Development and Application of Enhanced Toughness and Fill Masterbatch

Add time:2020-11-10


  With the rapid development of polymer science and technology, society's demands for polymer materials are becoming increasingly higher. Single polymer materials often fail to meet these requirements, necessitating the modification of polymer materials using alloying, blending, and compounding (referred to as abc) methods to maximize the characteristics of each component and impart superior qualities not possessed by single materials. The research and development of high-performance composite materials have become an important part of contemporary high technology and a major development trend in polymer materials, moving towards higher specific strength, higher specific modulus, higher toughness, high-temperature resistance, corrosion resistance, and wear resistance. Among them, polymer composite materials that enhance both toughness and strength have become a research hotspot in engineering plastics modification. However, from the perspective of materials science, strength and toughness are two particularly important yet contradictory mechanical properties of structural materials. The problem of simultaneously enhancing and toughening materials has been one of the important challenges yet to be solved in polymer materials science. Generally, filling rigid particles into a polymer matrix can effectively improve the material's strength, stiffness, and dimensional stability, but it also easily leads to increased polymer brittleness. While using elastomers to toughen thermoplastic plastics enhances toughness, it significantly reduces the material's stiffness, strength, and operating temperature. Using mechanical blending to simultaneously add rigid particles and rubber to form a polymer/elastomer/filler three-phase composite material can balance the contradiction between material rigidity and toughness within a certain range, but it cannot simultaneously achieve high-strength, high-performance polymer materials. Therefore, since the 1980s, a new approach to modifying polymers using non-elastomers (rigid particles) has been proposed. Under the support of the National Natural Science Foundation of China's key project, our laboratory was the first in China to conduct basic and applied research on polymer non-elastomer toughening. After years of effort, we have conducted systematic and in-depth research on inorganic rigid particle replacement of rubber toughening polymer composites and their toughening mechanisms, achieving breakthrough progress. Theoretically, we have clarified that in addition to the requirements for the particle size and particle size distribution of inorganic rigid particle toughening polymers, a new structural form must be proposed for its interfacial structure, that is, a flexible interfacial phase with good interfacial bonding and a certain thickness embedded around uniformly dispersed rigid particles. This allows for the initiation of crazing and termination of crack propagation when the material undergoes damage, and under certain morphological structural conditions, it can also initiate matrix shear yielding, thereby dissipating a large amount of impact energy. However, the above interfacial phase structures are formed during reactive extrusion processing, resulting in unstable material properties, long operation cycles, and difficulty in control. Therefore, it is difficult to bring the high-rigidity, high-toughness polymer composite materials developed in the laboratory into the industrial production stage. For this reason, with the support of the National "863" Program, the concept of preparing high-performance composite materials using enhanced toughening filler masterbatches was proposed, and under the guidance of this concept, polypropylene enhanced toughening filler masterbatches and toughening agent masterbatches for nylon modification were successfully developed. The development of enhanced toughening filler masterbatches involves numerous interdisciplinary fields: interfacial molecular design, modification of the physical and chemical properties of filler and polymer surfaces, surface property characterization, synthesis of interfacial compatibilizers, interfacial interactions, rheological behavior, filler dispersion rate and degree of dispersion, polymer crystallization behavior, material mechanical properties, and enhanced toughening mechanisms. Therefore, it is a very complex yet very meaningful undertaking. After studying the relationship between the surface properties of inorganic particles, the microstructure of the dispersed phase, and the mechanical properties of the material, we have summarized the four basic principles for preparing high-performance polymer composite materials using enhanced toughening filler masterbatches and creatively solved the key technical problem of the contradiction between uniform dispersion and interfacial bonding of inorganic particles. Through the use of highly efficient interfacial modifiers and the application of reactive extrusion processing methods, the concept of in-situ wetting and coating of inorganic rigid particles with a small amount of rubber has been realized, and a novel polymer/inorganic particle "shell-core" structure enhanced toughening filler masterbatch with monodisperse inorganic particles as the core and a small amount of elastomer as the shell has been successfully developed. Enhanced toughening filler masterbatches have the following characteristics: 1. The addition of filler masterbatches not only significantly improves the processing rheological properties of the polymer but also allows for rapid and uniform redispersion in the polymer matrix. Therefore, the compounding process of filler masterbatches and polymers can be simplified from secondary processing to primary processing. 2. The addition of filler masterbatches simultaneously improves the modulus and toughness of the polymer composite material, i.e., both the modulus and toughness of the material exceed the values of the polymer itself, resulting in a composite material that is both tough and rigid. Enhanced toughening effect of filler masterbatches on polypropylene: Mechanical property data of polypropylene modified with filler masterbatches (40 wt%) Homopolymer PP Masterbatch filled Homopolymer PP Copolymer PP Masterbatch filled Copolymer PP Notched impact strength (J/m) 20 80-90 150 300-400 Tensile strength (MPa) 30 25-30 25 20-25 Flexural strength (MPa) 35 40-50 30 30-36 Flexural modulus (GPa) 1.0 2.0~2.5 0.8 1.5-2.0 Among the numerous commercially available filler masterbatches and research reports at home and abroad, there have been no reports on filler masterbatches of highly dispersed, simultaneously enhanced and toughened polymer materials. Its successful development has contributed to the improvement of the inorganic rigid particle enhanced toughening polymer interface structure model and the level of composite material interface design and control, and will open up new avenues for upgrading China's large-volume general-purpose plastics to engineering plastics and further enhancing the performance of engineering plastics, expanding new fields for the application of polymer materials, and creating its due social and economic benefits. Currently, enhanced toughening filler masterbatches can be used to modify polypropylene and polyethylene plastics, simultaneously improving the rigidity and toughness of the materials and expanding their application range. For example, the modified polyolefin materials can be used in automotive and motor vehicle parts, household appliance casings, electric tool boxes, etc.

 

 

 

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