A heat-resistant, fatigue-resistant, halogen-free flame-retardant long glass fiber reinforced polystyrene material and its preparation method

Abstract

The present application relates to the technical field of composite material reinforcing and toughening, in particular to a heat-resistant, fatigue-resistant, halogen-free flame-retardant long glass fiber reinforced polystyrene material and a preparation method thereof.The heat-resistant, fatigue-resistant, halogen-free flame-retardant long glass fiber reinforced polystyrene material comprises the following raw material components by weight: GPPS resin 30-50 parts, polyphenyl ether resin 10-20 parts, toughening agent 5-15 parts, glass fiber 20-30 parts, compatibilizer 3-5 parts, flame retardant 10-20 parts, adhesive 3-5 parts, antioxidant 0.1-0.5 parts, and lubricant 0.1-0.5 parts.The preparation method comprises the following steps: (1) preparing materials; (2) mixing materials; and (3) extruding.The present application can significantly improve the fluidity of the formula system, realize the coatability of the material to the long glass fiber, and prepare particles with stable glass fiber content and smooth surface.

Description

Technical Field

[0001] This invention relates to the field of composite material reinforcement and toughening technology, specifically to a heat-resistant, fatigue-resistant, halogen-free flame-retardant long glass fiber reinforced polystyrene material and its preparation method. Background Technology

[0002] Ascorbyl acrylate (AS) resin is a thermoplastic produced by copolymerizing styrene (St) and acrylonitrile (AN) monomers. It possesses excellent mechanical properties and dimensional stability. Short glass fibers are typically added for reinforcement, giving it strong load-bearing capacity and resistance to heat distortion, making it widely used in products such as air conditioner fan blades and automotive dashboards. However, the inconsistent length of the glass fibers can lead to unstable product performance and poor fatigue resistance. Furthermore, the production process generates a large amount of powder from the short fibers, increasing material consumption and creating a harsh working environment that negatively impacts worker health.

[0003] General-purpose polystyrene resin, characterized by its low price, high transparency, good stiffness, and good dimensional stability, is widely used and is one of the world's five major general-purpose plastics. However, it is brittle and prone to cracking, especially when reinforced with a large amount of glass fiber, which significantly reduces its impact resistance and makes it difficult to meet application requirements. Improving the toughness of glass fiber reinforced polystyrene materials is a pressing technical challenge. Using long glass fibers can reduce the glass fiber content in the material, minimizing its impact on impact performance. It can also solve problems such as excessive material residue during production, uneven glass fiber dispersion, unstable quality, and poor fatigue resistance. Furthermore, since it is mainly used in home appliances and automobiles, where high requirements exist for fire resistance and environmental friendliness, developing a halogen-free, flame-retardant, fatigue-resistant long glass fiber reinforced polystyrene material is essential.

[0004] Currently, there are no publicly reported methods for preparing long glass fiber reinforced polystyrene (SAN) materials. The published Chinese patent CN110964270 describes a method for preparing a long glass fiber reinforced SAN material, but it suffers from poor heat resistance and fatigue resistance. Invention patent CN106380711 discloses a method for preparing a short glass fiber reinforced flame-retardant polystyrene material, but it suffers from low flowability, uneven glass fiber dispersion, and poor fatigue resistance, limiting its application range. Summary of the Invention

[0005] To address the aforementioned shortcomings of existing technologies, this invention provides a heat-resistant, fatigue-resistant, halogen-free, flame-retardant long glass fiber reinforced polystyrene material and its preparation method. The long glass fiber reinforced polystyrene material provided by this invention has the advantages of low cost, high heat resistance, fatigue resistance, and environmentally friendly flame retardancy.

[0006] The technical solution adopted by this invention to solve its technical problem is: a heat-resistant, fatigue-resistant, halogen-free flame-retardant long glass fiber reinforced polystyrene material, comprising the following raw material components by weight: 30-50 parts of GPPS resin, 10-20 parts of polyphenylene ether resin, 5-15 parts of toughening agent, 20-30 parts of glass fiber, 3-5 parts of compatibilizer, 10-20 parts of flame retardant, 3-5 parts of adhesive, 0.1-0.5 parts of antioxidant, and 0.1-0.5 parts of lubricant.

[0007] As an optimization, the melt flow rate of the GPPS resin is 8-12 g / 10 min at 200℃ / 5 kg, and the relative molecular weight is 150,000-250,000.

[0008] As an optimization, the polyphenylene ether resin is a low-viscosity polyphenylene ether resin with an intrinsic viscosity of 35 mL / g.

[0009] As an optimization, 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.

[0010] As an optimization, the glass fiber is a long glass fiber with a diameter of 12-15 μm, and the film-forming agent is a polyurethane emulsion.

[0011] As an optimization, the compatibilizer is a glycidyl methacrylate-grafted styrene-ethylene-butene-styrene block copolymer.

[0012] As an optimization, the flame retardant is a phosphate ester flame retardant, specifically one or more combinations of tributyl phosphate, triphenyl phosphate, and diphenyl phosphate flame retardants.

[0013] As an optimization, the adhesive is a mixture of C5 petroleum resin and C9 petroleum resin, wherein the ratio of C5 petroleum resin to C9 petroleum resin is (2.5-4):(6-7.5).

[0014] The antioxidants mentioned are amines and phosphites;

[0015] The lubricant is a compound of pentaerythritol stearate, N,N-ethylene bis-stearamide, and styrene-acrylonitrile grafted low molecular weight copolymer.

[0016] A method for preparing a heat-resistant, fatigue-resistant, halogen-free, flame-retardant long glass fiber reinforced polystyrene material, used to produce the heat-resistant, fatigue-resistant, halogen-free, flame-retardant long glass fiber reinforced polystyrene material described in any one of the above-mentioned methods, comprising the following steps:

[0017] (1) Preparation of materials: Weigh each raw material according to the raw material ratio and set aside;

[0018] (2) Mixing: Add GPPS resin, PPO resin, toughening agent, compatibilizer, adhesive, flame retardant, antioxidant and lubricant to a mixing tank according to the weight parts and mix thoroughly to obtain a premix for later use;

[0019] (3) Extrusion: 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 polystyrene granules.

[0020] The beneficial effects of this solution are as follows: A heat-resistant, fatigue-resistant, halogen-free, flame-retardant long glass fiber reinforced polystyrene material and its preparation method have the following advantages:

[0021] 1. The material prepared by this invention has high fluidity and can be processed for coating long glass fibers. Polyphenylene ether resin has high melt viscosity and low flowability, making it difficult to process. Blending with low molecular weight, high-flow GPPS resin ensures that the base resin has good fluidity. Phosphate esters not only act as flame retardants in the formulation but also as flow modifiers, significantly improving the fluidity of the formulation system, enabling the material to be coated with long glass fibers, and producing particles with stable glass fiber content and smooth surfaces.

[0022] 2. The material of this invention exhibits high fatigue resistance and resistance to heat deformation. By using long glass fibers as the reinforcing phase and petroleum resin as the binder, the interfacial bonding between the glass fibers and the matrix resin is enhanced. This not only improves the problem of excessive powder during material processing but also gives the material a high heat distortion temperature and fatigue resistance. Furthermore, the addition of polyphenylene ether resin further improves the material's resistance to heat deformation and load-bearing capacity.

[0023] 3. This invention introduces glycidyl methacrylate-grafted styrene-ethylene-butene-styrene block copolymer (SEBS-g-GMA) as a compatibilizer. Compared to the commonly used compatibilizer styrene-grafted maleic anhydride copolymer (SMA), SEBS-g-GMA plays a dual role as a compatibilizer and toughening agent. On the one hand, it can improve material properties by increasing the compatibility between the matrix resin and glass fiber. On the other hand, having SEBS blocks, it not only has a strong toughening effect itself, but can also significantly enhance the toughening effect of toughening agents in the formulation. Detailed Implementation

[0024] Example 1:

[0025] A heat-resistant, fatigue-resistant, halogen-free, flame-retardant long glass fiber reinforced polystyrene material comprises the following raw material components by weight: 50 parts GPPS resin, 10 parts polyphenylene ether resin, 10 parts toughening agent, 25 parts glass fiber, 4 parts compatibilizer, 10 parts flame retardant, 4 parts adhesive, 0.1 parts antioxidant, and 0.5 parts lubricant.

[0026] The melt flow rate of the GPPS resin is 8 g / 10 min at 200℃ / 5 kg, and the relative molecular weight is 250,000.

[0027] The polyphenylene ether resin is a low-viscosity polyphenylene ether resin with an intrinsic viscosity of 35 mL / g.

[0028] The toughening agent is a styrene-butadiene-styrene triblock copolymer.

[0029] The glass fiber is a long glass fiber with a diameter of 12 μm, and the film-forming agent is a polyurethane emulsion.

[0030] The compatibilizer is a glycidyl methacrylate-grafted styrene-ethylene-butene-styrene block copolymer.

[0031] The flame retardant is a phosphate ester flame retardant, which is a combination of tributyl phosphate and diphenyl phosphate flame retardants.

[0032] The adhesive is a mixture of C5 petroleum resin and C9 petroleum resin, with a C5 petroleum resin:C9 petroleum resin ratio of 2.5:7.5.

[0033] The antioxidants mentioned are amines and phosphites;

[0034] The lubricant is a compound of pentaerythritol stearate, N,N-ethylene bis-stearamide, and styrene-acrylonitrile grafted low molecular weight copolymer.

[0035] A method for preparing a heat-resistant, fatigue-resistant, halogen-free, flame-retardant long glass fiber reinforced polystyrene material, used to produce the heat-resistant, fatigue-resistant, halogen-free, flame-retardant long glass fiber reinforced polystyrene material described in any one of the above-mentioned methods, comprising the following steps:

[0036] (1) Preparation of materials: Weigh each raw material according to the raw material ratio and set aside;

[0037] (2) Mixing: Add GPPS resin, PPO resin, toughening agent, compatibilizer, adhesive, flame retardant, antioxidant and lubricant to a mixing tank according to the weight parts and mix thoroughly to obtain a premix for later use;

[0038] (3) Extrusion: 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 polystyrene granules.

[0039] Example 2:

[0040] A heat-resistant, fatigue-resistant, halogen-free, flame-retardant long glass fiber reinforced polystyrene material comprises the following raw material components by weight: 40 parts GPPS resin, 15 parts polyphenylene ether resin, 5 parts toughening agent, 30 parts glass fiber, 3 parts compatibilizer, 20 parts flame retardant, 3 parts adhesive, 0.3 parts antioxidant, and 0.3 parts lubricant.

[0041] The melt flow rate of the GPPS resin is 12 g / 10 min at 200℃ / 5 kg, and the relative molecular weight is 150,000.

[0042] The polyphenylene ether resin is a low-viscosity polyphenylene ether resin with an intrinsic viscosity of 35 mL / g.

[0043] The toughening agent is a mixture of styrene-butadiene-styrene triblock copolymer and methyl methacrylate-butadiene-styrene copolymer.

[0044] The glass fiber is a long glass fiber with a diameter of 15 μm, and the film-forming agent is a polyurethane emulsion.

[0045] The compatibilizer is a glycidyl methacrylate-grafted styrene-ethylene-butene-styrene block copolymer.

[0046] The flame retardant is a phosphate ester flame retardant, which is a combination of tributyl phosphate and triphenyl phosphate.

[0047] The adhesive is a mixture of C5 petroleum resin and C9 petroleum resin, with a C5 petroleum resin:C9 petroleum resin ratio of 3.3:6.7.

[0048] The antioxidants mentioned are amines and phosphites;

[0049] The lubricant is a compound of pentaerythritol stearate, N,N-ethylene bis-stearamide, and styrene-acrylonitrile grafted low molecular weight copolymer.

[0050] A method for preparing a heat-resistant, fatigue-resistant, halogen-free, flame-retardant long glass fiber reinforced polystyrene material, used to produce the heat-resistant, fatigue-resistant, halogen-free, flame-retardant long glass fiber reinforced polystyrene material described in any one of the above-mentioned methods, comprising the following steps:

[0051] (1) Preparation of materials: Weigh each raw material according to the raw material ratio and set aside;

[0052] (2) Mixing: Add GPPS resin, PPO resin, toughening agent, compatibilizer, adhesive, flame retardant, antioxidant and lubricant to a mixing tank according to the weight parts and mix thoroughly to obtain a premix for later use;

[0053] (3) Extrusion: 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 polystyrene granules.

[0054] Example 3:

[0055] A heat-resistant, fatigue-resistant, halogen-free, flame-retardant long glass fiber reinforced polystyrene material comprises the following raw material components by weight: 30 parts GPPS resin, 20 parts polyphenylene ether resin, 15 parts toughening agent, 20 parts glass fiber, 5 parts compatibilizer, 15 parts flame retardant, 5 parts adhesive, 0.5 parts antioxidant, and 0.1 parts lubricant.

[0056] The melt flow rate of the GPPS resin is 10 g / 10 min at 200℃ / 5 kg, and the relative molecular weight is 200,000.

[0057] The polyphenylene ether resin is a low-viscosity polyphenylene ether resin with an intrinsic viscosity of 35 mL / g.

[0058] The toughening agent is a methyl methacrylate-butadiene-styrene copolymer.

[0059] The glass fiber is a long glass fiber with a diameter of 14 μm, and the film-forming agent is a polyurethane emulsion.

[0060] The compatibilizer is a glycidyl methacrylate-grafted styrene-ethylene-butene-styrene block copolymer.

[0061] The flame retardant mentioned is a phosphate ester flame retardant, specifically a diphenyl phosphate flame retardant.

[0062] The adhesive is a mixture of C5 petroleum resin and C9 petroleum resin, with a C5 petroleum resin:C9 petroleum resin ratio of 4:6;

[0063] The antioxidants mentioned are amines and phosphites;

[0064] The lubricant is a compound of pentaerythritol stearate, N,N-ethylene bis-stearamide, and styrene-acrylonitrile grafted low molecular weight copolymer.

[0065] A method for preparing a heat-resistant, fatigue-resistant, halogen-free, flame-retardant long glass fiber reinforced polystyrene material, used to produce the heat-resistant, fatigue-resistant, halogen-free, flame-retardant long glass fiber reinforced polystyrene material described in any one of the above-mentioned methods, characterized by comprising the following steps:

[0066] (1) Preparation of materials: Weigh each raw material according to the raw material ratio and set aside;

[0067] (2) Mixing: Add GPPS resin, PPO resin, toughening agent, compatibilizer, adhesive, flame retardant, antioxidant and lubricant to a mixing tank according to the weight parts and mix thoroughly to obtain a premix for later use;

[0068] (3) Extrusion: 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 polystyrene granules.

[0069] Comparative Example 1:

[0070] Short glass fibers were used, and the other parameters were the same as in Example 1.

[0071] Comparative Example 2:

[0072] No compatibilizer was used, and the other parameters were the same as in Example 2.

[0073] Comparative Example 3:

[0074] A styrene-based compatibilizer was used, and the other parameters were the same as in Example 2.

[0075] Comparative Example 4:

[0076] C5 and C9 adhesive resins were not used, and the remaining parameters were the same as in Example 3.

[0077] The polystyrene materials produced in Examples 1-3 and Comparative Examples 1-4 were subjected to performance tests, and the results are shown in the table below.

[0078] Table 1: Performance Test Results of Examples and Comparative Examples

[0079]

[0080]

[0081] 1. Tensile strength: Tested according to ASTM D638 standard at a test speed of 50 mm / min.

[0082] 2. Flexural strength modulus: Tested according to ASTM D790 standard at a test speed of 2 mm / min.

[0083] 3. Notched impact strength: Tested according to ASTM D256 standard, with a specimen thickness of 3.2 mm and a test temperature of 23°C.

[0084] 4. Heat distortion temperature: Tested according to ASTM D648 standard, test conditions are 1.82 MPa (unannealed) and heating rate is 120℃ / h.

[0085] 5. Glass fiber wetting characterization:

[0086] (1) Sampling requirements: At different times, cut 10 sample strips at once between the traction machine and the pelletizer. The length of the sample strips shall not be less than 30cm.

[0087] (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.

[0088] (3) Soaking time: The soaking time of the sample is 1 min.

[0089] (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.

[0090] (5) Result judgment: Crawling height within 30mm is qualified.

[0091] 6. Fatigue resistance test: Based on the fan speed of 1200 rpm / min, the test is conducted at a frequency of 20 Hz / s. The sample size is 127 mm * 12.7 mm * 3.2 mm. A stress of 100 N is applied until the sample breaks. The longer the time, the better the fatigue resistance.

[0092] As can be seen from Example 1 and Comparative Example 1, compared with short glass fibers, using long glass fibers can comprehensively enhance the tensile, bending, and impact properties of the material, and improve fatigue resistance by 3.75 times. Comparing Example 2 with Comparative Examples 2-3, it can be seen that without a compatibilizer or by using other compatibilizers, the interfacial bonding force is poor, resulting in reduced material performance, especially a significant decrease in impact strength. Comparing Example 3 with Comparative Example 4, it can be seen that by selecting a petroleum resin blended with C5 and C9, GPPS resin can be better bonded to glass fibers, improving overall mechanical properties while also improving the wetting of the substrate and glass fiber surfaces.

[0093] The above-described specific embodiments are merely specific examples of the present invention. The patent protection scope of the present invention includes, but is not limited to, the product forms and styles of the above-described specific embodiments. Any heat-resistant, fatigue-resistant, halogen-free flame-retardant long glass fiber reinforced polystyrene material and its preparation method that conform to the claims of the present invention, and any appropriate changes or modifications made thereto by those skilled in the art, shall fall within the patent protection scope of the present invention.

Claims

1. A method for preparing a heat-resistant, fatigue-resistant, halogen-free flame-retardant long glass fiber reinforced polystyrene material, comprising the following steps: (1) preparing materials: according to the raw material ratio, each raw material is weighed and prepared; (2) mixing: GPPS resin, PPO resin, toughening agent, compatibilizer, adhesive, flame retardant, antioxidant, lubricant are added into the stirring kettle according to the weight fraction to obtain a premix, which is used for later; (3) extrusion: the premix is added into a double screw extruder, after double screw mixing, the extruded melt is introduced into an impregnation mold, the continuous glass fiber is pulled through the impregnation mold filled with the melt by a traction machine, and then a continuous fiber reinforced resin strip with smooth appearance and stable fiber content is obtained through a specific size die, the strip is cooled, pulled and cut into particles, and finally a long glass fiber reinforced polystyrene particle material is obtained; The heat-resistant, fatigue-resistant, halogen-free flame-retardant long glass fiber reinforced polystyrene material comprises the following raw material components by weight: GPPS resin 30-50 parts, polyphenyl ether resin 10-20 parts, toughening agent 5-15 parts, glass fiber 20-30 parts, compatibilizer 3-5 parts, flame retardant 10-20 parts, adhesive 3-5 parts, antioxidant 0.1-0.5 parts, and lubricant 0.1-0.5 parts; The GPPS resin has a melt flow rate of 8-12 g / 10 min at 200℃ / 5kg, and a relative molecular weight of 150-250 thousand; The polyphenyl ether resin is a low viscosity polyphenyl ether resin with a characteristic viscosity of 35 mL / g; The glass fiber is long glass fiber with a diameter of 12-15 um, and the film former is polyurethane emulsion; The adhesive is a mixture of C5 petroleum resin and C9 petroleum resin; The antioxidant is amine and phosphite; the lubricant is pentaerythritol stearate, N,N-ethylene bis-stearamide, and styrene-acrylonitrile grafted low molecular weight copolymer; The compatibilizer is methyl methacrylate glycidyl ester grafted styrene-ethylene-butylene-styrene block copolymer.

2. The process for preparing a heat-resistant, fatigue-resistant, halogen-free flame-retardant long glass fiber reinforced polystyrene material according to claim 1, characterized in that: The toughening agent is one or a mixture of two or more of styrene-butadiene-styrene triblock copolymer, styrene-butadiene diblock copolymer, styrene-ethylene-butylene-styrene block copolymer, and methyl methacrylate-butadiene-styrene copolymer.

3. The process for preparing a heat resistant, fatigue resistant, halogen free, flame retardant long glass fiber reinforced polystyrene material according to claim 1, characterized in that: The flame retardant is a phosphate ester flame retardant, which is a combination of one or more of tributyl phosphate, triphenyl phosphate, and diphenyl methyl phosphate flame retardant.

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