Sulfide polyphenol acrylate intramolecular complex antioxidant, preparation method thereof and abs resin material

Abstract

The application discloses a thioether polyphenol acrylic ester intramolecular composite antioxidant, a preparation method thereof and an ABS resin material, and has a structure shown in formula (1), formula (2) or formula (3). The antioxidant contains phenolic hydroxyl groups in a hindered phenol antioxidant which play a role in inactivating peroxide radicals, thioether groups in a thio antioxidant which play a role in decomposing hydrogen peroxide, and mono-acrylic esters which have a carbon radical capturing agent function, so that three effects can be realized in one molecule.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of polyolefin resin processing, and particularly relates to a sulfide polyphenol acrylate intramolecular composite antioxidant, a preparation method thereof and an ABS resin material. BACKGROUND

[0002] ABS resin (acrylonitrile-butadiene-styrene copolymer) is also known as propylene-butadiene-styrene resin, which is a large variety of engineering plastics with excellent comprehensive performance. Due to its advantages such as impact resistance, high rigidity, corrosion resistance and easy molding processing, it is widely used in the fields of machinery, electronics and household appliances, and the market demand is increasing.

[0003] The unsaturated segments in the olefin polymer are easily oxidized and broken during use due to the influence of heat, oxygen, mechanical factors and the like, resulting in yellowing and brittleness, which affects the use performance of the product. The addition of appropriate antioxidants can inhibit and alleviate the aging problem and improve the comprehensive performance of the product. Since single-function antioxidants cannot meet the performance requirements of high-end polyolefin materials in multiple aspects, low-cost and comprehensive performance composite antioxidants are generally used, which are generally composed of two or more than two antioxidants, have a synergistic effect, have higher antioxidant activity than single antioxidants, can effectively cope with the gel of butadiene homopolymer and copolymer in the high-temperature processing process under oxygen-deficient conditions, and can meet the performance requirements of high-end polyolefin materials in multiple aspects. Therefore, multifunctional and composite antioxidants have become one of the main trends in the development of antioxidants. However, there are few reports on intramolecular composite additives. Patent CN102516157B reports a hindered phenol / hindered amine molecular composite antioxidant, which has the following molecular structure:

[0004]

[0005] wherein R1 and R2 are independently selected from C1-C8 alkyl; and n is an integer from 0 to 8. However, there is a problem of discoloration, which limits their application in light-colored and white products. Patent CN201910752684.3 reports a hindered phenol and amide group intramolecular composite bifunctional antioxidant, which has the following molecular structure:

[0006]

[0007] The antioxidant is prepared by first preparing an ethylenediamine dendritic molecular skeleton from ethylenediamine, methanol and methyl acrylate, and then sealing the end group of the ethylenediamine dendritic molecular skeleton with DtBHP. The intramolecular composite antioxidants reported in the above two patents are binary composite, and the self-synergistic effect of the ternary composite intramolecular composite additive is weaker in terms of mechanism.

[0008] Patent CN110183364B discloses a kind of thio double phenol acrylate multi-effect antioxidant and preparation method thereof, the antioxidant has the molecular structure shown in the following formula:

[0009]

[0010] Wherein, R1 is C1-C5 straight chain or branched alkyl, R2 is C1-C5 straight chain or branched alkyl. But there are small molecular weight, poor resistance to extraction and migration problems. SUMMARY

[0011] The purpose of the present application is to provide a kind of thio polyphenol acrylate intramolecular complex antioxidant.

[0012] The purpose of the present application is also to provide a kind of preparation method of thio polyphenol acrylate intramolecular complex antioxidant.

[0013] The purpose of the present application is also to provide a kind of ABS resin material.

[0014] To achieve the above-mentioned purpose, the present application provides a kind of thio polyphenol acrylate intramolecular complex antioxidant, with formula (1), formula (2) or formula (3) structure:

[0015]

[0016] To achieve the above-mentioned purpose, the present application also provides a kind of preparation method of the thio polyphenol acrylate intramolecular complex antioxidant, comprising the following steps:

[0017] S1, bis (2-hydroxyphenyl) methane or 2,2-bis (4'-hydroxyphenyl) propane or bis (3,5-di-tert-butyl-2-hydroxyphenyl) methane is dissolved in petroleum solvent, after cooling, drop sulfur dichloride to occur condensation reaction, the product is obtained after recrystallization, filtration, drying to obtain intermediate I;

[0018] S2, intermediate I and acrylic acid and halogenating agent are dissolved in organic solvent, esterification reaction is carried out under the action of catalyst, and the product is obtained after recrystallization.

[0019] The preparation method of the thio polyphenol acrylate intramolecular complex antioxidant provided by the present application, the petroleum solvent in step S1 is one of petroleum ether, xylene or benzene.

[0020] The preparation method of the thio polyphenol acrylate intramolecular complex antioxidant provided by the present application, the cooling temperature in step S1 is 5-10 DEG C, and the condensation reaction is carried out at 18-25 DEG C.

[0021] The preparation method of the thioether polyphenol acrylate intramolecular complex antioxidant according to the application, and the molar ratio of the reactant bis(2-hydroxyphenyl)methane or 2,2-bis(4'-hydroxyphenyl)propane or bis(3,5-di-tert-butyl-2-hydroxyphenyl)methane to SCl2 is 2.0-3.0:1.

[0022] The preparation method of the thioether polyphenol acrylate intramolecular complex antioxidant according to the application, wherein the halogenating agent is phosphorus oxychloride; the catalyst is triethylamine; and the organic solvent is one of octafluorotoluene, n-heptane and dimethylbenzene.

[0023] The preparation method of the thioether polyphenol acrylate intramolecular complex antioxidant according to the application, wherein the esterification reaction is carried out at a temperature of 70-75 DEG C for 1.5-2 hours; the molar ratio of the intermediate I, acrylic acid and the halogenating agent is 1:1.25-1.5:0.3-0.4; and the molar ratio of the halogenating agent and the catalyst is 1:3.0-4.0.

[0024] To achieve the above object, the application further provides an ABS resin material, which comprises:

[0025] ABS resin 100 parts by mass;

[0026] Composite auxiliary agent 0.40-0.65 parts by mass;

[0027] The composite auxiliary agent comprises the antioxidant of claim 1, a lubricant and an antistatic agent.

[0028] The ABS resin material according to the application, wherein the lubricant is one or more of calcium stearate, magnesium stearate and zinc stearate; and the antistatic agent is ethylene bis stearamide GMS.

[0029] The ABS resin material according to the application, wherein the mass ratio of the antioxidant, the lubricant and the antistatic agent is 1-1.6:0.3-1:0.06-0.1.

[0030] The application has the following beneficial effects:

[0031] (1) The antioxidant contains phenolic hydroxyl groups in the hindered phenol antioxidant for inactivating peroxide radicals, thioether groups in the thio antioxidant for decomposing hydroperoxide, and monoacrylate groups with carbon radical capture function, so that three effects are combined in one molecule.

[0032] (2) The antioxidant contains three molecules of phenolic hydroxyl groups, has stronger intramolecular hydrogen bonds, produces stronger self-synergistic effect, greatly improves the antioxidation effect, and has better extraction resistance and migration resistance.

[0033] (3) The intramolecular complex antioxidant has a plurality of rigid benzene ring structures in its structure, and is not easy to decompose during processing, and has better thermal stability.

[0034] (4) The method is simple to operate, has mild process conditions, and uses easily available raw materials, and only two steps are needed to synthesize the intramolecular ternary complex antioxidant with high antioxidant performance. BRIEF DESCRIPTION OF DRAWINGS

[0035] Figure 1 The nuclear magnetic hydrogen spectrum of the intramolecular complex antioxidant (A1) is shown in the following figure:

[0036] Figure 2 The carbon spectrum of the intramolecular complex antioxidant (A1) is shown in the following figure:

[0037] Figure 3 The nuclear magnetic hydrogen spectrum of the intramolecular complex antioxidant (A2) is shown in the following figure:

[0038] Figure 4 The carbon spectrum of the intramolecular complex antioxidant (A2) is shown in the following figure:

[0039] Figure 5 The nuclear magnetic hydrogen spectrum of the intramolecular complex antioxidant (A3) is shown in the following figure:

[0040] Figure 6 The carbon spectrum of the intramolecular complex antioxidant (A3) is shown in the following figure. DETAILED DESCRIPTION

[0041] The application will be specifically described below by examples. It is necessary to point out here that the following examples are only used to further illustrate the application, and cannot be understood as limiting the protection scope of the application. Those skilled in the art can make some non-essential improvements and adjustments to the application according to the above content of the application.

[0042] Example 1:

[0043] The preparation process of the antioxidant intermediate and the thiamine complex antioxidant (A1) in this example is as follows:

[0044] The preparation route is shown in the following figure:

[0045]

[0046] Synthesis of intramolecular complex antioxidant (A1): Bis(2-hydroxyphenyl)methane 200 g (1 mol) was accurately weighed and dissolved in 200 ml of petroleum ether, and placed in a four-necked flask (1000 ml) with a stirrer, condenser, dropping funnel, and gas inlet tube. After cooling to 10°C, SCl 250 g (0.5 mol) dissolved in 500 ml of petroleum ether was added dropwise while stirring, and the whole dropwise addition process was not less than 3 h. After 30 min of continuous stirring after the dropwise addition was completed, the temperature was increased to room temperature under nitrogen protection. The obtained white precipitate was filtered and dried to obtain intermediate I 215.8 g with a yield of 86 wt%.

[0047] Intermediate I 62 g (0.14 mol), acrylic acid 12.67 g (0.19 mol), triethylamine 22.67 g (0.224 mol), and xylene (150 ml) were sequentially placed in a four-necked flask (500 ml) with a stirrer, thermometer, and reflux condenser, and stirred and heated to 75°C. Phosphorus oxychloride 18.81 g (0.056 mol) was added dropwise within 30 min, and the temperature was maintained for 2 h. After the reaction was completed, the obtained organic layer was separated as the reaction product, and analyzed by liquid chromatography. Xylene was used for elution, and the organic phase was combined. Xylene was distilled off under reduced pressure, and the remaining organic phase was recrystallized. Intramolecular complex antioxidant (A1) 105.67 g was obtained by suction filtration with a yield of 91 wt%.

[0048] Figure 1 For the nuclear magnetic resonance hydrogen spectrum of intramolecular complex antioxidant (A1), it can be seen that the characterization data of intramolecular complex antioxidant (A1) are as follows: 1 H NMR (CD3Cl, 400 MHz): δ (ppm) 3.96 (s, CH 2, 4H), 5.35 (d, Ar-OH, 3H), 5.50 (d, C(=O)O-CH2, 1H), 6.03 (s, C(=O)O-CH, 1H), 6.10 (d, C(=O)O-CH2, 1H), 6.69-6.80 (t, Ar-H, 6H), 6.97 (t, O=C-Ar-H, 1H), 7.05-7.16 (s, Ar-H, 5H), 7.30 (d, O=C-Ar-H, 1H), 7.31 (d, O=C-Ar-H, 1H).

[0049] Figure 2 For the carbon spectrum of intramolecular complex antioxidant (A1), it can be seen that m / z = 484.56 is the molecular ion peak of intramolecular complex antioxidant (A1).

[0050] The ABS resin was added with 0.45% of the above-mentioned intramolecularly compounded antioxidant in the granulation section of the ABS resin, and then was melt-extruded and granulated by an extruder. The mechanical properties and oxidation induction period of the obtained ABS resin were tested, and the physical property test results of the ABS resin are shown in Table 1.

[0051] Example 2:

[0052] The intramolecularly compounded antioxidant was synthesized according to the reaction in Example 1. The antioxidant, calcium stearate and GMS were put into a high-speed mixer at a mass ratio of 1:0.8:0.1, mixed at room temperature for 5 minutes, and then were sent into a powder extruder for extrusion to obtain a compounded aid package.

[0053] The ABS resin was added with 0.45% of the above-mentioned intramolecularly compounded antioxidant in the granulation section of the ABS resin, and then was melt-extruded and granulated by an extruder. The mechanical properties and oxidation induction period of the obtained ABS resin were tested, and the physical property test results of the ABS resin are shown in Table 1.

[0054] Example 3:

[0055] The intramolecularly compounded antioxidant was synthesized according to the reaction in Example 1. The intramolecularly compounded antioxidant, zinc stearate and GMS were put into a high-speed mixer at a mass ratio of 1.3:0.3:0.06, mixed at room temperature for 5 minutes, and then were sent into a powder extruder for extrusion to obtain a compounded aid package.

[0056] The ABS resin was added with 0.45% of the above-mentioned intramolecularly compounded antioxidant in the granulation section of the ABS resin, and then was melt-extruded and granulated by an extruder. The mechanical properties and oxidation induction period of the obtained ABS resin were tested, and the physical property test results of the ABS resin are shown in Table 1.

[0057] Example 4:

[0058] The preparation steps of the antioxidant intermediate and the intramolecularly compounded antioxidant (A2) in this example are basically the same as those of the intramolecularly compounded antioxidant described in Example 1, except that the bis(2-hydroxyphenyl)methane in step (1) is replaced by 2,2-bis(4'-hydroxyphenyl)propane.

[0059] The preparation route is shown as follows:

[0060]

[0061] Figure 3 For the nuclear magnetic resonance hydrogen spectrum of the intramolecularly compounded antioxidant (A2), it can be seen that the characterization data of the intramolecularly compounded antioxidant (A2) are as follows: 1H NMR (CD3Cl, 400 MHz): δ (ppm) 1.72 (s, CH3, 12H), 2.53 (Ar-S-H, 1H), 5.35 (d, Ar-OH, 3H), 5.50 (d, C(=O)O-CH2, 1H), 6.03 (s, C(=O)O-CH, 1H), 6.10 (d, C(=O)O-CH2, 1H), 6.67 (t, Ar-H, 3H), 6.77 (d, OH-Ar-H, 1H), 6.89 (d, OH-Ar-CH2-Ar-H, 1H), 7.13 (d, CH3(C)-Ar-H, 4H), 7.21 (d(O=)CO-Ar-H, 2H), 7.27 (d, CH3(C)-Ar-H, 2H), 7.28 (S, OH-Ar-S-Ar-H, 1H).

[0062] Figure 4 The carbon spectrum of the intramolecular complex antioxidant (A2) can be seen that m / z = 540.20 is the molecular ion peak of the intramolecular complex antioxidant (A2).

[0063] The intramolecular complex antioxidant, zinc stearate and GMS were put into a high-speed mixer at a mass ratio of 1.6:1:0.08, mixed at room temperature for 5 minutes, and then sent into a powder extruder for extrusion to obtain a complex additive package.

[0064] In the granulation section of the ABS resin, 0.45% of the above-mentioned complex additive was added, and the granulation was carried out by melt extrusion through an extruder. Then the mechanical properties and oxidation induction period of the obtained ABS resin were tested, and the ABS resin physical property test results are shown in Table 1.

[0065] Example 5:

[0066] The preparation steps of the antioxidant intermediate and the intramolecular complex antioxidant (A3) of the present example are basically the same as the preparation steps of the intramolecular complex antioxidant described in Example 1, except that bis(2-hydroxyphenyl)methane in step (1) is replaced by bis(3,5-di-tert-butyl-2-hydroxyphenyl)methane.

[0067] The preparation route is as shown below:

[0068]

[0069] Figure 5 The hydrogen spectrum of the intramolecular complex antioxidant (A3) can be seen that the characterization data of the intramolecular complex antioxidant (A3) are: 1H NMR (CD3Cl, 400 MHz): δ (ppm) 1.35 (S, C(CH3)3, 72H), 3.96 (d, Ar-CH2-Ar, 4H), 5.35 (s, OH, 3H), 5.50 (d, R-O(O=)C-C=C-H, 1H), 6.03 (s, R-O(O=)C-H, 1H), 6.10 (s, R-O(O=)C-C=C-H, 1H), 6.76 (d, Ar-H, 2H), 6.96-7.10 (d, -Ar-CH2-Ar-H, 2H), 7.34 (d, (CH3)3C-Ar-H, 2H).

[0070] Figure 6 The carbon spectrum of the intramolecular complex antioxidant (A3) can be seen that m / z = 932.64 is the molecular ion peak of the intramolecular complex antioxidant (A3).

[0071] The intramolecular complex antioxidant, zinc stearate and GMS were put into a high-speed mixer in a mass ratio of 1:0.8:0.1, mixed at room temperature for 5 minutes, and then sent into a powder extruder for extrusion to obtain a complex additive package.

[0072] In the ABS resin granulation section, 0.45% of the above-mentioned complex additive was added, and the ABS resin was granulated by melt extrusion through an extruder. Then the mechanical properties and oxidation induction period of the obtained ABS resin were tested, and the ABS resin physical property test results are shown in Table 1.

[0073] Comparative Example 1:

[0074] In the ABS resin granulation section, 0.45% of the complex additive package (antioxidant 1076 + antioxidant 168 in a mass ratio of 1:1) was added, and the ABS resin was granulated by melt extrusion through a twin-screw extruder. Then the oxidation induction period and mechanical properties of the ABS resin were tested. The test results are shown in Table 1.

[0075] Comparative Example 2:

[0076] In the ABS resin granulation section, 0.45% of the complex additive package (antioxidant 1010 + antioxidant DLTP in a mass ratio of 1:1) was added, and the ABS resin was granulated by melt extrusion through a twin-screw extruder. Then the oxidation induction period and mechanical properties of the ABS resin were tested. The test results are shown in Table 1.

[0077] Table 1 Analysis test results of ABS resin

[0078]

[0079] As can be seen from the data in Table 1, the intramolecular composite antioxidant A1-A3 provided by the application can effectively improve the mechanical properties and oxidation induction period of the polyolefin material. As can be seen from Example 2, Example 4 and Example 5, the antioxidant A3 has the best antioxidant effect. As can be seen from the comparison of Example 1, Example 2 and Example 3, when the antioxidant is added alone, the mechanical properties of the product are poor, and when the appropriate proportion of other additives is added, the mechanical properties of the product are improved while the oxidation induction period is ensured. Compared with the commonly used hindered phenol + sulfide composite antioxidant and hindered phenol + phosphite composite antioxidant, i.e., the comparison of Example 1 and Comparative Example 1 and Comparative Example 2, it can be seen that the antioxidant effect of the synthesized intramolecular composite antioxidant is obviously better than that of the commonly used composite antioxidant.

[0080] In summary, the application provides an intramolecular composite antioxidant, which contains three molecules of phenolic hydroxyl groups of hindered phenolic antioxidant for inactivating peroxide radicals, and thio-antioxidant for decomposing hydroperoxide, and a single acrylate with carbon radical capture function. The intramolecular composite antioxidant not only realizes the three-in-one effect in the molecule, but also has more phenolic hydroxyl groups, so that the intramolecular composite additive of the application has stronger intramolecular hydrogen bonds and stronger self-synergistic effect, which greatly improves the antioxidant effect. At the same time, the structure of the intramolecular composite antioxidant contains multiple rigid benzene ring structures, which are not easy to decompose during processing and have better thermal stability. When the intramolecular composite antioxidant is applied to ABS resin, polybutene-1 resin material and the like, the antioxidant performance of the material can be effectively improved, which has important guiding significance for the development and use of high-end resin additives.

[0081] Of course, the application can have other various embodiments, and those skilled in the art can make various corresponding changes and modifications according to the application without departing from the spirit and essence of the application. However, these corresponding changes and modifications should all belong to the protection scope of the claims of the application.

Claims

1. A thioether polyphenol acrylate intramolecular complex antioxidant characterized by, having the structure of formula (1), formula (2) or formula (3): (1) (2) (3) 2. The method of producing a thio-phenolic polyol acrylate intramolecular complex antioxidant according to claim 1, characterized by, The method comprises the following steps: S1, dissolving bis(2-hydroxyphenyl)methane or 2,2-bis(4'-hydroxyphenyl)propane or bis(3,5-di-tert-butyl-2-hydroxyphenyl)methane in petroleum solvent, adding dropwise dichlorosulfur after cooling to carry out condensation reaction, and obtaining the product by recrystallization, filtration and drying to obtain intermediate I; S2, dissolving intermediate I, acrylic acid and halogenating agent in organic solvent, and carrying out esterification reaction under the action of catalyst to obtain the product by recrystallization to obtain the final product.

3. The method for preparing the intramolecular composite antioxidant of thioether polyphenol acrylate according to claim 2, characterized in that, The petroleum solvent in step S1 is one of petroleum ether, xylene or benzene.

4. The method for preparing the intramolecular composite antioxidant of thioether polyphenol acrylate according to claim 2, characterized in that, The cooling temperature in step S1 is 5-10℃, and the condensation reaction is carried out at 18-25℃.

5. The method for preparing the intramolecular composite antioxidant of thioether polyphenol acrylate according to claim 2, characterized in that, The molar ratio of the reactant bis(2-hydroxyphenyl)methane or 2,2-bis(4'-hydroxyphenyl)propane or bis(3,5-di-tert-butyl-2-hydroxyphenyl)methane to SCl2 is 2.0-3.0:

1.

6. The method for preparing the intramolecular composite antioxidant of thioether polyphenol acrylate according to claim 2, characterized in that, The halogenating agent is phosphorus oxychloride, the catalyst is triethylamine, and the organic solvent is one of octafluorotoluene, n-heptane and xylene.

7. The method for preparing the intramolecular composite antioxidant of thioether polyphenol acrylate according to claim 2, characterized in that, The esterification reaction is carried out at 70-75℃ for 1.5-2h, the molar ratio of intermediate I, acrylic acid and halogenating agent is 1:1.25-1.5:0.3-0.4, and the molar ratio of halogenating agent to catalyst is 1:3.0-4.

0.

8. An ABS resin material characterized by, It comprises: 100 parts by mass of ABS resin; 0.40-0.65 parts by mass of composite auxiliary agent; The composite auxiliary agent comprises the antioxidant, lubricant and antistatic agent of claim 1.

9. The ABS resin material of claim 8, wherein, The lubricant is one or more of calcium stearate, magnesium stearate and zinc stearate, and the antistatic agent is ethylene bis stearamide GMS.

10. The ABS resin material of claim 8, wherein The mass ratio of the antioxidant, lubricant and antistatic agent is 1-1.6:0.3-1:0.06-0.1.

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