Modified resin powder filled master batch as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of composite materials, and particularly relates to a modified resin powder filling master batch and a preparation method and application thereof.The filling master batch takes recycled waste circuit board epoxy resin as a matrix, modified resin powder is obtained after coupling agent modification treatment, and efficient recycling of waste resources is achieved. Through synergistic toughening modification of linear low-density polyethylene and maleic anhydride grafted polyethylene, the mechanical properties of the material are significantly improved. Meanwhile, activated aluminum oxide and nano silicon dioxide are adopted, so that the heat resistance and the size stability of the material are improved. In addition, by optimizing the anti-aging agent and the lubricant, the processability and durability of the material are further improved. The filling master batch has the excellent characteristics of light specific gravity, high strength, good heat resistance, strong corrosion resistance and the like, has the advantages of environmental protection and cost, not only solves the problem of recovery of waste resin, but also remarkably reduces the production cost, conforms to the development concept of green manufacturing, and can be widely applied to the fields of electronic packaging, automobile parts and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of composite materials, and in particular relates to a modified resin powder filling masterbatch, a preparation method and application thereof. Background Art

[0002] Modified resin filler masterbatch is a granular composite material, which is made by compounding functional additives with resin matrix and is widely used in the production of plastic products. Its core value lies in achieving cost optimization through high proportion of filling, while giving the base material enhanced performance or special functions.

[0003] In the field of PCB manufacturing, epoxy resin, as a key substrate, is still mainly disposed of by landfill or incineration, which not only causes waste of resources, but also produces harmful pollutants, posing a serious threat to the environment.

[0004] In recent years, with the tightening of environmental protection regulations, the growing demand for high-performance materials and the industry's demands for cost reduction and efficiency improvement, the application of modified resin filler masterbatches in the field of plastic modification has continued to expand, and the market has shown a significant growth trend.

[0005] Therefore, there is a need for a modified resin filled masterbatch that has environmentally friendly properties and conforms to industry development trends. Summary of the invention

[0006] Based on this, it is necessary to provide a modified resin powder filling masterbatch, a preparation method and its application. The filling masterbatch has excellent heat resistance and mechanical strength, outstanding high-frequency electrical properties, strong environmental adaptability, and meets the development requirements of the green economy.

[0007] The technical solution of the present invention to solve the above technical problems is as follows:

[0008] A modified resin powder filling masterbatch, comprising the following components in parts by weight:

[0009] Component a, 55-85 parts of modified epoxy resin, with an epoxy value of 0.45-0.55eq / 100g and a glass transition temperature Tg ≥ 120°C;

[0010] Component b, 10-40 parts of linear low-density polyethylene, with a melt index of 2-5 g / 10 min;

[0011] Component c, maleic anhydride grafted polyethylene 5-15 parts, grafting rate ≥1.0%, melt index 2-3g / 10min;

[0012] Component d, 3-8 parts of activated alumina, specific surface area ≥150m 2 / g, average particle size ≤5μm;

[0013] Component e, 0.5 - 2 parts of compound antioxidant, which is composed of phosphite antioxidant and phenolic antioxidant;

[0014] Component f, 1 - 4 parts of calcium stearate, with a purity ≥ 98%;

[0015] Component g, 1 - 4 parts of polyethylene wax, with a molecular weight of 2000 - 5000;

[0016] Component h, 2 - 6 parts of nano - silica, with a particle size of 20 - 50 nm, and the surface is modified by silane coupling agent.

[0017] Optionally, in an embodiment of the present invention, for the component a, the modified epoxy resin is bisphenol A epoxy resin modified by silane coupling agent KH - 550 or KH - 560, which forms a three - dimensional cross - linked network structure after curing, and the bisphenol A epoxy resin is obtained by recycling waste printed circuit boards.

[0018] Optionally, in an embodiment of the present invention, for the component b, the density of linear low - density polyethylene is 0.915 - 0.925 g / cm 3 , and the melt index difference from maleic anhydride - grafted polyethylene ≤ 1 g / 10 min.

[0019] Optionally, in an embodiment of the present invention, for the component h, the surface grafting rate of nano - silica is 2 - 2.5%, and the mass ratio with activated alumina is 0.8 - 1.2:1.

[0020] Optionally, in an embodiment of the present invention, for the component e, in the compound antioxidant, the proportion of phosphite is 0.1 - 0.27%, and the proportion of phenolic is 0.2 - 0.53%.

[0021] A preparation method of a modified resin powder - filled masterbatch specifically includes the following steps:

[0022] Step S1, ultrasonically disperse component h and silane coupling agent in an ethanol solution, and reflux and react at 80 °C for 4 - 6 h to ensure that the surface grafting rate ≥ 2.0%;

[0023] Step S2, first mix component a, d and h treated in step S1 at 90 - 100 °C and 500 rpm for 5 minutes to form an epoxy - nano composite matrix, then add component b, c, adjust the temperature to 70 °C and mix at 1000 rpm for 10 minutes to obtain a premixed material;

[0024] Step S3, transfer the premixed material to a twin - screw extruder for melt blending. Pre - mix component e, f, g at 80 - 90 °C and 800 rpm for 3 minutes and add them uniformly through the side feeding port of the twin - screw extruder;

[0025] Step S4: The melt-blended material is processed by water-cooled strand pelletizing or underwater pelletizing, and then undergoes gradient cooling. After pelletizing, it is dried until the water content ≤ 0.05%.

[0026] Step S5: The dried masterbatch is screened, and after surface passivation treatment of the screened masterbatch, a filled masterbatch is obtained.

[0027] Optionally, in an embodiment of the present invention, the twin-screw extruder in step S3 is divided into three zones for temperature control, and the temperature is set at 160 - 190 °C.

[0028] Optionally, in an embodiment of the present invention, the aspect ratio of the twin-screw extruder in step S3 is 40:1 - 48:1, and the pressure in the vacuum degassing section is -0.05 MPa to -0.08 MPa.

[0029] The application of a modified resin powder-filled masterbatch in an electronic packaging material enables the composite material to have a peel strength of 8 - 12 N / cm to copper foil and a dielectric constant ≤ 3.2 at a frequency of 1 MHz.

[0030] The application of a modified resin powder-filled masterbatch in automotive lightweight components. After the parts are aged at 180 °C for 500 h, the bending strength retention rate ≥ 85%, and the tensile strength ≥ 40 MPa at a high temperature of 150 °C.

[0031] Advantages of the present invention:

[0032] A modified resin powder-filled masterbatch, its preparation method and application disclosed by the present invention

[0033] 1. Modified by bisphenol A epoxy resin and silane coupling agent to form a three-dimensional cross-linked network, endowing the material with high heat distortion temperature and dimensional stability; the synergistic effect of activated alumina and surface-grafted nano-silica enhances rigidity and wear resistance; the melt index difference between linear low-density polyethylene and maleic anhydride-grafted polyethylene ≤ 1 g / 10 min, ensuring interface compatibility and achieving high notched impact strength.

[0034] 2. The surface grafting of nano-silica reduces polarity and inhibits dipole polarization, meeting the requirements of high-frequency circuit substrates for signal transmission rate and stability; activated alumina adsorbs impurity ions, combined with the surface passivation treatment of zinc stearate, blocking the leakage current path.

[0035] 3. The composite antioxidant synergistically inhibits thermal-oxidative degradation and maintains excellent mechanical properties in high-temperature and high-humidity environments;

[0036] The synergistic effect of the epoxy-nano composite matrix and linear low-density polyethylene reduces the dimensional deformation caused by temperature fluctuations.

[0037] 4. By using recycled bisphenol A epoxy resin, the use of virgin resin is reduced, carbon emissions are lowered, meeting the requirements of circular economy; the lightweight property can reduce raw material consumption, especially suitable for automotive lightweight components; in terms of process, low-temperature premixing is adopted to reduce energy consumption and avoid resin pre-curing. Through high-shear kneading and vacuum degassing, efficient dispersion and low porosity are achieved, reducing subsequent processing defects. The formulation design is compatible with various molding processes such as injection molding, extrusion, and blow molding. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for use in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present application, and thus should not be regarded as limiting the scope. For those of ordinary skill in the art, other related drawings can be obtained based on these drawings without creative efforts.

[0039] Figure 1 Schematic flow diagram of a preparation method of a modified resin powder-filled masterbatch for Embodiment 1 of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0040] To facilitate the understanding of the present invention, the present invention will be described more comprehensively below with reference to the relevant drawings. Preferred embodiments of the present invention are shown in the drawings. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present invention more thorough and comprehensive.

[0041] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the technical field to which the present invention belongs. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more of the related listed items.

[0042] Based on the increasingly strict environmental protection regulations, the growing demand for high-performance materials, and the industry's demands for cost reduction and efficiency improvement, the application of modified resin-filled masterbatches in the field of plastic modification continues to expand. It is necessary to develop a modified resin powder-filled masterbatch, a corresponding preparation method, and its application. The specific solutions are as follows:

[0043] Embodiment 1

[0044] A modified resin powder-filled masterbatch includes the following components by weight:

[0045] Component a, 55 - 85 parts of modified epoxy resin, with an epoxy value of 0.45 - 0.55 eq / 100g and a glass transition temperature Tg ≥ 120°C;

[0046] Component b, 10 - 40 parts of linear low density polyethylene, with a melt index of 2 - 5 g / 10 min;

[0047] Component c, 5 - 15 parts of maleic anhydride grafted polyethylene, with a grafting rate ≥ 1.0%, and a melt index of 2 - 3 g / 10 min;

[0048] Component d, 3 - 8 parts of activated alumina, with a specific surface area ≥ 150 m 2 / g and an average particle size ≤ 5 μm;

[0049] Component e, 0.5 - 2 parts of compound antioxidant, which is composed of a phosphite antioxidant and a phenolic antioxidant;

[0050] Component f, 1 - 4 parts of calcium stearate, with a purity ≥ 98%;

[0051] Component g, 1 - 4 parts of polyethylene wax, with a molecular weight of 2000 - 5000;

[0052] Component h, 2 - 6 parts of nano - silica, with a particle size of 20 - 50 nm, and the surface is modified by a silane coupling agent.

[0053] Component a, as a rigid matrix, provides high strength, high heat resistance and dimensional stability. An epoxy value of 0.45 - 0.55 eq / 100 g ensures sufficient cross - linking reaction activity, and Tg ≥ 120 °C endows the material with high - temperature load - bearing capacity. If the modified epoxy resin is less than 55 parts, the overall rigidity of the material is insufficient, Tg is lower than 120 °C, and the high - temperature deformation resistance decreases; the adhesion performance and mechanical strength are significantly reduced. If the modified epoxy resin is more than 85 parts, the system viscosity increases sharply, resulting in processing difficulties, increased brittleness and easy cracking, and uneven dispersion of other components may cause phase separation. The modified epoxy resin is a bisphenol A type epoxy resin modified by silane coupling agent KH - 550 or KH - 560, and a three - dimensional cross - linked network structure is formed after curing. The bisphenol A type epoxy resin is obtained by recycling waste printed circuit boards. In this embodiment, the silane coupling agent is preferably KH - 560. For the specific method of recycling epoxy resin and modifying it, reference can be made to the Chinese invention patent CN117466602B that has been applied for.

[0054] If the formulation needs to enhance the filler dispersion, or needs to produce a synergistic compatibilization effect through the amino group and the anhydride group of maleic anhydride grafted polyethylene, select the silane coupling agent KH - 550;

[0055] If the formulation requires higher heat - resistant stability or the product needs to be in contact with a humid environment for a long time, its epoxy group can improve the chemical stability of the resin - filler interface, select the silane coupling agent KH - 560;

[0056] The epoxy value is 0.45 - 0.55 eq / 100g, controlling the crosslinking density to ensure sufficient mechanical strength and chemical resistance. When it is too low, crosslinking is insufficient and the material becomes brittle; when it is too high, it may lead to over-crosslinking and reduce toughness.

[0057] Component b, the flexible toughening phase, absorbs impact energy through molecular chain entanglement, reducing the brittleness of the material. The melt index is 2 - 5 g / 10min to balance processability and mechanical properties. When the linear low-density polyethylene is less than 10 parts, the flexibility of the material is insufficient, the impact strength decreases, and the processing fluidity becomes poor. When the linear low-density polyethylene is higher than 40 parts, the heat resistance is significantly reduced, and the compatibility with epoxy resin deteriorates, resulting in interfacial defects. The density of the linear low-density polyethylene is 0.915 - 0.925 g / cm 3 , while ensuring moderate crystallinity, endows the material with good toughness and impact resistance, avoiding brittleness caused by excessive crystallization, thus forming a complement to the rigidity of epoxy resin and enhancing the comprehensive mechanical properties of the composite material. It has a moderate melt strength. Combining with its melt index, it ensures uniform mixing with other components during processing, avoiding insufficient flow or excessive degradation, improving the processing stability and molding efficiency of the masterbatch, helping to control the overall density of the filled masterbatch, and avoiding the finished product from being too heavy due to the addition of activated alumina and nano-silica. Under the synergistic effect of maleic anhydride grafted polyethylene, the linear low-density polyethylene and epoxy resin form a more uniform phase structure, reducing phase separation and improving interfacial bonding force, thereby enhancing the overall strength and durability of the material; the melt index difference between the linear low-density polyethylene and maleic anhydride grafted polyethylene ≤ 1 g / 10min can reduce the shear force fluctuation during processing, reduce the risk of melt fracture, improve production efficiency and product consistency. The synergistic flow of the two helps to form a tighter interfacial bond, improving the tensile strength and impact toughness of the composite material, making the melting and cooling processes of the two tend to be synchronized at the processing temperature, reducing internal stress caused by thermal shrinkage differences, and enhancing the dimensional stability and warpage resistance of the product. The melt index is 2 - 5 g / 10min. If the melt index is too low, extrusion will be difficult; if it is too high, the material strength will be insufficient.

[0058] Component c, as an interfacial compatibilizer, forms a chemically bonded epoxy-PE graft copolymer through the ring-opening reaction of the anhydride group and the epoxy group. When the maleic anhydride grafted polyethylene is less than 5 parts, the interfacial compatibility is insufficient, resulting in a 20 - 30% decrease in tensile strength and obvious phase separation. When the maleic anhydride grafted polyethylene is higher than 15 parts, the excessive anhydride groups may cause pre-curing of the epoxy resin, and the melt flow rate decreases, affecting processing. The grafting rate ≥ 1.0% ensures sufficient polar groups to improve the compatibility between epoxy resin and polyethylene. A low grafting rate will lead to poor interfacial bonding and an increased risk of delamination; the melt index is 2 - 3 g / 10min to match the processing performance of the matrix resin and avoid uneven dispersion.

[0059] Component d, specific surface area ≥ 150 m 2 / g, forms a hydrogen bond network with the polar groups of the resin through surface hydroxyl groups, improving thermal conductivity and wear resistance. When the amount of activated alumina is less than 3 parts, the improvement of dielectric properties is limited and the thermal conductivity does not meet the expectations. When the amount of activated alumina is more than 8 parts, the impact strength decreases by more than 30% due to filler agglomeration, and the melt viscosity increases by 50%, affecting molding. The average particle size ≤ 5 μm is conducive to uniform dispersion and avoids stress concentration; the surface of activated alumina can also be modified by silane coupling agent KH-560 to enhance the interfacial bonding with the resin. In terms of flame retardancy, activated alumina will absorb heat and decompose to generate an Al2O3 layer, delaying combustion.

[0060] Component e, phosphite captures peroxy radicals, and phenols provide hydrogen atoms to terminate the chain reaction, synergistically prolonging the thermal oxygen aging life. When the compound antioxidant is less than 0.5 part, the thermal oxygen aging life is shortened by more than 50%. When the compound antioxidant is more than 2 parts, the antioxidant migrates and precipitates, causing the surface to become sticky and possibly inhibiting the curing reaction. In the compound antioxidant, the proportion of phosphite is 30 - 40%, and the proportion of phenols is 60 - 70%; the phosphite antioxidant is antioxidant 168, and the phenolic antioxidant is antioxidant 1010. The compound antioxidant delays the thermal oxygen degradation of the material through the free radical capture and peroxide decomposition mechanisms. Component e plays an anti-aging role for the material. Component e also includes 0.2 - 0.5 part of benzotriazole ultraviolet absorber to improve the ultraviolet protection performance. When component e also includes the above ultraviolet absorber, the proportion of component a needs to be adjusted appropriately.

[0061] Component f, metal soap lubricant, reduces the friction coefficient between the resin and the filler through the long-chain alkyl groups of the molecule, improving the demolding property. When calcium stearate is less than 1 part, demolding is difficult, the extrusion torque increases by 30%, and the surface roughness of the product is large. When calcium stearate is more than 4 parts, it weakens the filler-resin interface, reduces the tensile strength, and oil spot defects appear on the surface. Calcium stearate reduces sticking to the mold, reduces impurity interference, ensures stable lubrication effect, captures residual acidic substances in the resin or filler, such as unreacted maleic anhydride, and prevents corrosion of equipment or degradation of materials.

[0062] Component g, polyethylene wax forms an interfacial lubricating film through melting and spreading, reducing the melt viscosity and balancing lubricity and dispersibility. When polyethylene wax is less than 1 part, the melt fracture phenomenon is obvious and the extrusion pressure fluctuates. When polyethylene wax is more than 4 parts, the surface friction coefficient of the product decreases excessively and the interlayer peel strength decreases. If the molecular weight of polyethylene wax is too low, it is easy to volatilize, and if it is too high, it is difficult to disperse.

[0063] Component h forms Si-O-epoxy bonds through the modification of the surface with a silane coupling agent, and improves the flexural modulus and dielectric properties through the nano effect. When the content of nano-silica is less than 2 parts, the improvement of wear resistance is limited, and the anti-creep performance does not meet the design index. When the content of nano-silica is higher than 6 parts, the notch impact strength decreases due to agglomerates, and the melt flow rate decreases. In this embodiment, the surface grafting rate of nano-silica is 2-2.5%, and the preferred mass ratio of nano-silica to activated alumina is 1:1-2. When used for electronic packaging materials, the mass ratio of nano-silica to activated alumina is 1:1.2. When used for automotive parts requiring flame retardant properties, the mass ratio of nano-silica to activated alumina is 1:2. When used for high-flow thin-walled products, the mass ratio of nano-silica to activated alumina is 1:1.

[0064] This formulation is modified by bisphenol A epoxy resin and a silane coupling agent to form a three-dimensional cross-linked network, endowing the material with a high heat distortion temperature and dimensional stability; the synergistic effect of activated alumina and surface-grafted nano-silica enhances rigidity and wear resistance; the melt index difference between linear low-density polyethylene and maleic anhydride-grafted polyethylene is ≤1 g / 10 min, ensuring interfacial compatibility and achieving high notch impact strength. The surface grafting of nano-silica reduces polarity and inhibits dipole polarization, meeting the requirements of high-frequency circuit boards for signal transmission rate and stability; activated alumina adsorbs impurity ions, combined with the surface passivation treatment of zinc stearate to block the leakage current path, and the composite antioxidant synergistically inhibits thermal oxygen degradation, maintaining excellent mechanical properties in high-temperature and high-humidity environments; the synergistic effect of the epoxy-nano composite matrix and linear low-density polyethylene reduces the dimensional deformation caused by temperature fluctuations.

[0065] On the other hand, this formulation reduces the use of virgin resin and carbon emissions, meeting the requirements of circular economy; the lightweight characteristic can reduce raw material consumption, especially suitable for automotive lightweight parts; in terms of process, low-temperature premixing is adopted to reduce energy consumption and avoid resin pre-curing. Through high-shear kneading and vacuum degassing, efficient dispersion and low porosity are achieved, reducing subsequent processing defects. The formulation design is suitable for various molding processes such as injection molding, extrusion, and blow molding.

[0066] Example 2

[0067] This example discloses a preparation method of a modified resin powder-filled masterbatch, which specifically includes the following steps:

[0068] Step S1, ultrasonically disperse component h and a silane coupling agent in an ethanol solution, and reflux at 80 °C for 4-6 h to ensure that the surface grafting rate ≥2.0%;

[0069] Specifically, step S1 is the pretreatment step of nano-silica. Component h and silane coupling agent KH-560 are ultrasonically dispersed in an ethanol solution and then left to hydrolyze for 2 hours. The ethanol solution is a mixed solvent of ethanol:water at 4:1, and acetic acid is used to adjust the pH to 4.5 - 5.5. The ultrasonic dispersion parameters are 40 kHz and 30 minutes. The silane coupling agent KH-560 is 2.5 - 3% of component h.

[0070] In step S2, first, components a, d and h treated in step S1 are mixed at 90 - 100 °C and 500 rpm for 5 minutes to form an epoxy-nano composite matrix, and then components b and c are added. The temperature is adjusted to 70 °C and mixed at 1000 rpm for 10 minutes to obtain a premixed material.

[0071] First add components a, d, and h, and then add components b and c to avoid premature melting of polyethylene to wrap the filler.

[0072] In step S3, the premixed material is transferred to a twin-screw extruder for melt blending. First, components e, f, and g are pre-mixed at 80 - 90 °C and 800 rpm for 3 minutes and added uniformly through the side feeding port of the twin-screw extruder.

[0073] Then components a, b, c, d, and h are added from the main inlet. The temperature of the melting section is set at 160 - 190 °C, and then the premixed components e, f, and g are added from the middle of the melting section to avoid staying in the high-temperature range for too long. Components e are added separately from components f and g.

[0074] In step S4, the melt-blended material is processed by water-cooled strand pelletizing or underwater pelletizing, and then gradient cooling is carried out. After pelletizing, it is dried to a water content ≤ 0.05%.

[0075] Specifically, gradient cooling is first slow cooling with warm water at 50 - 60 °C to reduce internal stress, and the cooling rate ≤ 5 °C / min. Then it is water-cooled and shaped at 25 °C. After pelletizing, it is vacuum-dried at 50 °C - 60 °C for 4 - 6 h.

[0076] In step S5, the dried masterbatch is screened. After the screened masterbatch is subjected to surface passivation treatment, a filled masterbatch is obtained. The screening requirements of this embodiment are: sieving out particles with a particle size > 2 mm, < 0.3 mm and an aspect ratio > 1.5; immersing the screened masterbatch in a 0.3 - 0.5% silicone powder ethanol solution for 10 - 15 seconds or using atomized spraying, drying at 80 °C, and then performing secondary drying through a fluidized bed, that is, passivation treatment, to improve the fluidity and moisture resistance of the masterbatch. Among them, the temperature of the fluidized bed is 90 - 100 °C and the time is 15 minutes.

[0077] The twin-screw extruder in step S3 is divided into three zones for temperature control, and the temperature is set at 160 - 190 °C. The twin-screw extruder includes zone 1, zone 2, and zone 3. Among them, during melt blending, the temperature of zone 1 is 160 °C, the temperature of zone 2 is 190 °C, and the temperature of zone 3 is 180 °C. There is a high-shear kneading block at the end of zone 2, and the residence time of the material is extended to 8 - 10 minutes to ensure the full dispersion of the nano-filler and activated alumina.

[0078] The ratio of the length to the diameter L / D of the twin-screw extruder in step S3 is 40:1 - 48:1, and the pressure in the vacuum degassing section is -0.05 MPa to -0.08 Mpa. Axial grooves are provided on the inner wall of the degassing section barrel to improve the degassing efficiency; the primary degassing is carried out when L / D is 15 - 20, and the pressure is -0.05 MPa; the main degassing is carried out when L / D is 35 - 40, and the pressure is -0.08 MPa.

[0079] This preparation method has high-precision interface modification and dispersion control, high thermal stability, and good processing safety for the formulation of Example 1. It can achieve efficient degassing, homogenize the melt structure, and the post-treatment process helps to improve the product performance. It combines the feasibility of large-scale production and the consistency of product performance.

[0080] Comparative Example 1

[0081] In this example, a modified resin powder-filled masterbatch includes the following components by weight:

[0082] Component a, 55 parts of modified epoxy resin;

[0083] Component b, 40 parts of linear low-density polyethylene;

[0084] Component c, 12 parts of maleic anhydride-grafted polyethylene;

[0085] Component d, 6 parts of activated alumina;

[0086] Component e, 1.2 parts of compound antioxidant;

[0087] Component f, 2 parts of calcium stearate;

[0088] Component g, 3 parts of polyethylene wax;

[0089] Component h, 5 parts of nano-silica.

[0090] Comparative Example 2

[0091] In this example, a modified resin powder-filled masterbatch includes the following components by weight:

[0092] Component a, 60 parts of modified epoxy resin;

[0093] Component b, 35 parts of linear low-density polyethylene;

[0094] Component c, 10 parts of maleic anhydride grafted polyethylene;

[0095] Component d, 5 parts of activated alumina;

[0096] Component e, 1 part of compound antioxidant;

[0097] Component f, 2 parts of calcium stearate;

[0098] Component g, 3 parts of polyethylene wax;

[0099] Component h, 4 parts of nano-silica.

[0100] Comparative Example 3

[0101] In this example, a modified resin powder filled masterbatch comprises the following components by weight parts:

[0102] Component a, 65 parts of modified epoxy resin;

[0103] Component b, 30 parts of linear low density polyethylene;

[0104] Component c, 10 parts of maleic anhydride grafted polyethylene;

[0105] Component d, 5 parts of activated alumina;

[0106] Component e, 1 part of compound antioxidant;

[0107] Component f, 2 parts of calcium stearate;

[0108] Component g, 3 parts of polyethylene wax;

[0109] Component h, 4 parts of nano-silica.

[0110] Comparative Example 4

[0111] In this example, a modified resin powder filled masterbatch comprises the following components by weight parts:

[0112] Component a, 70 parts of modified epoxy resin;

[0113] Component b, 25 parts of linear low density polyethylene;

[0114] Component c, 10 parts of maleic anhydride grafted polyethylene;

[0115] Component d, 5 parts of activated alumina;

[0116] Component e, 1 part of compound antioxidant;

[0117] Component f, 2 parts of calcium stearate;

[0118] Component g, 3 parts of polyethylene wax;

[0119] Component h, 4 parts of nano-silica.

[0120] Comparative Example 5

[0121] In this example, a modified resin powder filled masterbatch includes the following components by weight parts:

[0122] Component a, 75 parts of modified epoxy resin;

[0123] Component b, 20 parts of linear low density polyethylene;

[0124] Component c, 10 parts of maleic anhydride grafted polyethylene;

[0125] Component d, 5 parts of activated alumina;

[0126] Component e, 1 part of compound antioxidant;

[0127] Component f, 2 parts of calcium stearate;

[0128] Component g, 3 parts of polyethylene wax;

[0129] Component h, 4 parts of nano-silica.

[0130] Comparative Example 6

[0131] In this example, a modified resin powder filled masterbatch includes the following components by weight parts:

[0132] Component a, 80 parts of modified epoxy resin;

[0133] Component b, 15 parts of linear low density polyethylene;

[0134] Component c, 12 parts of maleic anhydride grafted polyethylene;

[0135] Component d, 6 parts of activated alumina;

[0136] Component e, 1.5 parts of compound antioxidant;

[0137] Component f, 2 parts of calcium stearate;

[0138] Component g, 3 parts of polyethylene wax;

[0139] Component h, 5 parts of nano-silica.

[0140] Comparative Example 7

[0141] In this example, a modified resin powder filled masterbatch includes the following components by weight parts:

[0142] Component a, 85 parts of modified epoxy resin;

[0143] Component b, 10 parts of linear low density polyethylene;

[0144] Component c, 15 parts of maleic anhydride grafted polyethylene;

[0145] Component d, 5 parts of activated alumina;

[0146] Component e, 1.5 parts of compound antioxidant;

[0147] Component f, 2 parts of calcium stearate;

[0148] Component g, 3 parts of polyethylene wax;

[0149] Component h, 4 parts of nano-silica.

[0150] The modified resin powder filled masterbatch prepared in Comparative Examples 1-7 was mixed with polyethylene resin. The mass ratio of the filled masterbatch to polyethylene resin was 1:1.5. After mixing evenly, it was extruded and pelletized by a twin-screw extruder and dried. Then, specimens (15×10×120) mm3 were obtained by injection molding for performance testing. The tensile performance was tested according to GB / T 1040—2006; the flexural performance was tested according to GB / T 9341—2008. The performance test data are shown in Table 1.

[0151] Table 1 Mechanical property data of Examples 1-7

[0152]

[0153] As can be seen from Table 1, as the epoxy resin content in Examples 1-7 increased from 55 parts to 85 parts, the tensile modulus and flexural modulus increased from 1.3 to 1.9 GPa and from 2.1 to 2.8 GPa, respectively, due to the high rigidity of the epoxy resin. However, excessive epoxy resin may lead to a decrease in tensile strength due to increased brittleness. As can be seen from Comparative Examples 6 and 7, the tensile strength decreased from 42.5 to 39.2 MPa. This phenomenon can be attributed to the decrease in the proportion of linear low-density polyethylene as a flexible carrier, which weakens the compatibility and interfacial interaction of the system.

[0154] Linear low-density polyethylene provides toughness. When its proportion decreases, as in Comparative Example 4 where Component b is 25 parts, it is necessary to improve the interfacial bonding through maleic anhydride grafted polyethylene. When Component c increases from 10 parts to 12 parts, the tensile strength is significantly restored.

[0155] When nano-silica, Component h is 5 parts, and activated alumina, Component d is 6 parts, act together, the flexural strength reaches a peak value of 57.3 MPa.

[0156] Example 8

[0157] This embodiment discloses the application of a modified resin powder filled masterbatch in the field of electronic packaging. The peel strength of the composite material to copper foil reaches 8 - 12 N / cm, and the dielectric constant at 1 MHz frequency is ≤ 3.2.

[0158] Example 9

[0159] This embodiment discloses the application of a modified resin powder filled masterbatch in the field of automotive parts. After the parts are aged at 180 °C for 500 h, the bending strength retention rate is ≥ 85%, and the tensile strength at 150 °C is ≥ 40 MPa.

[0160] The technical features of the above embodiments can be combined arbitrarily. For the sake of concise description, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered as the scope recorded in this specification.

[0161] The above embodiments only represent several embodiments of the present application. The description is relatively specific and detailed, but it cannot be understood as a limitation on the scope of the invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present application, several deformations and improvements can be made, and these all belong to the protection scope of the present application. Therefore, the protection scope of the patent of the present application should be subject to the appended claims.

Claims

1. A modified resin powder filled masterbatch, characterized in that, Comprising the following components by weight parts: Component a, 55 - 85 parts of modified epoxy resin, with an epoxy value of 0.45 - 0.55 eq / 100g and a glass transition temperature Tg ≥ 120 °C; Component b, 10 - 40 parts of linear low - density polyethylene, with a melt index of 2 - 5 g / 10min; Component c, 5 - 15 parts of maleic anhydride grafted polyethylene, with a grafting rate ≥ 1.0% and a melt index of 2 - 3 g / 10min; Component d, 3 - 8 parts of activated alumina, specific surface area ≥ 150 m 2 / g, average particle size ≤ 5 μm; Component e, 0.5 - 2 parts of compound antioxidant, which is composed of a phosphite antioxidant and a phenolic antioxidant; Component f, 1 - 4 parts of calcium stearate, with a purity ≥ 98%; Component g, 1 - 4 parts of polyethylene wax, with a molecular weight of 2000 - 5000; Component h, 2 - 6 parts of nano - silica, with a particle size of 20 - 50 nm, and the surface is modified by a silane coupling agent.

2. The modified resin powder-filled masterbatch according to claim 1, wherein For the said component a, the modified epoxy resin is a bisphenol A epoxy resin modified by silane coupling agent KH - 550 or KH - 560, which forms a three - dimensional cross - linked network structure after curing, and the bisphenol A epoxy resin is obtained by recycling waste printed circuit boards.

3. The modified resin powder-filled masterbatch according to claim 2, characterized in that, The component b, the density of the linear low-density polyethylene is 0.915 - 0.925 g / cm 3 , and the difference in melt index from the maleic anhydride grafted polyethylene ≤ 1 g / 10 min.

4. A modified resin powder filled masterbatch according to claim 1, characterized in that, For the said component h, the surface grafting rate of nano - silica is 2 - 2.5%, and the mass ratio with activated alumina is 0.8 - 1.2:

1.

5. The modified resin powder-filled masterbatch according to claim 1, wherein, For the said component e, in the compound antioxidant, the phosphite accounts for 0.1 - 0.27%, and the phenolic accounts for 0.2 - 0.53%.

6. A preparation method of a modified resin powder-filled masterbatch according to any one of claims 1-5, characterized in that, Specifically, it includes the following steps: Step S1, ultrasonically disperse component h and the silane coupling agent in an ethanol solution, and reflux react at 80 °C for 4 - 6 h to ensure that the surface grafting rate ≥ 2.0%; Step S2, first mix component a, d and h treated in step S1 at 100 - 110 °C and 500 rpm for 5 minutes to form an epoxy - nano composite matrix, then add component b, c, adjust the temperature to 70 °C and mix at 1000 rpm for 10 minutes to obtain a premixed material; Step S3, transfer the premixed material to a twin - screw extruder for melt blending. Pre - mix component e, f, g at 80 - 90 °C and 800 rpm for 3 minutes and uniformly add them through the side feeding port of the twin - screw extruder; Step S4, the melt - blended material is processed by water - cooling strand pelletizing or underwater pelletizing, and then undergoes gradient cooling, and after pelletizing, it is dried to a water content ≤ 0.05%; Step S5, screen the dried masterbatch, and after surface passivation treatment of the screened masterbatch, a filled masterbatch is obtained.

7. The preparation method of a modified resin powder filled masterbatch according to claim 6, characterized in that, The twin - screw extruder in step S3 is divided into three zones for temperature control, and the temperature is set at 190 - 210 °C.

8. The preparation method of a modified resin powder filled masterbatch according to claim 6, characterized in that, The aspect ratio of the twin - screw extruder in step S3 is 40:1 - 48:1, and the pressure in the vacuum degassing section is - 0.05 MPa to - 0.08 MPa.

9. Use of a modified resin powder-filled masterbatch according to any one of claims 1-8 in an electronic packaging material, characterized in that, The peel strength of the composite material against copper foil reaches 8 - 12 N / cm, and the dielectric constant at 1 MHz frequency ≤ 3.

2.

10. Use of a modified resin powder filled masterbatch according to any one of claims 1-8 in automotive lightweight components, characterized in that, After the parts are aged at 180 °C for 500 h, the bending strength retention rate ≥ 85%, and the tensile strength at 150 °C ≥ 40 MPa.

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