Method for preparing multifunctional nylon auxiliary agent based on solvent-free method

Abstract

The invention discloses a method for preparing a multifunctional nylon auxiliary agent based on a solvent-free method, belongs to the technical field of nylon auxiliary agent processing, and aims to solve the technical problem that the yield, the purity and the environmental protection property of the multifunctional nylon auxiliary agent need to be further improved in the prior art. The isophthaloyl dichloride and the tetramethyl piperidylamine are added into a ball milling tank for ball milling to obtain an acylated intermediate, the acylated intermediate is subjected to a neutralization reaction with sodium hydroxide and treated to obtain the multifunctional nylon additive, the multifunctional nylon additive is prepared through ball milling under the solvent-free condition, the preparation process is simple and efficient, the safety is high, the reaction time is short, and the preparation cost is low. And the product has excellent performance, and the comprehensive performance of the nylon material in practical application is improved.

Description

Technical Field

[0001] The invention relates to the technical field of nylon auxiliary agent processing, and in particular to a method for preparing a multifunctional nylon auxiliary agent based on a solvent-free method. Background Art

[0002] Nylon, as an important engineering plastic, is widely used in many fields. In order to further improve the performance of nylon and meet the needs of different application scenarios, it is usually necessary to add various additives, such as toughening agents, flame retardants and antioxidants. Traditional methods for preparing nylon additives mostly adopt the solvent method, using a large amount of organic solvents as the reaction medium, but its process defects are becoming increasingly prominent.

[0003] The limitations of the traditional solvent method lie in the residual organic solvents and environmental pressures. The solvent method relies on a large amount of volatile organic solvents as the reaction medium. Although they are subsequently recovered by distillation, it is difficult to completely avoid trace amounts of solvent residues in the additive products in actual production. These residues may migrate into nylon products, not only affecting the hygienic safety of the materials but also increasing volatile organic compound emissions in the product production process, resulting in high environmental treatment costs for companies.

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

[0005] Therefore, it is of great practical significance to develop a green, efficient and low-cost method for preparing multifunctional nylon additives. For this purpose, a solution is proposed. Summary of the Invention

[0006] The purpose of the present invention is to provide a method for preparing a multifunctional nylon additive based on a solvent-free method, which is used to solve the technical problem in the prior art that the yield, purity and environmental protection of the multifunctional nylon additive need to be further improved.

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

[0008]

[0009] The method for preparing a multifunctional nylon additive based on a solvent-free method comprises: using isophthaloyl chloride and tetramethylpiperidinamine as raw materials, promoting an acylation reaction between the isophthaloyl chloride and tetramethylpiperidinamine through ball milling, obtaining an acylated intermediate, and post-treating the acylated intermediate with an inorganic base to prepare the multifunctional nylon additive.

[0010] The reaction mechanism of the acylation intermediate synthesis is:

[0011]

[0012] Furthermore, the molar ratio of isophthaloyl chloride to tetramethylpiperidinamine is 1:2.0-2.5. The H-NMR spectrum data of the multifunctional nylon additive are: 1 HNMR (600 MHz, DMSO-d6) 8.27 (d, J = 7.86 Hz, 2H), 8.24 (t, J = 1.8 Hz, 1H), 7.93 (d, J = 1.80 Hz, 1H), 7.92 (d, J = 1.8 Hz, 1H), 7.52 (t, J = 7.74 Hz, 1H), 4.29 (m, 2H), 1.70 (dd, J = 3.66, 8.52 Hz, 4H), 1.18 (s, 12H), 1.12-1.17 (m, 4H), 1.04-1.07 (m, 12H); NMR analysis data are: 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° C., and the temperature is controlled by a jacket, with circulating warm water / cooling liquid.

[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 balls with a diameter of 2-5 mm.

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

[0016] Furthermore, the post-treatment step is: adding the acylated intermediate and deionized water into a beaker and stirring, adding an inorganic base to adjust the pH to 9-12, reacting at room temperature for 15-20 minutes, washing and drying to obtain a multifunctional auxiliary agent.

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

[0018] Furthermore, the washing and drying comprises: after the reaction is completed, filtering, washing the filter cake with deionized water 2-3 times, and then transferring to a drying oven at 100-110° C. and drying to constant weight to obtain a multifunctional nylon additive.

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

[0020] 1. The present invention is a multifunctional additive prepared by ball milling under solvent-free conditions, avoiding the use of organic solvents in traditional solution reactions, reducing air pollution caused by organic solvent volatilization, as well as environmental pollution problems and costs caused by subsequent organic solvent recovery and treatment, and realizing the development trend of green chemistry.

[0021] 2. The present invention also realizes the reaction through ball milling, which does not require complex reaction equipment and complex reaction conditions of high temperature and high pressure. The equipment process is simple and easy to operate. The ball milling process can accelerate the diffusion and collision frequency of the reactant molecules, so that the reactants can fully contact and react, improve the utilization rate of raw materials, reduce production costs, shorten the reaction time, and improve the reaction efficiency. The cyclohexane in the structure of the multifunctional nylon additive is a rigid skeleton. The large steric hindered alkyl group on the ring reduces the crowding of atoms in the ring, relieves angular tension, and is not easily attacked by external reagents. The π bond of the carbonyl group is conjugated with the lone pair of electrons of the nitrogen atom, the bond energy is higher, it is not easy to break, and the stability of the material is improved. During the ball milling process, this experiment adopts a comparative test. By adjusting the ball milling ratio and various ball milling parameters, the ball milling efficiency is optimized, thereby obtaining a multifunctional nylon additive with the best effect.

[0022] 3. The multifunctional additive prepared by the present invention has a unique molecular structure that can impart multiple properties to nylon materials. Among them, the tetramethylpiperidinamine structure inhibits ultraviolet-induced free radical oxidation, providing anti-aging properties for nylon materials. The conjugated structure of the benzene ring in isophthaloyl enhances the rigidity of the molecular chain and improves the mechanical properties of the nylon material, thereby enhancing the overall performance of the material in practical applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. 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 any creative work.

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

[0025] Figure 2 This is the C-NMR spectrum of the multifunctional nylon additive of the present invention. DETAILED DESCRIPTION

[0026] The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0027] Example 1

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

[0029] S1. Preparation of acylated intermediate

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

[0031] S2. Preparation of multifunctional nylon additives

[0032] Weigh: 10 g of the acylated intermediate and 100 mL of deionized water were added to a beaker and stirred, 30 wt % sodium hydroxide solution was added to adjust the pH to 9, and the reaction was carried out at room temperature for 15 min. After the reaction was completed, the filter cake was filtered and washed twice with deionized water, and then transferred to a 100 ° C drying oven to dry to constant weight to obtain a multifunctional nylon additive.

[0033] Example 2

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

[0035] S1. Preparation of acylated intermediate

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

[0037] S2. Preparation of multifunctional nylon additives

[0038] Weigh: 10g of the acylated intermediate and 150mL of deionized water were added to a beaker and stirred, 30wt% sodium hydroxide solution was added to adjust the pH to 10, and the reaction was carried out at room temperature for 17min. After the reaction was completed, the filter cake was washed 3 times with deionized water and then transferred to a 105°C drying oven and dried to constant weight to obtain a multifunctional nylon additive.

[0039] Example 3

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

[0041] S1. Preparation of acylated intermediate

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

[0043] S2. Preparation of multifunctional nylon additives

[0044] Weigh: 10g of the acylated intermediate and 200mL of deionized water are added to a beaker and stirred, 30wt% sodium hydroxide solution is added to adjust the pH to 10, and the reaction is carried out at room temperature for 20min. After the reaction is completed, filter and wash the filter cake with deionized water 3 times, and then transfer to a 110°C drying oven and dry to constant weight to obtain a multifunctional nylon additive.

[0045] Comparative Example 1

[0046] The difference between this comparative example and Example 3 is that step S1 is omitted and the acylated intermediate is prepared using a solvent method.

[0047] Comparative Example 2

[0048] 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.

[0049] Comparative Example 3

[0050] 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 grinding balls for reaction.

[0051] Performance testing:

[0052] According to the formula , test the yield of the multifunctional nylon additive, where m1 is the actual mass of the multifunctional nylon additive and m2 is the theoretical mass of the multifunctional nylon additive;

[0053] According to the formula , test the conversion rate of the multifunctional nylon additive, where 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;

[0054] The purity of the multifunctional nylon additives prepared in Examples 1-3 and Comparative Examples 1-3 was determined in accordance with the standard SH / T 1674-2023 "Determination of Purity and Hydrocarbon Impurities in Industrial Cyclohexane by Gas Chromatography". The specific test results are shown in Table 1 below:

[0055] Table 1-Performance test data of the sample

[0056]

[0057] Data Analysis:

[0058] A comparative analysis of the data in Table 1 above shows that the yield of the multifunctional additive prepared by the present 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 in the absence of solvents has a simple and efficient preparation process, high safety, fast reaction time, and excellent product performance, thereby improving the comprehensive performance of nylon materials in practical applications.

[0059] Compared with the embodiment, the solvent-free method in Comparative Example 1 is more environmentally friendly, avoids air pollution caused by organic solvents and environmental pollution caused by subsequent recycling, and reduces costs.

[0060] Comparative Example 2 Compared with the embodiment, the present invention obtains the best experimental reaction time and the molar ratio of the sample under solvent-free conditions through comparative experiments, so that the product yield, reaction conversion rate and product purity achieve the best results, which not only reduces time and production costs, but also increases output.

[0061] Comparative Example 3 Compared with the embodiment, the ball milling process can accelerate the diffusion and collision frequency of the reactant molecules, so that the reactants can fully contact and react, improve the utilization rate of raw materials, reduce production costs, shorten the reaction time, and improve the reaction efficiency.

[0062] Attachment Figure 1 In the , the proton spectrum data is: 1HNMR(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);

[0063] Attachment Figure 2 The NMR analysis data are:

[0064] 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.

[0065] The above contents are merely examples and explanations of the structure of the present invention. Those skilled in the art may make various modifications or additions to the described specific embodiments or replace them in a similar manner. As long as they do not deviate from the structure of the invention or exceed the scope defined by the claims, they shall fall within the scope of protection of the present invention.

[0066] Throughout this specification, references to terms such as "one embodiment," "example," or "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these 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 any one or more embodiments or examples.

[0067] The preferred embodiments of the present invention disclosed above are intended only to help illustrate the present invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the present invention to specific embodiments. Obviously, many modifications and variations are possible based on the contents of this specification. These embodiments are selected and described in detail in this specification to better explain the principles and practical applications of the present invention, thereby enabling those skilled in the art to better understand and utilize the present invention. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A method for preparing a multifunctional nylon additive based on a solvent-free process, characterized in that: The structural formula of the multifunctional nylon additive is: ， The method for preparing a multifunctional nylon additive based on a solvent-free method comprises: using isophthaloyl chloride and tetramethylpiperidinamine as raw materials, promoting an acylation reaction between the isophthaloyl chloride and tetramethylpiperidinamine through ball milling, obtaining an acylated intermediate, and post-treating the acylated intermediate with an inorganic base to prepare the multifunctional nylon additive.

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

5.

3. The method for preparing a multifunctional nylon additive based on a solvent-free method according to claim 1, characterized in that: The temperature of the acylation reaction is 25-45° C., and the temperature is controlled by jacket temperature control, with circulating warm water / cooling liquid.

4. The method for preparing a multifunctional nylon additive based on a solvent-free method according to claim 1, characterized in that: The ball mill 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 balls with a diameter of 2-5 mm.

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

6. The method for preparing a multifunctional nylon additive based on a solvent-free method according to claim 1, characterized in that: The post-treatment steps include: adding the acylated intermediate and deionized water into a beaker and stirring, adding an inorganic base to adjust the pH to 9-12, reacting at room temperature for 15-20 minutes, washing and drying to obtain a multifunctional auxiliary agent.

7. The method for preparing a multifunctional nylon additive based on a solvent-free method according to claim 5, characterized in that: The usage ratio of the acylated intermediate and deionized water is 1 g:5-20 mL.

8. The method for preparing a multifunctional nylon additive based on a solvent-free method according to claim 6, characterized in that: The washing and drying comprises: after the reaction is completed, filtering, washing the filter cake with deionized water for 2-3 times, and then transferring it to a drying oven at 100-110° C. and drying it to a constant weight to obtain a multifunctional nylon additive.

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