Preparation method of anti-aging daily plastic

Abstract

The invention relates to the technical field of plastic production and manufacturing, in particular to an anti-aging daily plastic preparation method which specifically comprises the following steps: weighing alpha-olefin, adding a guiding base reagent, and stirring at room temperature to form a complex; detecting and confirming successful introduction of a guiding base; adding palladium acetate into the complex, and then adding a phosphorus ligand; adding alkali into the complex, and then adding diphenylamine or a derivative thereof; adding a solvent, carrying out gas replacement to ensure an inert atmosphere, heating to 60-100 DEG C, and stirring; after the reaction is completed, cooling to room temperature, extracting, drying, purifying and separating to obtain a long-chain alpha-olefin monomer; functional polypropylene is prepared from a long-chain alpha-olefin monomer, and the functional polypropylene, the modified nanoparticles and an auxiliary agent are subjected to melting, blending, extrusion and granulation to obtain the plastic master batch, so that the reaction environment requirement in the preparation process of the functional polypropylene is reduced, the danger in the preparation process of the functional polypropylene is reduced, and the utilization rate of raw materials can be increased.

Description

Technical Field

[0001] The present application relates to the field of plastic production and manufacturing technology, and in particular to a method for preparing anti-aging daily-use plastics. Background Art

[0002] Plastic products are commonly used in daily life. For example, PP plastic, due to its excellent corrosion resistance and high melting point, is widely used in plastic wrap, plastic lunch boxes, and food packaging. However, conventional PP plastic is prone to aging and yellowing, making it difficult to use for a long time.

[0003] In order to solve the problem of PP plastic being easily aged, functionalized polypropylene is added to some plastic products. That is, propylene monomer is copolymerized with long-chain α-olefin monomer containing diphenylamine group, and diphenylamine group is introduced into the polymer chain to obtain polypropylene material containing diphenylamine group in the side chain, thereby improving its anti-aging performance. For example, an anti-aging reinforced PP Japanese plastic product and its preparation method are disclosed with publication number CN119505419A.

[0004] Regarding the above-mentioned related technologies, the preparation of functionalized polypropylene requires the use of 4-bromophenylaniline as a raw material at -50°C, generating aromatic lithium under the action of potassium tert-butoxide and tert-butyl lithium, and then adding 8-bromo-1-octene to obtain the target long-chain α-olefin monomer. The reaction environment temperature is relatively low and the reaction environment requirements are high. In addition, lithium reagents such as tert-butyl lithium are highly active and dangerous. At the same time, aromatic lithium intermediates are prone to side reactions such as disproportionation, polymerization and protonation at low temperatures, resulting in a low yield of long-chain α-olefin monomers and low raw material utilization. Summary of the Invention

[0005] In order to reduce the reaction environment requirements and the risk of the functionalized polypropylene preparation process, and also to help improve the utilization rate of raw materials, the present application provides a method for preparing anti-aging daily-use plastics.

[0006] The present application provides a method for preparing anti-aging daily-use plastics using the following technical solution.

[0007] A method for preparing anti-aging daily-use plastics specifically comprises the following steps.

[0008] Step 1: Weigh an α-olefin, add a directing group reagent, and stir at room temperature to form a complex;

[0009] Step 2: Detect and confirm that the guiding group is successfully introduced;

[0010] Step 3: adding palladium acetate to the complex, and then adding the phosphorus ligand;

[0011] Step 4: adding a base to the complex, and then adding diphenylamine or its derivative;

[0012] Step 5: Add the solvent, perform gas replacement to ensure an inert atmosphere, then heat to 60°C-100°C and stir;

[0013] Step 6: After the reaction is completed, the temperature is lowered to room temperature, and quenching, extraction, drying, purification and separation are performed to obtain a long-chain α-olefin monomer;

[0014] Step 7: Prepare functionalized polypropylene using long-chain α-olefin monomers, and melt, blend, extrude and granulate with modified nanoparticles and additives to obtain plastic masterbatch.

[0015] By adopting the above technical solution, the process of preparing long-chain α-olefin monomers has a low difficulty in reaction temperature, low equipment requirements, and no strong base and active metal, so it is relatively safe. In addition, the yield of long-chain α-olefin monomers is also high, the raw material utilization rate is high, and the overall process flow is more suitable for industrialization.

[0016] Optionally, in step five, the temperature is raised to 75° C.-85° C.

[0017] By adopting the above technical solution, the reaction rate and conversion rate are balanced and it is applicable to most reaction systems.

[0018] Optionally, the α-olefin is any one of 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene, cyclohexene and styrene derivatives.

[0019] Optionally, the directing group reagent is selected from any one of N,N-dimethylformamide-methylamine, 2-pyridinecarboxamide, N-pyridinebenzamide, acetamide, benzoyl arylamine, 2-aminopyridine, 8-aminoquinoline, acetaldehyde oxime, benzaldehyde oxime, p-toluenesulfonyl arylamine, methanesulfonyl arylamine, phenylhydrazone and hydrazine amide.

[0020] Optionally, the phosphorus ligand is selected from any one of 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, 1,2-bis(di-tert-butylphosphino)ethane, triphenylphosphine, 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, 2-dicyclohexylphosphino-2',6'-diisopropoxybiphenyl, 2-di-tert-butylphosphino-2',4',6'-triisopropylbiphenyl and 2,2'-bisdiphenylphosphino-1,1'-binaphthyl.

[0021] Optionally, the base is any one of potassium carbonate, cesium carbonate, sodium acetate, potassium acetate and potassium phosphate.

[0022] Optionally, the solvent is selected from any one of toluene, acetonitrile, dimethylformamide, dimethylacetamide and hexafluoroisopropanol.

[0023] By adopting the above technical solution, the corresponding α-olefin, directing group reagent, phosphorus ligand, base and solvent are selected according to needs.

[0024] Optionally, the stirring reaction time in step 5 is 6 h to 12 h.

[0025] By adopting the above technical solution, it is ensured that the reaction is fully completed without excessive reaction leading to an increase in by-products.

[0026] Optionally, during the stirring process in step 5, samples are taken every 1-2 hours to analyze the conversion rate.

[0027] By adopting the above technical solution, the reaction process can be monitored, making it easier to adjust parameters in a timely manner.

[0028] Optionally, the phosphorus ligand and diphenylamine or its derivative are first dissolved in a solvent and then added.

[0029] By adopting the above technical solution, pre-dissolution can avoid excessive local concentration, reduce side reactions, ensure the uniformity of the reaction system, and improve utilization rate.

[0030] In summary, this application has at least the following beneficial effects.

[0031] By directly introducing diphenylamine groups through a palladium-catalyzed CH activation reaction, the process for preparing long-chain α-olefin monomers has low reaction temperature and equipment requirements, and does not require strong bases or active metals, making it relatively safe. In addition, the yield of long-chain α-olefin monomers is also high, the raw material utilization rate is high, and the overall process flow is more suitable for industrialization. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 This is a flowchart of a method for preparing anti-aging daily-use plastics in this application. DETAILED DESCRIPTION

[0033] The present application is further described in detail below with reference to the accompanying drawings.

[0034] This application discloses a method for preparing anti-aging daily-use plastics, referring to Figure 1 , specifically including the following steps.

[0035] Step 1: Weigh an α-olefin, add a directing group reagent, and stir at room temperature to form a complex;

[0036] Step 2: Detect and confirm the successful introduction of the directing group by thin layer chromatography or nuclear magnetic resonance;

[0037] Step 3: Add palladium acetate to the complex, and then dissolve the phosphorus ligand in a small amount of solvent and add it;

[0038] Step 4: adding a base to the complex, and then slowly adding dropwise diphenylamine or its derivative dissolved in a small amount of solvent;

[0039] Step 5: Add the solvent, and control the volume of the solution after addition to 5 ml-10 ml, then use nitrogen or argon to replace the gas to ensure an inert atmosphere, then heat to 60 ° C -100 ° C and stir for 6 h -12 h, and sample and analyze the conversion rate every 1 h -2 h until the conversion rate reaches 90% or more, and then proceed to the next step. The analysis method is thin layer chromatography, gas chromatography or high performance liquid chromatography;

[0040] Step 6: After the reaction is completed, the temperature is lowered to room temperature, and quenching, extraction, drying, purification and separation are performed to obtain a long-chain α-olefin monomer;

[0041] Step 7: Prepare functionalized polypropylene using long-chain α-olefin monomers, and melt, blend, extrude and granulate with modified nanoparticles and additives to obtain plastic masterbatch.

[0042] The specific contents of step six and step seven can be referred to the relevant process flow in the background technology, so this application will not repeat them again.

[0043] The α-olefin is selected from any one of 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene, cyclohexene and styrene derivatives.

[0044] The directing group reagent is selected from any one of N,N-dimethylformamide-methylamine, 2-pyridinecarboxamide, N-pyridinebenzamide, acetamide, benzoyl arylamine, 2-aminopyridine, 8-aminoquinoline, acetaldehyde oxime, benzaldehyde oxime, p-toluenesulfonyl arylamine, methanesulfonyl arylamine, phenylhydrazone and hydrazineamide.

[0045] The phosphorus ligand is selected from any one of 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, 1,2-bis(di-tert-butylphosphino)ethane, triphenylphosphine, 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, 2-dicyclohexylphosphino-2',6'-diisopropoxybiphenyl, 2-di-tert-butylphosphino-2',4',6'-triisopropylbiphenyl and 2,2'-bisdiphenylphosphino-1,1'-binaphthyl.

[0046] The base is selected from any one of potassium carbonate, cesium carbonate, sodium acetate, potassium acetate and potassium phosphate. The solvent is selected from any one of toluene, acetonitrile, dimethylformamide, dimethylacetamide and hexafluoroisopropanol.

[0047] The following is further explained with reference to specific examples and comparative examples.

[0048] Example 1:

[0049] Step 1: Weigh 1 mmol of 1-decene as a substrate, add 1.5 eq of N,N-dimethylformamide-methylamine, and stir at room temperature for 30 minutes to form a complex;

[0050] Step 2: Detect and confirm the successful introduction of the directing group by thin layer chromatography or nuclear magnetic resonance;

[0051] Step 3: Add 0.25eq of palladium acetate to the complex, and then dissolve 0.1eq of 4,5-bis(diphenylphosphine)-9,9-dimethylxanthene in a small amount of toluene and add the mixture;

[0052] Step 4: Add 2eq of potassium carbonate to the complex, and then slowly dropwise dissolve 2eq of diphenylamine in a small amount of toluene;

[0053] Step 5: Add toluene, and control the volume of the solution after addition to 8 ml, then use nitrogen to replace the gas to ensure an inert atmosphere, then heat to 60 ° C and stir for 6h-12h, and sample and analyze the conversion rate every 1h until the conversion rate reaches 90% or more, and then proceed to the next step. The analysis method is thin layer chromatography, gas chromatography or high performance liquid chromatography;

[0054] Step 6: After the reaction is completed, the temperature is lowered to room temperature, and quenching, extraction, drying, purification and separation are performed to obtain a long-chain α-olefin monomer;

[0055] Step 7: Prepare functionalized polypropylene using long-chain α-olefin monomers, and melt, blend, extrude and granulate with modified nanoparticles and additives to obtain plastic masterbatch.

[0056] Example 2:

[0057] The difference from Example 1 is that:

[0058] Step 1: Weigh 1 mmol of 1-nonene as a substrate, add 1.5 eq of 2-pyridinecarboxamide, and stir at room temperature for 30 min to form a complex;

[0059] Step 2: Detect and confirm the successful introduction of the directing group by thin layer chromatography or nuclear magnetic resonance;

[0060] Step 3: Add 0.25eq of palladium acetate to the complex, and then dissolve 0.1eq of 1,2-bis(di-tert-butylphosphine)ethane in a small amount of acetonitrile and add;

[0061] Step 4: Add 2eq of cesium carbonate to the complex, and then slowly drop 2eq of diphenylamine dissolved in a small amount of acetonitrile;

[0062] Step 5: Add acetonitrile, and control the volume of the solution after addition to 8 ml, then use nitrogen to replace the gas to ensure an inert atmosphere, then heat to 60°C and stir for 6h-12h, and sample and analyze the conversion rate every 1h until the conversion rate reaches 90% or above, and then proceed to the next step.

[0063] Example 3:

[0064] The difference from Example 1 is that:

[0065] In step five, the temperature is raised to 70°C.

[0066] Example 4:

[0067] The difference from Example 1 is that:

[0068] In step five, the temperature is raised to 75°C.

[0069] Embodiment 5:

[0070] The difference from Example 1 is that:

[0071] In step five, the temperature is raised to 85°C.

[0072] Example 6:

[0073] The difference from Example 1 is that:

[0074] In step five, the temperature is raised to 90°C.

[0075] Embodiment seven:

[0076] The difference from Example 1 is that:

[0077] In step five, the temperature is raised to 100°C.

[0078] Comparative Example 1:

[0079] The difference from Example 1 is that:

[0080] Steps 1 to 5 were replaced by adding 4.9 g of 4-bromophenylaniline and 0.27 g of potassium tert-butoxide to 60 ml of tetrahydrofuran under a nitrogen atmosphere, stirring at -50°C to dissolve. Then, 40 ml of a pentane solution of tert-butyllithium was slowly added dropwise. After the addition was complete, the temperature was raised to 0°C, 8.1 g of 8-bromo-1-octene was added, and the reaction was stirred for 10 hours. This was similar to the method described in the prior art for preparing long-chain α-olefin monomers using lithium reagents at extremely low temperatures. Steps 6 and 7 were then carried out.

[0081] Comparative Example 2:

[0082] The difference from Example 1 is that:

[0083] In step five, the temperature is raised to 50°C.

[0084] Comparative Example 3:

[0085] The difference from Example 1 is that:

[0086] In step five, the temperature is raised to 110°C.

[0087] The conversion times and yields in the above examples and comparative examples were statistically analyzed and presented in the following table.

[0088]

[0089] As can be seen from the above table, the present application utilizes palladium-catalyzed C–H activation reaction to introduce diphenylamine groups to prepare long-chain α-olefin monomers. Compared with the traditional method of using a strong alkaline lithium reagent to prepare long-chain α-olefin monomers at extremely low temperatures, the reaction time and yield can be improved to a certain extent. In addition, the entire preparation process is relatively safer and has relatively lower temperature requirements. Moreover, when the reaction temperature is between 75°C and 85°C, the yield is relatively high and the raw materials are fully utilized.

[0090] The above are all preferred embodiments of the present application, and are not intended to limit the scope of protection of the present application. Therefore, any equivalent changes made based on the structure, shape, and principle of the present application should be included in the scope of protection of the present application.

Claims

1. A method for preparing anti-aging daily-use plastics, characterized by: The specific steps include: Step 1: Weigh an α-olefin, add a directing group reagent, and stir at room temperature to form a complex; Step 2: Detect and confirm that the guiding group is successfully introduced; Step 3: adding palladium acetate to the complex, and then adding the phosphorus ligand; Step 4: adding a base to the complex, and then adding diphenylamine or its derivative; Step 5: Add the solvent, perform gas replacement to ensure an inert atmosphere, then heat to 60°C-100°C and stir; Step 6: After the reaction is completed, the temperature is lowered to room temperature, and quenching, extraction, drying, purification and separation are performed to obtain a long-chain α-olefin monomer; Step 7: Prepare functionalized polypropylene using long-chain α-olefin monomers, and melt, blend, extrude and granulate with modified nanoparticles and additives to obtain plastic masterbatch.

2. The method for preparing an anti-aging daily-use plastic according to claim 1, characterized in that: In the step 5, the temperature is raised to 75° C.-85° C.

3. The method for preparing an anti-aging daily-use plastic according to claim 1, characterized in that: The α-olefin is selected from any one of 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 4-methyl-1-pentene, cyclohexene and styrene derivatives.

4. The method for preparing an anti-aging daily-use plastic according to claim 1, characterized in that: The directing group reagent is selected from any one of N,N-dimethylformamide-methylamine, 2-pyridinecarboxamide, N-pyridinebenzamide, acetamide, benzoyl arylamine, 2-aminopyridine, 8-aminoquinoline, acetaldehyde oxime, benzaldehyde oxime, p-toluenesulfonyl arylamine, methanesulfonyl arylamine, phenylhydrazone and hydrazineamide.

5. The method for preparing an anti-aging daily-use plastic according to claim 1, characterized in that: The phosphorus ligand is selected from any one of 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, 1,2-bis(di-tert-butylphosphino)ethane, triphenylphosphine, 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl, 2-dicyclohexylphosphino-2',6'-diisopropoxybiphenyl, 2-di-tert-butylphosphino-2',4',6'-triisopropylbiphenyl and 2,2'-bisdiphenylphosphino-1,1'-binaphthyl.

6. The method for preparing an anti-aging daily-use plastic according to claim 1, characterized in that: The base is selected from any one of potassium carbonate, cesium carbonate, sodium acetate, potassium acetate and potassium phosphate.

7. The method for preparing an anti-aging daily-use plastic according to claim 1, characterized in that: The solvent is selected from any one of toluene, acetonitrile, dimethylformamide, dimethylacetamide and hexafluoroisopropanol.

8. The method for preparing anti-aging daily-use plastic according to claim 1, characterized in that: The stirring reaction time in step 5 is 6h-12h.

9. The method for preparing anti-aging daily-use plastic according to claim 8, characterized in that: During the stirring process in step 5, samples were taken every 1-2 hours to analyze the conversion rate.

10. The method for preparing anti-aging daily-use plastic according to claim 1, characterized in that: The phosphorus ligand and diphenylamine or its derivative are first dissolved in a solvent and then added.

Images