Thioether polyphenol acrylate intramolecular composite antioxidant, preparation method thereof and ABS (Acrylonitrile Butadiene Styrene) resin material

Abstract

The invention discloses a thioether polyphenol acrylate intramolecular composite antioxidant, a preparation method thereof and an ABS (Acrylonitrile Butadiene Styrene) resin material, the thioether polyphenol acrylate intramolecular composite antioxidant has a structure as shown in a formula (1), a formula (2) or a formula (3): # imgabs 0 # imgabs 1 #. The antioxidant not only contains phenolic hydroxyl groups which play a role in inactivating peroxidation free radicals in hindered phenol antioxidants, but also contains thioether groups which play a role in decomposing hydroperoxides in sulfo antioxidants, and monoacrylate with the function of a carbon free radical capturing agent is also contained, so that three effects in molecules can be integrated.

Description

Technical Field

[0001] The invention belongs to the field of polyolefin resin processing, and in particular relates to a thioether polyphenol acrylate intramolecular composite antioxidant and a preparation method thereof, and an ABS resin material. Background Art

[0002] ABS resin (acrylonitrile-butadiene-styrene copolymer), also known as butylbenzene-acrylonitrile resin, 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 and processing, it is widely used in machinery, electronics, home appliances and other fields, and the market demand is increasing.

[0003] The unsaturated segments in olefin polymers are affected by heat, oxygen, mechanical factors, etc. during use, and are prone to oxidation and fracture, resulting in yellowing and brittleness, which affects the performance of the product. Adding appropriate antioxidants can inhibit and alleviate aging problems and improve the overall performance of the product. Since antioxidants with a single function cannot meet the various performance requirements of high-end polyolefin materials, composite antioxidants with low cost and good overall performance are often used. They are generally composed of two or more main and auxiliary antioxidants, which produce a synergistic effect and have higher antioxidant activity than single antioxidants. They can effectively deal with butadiene homopolymers and copolymers in high-temperature processing under anaerobic conditions. Gel, can meet the various performance requirements of high-end polyolefin materials, so multifunctional, composite antioxidants have become one of the main trends in the current development of antioxidants. However, there are few reports on related intramolecular composite additives. For example, patent CN102516157B reports a hindered phenol / hindered amine molecular composite antioxidant, which has a molecular structure shown in the following formula:

[0004]

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

[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 groups of the ethylenediamine dendritic molecular skeleton with DtBHP. The intramolecular composite antioxidants reported in the above two patents are both binary composites, and their self-synergistic effect is weaker than that of the ternary composite intramolecular composite additives in terms of action mechanism.

[0008] Patent CN110183364B discloses a thiobisphenol acrylate multi-effect antioxidant and a preparation method thereof. The antioxidant has a molecular structure shown in the following formula:

[0009]

[0010] Among them, R1 is a C1-C5 straight chain or branched alkyl group, and R2 is a C1-C5 straight chain or branched alkyl group. However, there are problems such as small molecular weight, poor extraction resistance and poor migration. Summary of the invention

[0011] The purpose of the present invention is to provide a thioether polyphenol acrylate intramolecular composite antioxidant.

[0012] The present invention also aims to provide a method for preparing a thioether polyphenol acrylate intramolecular composite antioxidant.

[0013] Another object of the present invention is to provide an ABS resin material.

[0014] To achieve the above object, the present invention provides a thioether polyphenol acrylate intramolecular composite antioxidant having a structure shown in formula (1), formula (2) or formula (3):

[0015]

[0016] To achieve the above object, the present invention also provides a method for preparing the thioether polyphenol acrylate intramolecular composite antioxidant, comprising the following steps:

[0017] 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 sulfur dichloride dropwise after cooling to cause condensation reaction, and the obtained product is recrystallized, filtered and dried to obtain intermediate I;

[0018] S2, dissolving the intermediate I, acrylic acid and a halogenating agent in an organic solvent, carrying out an esterification reaction under the action of a catalyst, and obtaining the final product after recrystallization.

[0019] In the method for preparing the thioether polyphenol acrylate intramolecular composite antioxidant of the present invention, the petroleum solvent in step S1 is one of petroleum ether, xylene or benzene.

[0020] In the method for preparing the thioether polyphenol acrylate intramolecular composite antioxidant of the present invention, the cooling temperature in step S1 is 5-10° C., and the condensation reaction is carried out at 18-25° C.

[0021] The method for preparing the thioether polyphenol acrylate intramolecular composite antioxidant of the present invention comprises the following steps: the molar ratio of the reactants 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 method for preparing the thioether polyphenol acrylate intramolecular composite antioxidant of the present invention comprises the following steps: the halogenating agent is phosphorus oxychloride; the catalyst is triethylamine; and the organic solvent is one of octafluorotoluene, n-heptane and xylene.

[0023] The preparation method of the thioether polyphenol acrylate intramolecular composite antioxidant of the present invention comprises the following conditions for the esterification reaction: temperature of 70°C to 75°C and time of 1.5 to 2 hours; the molar ratio of the intermediate I, acrylic acid and halogenating agent is 1:1.25 to 1.5:0.3 to 0.4; and the molar ratio of the halogenating agent to the catalyst is 1:3.0 to 4.0.

[0024] To achieve the above object, the present invention further provides an ABS resin material, comprising:

[0025] ABS resin 100 parts by mass;

[0026] Composite additives 0.40-0.65 parts by weight;

[0027] The composite auxiliary agent comprises the antioxidant, lubricant and antistatic agent as claimed in claim 1.

[0028] In the ABS resin material of the present invention, the lubricant is one or more of calcium stearate, magnesium stearate and zinc stearate; and the antistatic agent is ethylene bis stearamide GMS.

[0029] In the ABS resin material of the present invention, the mass ratio of the antioxidant, the lubricant and the antistatic agent is 1-1.6:0.3-1:0.06-0.1.

[0030] Beneficial effects of the present invention:

[0031] (1) The antioxidant contains not only the phenolic hydroxyl group in the hindered phenol antioxidant that inactivates peroxyl free radicals, but also the thioether group in the thio antioxidant that decomposes hydroperoxides, and the monoacrylate that functions as a carbon free radical scavenger, thereby achieving three effects in one molecule;

[0032] (2) The antioxidant contains three molecules of phenolic hydroxyl groups in the molecule, which has stronger intramolecular hydrogen bonds, produces stronger self-synergistic effects, greatly enhances the antioxidant effect, and has better resistance to extraction and migration;

[0033] (3) The structure of the intramolecular composite antioxidant contains multiple rigid benzene ring structures, which is not easy to decompose during processing and has better thermal stability.

[0034] (4) This method is easy to operate, has mild process conditions, and has readily available raw materials. It can synthesize an intramolecular ternary composite antioxidant with high antioxidant properties in just two steps. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 This is the H-NMR spectrum of the intramolecular composite antioxidant (A1);

[0036] Figure 2 is the carbon spectrum of the intramolecular composite antioxidant (A1);

[0037] Figure 3 This is the H-NMR spectrum of the intramolecular composite antioxidant (A2);

[0038] Figure 4 is the carbon spectrum of the intramolecular composite antioxidant (A2);

[0039] Figure 5 This is the H-NMR spectrum of the intramolecular composite antioxidant (A3);

[0040] Figure 6 This is the carbon spectrum of the intramolecular composite antioxidant (A3). DETAILED DESCRIPTION

[0041] The present invention is described in detail below by way of examples. It is necessary to point out that the following examples are only used to further illustrate the present invention and cannot be understood as limiting the scope of protection of the present invention. Those skilled in the art in this field can make some non-essential improvements and adjustments to the present invention based on the above content of the present invention.

[0042] Embodiment 1:

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

[0044] The preparation route is as follows:

[0045]

[0046] Synthesis of intramolecular composite antioxidant (A1): Accurately weigh 200g (1mol) of bis(2-hydroxyphenyl)methane and dissolve it in 200ml of petroleum ether. Place it in a four-necked flask (1000ml) equipped with a stirrer, condenser, dropping funnel, and vent pipe. After cooling to 10°C, add 250g (0.5mol) of SCl dissolved in 500ml of petroleum ether while stirring. The entire dropping process should not be less than 3h. After the dropping is completed, continue stirring for 30min and heat to room temperature under nitrogen protection. The resulting white precipitate is filtered and dried to obtain 215.8g of intermediate I with a yield of 86wt%.

[0047] 62g (0.14mol) of intermediate I, 12.67g (0.19mol) of acrylic acid, 22.67g (0.224mol) of triethylamine, and 150ml of xylene were placed in a four-necked flask (500ml) with stirring, a thermometer, and a reflux condenser, stirred and heated to 75°C, and 18.81g (0.056mol was added within 30min) of phosphorus oxychloride was added dropwise, and the temperature was kept for 2h. After the reaction was completed, the organic layer was separated as the reaction product and analyzed by liquid chromatography. The organic phases were washed with xylene and combined. The xylene was distilled off under reduced pressure, and the remaining organic phase was recrystallized and filtered to obtain 105.67g of intramolecular composite antioxidant (A1) with a yield of 91wt%.

[0048] Figure 1 This is the nuclear magnetic hydrogen spectrum of the intramolecular composite antioxidant (A1). It can be seen that the characterization data of the intramolecular composite antioxidant (A1) are: 1 H NMR (CD3Cl, 400MHz): 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),6.69-6.8 0(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 This is the carbon spectrum of the intramolecular composite antioxidant (A1). It can be seen that m / z=484.56 is the molecular ion peak of the intramolecular composite antioxidant (A1).

[0050] In the granulation section of the ABS resin, 0.45% of the intramolecular composite antioxidant synthesized by the above method was added, and the granules were melt-extruded by an extruder. Then, the mechanical properties and oxidation induction period of the obtained ABS resin were tested, and the test results of the physical properties of the obtained ABS resin are shown in Table 1.

[0051] Embodiment 2:

[0052] The intramolecular composite antioxidant was synthesized according to the reaction in Example 1. The antioxidant, calcium 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 to a powder extruder for extrusion to obtain a composite auxiliary agent package.

[0053] In the granulation section of ABS resin, 0.45% of the above composite additive was added and granulated by melt extrusion through an extruder. Then the mechanical properties and oxidation induction period of ABS resin were tested. The physical property test results are shown in Table 1.

[0054] Embodiment 3:

[0055] The intramolecular composite antioxidant was synthesized according to the reaction in Example 1. The intramolecular composite 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 fed into a powder extruder for extrusion to obtain a composite additive package.

[0056] In the granulation section of ABS resin, 0.5% of the above composite additive is added, and the resin is melted, extruded, drawn and granulated by an extruder. Then the mechanical properties and oxidation induction period of ABS resin are tested, and the obtained physical property test results are shown in Table 1.

[0057] Embodiment 4:

[0058] The preparation steps of the antioxidant intermediate and the intramolecular composite antioxidant (A2) of this embodiment are basically the same as the preparation steps of the intramolecular composite 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 as follows:

[0060]

[0061] Figure 3 This is the nuclear magnetic hydrogen spectrum of the intramolecular composite antioxidant (A2). It can be seen that the characterization data of the intramolecular composite antioxidant (A2) are: 1H NMR (CD3Cl, 400MHz): δ (ppm) 1.72 (s, CH3, 12H), 2.53 (Ar-SH, 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,A r-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 This is the carbon spectrum of the intramolecular composite antioxidant (A2). It can be seen that m / z=540.20 is the molecular ion peak of the intramolecular composite antioxidant (A2).

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

[0064] In the granulation section of ABS resin, 0.45% of the above composite additive is added, and the granules are melt-extruded by an extruder. Then the mechanical properties and oxidation induction period of the obtained ABS resin are tested, and the test results of the physical properties of the obtained ABS resin are shown in Table 1.

[0065] Embodiment 5:

[0066] The preparation steps of the antioxidant intermediate and the intramolecular composite antioxidant (A3) of this embodiment are basically the same as the preparation steps of the intramolecular composite 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 follows:

[0068]

[0069] Figure 5 This is the nuclear magnetic hydrogen spectrum of the intramolecular composite antioxidant (A3). It can be seen that the characterization data of the intramolecular composite antioxidant (A3) are: 1H NMR (CD3Cl, 400MHz): δ (ppm) 1.35 (S, C (CH3) 3, 72H), 3.96 (d, Ar-CH2-Ar, 4H), 5.35 (s, OH, 3H), 5.50 (d, RO (O=) CC=CH, 1H), 6.03 ( s,RO(O=)CH,1H),6.10(s,RO(O=)CC=CH,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 : is the carbon spectrum of the intramolecular composite antioxidant (A3). It can be seen that m / z=932.64 is the molecular ion peak of the intramolecular composite antioxidant (A3).

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

[0072] In the granulation section of ABS resin, 0.45% of the above composite additive is added, and the granules are melt-extruded by an extruder. Then the mechanical properties and oxidation induction period of the obtained ABS resin are tested, and the test results of the physical properties of the obtained ABS resin are shown in Table 1.

[0073] Comparative Example 1:

[0074] In the ABS resin granulation section, 0.45% of the composite additive package (antioxidant 1076 + antioxidant 168 with a mass ratio of 1:1) was added thereto, and granulation was performed by 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 composite additive package (antioxidant 1010 + antioxidant DLTP with a mass ratio of 1:1) was added thereto, and the ABS resin was extruded, drawn and granulated by 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 and test results of ABS resin

[0078]

[0079] As can be seen from the data in Table 1, the intramolecular composite antioxidants A1-A3 provided by the present invention can effectively improve the mechanical properties and oxidation induction period of polyolefin materials. Through Example 2, Example 4 and Example 5, it can be seen that the antioxidant effect of antioxidant A3 is the best. Through the comparison of Example 1, Example 2 and Example 3, it can be seen that when the antioxidant is added alone, the mechanical properties of the product are poor, and by adding other auxiliary agents in an appropriate proportion, the mechanical properties of the product are improved while ensuring the oxidation induction period. At the same time, the synthesized intramolecular composite antioxidant is compared with the commonly used hindered phenols + thioether composite antioxidants and hindered phenols + phosphites composite antioxidants, that is, Example 1 is compared with Comparative Example 1 and Comparative Example 2, it can be seen that the antioxidant effect of the synthesized intramolecular composite antioxidant is significantly better than that of the commonly used composite antioxidants.

[0080] In summary, the present invention provides an intramolecular composite antioxidant, which contains phenolic hydroxyl groups in three molecules of hindered phenolic antioxidants that play a role in inactivating peroxyl radicals, and thioester groups in thio antioxidants that play a role in decomposing hydroperoxides, and monoacrylates with carbon radical scavenger functions, which can not only achieve the three-in-one effect within the molecule, but also more phenolic hydroxyl groups, so that the intramolecular composite additive of the present invention has stronger intramolecular hydrogen bonds, produces stronger self-synergistic effects, and while greatly improving the antioxidant effect, the structure of the intramolecular composite antioxidant contains multiple rigid benzene ring structures, which is not easy to decompose during processing and has better thermal stability. It is applied to resin materials such as ABS resin and polybutene-1, which can effectively improve the antioxidant properties of the material, and has important guiding significance for the development and use of high-end resin additives.

[0081] Of course, the present invention may have many other embodiments. Without departing from the spirit and essence of the present invention, technicians familiar with the field may make various corresponding changes and deformations based on the present invention, but these corresponding changes and deformations should all fall within the scope of protection of the claims of the present invention.

Claims

1. A thioether polyphenol acrylate intramolecular composite antioxidant, characterized in that: Having the structure shown in formula (1), formula (2) or formula (3): (1) (2) (3) 2. The method for preparing the thioether polyphenol acrylate intramolecular composite antioxidant according to claim 1, characterized in that: The following steps are involved: 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 sulfur dichloride dropwise after cooling to cause condensation reaction, and the obtained product is recrystallized, filtered and dried to obtain intermediate I; S2, dissolving the intermediate I, acrylic acid and a halogenating agent in an organic solvent, carrying out an esterification reaction under the action of a catalyst, and obtaining the final product after recrystallization.

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

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

5. The method for preparing the thioether polyphenol acrylate intramolecular composite antioxidant 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 thioether polyphenol acrylate intramolecular composite antioxidant 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 conditions of the esterification reaction are: temperature 70°C-75°C, time 1.5-2h; the molar ratio of the intermediate I, acrylic acid and halogenating agent is 1:1.25-1.5:0.3-0.4; the molar ratio of the halogenating agent to the catalyst is 1:3.0-4.

0.

8. An ABS resin material, characterized in that: include: ABS resin 100 parts by mass; Composite additives 0.40-0.65 parts by weight; The composite auxiliary agent comprises the antioxidant, lubricant and antistatic agent as claimed in claim 1.

9. The ABS resin material according to claim 8, characterized in that: 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 according to claim 8, characterized in that: 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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