High-rigidity, high-impact, fatigue-resistant long glass fiber reinforced recycled styrene material and preparation method thereof

Abstract

The application provides a high-rigidity, high-impact, fatigue-resistant long glass fiber reinforced recycled polystyrene material and a preparation method thereof. The polystyrene material comprises GPPS resin, a toughening agent, glass fiber, a compatilizer, an adhesive, an antioxidant and a lubricant. In the polystyrene material, the recycled GPPS resin is used as the main material, and the low molecular weight and high fluidity of the recycled material are fully utilized. In combination with a specific preparation process, the melt can be uniformly and continuously coated on the long glass fiber, so that the long glass fiber reinforced polystyrene material with stable glass fiber content and smooth surface is obtained, and the pulling speed can reach 80 m / s. The long glass fiber is used as the reinforcing phase, and the low-melting-point carbon five and carbon nine petroleum resin adhesives are selected, so that the long glass fiber reinforced polystyrene material with high glass fiber content, strong bonding force and excellent performance is prepared. The long glass fiber polystyrene material has the advantages of low cost, high rigidity, strong impact resistance and strong fatigue resistance.

Description

Technical Field

[0001] This invention relates to the field of composite material reinforcement and toughening technology, specifically to a high-rigidity, high-impact, fatigue-resistant long glass fiber reinforced recycled styrene material and its preparation method. Background Technology

[0002] With the widespread use of plastic products, the waste problem caused by plastic products has gradually become one of the environmental burdens. Humans generate about 30 million tons of plastic waste every year, of which 14.1 million tons are plastic packaging waste. Of this plastic waste, only a very small portion is properly disposed of. According to data, the recycling rate is only 14%.

[0003] Plastic packaging materials are mainly made of polystyrene (GPPS) foam and are widely used in food delivery, express delivery, and cold chain transportation. Developing a material made from recycled waste foam boxes can further improve the recycling of waste plastics and reduce the amount of waste plastics that end up in landfills, incineration, and the natural environment.

[0004] Air conditioner fan blades on the market mainly use short glass fiber reinforced SAN material. During the production process, a large amount of material dust is generated, resulting in material waste. In addition, the difference in glass fiber length can easily lead to uneven distribution in injection molded parts, affecting the quality of the parts.

[0005] GPPS, or general-purpose polystyrene, is brittle and its properties deteriorate significantly after recycling due to aging and degradation. Adding a large amount of glass fiber increases rigidity but significantly reduces impact resistance, making it difficult to meet application requirements. Therefore, how to utilize glass fiber to enhance the toughness of polystyrene is a pressing technical challenge that needs to be addressed.

[0006] Although the published patents CN.102827432B and CN110964270A both describe the preparation method of continuous long glass fiber reinforced SAN masterbatch, the toughening system used in them is costly and not suitable for commercial application and promotion.

[0007] It is evident that providing a low-cost polystyrene material that can effectively avoid excessive material residue and uneven glass fiber dispersion in the production of air conditioner fan blades is of great significance in the field of air conditioner fan blade manufacturing. Summary of the Invention

[0008] To address the shortcomings of existing technologies, this invention provides a high-rigidity, high-impact, and fatigue-resistant long glass fiber reinforced recycled styrene material and its preparation method. In this styrene material, recycled GPPS resin is used as the main material, fully utilizing the low molecular weight and high flowability of the recycled material. Combined with a specific preparation process, the melt can be uniformly and continuously coated onto the long glass fibers, resulting in particles with stable glass fiber content and smooth surfaces, achieving a drawing speed of up to 80 m / s. By using long glass fibers as the reinforcing phase and selecting low-melting-point C5 and C9 petroleum resin binders, a long glass fiber reinforced polystyrene material with high glass fiber content, strong bonding force, and excellent performance is prepared. The long glass fiber styrene material provided by this invention has the advantages of low cost, high rigidity, high impact resistance, and high fatigue resistance.

[0009] The technical solution of the present invention is as follows:

[0010] A high-rigidity, high-impact, and fatigue-resistant long glass fiber reinforced recycled styrene material, comprising the following raw materials in parts by weight:

[0011] GPPS resin 45-70 parts, toughening agent 5-10 parts, glass fiber 30-40 parts, compatibilizer 3-5 parts, adhesive 5-15 parts, antioxidant 0.1-1 part, lubricant 0.1-2 parts.

[0012] Preferably, the GPPS resin is a GPPS regenerated resin recovered by the hot melt physical method, with a melt flow rate of 20-30 g / 10 min at 200℃ / 5 kg and a relative molecular weight of 50,000-100,000 g / mol.

[0013] Preferably, the toughening agent is one or a mixture of two or more of the following: styrene-butadiene-styrene triblock copolymer, styrene-butadiene diblock copolymer (K ​​glue), styrene-ethylene-butene-styrene block copolymer, and methyl methacrylate-butadiene-styrene copolymer.

[0014] Preferably, the glass fiber is impregnated with a sizing agent containing a polyurethane emulsion film-forming agent, a silane coupling agent, and a pH adjuster, and the glass fiber diameter is 14 μm.

[0015] Preferably, the compatibilizer is glycidyl methacrylate grafted styrene-ethylene-butene-styrene block copolymer (SEBS-g-GMA).

[0016] Preferably, the adhesive is a mixture of cyclic C5 and C9 petroleum resins, compounded in a 1:1 ratio.

[0017] Preferably, the antioxidant is an amine antioxidant or a phosphite antioxidant.

[0018] Preferably, the lubricant is a compound of pentaerythritol stearate, N,N-ethylene bis-stearamide, and styrene-acrylonitrile graft low molecular weight copolymer.

[0019] The preparation method of the above-mentioned styrene material is as follows:

[0020] (1) Preparation of materials: Weigh each raw material according to the raw material ratio and set aside;

[0021] (2) Mixing: Add GPPS resin, toughening agent, compatibilizer, adhesive, antioxidant and lubricant to a mixing tank according to the weight parts and mix thoroughly to obtain a premix for later use;

[0022] (3) The premix is ​​added to the twin-screw extruder. After the twin-screw mixing, the melt is extruded into the impregnation die. The traction machine pulls the continuous glass fiber through the impregnation die filled with melt, and then through a die of a specific size to obtain a continuous fiber reinforced resin strip with a smooth appearance and stable fiber content. The strip is cooled, pulled, and granulated to finally obtain long glass fiber reinforced recycled styrene granules.

[0023] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0024] 1. This invention uses GPPS recycled resin as the main material, fully utilizing the low molecular weight and high fluidity of recycled materials. Combined with the preparation process of this invention, the melt can be uniformly and continuously coated onto long glass fibers, resulting in particles with stable glass fiber content and smooth surfaces, achieving a drawing speed of up to 80 m / s. Furthermore, the application of recycled materials not only contributes to green and sustainable circular development but also significantly reduces material costs.

[0025] 2. This invention uses long glass fibers as the reinforcing phase and selects low-melting-point C5 and C9 petroleum resin binders to prepare a long glass fiber reinforced polystyrene material with high glass fiber content, strong bonding force, and excellent performance. This solves the problem of GPPS being hard and brittle, while also improving the issue of excessive powder production during pelleting.

[0026] 3. Compared to commonly used compatibilizers such as styrene-grafted maleic anhydride copolymers, this invention introduces glycidyl methacrylate-grafted styrene-ethylene-butene-styrene block copolymer (SEBS-g-GMA) as a compatibilizer. On the one hand, the material performance can be improved by enhancing the compatibility between GPPS resin and glass fiber. On the other hand, because the compatibilizer has SEBS blocks, it not only has a toughening effect itself, but can also further improve the dispersion of the toughening agent in the system and its compatibility with GPPS resin, thus endowing the material with excellent fatigue resistance. Detailed Implementation

[0027] To enable those skilled in the art to better understand the technical solutions of this invention, the technical solutions in the embodiments of this invention will be clearly and completely described below in conjunction with the embodiments of this invention. Obviously, the described embodiments are only some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of this invention.

[0028] Example

[0029] The raw materials for the embodiments and comparative examples of a high-rigidity, high-impact, and fatigue-resistant long glass fiber reinforced recycled polystyrene material were weighed and prepared according to Table 1.

[0030] Table 1: Raw material formulations of a high-rigidity, high-impact, fatigue-resistant long glass fiber reinforced recycled polystyrene material in Examples 1-3 and Comparative Examples 1-5.

[0031]

[0032]

[0033] The GPPS regenerated resin recovered by the hot melt physical method has a melt flow rate of 25 g / 10 min at 200℃ / 5 kg and a relative molecular weight of 80000 g / mol.

[0034] The glass fiber is impregnated with a polyurethane emulsion film-forming agent, silane coupling agent and pH adjuster, and the glass fiber diameter is 14μm;

[0035] The compatibilizer is glycidyl methacrylate grafted styrene-ethylene-butene-styrene block copolymer (SEBS-g-GMA);

[0036] The adhesive is a mixture of cyclic C5 and C9 petroleum resins, compounded in a mass ratio of 1:1.

[0037] The toughening agent is a styrene-butadiene-styrene triblock copolymer;

[0038] Lubricant (Lub-1) is pentaerythritol stearate, and lubricant (Lub-2) is a mixture of N,N-ethylene bis-stearamide and styrene-acrylonitrile grafted low molecular weight copolymer. The mass ratio of Lub-1 to Lub-2 is 1:2, and they are used after compounding.

[0039] The following preparation method is used to prepare recycled styrene materials, and the process is as follows:

[0040] (1) Material preparation: Weigh each raw material according to the raw material ratio in Table 1 and set aside;

[0041] (2) Mixing: Add the weighed GPPS resin, toughening agent, compatibilizer, adhesive, antioxidant and lubricant to the mixing tank and mix thoroughly to obtain a premix for later use;

[0042] (3) The premix is ​​added to the twin-screw extruder. After the twin-screw mixing, the melt is extruded into the impregnation die. The traction machine pulls the glass fiber through the impregnation die filled with melt. The glass fiber is purchased from Taishan Glass Fiber and is for LFT-styrene. The continuous fiber-reinforced resin strip with a smooth appearance and stable fiber content is obtained through the die head. The strip is cooled, pulled, and granulated to finally obtain long glass fiber reinforced recycled styrene granules.

[0043] The operating conditions of the twin-screw extruder are as follows: screw speed 300 rpm / min, temperature of zone 1-3 220℃, temperature of zone 4-6 270℃, temperature of zone 7-10 290℃; temperature of start-up valve, transition valve, distributor, and impregnation die 300℃; main feed speed 45 kg / min, glass fiber traction speed 70 m / min.

[0044] The high rigidity, high impact resistance, and fatigue resistance long glass fiber reinforced recycled polystyrene materials prepared in Examples 1-3 and Comparative Examples 1-5 were subjected to performance tests, and the test results are shown in Table 2.

[0045] Table 2 Detection Results

[0046]

[0047] 1. Tensile strength: Tested according to ASTM D638 standard at a test speed of 50 mm / min.

[0048] 2. Flexural strength modulus: Tested according to ASTM D790 standard at a test speed of 2 mm / min.

[0049] 3. Notched impact strength: Tested according to ISO 179 standard, with a sample thickness of 4 mm and a test temperature of 23℃.

[0050] 4. Heat distortion temperature: Tested according to ASTM D648 standard, test conditions are 1.82MPa (unannealed) and heating rate is 120℃ / h.

[0051] 5. Glass fiber wetting characterization:

[0052] (1) Sampling requirements: At different times, 10 sample strips are cut at once between the traction machine and the pelletizer, and the length of the sample strips is not less than 30cm.

[0053] (2) Solution preparation: Take 5 grams of fuchsin reagent and place it in a measuring cup. Add an appropriate amount of ethanol using a burette. After mixing, the liquid level should not be less than 25 ml.

[0054] (3) Soaking time: The soaking time of the sample is 1 min.

[0055] (4) Test requirements: After the sample is taken out, rinse the surface color with running water, observe whether the solution enters the sample and climbs up, measure the climbing height with calipers and record the data.

[0056] (5) Result judgment: Crawling height within 30mm is qualified.

[0057] 6. Bending fatigue strength: Based on the fan speed of 1200 rpm / min, the test was conducted at a frequency of 20 Hz / s. The sample size was 127 mm * 12.7 mm * 3.2 mm. A stress of 100 N was applied until the sample broke. The more bending cycles the sample could withstand, the better its fatigue resistance.

[0058] Table 2 shows that, based on Examples 1 and 1 Comparative, long glass fiber reinforcement exhibits the best mechanical properties and fatigue resistance. Compared to Comparative Examples 2-3, Example 2 shows poor interfacial bonding between the resin and glass fiber when using conventional styrene-maleic anhydride compatibilizers or without compatibilizers, resulting in lower material performance. Compared to Comparative Examples 4-5, Example 3 demonstrates that the styrene-acrylonitrile grafted low molecular weight copolymer used in the compound exhibits high fluidity, good dispersibility, and excellent wettability. By selecting C5 and C9 compounded petroleum resins, GPPS resin can be better bonded to glass fiber, improving overall mechanical properties while also enhancing the surface wetting of the substrate and glass fiber. Both C5 and C9 are byproducts of petroleum cracking. C5 petroleum resin has good fluidity, improves the wettability of the main material, and strengthens the bond between the tackifying resin and glass fiber. C9 petroleum resin has a cyclic structure and good chemical resistance.

[0059] Although the present invention has been described in detail with reference to preferred embodiments, it is not limited thereto. Various equivalent modifications or substitutions can be made to the embodiments of the present invention by those skilled in the art without departing from the spirit and essence of the invention, and such modifications or substitutions should all be within the scope of the present invention. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should also be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be determined by the scope of the claims.

Claims

1. A high-rigidity, high-impact, fatigue-resistant long glass fiber reinforced recycled styrene material, characterized in that, Including the following parts by weight of raw materials: GPPS resin 45-70 parts, toughening agent 5-10 parts, glass fiber 30-40 parts, compatibilizer 3-5 parts, adhesive 5-15 parts, antioxidant 0.1-1 part, lubricant 0.1-2 parts; The GPPS resin mentioned is a GPPS regenerated resin recovered by the hot melt physical method, with a melt flow rate of 20-30 g / 10 min at 200℃ / 5 kg and a relative molecular weight of 50,000-100,000 g / mol. The glass fiber is impregnated with a wetting agent containing a polyurethane emulsion film-forming agent, a silane coupling agent and a pH adjuster, and the glass fiber diameter is 14 μm. The compatibilizer is a glycidyl methacrylate-grafted styrene-ethylene-butene-styrene block copolymer. The adhesive is a mixture of cyclic C5 and C9 petroleum resins, compounded in a 1:1 ratio. The lubricant is a compound of pentaerythritol stearate, N,N-ethylene bis-stearamide, and styrene-acrylonitrile grafted low molecular weight copolymer.

2. The high-rigidity, high-impact, fatigue-resistant long glass fiber reinforced recycled styrene material as described in claim 1, characterized in that, The toughening agent is one or a mixture of two or more of the following: styrene-butadiene-styrene triblock copolymer, styrene-butadiene diblock copolymer, styrene-ethylene-butene-styrene block copolymer, and methyl methacrylate-butadiene-styrene copolymer.

3. The high-rigidity, high-impact, fatigue-resistant long glass fiber reinforced recycled styrene material as described in claim 1, characterized in that, The antioxidants are amine antioxidants and phosphite antioxidants.

4. The high-rigidity, high-impact, fatigue-resistant long glass fiber reinforced recycled styrene material as described in any one of claims 1-3, characterized in that, The process is as follows: (1) Preparation of materials: Weigh each raw material according to the raw material ratio and set aside; (2) Mixing: Add GPPS resin, toughening agent, compatibilizer, adhesive, antioxidant and lubricant to a mixing tank according to the weight parts and mix thoroughly to obtain a premix for later use; (3) The premix is ​​added to the twin-screw extruder. After the twin-screw mixing, the melt is extruded into the impregnation die. The traction machine pulls the continuous glass fiber through the impregnation die filled with melt, and then through a die of a specific size to obtain a continuous fiber reinforced resin strip with a smooth appearance and stable fiber content. The strip is cooled, pulled, and granulated to finally obtain long glass fiber reinforced recycled styrene granules.

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