A polystyrene material, its preparation method and use

Abstract

The present application relates to a kind of polystyrene material and its preparation method and application.The polystyrene material includes the following weight parts of components:GPPS resin, toughening agent, PBAT resin, flame retardant, flame retardant synergist, flame-retardant filler and anti-dripping agent.The polystyrene material of the present application has high glow wire ignition temperature and good ultrasonic welding strength, and is suitable for the shell of unattended household appliances, commercial appliances, door control automation and electronic and electrical products.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and more specifically, to a polystyrene material, its preparation method, and its applications. Background Technology

[0002] The glow wire ignition temperature refers to the temperature at which materials such as velvet begin to spontaneously combust when exposed to high temperatures or open flames. According to relevant standards in the European market, the GWIT (glow wire temperature) of materials used in unattended electronic and electrical equipment components (such as housings) must be ≥775°C.

[0003] Polystyrene possesses excellent processing and electrical properties, making it a common material for components in electronic and electrical equipment. HIPS (High-Strength Insulated Polystyrene) is one such commonly used polystyrene. However, existing HIPS exhibits relatively low GWIT (Gross Temperature Interval), typically only reaching 675–700°C.

[0004] Furthermore, electronic and electrical equipment requires high reliability and durability, often necessitating the assembly and welding of housing components. Compared to friction welding, adhesive bonding, and laser welding, ultrasonic welding offers higher strength, is more environmentally friendly, and has a wider range of applications, showing great promise. Therefore, the ultrasonic welding performance of electronic and electrical equipment housing materials deserves attention.

[0005] Based on the above, it is necessary to develop GWIT materials with a temperature of 775℃ or higher, and to pay attention to the ultrasonic welding performance of the materials. Summary of the Invention

[0006] The primary objective of this invention is to overcome the problems mentioned above, such as the inability of existing materials to reach temperatures above 775°C and insufficient attention being paid to their ultrasonic welding performance, and to provide a polystyrene material.

[0007] A further object of the present invention is to provide a method for preparing the above-mentioned polystyrene material.

[0008] A further object of the present invention is to provide the application of the above-mentioned polystyrene material in the manufacture of housings for household appliances.

[0009] The above-mentioned objective of this invention is achieved through the following technical solution:

[0010] A polystyrene material comprising the following components in parts by weight:

[0011]

[0012]

[0013] The melt flow rate of the PBAT resin measured at 190°C and 2.16 kg was 2.0–6.0 g / 10 min.

[0014] The addition of flame retardants, flame retardant synergists, anti-dripping agents, and flame retardant fillers can improve the flame retardant properties of polystyrene materials, thereby benefiting the improvement of the GWIT of polystyrene materials.

[0015] The inventors of this invention discovered through research that the addition of PBAT resin at a certain melt flow rate can significantly improve the GWIT (glow-in-the-wire) temperature of polystyrene materials. This is because: when polystyrene material comes into contact with a hot wire, the addition of PBAT resin makes the polystyrene material melt more easily, thereby rapidly expanding the pores formed by melting. This allows the polystyrene material to detach from the hot wire, preventing further high-temperature degradation and the generation of more flammable gases, thus increasing the GWIT temperature of the polystyrene material.

[0016] Controlling the melt flow rate of PBAT resin is crucial. In the molten state, the polystyrene material of this invention exhibits lower flowability of GPPS resin compared to PBAT resin. If the melt flow rate of PBAT resin is too high, the flowability difference between the two resins becomes too significant, hindering the proper dispersion of PBAT resin within the GPPS resin and preventing an effective increase in the glow wire ignition temperature. Conversely, if the melt flow rate of PBAT resin is too low, the polystyrene material cannot rapidly melt and detach from the glow wire upon contact, thus failing to significantly improve the GWIT (glow wire ignition temperature).

[0017] The ultrasonic welding strength of GPPS resin is generally weak. The inventors of this invention also unexpectedly discovered that the addition of PBAT resin with a certain degree of fluidity can improve the ultrasonic welding strength of polystyrene materials. This may be because the melting point of PBAT resin is only between 110-130℃, far lower than the melting temperature of GPPS resin. When polystyrene materials are subjected to high-frequency vibration, PBAT resin can act like a plasticizer, allowing the polystyrene material to melt more fully, thereby improving the welding strength. If the fluidity of PBAT resin is too low, the plasticizing effect is not obvious; if the fluidity of PBAT is too high, during the high-temperature melting and pressure process, too much molten polymer is squeezed out from the welding interface, resulting in a thinner interfacial adhesive layer after cooling and solidification, leading to a decrease in welding strength.

[0018] In this invention, GPPS resin is used as the main resin, and its content is more than 35 wt% of the polystyrene material.

[0019] Preferably, the melt flow rate of the GPPS resin measured at 200°C and 5 kg is 6.0–11 g / 10 min.

[0020] More preferably, the melt flow rate of the GPPS resin measured at 200°C and 5 kg is 8.0–10 g / 10 min.

[0021] Within this melt flow rate range, the resulting polystyrene material exhibits higher ultrasonic welding strength.

[0022] In this invention, the melt flow rate of GPPS resin can be measured according to standard GB / T 3682.1-2018.

[0023] In this invention, the melt flow rate of PBAT resin can be measured according to standard GB / T 3682.1-2018.

[0024] The PBAT resin of this invention can be commercially available or prepared in-house, as long as its melt flow rate meets the requirements of this invention.

[0025] The process of making PBAT resin is as follows:

[0026] 1) Terephthalic acid and / or its ester derivatives, butanediol and catalyst are mixed and reacted at 170-240℃ and 40-80kPa for 1-3 hours to obtain esterified product A1;

[0027] 2) Mix adipic acid and / or its ester derivatives, butanediol and catalyst, and react at 170-240°C and atmospheric pressure for 1-3 hours to obtain ester A2;

[0028] 3) Esterified compound A1 and esterified compound A2 are reacted at 235-255°C and 100-300 Pa for 75-155 min to obtain the PBAT resin.

[0029] Optionally, the amount of catalyst used in step 1) is 0.01-2% of the sum of the mass of terephthalic acid and / or its esterified derivatives and butanediol. The catalyst may be a tin compound, antimony compound, cobalt compound, lead compound, zinc compound, aluminum compound, or titanium compound, more preferably a zinc compound, aluminum compound, or titanium compound, and most preferably a titanium compound; the titanium compound may be tetrabutyl titanate or tetraisopropyl titanate.

[0030] Optionally, the amount of catalyst used in step 2) is 0.01-2% of the sum of the mass of adipic acid and / or its esterified derivatives and butanediol. The catalyst may be a tin compound, antimony compound, cobalt compound, lead compound, zinc compound, aluminum compound, or titanium compound, more preferably a zinc compound, aluminum compound, or titanium compound, and most preferably a titanium compound; the titanium compound may be tetrabutyl titanate or tetraisopropyl titanate.

[0031] In this invention, the melt flow rate of PBAT resin measured at 190°C and 2.16 kg can be 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5 or 6.0 g / 10 min.

[0032] Preferably, the melt flow rate of the PBAT resin measured at 190°C and 2.16 kg is 4.5–5.7 g / 10 min.

[0033] When the melt flow rate of PBAT resin is controlled within this range, the resulting polystyrene material exhibits higher ultrasonic welding strength and a higher GWIT temperature.

[0034] Preferably, in the PBAT resin, the repeating units from terephthalic acid account for 45-92 mol of the sum of the repeating units from terephthalic acid and the repeating units from bisaccharide.

[0035] More preferably, in the PBAT resin, the repeating units from terephthalic acid account for 80-91 mol of the sum of the repeating units from terephthalic acid and the repeating units from bisacrylic acid.

[0036] When the content of repeating phthalic acid units in PBAT resin is within this range, the resulting polystyrene material exhibits higher ultrasonic welding strength.

[0037] Preferably, the toughening agent is at least one of styrene-butadiene-styrene block copolymer or hydrogenated styrene-butadiene-styrene block copolymer.

[0038] Preferably, the flame retardant is a brominated flame retardant.

[0039] More preferably, the brominated flame retardant is at least one of tris(tribromophenoxy)triazine, brominated epoxy, decabromodiphenyl ethane, brominated polyimide, brominated polystyrene, and polybrominated styrene.

[0040] Preferably, the flame retardant synergist is an antimony-containing compound.

[0041] More preferably, the antimony-containing compound is at least one of antimony trioxide or sodium antimonate.

[0042] Preferably, the flame-retardant filler is at least one of magnesium hydroxide, magnesium carbonate, zinc carbonate, ammonium polyphosphate, melamine polyphosphate, zinc hydroxide, or melamine cyanurate.

[0043] More preferably, the flame-retardant filler includes a first flame-retardant filler and a second flame-retardant filler in a mass ratio of 1:(0.5-2); the first flame-retardant filler is at least one of magnesium hydroxide, magnesium carbonate, zinc carbonate, ammonium polyphosphate or melamine polyphosphate, and the second flame-retardant filler is at least one of zinc hydroxide or melamine cyanurate.

[0044] Using a single flame-retardant filler is sufficient to give the polystyrene material of the present invention the required glow wire ignition temperature, while further compounding two different flame-retardant fillers can make the GWIT temperature of the polystyrene material even higher.

[0045] More preferably, the average degree of polymerization of the ammonium polyphosphate is ≥100.

[0046] Preferably, the flame-retardant filler surface is modified with a silane coupling agent.

[0047] The flame-retardant filler surface is modified with a silane coupling agent, which can increase the GWIT temperature of the resulting polystyrene material.

[0048] More preferably, the silane coupling agent contains at least one of an epoxy group or a base group.

[0049] More preferably, the silane coupling agent is at least one of 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-n-butyl-3-aminopropyltriethoxysilane, or anilinemethyltriethoxysilane.

[0050] Preferably, the anti-dripping agent includes, but is not limited to, polytetrafluoroethylene.

[0051] Preferably, the polystyrene material further includes 0.1 to 1 part of other additives.

[0052] More preferably, the other additives include, but are not limited to, at least one of antioxidants, lubricants, weathering agents, or colorants.

[0053] Optionally, the antioxidants include, but are not limited to, hindered phenolic antioxidants or phosphites.

[0054] Optionally, the lubricant includes, but is not limited to, at least one of amide lubricants, stearate lubricants, ester lubricants, or silicone lubricants.

[0055] Optionally, the weathering agent includes, but is not limited to, at least one of benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, or hindered amine light stabilizers.

[0056] Optionally, the colorant includes at least one of pigment-type colorants, dye-type colorants, or other colorants with special aesthetic effects.

[0057] The preparation method of the above-mentioned polystyrene material includes the following steps: mixing the components, melt extruding, and granulating to obtain the polystyrene material.

[0058] Preferably, the temperature of the melt extrusion is 150–190°C.

[0059] Preferably, the screw length-to-diameter ratio of the extruder used for melt extrusion is 30 to 45:1, and the screw speed is 200 to 800 rpm.

[0060] The application of the above-mentioned polystyrene material in the manufacture of housings for household appliances is also within the scope of protection of this invention.

[0061] This invention also provides the use of the above-mentioned polystyrene material in the manufacture of household goods, electronic components, household appliances, gardening equipment, medical technology equipment, motor vehicle parts, and vehicle body parts. In particular, the above-mentioned polystyrene material can be used to manufacture parts possessing a high glow wire ignition temperature. Specifically, it can be used to manufacture the casing material for household appliances.

[0062] Preferably, the household appliance is an unattended household appliance or a commercial appliance.

[0063] More preferably, the household appliance is a vacuum cleaner, air purifier, electric blanket, humidifier, etc.

[0064] Compared with the prior art, the beneficial effects of the present invention are:

[0065] The polystyrene material of this invention has a high glow wire ignition temperature and good ultrasonic welding strength, making it suitable for use in the housings of unattended household appliances, commercial appliances, door control automation, and electronic and electrical products (such as electrical switches). Detailed Implementation

[0066] To more clearly and completely describe the technical solution of the present invention, the present invention will be further described in detail below through specific embodiments. It should be understood that the specific embodiments described herein are only for explaining the present invention and are not intended to limit the present invention. Various changes can be made within the scope of the claims of the present invention.

[0067] The reagents used in the various embodiments and comparative examples of this invention are described below:

[0068] GPPS resin 1#: melt flow rate (200℃, 5kg) is 8g / 10min, GPPS1441, INEOS Styrol Group Co., Ltd.

[0069] GPPS resin #2: melt flow rate (200℃, 5kg) is 6.5g / 10min, GP5250, Taiwan Chemical Fiber Co., Ltd.

[0070] GPPS resin #3: melt flow rate (200℃, 5kg) is 10g / 10min, N1841H, Hong Kong Petrochemical Company Limited;

[0071] PBAT Resin #1: Self-made, preparation process is as follows:

[0072] 1) Terephthalic acid (PTA) and 1,4-butanediol (BDO) were added to the esterification reactor at a molar ratio of 1:1.50, and 1% of the total mass of the raw materials was added as catalyst n-butyl titanate. The reaction was carried out at 210℃ and 80kPa for 180 min to obtain esterified product A1.

[0073] 2) Add adipic acid (AA) and 1,4-butanediol (BDO) to the esterification reactor at a molar ratio of 1:1.50, and add 1% of the total mass of the raw materials as catalyst n-butyl titanate. React at 210℃ and atmospheric pressure for 160 min to obtain esterified product A2.

[0074] 3) Two esters, A1 and A2, were continuously fed into a mixer for mixing. The ratio of repeating units from terephthalic acid to repeating units from succinic acid was controlled by adjusting the mass flow rate ratio of the two esters. The reaction was carried out at 240℃ and 100Pa for 95 minutes to obtain PBAT resin 1#. The melt flow rate of PBAT resin 1# was 4.8 g / 10 min; terephthalic acid accounted for 81% of the total molar amount of the dicarboxylic acids.

[0075] PBAT Resin 2#: Self-made, its main difference from PBAT Resin 1# is that in step 3), the temperature is 235℃ and the reaction time is 75 min. The melt flow rate of PBAT Resin 2# is 5.5 g / 10 min; terephthalic acid accounts for 81% of the total molar amount of the dicarboxylic acid.

[0076] PBAT Resin 3#: Self-made, its main difference from PBAT Resin 1# is that in step 3), the temperature is 255℃ and the reaction time is 155min. The melt flow rate of PBAT Resin 3# is 2.2g / 10min; terephthalic acid accounts for 81% of the total molar amount of the dicarboxylic acid.

[0077] PBAT Resin 4#: Self-made, its main difference from PBAT Resin 1# is that in step 3), the mass flow ratio of the two esters is changed, and the temperature is 245℃ with a reaction time of 105 min. The melt flow rate of PBAT Resin 4# is 4.8 g / 10 min; terephthalic acid accounts for 69% of the total molar amount of the dicarboxylic acid.

[0078] PBAT Resin 5#: Self-made, its main difference from PBAT Resin 1# is that in step 3), the mass flow ratio of the two esters is changed, and the temperature is 235℃ with a reaction time of 85 min. The melt flow rate of PBAT Resin 5# is 4.7 g / 10 min; terephthalic acid accounts for 91% of the total molar amount of the dicarboxylic acid.

[0079] PBAT Resin 6#: Self-made, its main difference from PBAT Resin 1# is that in step 3), the temperature is 225℃ and the reaction time is 75min. The melt flow rate of PBAT Resin 6# is 7.0g / 10min; terephthalic acid accounts for 80% of the total molar amount of the dicarboxylic acid.

[0080] PBAT Resin 7#: Self-made, its main difference from PBAT Resin 1# is that in step 3), the temperature is 260℃ and the reaction time is 160min. The melt flow rate of PBAT Resin 7# is 1.5g / 10min; terephthalic acid accounts for 81% of the total molar amount of the dicarboxylic acid.

[0081] PBAT resin A#: A400, melt flow rate of 3.7 g / 10 min, terephthalic acid accounts for 48 wt% of the total molar amount of dicarboxylic acids, purchased from Zhuhai Wantong Chemical Co., Ltd., China.

[0082] Toughening agent 1#: YH-792E, styrene-butadiene-styrene block copolymer (SBS), Sinopec Baling Petrochemical Co., Ltd.;

[0083] Toughening Agent 2#: YH-503T, hydrogenated styrene-butadiene-styrene block copolymer (SEBS), Sinopec Baling Petrochemical Co., Ltd.

[0084] Flame retardant 1#: RDT-3K, decabromodiphenyl ethane, Shouguang Weidong Chemical Co., Ltd., China;

[0085] Flame retardant #2: F-3014, brominated epoxy, Israel Chemicals;

[0086] Flame retardant synergist: Antimony trioxide is a commercially available product.

[0087] First flame retardant filler #1: Magnesium hydroxide, Aitemag 12FD, Jiangsu Aitemag Flame Retardant Materials Co., Ltd., China;

[0088] First flame retardant filler #2: Ammonium polyphosphate, APP101, Shouguang Weidong Chemical Co., Ltd., China;

[0089] Second flame retardant filler #1: Melamine cyanurate, MCA, Shandong Haiwang Chemical Co., Ltd., China;

[0090] Composite flame retardant filler 1#: self-made, the process is as follows: mix the first flame retardant filler 1# and the second flame retardant filler 1# in a mass ratio of 1:1 to obtain the modified flame retardant filler 1#;

[0091] Composite flame retardant filler #2: self-made, the difference from modified flame retardant filler #1 is that the first flame retardant filler #1 is replaced with the first flame retardant filler #2.

[0092] Anti-dripping agent: polytetrafluoroethylene, SN3201, Guangzhou Entropy Energy Innovation Materials Co., Ltd., China;

[0093] Other additives #1: Antioxidant 1010 and Antioxidant 168 are mixed at a mass ratio of 1:2. Both Antioxidant 1010 and Antioxidant 168 are commercially available products.

[0094] Unless otherwise specified, all components (e.g., anti-dripping agents, other additives #1) used in each parallel embodiment and comparative example are the same commercially available products.

[0095] The polystyrene materials provided in the embodiments and comparative examples of this invention were subjected to performance testing according to the following test methods:

[0096] (1) Glow wire ignition (GWIT) temperature: in accordance with standard IEC 60695-2-13 (using

[0097] (A square plate measuring 100mm*100mm*2.0mm);

[0098] (2) Welding strength: A 30*50*2mm sample was injection molded using an injection molding machine (injection molding process: temperature 220℃, speed and pressure both 50%), followed by ultrasonic welding. The welding power was 2200W, the pressure was 50psi, and the welding time was 0.5 seconds. The maximum tensile force of the welded sample was tested on a universal tensile testing machine at a speed of 10mm / min. This result is the welding strength, in N.

[0099] The polystyrene materials of the embodiments and comparative examples of the present invention were prepared by the following method:

[0100] Weigh each component according to the formula; mix the components evenly, and then melt-extrude and granulate them using a twin-screw extruder to obtain polystyrene material. The temperatures of the twin-screw extruder from zone one to zone ten are 150℃, 155℃, 160℃, 160℃, 170℃, 170℃, 170℃, 170℃, 180℃, and 190℃ respectively; the screw length-to-diameter ratio is 40:1; and the screw speed is 600 rpm.

[0101] Examples 1-16

[0102] Examples 1-16 provide a series of polystyrene materials, the formulations of which are shown in Tables 1 and 2.

[0103] Table 1. Formulations (parts by weight) for Examples 1-11

[0104]

[0105]

[0106] Table 2. Formulations (parts by weight) for Examples 12-16

[0107]

[0108] Comparative Examples 1-3

[0109] Comparative Examples 1-3 provide a series of polystyrene materials, the formulations of which are shown in Table 3.

[0110] Table 3 shows the formulations (parts by weight) for Comparative Examples 1-3.

[0111]

[0112]

[0113] The properties of the polystyrene materials in each embodiment and comparative example were determined according to the test methods mentioned above, and the test results are shown in Table 4.

[0114] Table 4. Performance test results of polystyrene materials in each example and comparative example.

[0115]

[0116]

[0117] As can be seen from Table 4:

[0118] The GWIT of the polystyrene materials in Examples 1 to 16 can reach above 775°C, and the ultrasonic welding strength can reach above 1450N, indicating that the polystyrene material of the present invention has a high glow wire ignition temperature and good ultrasonic welding performance.

[0119] Comparative Example 1, without the addition of PBAT resin, resulted in polystyrene material with low GWIT and ultrasonic welding strength. Comparative Examples 2 and 3, with the addition of PBAT resin, had unsuitable fluidity, resulting in polystyrene material with GWIT that could not reach above 775℃ and low ultrasonic welding strength.

[0120] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. Those skilled in the art can make other variations or modifications based on the above description. It is neither necessary nor possible to exhaustively describe all embodiments here. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A polystyrene material, characterized in that, The components include the following parts by weight: 39-47.5 parts of GPPS resin 7-12 parts toughening agent, 15-20 parts of PBAT resin, 6-8 parts flame retardant 2-4 parts of flame retardant synergist 15-20 parts of flame retardant filler Anti-dripping agent 0.8~2 parts; The melt flow rate of the PBAT resin measured at 190°C and 2.16 kg was 3.0~6.0 g / 10 min.

2. The polystyrene material according to claim 1, characterized in that, The melt flow rate of the GPPS resin measured at 200°C and 5 kg was 6.0~11 g / 10 min.

3. The polystyrene material according to claim 1, characterized in that, The toughening agent is at least one of styrene-butadiene-styrene block copolymer or hydrogenated styrene-butadiene-styrene block copolymer.

4. The polystyrene material according to claim 1, characterized in that, In the PBAT resin, the repeating units from terephthalic acid account for 45-92 mol of the sum of the repeating units from terephthalic acid and the repeating units from bisacrylic acid.

5. The polystyrene material according to claim 1, characterized in that, The flame retardant is a brominated flame retardant.

6. The polystyrene material according to claim 1, characterized in that, The flame retardant synergist is an antimony-containing compound.

7. The polystyrene material according to claim 1, characterized in that, The flame-retardant filler is at least one of magnesium hydroxide, magnesium carbonate, zinc carbonate, ammonium polyphosphate, melamine polyphosphate, zinc hydroxide, or melamine cyanurate.

8. The polystyrene material according to claim 1, characterized in that, The polystyrene material also includes 0.1 to 2 parts of other additives.

9. A method for preparing the polystyrene material according to any one of claims 1 to 8, characterized in that, The process includes the following steps: mixing the components, melt extruding, and granulating to obtain the polystyrene material.

10. The use of the polystyrene material according to any one of claims 1 to 8 in the manufacture of housings for household appliances.

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