Low-addition efficient anti-yellowing auxiliary agent for ABS material and anti-yellowing ABS

Abstract

The invention discloses a low-additive high-efficiency anti-yellowing auxiliary agent for an ABS (Acrylonitrile Butadiene Styrene) material. The low-additive high-efficiency anti-yellowing auxiliary agent comprises a styrene-methyl methacrylate-glycidyl methacrylate copolymer and an antioxidant. Specifically, the anti-yellowing modifier is composed of the styrene-methyl methacrylate-glycidyl methacrylate copolymer with the addition amount being 0.05-0.55 wt% of the ABS resin and the antioxidant 1010, unexpected technical progress that the yellow index is smaller than 30 is achieved under the condition of small addition amount, compared with existing similar products, the use amount is obviously reduced, the cost is reduced, and the anti-yellowing performance is improved. Not only is the cost reduced, but also the application performance of the ABS is not influenced.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ABS material, in particular to a low-addition high-efficiency anti-yellowing additive for ABS material. BACKGROUND

[0002] ABS resin (Chinese name: acrylonitrile-butadiene-styrene copolymer) is a high polymer material obtained by copolymerization of acrylonitrile (A), butadiene (B), and styrene (S). ABS resin is developed on the basis of styrene-acrylonitrile copolymer (SAN), and uses the principle of rubber toughening plastic to disperse polybutadiene rubber (PB) in SAN resin, thereby obtaining a new polymer product. ABS resin organically unifies the various properties of PS, SAN, and PB, has excellent mechanical properties with balanced toughness, hardness, and rigidity, and also has good processing and molding properties, and has become one of the world's five general-purpose plastics. It has good dimensional stability, good chemical resistance, excellent electrical properties, convenient molding and mechanical processing capability, and high cost performance, and has made a great contribution in many industries, especially in the field of electrical appliance manufacturing, and is widely used in the manufacture of housings of various electrical appliances, such as telephones and air conditioners. However, with the passage of time, the surface of ABS products gradually yellows, and the performance also gradually declines, which not only affects the appearance of the product, but also may reduce its use value.

[0003] At the same time, with the global supply chain, many modified plastics need to be transported by sea for a long distance, and in the transportation process, they inevitably experience long-term high temperature in the cabin. The material will obviously yellow during transportation, resulting in a decline in mechanical properties and a decline in appearance quality, leading to a large number of complaints about the product.

[0004] Therefore, it is of great practical significance to develop a technology that can significantly improve the anti-yellowing performance of ABS material, so that it can maintain its appearance and performance during long-term use.

[0005] In the prior art, in order to overcome the problem that ABS resin is prone to degradation, aging discoloration and even cracking under long-term light, thereby causing the decline of physical properties, CN101709133A selects to add a series of light stabilizers, ultraviolet absorbers and the like in the ABS material, but the addition of the auxiliary not only increases the cost, and the auxiliary is easy to precipitate, causing the heat resistance and heat aging resistance of the material to be unstable, and the service life is short. In order to overcome the heat resistance and yellowing resistance of ABS resin, patent CN118994806A 1 controls the unsaturation of ABS grafting in ABS, and controls the unsaturation of ABS grafting copolymer to 0.1-10 mol / g, but causes the impact property of ABS to decrease obviously, and the method adopts polymerization technology, and the process regulation is complex, and the input cost is high. ABS resin will cause a series of chemical reactions during processing and long-term use, generate colored groups, and then cause the color of the product to become dark, and yellowing phenomenon occurs. In order to solve this problem, the traditional method mainly depends on the addition of antioxidants. However, the effect of the antioxidant mainly concentrates in the processing stage, and only the yellowing caused by short-term thermal oxidation aging can be effectively coped with, and for the yellowing resistance demand of ABS products in the long-term use process, the effect is not ideal. In addition, the antioxidant belongs to a small molecule, and a higher addition amount will also cause performance decline, and precipitation on the surface of the product.

[0006] Therefore, it is still necessary to explore a more efficient solution with excellent performance and a lower addition amount to meet the higher requirements of the market on the yellowing resistance of ABS material. SUMMARY

[0007] In view of the defects of high production cost and difficult-to-meet performance in the prior art, the purpose of the present application is to solve the problem of the yellowing resistance of ABS material, and to provide a low-addition and high-efficiency yellowing resistance auxiliary for ABS material. It is generally believed or originally believed that the resin with SAN as the matrix blended with ABS will cause incompatibility, or if the content of epoxy is too high and the content of SAN matrix is reduced, compatibility problems will occur, thereby causing the mechanical properties of ABS to decrease. However, the present application discloses a new low-addition and high-efficiency yellowing resistance auxiliary for ABS material, which does not cause compatibility problems and almost has no effect on the mechanical properties even if the polymer without AN is added to the ABS material at a low addition amount; the addition of the yellowing resistance agent to the ABS material greatly improves the yellowing resistance of the material; in addition, the present application is more simple to process and has lower production cost, so that it can be used in production practice.

[0008] The purpose of the present application is realized by the following technical scheme: A low-addition and high-efficiency yellowing resistance auxiliary for ABS material, comprising a styrene-methyl methacrylate-glycidyl methacrylate copolymer and an antioxidant.

[0009] The application discloses a preparation method of a low-addition high-efficiency anti-yellowing additive for ABS material.

[0010] Preferably, the mass ratio of the styrene-methyl methacrylate-glycidyl methacrylate copolymer and the antioxidant is (0.5-5):1.

[0011] Preferably, the antioxidant comprises antioxidant 1010; and more preferably, the antioxidant 1010.

[0012] The application discloses application of the low-addition high-efficiency anti-yellowing additive for ABS material in ABS material.

[0013] The application discloses application of the low-addition high-efficiency anti-yellowing additive for ABS material in improving the yellowing resistance of ABS material.

[0014] The application discloses an anti-yellowing ABS, which comprises ABS resin and the low-addition high-efficiency anti-yellowing additive for ABS material.

[0015] In the technical solution, the addition amount of the styrene-methyl methacrylate-glycidyl methacrylate copolymer in the low-addition high-efficiency anti-yellowing additive for ABS material is 0.05-0.55 wt% of the ABS resin; and preferably, the styrene-methyl methacrylate-glycidyl methacrylate copolymer is HPC-3510.

[0016] Preferably, in the low-addition high-efficiency anti-yellowing additive for ABS material, the addition amount of the styrene-methyl methacrylate-glycidyl methacrylate copolymer is 0.1-0.5 wt% of the ABS resin, such as 0.2 wt%, 0.25 wt%, 0.3 wt%, 0.35 wt%, 0.4 wt%, 0.45 wt% or any percentage within the range.

[0017] Preferably, in the low-addition high-efficiency anti-yellowing additive for ABS material, the addition amount of the antioxidant is 0.1-0.3 wt% of the ABS resin, such as 0.15-0.2 wt%.

[0018] The application discloses a preparation method of the anti-yellowing ABS, which comprises the following steps: melting and mixing ABS resin and the low-addition high-efficiency anti-yellowing additive for ABS material to obtain the anti-yellowing ABS.

[0019] The application discloses application of the anti-yellowing ABS in preparing yellowing-resistant materials.

[0020] The ABS resin is a prior art product, which can be pure ABS or ABS containing a modifier (ABS modified material); the ABS is a bulk method or emulsion blending method ABS, and the weight percentage content of butadiene is 10-30%.

[0021] The low-addition high-efficiency anti-yellowing aid for ABS material is used in the ABS and its modified material in an adding amount of 0.3-0.5 wt%, and can significantly improve the long-term thermal stability of the ABS and its modified material, and the discoloration is greatly improved after 3 hours of thermal oxygen aging at 200 DEG C.

[0022] Compared with the prior art, the low-addition high-efficiency anti-yellowing aid for ABS material has the following beneficial effects: The low-addition high-efficiency anti-yellowing aid for ABS material improves the anti-yellowing property of the ABS material, and has no influence on the processing fluidity and mechanical property, so that a more excellent ABS material is obtained. BRIEF DESCRIPTION OF DRAWINGS

[0023] Other features, objects and advantages of the present application will become more apparent from the following detailed description of non-limiting embodiments with reference to the attached drawings: Figure 1 ABS material aging comparison chart at 200 DEG C for 3h in an aging oven. DETAILED DESCRIPTION

[0024] The low-addition high-efficiency anti-yellowing aid for ABS material comprises a polymer containing a glycidyl methacrylate monomer, which is HPC-3510, and the mass fraction of the glycidyl methacrylate monomer unit in the polymer is 45-55 wt% for ABS and its modified material.

[0025] The low-addition high-efficiency anti-yellowing aid for ABS material is used in the ABS and its modified material in an adding amount of 0.05-0.55 wt%, and can significantly improve the long-term thermal stability of the ABS and its modified material, and the discoloration is greatly improved after 3 hours of thermal oxygen aging at 200 DEG C; wherein the ABS resin is ABS or its modified material, the ABS is a bulk method or emulsion blending method ABS, and the weight percentage content of butadiene is 10-30%, which is a conventional product.

[0026] The application will be described in detail below with reference to specific examples, each of which is 1 kg. The following examples will help those skilled in the art to further understand the application, but do not limit the application in any form. It should be noted that those skilled in the art can make several modifications and improvements without departing from the concept of the application. These are within the scope of the application.

[0027] The raw materials are existing products, among which: ABS: ABS8391 of Gaoqiao Petrochemical, the ABS resin is dried in a forced air drying oven at 80°C for 3 hours before use; antioxidant 1010: BASF Company; antioxidant 168: Tianjin Li'anlong New Material Co., Ltd.; SAG-008 (styrene-acrylonitrile-glycidyl methacrylate copolymer), HPC-3510 (styrene-methyl methacrylate-glycidyl methacrylate copolymer), ECO-1120 (styrene-methyl methacrylate-glycidyl methacrylate copolymer) are all sold by Jiaiyirong Polymer (Shanghai) Co., Ltd.

[0028] The physical and mechanical properties are tested according to the following standards: tensile strength: ISO 527, bending strength: ISO 178; impact performance: ISO 179. The oxidation induction time is tested according to GB / T 19466.6-2009, "Differential Scanning Calorimetry (DSC) - Part 6: Determination of Oxidation Induction Time (isothermal OIT) and Oxidation Induction Temperature (dynamic OIT)".

[0029] Comparative Example 1 ABS resin 100 parts, 0.15 parts of antioxidant 1010 were added to a high-speed mixer and mixed at room temperature for 2 hours, and the mixed resin mixture was taken out.

[0030] Comparative Example 2 ABS resin 100 parts, 0.35 parts of SAG-008, 0.15 parts of antioxidant 1010 were added to a high-speed mixer and mixed at room temperature for 2 hours, and the mixed resin mixture was taken out.

[0031] Comparative Example 3 ABS resin 100 parts, 0.5 parts of SAG-008, 0.15 parts of antioxidant 1010 were added to a high-speed mixer and mixed at room temperature for 2 hours, and the mixed resin mixture was taken out.

[0032] Comparative Example 4 ABS resin 100 parts, 1.0 parts of SAG-008, 0.15 parts of antioxidant 1010 were added to a high-speed mixer and mixed at room temperature for 2 hours, and the mixed resin mixture was taken out.

[0033] Comparative Example 5 ABS resin 100 parts, 0.5 parts of ECO-1120, 0.15 parts of antioxidant 1010 were added into a high-speed mixer and mixed at room temperature for 2 hours, and the mixed resin mixture was taken out.

[0034] Example 1 ABS resin 100 parts, 0.1 parts of HPC-3510, 0.15 parts of antioxidant 1010 were added into a high-speed mixer and mixed at room temperature for 2 hours, and the mixed resin mixture was taken out.

[0035] Example 2 ABS resin 100 parts, 0.2 parts of HPC-3510, 0.15 parts of antioxidant 1010 were added into a high-speed mixer and mixed at room temperature for 2 hours, and the mixed resin mixture was taken out.

[0036] Example 3 ABS resin 100 parts, 0.35 parts of HPC-3510, 0.15 parts of antioxidant 1010 were added into a high-speed mixer and mixed at room temperature for 2 hours, and the mixed resin mixture was taken out.

[0037] Example 4 ABS resin 100 parts, 0.5 parts of HPC-3510, 0.15 parts of antioxidant 1010 were added into a high-speed mixer and mixed at room temperature for 2 hours, and the mixed resin mixture was taken out.

[0038] The above obtained resin mixture was respectively added into the hopper of a twin-screw extruder with a diameter of 50 mm and a length-diameter ratio of 44:1, and was melt blended and extruded to obtain ABS material granules; during the melt extrusion process, the temperature of the first zone was 200°C, the temperature of the second zone was 210°C, the temperature of the third zone was 220°C, the temperature of the fourth and fifth zones was 230°C, and the temperature of the sixth zone was 220°C; after the ABS material granules were obtained, the granules were placed in an air drying oven at 85°C for 8h; the dried granules were injection molded at a temperature of 220°C to obtain various test samples.

[0039] The samples were subjected to yellowing resistance performance test at 200°C for 3h; the oxidation induction time was required to be greater than 10 minutes and the yellowness index was required to be less than 30; the content of yellowing resistance auxiliary and the aging test results are shown in Table 1, and the photos after aging for 3h are shown in Figure 1

[0040] Table 1 Comparison of mechanical properties of ABS materials of various examples

[0041] ​Note: In Table 1, the anti-oxidant is not written in Comparative Example 2 to Example 4, and the actual formula contains 0.15 parts of the anti-oxidant.

[0042] As can be seen from the results in Table 1, only the anti-oxidant, the product is visibly yellow after heating; after adding the anti-yellowing agent, the oxidation induction time of HPC-3510 is increased by a much larger margin than SAG, and the effect is much better; after the sample is aged at 200℃ for 3h, the yellowing index δYI is significantly reduced. Figure 1 As can also be seen from Table 1, when the amount of HPC-3510 added is 0.2 parts, the color after aging is white, and the anti-yellowing effect is good; when the amount of ECO-1120 added is 0.5 parts, the color after aging is also white; when the amount of SAG-008 added is 0.35 parts or 0.5 parts, the product is visibly yellow after heating, and only when the amount of SAG-008 added is 1 part, the effect is good, and the product looks white, but the yellowness index is still high.

[0043] In particular, after the addition of HPC-3510, the mechanical properties of the material are basically unchanged or even slightly improved. Comparative Example 1 is an ABS / anti-oxidant system, with an elongation at break of 18.5%, a tensile strength of 41.8MPa, a bending strength of 55.2MPa, and a notched impact strength of 17.4kJ / m 2 ; Example 3 is an ABS / HPC-3510 / anti-oxidant product, with an elongation at break of 36.1%, a tensile strength of 43.6MPa, a bending strength of 56.8MPa, and a notched impact strength of 18.9kJ / m 2 ; the elongation at break of the products of the other examples is greater than 20% (even reaching 38.1% in Example 4), the tensile strength is greater than 43MPa, the bending strength is greater than 55MPa, and the notched impact strength is greater than 17.5kJ / m 2 ; Comparative Example 5 is an ABS / ECO-1120 / anti-oxidant system, with an elongation at break of 20.1%, a tensile strength of 43.3MPa, a bending strength of 55.7MPa, and a notched impact strength of 18.1kJ / m 2 ; Comparative Examples 2 to 4 are ABS / SAG / anti-oxidant systems, with a tensile strength of less than 4.25MPa, an elongation at break of less than 20% (especially in Comparative Example 4, which is reduced to 17.3%), and a notched impact strength of less than 18kJ / m 2 .

[0044] It can be seen that the present application first uses HPC-3510 for ABS anti-yellowing, significantly improves the yellowing resistance, and maintains or even improves the mechanical properties, and in particular, the present application achieves good technical progress with a small amount of HPC-3510, which exceeds people's imagination.

[0045] Comparative Example 6 Referring to Example 3, antioxidant 1010 is replaced by antioxidant 168, the product is injection molded to prepare the test sample, the yellowness index of which is 36.7, and the anti-yellowing property is poor.

[0046] Comparative Example 7 Referring to Comparative Example 1, 0.15 parts of antioxidant 168 is added on the basis of Comparative Example 1, the product is injection molded to prepare the test sample, the sample is obviously yellow under visual observation after heating, and has no anti-yellowing property.

[0047] Referring to Comparative Example 1, 0.2 parts of antioxidant 1010 is added on the basis of Comparative Example 1, i.e. 0.35 parts of antioxidant is used, the product is injection molded to prepare the sample, the sample is obviously yellow under visual observation after heating, and has no anti-yellowing property.

[0048] Comparative Example 8 Referring to Comparative Example 1, 0.35 parts of glycidyl methacrylate is added on the basis of Comparative Example 1, the product is injection molded to prepare the test sample, the sample is obviously yellow under visual observation after heating, and has no anti-yellowing property.

[0049] Comparative Example 9 Referring to Comparative Example 1, 0.35 parts of ethylene-butyl acrylate-glycidyl methacrylate copolymer (PTW) is added on the basis of Comparative Example 1, the product is injection molded to prepare the test sample, the sample is yellow under visual observation after heating, and has poor anti-yellowing property.

[0050] The present application has many specific application approaches, and the above description is only a preferred embodiment of the present application. It should be noted that the above examples are only used to illustrate the present application, and are not used to limit the protection scope of the present application. For ordinary skilled in the art, some improvements can be made without departing from the principles of the present application, and these improvements should also be considered as the protection scope of the present application.

Claims

1. A low-addition, high-efficiency anti-yellowing additive for ABS materials, characterized in that, Styrene-methyl methacrylate-glycidyl methacrylate copolymer and antioxidant.

2. The low-addition high-efficiency anti-yellowing aid for ABS material according to claim 1, characterized in that, The mass ratio of styrene-methyl methacrylate-glycidyl methacrylate copolymer to antioxidant is (0.5-5):

1.

3. The low-addition high-efficiency anti-yellowing aid for ABS material according to claim 1, characterized in that, The antioxidant comprises antioxidant 1010.

4. The method for preparing ABS material with low additive high efficiency anti-yellowing aid of claim 1, characterized in that, The combination of styrene-methyl methacrylate-glycidyl methacrylate copolymer and antioxidant is a low-addition high-efficiency anti-yellowing aid for ABS material.

5. The low-addition high-efficiency anti-yellowing aid for ABS material of claim 1 is applied to ABS material.

6. The low-addition high-efficiency anti-yellowing aid for ABS material of claim 1 is applied to improve the anti-yellowing performance of ABS material.

7. An anti-yellowing ABS comprising an ABS resin, characterized in that, The low-addition high-efficiency anti-yellowing aid for ABS material of claim 1 is also included.

8. The anti-yellowing ABS of claim 7, wherein, In the low-addition high-efficiency anti-yellowing aid for ABS material, the addition amount of styrene-methyl methacrylate-glycidyl methacrylate copolymer is 0.05-0.55 wt% of ABS resin.

9. The method of making the anti-yellowing ABS of claim 7, wherein, ABS resin and the low-addition high-efficiency anti-yellowing aid for ABS material are melt-mixed to obtain the anti-yellowing ABS.

10. The anti-yellowing ABS of claim 7 is applied to prepare anti-yellowing material.

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