An impact-resistant polycarbonate composite material and a method for preparing the same
By introducing specific components and processing techniques into polycarbonate materials, an elastic toughening network and good interfacial bonding are formed, which solves the problem of insufficient impact resistance of polycarbonate materials at low temperatures and achieves high toughness and structural stability of the material at both room temperature and low temperature.
Patent Information
- Application Number
- CN202610600715.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-04-30
- Publication Date
- 2026-08-25
AI Technical Summary
Existing polycarbonate materials have insufficient impact resistance at low temperatures and are prone to brittle fracture. Existing modification methods are difficult to achieve both room temperature and low temperature toughening effects, and the interfacial compatibility between components is poor.
Using styrene-butadiene-styrene block copolymer as a carrier, and combined with polymethyl methacrylate, amino-modified silicone oil and maleic anhydride-grafted ethylene propylene rubber, an impact synergist was prepared through activation, melt blending and other processes. Combined with epoxidized polybutadiene and norbornene adiene anhydride copolymer, glyceryl stearate and other components, an elastic toughening network and good interfacial bonding were formed.
It significantly improves the impact resistance of polycarbonate composite materials, especially the toughness and structural stability at room temperature and low temperature, meeting the requirements of high stress and outdoor use.
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Abstract
Description
Technical Field
[0001] This application relates to the field of polycarbonate composite materials technology, and in particular to an impact-resistant polycarbonate composite material and its preparation method. Background Technology
[0002] Polycarbonate resins possess excellent mechanical strength, light transmittance, and processability, and are widely used in electronics, structural components, and consumer products. However, pure polycarbonate suffers from insufficient low-temperature toughness and limited impact resistance, making it prone to cracking and brittle fracture under external impact, thus failing to meet the requirements for use in high-stress, complex working conditions, and low-temperature environments. Existing modified polycarbonate formulations often employ simple blending of single elastomers, resulting in poor interfacial compatibility between components, a tendency for phase separation, and limited toughening effects, making it difficult to achieve both room-temperature and low-temperature impact toughness. Therefore, there is an urgent need to develop a polycarbonate composite material with better room-temperature and low-temperature impact resistance to effectively meet the required performance requirements. Summary of the Invention
[0003] The technical problem to be solved by this application is to solve at least one of the technical problems mentioned above.
[0004] The solution to the technical problem in this application is: In a first aspect, this application provides an impact-resistant polycarbonate composite material, wherein, by weight, the raw materials comprise the following components: 60-75 parts polycarbonate resin, 6-13 parts impact synergist, 5-9 parts compatibilizer, 1-3 parts antioxidant, 2-6 parts lubricant, and 3-6 parts toughening filler; The raw materials for preparing the impact synergist include styrene-butadiene-styrene block copolymer particles, polymethyl methacrylate, amino-modified silicone oil, and maleic anhydride-grafted ethylene propylene rubber.
[0005] Furthermore, the preparation method of the impact-resistant synergist includes the following steps: The styrene-butadiene-styrene block copolymer particles and silane coupling agent dry powder were mixed and then continuously stirred at 1200-1600 r / min for 0.5-1 h to activate the mixture. The polymethyl methacrylate, the amino-modified silicone oil, and the maleic anhydride-grafted ethylene propylene rubber are mixed and dispersed at 120-140°C for 10-20 minutes to obtain an elastomer premix. The activated styrene-butadiene-styrene block copolymer particles and the elastomer premix are mixed and melt-blended at 165-195°C, and then extruded and granulated by screw extrusion to obtain the impact synergist.
[0006] Furthermore, the particle size of the styrene-butadiene-styrene block copolymer particles is 400-800 mesh; The weight ratio of the styrene-butadiene-styrene block copolymer particles to the silane coupling agent dry powder is 1:0.1-0.2; The weight ratio of polymethyl methacrylate, amino-modified silicone oil and maleic anhydride-grafted ethylene propylene rubber is 4:1-2:6-8; the weight ratio of the activated styrene-butadiene-styrene block copolymer particles and the elastomer premix is 1:2.5-4.5.
[0007] Furthermore, the polycarbonate resin is an aromatic polycarbonate with a weight-average molecular weight of 25,000-40,000 and a melt flow rate of 5-9 g / 10 min.
[0008] Furthermore, the compatibilizer is a combination of epoxidized polybutadiene and norbornene copolymer, wherein the weight ratio of epoxidized polybutadiene to norbornene copolymer is 4-7:2.
[0009] Furthermore, the lubricant is a combination of glyceryl monostearate, polyethylene wax, and silicone masterbatch, wherein the weight ratio of glyceryl monostearate, polyethylene wax, and silicone masterbatch is 2:3:6-10.
[0010] Furthermore, the antioxidant is a combination of dioctadecyl thiodipropionate and tris(2,4-di-tert-butylphenyl) phosphite, wherein the weight ratio of dioctadecyl thiodipropionate to tris(2,4-di-tert-butylphenyl) phosphite is 1:2-4.
[0011] Furthermore, the toughening filler is a combination of wollastonite whiskers and nano-silica, wherein the weight ratio of the wollastonite whiskers to the nano-silica is 3-5:1, and the particle size of both the wollastonite whiskers and the nano-silica is 800-1250 mesh.
[0012] Secondly, this application provides a method for preparing the impact-resistant polycarbonate composite material as described in the first aspect, comprising the following steps: The polycarbonate resin, the compatibilizer, the antioxidant, and the lubricant are mixed in proportion and then mixed at high speed at 130-150°C for 10-15 minutes to obtain a premix. The premix, the impact synergist, and the toughening filler are mixed and melt-blended in a twin-screw extruder at an extrusion temperature of 250-280℃, a screw speed of 250-350 r / min, and a screw length-to-diameter ratio of 40-48:1. After stranding, water cooling, and pelletizing, the impact-resistant polycarbonate composite material is obtained. The beneficial effects of this application are as follows: By defining the specific components and proportions of the impact-resistant polycarbonate composite material, the raw materials can form a good synergy within the system. The impact-resistant synergist uses styrene-butadiene-styrene block copolymer as a carrier, combined with polymethyl methacrylate, amino-modified silicone oil and maleic anhydride-grafted ethylene propylene rubber, to construct an elastic toughening network in the matrix, which is beneficial to improving the overall impact strength and structural stability of the material. At the same time, the reasonable combination of compatibilizer, antioxidant, lubricant and toughening filler can effectively improve the impact resistance of the composite material and meet the needs of outdoor and high-stress conditions. Detailed Implementation
[0013] The following will clearly and completely describe the concept and technical effects of this application in conjunction with embodiments, so as to fully understand the purpose, features and effects of this application. Obviously, the described embodiments are only a part of the embodiments of this application, not all of them. Other embodiments obtained by those skilled in the art based on the embodiments of this application without creative effort are all within the scope of protection of this application. The various technical features in this application can be combined interactively without contradicting each other.
[0014] This application provides an impact-resistant polycarbonate composite material, wherein the raw materials, by weight, include the following components: 60-75 parts polycarbonate resin, 6-13 parts impact synergist, 5-9 parts compatibilizer, 1-3 parts antioxidant, 2-6 parts lubricant, and 3-6 parts toughening filler; The raw materials for preparing the impact synergist include styrene-butadiene-styrene block copolymer particles, polymethyl methacrylate, amino-modified silicone oil, and maleic anhydride-grafted ethylene propylene rubber.
[0015] In this application, by defining the specific components and proportions of the impact-resistant polycarbonate composite material, the raw materials can form a good synergy within the system. The impact synergist uses styrene-butadiene-styrene block copolymer as a carrier, combined with polymethyl methacrylate, amino-modified silicone oil and maleic anhydride-grafted ethylene propylene rubber, to construct an elastic toughening network in the matrix, which is beneficial to improving the overall impact strength and structural stability of the material. At the same time, the reasonable combination of compatibilizer, antioxidant, lubricant and toughening filler can effectively improve the impact resistance of the composite material and meet the needs of outdoor and high-stress conditions.
[0016] Furthermore, the preparation method of the impact-resistant synergist includes the following steps: The styrene-butadiene-styrene block copolymer particles and silane coupling agent dry powder were mixed and then continuously stirred at 1200-1600 r / min for 0.5-1 h to activate the mixture. Polymethyl methacrylate, amino-modified silicone oil and maleic anhydride-grafted ethylene propylene rubber are mixed and dispersed at 120-140℃ for 10-20 min to obtain an elastomer premix. The activated styrene-butadiene-styrene block copolymer particles and elastomer premix were mixed and melt-blended at 165-195℃, and then extruded and granulated by screw extrusion to obtain the impact synergist.
[0017] In this application, a styrene-butadiene-styrene block copolymer is activated by high-speed stirring of dry silane coupling agent powder. High-speed stirring can raise the temperature and soften the silane coupling agent, and coat the particle surface, thereby improving the interfacial bonding activity. The impact synergist is prepared by stepwise activation and intensive mixing. The elastomer component is pre-dispersed by intensive mixing to ensure that the components are fully mixed and reduce local agglomeration. Then, by melt blending and extrusion granulation, the elastomer and the activated styrene-butadiene-styrene block copolymer particles can form a composite structure, which is beneficial to the dispersion and interfacial bonding of the impact synergist in the polycarbonate matrix, thereby improving the impact resistance of the polycarbonate composite material.
[0018] Furthermore, the particle size of the styrene-butadiene-styrene block copolymer particles is 400-800 mesh; The weight ratio of styrene-butadiene-styrene block copolymer particles to silane coupling agent dry powder is 1:0.1-0.2; The weight ratio of polymethyl methacrylate, amino-modified silicone oil and maleic anhydride-grafted ethylene propylene rubber is 4:1-2:6-8; the weight ratio of activated styrene-butadiene-styrene block copolymer particles and elastomer premix is 1:2.5-4.5.
[0019] In this application, the styrene-butadiene-styrene block copolymer particles are controlled at 400-800 mesh, which makes the particles more uniformly dispersed in the system and less prone to stress concentration, thus improving the transfer and dissipation effect. By adjusting the amount of silane coupling agent added, the activation effect can be ensured while avoiding local over-crosslinking. Optimizing the ratio of polymethyl methacrylate, amino-modified silicone oil and maleic anhydride-grafted ethylene propylene rubber can balance the toughening effect and supporting effect of the elastomer, which is beneficial to ensuring the rigidity of the polycarbonate composite material and improving the impact strength and dimensional stability.
[0020] Furthermore, the polycarbonate resin is an aromatic polycarbonate with a weight-average molecular weight of 25,000-40,000 and a melt flow rate of 5-9 g / 10 min.
[0021] In this application, by selecting aromatic polycarbonates with a weight-average molecular weight of 25,000-40,000 and a melt flow rate of 5-9 g / 10 min, the resin matrix can possess both high mechanical strength and suitable processing fluidity. The molecular chain structure has good regularity and can form a stable bond with impact synergists and toughening fillers, which is beneficial to improving the overall rigidity, impact resistance, and dimensional stability of the composite material at high temperatures, and broadening the application scenarios of the material.
[0022] Furthermore, the compatibilizer is a combination of epoxidized polybutadiene and norbornene copolymer, with a weight ratio of 4-7:2.
[0023] In this application, epoxidized polybutadiene and norbornene anhydride copolymer are used as composite compatibilizers. The two can form a complementary reactive interface system. Epoxidized polybutadiene can form chemical bonds with the matrix and fillers, while norbornene anhydride copolymer can improve the compatibility of polar components, reduce the interfacial tension between phases, and make the bonding tighter. This helps to reduce phase separation defects and significantly improve the mechanical properties and durability of the composite material.
[0024] Furthermore, the lubricant is a combination of glyceryl monostearate, polyethylene wax, and silicone masterbatch, with a weight ratio of glyceryl monostearate, polyethylene wax, and silicone masterbatch of 2:3:6-10.
[0025] In this application, glyceryl monostearate and polyethylene wax can improve the material flowability during processing, and silicone masterbatch can improve the surface smoothness and mold release properties of the product. This allows the material to flow more smoothly during extrusion and injection molding, reducing equipment wear and residual internal stress, which is beneficial to improving processing stability and product appearance quality.
[0026] Furthermore, the antioxidant is a combination of dioctadecyl thiodipropionate and tris(2,4-di-tert-butylphenyl) phosphite, with a weight ratio of dioctadecyl thiodipropionate to tris(2,4-di-tert-butylphenyl) phosphite of 1:2-4.
[0027] In this application, dioctadecyl thiodipropionate can inhibit thermo-oxidative aging for a long time, and tris(2,4-di-tert-butylphenyl)phosphite can quickly capture free radicals generated during processing, making the material less prone to degradation and yellowing during high-temperature processing and long-term use, which is beneficial to improving the thermal stability and service life of the composite material.
[0028] Furthermore, the toughening filler is a combination of wollastonite whiskers and nano-silica, with a weight ratio of wollastonite whiskers to nano-silica of 3-5:1, and both wollastonite whiskers and nano-silica having a particle size of 800-1250 mesh.
[0029] In this application, wollastonite whiskers and nano-silica are used as toughening fillers. The whisker structure can bear external forces and transmit stress, while the nano-silica can fill micropores and refine the matrix structure. Reasonable ratio and particle size control can make the filler uniformly dispersed in the matrix, so that the material can improve rigidity and wear resistance without losing toughness. This is conducive to achieving simultaneous reinforcement and toughening, and improving the comprehensive mechanical properties of composite materials.
[0030] This application also provides a method for preparing the impact-resistant polycarbonate composite material as described above, comprising the following steps: Polycarbonate resin, compatibilizer, antioxidant and lubricant are mixed in proportion and mixed at high speed at 130-150℃ for 10-15 minutes to obtain premix; The premix, impact synergist, and toughening filler are mixed and melt-blended in a twin-screw extruder at an extrusion temperature of 250-280℃, a screw speed of 250-350 r / min, and a screw length-to-diameter ratio of 40-48:1. After stretching, water cooling, and pelletizing, the impact-resistant polycarbonate composite material is obtained.
[0031] In this application, the resin and additives are first mixed at high speed to form a uniform premix, and then co-extruded with impact synergists and fillers. This allows for more complete dispersion of each component and more stable interfacial bonding. The material is less prone to thermal degradation during the melting process, and a polycarbonate composite material with good impact resistance can be obtained after preparation.
[0032] The following specific examples provide further details.
[0033] The preparation method of the impact-resistant synergist used in the embodiments and comparative examples of this application includes the following steps: Styrene-butadiene-styrene block copolymer particles and silane coupling agent dry powder were mixed and continuously stirred at 1500 r / min for 1 h for activation. Polymethyl methacrylate, amino-modified silicone oil and maleic anhydride-grafted ethylene propylene rubber were mixed and dispersed at 130°C for 15 min to obtain an elastomer premix. The activated styrene-butadiene-styrene block copolymer particles and elastomer premix were mixed and melt-blended at 180°C, and then extruded and granulated by screw extrusion to obtain the impact synergist.
[0034] The particle size of the styrene-butadiene-styrene block copolymer particles is 600 mesh; the weight ratio of styrene-butadiene-styrene block copolymer particles to silane coupling agent dry powder is 1:0.2; the weight ratio of polymethyl methacrylate, amino-modified silicone oil and maleic anhydride-grafted ethylene propylene rubber is 4:2:7; and the weight ratio of activated styrene-butadiene-styrene block copolymer particles to elastomer premix is 1:4.
[0035] The preparation methods of the composite materials in the embodiments and comparative examples of this application include the following steps: Aromatic polycarbonate, epoxidized polybutadiene, norbornene copolymer, dioctadecyl thiodipropionate, tris(2,4-di-tert-butylphenyl) phosphite, glyceryl monostearate, polyethylene wax and silicone masterbatch were mixed in proportion and then mixed at high speed at 140°C for 12 min to obtain a premix. The premix, impact enhancer, wollastonite whiskers and nano-silica are mixed and melt-blended in a twin-screw extruder at an extrusion temperature of 260℃, a screw speed of 300r / min and a screw length-to-diameter ratio of 44:1. The mixture is then stretched, water-cooled and pelletized.
[0036] The aromatic polycarbonate has a weight-average molecular weight of 30,000 and a melt flow rate of 8 g / 10 min; the wollastonite whiskers and the nano-silica both have a particle size of 800 mesh.
[0037] The component ratios of the impact-resistant polycarbonate composite materials of Examples 1-5 of this application are shown in Table 1: Table 1 The component ratios of the plastic alloys in Comparative Examples 1-6 of this application are shown in Table 2: Table 2 The component ratios and preparation methods of Comparative Example 6 are basically the same as those of Example 1, except that talc powder is used in Comparative Example 6 instead of an impact synergist.
[0038] The component ratios of the plastic alloys in Comparative Examples 7-12 of this application are shown in Table 3: Table 3 The composite materials prepared in Examples 1-6 and Comparative Examples 1-11 were subjected to performance tests. The test items included: (1) Cantilever beam notched impact strength: The specimen was placed in a standard environment and a cantilever beam impact tester was used. The notched specimen was placed and the pendulum was released to impact it. The impact energy was recorded. The specimen size was 80×10×4mm, the notch type was V, and the pendulum energy was 2.75J. The temperature was 23℃. (2) Low temperature cantilever beam notched impact strength: The specimen was placed in a -20℃ low temperature chamber for constant temperature treatment for 2h. It was then quickly transferred to a low temperature impact tester for testing. The low temperature impact strength was recorded. The specimen size was 80×10×4mm and the notch type was V. (3) Simply supported beam unnotched impact strength: An unnotched specimen was used. The specimen was supported in a simply supported beam mode. The pendulum impacted the middle of the specimen and the energy required for the specimen to break was measured. The specimen size was 80×10×4mm, the span was 60mm, and the pendulum energy was 5.5J.
[0039] The performance test results of Examples 1-6 and Comparative Examples 1-11 of this application are shown in Table 4: Table 4 Comparative test results show that the impact-resistant polycarbonate composites prepared in Examples 1-6 of this application exhibit good overall performance in room temperature impact, low temperature impact, and unnotched impact. Example 1 shows the best overall performance, and by appropriately proportioning the components, it can effectively meet the required performance requirements. Comparative Examples 1-5 lack key components, resulting in weak synergistic effects, decreased interfacial bonding and stress transfer capabilities, and a significant reduction in all three impact properties. Comparative Example 6 did not activate and modify the styrene-butadiene-styrene block copolymer particles, leading to poor material interfacial compatibility and an inability to fully utilize the toughening synergistic effect, resulting in significantly lower impact performance than the examples. Comparative Examples 7-11, due to excessive addition of a single component, are prone to problems such as uneven system dispersion, increased internal stress, or component separation, also resulting in significantly inferior room temperature, low temperature, and unnotched impact toughness compared to the examples. In summary, the component proportions, raw material combinations, and modification processes specified in this invention can effectively improve the impact toughness of polycarbonate composites at room temperature and low temperatures. The absence of any component, lack of surface activation, or excessive addition can easily lead to a significant decrease in the impact performance of the polycarbonate composites.
[0040] The preferred embodiments of this application have been described in detail above, but the invention of this application is not limited to the embodiments described. Those skilled in the art can make various equivalent modifications or substitutions without departing from the spirit of this application, and these equivalent modifications or substitutions are all included within the scope defined by the claims of this application.
Claims
1. An impact-resistant polycarbonate composite material, characterized in that, By weight, the raw materials comprise the following components: 60-75 parts polycarbonate resin, 6-13 parts impact synergist, 5-9 parts compatibilizer, 1-3 parts antioxidant, 2-6 parts lubricant, and 3-6 parts toughening filler; The raw materials for preparing the impact synergist include styrene-butadiene-styrene block copolymer particles, polymethyl methacrylate, amino-modified silicone oil, and maleic anhydride-grafted ethylene propylene rubber.
2. The impact-resistant polycarbonate composite material according to claim 1, characterized in that, The preparation method of the impact-resistant synergist includes the following steps: The styrene-butadiene-styrene block copolymer particles and silane coupling agent dry powder were mixed and then continuously stirred at 1200-1600 r / min for 0.5-1 h to activate the mixture. The polymethyl methacrylate, the amino-modified silicone oil, and the maleic anhydride-grafted ethylene propylene rubber are mixed and dispersed at 120-140°C for 10-20 minutes to obtain an elastomer premix. The activated styrene-butadiene-styrene block copolymer particles and the elastomer premix are mixed and melt-blended at 165-195°C, and then extruded and granulated by screw extrusion to obtain the impact synergist.
3. The impact-resistant polycarbonate composite material according to claim 2, characterized in that, The particle size of the styrene-butadiene-styrene block copolymer particles is 400-800 mesh. The weight ratio of the styrene-butadiene-styrene block copolymer particles to the silane coupling agent dry powder is 1:0.1-0.2; The weight ratio of polymethyl methacrylate, amino-modified silicone oil and maleic anhydride-grafted ethylene propylene rubber is 4:1-2:6-8; the weight ratio of the activated styrene-butadiene-styrene block copolymer particles and the elastomer premix is 1:2.5-4.
5.
4. The impact-resistant polycarbonate composite material according to claim 2, characterized in that, The polycarbonate resin is an aromatic polycarbonate with a weight-average molecular weight of 25,000-40,000 and a melt flow rate of 5-9 g / 10 min.
5. The impact-resistant polycarbonate composite material according to claim 2, characterized in that, The compatibilizer is a combination of epoxidized polybutadiene and norbornene copolymer, wherein the weight ratio of epoxidized polybutadiene to norbornene copolymer is 4-7:
2.
6. The impact-resistant polycarbonate composite material according to claim 2, characterized in that, The lubricant is a combination of glyceryl monostearate, polyethylene wax and silicone masterbatch, wherein the weight ratio of glyceryl monostearate, polyethylene wax and silicone masterbatch is 2:3:6-10.
7. The impact-resistant polycarbonate composite material according to claim 2, characterized in that, The antioxidant is a combination of dioctadecyl thiodipropionate and tris(2,4-di-tert-butylphenyl) phosphite, wherein the weight ratio of dioctadecyl thiodipropionate to tris(2,4-di-tert-butylphenyl) phosphite is 1:2-4.
8. The impact-resistant polycarbonate composite material according to claim 2, characterized in that, The toughening filler is a combination of wollastonite whiskers and nano-silica, wherein the weight ratio of wollastonite whiskers to nano-silica is 3-5:1, and the particle size of both wollastonite whiskers and nano-silica is 800-1250 mesh.
9. A method for preparing an impact-resistant polycarbonate composite material as described in any one of claims 1-8, characterized in that, Includes the following steps: The polycarbonate resin, the compatibilizer, the antioxidant, and the lubricant are mixed in proportion and then mixed at high speed at 130-150°C for 10-15 minutes to obtain a premix. The premix, the impact synergist, and the toughening filler are mixed and melt-blended in a twin-screw extruder at an extrusion temperature of 250-280°C, a screw speed of 250-350 r / min, and a screw length-to-diameter ratio of 40-48:
1. After stretching, water cooling, and pelletizing, the impact-resistant polycarbonate composite material is obtained.