An ABS composition resistant to long-term plugging and unplugging, and its preparation method and application

Abstract

The present invention discloses an ABS composition resistant to long-term plugging and unplugging, as well as its preparation method and application, and relates to the technical field of polymer materials. An ABS composition comprises: SAN resin, an ABS-type toughening agent, PET resin, a compatibilizer, a thermal conductor, and phase-change microcapsules; the phase-change microcapsules have a phase transition point of 25-30°C. The present invention compounds the SAN resin and the ABS-type toughening agent and adjusts the ratio, while introducing PET resin and a compatibilizer, so that the ABS composition has good mechanical properties. The simultaneous introduction of a thermal conductor and phase-change microcapsules with a specific phase transition point can reduce the magnitude of frictional temperature rise of the material during continuous plugging and unplugging, improve thermal stability, and thus improve the material's plug-in force retention rate during long-term plugging and unplugging. The ABS composition can be used in building block toys to meet the requirements of building blocks being resistant to long-term plugging and unplugging.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and more particularly to an ABS composition resistant to long-term plugging and unplugging, and a preparation method and application thereof. Background Art

[0002] Acrylonitrile-butadiene-styrene (ABS) resin boasts excellent mechanical properties, a high-gloss aesthetic, and superior processing properties, making it widely used across various industries. The toy industry primarily uses ABS resin as the primary material for its products. For building block toys, the demand for long-term plug-in / plug-out performance is increasing.

[0003] Polyethylene terephthalate (PET) is a crystalline saturated polyester with excellent physical and mechanical properties and resistance to organic solvents over a wide temperature range. It is widely used in various packaging containers and the textile industry. Most PET plastics are used in food-contact drinking water bottles and beverage bottles. The recycled PCR-PET plastics can meet the chemical control requirements of the toy industry and are a potential material for reducing carbon emissions in the toy industry. However, PET has a significant disadvantage: its slow crystallization rate, difficulty in injection molding, long production cycles, and average dimensional stability. Toy building blocks require very high dimensional stability and long-term insertion and removal forces, as well as high injection molding efficiency, which pure PET cannot meet. The ABS / PET alloy formed by blending it with ABS can improve injection molding processability and has good mechanical properties, but when used in building block products, it cannot meet the requirements for long-term insertion and removal resistance.

[0004] Patent CN114836002A proposes a high-toughness and high-magnetic ABS alloy, its preparation method and application. ABS resin and polyester resin are compounded to obtain a high-toughness ABS alloy, which can be used in the preparation of household appliances and toys; however, it also fails to meet the requirements of long-term plug-in resistance and is not suitable for the preparation of building block products. Summary of the Invention

[0005] The purpose of the present invention is to overcome the defects and shortcomings of existing ABS compositions that fail to have both toughness and long-term plugging and unplugging resistance, and to provide an ABS composition.

[0006] Another object of the present invention is to provide a method for preparing the ABS composition.

[0007] Another object of the present invention is to provide use of the above-mentioned ABS composition in the preparation of building block toys.

[0008] The above-mentioned purpose of the present invention is achieved through the following technical solutions:

[0009] The present invention protects an ABS composition comprising the following components in parts by weight:

[0010]

[0011] The phase change point of the phase change microcapsule is 25-30°C; the phase change point is tested by differential scanning calorimetry (DSC);

[0012] The intrinsic viscosity of the PET resin is 0.6-0.9 dL / g, and the test standard is GB / T 17931-2018.

[0013] The ABS composition of the present invention combines SAN resin and an ABS-type toughening agent in a controlled ratio, while simultaneously introducing PET resin and a compatibilizer, resulting in excellent mechanical properties. The simultaneous introduction of a thermal conductor and phase-change microcapsules with a specific phase transition point can reduce the frictional temperature rise during continuous insertion and removal, improving thermal stability and thus increasing the material's insertion and removal force retention during long-term insertion and removal. Furthermore, the PET resin with a specific intrinsic viscosity migrates to the surface of the part during the injection molding process, driving the accumulation of phase-change microcapsules on the part's surface, thereby improving the material's resistance to long-term insertion and removal. This improves the material's resistance to long-term insertion and removal, enabling its application in building block toys and meeting the requirements for long-term insertion and removal resistance.

[0014] In addition, controlling the intrinsic viscosity of PET resin is beneficial for improving toughness and enhancing system compatibility. If the intrinsic viscosity is too low, toughness will deteriorate and notched impact strength will drop significantly; if the intrinsic viscosity is too high, compatibility with other materials will decrease, affecting mechanical properties.

[0015] Phase-change microcapsules are energy (and heat) storage materials made by encapsulating specific phase-change materials. When the external temperature changes, the phase-change material inside the microcapsules changes state, absorbing or releasing large amounts of latent heat. When the external temperature is above the phase-change temperature, the core material actively absorbs heat. When the external temperature is below the phase-change temperature, the microcapsules release heat, maintaining a constant temperature, thereby mitigating thermal shock and providing intelligent temperature control.

[0016] Existing core materials for phase-change microcapsules can be categorized as solid-liquid, solid-gas, liquid-gas, and solid-solid phase-change materials. The present invention prefers solid-liquid phase-change materials. Preferably, the phase-change material for the phase-change microcapsules of the present invention is paraffin and / or a fatty acid. More preferably, the fatty acid is selected from butyl stearate.

[0017] The wall materials of existing phase change microcapsules are divided into natural polymer materials (such as chitosan, starch), synthetic polymer materials (such as acrylic urea-formaldehyde resin, melamine formaldehyde resin) and inorganic materials (such as silica, calcium carbonate); preferably, the wall material of the phase change microcapsule of the present invention is selected from polymer materials with good high-temperature stability, including but not limited to acrylic acid, polystyrene, urea-formaldehyde resin, melamine formaldehyde resin; more preferably, the capsule wall material of the phase change microcapsule of the present invention is melamine resin, and its heat-resistant temperature is ≥260°C.

[0018] Preferably, the intrinsic viscosity of the PET resin is 0.6-0.8 dL / g; more preferably, the intrinsic viscosity of the PET resin is 0.6-0.7 dL / g.

[0019] In some embodiments, the SAN resin content that can achieve the purpose of the present invention can be 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 ​​parts, 49 parts, 50 parts, 51 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts, 58 parts, 59 parts, and 60 parts.

[0020] In some embodiments, the mass fraction of acrylonitrile (AN) monomer in the SAN resin is 22-28%, and the acrylonitrile content is tested by infrared spectroscopy. Using a SAN resin with a specific AN content is beneficial for improving the compatibility of the system and giving the material good mechanical properties.

[0021] In some embodiments, the SAN resin has a melt mass flow rate of 20-40 g / 10 min at a temperature of 220° C. and a load of 10 kg, and the melt mass flow rate is measured according to ISO 1133.

[0022] In some embodiments, the content of the ABS toughening agent that can achieve the purpose of the present invention can be 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, or 27 parts.

[0023] In some embodiments, the mass fraction of butadiene monomer in the ABS toughening agent is greater than 60%, preferably 60-65%. The butadiene monomer content is tested by infrared spectroscopy.

[0024] In some embodiments, the PET resin content that can achieve the purpose of the present invention can be 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, and 30 parts.

[0025] The PET resin can also achieve the purpose of the present invention if it is post-consumer recycled (PCR) PET plastic. Preferably, the PCR plastic is PET recycled from food-grade PET plastic (such as drinking water bottles), which can solve the problem of lack of PCR solutions for ABS products in the toy industry and enable low-carbon sustainable development of the toy industry.

[0026] In some embodiments, the compatibilizer is styrene-acrylonitrile-glycidyl methacrylate and / or styrene-acrylonitrile-maleic anhydride copolymer.

[0027] In some embodiments, the thermal conductor is one or more of zinc oxide, magnesium oxide, or aluminum oxide.

[0028] Preferably, the thermal conductor is zinc oxide and / or magnesium oxide; introducing an appropriate amount of the thermal conductor can not only improve the thermal conductivity of the composition, but also help accelerate the crystallization rate of PET in the composition, improve the dimensional stability of the product and the injection molding processing efficiency, and at the same time, the thermal conductor can also inhibit the enrichment of bacteria on the surface of the material, thereby improving the antibacterial properties of the material.

[0029] The present invention has no special requirements on the particle size of the thermal conductor; preferably, the particle size of the thermal conductor is 0.1 μm-50 μm.

[0030] In some embodiments, the ABS composition further comprises: 0.1-2 parts of an antioxidant and 0.1-2 parts of a lubricant.

[0031] Preferably, the antioxidant is a hindered phenol antioxidant and / or a phosphite antioxidant.

[0032] More preferably, the antioxidant is antioxidant 1010 and / or antioxidant 168.

[0033] Preferably, the lubricant is at least one of vinyl bisstearamide, polysiloxane, calcium stearate, magnesium stearate, zinc stearate, PE wax, and PP wax; preferably polysiloxane.

[0034] The present invention provides a method for preparing an ABS composition, comprising the following steps: uniformly mixing various raw material components in a formula, melt-blending and extruding at a processing temperature of 150-240° C., thereby obtaining the ABS composition.

[0035] In some embodiments, the melt blending is performed using a twin-screw extruder or an internal mixer, with a processing temperature of 150° C. to 240° C. and a rotation speed of 50 rpm to 400 rpm.

[0036] When a twin-screw extruder was used, the temperature of zones 1 and 2 was 120°C to 190°C, the temperature of zones 3 to 5 was 200°C to 240°C, the temperature of zones 5 to 10 was 200°C to 240°C, and the screw speed was 200rpm to 400rpm.

[0037] The present invention protects the use of an ABS composition in preparing building block toys.

[0038] Compared with the prior art, the present invention has the following beneficial effects:

[0039] The present invention provides an ABS composition comprising a SAN resin and an ABS-type toughening agent, the ratio of which is adjusted, and a PET resin and a compatibilizer, thereby imparting excellent mechanical properties to the ABS composition. The simultaneous introduction of a thermal conductor and phase-change microcapsules with a specific phase transition point can reduce the magnitude of frictional temperature rise during continuous insertion and removal, improving thermal stability and thereby increasing the material's insertion and removal force retention during long-term insertion and removal. Furthermore, the PET resin with a specific intrinsic viscosity migrates to the surface of the part during the injection molding process, driving the accumulation of the phase-change microcapsules on the part's surface, thereby improving the material's resistance to long-term insertion and removal. The composition can be applied to building block toys, meeting the requirements for long-term insertion and removal resistance.

[0040] The notched impact strength of the ABS composition of the present invention is 13.8 KJ / m 2 The thermal conductivity is above 0.29W / (m*K), the plugging and unplugging force retention rate is above 84.6% after 30,000 times, and the 24-hour antibacterial rate is above 93.3%. It has excellent toughness, long-term plugging and unplugging resistance and antibacterial properties. DETAILED DESCRIPTION

[0041] The present invention will be further described below in conjunction with specific embodiments, but the examples do not limit the present invention in any form. Unless otherwise specified, the raw materials and reagents used in the examples of the present invention are conventionally purchased raw materials and reagents.

[0042] The raw materials used in the following examples and comparative examples are as follows:

[0043] SAN resin 1#: SAN KFA-130, Liaoning Jinfa Technology Co., Ltd., AN content 25%.

[0044] SAN resin 2#: SAN SA30, LG Chemical (Huizhou) Chemical Co., Ltd., AN content 23%.

[0045] SAN resin 3#: SAN 300N H, Kumho Chemical Co., Ltd., South Korea, AN content 28%.

[0046] PET resin 1#: PET CR-7702, China Resources Chemical Technology Co., Ltd., intrinsic viscosity 0.5 dL / g.

[0047] PET resin 2#: PET FG718H, Sinopec Yizheng Chemical Fiber Co., Ltd., intrinsic viscosity 0.68 dL / g.

[0048] PET resin 3#: PET SY-G105, Wujiang Shuangyang Polyester Modifier Factory, intrinsic viscosity 1.1 dL / g.

[0049] rPET 1#, derived from recycled drinking water bottles on land, has an intrinsic viscosity of 0.65dL / g.

[0050] rPET 2#, derived from recycled drinking water bottles from the ocean, has an intrinsic viscosity of 0.61dL / g.

[0051] ABS toughening agent 1#: ABS high rubber powder, ABS POW HR181, Kumho Chemical of South Korea, butadiene content is 60wt%.

[0052] ABS toughening agent 2#: ABS high rubber powder, WD-133, Wanda Chemical Company, butadiene content is 65wt%.

[0053] Thermal conductor 1#: zinc oxide, D50 particle size is 5μm.

[0054] Thermal conductor 2#: magnesium oxide, modified ultrafine magnesium hydroxide (2500-GT), Yingkou Global Powder Engineering Co., Ltd., D50 particle size is 6.5μm.

[0055] Compatibilizer: ternary random copolymer of styrene, acrylonitrile and glycidyl methacrylate, SAG-005, produced by Jiangsu Jiayirong Compatibilizer Co., Ltd.

[0056] Phase change microcapsule 1#: phase change material is paraffin, wall material is melamine formaldehyde resin, XR-XB28-HA, Hefei Ruixue New Material Technology Co., Ltd., phase change at 28℃;

[0057] Phase change microcapsule 2#: phase change material is butyl stearate, wall material is cross-linked polyurethane, phase change material FSM-PCM98, Forsman Technology (Beijing) Co., Ltd., phase change at 25°C;

[0058] Phase change microcapsule 3#: The phase change material is a paraffin-containing compound, the wall material is melamine formaldehyde resin, XR-XB42-HA, Hefei Ruixue New Material Technology Co., Ltd., 42℃ phase change.

[0059] Antioxidant: A commercially available mixture of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:1.

[0060] Lubricant: polysiloxane, GT-630, Zhejiang Jiahua Jinghua Co., Ltd.

[0061] The preparation method of the ABS composition of the following examples or comparative examples comprises the following steps: uniformly mixing the formulated raw material components using a low-speed mixer at a rotational speed of 175 rpm; and melt-blending and extruding the mixture using a twin-screw extruder to obtain the ABS composition. The temperatures of zones 1 and 2 of the twin-screw extruder were 155°C, the temperatures of zones 3 to 5 were 220°C, and the temperatures of zones 5 to 10 were 220°C. The screw speed was 300 rpm.

[0062] Examples 1 to 12

[0063] This embodiment provides a series of ABS compositions, the raw material components of which are shown in Table 1 in parts by mass.

[0064] Table 1

[0065]

[0066]

[0067] Comparative Examples 1 to 9

[0068] This comparative example provides a series of ABS compositions, the raw material components of which are shown in Table 2 in parts by mass.

[0069] Table 2

[0070]

[0071] Performance Testing

[0072] The ABS compositions of Examples 1-12 and Comparative Examples 1-9 were subjected to the following tests. The results are shown in Table 3:

[0073] Notched impact strength: tested in accordance with ISO 180-2023, notch type A;

[0074] Thermal conductivity: tested in accordance with ISO 22007-2-2015 standard;

[0075] Insertion force retention after 30,000 insertions and removals: Injection molded into a medium-sized building block with 2×2 bosses (30mm×30mm×25mm), use an insertion force tester to continuously insert and remove the blocks 30,000 times, and test the insertion force retention rate after the 30,000th insertion and removal cycle.

[0076] Antibacterial performance: The sample of Example 1 was tested according to ISO 22196:2011 standard, and the bacterial species were Escherichia coli and Staphylococcus aureus. The results showed that the 24-hour antibacterial rate reached more than 98.5%.

[0077] Table 3

[0078]

[0079]

[0080] As can be seen from Table 3, the notched impact strength of the ABS composition of the present invention is 16.6 KJ / m 2 The thermal conductivity is above 0.29W / (m*K), the plugging and unplugging force retention rate is above 84.6% after 30,000 times, and the 24-hour antibacterial rate is above 93.3%. It has excellent toughness, long-term plugging and unplugging resistance and antibacterial properties.

[0081] Compared with Example 1, when the thermal conductive agent in Comparative Example 1 is too little, the thermal conductivity is low and the retention rate of the insertion and removal force after 30,000 times is significantly reduced; when the thermal conductive agent in Comparative Example 2 is too much, the compatibility is poor, resulting in a significant decrease in the notched impact strength.

[0082] Compared with Example 1, Comparative Example 3 does not contain phase change microcapsules, and its 30,000 insertion and extraction force retention rate is significantly reduced; when the phase change microcapsules in Comparative Example 4 are excessive, the notched impact strength is reduced.

[0083] Compared with Example 1, the omission of PET in Comparative Example 5 hinders the accumulation of phase change capsules on the product surface, resulting in a decrease in insertion and extraction force retention. The excessive addition of PET in Comparative Example 6 significantly reduces the toughness of the material and results in low notched impact strength. The inherent viscosity of PET in Comparative Example 7 is too low, resulting in poor toughness and a significant decrease in notched impact strength. The inherent viscosity of PET in Comparative Example 8 is too high, reducing compatibility with ABS resin and resulting in a decrease in notched impact strength. The phase change point of the phase change microcapsules in Comparative Example 9 is too high, resulting in a significant increase in frictional temperature during continuous insertion and extraction, resulting in a decrease in insertion and extraction force retention after 30,000 cycles.

[0084] The above embodiments of the present invention are merely examples for the purpose of clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Those skilled in the art will appreciate that other variations or modifications may be made based on the above description. It is not necessary and impossible to enumerate all embodiments here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention are intended to be included within the scope of protection of the claims of the present invention.

Claims

1. An ABS composition, characterized in that: The composition includes the following components in parts by mass: The phase change point of the phase change microcapsules is 25-30°C; The intrinsic viscosity of the PET resin is 0.6-0.9 dL / g.

2. The ABS composition according to claim 1, characterized in that The capsule wall material of the phase change microcapsule is melamine resin.

3. The ABS composition according to claim 1, characterized in that The mass fraction of acrylonitrile monomer in the SAN resin is 22-28%.

4. The ABS composition according to claim 1 or 3, characterized in that The SAN resin has a melt mass flow rate of 20-40 g / 10 min at a temperature of 220° C. and a load of 10 kg. The melt mass flow rate is measured according to ISO 1133.

5. The ABS composition according to claim 1, characterized in that The mass fraction of butadiene monomer in the ABS toughening agent is 60-65%.

6. The ABS composition according to claim 1, characterized in that The PET resin is post-consumer recycled PET plastic.

7. The ABS composition according to claim 1, characterized in that The compatibilizer is styrene-acrylonitrile-glycidyl methacrylate and / or styrene-acrylonitrile-maleic anhydride copolymer.

8. The ABS composition according to claim 1, wherein The thermal conductor is one or more of zinc oxide, magnesium oxide or aluminum oxide.

9. A method for preparing the ABS composition according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: uniformly mixing various raw material components in a formula amount, melt-blending and extruding at a processing temperature of 150-240° C., thereby obtaining the ABS composition.

10. Use of the ABS composition according to any one of claims 1 to 8 in the preparation of building block toys.

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