Composite antioxidant stabilizer composition as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of high polymer material additives, and particularly relates to a composite antioxidant stabilizer composition as well as a preparation method and application thereof, in particular to the composite antioxidant stabilizer composition and a one-pot preparation process thereof. According to the preparation method, 3, 5-methyl ester or meta-3, 5-methyl ester, octadecanol, pentaerythritol, trimethyl phosphite and absolute methanol are taken as raw materials, a zinc-containing compound is added as a catalyst, transesterification is catalyzed, and the composite antioxidant stabilizer composition containing an antioxidant 1076, an antioxidant 1010 and a phosphite antioxidant 618 at the same time can be prepared through a one-pot method. The antioxidant composition prepared by the method has the advantages that the antioxidant effect of the ABS resin can be obviously improved and the comprehensive performance of the ABS resin can be improved when the antioxidant composition prepared by the method is applied to the ABS resin as compared with the antioxidant composition prepared by the traditional method after auxiliaries such as the acid acceptor are added into the composition.

Description

Technical Field

[0001] This invention belongs to the field of polymer material additives technology, specifically relating to a composite antioxidant stabilizer composition and its preparation method and application, particularly to the composite antioxidant stabilizer composition and its one-pot preparation process. Background Technology

[0002] During processing and daily use, polymer materials are highly susceptible to the effects of oxygen, light, heat, or metal ion impurities in the air, which can cause free radical oxidation and aging reactions. This can lead to discoloration, cracking, and loss of gloss in the polymer, resulting not only in an unattractive appearance but, more seriously, a significant decrease in mechanical properties and stability.

[0003] ABS engineering plastic is a widely used thermoplastic non-crystalline amorphous polymer material with excellent properties. It has high impact strength and surface hardness over a wide temperature range, and its heat distortion temperature is higher than that of polyamide (PA) and polyvinyl chloride (PVC), resulting in better dimensional stability.

[0004] ABS engineering plastic is synthesized from three chemical monomers: acrylonitrile, butadiene, and styrene. The polymerization of these three monomers produces a two-phase ternary copolymer: a continuous phase of styrene-acrylonitrile and a dispersed phase of polybutadiene rubber. However, the easy oxidation and aging of butadiene makes ABS have poor aging resistance and weather resistance. Therefore, the initial aging of ABS is caused by the degradation and cross-linking of the PB phase due to thermal oxidation.

[0005] Currently, the commonly used antioxidant stabilizers for ABS engineering plastics on the market are conventional products such as 1010, 1076, and 168. Although they have a certain antioxidant effect, the effect is very limited, and there are problems such as unstable application effect, easy color change, and poor storage stability. In addition, in order to improve the antioxidant effect, the existing technology generally adopts a process of compounding various antioxidant stabilizers. However, at present, the commonly used ABS stabilizer compound still has problems such as complex preparation process, low efficiency, high energy consumption, high cost, and unstable performance.

[0006] Therefore, developing a high-efficiency, high-quality ABS-specific antioxidant stabilizer composition and its green and energy-saving preparation method is of great practical significance and application value. Summary of the Invention

[0007] To address the aforementioned technical problems, this invention provides a composite antioxidant stabilizer composition, its preparation method, and its application.

[0008] The first aspect of the present invention is to provide a composite antioxidant stabilizer composition, the composition comprising a primary antioxidant, a secondary antioxidant 618, and an acid scavenger, wherein the primary antioxidant is selected from at least one of antioxidant 1076, antioxidant 1010, pentaerythritol tetrakis[-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], and octadecyl tetrakis[-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]; and the mass ratio of the primary antioxidant to the secondary antioxidant 618 to the acid scavenger is 20-75:20-60:0-40.

[0009] A second aspect of the present invention is to provide a method for preparing the above-mentioned composite antioxidant stabilizer composition, specifically a one-pot method, wherein the preparation method includes the following steps: S1 Raw material preparation: 3,5-methyl ester or meta-3,5-methyl ester, octadecyl alcohol, pentaerythritol, and trimethyl phosphite are used as reaction raw materials. The reaction raw materials 3,5-methyl ester or meta-3,5-methyl ester, octadecyl alcohol, pentaerythritol, and trimethyl phosphite are accurately weighed. Anhydrous methanol is used as the reaction solvent. The mass ratio of 3,5-methyl ester or meta-3,5-methyl ester: octadecyl alcohol: pentaerythritol: trimethyl phosphite in the reaction raw materials is 10-60: 30-80: 2-25: 5-30. The mass-volume ratio of 3,5-methyl ester or meta-3,5-methyl ester to anhydrous methanol is 1 g: 0.2-1.0 mL. S2 involves sequentially adding the reactants and solvents from S1 into the transesterification reaction vessel, adding a zinc-containing compound as a catalyst, purging with nitrogen and providing nitrogen protection, and carrying out the transesterification reaction to obtain a reaction solution while recovering the by-product methanol. S3 adds an acid-absorbing agent to the reaction solution of S2, stirs at 65-75℃, and mixes evenly to obtain a mixed reaction solution; S4 adds diatomaceous earth to the mixed reaction solution obtained in S3, filters and collects the filtrate, granulates it, and obtains the composite antioxidant stabilizer composition.

[0010] In the preparation method of the above-mentioned composite antioxidant stabilizer composition provided by the present invention, preferably, the zinc-containing compound in S2 is selected from at least one of zinc oxide, zinc stearate, and zinc sulfide, and the catalyst accounts for 0.05%-0.15% of the mass of the reaction raw materials.

[0011] As a further preferred embodiment, the zinc-containing compound in S2 is selected from at least one of zinc stearate and zinc sulfide.

[0012] As a preferred embodiment, the specific reaction conditions for the transesterification reaction described in S2 are as follows: first, react at 30-60℃ for 10-20 min, then react at 60-70℃ under slight positive pressure for 10-30 min, turn on the gas receiving device, control the valve opening to allow methanol to escape steadily and continuously to the receiving bottle for condensation and recovery, then uniformly raise the temperature of the reaction system to 120-140℃ within 10-30 min, and maintain the reaction at atmospheric pressure for 15-30 min at this temperature, gradually adjust the vacuum from slight negative pressure to an absolute pressure of 4000-6000 Pa, and continuously collect and recover methanol; continue the gradient heating reaction, raising the temperature to 160-190℃ within 20-30 min, and maintaining it for 5-20 min, finally, gradually adjust the vacuum to an absolute pressure of 300-500 Pa, and maintain the reaction for 20-40 min, and after the reaction is completed, lower the system temperature to 70-100℃.

[0013] Preferably, the acid absorbent in S3 is selected from at least one of magnesium oxide, zinc oxide, calcium stearate, zinc stearate, zinc sulfide, and calcium sulfide, and the amount of acid absorbent added accounts for 0-40% of the mass of the reaction solution in S2.

[0014] A third aspect of the present invention is to provide an ABS resin comprising blank ABS powder and the composite antioxidant stabilizer composition provided by the present invention.

[0015] Furthermore, the ABS resin provided by the present invention is prepared by the following method: first, the blank ABS powder is dried in an air-conditioned oven, then it is mixed evenly with a composite antioxidant stabilizer composition, extruded and granulated using a twin-screw extruder, and then water-cooled and pelletized to obtain the ABS resin.

[0016] Preferably, the amount of the composite antioxidant stabilizer composition added to the ABS resin accounts for 0.1%-0.3% of the total mass of the resin.

[0017] Preferably, when using a twin-screw extruder for extrusion granulation, the temperature of the twin-screw extruder is 185-190℃ in zone 1, 180-185℃ in zone 2, 180-185℃ in zone 3, 175-180℃ in zone 4, 175-180℃ in zone 5, 170-175℃ in the die head, 5.0-6.0 A in the main extruder current, 15-25 r / min in the main extruder speed, and 15-30 r / min in the main feed speed.

[0018] It should be stated that the granulation process described above in this invention is a conventional process in the field. It can be drip cooling granulation or other cooling granulation processes, such as spraying or spraying. The purpose of the granulation is only to make the mixed reaction liquid into granules, and after cooling, obtain a white solid granular product with specific components.

[0019] The beneficial effects of this invention are as follows: Compared to the traditional method of preparing antioxidant compositions by first preparing individual antioxidants 1010, 1076, and 618, purifying them separately, and then mixing and granulating the individual antioxidants, the advantages of this invention are as follows: (1) The present invention adopts a one-pot preparation process, which can simultaneously produce a mixed antioxidant composition product containing auxiliary antioxidant 618 and main antioxidants 1076, 1010, pentaerythritol tetrakis[-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] and octadecyl β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate in the reaction product through a one-step reaction. The one-step preparation process of the present invention has the advantages of fewer preparation steps, green, energy saving and high efficiency. (2) By adjusting the ratio of the raw materials and using a specific process, the composite antioxidant stabilizer composition prepared by the present invention contains multiple antioxidant components. In addition, in the product of the present invention, trimethyl phosphite not only plays the role of a reactant in the reaction, but also plays the role of color stabilization and auxiliary catalysis. The addition of this component significantly improves the reaction rate and efficiency of the one-step reaction in the present invention. At the same time, trimethyl phosphite can also protect the color of the product and give it good appearance properties. (3) The method of the present invention also has the advantages of short product manufacturing process, stable performance and good hydrolysis resistance, which can significantly improve the stability and service life of ABS materials. Attached Figure Description

[0020] Figure 1 The FTIR spectrum of the composition obtained in Example 1 of this invention; Figure 2 The HPLC chromatogram of the composition obtained in Example 1 of this invention; Figure 3 The FTIR spectrum of the composition obtained in Example 2 of this invention; Figure 4 The HPLC chromatogram of the composition obtained in Example 2 of this invention; Figure 5 The FTIR spectrum of the composition obtained in Example 4 of this invention; Figure 6The HPLC chromatogram of the composition obtained in Example 4 of this invention; Figure 7 The FTIR spectrum of the composition obtained in Example 5 of this invention; Figure 8 The HPLC chromatogram of the composition obtained in Example 5 of this invention; Figure 9 The FTIR spectrum of the composition obtained in Example 6 of this invention; Figure 10 The HPLC chromatogram of the composition obtained in Example 6 of this invention; Figure 11 The FTIR spectrum of the composition obtained in Example 7 of this invention; Figure 12 The HPLC chromatogram of the composition obtained in Example 7 of this invention; Figure 13 The FTIR spectrum of the composition obtained in Example 10 of this invention; Figure 14 This is an HPLC chromatogram of the composition prepared in Example 10 of the present invention. Detailed Implementation

[0021] To enable those skilled in the art to better understand the present invention, the present invention will now be further described in conjunction with specific embodiments.

[0022] Example 1 A composite antioxidant stabilizer composition is prepared as follows: S1 Raw material preparation: Accurately weigh 20.0 g of 3,5-methyl ester, 51.0 g of octadecyl alcohol, 8.2 g of pentaerythritol, and 15.0 g of trimethyl phosphite, and 50 mL of anhydrous methanol as solvent; S2 involves sequentially adding each reactant and anhydrous methanol into a transesterification reaction vessel equipped with a stirrer, condensation recovery device, gas absorption control device, temperature and pressure control and detection device. Simultaneously, 0.05 g of zinc stearate and 0.05 g of zinc sulfide are added as catalysts. After the feeding is completed, the feeding port is covered, sealed, and a vacuum is drawn. The nitrogen content in the flask is replaced with nitrogen until it is not less than 99%. Then, the pressure is balanced with nitrogen, the gas receiving device is turned off, and the transesterification reaction is carried out to obtain the reaction liquid. At the same time, the by-product methanol is recovered. The conditions for the transesterification reaction are as follows: First, the temperature is uniformly raised from room temperature to 50°C over 5 minutes. Stirring is started, and the reaction is carried out at 50°C for 10 minutes. The temperature is then raised to 65°C, and methanol is refluxed while maintaining a slight positive pressure in the flask. The reflux reaction is carried out for 20 minutes. The gas receiving device is then turned on, and the valve opening is controlled to allow methanol to escape steadily and continuously to the receiving flask for condensation and recovery. The reaction system is then uniformly raised to 130°C over 20 minutes and maintained at this temperature for 20 minutes. Methanol is continuously collected and recovered, with the amount of methanol gradually decreasing. The vacuum is gradually adjusted from a slight negative pressure to an absolute pressure of 5000 Pa, and methanol is continuously collected and recovered. The reaction is then continued with a gradient temperature increase, raising the temperature to 180°C over 20 minutes and reacting at this temperature for 10 minutes. Finally, the vacuum is gradually adjusted to an absolute pressure of 400 Pa, and the reaction is carried out for 30 minutes. After the reaction is completed, the system temperature is lowered to 90°C, and nitrogen is used to equalize the pressure. After the transesterification reaction in S2 is completed, add 1 g of diatomaceous earth to the reaction solution obtained in S2, stir, filter while hot and at a constant temperature, collect the filtrate, and granulate it by drip cooling to obtain the composite antioxidant stabilizer composition particles.

[0023] The composite antioxidant stabilizer composition prepared by the method of this embodiment has a mass of 80.1 g. Sampling and testing of this composite antioxidant stabilizer composition revealed a melting range of 52.3-65.2℃. Furthermore, the content of each component in the composition obtained in this embodiment was determined by high-performance liquid chromatography with external standard method. The Fourier transform infrared (FTIR) spectrum of the composite antioxidant stabilizer composition is shown below. Figure 1 As shown, the HPLC chromatogram is shown below. Figure 2 As shown.

[0024] Testing revealed that antioxidant 1076 comprised 44.999% of the composite antioxidant stabilizer composition by mass, and the phosphorus content in the composition was determined to be 4.65% by titration.

[0025] Example 2 A composite antioxidant stabilizer composition, the preparation method of which differs from that in Example 1, is as follows: The reaction raw materials in S1 are as follows: 48.0 g of 3,5-methyl ester, 36.5 g of octadecyl alcohol, 15.0 g of pentaerythritol, 16.6 g of trimethyl phosphite, and 50 mL of anhydrous methanol as solvent; In S2, 0.1 g of zinc sulfide was used as the catalyst for the reaction; The conditions for the transesterification reaction are as follows: First, the temperature is uniformly raised from room temperature to 45°C over 8 minutes. Stirring is started, and the reaction is carried out at 45°C for 10 minutes. The temperature is then raised to 55°C, and methanol is refluxed while maintaining a slight positive pressure in the flask. The reflux reaction is carried out for 20 minutes. The gas receiving device is then turned on, and the valve opening is controlled to allow methanol to escape steadily and continuously to the receiving flask for condensation and recovery. The reaction system is then uniformly raised to 130°C over 20 minutes and maintained at this temperature for 20 minutes. Methanol is continuously collected and recovered, with the amount of methanol gradually decreasing. The vacuum is gradually adjusted from a slight negative pressure to an absolute pressure of 5000 Pa, and methanol is continuously collected and recovered. The reaction is then continued with a gradient temperature increase, raising the temperature to 180°C over 20 minutes and reacting at this temperature for 10 minutes. Finally, the vacuum is gradually adjusted to an absolute pressure of 400 Pa, and the reaction is carried out for 30 minutes. After the reaction is completed, the system temperature is lowered to 90°C, and nitrogen is used to equalize the pressure. S3 is the same as in Example 1.

[0026] The composite antioxidant stabilizer composition prepared by the method of this embodiment has a mass of 96.9 g. The composite antioxidant stabilizer composition was sampled and tested, and the results showed that its melting range was 63.1-124.3℃.

[0027] Furthermore, the content of each component in the composition obtained in this embodiment was detected by high performance liquid chromatography with external standard method. The mass of antioxidant 1010 in the composite antioxidant stabilizer composition was 49.455%, and the phosphorus content in the composition was determined to be 4.269% by titration.

[0028] The FTIR spectrum of the composite antioxidant stabilizer composition prepared in this embodiment is shown in the figure. Figure 3 The HPLC chromatogram is shown below. Figure 4 .

[0029] Example 3 A composite antioxidant stabilizer composition, the preparation method of which differs from that in Example 1, is as follows: The reaction raw materials in S1 are as follows: 41.0 g of 3,5-methyl ester, 57.0 g of octadecyl alcohol, 4.8 g of pentaerythritol, 8.5 g of trimethyl phosphite, and 50 mL of anhydrous methanol; In S2, 0.1 g of zinc sulfide was used as the catalyst for the reaction, and the conditions for the transesterification reaction were the same as in Example 2. S3 is the same as in Example 1.

[0030] The composite antioxidant stabilizer composition prepared by the method of this embodiment has a mass of 99.05 g. The composite antioxidant stabilizer composition was sampled and tested, and the results showed that its melting range was 52.0-64.3℃.

[0031] Furthermore, the content of each component in the composition obtained in this embodiment was detected by high performance liquid chromatography with external standard method. The mass of antioxidant 1076 in the composite antioxidant stabilizer composition was 74.75%, and the phosphorus content in the composition was determined to be 2.134% by titration.

[0032] Example 4 A composite antioxidant stabilizer composition is prepared as follows: S1 Raw material preparation: Accurately weigh 20.0 g of 3,5-methyl ester, 44.0 g of octadecyl alcohol, 6.5 g of pentaerythritol, and 12.0 g of trimethyl phosphite, and 50 mL of anhydrous methanol as solvent; S2. Add each reaction raw material and anhydrous methanol sequentially to the same transesterification reaction vessel as in Example 1. At the same time, add 0.1 g of zinc oxide as a catalyst. After the feeding is completed, cover the feeding port, seal the flask, evacuate the vacuum, replace the nitrogen with nitrogen until the nitrogen content in the flask is not less than 99%, and then use nitrogen to equalize the pressure to carry out the transesterification reaction to obtain the reaction solution. The conditions for the transesterification reaction are the same as in Example 1. S3 adds an acid absorbent to the reaction solution obtained in S2 while it is still hot, and stirs and mixes it evenly at 70°C to obtain a mixed reaction solution, wherein the acid absorbent is 20.0 g zinc sulfide and 10 g magnesium oxide; S4 adds diatomaceous earth to the mixed reaction solution obtained in S3, filters and collects the filtrate, then granulates it by drip cooling, and after cooling, obtains a granular product containing a composite antioxidant stabilizer composition.

[0033] The antioxidant product prepared by the method of this embodiment has a mass of 99.5 g. The melting range of the sampled product is 54.5°C (initial melting point) and has no final melting point. The content of each component in the antioxidant product is determined by high performance liquid chromatography with external standard method. The content of antioxidant 1076 is 34.668%. The phosphorus content in the product is 2.973% as determined by titration.

[0034] The FTIR spectrum of the composite antioxidant stabilizer composition prepared in this embodiment is shown in the figure. Figure 5 The HPLC chromatogram is shown below. Figure 6 .

[0035] Example 5 A composite antioxidant stabilizer composition, the preparation method of which differs from that in Example 1, is as follows: The reaction raw materials in S1 are as follows: 3,5-methyl ester 34.0 g, octadecyl alcohol 54.5 g, pentaerythritol 13.5 g, trimethyl phosphite 20.0 g, and anhydrous methanol 50 mL; In S2, 0.05 g of zinc stearate and 0.05 g of zinc sulfide were used as reaction catalysts, and the transesterification reaction conditions were the same as in Example 2. S3 is the same as in Example 1.

[0036] The composite antioxidant stabilizer composition prepared by the method of this embodiment has a mass of 102.0 g. The composite antioxidant stabilizer composition was sampled and tested, and its melting range was 52.9-122.8℃. Furthermore, the content of each component in the composition obtained in this embodiment was detected by high performance liquid chromatography with external standard method. Among them, antioxidant 1010 accounted for 21.157% by mass and antioxidant 1076 accounted for 21.992% by mass. The phosphorus content in the composition was determined by titration to be 4.805%.

[0037] The FTIR spectrum of the composite antioxidant stabilizer composition prepared in this embodiment is shown in the figure. Figure 7 The HPLC chromatogram is shown below. Figure 8 .

[0038] Example 6 A composite antioxidant stabilizer composition is prepared as follows: S1 Raw material preparation: Accurately weigh 17.0 g 3,5-methyl ester, 40.5 g octadecyl alcohol, 6.5 g pentaerythritol, 11.5 g trimethyl phosphite, and 50 mL anhydrous methanol; S2: The reactants and solvents from S1 are sequentially added to the transesterification reaction vessel, and 0.1 g of zinc sulfide is added as a reaction catalyst. The reaction solution is obtained according to the preparation process of Example 5. S3 adds an acid scavenger to the reaction solution obtained in S2 and stirs and mixes it evenly at 70°C to obtain a mixed reaction solution, wherein the acid scavenger is 4.6 g zinc sulfide, 9.15 g magnesium oxide, and 9.15 g calcium stearate. S4 adds diatomaceous earth to the mixed reaction solution obtained in S3, filters and collects the filtrate, then granulates it by drip cooling, and after cooling, obtains a granular product containing a composite antioxidant stabilizer composition.

[0039] The antioxidant product prepared by the method of this embodiment has a mass of 86.4 g. The melting range of the sampled product is 52.9°C (initial melting point) and has no final melting point. The component content of the antioxidant product is detected by high performance liquid chromatography with external standard method. The content of antioxidant 1076 is 34.886%. The phosphorus content in the product is 3.277% as determined by titration.

[0040] The FTIR spectrum of the composite antioxidant stabilizer composition prepared in this embodiment is shown in the figure. Figure 9 The HPLC chromatogram is shown below. Figure 10 .

[0041] Example 7 A composite antioxidant stabilizer composition is prepared as follows: S1 Raw Material Preparation: Accurately weigh 18.0 g 3,5-methyl ester, 41.5 g octadecyl alcohol, 6.5 g pentaerythritol, 12.0 g trimethyl phosphite, and 50 mL anhydrous methanol; S2: The reactants and solvents from S1 are sequentially added to the transesterification reactor, and 0.1 g of zinc oxide is added as a catalyst. The reaction solution is obtained according to the preparation process of Example 5. S3 adds an acid absorbent to the reaction solution obtained in S2 while it is still hot and stirs and mixes it evenly at 70°C to obtain a mixed reaction solution, wherein the acid absorbent is 19.5 g of zinc stearate and 5.0 g of calcium sulfide. S4 adds diatomaceous earth to the mixed reaction solution obtained in S3, filters and collects the filtrate, then granulates it by drip cooling, and after cooling, obtains a granular product containing a composite antioxidant stabilizer composition.

[0042] The antioxidant product prepared by the method of this embodiment has a mass of 90.5 g. The melting range of the antioxidant product was tested and found to be an initial melting point of 52.6°C with no final melting point. The content of each component in the antioxidant product was determined by high performance liquid chromatography with external standard method. The content of antioxidant 1076 was 35.418%, and the phosphorus content in the product was determined by titration to be 3.175%.

[0043] The FTIR spectrum of the composite antioxidant stabilizer composition prepared in this embodiment is shown in the figure. Figure 11 The HPLC chromatogram is shown below. Figure 12 .

[0044] Example 8 A composite antioxidant stabilizer composition is prepared as follows: S1 Raw material preparation: Accurately weigh 19.5 g 3,5-methyl ester, 44.0 g octadecyl alcohol, 6.5 g pentaerythritol, 12.0 g trimethyl phosphite, and 50 mL anhydrous methanol; S2: The reactants and solvents from S1 are sequentially added to the transesterification reactor, and 0.05 g of zinc sulfide and 0.05 g of zinc stearate are added as reaction catalysts. The reaction solution is obtained according to the preparation process of Example 5. S3 is added to the reaction solution obtained by S2 while it is still hot and stirred at 70°C to obtain a mixed reaction solution, wherein the acid scavenger is 10.0 g zinc stearate and 20.0 g calcium stearate; S4 adds diatomaceous earth to the mixed reaction solution obtained in S3, filters and collects the filtrate, then granulates it by drip cooling, and after cooling, obtains a granular product containing a composite antioxidant stabilizer composition.

[0045] The antioxidant product prepared by the method of this embodiment has a mass of 99.8 g. The melting range of the sampled product is 53.0°C (initial melting point) and has no final melting point. The content of each component in the product is determined by high performance liquid chromatography with external standard method. The content of antioxidant 1076 is 34.934%, and the phosphorus content in the product is 2.958% as determined by titration.

[0046] Example 9 A composite antioxidant stabilizer composition is prepared as follows: S1 Raw material preparation: Accurately weigh 17.0 g 3,5-methyl ester, 42.0 g octadecyl alcohol, 7.0 g pentaerythritol, 12.5 g trimethyl phosphite, and 50 mL anhydrous methanol; S2: The reactants and solvents from S1 are sequentially added to the transesterification reactor, and 0.1 g of zinc oxide is added as a catalyst. The reaction solution is obtained according to the preparation process of Example 5. S3 adds an acid absorbent to the reaction solution obtained in S2 while it is still hot, and stirs and mixes it evenly at 70°C to obtain a mixed reaction solution, wherein the acid absorbent is 10.0 g zinc sulfide and 10.0 g calcium sulfide. S4 adds diatomaceous earth to the mixed reaction solution obtained in S3, filters and collects the filtrate, then granulates it by drip cooling, and after cooling, obtains a granular product containing a composite antioxidant stabilizer composition.

[0047] The antioxidant product prepared by the method of this embodiment has a mass of 86.0 g. The melting range of the sampled product is 54.8°C (initial melting point) and has no final melting point. The content of each component in the antioxidant product is determined by high performance liquid chromatography with external standard method. The content of antioxidant 1076 is 34.665%. The phosphorus content in the product is 3.538% as determined by titration.

[0048] Example 10 A composite antioxidant stabilizer composition is prepared as follows: S1 Raw material preparation: Accurately weigh 21.0 g 3,5-methyl ester, 44.0 g octadecyl alcohol, 6.5 g pentaerythritol, 11.5 g trimethyl phosphite, and 50 mL anhydrous methanol; S2: The reactants and solvents from S1 are sequentially added to the transesterification reactor, and 0.05 g of zinc sulfide and 0.05 g of zinc stearate are added as catalysts for the reaction. The reaction solution is obtained according to the preparation process of Example 5. S3 adds an acid absorbent to the reaction solution obtained in S2 while it is still hot, and stirs and mixes it evenly at 70°C to obtain a mixed reaction solution, wherein the acid absorbent is 10.0 g magnesium oxide, 10.0 g zinc oxide and 10.0 g calcium sulfide. S4 adds diatomaceous earth to the mixed reaction solution obtained in S3, filters and collects the filtrate, then granulates it by drip cooling, and after cooling, obtains a granular product containing a composite antioxidant stabilizer composition.

[0049] The antioxidant product prepared by the method of this embodiment has a mass of 101.05 g. The melting range of the sampled product is 52.6°C (initial melting point) and has no final melting point. The component content of the product is detected by high performance liquid chromatography with external standard method. The content of antioxidant 1076 is 37.594%. The phosphorus content in the product is 2.76% as determined by titration.

[0050] The FTIR spectrum of the composite antioxidant stabilizer composition prepared in this embodiment is shown in the figure. Figure 13 The HPLC chromatogram is shown below. Figure 14 .

[0051] Example 11 A composite antioxidant stabilizer composition is prepared as follows: S1 Raw material preparation: Accurately weigh 20.0 g 3,5-methyl ester, 51.0 g octadecyl alcohol, 8.2 g pentaerythritol, 15.0 g trimethyl phosphite, and 50 mL anhydrous methanol; S2: The reactants and solvents from S1 are sequentially added to the transesterification reactor, and a particulate product is obtained according to the preparation process of Example 6.

[0052] The composite antioxidant stabilizer composition prepared by the method of this comparative example has a product mass of 79.89 g. The melting range of the composition was tested by sampling and found to be 53.6-64.7℃. The content of each component in the composition was determined by high performance liquid chromatography with external standard method. Among them, the content of antioxidant 1076 was 37.594%, and the phosphorus content in the composition was determined by titration to be 4.02%.

[0053] Table 1 shows the reaction raw materials of the products in each embodiment of the present invention.

[0054] Table 1 Comparison of reaction raw materials for products in various embodiments of the present invention

[0055] Experimental Example 1 An ABS resin is prepared by the following method: Blank ABS powder (0215A) was placed in a tray and dried in a ventilated oven for 4 hours. 499 g of the dried ABS powder was sampled and mixed with 1 g of the composite antioxidant stabilizer composition or antioxidant product prepared in Examples 1-11 to obtain a total of 11 mixture samples. The 11 mixtures were extruded and granulated in a twin-screw extruder and then water-cooled and pelletized to obtain different ABS resins.

[0056] In the above-mentioned ABS resin preparation process, the temperature of the twin-screw extruder is 185℃ in zone 1, 180℃ in zone 2, 180℃ in zone 3, 175℃ in zone 4, 175℃ in zone 5, 170℃ in the die head, 5.5A in the main extruder current, 20 r / min in the main extruder speed, and 18 r / min in the main feed speed.

[0057] In addition, 499 g of dried ABS and 0.5 g of conventional industrial 618 antioxidant were mixed evenly and extruded and granulated using the same basic process to obtain ABS resin as a control example.

[0058] Meanwhile, 500 g of dried ABS powder was used as a blank control.

[0059] The melt index (Mr), yellow index (YI), and oxidation induction time (OIT) of the third extruded particles of the ABS resin samples were tested when the compositions or products prepared in each example and comparative example were applied to the ABS resin preparation process.

[0060] During the switching of each mixture, the screw was washed with blank ABS tubing. 100g samples were taken after the first, third and fifth extrusions and retained. The Mr and YI of the extruded particles from the first, third and fifth extrusions of each mixture sample and the OIT of the extruded particles from the third extrusion were tested.

[0061] The test results of various parameters during the ABS resin particle extrusion process are shown in Table 2.

[0062] Table 2 Statistical table of test results for various parameters during the extrusion of ABS resin granules

[0063] As can be seen from Table 2, the composite antioxidant stabilizer compositions prepared by the processes of Examples 1-5, 9, and 10 showed a smaller increase in melt index after five extrusions and good processing stability. In particular, Examples 4, 9, and 10 showed outstanding processing stability. Example 11 was slightly worse, but still better than the control example. The melt index of all the aforementioned examples after five extrusions showed a significant improvement in stability compared to the blank sample.

[0064] The composite antioxidant stabilizer compositions prepared by the processes of Examples 1-10 showed good yellow index performance in five-time extrusion processing, significantly better than that of Example 11. In particular, Examples 6, 7, and 10 showed outstanding color stability. Example 11 showed improvement compared to the control example. The yellow index of all the aforementioned examples in five-time extrusion processing showed a significant improvement in stability compared to the blank sample. That is, the stabilizer compositions prepared by the one-pot method of the present invention showed good color stability in processing.

[0065] The composite antioxidant stabilizer compositions prepared by the processes in Examples 1-10 showed good oxidation induction period after three extrusion processes, especially Examples 2, 3 and 5, which were significantly better than Example 11. Example 11 showed improvement over the control example. The yellow index of all the aforementioned examples after five extrusion processes was significantly improved compared to the blank sample.

[0066] In addition, in Examples 5-10, different types and amounts of acid absorbers were added based on Examples 1-4, and the yellow index of the obtained antioxidant products was significantly reduced. Among them, the antioxidant product of Example 10 had the lightest color and a longer oxidation induction time, showing the best antioxidant product effect.

[0067] Furthermore, compared with ABS with added conventional antioxidants (i.e., control examples), the ABS resin with added composite antioxidant stabilizer compositions prepared in the various embodiments of the present invention exhibits significantly improved processing stability and anti-extraction properties, significantly prolonged oxidation induction period, and significantly improved overall resistance to thermo-oxidative aging.

[0068] The above results show that the composite antioxidant stabilizer composition prepared by the one-pot method of the present invention has the characteristics of good antioxidant effect, water extraction resistance and non-migration. Adding it to ABS can significantly improve the antioxidant performance and quality of ABS.

Claims

1. A composite antioxidant stabilizer composition, characterized in that, It includes a primary antioxidant, a secondary antioxidant 618, and an acid scavenger. The primary antioxidant is selected from at least one of antioxidant 1076, antioxidant 1010, pentaerythritol tetrakis[-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], and octadecyl β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate. The mass ratio of the primary antioxidant, auxiliary antioxidant 618, and acid absorber is 20-75:20-60:0-40.

2. A method for preparing the composite antioxidant stabilizer composition as described in claim 1, characterized in that, The steps include the following: S1 Raw material preparation: Accurately weigh the reaction raw materials 3,5-methyl ester or meta-3,5-methyl ester, octadecyl alcohol, pentaerythritol, and trimethyl phosphite, and use anhydrous methanol as the reaction solvent. In the reaction raw materials, the mass ratio of 3,5-methyl ester or meta-3,5-methyl ester: octadecyl alcohol: pentaerythritol: trimethyl phosphite is 10-60: 30-80: 2-25: 5-30, and the mass-volume ratio of 3,5-methyl ester or meta-3,5-methyl ester to anhydrous methanol is 1 g: 0.2-1 mL. S2 involves sequentially adding the reactants and solvents from S1 into the transesterification reaction vessel, adding a zinc-containing compound as a catalyst, purging with nitrogen and providing nitrogen protection, and carrying out the transesterification reaction to obtain a reaction solution while recovering the by-product methanol. S3 adds an acid-absorbing agent to the reaction solution of S2, stirs at 65-75℃, and mixes evenly to obtain a mixed reaction solution; S4 adds diatomaceous earth to the mixed reaction solution obtained in S3, filters and collects the filtrate, granulates it, and obtains the composite antioxidant stabilizer composition.

3. The preparation method according to claim 2, characterized in that, The zinc-containing compound mentioned in S2 is selected from at least one of zinc oxide, zinc stearate, and zinc sulfide, and the catalyst accounts for 0.05%-0.15% of the mass of the reaction raw materials.

4. The preparation method according to claim 2, characterized in that, The specific reaction conditions for the transesterification reaction described in S2 are as follows: First, react at 30-60℃ for 10-20 min, then react at 60-70℃ under slight positive pressure for 10-30 min. Turn on the gas receiving device, control the valve opening, and allow methanol to escape steadily and continuously to the receiving bottle for condensation and recovery. Then, uniformly raise the temperature of the reaction system to 120-140℃ within 10-30 min, and maintain the reaction at atmospheric pressure at this temperature for 15-30 min. Adjust the vacuum from slight negative pressure to an absolute pressure of 4000-6000 Pa, and continuously collect and recover methanol. Continue to raise the temperature gradient to 160-190℃ within 20-30 min, and maintain it for 5-20 min. Finally, gradually adjust the vacuum to an absolute pressure of 300-500 Pa, and maintain the reaction for 20-40 min. After the reaction is completed, lower the system temperature to 70-100℃.

5. The preparation method according to claim 2, characterized in that, In S3, the acid absorbent is selected from at least one of magnesium oxide, zinc oxide, calcium stearate, zinc stearate, zinc sulfide, and calcium sulfide, and the amount of acid absorbent added accounts for 0-40% of the mass of the reaction solution in S2.

6. An ABS resin, characterized in that, The ABS resin includes blank ABS powder and the composite antioxidant stabilizer composition according to claim 1.

7. The method for preparing the ABS resin according to claim 6, characterized in that, First, the blank ABS powder is dried in a ventilation oven. Then, it is mixed evenly with a composite antioxidant stabilizer composition, extruded and granulated using a twin-screw extruder, and then water-cooled and pelletized to obtain the ABS resin.

8. The preparation method according to claim 7, characterized in that, In the ABS resin, the amount of the composite antioxidant stabilizer composition added accounts for 0.1%-0.3% of the total mass of the ABS resin.

9. The preparation method according to claim 7, characterized in that, When using a twin-screw extruder for extrusion granulation, the temperatures in the first zone of the twin-screw extruder are 185-190℃, the second zone is 180-185℃, the third zone is 180-185℃, the fourth zone is 175-180℃, the fifth zone is 175-180℃, the die head temperature is 170-175℃, the main extruder current is 5.0-6.0 A, the main extruder speed is 15-25 r / min, and the main feed speed is 15-30 r / min.

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