferric chloride solution, then dissolve the carbazole-based substance in 1,2-dichloroethane and add it dropwise to the ferric chloride solution for reaction, then add methanol, stir and filter, wash the filter cake with methanol and water, then place it in a hydrochloric acid solution, stir, filter, wash, extract, and vacuum dry to obtain a carbazole-based thermal stabilizer.

2. The method for preparing a high viscosity epoxide polymerization product according to claim 1, characterized in that: The high-viscosity epoxide polymerization product is composed of the following components in parts by weight: 36-52 parts of polyepoxide, 4-8 parts of composite silicon-cellulose, 1-3 parts of carbazole-based heat stabilizer, 1-2 parts of compatibilizer, and 30-50 parts of deionized water.

3. The method for preparing a high viscosity epoxide polymerization product according to claim 1, characterized in that: In the R1, the dosage ratio of 1-ethyl-3-methylimidazolium chloride, phthalic anhydride, valerolactone, tetrahydrofuran and propylene oxide is (0.1-0.5) g: (3.46-17.3) g: (3.31-16.55) mL: (5-25) mL: (4.77-23.85) mL, the vacuuming time is 30-40 min, the oil bath temperature is 100-110° C., and the oil bath reaction time is 1-3 h; in the R2, the operation is repeated 3-5 times, and the drying temperature is 60-70° C.

4. The method for preparing a high viscosity epoxide polymerization product according to claim 1, characterized in that: In Q1, the particle size of bamboo pulp is 20-40 mesh, the dosage ratio of bamboo pulp, sodium hydroxide, ethylene glycol and chloroacetic acid is (5-7) g: (15-20) mL: (150-200) mL: (11-14) g, the volume fraction of sodium hydroxide is 30 vt%, the stirring time is 1-2 h, the heating temperature is 60-70°C, the etherification reaction time is 2-4 h, and the volume fraction of acetic acid solution is 10 vt%.

5. The method for preparing a high viscosity epoxide polymerization product according to claim 1, characterized in that: In Q2, the amount ratio of Custer catalyst, 4-allyl-2-methoxyphenol, toluene and 1,1,3,3-tetramethyldisiloxane is (0.35-0.44) g: (16-17) g: (18-22) mL: (6.5-6.94) g, the three-necked flask is equipped with a reflux condenser, a nitrogen inlet and outlet and a magnetic stirrer, the heating temperature is 60-70°C, the reaction time is 48-52h, and the heating vacuum rotary evaporation temperature is 70-80°C; in Q3, the amount ratio of carboxymethyl cellulose and modified silicone is (10-20) mg: (40-60) mL, the stirring time is 20-40min, and the heating temperature is 60-70°C.

6. The method for preparing a high viscosity epoxide polymerization product according to claim 1, characterized in that: In S1, the amount ratio of carbazole, 4-tert-butyl-iodobenzene, cuprous iodide, potassium phosphate, and N,N-dimethylformamide is (3-3.68) g: (6-6.48) g: (3.49-4.29) g: (5.1-5.53) g: (70-90) mL, the heating reaction temperature is 150-170°C, and the reaction time is 20-24 h; in S2, the amount ratio of white powder, 2,6-difluoro-4-bromoacetophenone, tetrahydrofuran, potassium carbonate, and PdCl2(PPh3)2 is (1.48-1.56) g: (0.78-0.84) g: 20 mL: (10-15) mL: (0.18-0.38) g, and the amount ratio of carbonic acid is (1.48-1.56) g: (0.78-0.84) g: 20 mL: (10-15) mL: (0.18-0.38) g. The concentration of the potassium aqueous solution is 2 mol / L, the temperature of the heating reaction is 70-90°C, and the heating reaction time is 40-50h; in the S3, the dosage ratio of ferric chloride and 1,2-dichloroethane is (0.7-0.77) g: 20 mL, the dosage ratio of the carbazole-based substance and 1,2-dichloroethane is (0.01-0.21) g: 5 mL, the reaction time is 22-26h, the stirring time for adding methanol is 30-45min, the volume fraction of the hydrochloric acid solution is 10vt%, and the stirring time is 1-2h. During the extraction process, methanol is first used for extraction for 20-24h, and then tetrahydrofuran is used for extraction for 20-24h, and the vacuum drying temperature is 100-110°C.

7. The method for preparing a high viscosity epoxide polymerization product according to claim 1, characterized in that: In the step (1), the temperature during stirring is 60-70°C and the stirring time is 12-14h; in the step (2), the stirring time is 7-9h, the stirring time is continued for 12-14h, and the drying temperature is 70-80°C and the time is 16-20h.

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