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CN-121973485-A - High-elastic degradable pick ball and preparation method thereof

CN121973485ACN 121973485 ACN121973485 ACN 121973485ACN-121973485-A

Abstract

The invention discloses a high-elastic degradable picoball and a preparation method thereof, comprising the steps of providing elastic master batches, and performing foaming treatment with a foaming agent to form microporous elastic core particles with closed pore or semi-closed pore structures; the method comprises the steps of preparing annular reinforcing bands from biodegradable fiber materials through winding or preforming, preparing hemispherical microporous elastic inner shells from first biodegradable materials through rotational molding, positioning the annular reinforcing bands at preset positions on the outer surfaces of the hemispherical microporous elastic inner shells, achieving pre-fixing through heating or bonding, providing second biodegradable materials, forming hemispherical compact outer shells on the outer surfaces of the two hemispherical microporous elastic inner shells through rotational molding, and accordingly obtaining hemispherical composite bodies with inner shells, reinforcing bands and outer shells, aligning and welding the two hemispherical composite bodies to form high-elasticity degradable picoballs, and achieving high-elasticity performance and degradability.

Inventors

  • LIU YUE
  • ZHONG RONGDONG
  • RAN JINCHENG
  • LI TONGBING
  • Gu Yuanze

Assignees

  • 东莞市平客体育用品有限公司

Dates

Publication Date
20260505
Application Date
20260323

Claims (10)

  1. 1. The preparation method of the high-elastic degradable picoballs is characterized by comprising the following steps of: a) Providing elastic master batches, and performing foaming treatment with a foaming agent to form microporous elastic core particles with closed pore or semi-closed pore structures; b) Preparing an annular reinforcing band from biodegradable fiber materials through winding or preforming; c) Preparing a hemispherical microporous elastic inner shell layer by adopting a first biodegradable material through a rotational molding process; d) Positioning the annular reinforcing band at a predetermined position on the outer surface of the hemispherical microporous elastic inner shell layer, and realizing pre-fixing by heating or bonding; e) Providing a second biodegradable material, and forming the second biodegradable material on the outer surfaces of the two hemispherical microporous elastic inner shells respectively by adopting a rotational molding process to form a hemispherical compact outer shell layer, thereby obtaining a hemispherical composite body with the inner shells, the reinforcing bands and the outer shell layers; f) And aligning and welding the two hemispherical composites to form the high-elastic degradable picoballs.
  2. 2. The method for preparing the high-elastic degradable picoballs according to claim 1, wherein the elastic master batch in the step a) comprises the following components: 40% -90% of polylactic acid, 5% -40% of polycaprolactone, 0.1% -5% of chain extender, 0.1% -10% of surface modified nano filler, 0.05% -2% of heat stabilizer and 0.1% -5% of flow aid.
  3. 3. The method of preparing high-elastic degradable picoballs according to claim 2, wherein the chain extender is one or more of a multifunctional epoxy compound or a multifunctional isocyanate, carbodiimide or maleic anhydride graft copolymer; the surface modified nano-filler is selected from any one of surface modified silicon dioxide, modified nano-clay, graphene oxide or surface grafted nano-cellulose.
  4. 4. The method for preparing high-elastic degradable picoballs according to claim 2, wherein the elastic master batch in step a) is a modified elastic master batch, and the modified elastic master batch is prepared by the following steps: a1 Mixing the components of the elastic master batch according to a preset proportion, and carrying out dehumidification treatment on the mixture until the water content is less than 0.02wt%; a2 Feeding the dehumidified mixture into a double-screw reaction extruder, performing reaction extrusion through a set temperature and a set rotating speed, and performing chain extension/graft modification in a molten state to enable the chain extender to perform chemical reaction with polylactic acid and polycaprolactone to form grafting or increase molecular weight; a3 Adding the surface modified nano filler in a sectional feeding mode in the reaction extrusion process, dispersing in an extrusion section, and obtaining the modified elastic master batch through melt granulating and cooling.
  5. 5. The method of preparing highly elastic degradable pick balls according to claim 1, wherein the first biodegradable material in step b) is selected from one or more of the group consisting of polylactic acid monofilament or drawn filament, polyhydroxybutyrate fiber, PLA/PHB blend fiber, PLA/PBAT blend fiber tape, and bio-based thermoplastic fiber tape that has been stretched, oriented and heat set in sequence; The first biodegradable fiber material has the following performance parameters that the linear density is in the range of 0.5-5 dtex, the breaking strength is more than or equal to 200MPa, and the initial modulus is in the range of 1-10 GPa.
  6. 6. The method of preparing a highly elastic degradable pick ball according to claim 1, wherein the endless reinforcing belt in step b) further comprises a surface affinity treatment after molding; the surface affinity treatment comprises the following steps: b1 Cleaning and dehumidifying the annular reinforcing band; b2 An activation treatment selected from any one of corona treatment, plasma treatment, or chemical oxidation treatment is performed on the surface of the endless reinforcing belt; b3 Coating an affinity interface prime coat on the surface of the activated annular reinforced belt, wherein the affinity interface prime coat is selected from any one of maleic anhydride grafted polymer solution, polyurethane prepolymer at the tail end of isocyanate, epoxy group-containing grafted resin or multifunctional hydroxyl/amine prepolymer, and the coating amount of the affinity interface is 1-50 mu m of dry film thickness; b4 And (3) carrying out constant-temperature drying or low-temperature curing on the coated annular reinforcing belt, wherein the drying/curing temperature is 60-140 ℃ and the time is 1-30 minutes, so as to obtain the surface with high affinity.
  7. 7. The method of preparing highly elastic degradable picoballs according to claim 1, wherein the second biodegradable material in step e) is selected from one or more of polylactic acid, polycaprolactone, polybutylene terephthalate-adipate, or polyhydroxyalkanoate; The second biodegradable material is in the form of particles or powder suitable for rotational moulding and has a melt flow rate in the range of 5-50g/10 min.
  8. 8. The method for preparing high-elastic degradable picoballs according to claim 1, further comprising a post-forming step d) of performing heat setting treatment on the obtained high-elastic degradable picoballs to stabilize the micropore structure and strengthen interlayer bonding, and performing surface micro-texturing treatment to obtain finished picoballs.
  9. 9. The method for preparing the high-elastic degradable picoballs according to claim 8, wherein the specific process of the heat setting treatment in the step d) comprises the following steps: Placing the obtained multilayer composite sphere in a drying box with controllable temperature, heating and maintaining the temperature in the range of 60-120 ℃ for 30-180 minutes, enabling the microporous elastic inner core to undergo stress relaxation and crystallization/rearrangement under the condition that the temperature is higher than the glass transition temperature and lower than the melting temperature so as to stabilize the pore structure and promote interlayer interface reaction, and then slowly cooling to room temperature at the speed of 0.5-5 ℃ per minute.
  10. 10. A high-elastic degradable picoball, characterized in that the high-elastic degradable picoball is prepared by the preparation method of the high-elastic degradable picoball as claimed in any one of claims 1 to 9, and is of a three-layer functional structure, which sequentially comprises a microporous elastic inner shell layer, a ring-shaped fiber reinforcing band and a degradable outer skin layer, wherein all layers are embedded in a mold and are combined with partial chemical bonding to form an integral complex, and the material is biodegradable polymer or a blend thereof.

Description

High-elastic degradable pick ball and preparation method thereof Technical Field The invention relates to the technical field of Peak balls, in particular to a high-elastic degradable Peak ball and a preparation method thereof. Background The Peak ball is used as light sports equipment for mass entertainment and sports training, and is widely used for long-term outdoor or semi-outdoor scenes such as community playgrounds, school sports classes, beach, vacation areas and home backyards. The ball is required to be portable, bounces well, safe and free of sharp sheets (especially aiming at the use scene of children), can bear frequent impact and bending, and meanwhile, with the improvement of environmental protection regulations and environmental protection consciousness of consumers, the demand of the market for recyclable, compostable or biodegradable materials is increasingly enhanced, so that the product is expected to be effectively degraded under industrial or household conditions on the premise that the outdoor service life of at least 1-2 years can be ensured, and the persistent plastic pollution is avoided. The existing sphere preparation technology mostly adopts the processes of single material injection molding or compression molding (such as thermoplastic elastomer/TPR, polyvinyl chloride or non-degradable TPU), hollow blow molding, foam molding and the like, and part of high-performance products also improve rebound and impact resistance through multilayer co-injection, coating or filling air chambers. In an effort to achieve light weight and resiliency, some have employed closed cell or open cell foam cores in combination with dense skins, and others have attempted to make skins or structures from bio-based polymers (e.g., PLA) or blends thereof to enhance degradability. In terms of material and performance trade-off, the main disadvantage of the prior art is that the direct use of biodegradable polymers (especially PLA systems) tends to bring about brittleness, poor weather resistance and insufficient impact resistance, resulting in a significant decrease in resilience and chipping resistance under long-term outdoor light, temperature cycling and impact load, forming a contradiction that "performance and degradability are difficult to compromise". Disclosure of Invention The invention aims to provide a high-elastic degradable pick ball and a preparation method thereof, which solve the technical problem that high-performance sport balls and environmental-friendly degradability are difficult to be compatible. To achieve the purpose, the invention adopts the following technical scheme: The preparation method of the high-elastic degradable picoballs comprises the following steps: a) Providing elastic master batches, and performing foaming treatment with a foaming agent to form microporous elastic core particles with closed pore or semi-closed pore structures; b) Preparing an annular reinforcing band from biodegradable fiber materials through winding or preforming; c) Preparing a hemispherical microporous elastic inner shell layer by adopting a first biodegradable material through a rotational molding process; d) Positioning the annular reinforcing band at a predetermined position on the outer surface of the hemispherical microporous elastic inner shell layer, and realizing pre-fixing by heating or bonding; e) Providing a second biodegradable material, and forming the second biodegradable material on the outer surfaces of the two hemispherical microporous elastic inner shells respectively by adopting a rotational molding process to form a hemispherical compact outer shell layer, thereby obtaining a hemispherical composite body with the inner shells, the reinforcing bands and the outer shell layers; f) And aligning and welding the two hemispherical composites to form the high-elastic degradable picoballs. Optionally, the elastic masterbatch in the step a) includes the following components: 40% -90% of polylactic acid, 5% -40% of polycaprolactone, 0.1% -5% of chain extender, 0.1% -10% of surface modified nano filler, 0.05% -2% of heat stabilizer and 0.1% -5% of flow aid. Optionally, wherein the chain extender is a multifunctional epoxy compound or one or more combinations of multifunctional isocyanate, carbodiimide or maleic anhydride graft copolymer; the surface modified nano-filler is selected from any one of surface modified silicon dioxide, modified nano-clay, graphene oxide or surface grafted nano-cellulose. Optionally, the elastic masterbatch in step a) is a modified elastic masterbatch, and the modified elastic masterbatch is prepared by the following steps: a1 Mixing the components of the elastic master batch according to a preset proportion, and carrying out dehumidification treatment on the mixture until the water content is less than 0.02wt%; a2 Feeding the dehumidified mixture into a double-screw reaction extruder, performing reaction extrusion through a set temperature and a set rotating s