A method for preparing multifunctional nylon additives based on a solvent-free method

Abstract

This invention discloses a solvent-free method for preparing multifunctional nylon additives, belonging to the field of nylon additive processing technology. It addresses the technical problem that the yield, purity, and environmental friendliness of existing multifunctional nylon additives need further improvement. The invention involves ball milling isophthaloyl chloride and tetramethylpiperidinamine in a ball mill jar to obtain an acylated intermediate, followed by neutralization with sodium hydroxide to obtain the multifunctional nylon additive. This multifunctional nylon additive, prepared by ball milling under solvent-free conditions, has a simple, efficient, and safe preparation process with fast reaction time, and produces a product with excellent performance, thus improving the overall performance of nylon materials in practical applications.

Description

Technical Field

[0001] This invention relates to the field of nylon additives processing technology, and more specifically to a method for preparing multifunctional nylon additives based on a solvent-free method. Background Technology

[0002] Nylon, as an important engineering plastic, has a wide range of applications in many fields. In order to further improve the performance of nylon and meet the needs of different application scenarios, various additives are usually added, such as toughening agents, flame retardants and antioxidants. Traditional nylon additive preparation methods mostly adopt solvent methods, using a large amount of organic solvents as reaction media, but its process defects are becoming increasingly prominent.

[0003] The limitations of the traditional solvent method lie in the residue of organic solvents and environmental pressure. The solvent method relies on a large amount of volatile organic solvents as the reaction medium. Although they need to be recovered by distillation afterward, it is difficult to completely avoid the presence of trace amounts of solvents in the auxiliary products during actual production. These residues may migrate into nylon products, which not only affects the hygiene and safety of the materials, but also increases the emission of volatile organic compounds in the product production process, leading to high environmental treatment costs for enterprises.

[0004] In addition, to ensure solvent recovery efficiency, the solvent method requires complex equipment such as condensation / distillation. The energy consumption of the whole process is significantly higher than that of the solvent-free process. The loss of solvent by evaporation and the wear and tear of equipment cleaning further aggravate the waste of resources and drive up production costs, which is not in line with the development trend of green chemical industry. The presence of solvent may affect the purity and performance of additives. The subsequent complex separation and purification steps to remove residual solvent lead to low production efficiency.

[0005] Therefore, developing a green, efficient, and low-cost method for preparing multifunctional nylon additives is of great practical significance, and a solution is proposed here. Summary of the Invention

[0006] The purpose of this invention is to provide a method for preparing multifunctional nylon additives based on a solvent-free method, which solves the technical problems that the yield, purity and environmental friendliness of multifunctional nylon additives need to be further improved in the prior art.

[0007] The objective of this invention can be achieved through the following technical solution: a method for preparing multifunctional nylon additives based on a solvent-free method, wherein the structural formula of the multifunctional nylon additive is:

[0008]

[0009] The method for preparing multifunctional nylon additives based on solvent-free method is as follows: using isophthaloyl chloride and tetramethylpiperidineamine as raw materials, after ball milling and mixing to promote the acylation reaction of isophthaloyl chloride and tetramethylpiperidineamine, an acylation intermediate is obtained, which is then post-treated with an inorganic base to prepare the multifunctional nylon additive.

[0010] The synthesis mechanism of acylation intermediates is as follows:

[0011]

[0012] Furthermore, the molar ratio of isophthaloyl chloride to tetramethylpiperidineamine is 1:2.0-2.5. The 1H NMR spectroscopy data of the multifunctional nylon additive are as follows: 1 H NMR (600MHz, DMSO-d6) 8.27 (d, J=7.86Hz, 2H), 8.24 (t, J=1.8Hz, 1H), 7.93 (d, J=1.80Hz, 1H), 7.92 (d, J=1.8Hz, 1H), 7.52 (t, J=7.74Hz, 1H), 4.29 (m, 2H), 1.70 (dd, J=3.66, 8.52Hz, 4H), 1.18 (s, 12H), 1.12–1.17 (m, 4H), 1.04–1.07 (m, 12H); NMR analysis data are as follows: 13 CNMR(150MHz,DMSO-d6) 165.7,135.6,130.0,128.5,126.8,50.9,44.9,42.9,35.1,29.1.

[0013] Furthermore, the temperature of the acylation reaction is 25-45℃, and the temperature control method is jacket temperature control, with circulating warm water / coolant introduced.

[0014] Furthermore, the ball milling speed is 200-400 rpm, the ball milling time is 25-40 min, the single grinding time is 5-15 min, the grinding rest time is 2-5 min, the ball-to-material ratio is 45-75:1, and the grinding balls are made of agate with a diameter of 2-5 mm.

[0015] Furthermore, the inorganic base is an aqueous solution or solid powder of either sodium hydroxide or potassium hydroxide.

[0016] Further, the post-processing step is as follows: add the acylation intermediate and deionized water into a beaker and stir, add an inorganic base to adjust the pH to 9-12, react at room temperature for 15-20 minutes, wash and dry to obtain a multifunctional auxiliary agent.

[0017] Furthermore, the ratio of the acylation intermediate to deionized water is 1g:5-20mL.

[0018] Furthermore, the washing and drying process includes: after the reaction is completed, filtration is performed, the filter cake is washed 2-3 times with deionized water, and then transferred to a drying oven at 100-110℃ to dry to constant weight, thereby obtaining a multifunctional nylon additive.

[0019] The present invention has the following beneficial effects:

[0020] 1. This invention is a multifunctional additive prepared by ball milling under solvent-free conditions, which avoids the use of organic solvents in traditional solution reactions, reduces air pollution caused by the volatilization of organic solvents, and reduces the environmental pollution problems and costs caused by subsequent organic solvent recycling and treatment, thus realizing the development trend of green chemistry.

[0021] 2. This invention also achieves the reaction through ball milling, eliminating the need for complex reaction equipment and high-temperature, high-pressure reaction conditions. The equipment and process are simple and easy to operate. The ball milling process accelerates the diffusion and collision frequency of reactant molecules, allowing the reactants to fully contact and react, improving raw material utilization, reducing production costs, shortening reaction time, and increasing reaction efficiency. The cyclohexane in the multifunctional nylon additive structure is a rigid skeleton, and the sterically hindered alkyl groups on the ring reduce atomic crowding within the ring, alleviate angular tension, and are less susceptible to attack by external reagents. The π bond of the carbonyl group is conjugated with the lone pair electrons of the nitrogen atom, resulting in higher bond energy, making it less prone to breakage and improving the stability of the material. During the ball milling process, this experiment adopted comparative tests. By adjusting the ball milling ratio and various ball milling parameters, the ball milling efficiency was optimized, thereby obtaining a multifunctional nylon additive with the best performance.

[0022] 3. The multifunctional additive prepared by this invention has a unique molecular structure that can endow nylon materials with a variety of properties. Among them, the tetramethylpiperidine structure inhibits UV-induced free radical oxidation, providing anti-aging properties to nylon materials. The conjugated structure of the benzene ring in isophthaloyl enhances the rigidity of the molecular chain, improving the mechanical properties of nylon materials, thereby enhancing the comprehensive performance of materials in practical applications. Attached Figure Description

[0023] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0024] Figure 1 This is the 1H NMR spectrum of the multifunctional nylon additive of the present invention;

[0025] Figure 2 This is the carbon NMR spectrum of the multifunctional nylon additive of the present invention. Detailed Implementation

[0026] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0027] Example 1

[0028] This embodiment provides a method for preparing multifunctional nylon additives based on a solvent-free method, including the following steps:

[0029] S1. Preparation of acylation intermediates

[0030] Weigh 4.46g of isophthaloyl chloride and grind it in a mortar. Then, put 6.26g of tetramethylpiperidinamine and 200g of 2-5mm agate balls into a grinding jar with a heat exchange jacket. Circulate coolant into the heat exchange jacket, control the temperature of the grinding jar at 25℃, set the grinding speed of the grinding jar to 200rpm, set the grinding rest time to 2min, and ball mill for 25min to obtain the acylated intermediate.

[0031] S2. Preparation of multifunctional nylon additives

[0032] Weigh 10g of acylation intermediate and 100mL of deionized water and add them to a beaker. Stir and add 30wt% sodium hydroxide solution to adjust the pH to 9. React at room temperature for 15min. After the reaction is complete, filter the mixture and wash the filter cake twice with deionized water. Then transfer it to a 100℃ drying oven and dry it to constant weight to obtain a multifunctional nylon additive.

[0033] Example 2

[0034] This embodiment provides a method for preparing multifunctional nylon additives based on a solvent-free method, including the following steps:

[0035] S1. Preparation of acylation intermediates

[0036] Weigh 4.40g of isophthaloyl chloride and grind it in a mortar. Then, put 6.28g of tetramethylpiperidinamine and 200g of 2-5mm agate balls into a grinding jar with a heat exchange jacket. Circulate coolant into the heat exchange jacket, control the temperature of the grinding jar at 35℃, set the grinding speed of the grinding jar at 300rpm, and ball mill for 32min to obtain the acylated intermediate.

[0037] S2. Preparation of multifunctional nylon additives

[0038] Weigh 10g of acylation intermediate and 150mL of deionized water and add them to a beaker. Stir and add 30wt% sodium hydroxide solution to adjust the pH to 10. React at room temperature for 17min. After the reaction is complete, filter and wash the filter cake three times with deionized water. Then transfer it to a 105℃ drying oven and dry to constant weight to obtain the multifunctional nylon additive.

[0039] Example 3

[0040] This embodiment provides a method for preparing multifunctional nylon additives based on a solvent-free method, including the following steps:

[0041] S1. Preparation of acylation intermediates

[0042] Weigh 4.40g of isophthaloyl chloride and grind it in a mortar. Then, put 7.06g of tetramethylpiperidinamine and 220g of 2-5mm agate balls into a grinding jar with a heat exchange jacket. Circulate coolant into the heat exchange jacket, control the temperature of the grinding jar at 45℃, set the grinding speed of the grinding jar at 400rpm, and ball mill for 40min to obtain the acylated intermediate.

[0043] S2. Preparation of multifunctional nylon additives

[0044] Weigh 10g of acylation intermediate and 200mL of deionized water and add them to a beaker. Stir and add 30wt% sodium hydroxide solution to adjust the pH to 10. React at room temperature for 20min. After the reaction is complete, filter and wash the filter cake three times with deionized water. Then transfer it to a 110℃ drying oven and dry to constant weight to obtain the multifunctional nylon additive.

[0045] Comparative Example 1

[0046] The difference between this comparative example and Example 3 is that the rotation speed ratio in step S1 is changed to 70 and the ball milling time is changed to 10 min.

[0047] Comparative Example 2

[0048] The difference between this comparative example and Example 3 is that step S1 is omitted, and the raw materials are directly added to the three-necked flask without using a grinding ball for the reaction.

[0049] Performance testing:

[0050] According to the formula The yield of the multifunctional nylon additive was tested, where m1 is the actual mass of the multifunctional nylon additive and m2 is the theoretical mass of the multifunctional nylon additive.

[0051] According to the formula The conversion rate of the multifunctional nylon additive was tested. In the formula, m1 is the mass of the multifunctional nylon additive, M1 is the relative molecular mass of the multifunctional nylon additive, m0 is the mass of isophthaloyl chloride, and M0 is the relative molecular mass of isophthaloyl chloride.

[0052] The purity of the multifunctional nylon additives prepared in Examples 1-3 and Comparative Examples 1-2 was determined according to the standard SH / T 1674-2023 "Determination of Purity and Hydrocarbon Impurities of Cyclohexane for Industrial Use by Gas Chromatography". The specific test results are shown in Table 1 below:

[0053] Table 1 - Performance Test Data of Samples

[0054]

[0055] Data Analysis:

[0056] Comparative analysis of the data in Table 1 shows that the yield of the multifunctional additive prepared by this invention reached 93.6%, the reaction conversion rate reached 93.9%, and the purity reached 99.3%. This indicates that the multifunctional nylon additive prepared by ball milling under solvent-free conditions by this invention has a simple and efficient preparation process, high safety, fast reaction time, and excellent product performance, thus improving the comprehensive performance of nylon materials in practical applications.

[0057] Compared with the examples, the present invention, through comparative experiments, determined the optimal experimental reaction time and sample molar ratio under solvent-free conditions, thereby achieving the best results in product yield, reaction conversion rate and product purity, which reduced time and production costs and increased output.

[0058] Compared with the examples, the ball milling process in Comparative Example 2 can accelerate the diffusion and collision frequency of reactant molecules, allowing the reactants to fully contact and react, improving raw material utilization, reducing production costs, shortening reaction time, and improving reaction efficiency.

[0059] Appendix Figure 1 In the middle, the proton spectrum data are:

[0060] 1 HNMR(600MHz,DMSO-d6)8.27(d,J=7.86Hz,2H),8.24(t,J=1.8Hz,1H),7.93(d,J=1.80Hz,1H),7.92(d,J=1.8Hz,1H),7. 52(t,J=7.74Hz,1H),4.29(m,2H),1.70(dd,J=3.66,8.52Hz,4H),1.18(s,12H),1.12-1.17(m,4H),1.04-1.07(m,12H);

[0061] Appendix Figure 2 The NMR analysis data are as follows:

[0062] 13 CNMR(150MHz,DMSO-d6)165.7,135.6,130.0,128.5,126.8,50.9,44.9,42.9,35.1,29.1.

[0063] The above description is merely an example and illustration of the structure of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the structure of the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.

[0064] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0065] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to specific implementations. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A method for preparing multifunctional nylon additives based on a solvent-free method, characterized in that: The structural formula of the multifunctional nylon additive is: ， The method for preparing multifunctional nylon additives based on a solvent-free method is as follows: using isophthaloyl chloride and tetramethylpiperidineamine as raw materials, under a solvent-free environment, the isophthaloyl chloride and tetramethylpiperidineamine are ball-milled and mixed to promote the acylation reaction, thereby obtaining an acylation intermediate. The acylation intermediate and deionized water are added to a beaker and stirred. An inorganic base is added to adjust the pH to 9-12, and the reaction is carried out at room temperature for 15-20 min. After washing and drying, the multifunctional additive is obtained. The acylation reaction temperature is 25-45℃, the ball milling speed is 200-400 rpm, and the ball milling time is 25-40 min. The ratio of the acylation intermediate to deionized water is 1 g: 5-20 mL.

2. The method for preparing multifunctional nylon additives based on a solvent-free method according to claim 1, characterized in that, The molar ratio of isophthaloyl chloride and tetramethylpiperidine is 1:2.0-2.

5.

3. The method for preparing multifunctional nylon additives based on a solvent-free method according to claim 1, characterized in that, The acylation reaction is controlled by a jacket temperature control system, which involves circulating warm water / coolant.

4. The method for preparing multifunctional nylon additives based on a solvent-free method according to claim 1, characterized in that, The grinding time during ball milling is 5-15 minutes, the grinding rest time is 2-5 minutes, the ball-to-material ratio is 45-75:1, and the grinding balls are made of agate with a diameter of 2-5 mm.

5. The method for preparing multifunctional nylon additives based on a solvent-free method according to claim 1, characterized in that, The inorganic base is an aqueous solution or solid powder of either sodium hydroxide or potassium hydroxide.

6. The method for preparing multifunctional nylon additives based on a solvent-free method according to claim 1, characterized in that, The washing and drying process includes: after the reaction is completed, the filter cake is filtered, washed with deionized water 2-3 times, and then transferred to a drying oven at 100-110℃ to dry to constant weight, thereby obtaining a multifunctional nylon additive.

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