High-flowability and high-chemical-resistance ABS (acrylonitrile butadiene styrene) composition and preparation method thereof

Abstract

The invention provides a high-flowability and high-chemical-resistance ABS (acrylonitrile butadiene styrene) composition and a preparation method thereof. The composition is prepared from the following components in percentage by weight: 20 to 65 parts of ABS (Acrylonitrile Butadiene Styrene) resin, 0.5 to 1.5 parts of compatilizer, 30 to 50 parts of PET (Polyethylene Terephthalate) ester exchange master batch, 5 to 30 parts of ABS rubber powder, 0.01 to 0.05 part of chain extender, 0.1 to 0.5 part of antioxidant and 0.3 to 0.5 part of lubricant. Compared with the prior art, the PET resin with specific viscosity is selected, and more block copolymers are generated by utilizing the characteristic that the PET resin and a polyester resin material are easy to generate ester exchange reaction, so that the crystallization degree and the viscosity of the PET resin are reduced, the flowability of the PET resin is higher, and the preparation of the high-flowability ABS composition is facilitated; meanwhile, the crystallinity of the PET resin is reduced, so that the dispersed phase of the PET resin in the ABS is not easy to crystallize, the toughness of the composition can be improved, and the mechanical property and the fluidity of the composition are considered on the basis of improving the chemical resistance.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials and relates to a high-flow and highly chemical-resistant ABS composition and a preparation method thereof. Background Art

[0002] Acrylonitrile-butadiene-styrene terpolymer (ABS) has the advantages of high impact resistance, high gloss, and easy processing, and is widely used in consumer and industrial product markets such as electronics and electrical appliances, the automotive industry, and household construction. Polyethylene terephthalate (PET) has the advantages of low cost, high strength, good transparency, good heat resistance, and chemical corrosion resistance. Preparing an ABS / PET alloy can improve the disadvantages of poor chemical resistance of ABS and poor impact performance of PET, and is an alloy material with excellent application prospects. At the same time, PET is a crystalline polymer and can exhibit good fluidity when the melting temperature exceeds the melting point. In the prior art, for example, Patent CN114736483B discloses a method for blending ABS and low-viscosity PET to prepare a high-flow and high-heat-resistant material with good appearance. However, the ultra-low-viscosity PET resin selected by this method has a low molecular weight, and the impact strength of the composition is not high. At the same time, due to the low molecular weight of PET and the low PET addition content, the improvement of the chemical resistance of the material will be very limited. Therefore, in the face of some application occasions with high requirements for high flow, high appearance, and high chemical resistance, new solutions are needed. Summary of the Invention

[0003] The purpose of the present invention is to overcome the disadvantages and deficiencies of the prior art and provide a high-flow and highly chemical-resistant ABS composition and a preparation method thereof.

[0004] The purpose of the present invention can be achieved by the following solutions:

[0005] In the first aspect, the present invention provides a high-flow and highly chemical-resistant ABS composition, which comprises the following components in weight percentages: 20-65 parts of ABS resin, 0.5-1.5 parts of compatibilizer, 30-50 parts of PET transesterification masterbatch, 5-30 parts of ABS powder, 0.01-0.05 parts of chain extender, 0.1-0.5 parts of antioxidant, and 0.3-0.5 parts of lubricant.

[0006] Preferably, the melt index of the ABS resin under the conditions of 220°C * 10 kg is 15-30 g / 10 min. Further, the ABS resin is a high-flow ABS resin, and its source includes any one of bulk polymerization, emulsion polymerization, and recycling from household appliance disassembly.

[0007] Preferably, the rubber content of the ABS powder is 50%-60%.

[0008] Preferably, the compatibilizer includes acrylonitrile-styrene-glycidyl methacrylate copolymer (SAG), and the content of glycidyl methacrylate (GMA) in it is 1%-5%.

[0009] Preferably, the PET transesterification masterbatch includes the following components in weight percentages: 80-95 parts of PET resin, 5-20 parts of polyester resin, and 0.1-0.5 part of antioxidant.

[0010] Further, the polyester resin includes one or more of polybutylene terephthalate (PBT), polyethylene terephthalate-1,4-cyclohexanedimethanol ester (PETG), and polycarbonate (PC).

[0011] Further, the intrinsic viscosity of the polybutylene terephthalate (PBT) is 0.65-0.85 dL / g, the intrinsic viscosity of the polyethylene terephthalate-1,4-cyclohexanedimethanol ester (PETG) is 0.65-0.85 dL / g, and the melt index of the polycarbonate (PC) under the conditions of 300 °C * 1.2 kg is 30-70 g / 10 min.

[0012] Further, the intrinsic viscosity of the PET resin is 0.87-1.0 dL / g. When the viscosity is too high, the fluidity of the final ABS / PET material will be reduced. The source of the PET resin in the present invention includes any one of virgin and recycled.

[0013] Further, the PET transesterification masterbatch is obtained by blending each component and then performing extrusion granulation; the extrusion granulation is carried out using a twin-screw extruder, wherein the rotation speed of the twin-screw extruder is 300-500 rpm and the temperature is 200-280 °C. The blending is carried out using a high-speed mixer.

[0014] Preferably, the chain extender includes epoxy chain extender ADR.

[0015] Preferably, the antioxidant includes one or more of hindered phenol antioxidants and phosphite antioxidants; the hindered phenol antioxidant includes pentaerythritol tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and the phosphite antioxidant includes one or more of triphenyl phosphate, tris(2,4-di-tert-butylphenyl) phosphite, and pentaerythritol bis(2,4-di-tert-butylphenyl) phosphite.

[0016] Preferably, the lubricant includes one or more of silane polymers, butyl stearate, stearic acid, fatty acid salts, fatty acid amides, ethylene bisstearamide, and polyethylene wax.

[0017] In a second aspect, the present invention provides a method for preparing a high-flow and high-chemical-resistant ABS composition, comprising the following steps:

[0018] S1. Weigh each ingredient by weight;

[0019] S2, after blending the components, extrusion granulation is performed to obtain.

[0020] Preferably, in step S2, the blending is performed using a high-speed mixer.

[0021] Preferably, in step S2, the extrusion granulation is performed using a twin-screw extruder; wherein the rotation speed of the twin-screw extruder is 300-500 rpm, and the temperature is controlled at 200-250°C.

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] 1. The present invention utilizes the property that polyester resin (such as PBT, PETG, PC) materials and PET resin are easy to undergo ester exchange reaction, and pre-esterifies the PET resin in the screw through a twin-screw extruder to generate more block copolymers, while reducing the crystallinity and viscosity of the PET resin, so that the fluidity of the PET resin is higher, which is conducive to the preparation of a high-flow ABS composition. At the same time, the crystallinity of the PET resin is reduced, and the dispersed phase of the PET resin in the ABS is not easy to crystallize, which can improve the toughness of the composition.

[0024] 2. The present invention selects a PET resin with a specific viscosity so that when it undergoes an ester exchange reaction with a polyester resin material, it can not only avoid the problem that the viscosity of the PET resin is significantly reduced due to its too low viscosity, thereby causing a significant reduction in the mechanical properties of the composition, but also avoid the use of styrene-acrylonitrile-methacrylate glycidyl ester copolymer during the ester exchange reaction, thereby improving the fluidity of the composition, so that the composition has excellent mechanical properties and fluidity on the basis of improving chemical resistance. In addition, the specific viscosity PET resin used in the present invention can also reduce the crystallization degree of the PET resin in the ester exchange reaction with the polyester resin, further improving the mechanical properties (i.e., toughness) of the composition.

[0025] 3. By introducing a specific chain extender (i.e., polyester chain extender ADR), the present invention moderately increases the viscosity of the transesterification masterbatch, prevents further transesterification degradation of the transesterification masterbatch during secondary extrusion, promotes the stability of the product, and enhances the impact resistance of the composition. At the same time, compared with traditional chain extenders, the epoxy group density of the polyester chain extender ADR is higher, with 9 epoxy groups per molecule, high chain extension efficiency, fast reaction speed, and the PET after being chain-extended by ADR has a highly branched structure, improving the fluidity and glossiness of PET during injection molding. In addition, the present invention further improves the fluidity of the ABS composition by optimizing the content of the polyester chain extender ADR.

[0026] 4. By adding a compatibilizer SAG, the present invention improves the compatibility between ABS and PET resins and promotes the dispersion of PET resin in ABS. At the same time, the PET content in the composition is relatively high, resulting in good chemical resistance. Detailed Embodiments

[0027] The present invention will be described in detail below with reference to specific embodiments. The following examples are implemented under the premise of the technical solution of the present invention, providing detailed implementation methods and specific operation processes, which will help those skilled in the art to further understand the present invention. It should be noted that the protection scope of the present invention is not limited to the following embodiments. Any adjustments and improvements made under the premise of the concept of the present invention fall within the protection scope of the present invention.

[0028] This embodiment provides a preparation method for a high-flow and high-chemical-resistance ABS composition, including the following steps:

[0029] First, prepare the PET transesterification masterbatch:

[0030] The transesterification masterbatches A, B, C, D, and E of the examples and the masterbatch F of the comparative example are prepared as follows:

[0031] According to the weight percentages of the formula components of the transesterification masterbatches A - E in Table 1, add the raw materials to a high-speed mixer and mix well, then place them in a twin-screw extruder, control the rotation speed of the screw machine at 500 rpm, and the temperature at 270 °C, and extrude and pelletize to obtain the transesterification masterbatches A - E of the examples. In contrast, the masterbatch F of the comparative example is not extruded and pelletized by an extruder.

[0032] Among them, the material composition of Table 1 is as follows:

[0033] The component PET resin grade is China Resources carbonated PET CR 8828, and the intrinsic viscosity is 0.87 dL / g;

[0034] The component PETG resin grade is Eastman GN071, and the intrinsic viscosity is 0.7 dL / g;

[0035] The PBT resin of the component is Hengli Kanghui KH2075, with an intrinsic viscosity of 0.75dL / g;

[0036] The PC resin grade is Idemitsu MD1500, and the melt index is 70g / 10min (300℃*1.2kg);

[0037] The component antioxidant is a compound antioxidant of a hindered phenol antioxidant and a phosphite antioxidant (hindered phenol antioxidant: pentaerythritol tetrakis[β-(3,5-di-tert-butyl 4-hydroxyphenyl) propionate, phosphite antioxidant: tris(2,4-di-tert-butylphenyl) phosphite, compounding ratio is 1:1).

[0038] The six kinds of masterbatches in Table 1 were subjected to melt index (MI) test and differential scanning calorimeter (DSC) test to detect the melting enthalpy △Hm of the PET resin in the masterbatch, wherein the melt index refers to ISO 1133-1-2011 standard, the test temperature is 265°C, the load is 2.16 kg, and the DSC test refers to GB / T 19466.3-2004 standard, and the heating rate is 10°C / min.

[0039] The melt index of the transesterification masterbatch AE shows that after adding the polyester material, an ester exchange reaction occurs with the PET resin to generate more block copolymers and more short-chain molecules, resulting in a significant increase in the material melt index (i.e., a decrease in viscosity). DSC scanning shows that after adding the polyester material, the melting enthalpy of the PET resin decreases, indicating that the crystallization ability of PET is destroyed after the ester exchange, resulting in a decrease in the crystallization performance of PET. Compared with the masterbatch B of the embodiment, the masterbatch G of the comparative example has a very high fluidity of the masterbatch prepared from the low-viscosity PET resin, which indicates that the viscosity of the low-viscosity PET resin decreases significantly after the ester exchange reaction. In addition, the melting enthalpy of the comparative masterbatch G is higher than that of the masterbatch B of the embodiment, which indicates that the masterbatch prepared from the high-viscosity PET resin has a lower crystallinity.

[0040] Secondly, prepare the ABS / PET transesterification masterbatch composition:

[0041] According to the weight percentage of the formula in the embodiments and comparative examples in Tables 2 and 3, the raw materials were added into a high-speed mixer and fully mixed, and then placed in a twin-screw extruder, the speed of the screw machine was controlled to be 300-500 rpm, the temperature was 200-250° C., and extrusion granulation was performed to obtain a high-flow and high-chemical-resistant ABS composition material.

[0042] Among them, the material compositions in Table 2 and Table 3 are as follows:

[0043] PET (low viscosity): brand: Yizheng FG600, viscosity: 0.65dL / g;

[0044] ABS resin: grade is Takahashi Petrochemical bulk ABS 8391, melt index is 27 g / 10 min (220 °C * 10 kg);

[0045] ABS rubber powder: grade is South Korea Kumho P / D180, rubber content is 58%;

[0046] PET transesterification masterbatch A-F, prepared by the aforementioned method;

[0047] Compatibilizer: grade is Rizhisheng Fine Chemicals SAG002, GMA content is 2%;

[0048] Chain extender: grade is BASF ADR 4468;

[0049] Conventional PET chain extender: PMDA, pyromellitic dianhydride, Sinopharm Chemical Reagent Co., Ltd.;

[0050] Antioxidant: the antioxidant is a compound antioxidant of hindered phenol antioxidant and phosphite antioxidant;

[0051] Lubricant: ethylene bisstearamide, commercially available.

[0052] Table 1. Transesterification masterbatch formula of the examples and masterbatch formula of the comparative examples

[0053]

[0054] Table 2. Formulas of Examples 1-9

[0055]

[0056]

[0057] Table 3. Formulas of Comparative Examples 1-10

[0058]

[0059] After drying the products of the above examples and comparative examples in a forced air oven at 90 °C for 4 hours, they were injection molded into standard specimens (referring to ISO specimen dimensions), composite screw post specimens (280 * 150 mm), and helical specimens (1 mm thickness) using an injection molding machine. After placing the injection molded specimens in an environment with a relative humidity of 50 ± 5% and a temperature of 23 ± 2 °C for at least 24 hours, performance tests were carried out. The composite screw post specimens were used to test the glossiness and the chemical resistance evaluation of the screw posts, and the helical specimens were used to test the material flow length, which can reflect the fluidity of the material during the injection molding process.

[0060] Performance test method:

[0061] (1) Notched impact strength: Referring to ISO 179-1-2010 standard, Type A notch, pendulum energy 4J, test temperature 23°C;

[0062] (2) Melt index: Referring to ISO 1133-1-2011 standard, test temperature 265°C, load 5 kg;

[0063] (3) Glossiness: Referring to ISO 2813-2014 standard, test angle 60°;

[0064] (4) Flow length ratio evaluation: Read the longest scale of the spiral after filling and molding in a 1 mm thick spiral mold.

[0065] (5) Chemical resistance evaluation: Immerse the screw post sample in glacial acetic acid for 5 minutes, then wash it with clean water, and observe the cracking situation on the surface of the screw post.

[0066] Table 4 Performance table of examples

[0067]

[0068] Table 5 Performance table of comparative examples

[0069]

[0070] Examples 1-5 illustrate the performance of ABS compositions with different transesterification masterbatches. Examples 6-7 take transesterification masterbatch B as the object to investigate the influence of the content of transesterification masterbatch on the performance. Examples 7-9, under the condition of high transesterification masterbatch content (50 parts addition), investigate the influence of different types of transesterification masterbatches on the performance. The above results show that: the increase in the polyester component in the transesterification masterbatch can strengthen the transesterification reaction, and the obtained ABS composition material has higher fluidity. At the same time, due to the inhibition of the crystallization of PET, the impact strength of the material is also improved.

[0071] Comparing Comparative Example 1 with Example 2, and Comparative Example 2 with Example 7, it can be seen that the impact strength of the combination of PET resin without transesterification reaction and ABS is very low, and the fluidity of the material is also significantly lower. Comparing Comparative Examples 3 and 4 with Example 2, it can be seen that the addition of compatibilizer SAG improves the compatibility of ABS and PET. When SAG is not contained, the impact strength of the material is very low, while too high SAG content will lead to a decrease in the fluidity of the composition. Comparing Comparative Examples 5 and 6 with Example 2, the addition of chain extender can increase the molecular weight of the transesterification masterbatch and prevent further transesterification in the screw from causing material degradation. When the chain extender is not added, the impact strength of the composition is very low. When the content of ADR chain extender is relatively low, ADR also plays a good branching role, enabling the material to still have good fluidity, while too high chain extender content will lead to a decrease in fluidity. Comparing Comparative Examples 6, 7, and 8 with Example 2, when both 0.03% and 0.1% of ADR chain extender and conventional PET chain extender PMDA are added, the impact strength of the material prepared with ADR chain extender is higher. Although the difference in melt index between the two is not significant, the glossiness and flow length ratio of the material prepared with ADR chain extender are significantly higher than those of PMDA chain extender. This is because the chain extension efficiency of ADR chain extender is higher. The epoxy functionality of ADR is 9, which is significantly higher than 4 of PMDA. At the same time, the degree of branching of PET after chain extension with ADR is higher, and the shear thinning degree during injection molding is stronger, thus enabling the material to have higher fluidity and glossiness. Comparative Example 9 is an example without adding PET material, and it can be seen that the chemical resistance of the material is very poor. Comparing with Example 2, Comparative Example 10 uses low-viscosity PET resin, resulting in a significant decrease in viscosity during the transesterification reaction while maintaining a relatively high degree of crystallization, thereby significantly reducing the notched impact strength of the material.

[0072] The specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the above specific embodiments, and those skilled in the art can make various deformations or modifications within the scope of the claims, which do not affect the essence of the present invention.

Claims

1. A high-flow and high-chemical-resistant ABS composition, characterized in that, It comprises components in the following weight percentages: 20 - 65 parts of ABS resin, 0.5 - 1.5 parts of compatibilizer, 30 - 50 parts of PET transesterification masterbatch, 5 - 30 parts of ABS rubber powder, 0.01 - 0.05 parts of chain extender, 0.1 - 0.5 parts of antioxidant, and 0.3 - 0.5 parts of lubricant; The intrinsic viscosity of the PET resin in the PET transesterification masterbatch is 0.87 - 1.0 dL / g.

2. The high-flow and high-weather-resistant ABS composition according to claim 1, characterized in that, The melt index of the ABS resin under the conditions of 220°C * 10 kg is 15 - 30 g / 10 min; The rubber content of the ABS rubber powder is 50% - 60%.

3. The high-flow and high-weather-resistant ABS composition according to claim 1, wherein The compatibilizer comprises acrylonitrile - styrene - glycidyl methacrylate copolymer, and the content of glycidyl methacrylate is 1% - 5%; The lubricant comprises one or more of silane polymer, butyl stearate, stearic acid, fatty acid salt, fatty acid amide, ethylene bisstearamide, and polyethylene wax.

4. The high-flow and high-chemical-resistant ABS composition according to claim 1, wherein The PET transesterification masterbatch comprises components in the following weight percentages: 80 - 95 parts of PET resin, 5 - 20 parts of polyester resin, and 0.1 - 0.5 parts of antioxidant.

5. The high-flow and high-weather-resistant ABS composition according to claim 4, characterized in that The polyester resin comprises one or more of polybutylene terephthalate, poly(ethylene terephthalate - co - 1,4 - cyclohexanedimethanol), and polycarbonate. The intrinsic viscosity of the polybutylene terephthalate is 0.65 - 0.85 dL / g, and the intrinsic viscosity of the poly(ethylene terephthalate - co - 1,4 - cyclohexanedimethanol) is 0.65 - 0.85 dL / g; the melt index of the polycarbonate under the conditions of 300°C * 1.2 kg is 30 - 70 g / 10 min.

6. The high-flow and high-weather-resistant ABS composition according to claim 4, wherein The PET transesterification masterbatch is obtained by blending each component and then performing extrusion granulation; the extrusion granulation is carried out using a twin - screw extruder, wherein the rotation speed of the twin - screw extruder is 300 - 500 rpm, and the temperature is 200 - 280°C.

7. The high-flow and high-chemical-resistant ABS composition according to claim 1 or 4, characterized in that, The antioxidant comprises one or more of hindered phenol antioxidants and phosphite antioxidants; the hindered phenol antioxidant comprises pentaerythritol tetrakis [β - (3,5 - di - tert - butyl - 4 - hydroxyphenyl) propionate], and the phosphite antioxidant comprises one or more of triphenyl phosphate, tris(2,4 - di - tert - butylphenyl) phosphite, and pentaerythritol bisphosphite di(2,4 - di - tert - butylphenyl) ester.

8. The high-flow and high-chemical-resistance ABS composition according to claim 1, characterized in that, The chain extender comprises epoxy chain extender ADR.

9. A method for preparing a high-flow and high-weather-resistant ABS composition according to any one of claims 1-8, characterized in that, It comprises the following steps: S1. Weigh each component by weight parts; S2. After blending each component, perform extrusion granulation to obtain the product.

10. The preparation method according to claim 9, wherein In step S2, the extrusion granulation is carried out using a twin - screw extruder; the rotation speed of the twin - screw extruder is 300 - 500 rpm, and the temperature is controlled at 200 - 250°C.

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