Preparation method of an additive and application thereof in polycarbonate engineering plastics

Abstract

The present invention relates to the technical field of polymer materials, and specifically relates to a preparation method of an additive and its application in polycarbonate engineering plastics. The preparation method includes the following steps: preparation of a Cu / TiO₂-CeO₂ core-shell body; modification with the surfactant PEG; preparation of the additive. In the present invention, Cu and Ti are introduced and compounded with Ce to prepare a Cu / TiO₂-CeO₂ core-shell body. The synergistic effect between Cu and Ti and Ce can improve the activity of the CeO₂ catalyst and enhance the catalytic reaction rate. At the same time, Cu and Ti as the outer shell increase the number of surface active sites of CeO₂ and improve the adsorption ability of CeO₂ as a catalyst for reactants, thereby ensuring that the additive prepared with the Cu / TiO₂-CeO₂ core-shell body as the main body can play a catalytic reaction in the preparation of polycarbonate and improve the yield and purity of polycarbonate.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and particularly relates to a preparation method of an additive and its application in polycarbonate engineering plastics. Background Art

[0002] Polycarbonate (PC for short) is a high-performance thermoplastic engineering plastic, well-known for its excellent mechanical properties, optical properties and heat resistance, and is commonly used in fields such as electronics and electrical appliances, automotive industry, medical treatment, packaging, etc. Preparing polycarbonate using carbon dioxide is an environmentally friendly and sustainable method, which can reduce the dependence on traditional petroleum-based raw materials and lower carbon emissions. This method is usually referred to as one of the "green chemistry" methods, specifically: by reacting CO 2 with propylene oxide or ethylene oxide to form cyclic carbonate, and then through ring-opening polymerization reaction to form polycarbonate. The advantages are mild reaction conditions and easy control, and the disadvantage is that an efficient catalyst is required to promote the reaction. Therefore, the present invention provides a preparation method of an additive and its application in polycarbonate engineering plastics, and solves the technical problem of the need for an efficient catalyst during the formation of polycarbonate by preparing an additive that can catalyze the synthesis of polycarbonate. Summary of the Invention

[0003] Aiming at the deficiencies existing in the prior art, the purpose of the present invention is to provide a preparation method of an additive.

[0004] A preparation method of an additive includes the following steps:

[0005] S1: Preparation of Cu / TiO 2 -CeO 2 Preparation of core-shell structure

[0006] Weigh Cu(NO 3 ) 2 ·3H 2 O and add it to ethanol, heat it in a water bath and stir magnetically, then add TiO 2 to it, add an aqueous NaOH solution to obtain a metal solution, add a glucose aqueous solution to the metal solution, perform suction filtration, washing, and drying to obtain Cu 2 O-TiO 2 , add Cu 2 O-TiO 2 to an ethanol solution, successively add an aqueous NaCl solution and an (NH 4 ) 2 Ce(NO 3 ) 6 ethanol solution to obtain a mixed solution, separate the mixed solution and dry the precipitate in a vacuum environment, and calcine to obtain Cu / TiO 2 -CeO2 Core-shell body;

[0007] S2: Surfactant PEG modification

[0008] S2.1: Dissolve DMPA in dichloromethane to obtain a DMPA solution, then dissolve PEG in dichloromethane to obtain a PEG solution. Add DPTS and DCC to the PEG solution, and then add the DMPA solution to obtain dendritic PEG. Dissolve the dendritic PEG in methanol, add DOWEX-H + resin, stir, filter, precipitate the filtrate with ether, and dry the precipitate to remove the solvent to obtain modified PEG;

[0009] S3: Preparation of additives

[0010] S3.1: Dissolve the Cu / TiO 2 -CeO 2 core-shell body and modified PEG in distilled water, dropwise add NaOH solution to obtain a suspension, transfer the suspension to a hydrothermal reactor for reaction, then naturally cool to room temperature, collect the precipitate by centrifugation, and heat it after drying to obtain the additive;

[0011] Furthermore, in step S1, the preparation of the Cu / TiO 2 -CeO 2 core-shell body includes the following steps:

[0012] S1.1: Weigh 0.2 - 0.5 parts by mass of Cu(NO 3 ) 2 ·3H 2 O and add it to ethanol, heat it in a water bath at 60 °C and stir magnetically for 5 - 10 min, then add 2 parts by mass of TiO 2 to it. After stirring magnetically for 30 min, add 50 parts by volume of 1 mol / L NaOH aqueous solution and continue stirring for 30 min to obtain a metal solution;

[0013] S1.2: Add 10 parts by volume of glucose aqueous solution to the metal solution, stir for 1 h, and finally filter the metal solution to obtain a yellow precipitate. Wash the precipitate 3 times each with deionized water and absolute ethanol, and then vacuum dry it at 50 °C for 24 h to obtain Cu 2 O-TiO 2 ;

[0014] S1.3: Add 2 - 2.5 parts by mass of Cu 2 O-TiO 2 to 80 parts by volume of ethanol solution, successively add 8 parts by volume of NaCl aqueous solution, and 0.8 - 1.2 parts by mass of (NH 4 ) 2 Ce(NO3 ) 6 An ethanol solution was obtained to get a mixture;

[0015] S1.4: The mixture was magnetically stirred at room temperature for 30 min, then transferred to a water bath and stirred at 40 °C for 1 h. Centrifugation was carried out to separate the solid from the liquid, and the precipitate was washed three times with deionized water and dried in a vacuum environment. Finally, the product was calcined in a muffle furnace at 400 °C for 1 h to obtain Cu / TiO 2 -CeO 2 core-shell structure.

[0016] Furthermore, the surfactant PEG modification in step S2 includes the following steps:

[0017] S2.1: 5.2 parts by mass of DMPA was dissolved in 15 parts by volume of dichloromethane to obtain a DMPA solution. Then, 4 - 4.5 parts by mass of PEG was dissolved in 15 parts by volume of dichloromethane to obtain a PEG solution. 0.2 - 0.3 parts by mass of DPTS and 0.5 - 0.6 parts by mass of DCC were added to the PEG solution, and then the DMPA solution was added. The reaction was stirred at room temperature for 48 h, filtered, and the precipitate product was dried to remove the solvent to obtain dendritic PEG;

[0018] S2.2: The dendritic PEG was dissolved in methanol, and DOWEX-H + resin was added, and the mixture was stirred at room temperature for 24 h, filtered, and the filtrate was precipitated with ether. The precipitate product was dried to remove the solvent to obtain modified PEG.

[0019] Furthermore, the preparation of the additive in step S3 includes the following steps:

[0020] S3.1: 10 - 12 parts by mass of Cu / TiO 2 -CeO 2 core-shell structure and 0.5 part by mass of modified PEG were dissolved in 200 parts by volume of distilled water, and 100 parts by volume of a NaOH solution with a concentration of 11.25 mol / L was slowly added dropwise. The mixture was stirred at room temperature for 30 min to obtain a suspension;

[0021] S3.2: The suspension was transferred to a hydrothermal autoclave and reacted at 110 °C for 10 h. After the reaction was completed, it was naturally cooled to room temperature. The precipitate was collected by centrifugation, washed three times with deionized water and ethanol respectively to remove impurities, and dried at 80 °C for 12 h. After drying, it was heated to 600 °C in air and maintained for 3 h to obtain the additive.

[0022] Furthermore, the feed ratio of dendritic PEG to methanol is 1:20 g / L.

[0023] Furthermore, the heating rate is 5 °C / min.

[0024] Further, the concentration of the glucose aqueous solution is 4 mol / L.

[0025] Further, the concentration of the NaCl aqueous solution is 0.855 mol / L.

[0026] Further, (NH 4 ) 2 Ce(NO 3 ) 6 The ethanol solution is prepared by dissolving (NH 4 ) 2 Ce(NO 3 ) 6 in ethanol at a material-liquid ratio of 1:50 g / ml.

[0027] The application of an additive in polycarbonate engineering plastics includes the following steps:

[0028] L1: Place 3.5 parts by mass of 1,6-hexanediol, 20 parts by mass of 2-cyanopyridine, and 0.5 part by mass of the additive in an autoclave. Replace the air in the autoclave three times with CO 2 , then pressurize to 5.0 MPa, heat up to 130 °C at a rate of 3 °C / min and react for 8 h. After the reaction, cool naturally to room temperature to obtain an intermediate.

[0029] L2: Then add 30 parts by volume of CH 3 OH to the intermediate at 45 °C for post-treatment. Centrifuge for 5 - 20 min to separate the liquid and the precipitate. After removing the precipitate, add 300 parts by volume of deionized water pre-cooled to 4 °C to the liquid part, store it in a refrigerator at 4 °C for 12 h, then centrifuge to recover the lower-layer liquid, and dry it in an oven at 60 °C for 24 h to obtain polycarbonate.

[0030] Compared with the prior art, the present invention has at least the following beneficial effects:

[0031] 1. The present invention introduces Cu and Ti and composes them with Ce to prepare a Cu / TiO 2 -CeO 2 core-shell structure. The synergistic effect between Cu and Ti and Ce can improve the activity of the CeO 2 catalyst. Moreover, Cu and Ti can promote the redox performance of Ce, thereby enhancing the catalytic reaction rate. At the same time, Cu and Ti as the shell increase the number of surface active sites of CeO 2 , improving the adsorption ability of CeO 2 as a catalyst for reactants. And the addition of Ti can reduce the agglomeration of CeO 2 particles and prevent their sintering at high temperatures, thus ensuring that Cu / TiO 2 -CeO 2The additive prepared with the core-shell body as the main body can play a catalytic role in the preparation of polycarbonate, improving the yield and purity of polycarbonate.

[0032] 2. In the present invention, PEG is dendrimerized by grafting DMPA. Due to its highly branched structure, dendritic PEG has higher water solubility, and dendritic PEG can be separated from the reaction system by simple physical methods such as centrifugation and filtration, facilitating the recovery and reuse of the catalyst. Moreover, the structure of dendritic PEG can promote the transfer of electrons on the surface of the catalyst, improving the catalytic reaction rate and efficiency. By adding a modified PEG with dendritic PEG as the main body to prepare an additive and applying the additive to the preparation of polycarbonate, the dispersibility and solubility of the additive in the aqueous reaction system can be greatly improved, thereby improving the purity of the polycarbonate prepared by the reaction.

[0033] 3. In the present invention, dendritic PEG is used to load Cu / TiO 2 -CeO 2 core-shell body. The structure of dendritic PEG generates a large number of internal cavities for loading Cu / TiO 2 -CeO 2 core-shell body, thereby improving the compatibility of dendritic PEG and Cu / TiO 2 -CeO 2 core-shell body in water, effectively preventing the aggregation of Cu / TiO 2 -CeO 2 core-shell body, and improving its stability during the reaction, thereby improving the purity of polycarbonate. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] The drawings incorporated herein and constituting a part of the specification illustrate embodiments of the present invention and, together with the specification, are further used to explain the principles of the present invention and enable those skilled in the relevant art to implement and use the present invention.

[0035] Figure 1 It is a flowchart of a preparation method of an additive adopted in an embodiment of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0036] The following describes in detail a preparation method of an additive provided by the present invention in combination with the drawings and specific embodiments. At the same time, it should be noted here that in order to make the embodiments more detailed, the following embodiments are the best and preferred embodiments. For some well-known technologies, those skilled in the art can also adopt other alternative methods for implementation; moreover, the drawing part is only for more specifically describing the embodiments and is not intended to specifically limit the present invention.

[0037] Example 1:

[0038] A preparation method of an additive, as Figure 1 shown, includes the following steps:

[0039] S1: Preparation of Cu / TiO 2 -CeO 2 core-shell structure

[0040] S1.1: Weigh 0.2 parts by mass of Cu(NO 3 ) 2 ·3H 2 O and add it to ethanol, heat it in a water bath at 60 °C and stir magnetically for 5 - 10 min. Then add 2 parts by mass of TiO 2 to it, stir magnetically for 30 min, add 50 parts by volume of 1 mol / L NaOH aqueous solution, and continue to stir for 30 min to obtain a metal solution;

[0041] S1.2: Add 10 parts by volume of 4 mol / L glucose aqueous solution to the metal solution, stir for 1 h, and finally filter the metal solution by suction to obtain a yellow precipitate. Wash the precipitate 3 times with deionized water and anhydrous ethanol respectively, and then dry it in vacuum at 50 °C for 24 h to obtain Cu 2 O-TiO 2 ;

[0042] S1.3: Add 2 parts by mass of Cu 2 O-TiO 2 to 80 parts by volume of ethanol solution, successively add 8 parts by volume of 0.855 mol / L NaCl aqueous solution and 0.8 parts by mass of (NH 4 ) 2 Ce(NO 3 ) 6 ethanol solution. The (NH 4 ) 2 Ce(NO 3 ) 6 ethanol solution is prepared by dissolving (NH 4 ) 2 Ce(NO 3 ) 6 in ethanol at a material-liquid ratio of 1:50 g / ml to obtain a mixed solution;

[0043] S1.4: Stir the mixed solution magnetically at room temperature for 30 min, then transfer it to a water bath at 40 °C and stir for 1 h, centrifuge to separate the solid and liquid, wash the precipitate 3 times with deionized water, and dry it in a vacuum environment. Finally, calcine the product in a muffle furnace at 400 °C for 1 h to obtain the Cu / TiO 2 -CeO 2 core-shell structure.

[0044] S2: Modification with surfactant PEG

[0045] S2.1: Dissolve 5.2 parts by mass of DMPA in 15 parts by volume of dichloromethane to obtain a DMPA solution. Then dissolve 4 parts by mass of PEG in 15 parts by volume of dichloromethane to obtain a PEG solution. Add 0.2 parts by mass of DPTS and 0.5 - 0.6 parts by mass of DCC to the PEG solution, and then add the DMPA solution. Stir the reaction at room temperature for 48 h, filter, dry the precipitate product, and remove the solvent to obtain dendritic PEG.

[0046] S2.2: Dissolve dendritic PEG in methanol. The material ratio of dendritic PEG to methanol is 1:20 g / L. Add DOWEX - H + resin, stir at room temperature for 24 h, filter, precipitate the filtrate with ether, and dry the precipitate product to remove the solvent to obtain modified PEG.

[0047] S3: Preparation of additives

[0048] S3.1: Dissolve 12 parts by mass of Cu / TiO 2 -CeO 2 core - shell particles and 0.5 parts by mass of modified PEG in 200 parts by volume of distilled water, slowly add 100 parts by volume of a NaOH solution with a concentration of 11.25 mol / L, and stir at room temperature for 30 min to obtain a suspension.

[0049] S3.2: Transfer the suspension to a hydrothermal autoclave, react at 110 °C for 10 h, naturally cool to room temperature after the reaction is completed, collect the precipitate by centrifugation, wash it three times with deionized water and ethanol respectively to remove impurities, and dry it at 80 °C for 12 h. After drying, heat it in air to 600 °C at a heating rate of 5 °C / min and hold for 3 h to obtain the additive.

[0050] Application of additives

[0051] L1: Place 3.5 parts by mass of 1,6 - hexanediol, 20 parts by mass of 2 - cyanopyridine, and 0.5 parts by mass of the additive in a high - pressure autoclave. Replace the air in the autoclave three times with CO 2 and then pressurize to 5.0 MPa. Heat it to 130 °C at a rate of 3 °C / min and react for 8 h. After the reaction is completed, naturally cool to room temperature to obtain an intermediate.

[0052] L2: Then add 30 parts by volume of CH 3 OH to the intermediate at 45 °C for post - treatment. Centrifuge for 20 min to separate the liquid and the precipitate. After removing the precipitate, add 300 parts by volume of pre - cooled deionized water to the liquid part, store it in a refrigerator at 4 °C for 12 h, then centrifuge to recover the lower - layer liquid, and dry it in an oven at 60 °C for 24 h to obtain polycarbonate.

[0053] Example 2:

[0054] A preparation method of an additive, as Figure 1 shown, includes the following steps:

[0055] S1: Preparation of Cu / TiO 2 -CeO 2 core-shell body

[0056] S1.1: Weigh 0.5 parts by mass of Cu(NO 3 ) 2 ·3H 2 O and add it to ethanol. Heat it in a water bath at 60°C and stir magnetically for 5 - 10 min. Then add 2 parts by mass of TiO 2 to it. After stirring magnetically for 30 min, add 50 parts by volume of 1 mol / L NaOH aqueous solution and continue stirring for 30 min to obtain a metal solution;

[0057] S1.2: Add 10 parts by volume of 4 mol / L glucose aqueous solution to the metal solution, stir for 1 h. Finally, filter the metal solution by suction to obtain a yellow precipitate. Wash the precipitate 3 times with deionized water and anhydrous ethanol respectively, and then dry it in vacuum at 50°C for 24 h to obtain Cu 2 O-TiO 2 ;

[0058] S1.3: Add 2 parts by mass of Cu 2 O-TiO 2 to 80 parts by volume of ethanol solution. Sequentially add 8 parts by volume of 0.855 mol / L NaCl aqueous solution and 0.8 parts by mass of (NH 4 ) 2 Ce(NO 3 ) 6 ethanol solution. The (NH 4 ) 2 Ce(NO 3 ) 6 ethanol solution is prepared by dissolving (NH 4 ) 2 Ce(NO 3 ) 6 in ethanol at a material-liquid ratio of 1:50 g / ml to obtain a mixed solution;

[0059] S1.4: Stir the mixed solution magnetically at room temperature for 30 min, then transfer it to a water bath at 40°C and stir for 1 h. Centrifuge to separate the solid from the liquid, wash the precipitate 3 times with deionized water, and dry it in a vacuum environment. Finally, calcine the product in a muffle furnace at 400°C for 1 h to obtain the Cu / TiO 2 -CeO 2 core-shell body.

[0060] S2: Surfactant PEG modification

[0061] S2.1: Dissolve 5.2 parts by mass of DMPA in 15 parts by volume of dichloromethane to obtain a DMPA solution. Then dissolve 4 parts by mass of PEG in 15 parts by volume of dichloromethane to obtain a PEG solution. Add 0.2 parts by mass of DPTS and 0.5 - 0.6 parts by mass of DCC to the PEG solution, and then add the DMPA solution. Stir the reaction at room temperature for 48 h, filter, dry the precipitate product, and remove the solvent to obtain dendritic PEG;

[0062] S2.2: Dissolve dendritic PEG in methanol. The material ratio of dendritic PEG to methanol is 1:20 g / L. Add DOWEX-H + resin, stir at room temperature for 24 h, filter, precipitate the filtrate with ether, and dry the precipitate product to remove the solvent to obtain modified PEG.

[0063] S3: Preparation of additives

[0064] S3.1: Dissolve 10 parts by mass of Cu / TiO 2 -CeO 2 core-shell particles and 0.5 parts by mass of modified PEG in 200 parts by volume of distilled water, slowly add 100 parts by volume of a NaOH solution with a concentration of 11.25 mol / L, and stir at room temperature for 30 min to obtain a suspension;

[0065] S3.2: Transfer the suspension to a hydrothermal autoclave, react at 110 °C for 10 h, naturally cool to room temperature after the reaction is completed, collect the precipitate by centrifugation, wash it three times with deionized water and ethanol respectively to remove impurities, and dry it at 80 °C for 12 h. After drying, heat it in air to 600 °C at a heating rate of 5 °C / min and hold for 3 h to obtain the additive.

[0066] Application of the additive

[0067] L1: Place 3.5 parts by mass of 1,6 - hexanediol, 20 parts by mass of 2 - cyanopyridine, and 0.5 parts by mass of the additive in a high-pressure autoclave. Replace the air in the autoclave three times with CO 2 and then pressurize to 5.0 MPa. Heat it to 130 °C at a rate of 3 °C / min and react for 8 h. Naturally cool to room temperature after the reaction is completed to obtain an intermediate;

[0068] L2: Then add 30 parts by volume of CH 3 OH to the intermediate at 45 °C for post-treatment. Centrifuge for 20 min to separate the liquid and the precipitate. After removing the precipitate, add 300 parts by volume of pre-cooled deionized water to the liquid part, store it in a refrigerator at 4 °C for 12 h, then centrifuge to recover the lower-layer liquid, and dry it in an oven at 60 °C for 24 h to obtain polycarbonate.

[0069] Example 3:

[0070] A preparation method of an additive, as Figure 1 shown, includes the following steps:

[0071] S1: Preparation of Cu / TiO 2 -CeO 2 core-shell body

[0072] S1.1: Weigh 0.2 parts by mass of Cu(NO 3 ) 2 ·3H 2 O and add it to ethanol. Heat it in a water bath at 60°C and stir magnetically for 5 - 10 min. Then add 2 parts by mass of TiO 2 to it. After stirring magnetically for 30 min, add 50 parts by volume of 1 mol / L NaOH aqueous solution and continue to stir for 30 min to obtain a metal solution;

[0073] S1.2: Add 10 parts by volume of 4 mol / L glucose aqueous solution to the metal solution, stir for 1 h. Finally, filter the metal solution by suction to obtain a yellow precipitate. Wash the precipitate 3 times each with deionized water and absolute ethanol, and then dry it in vacuum at 50°C for 24 h to obtain Cu 2 O-TiO 2 ;

[0074] S1.3: Add 2.5 parts by mass of Cu 2 O-TiO 2 to 80 parts by volume of ethanol solution. Add 8 parts by volume of 0.855 mol / L NaCl aqueous solution and 1.2 parts by mass of (NH 4 ) 2 Ce(NO 3 ) 6 ethanol solution in sequence. The (NH 4 ) 2 Ce(NO 3 ) 6 ethanol solution is prepared by dissolving (NH 4 ) 2 Ce(NO 3 ) 6 in ethanol at a material-liquid ratio of 1:50 g / ml to obtain a mixed solution;

[0075] S1.4: Stir the mixed solution magnetically at room temperature for 30 min, then transfer it to a water bath at 40°C and stir for 1 h. Centrifuge to separate the solid and liquid, wash the precipitate 3 times with deionized water, and dry it in a vacuum environment. Finally, calcine the product in a muffle furnace at 400°C for 1 h to obtain Cu / TiO 2-CeO 2 Core-shell structure

[0076] S2: Surfactant PEG modification

[0077] S2.1: Dissolve 5.2 parts by mass of DMPA in 15 parts by volume of dichloromethane to obtain a DMPA solution. Then dissolve 4 parts by mass of PEG in 15 parts by volume of dichloromethane to obtain a PEG solution. Add 0.2 parts by mass of DPTS and 0.5 - 0.6 parts by mass of DCC to the PEG solution, and then add the DMPA solution. Stir the reaction at room temperature for 48 h, filter, dry the precipitate product, and remove the solvent to obtain dendritic PEG;

[0078] S2.2: Dissolve dendritic PEG in methanol. The material ratio of dendritic PEG to methanol is 1:20 g / L. Add DOWEX-H + resin, stir at room temperature for 24 h, filter, precipitate the filtrate with ether, and dry the precipitate product to remove the solvent to obtain modified PEG.

[0079] S3: Preparation of additive

[0080] S3.1: Dissolve 12 parts by mass of Cu / TiO 2 -CeO 2 core-shell structure and 0.5 parts by mass of modified PEG in 200 parts by volume of distilled water, slowly add 100 parts by volume of a NaOH solution with a concentration of 11.25 mol / L, and stir at room temperature for 30 min to obtain a suspension;

[0081] S3.2: Transfer the suspension to a hydrothermal reactor, react at 110 °C for 10 h, naturally cool to room temperature after the reaction is completed, collect the precipitate by centrifugation, wash it three times with deionized water and ethanol respectively to remove impurities, and dry it at 80 °C for 12 h. After drying, heat it in air to 600 °C at a heating rate of 5 °C / min and hold for 3 h to obtain the additive.

[0082] Application of additive

[0083] L1: Place 3.5 parts by mass of 1,6-hexanediol, 20 parts by mass of 2-cyanopyridine, and 0.5 parts by mass of the additive in an autoclave, displace the air in the autoclave three times with CO 2 and then pressurize to 5.0 MPa, heat it to 130 °C at a rate of 3 °C / min and react for 8 h. After the reaction is completed, naturally cool to room temperature to obtain an intermediate;

[0084] L2: Then add 30 parts by volume of CH 3Perform post-treatment with OH, centrifuge for 5 min to separate the liquid and the precipitate. After removing the precipitate, add 300 volumes of pre-cooled deionized water to the liquid part, store it in the refrigerator at 4 °C for 12 h, then centrifuge to separate and recover the lower-layer liquid, and dry it in an oven at 60 °C for 24 h to obtain polycarbonate.

[0085] Comparative Example 1:

[0086] Compared with Example 1, the difference in Comparative Example 1 is that step S1 is not performed, and CeO is directly added in step S3 2 Prepare the additive, specifically: "S3.1: Dissolve 12 parts by mass of CeO 2 and 0.5 part by mass of modified PEG in 200 volumes of distilled water, slowly add dropwise 100 volumes of a NaOH solution with a concentration of 11.25 mol / L, and stir at room temperature for 30 min to obtain a suspension;

[0087] S3.2: Transfer the suspension to a hydrothermal reactor, react at 110 °C for 10 h, naturally cool to room temperature after the reaction is completed, collect the precipitate by centrifugation, wash it three times with deionized water and ethanol respectively to remove impurities, and dry it at 80 °C for 12 h. After drying, heat it to 600 °C in air and hold for 3 h to obtain the additive", apply the prepared additive to the preparation of polycarbonate, and test and calculate the yield and purity of the polycarbonate.

[0088] Comparative Example 2:

[0089] Compared with Example 1, the difference in Comparative Example 2 is that step S2 is not performed, and PEG is directly added in step S3 to prepare the additive, specifically: "S3.1: Dissolve 12 parts by mass of Cu / TiO 2 -CeO 2 core-shell particles and 0.5 part by mass of PEG in 200 volumes of distilled water, slowly add dropwise 100 volumes of a NaOH solution with a concentration of 11.25 mol / L, and stir at room temperature for 30 min to obtain a suspension;

[0090] S3.2: Transfer the suspension to a hydrothermal reactor, react at 110 °C for 10 h, naturally cool to room temperature after the reaction is completed, collect the precipitate by centrifugation, wash it three times with deionized water and ethanol respectively to remove impurities, and dry it at 80 °C for 12 h. After drying, heat it to 600 °C in air at a heating rate of 5 °C / min and hold for 3 h to obtain the additive", apply the prepared additive to the preparation of polycarbonate, and test and calculate the yield and purity of the polycarbonate.

[0091] The yields and purities of the polycarbonates prepared in Examples 1-3 and Comparative Examples 1-2 are shown in Table 1 below.

[0092]

[0093] The yields of Examples 1-3 were 92.5%, 91.7% and 92.2% respectively, and the purities were all 95%. It can be seen that by loading Cu / TiO with dendritic PEG 2 -CeO 2 core-shell particles, the yield and purity of the prepared additive are more excellent than those of the comparative example.

[0094] The yield of Comparative Example 1 was 79.6% and the purity was 91%. It can be seen that for CeO without introducing Cu and Ti 2 the catalytic effect of the prepared additive on polycarbonate is reduced, and the yield and purity are also reduced.

[0095] The yield of Comparative Example 2 was 83.8% and the purity was 89%. It can be seen that the non-dendritic PEG cannot improve the stability of the additive, resulting in a decrease in the yield and purity of polycarbonate.

[0096] The above embodiments merely illustrate the principles and effects of the present invention, rather than limiting the present invention. Any person familiar with this technology can modify or change the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or changes completed by those with ordinary knowledge in the technical field without departing from the spirit and technical idea disclosed by the present invention should still be covered by the claims of the present invention.

Claims

1. An application of an additive in polycarbonate engineering plastics, characterized in that: The steps include: L1: 3.5 parts by mass of 1,6-hexanediol, 20 parts by mass of 2-cyanopyridine and 0.5 parts by mass of additives were placed in an autoclave, the air in the autoclave was replaced with CO2 three times and then the pressure was filled to 5.0 MPa, the temperature was raised to 130°C at a rate of 3°C / min and the reaction was carried out for 8 hours. After the reaction was completed, the autoclave was naturally cooled to room temperature to obtain an intermediate; L2: Then add 30 parts by volume of CH3OH to the intermediate at 45°C for post-treatment, centrifuge for 5-20 minutes to separate the liquid and the precipitate, add 300 volumes of 4°C pre-cooled deionized water to the liquid part after removing the precipitate, store in a refrigerator at 4°C for 12 hours, centrifuge to recover the lower layer of liquid, and dry in an oven at 60°C for 24 hours to obtain polycarbonate; The preparation method of the additive comprises the following steps: S1: Preparation of Cu / TiO2-CeO2 core-shell Weighing Cu(NO3)2·3H2O and adding it to ethanol, heating it in a water bath with magnetic stirring, then adding TiO2 thereto, adding an aqueous NaOH solution to obtain a metal solution, adding an aqueous glucose solution to the metal solution, filtering, washing, and drying to obtain Cu2O-TiO2, adding Cu2O-TiO2 to an ethanol solution, and sequentially adding an aqueous NaCl solution and an ethanol solution of (NH4)2Ce(NO3)6 to obtain a mixed solution, separating the mixed solution, precipitating it, drying it in a vacuum environment, and calcining the obtained Cu / TiO2-CeO2 core-shell body; S2: Surfactant PEG modification S2.1: Dissolve DMPA in dichloromethane to obtain DMPA solution, then dissolve PEG in dichloromethane to obtain PEG solution, add DPTS and DCC to the PEG solution, then add DMPA solution to obtain dendritic PEG, dissolve the dendritic PEG in methanol, add DOWEX-H + The resin is stirred and filtered, the filtrate is precipitated with ether, and the precipitated product is dried to remove the solvent to obtain the modified PEG; S3: Preparation of additives S3.1: Dissolve the Cu / TiO2-CeO2 core-shell and modified PEG in distilled water, add NaOH solution dropwise to obtain a suspension, transfer the suspension to a hydrothermal kettle for reaction, then naturally cool to room temperature, collect the precipitate by centrifugation, dry and then heat to obtain an additive.

2. The use of an additive in polycarbonate engineering plastics according to claim 1, characterized in that: Step S1: Preparation of Cu / TiO2-CeO2 core-shell body, comprising the following steps: S1.1: Weigh 0.2-0.5 parts by mass of Cu(NO3)2·3H2O and add it to ethanol, heat it in a water bath at 60°C and stir it magnetically for 5-10 minutes, then add 2 parts by mass of TiO2, stir it magnetically for 30 minutes, then add 50 parts by volume of 1 mol / L NaOH aqueous solution, and continue stirring for 30 minutes to obtain a metal solution; S1.2: Add 10 parts by volume of glucose aqueous solution to the metal solution, stir for 1 hour, and finally filter the metal solution to obtain a yellow precipitate. Wash the precipitate with deionized water and anhydrous ethanol for 3 times respectively, and then vacuum dry it at 50°C for 24 hours to obtain Cu2O-TiO2; S1.3: Add 2-2.5 parts by mass of Cu2O-TiO2 to 80 parts by volume of ethanol solution, and add 8 parts by volume of NaCl aqueous solution and 0.8-1.2 parts by mass of (NH4)2Ce(NO3)6 ethanol solution in sequence to obtain a mixed solution; S1.4: The mixture was magnetically stirred at room temperature for 30 min, then moved to a water bath and stirred at 40°C for 1 h, centrifuged to separate the solid and liquid, and the precipitate was washed three times with deionized water and dried under vacuum. Finally, the product was calcined in a muffle furnace at 400°C for 1 h to obtain a Cu / TiO2-CeO2 core-shell body.

3. The use of an additive in polycarbonate engineering plastics according to claim 2, characterized in that: Step S2 surfactant PEG modification comprises the following steps: S2.1: Dissolve 5.2 parts by mass of DMPA in 15 parts by volume of dichloromethane to obtain a DMPA solution, then dissolve 4-4.5 parts by mass of PEG in 15 parts by volume of dichloromethane to obtain a PEG solution, add 0.2-0.3 parts by mass of DPTS and 0.5-0.6 parts by mass of DCC to the PEG solution, and then add the DMPA solution; stir the reaction at room temperature for 48 hours, filter, dry the precipitated product, and remove the solvent to obtain dendritic PEG; S2.2: Dissolve the dendrimerized PEG in methanol and add DOWEX-H + The resin was stirred at room temperature for 24 h, filtered, and the filtrate was precipitated with ether. The precipitated product was dried to remove the solvent to obtain modified PEG.

4. The use of an additive in polycarbonate engineering plastics according to claim 3, characterized in that: Step S3: Preparation of additives, comprising the following steps: S3.1: Dissolve 10-12 parts by mass of Cu / TiO2-CeO2 core-shell and 0.5 parts by mass of modified PEG in 200 parts by volume of distilled water, slowly dropwise add 100 parts by volume of 11.25 mol / L NaOH solution, and stir at room temperature for 30 min to obtain a suspension; S3.2: The suspension was transferred to a hydrothermal autoclave and reacted at 110°C for 10 hours. After the reaction was completed, it was naturally cooled to room temperature. The precipitate was collected by centrifugation, washed three times with deionized water and ethanol respectively to remove impurities, and dried at 80°C for 12 hours. After drying, it was heated to 600°C in air and maintained for 3 hours to obtain the additive.

5. The use of an additive in polycarbonate engineering plastics according to claim 4, characterized in that: The solid-liquid ratio of dendrimerized PEG and methanol was 1:20 g / L.

6. Use of an additive in polycarbonate engineering plastics according to claim 5, characterized in that: The heating rate is 5°C / min.

7. Use of an additive in polycarbonate engineering plastics according to claim 6, characterized in that: The concentration of the glucose aqueous solution is 4 mol / L.

8. Use of an additive in polycarbonate engineering plastics according to claim 7, characterized in that: The concentration of the NaCl aqueous solution is 0.855 mol / L.

9. Use of an additive in polycarbonate engineering plastics according to claim 8, characterized in that: The (NH4)2Ce(NO3)6 ethanol solution is prepared by dissolving (NH4)2Ce(NO3)6 in ethanol at a solid-liquid ratio of 1:50 g / ml.

Images