CN113583450B - P4U rubber-plastic composite foam material and preparation method and application thereof - Google Patents
P4U rubber-plastic composite foam material and preparation method and application thereof Download PDFInfo
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
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- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B13/00—Soles; Sole-and-heel integral units
- A43B13/02—Soles; Sole-and-heel integral units characterised by the material
- A43B13/04—Plastics, rubber or vulcanised fibre
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- C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2427/22—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers modified by chemical after-treatment
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- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
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- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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Abstract
The invention provides a P4U rubber-plastic composite foaming material, a preparation method and application thereof, belonging to the technical field of intelligent materials, wherein the P4U rubber-plastic composite foaming material comprises the following raw materials in parts by weight: 70-80 parts of dihydroxyl polydimethylsiloxane, 20-25 parts of boric acid, 15-18 parts of simethicone, 3-6 parts of beta-hydroxyethyl ether, 10-20 parts of white carbon black and 10-15 parts of thermosetting phenolic resin; the P4U rubber-plastic composite foaming material which is produced by adding the modified filler for assisting the forming of the P4U main material and the natural plant base material for adding natural plant macromolecules into the P4U main material and then foaming is used as an intelligent material with a shear thickening effect, and the P4U rubber-plastic composite foaming material has the self-repairing and self-proliferation capability, the recognition and identification capability, the stimulus response and the environmental strain performance of the P4U, and also has excellent rigidity strength, wear resistance, antibacterial property and deodorizing property.
Description
Technical Field
The invention belongs to the technical field of intelligent materials, and particularly relates to a P4U rubber-plastic composite foam material, and a preparation method and application thereof.
Background
The P4U intelligent material is a material which can sense and respond to environment and has the discovery capability, and the organic material has advanced functions endowed by biology through a molecular design and organic synthesis method: such as self-repair and self-proliferation capabilities, cognitive and discrimination capabilities, stimulus responses, and environmental strain capabilities. The P4U intelligent material is a non-Newtonian fluid substance, keeps a loose state in a normal state, is soft and elastic, is mutually locked immediately when being subjected to severe collision or impact, is quickly tightened and hardened to digest external force, forms a protective layer, and returns to an original loose soft elastic state after the external force disappears. It can respond differently to different impact situations instantaneously. The P4U intelligent material is applied to sole manufacture of sports shoes, and the excellent performance of the material has remarkable effect on quality improvement of the sports shoes.
The existing P4U intelligent material has single component, is far superior to the traditional rubber foaming material in elasticity performance and intelligent protection, but has the advantages of no absorption of the traditional material in wear resistance and rigidity strength, cannot be independently formed for manufacturing soles, and does not have natural antibacterial and deodorant components as one of manufacturing materials of sports shoes.
Disclosure of Invention
The invention aims to provide a P4U rubber-plastic composite foaming material, a preparation method and application thereof, and aims to solve the problems that the P4U rubber-plastic composite foaming material is far better than the traditional rubber-plastic foaming material in elasticity and intelligent protection due to single components in the prior art, has no advantages of absorbing the traditional material in wear resistance and rigidity strength, cannot be independently formed to be used for manufacturing soles, and does not have natural antibacterial and deodorant components as one of manufacturing materials of sports shoes.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the P4U rubber-plastic composite foaming material comprises the following raw materials in parts by weight: 70-80 parts of dihydroxyl polydimethylsiloxane, 20-25 parts of boric acid, 15-18 parts of simethicone, 3-6 parts of beta-hydroxyethyl ether, 10-20 parts of white carbon black, 4-6 parts of vinyl triethoxysilane, 2-5 parts of ethylene-vinyl acetate copolymer emulsion, 10-15 parts of thermosetting phenolic resin, 10-20 parts of epoxy resin, 2-5 parts of perchloroethylene resin, 15-20 parts of natural plant crude extract, 10 parts of acid solvent, 10-12 parts of cellulase, 5-8 parts of chloroform, 30-40 parts of foaming agent and 10-13 parts of compounding agent.
As a preferable scheme of the invention, the invention comprises the following raw materials in parts by weight: 75 parts of dihydroxypolydimethylsiloxane, 22 parts of boric acid, 16 parts of simethicone, 5 parts of beta-hydroxyethyl ether, 15 parts of white carbon black, 5 parts of vinyl triethoxysilane, 4 parts of ethylene-vinyl acetate copolymer emulsion, 12 parts of thermosetting phenolic resin, 15 parts of epoxy resin, 4 parts of perchloroethylene resin, 18 parts of natural plant crude extract, 10 parts of acid solvent, 11 parts of cellulase, 7 parts of chloroform, 35 parts of foaming agent and 12 parts of compounding agent.
As a preferred embodiment of the present invention, the acidic solvent includes n-butanol, water and acetic acid.
As a preferable scheme of the invention, the mass ratio of the n-butanol to the water to the acetic acid is 4:5:1.
As a preferable scheme of the invention, the compounding agent is prepared by mixing one or more raw materials of a plasticizer, an anti-aging agent and an anti-wear agent according to any proportion.
As a preferable scheme of the invention, the preparation method of the P4U rubber-plastic composite foam material comprises the following steps:
s1, preparing a main material:
s11, preparing main materials of P4U: preparing a P4U main material, and placing the main material into a constant-temperature storage bin for later use;
s12, preparing modified filler: preparing modified filler, and placing the modified filler into a constant-temperature storage bin for later use;
s13, preparing a natural plant base material: preparing natural plant base materials, and placing the natural plant base materials into a constant-temperature storage bin for later use;
s2, mixing: after the preparation of the P4U main material, the preparation of the modified filler and the preparation of the natural plant base material in the step S1 are completed, taking the modified filler out of the constant-temperature storage bin, putting the modified filler into a stirring kettle, stirring the modified filler in a low-power mode of the stirring kettle for 30min, and completing primary stirring and mixing;
s3, foaming: after the mixing in the step S2 is completed, the mixed materials are put into an internal mixer to slowly react in a low-power mode of the internal mixer, after the reaction is carried out for 10 minutes, the foaming agent is taken according to parts by weight and is added into the internal mixer, the internal mixer is set to be in a high-power mode to carry out rapid reaction, after the reaction is carried out for 5 minutes, the compounding agent is taken according to parts by weight and is added into the internal mixer, after the reaction is carried out for 30 minutes, the refined materials are poured into a model to be foamed, and after 60-90 seconds, the foaming is completed to generate P4U rubber-plastic composite foaming for standby;
s4, drying and demolding: after the foaming of the material in the step S3 is completed, placing the model into a drying chamber, drying and curing for 6-8 hours, and taking out the P4U rubber and plastic composite foaming for standby;
s5, forming: and (3) after the P4U rubber and plastic composite foam in the step (S4) is dried and subjected to demolding, further processing, slicing and shaping to obtain the P4U rubber and plastic composite foam material.
As a preferred embodiment of the present invention, the step S11 includes the following steps:
s111, gel preparation: taking dihydroxyl polydimethylsiloxane, boric acid and simethicone according to parts by weight, placing the dihydroxyl polydimethylsiloxane, the boric acid and the simethicone into a reaction kettle, reacting for 4-5 hours under the reaction environment of 90-95 ℃, placing beta-hydroxyethyl ether according to parts by weight into the reaction kettle, reacting for 3-4 hours, taking out the material, drying for 24 hours, and generating gel for later use;
s112, preparing master batches: after the gel in the step S111 is generated, placing the gel into a stirring kettle, then placing white carbon black into the stirring kettle according to parts by weight, stirring for 30min in a high-power mode of the stirring kettle, uniformly spraying vinyl triethoxysilane and ethylene-vinyl acetate copolymer emulsion into the stirring machine according to parts by weight in the stirring process, and then taking out materials in the stirring machine and placing the materials into a double-screw extruder to generate P4U master batch.
As a preferred embodiment of the present invention, the step S12 includes the following steps:
s121, raw rubber refining: the thermosetting phenolic resin, the epoxy resin and the perchloroethylene resin are sequentially put into a plasticator according to the weight parts, and raw rubber is generated after the reaction for 1h in a low-power mode of the plasticator;
s122, plasticating: after the raw rubber in the step S121 is generated, setting a plasticator to a high-power mode for quick reaction, and generating plasticator after 2 hours.
As a preferred embodiment of the present invention, the step S13 includes the following steps:
s131, breaking walls: placing the crude extract of the natural plant into a wall breaking device according to the weight parts, and carrying out wall breaking treatment on the crude extract of the natural plant at the rotating speed of 300r/s by a blade of the wall breaking device for 10min to obtain natural plant particles for later use;
s132, extracting: after the natural plant particles in the step S131 are generated, acid solvent, cellulase and chloroform are taken according to parts by weight and are placed into a wall breaking device, natural plant macromolecules are extracted after the reaction is carried out for 1 hour, and the natural plant macromolecules are ready for use;
s133, purifying: and (3) after the natural plant macromolecules in the step S132 are extracted, taking out the materials in the wall breaking device, and filtering and purifying to obtain the natural plant base material.
As a preferable scheme of the invention, the stirring kettle is used for stirring She Zhuaisu at 100r/min in a low-power mode, and the stirring kettle is used for stirring She Zhuaisu at 200r/min in a high-power mode.
As a preferable scheme of the invention, the rotation speed of the blades of the internal mixer is 500r/s and the temperature is 100 degrees in a low power mode, the rotation speed of the blades of the internal mixer is 800r/s and the temperature is 200 degrees in a high power mode, and the rotation speeds of two rollers of the internal mixer are 250r/s and 500r/s in a low power mode respectively.
As a preferable scheme of the invention, the P4U rubber-plastic composite foam material is used for manufacturing soles of sports shoes.
Compared with the prior art, the invention has the beneficial effects that:
1. in the scheme, the P4U rubber-plastic composite foaming material which is formed by adding the modified filler for assisting the forming of the P4U main material and the natural plant base material for adding natural plant macromolecules into the P4U main material and then foaming is used as an intelligent material with a shear thickening effect, and the intelligent material has the self-repairing and self-proliferation capability, the recognition and identification capability, the stimulus response and the environmental strain performance of the P4U, and also has excellent rigidity strength, wear resistance, antibacterial property and deodorizing property.
2. In the scheme, the specific preparation method is that the prepared P4U master batch, the modified filler prepared from the solid phenolic resin, the epoxy resin and a small amount of perchloroethylene resin and the natural plant base material prepared from the natural plant crude extract are added into an internal mixer, and then the mixture is added with a foaming agent and stirred and poured into a model to foam to generate the P4U rubber-plastic composite foam material, so that when the application force is slowly applied to the sole, the polymer chains move and rearrange in time, the viscosity is not affected, but when the application force is rapidly applied, the polymer chains have no time rearrangement and are entangled together, the viscosity is greatly increased, so that the sports shoe can be intelligently adapted to the motion state of a human body, is soft and comfortable when walking, and has excellent elasticity when running.
3. In the scheme, in the process of preparing the natural plant base material, the natural plant macromolecules with antibacterial and deodorizing functions in the natural plant crude extract can be fully released by firstly fully crushing in a physical mode, removing cell walls through an enzymolysis method and then removing cell membranes through an organic solvent treatment method.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention. In the drawings:
FIG. 1 is a flow chart of a preparation method of a P4U rubber-plastic composite foaming material.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Referring to fig. 1, the present invention provides the following technical solutions:
the P4U rubber-plastic composite foaming material comprises the following raw materials in parts by weight: 70 parts of dihydroxypolydimethylsiloxane, 20 parts of boric acid, 15 parts of simethicone, 3 parts of beta-hydroxyethyl ether, 10 parts of white carbon black, 4 parts of vinyl triethoxysilane, 2 parts of ethylene-vinyl acetate copolymer emulsion, 10 parts of thermosetting phenolic resin, 10 parts of epoxy resin, 2 parts of perchloroethylene resin, 15 parts of natural plant crude extract, 10 parts of acid solvent, 10 parts of cellulose, 5 parts of chloroform, 30 parts of foaming agent and 10 parts of compounding agent.
In the specific embodiment of the invention, dihydroxyl polydimethylsiloxane and boric acid are polymerized to generate a polymer, and simethicone is used as an oily liquid lubricant, and a shear thickening fluid which is a main body of a P4U material can be formed by mixing the dihydroxyl polydimethylsiloxane and the boric acid, is in gel form, beta-hydroxyethyl ether is a chain extender which is also known as a chain extender and can react with P4U functional groups to expand molecular chains and increase molecular weight, the mechanical property and the technological property of the P4U material can be improved, white carbon black is a filler and is used for compatibilizing and weighting the gel, the cost is reduced, vinyl triethoxysilane is a coupling agent which is also known as a surface modifier, the dispersity of the filler can be improved to improve the processing property, ethylene-vinyl acetate copolymer emulsion is a flexible agent and the flexibility and the elasticity of the P4U composite material can be improved, the gel is added with white carbon black, vinyl triethoxysilane and ethylene-vinyl acetate copolymer emulsion, which can be used for granulating to form P4U material master batch for synthesizing composite foaming material, thermosetting phenolic resin, epoxy resin and perchloroethylene resin are used for preparing modified filler to endow other properties for the P4U composite material, wherein the thermosetting phenolic resin, the epoxy resin and the resorcinol formaldehyde resin are used for improving the strength and the oil resistance of rubber, a small amount of perchloroethylene resin is used for improving the viscosity between different components in the mixing process, the crude extract of natural plants can be crude products of natural plants such as peppermint, olive and the like, the crude extract of natural plants can be used for providing natural antibacterial and deodorizing functions of natural plant macromolecular components for the P4U composite material, an acidic solvent and cellulose are used for specifically decomposing plant cell walls to release substances in the cell walls through hydrolysis reaction, chloroform is an organic solvent, the plant cell membrane can be dissolved, natural plant macromolecules can be fully released, the foaming agent is used for forming bubbles in the mixed material so as to form holes for foaming, and the complexing agent is used for further modifying the P4U composite material.
Referring specifically to fig. 1, the acidic solvent includes n-butanol, water and acetic acid;
the mass ratio of n-butanol, water and acetic acid is 4:5:1.
In this embodiment: n-butanol: water: acetic acid (40:50:10) is a commonly used mixed acidic solvent system that provides the cellulase with an optimal acidic reaction environment at pH 8.
Referring to fig. 1 specifically, the compounding agent is prepared by mixing one or more raw materials of plasticizer, anti-aging agent and antiwear agent according to any proportion.
In this embodiment: the plasticizer can increase the plasticity and flexibility of the P4U composite material; an anti-aging agent which can be used for preventing or delaying the aging of the P4U composite material; the wear-resistant agent can increase the wear resistance of the P4U composite material.
Referring to fig. 1 specifically, a preparation method of a P4U rubber-plastic composite foam material includes the following steps:
s1, preparing a main material:
s11, preparing main materials of P4U:
s111, gel preparation: taking dihydroxy polydimethylsiloxane, boric acid and simethicone according to parts by weight, placing the dihydroxy polydimethylsiloxane, the boric acid and the simethicone into a reaction kettle, reacting for 4 hours under a 90-DEG reaction environment, taking beta-hydroxyethyl ether according to parts by weight, placing the beta-hydroxyethyl ether into the reaction kettle, reacting for 3 hours, taking out the material, drying for 20 hours, and generating gel for later use;
s112, preparing master batches: after the gel in the step S111 is generated, placing the gel into a stirring kettle, then placing white carbon black into the stirring kettle according to parts by weight, stirring for 30min in a high-power mode of the stirring kettle, uniformly spraying vinyl triethoxysilane and ethylene-vinyl acetate copolymer emulsion into a stirrer according to parts by weight in the stirring process, and then taking out materials in the stirrer and placing the materials into a double-screw extruder to generate P4U master batch;
after preparing the P4U main material, placing the main material into a constant-temperature storage bin for standby;
s12, preparing modified filler:
s121, raw rubber refining: the thermosetting phenolic resin, the epoxy resin and the perchloroethylene resin are sequentially put into a plasticator according to the weight parts, and raw rubber is generated after the reaction for 1h in a low-power mode of the plasticator;
s122, plasticating: after the raw rubber in the step S121 is generated, setting a plasticator to a high-power mode for quick reaction, and generating plasticated rubber after 2 hours;
after preparing the modified filler, placing the modified filler into a constant-temperature storage bin for later use;
s13, preparing a natural plant base material:
s131, breaking walls: placing the crude extract of the natural plant into a wall breaking device according to the weight parts, and carrying out wall breaking treatment on the crude extract of the natural plant at the rotating speed of 300r/s by a blade of the wall breaking device for 10min to obtain natural plant particles for later use;
s132, extracting: after the natural plant particles in the step S131 are generated, acid solvent, cellulase and chloroform are taken according to parts by weight and are placed into a wall breaking device, natural plant macromolecules are extracted after the reaction is carried out for 1 hour, and the natural plant macromolecules are ready for use;
s133, purifying: after the natural plant macromolecules in the step S132 are extracted, the materials in the wall breaking device are taken out for filtering and purifying to obtain a natural plant base material;
after preparing the natural plant base material, placing the natural plant base material into a constant-temperature storage bin for standby;
s2, mixing: after the preparation of the P4U main material, the preparation of the modified filler and the preparation of the natural plant base material in the step S1 are completed, taking the modified filler out of the constant-temperature storage bin, putting the modified filler into a stirring kettle, stirring the modified filler in a low-power mode of the stirring kettle for 30min, and completing primary stirring and mixing;
s3, foaming: after the mixing in the step S2 is completed, the mixed materials are put into an internal mixer to slowly react in a low-power mode of the internal mixer, after the reaction is carried out for 10 minutes, the foaming agent is taken according to parts by weight and is added into the internal mixer, the internal mixer is set to be in a high-power mode to carry out rapid reaction, after the reaction is carried out for 5 minutes, the compounding agent is taken according to parts by weight and is added into the internal mixer, after the reaction is carried out for 30 minutes, the refined materials are poured into a model to be foamed, and after 60 seconds, the foaming is completed to generate P4U rubber-plastic composite foaming for standby;
s4, drying and demolding: after the foaming of the material in the step S3 is completed, placing the model into a drying chamber, drying and curing for 6 hours, and then taking out the P4U rubber and plastic composite foaming for standby;
s5, forming: and (3) after the P4U rubber and plastic composite foam in the step (S4) is dried and subjected to demolding, further processing, slicing and shaping to obtain the P4U rubber and plastic composite foam material.
In this embodiment: the P4U rubber-plastic composite foaming material can be produced by adding the modified filler and the natural plant base material into the P4U main material and then foaming.
Referring specifically to FIG. 1, the stirring kettle is stirred She Zhuaisu at 100r/min in the low power mode, and stirred She Zhuaisu at 200r/min in the high power mode;
the rotation speed of the blades of the internal mixer is 500r/s under the low power mode, the temperature is 100 degrees, the rotation speed of the blades of the internal mixer is 800r/s under the high power mode, the temperature is 200 degrees, and the rotation speeds of the two rollers of the plasticator under the low power mode are 250r/s and 500r/s respectively.
In this embodiment: the stirring kettle is used for stirring and mixing materials, the microstructure of raw rubber can be changed to generate plasticated rubber through strong shearing force formed between two rollers with different rotating speeds in the plasticator, and the banbury mixer can be used for mixing the plasticated rubber with added modified filler and natural plant base materials and assisting in foaming through high temperature.
Referring specifically to fig. 1, the P4U rubber-plastic composite foam material is used for making soles of sports shoes.
In this embodiment: the sole of the sports shoe made of the P4U rubber-plastic composite foam material has excellent anti-collision, anti-falling, shock absorption, energy absorption and buffering performances.
Example 2
The P4U rubber-plastic composite foaming material comprises the following raw materials in parts by weight: 75 parts of dihydroxypolydimethylsiloxane, 22 parts of boric acid, 16 parts of simethicone, 5 parts of beta-hydroxyethyl ether, 15 parts of white carbon black, 5 parts of vinyl triethoxysilane, 4 parts of ethylene-vinyl acetate copolymer emulsion, 12 parts of thermosetting phenolic resin, 15 parts of epoxy resin, 4 parts of perchloroethylene resin, 18 parts of natural plant crude extract, 10 parts of acid solvent, 11 parts of cellulase, 7 parts of chloroform, 35 parts of foaming agent and 12 parts of compounding agent.
Referring to fig. 1 specifically, a preparation method of a P4U rubber-plastic composite foam material includes the following steps:
s1, preparing a main material:
s11, preparing main materials of P4U:
s111, gel preparation: taking dihydroxyl polydimethylsiloxane, boric acid and simethicone according to parts by weight, placing the dihydroxyl polydimethylsiloxane, the boric acid and the simethicone into a reaction kettle, reacting for 4.5 hours under a 92-DEG reaction environment, taking beta-hydroxyethyl ether according to parts by weight, placing the beta-hydroxyethyl ether into the reaction kettle, reacting for 3.5 hours, taking out the material, drying for 22 hours, and generating gel for later use;
s112, preparing master batches: after the gel in the step S111 is generated, placing the gel into a stirring kettle, then placing white carbon black into the stirring kettle according to parts by weight, stirring for 30min in a high-power mode of the stirring kettle, uniformly spraying vinyl triethoxysilane and ethylene-vinyl acetate copolymer emulsion into a stirrer according to parts by weight in the stirring process, and then taking out materials in the stirrer and placing the materials into a double-screw extruder to generate P4U master batch;
after preparing the P4U main material, placing the main material into a constant-temperature storage bin for standby;
s12, preparing modified filler:
s121, raw rubber refining: the thermosetting phenolic resin, the epoxy resin and the perchloroethylene resin are sequentially put into a plasticator according to the weight parts, and raw rubber is generated after the reaction for 1h in a low-power mode of the plasticator;
s122, plasticating: after the raw rubber in the step S121 is generated, setting a plasticator to a high-power mode for quick reaction, and generating plasticated rubber after 2 hours;
after preparing the modified filler, placing the modified filler into a constant-temperature storage bin for later use;
s13, preparing a natural plant base material:
s131, breaking walls: placing the crude extract of the natural plant into a wall breaking device according to the weight parts, and carrying out wall breaking treatment on the crude extract of the natural plant at the rotating speed of 300r/s by a blade of the wall breaking device for 10min to obtain natural plant particles for later use;
s132, extracting: after the natural plant particles in the step S131 are generated, acid solvent, cellulase and chloroform are taken according to parts by weight and are placed into a wall breaking device, natural plant macromolecules are extracted after the reaction is carried out for 1 hour, and the natural plant macromolecules are ready for use;
s133, purifying: after the natural plant macromolecules in the step S132 are extracted, the materials in the wall breaking device are taken out for filtering and purifying to obtain a natural plant base material;
after preparing the natural plant base material, placing the natural plant base material into a constant-temperature storage bin for standby;
s2, mixing: after the preparation of the P4U main material, the preparation of the modified filler and the preparation of the natural plant base material in the step S1 are completed, taking the modified filler out of the constant-temperature storage bin, putting the modified filler into a stirring kettle, stirring the modified filler in a low-power mode of the stirring kettle for 30min, and completing primary stirring and mixing;
s3, foaming: after the mixing in the step S2 is completed, the mixed materials are put into an internal mixer to slowly react in a low-power mode of the internal mixer, after the reaction is carried out for 10 minutes, the foaming agent is taken according to parts by weight and is added into the internal mixer, the internal mixer is set to be in a high-power mode to carry out rapid reaction, after the reaction is carried out for 5 minutes, the compounding agent is taken according to parts by weight and is added into the internal mixer, after the reaction is carried out for 30 minutes, the refined materials are poured into a model to be foamed, and after 70 seconds, the foaming is completed to generate P4U rubber-plastic composite foaming for standby;
s4, drying and demolding: after the foaming of the material in the step S3 is completed, placing the model into a drying chamber, drying and curing for 7 hours, and then taking out the P4U rubber and plastic composite foaming for standby;
s5, forming: and (3) after the P4U rubber and plastic composite foam in the step (S4) is dried and subjected to demolding, further processing, slicing and shaping to obtain the P4U rubber and plastic composite foam material.
Example 3
The P4U rubber-plastic composite foaming material comprises the following raw materials in parts by weight: 80 parts of dihydroxypolydimethylsiloxane, 25 parts of boric acid, 18 parts of simethicone, 6 parts of beta-hydroxyethyl ether, 20 parts of white carbon black, 6 parts of vinyl triethoxysilane, 5 parts of ethylene-vinyl acetate copolymer emulsion, 15 parts of thermosetting phenolic resin, 20 parts of epoxy resin, 5 parts of perchloroethylene resin, 20 parts of natural plant crude extract, 10 parts of acid solvent, 12 parts of cellulose, 8 parts of chloroform, 40 parts of foaming agent and 13 parts of compounding agent.
Referring to fig. 1 specifically, a preparation method of a P4U rubber-plastic composite foam material includes the following steps:
s1, preparing a main material:
s11, preparing main materials of P4U:
s111, gel preparation: taking dihydroxy polydimethylsiloxane, boric acid and simethicone according to parts by weight, placing the dihydroxy polydimethylsiloxane, the boric acid and the simethicone into a reaction kettle, reacting for 5 hours under a 95-DEG reaction environment, taking beta-hydroxyethyl ether according to parts by weight, placing the beta-hydroxyethyl ether into the reaction kettle, reacting for 4 hours, taking out the material, drying for 24 hours, and generating gel for later use;
s112, preparing master batches: after the gel in the step S111 is generated, placing the gel into a stirring kettle, then placing white carbon black into the stirring kettle according to parts by weight, stirring for 30min in a high-power mode of the stirring kettle, uniformly spraying vinyl triethoxysilane and ethylene-vinyl acetate copolymer emulsion into a stirrer according to parts by weight in the stirring process, and then taking out materials in the stirrer and placing the materials into a double-screw extruder to generate P4U master batch;
after preparing the P4U main material, placing the main material into a constant-temperature storage bin for standby;
s12, preparing modified filler:
s121, raw rubber refining: the thermosetting phenolic resin, the epoxy resin and the perchloroethylene resin are sequentially put into a plasticator according to the weight parts, and raw rubber is generated after the reaction for 1h in a low-power mode of the plasticator;
s122, plasticating: after the raw rubber in the step S121 is generated, setting a plasticator to a high-power mode for quick reaction, and generating plasticated rubber after 2 hours;
after preparing the modified filler, placing the modified filler into a constant-temperature storage bin for later use;
s13, preparing a natural plant base material:
s131, breaking walls: placing the crude extract of the natural plant into a wall breaking device according to the weight parts, and carrying out wall breaking treatment on the crude extract of the natural plant at the rotating speed of 300r/s by a blade of the wall breaking device for 10min to obtain natural plant particles for later use;
s132, extracting: after the natural plant particles in the step S131 are generated, acid solvent, cellulase and chloroform are taken according to parts by weight and are placed into a wall breaking device, natural plant macromolecules are extracted after the reaction is carried out for 1 hour, and the natural plant macromolecules are ready for use;
s133, purifying: after the natural plant macromolecules in the step S132 are extracted, the materials in the wall breaking device are taken out for filtering and purifying to obtain a natural plant base material;
after preparing the natural plant base material, placing the natural plant base material into a constant-temperature storage bin for standby;
s2, mixing: after the preparation of the P4U main material, the preparation of the modified filler and the preparation of the natural plant base material in the step S1 are completed, taking the modified filler out of the constant-temperature storage bin, putting the modified filler into a stirring kettle, stirring the modified filler in a low-power mode of the stirring kettle for 30min, and completing primary stirring and mixing;
s3, foaming: after the mixing in the step S2 is completed, the mixed materials are put into an internal mixer to slowly react in a low-power mode of the internal mixer, after the reaction is carried out for 10 minutes, the foaming agent is taken according to parts by weight and is added into the internal mixer, the internal mixer is set to be in a high-power mode to carry out rapid reaction, after the reaction is carried out for 5 minutes, the compounding agent is taken according to parts by weight and is added into the internal mixer, after the reaction is carried out for 30 minutes, the refined materials are poured into a model to be foamed, and after 90 seconds, the foaming is completed to generate P4U rubber-plastic composite foaming for standby;
s4, drying and demolding: after the foaming of the material in the step S3 is completed, placing the model into a drying chamber, drying and curing for 8 hours, and then taking out the P4U rubber and plastic composite foaming for standby;
s5, forming: and (3) after the P4U rubber and plastic composite foam in the step (S4) is dried and subjected to demolding, further processing, slicing and shaping to obtain the P4U rubber and plastic composite foam material.
According to examples 1-3, the P4U rubber-plastic composite foam material prepared by the invention is respectively tested for hardness, rebound resilience, tensile strength and fracture growth rate according to related standards, and the obtained related data are shown in tables 1 and 2:
TABLE 1 hardness and resilience test results for examples 1-3
TABLE 2 tensile Strength and breaking growth Rate test results for examples 1-3
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. The preparation method of the P4U rubber-plastic composite foam material is characterized in that the P4U rubber-plastic composite foam material comprises the following raw materials in parts by weight: 70-80 parts of dihydroxyl polydimethylsiloxane, 20-25 parts of boric acid, 15-18 parts of simethicone, 3-6 parts of beta-hydroxyethyl ether, 10-20 parts of white carbon black, 4-6 parts of vinyl triethoxysilane, 2-5 parts of ethylene-vinyl acetate copolymer emulsion, 10-15 parts of thermosetting phenolic resin, 10-20 parts of epoxy resin, 2-5 parts of perchloroethylene resin, 15-20 parts of natural plant crude extract, 10 parts of acid solvent, 10-12 parts of cellulase, 5-8 parts of chloroform, 30-40 parts of foaming agent and 10-13 parts of compounding agent;
the method for preparing the P4U rubber-plastic composite foaming material comprises the following steps:
s1, preparing a main material:
s11, preparing main materials of P4U: preparing a P4U main material, and placing the main material into a constant-temperature storage bin for later use;
s12, preparing modified filler: preparing modified filler, and placing the modified filler into a constant-temperature storage bin for later use;
s13, preparing a natural plant base material: preparing natural plant base materials, and placing the natural plant base materials into a constant-temperature storage bin for later use;
s2, mixing: after the preparation of the P4U main material, the preparation of the modified filler and the preparation of the natural plant base material in the step S1 are completed, taking the modified filler out of the constant-temperature storage bin, putting the modified filler into a stirring kettle, stirring the modified filler in a low-power mode of the stirring kettle for 30min, and completing primary stirring and mixing;
s3, foaming: after the mixing in the step S2 is completed, the mixed materials are put into an internal mixer to slowly react in a low-power mode of the internal mixer, after the reaction is carried out for 10 minutes, the foaming agent is taken according to parts by weight and is added into the internal mixer, the internal mixer is set to be in a high-power mode to carry out rapid reaction, after the reaction is carried out for 5 minutes, the compounding agent is taken according to parts by weight and is added into the internal mixer, after the reaction is carried out for 30 minutes, the refined materials are poured into a model to be foamed, and after 60-90 seconds, the foaming is completed to generate P4U rubber-plastic composite foaming for standby;
s4, drying and demolding: after the foaming of the material in the step S3 is completed, placing the model into a drying chamber, drying and curing for 6-8 hours, and taking out the P4U rubber and plastic composite foaming for standby;
s5, forming: after the P4U rubber and plastic composite foaming and drying in the step S4 is demolding, further processing the same, and slicing and shaping to obtain the P4U rubber and plastic composite foaming material;
the step S11 comprises the following steps:
s111, gel preparation: taking dihydroxyl polydimethylsiloxane, boric acid and simethicone according to parts by weight, placing the dihydroxyl polydimethylsiloxane, the boric acid and the simethicone into a reaction kettle, reacting for 4-5 hours under the reaction environment of 90-95 ℃, placing beta-hydroxyethyl ether according to parts by weight into the reaction kettle, reacting for 3-4 hours, taking out the material, drying for 24 hours, and generating gel for later use;
s112, preparing master batches: after the gel in the step S111 is generated, placing the gel into a stirring kettle, then placing white carbon black into the stirring kettle according to parts by weight, stirring for 30min in a high-power mode of the stirring kettle, uniformly spraying vinyl triethoxysilane and ethylene-vinyl acetate copolymer emulsion into a stirrer according to parts by weight in the stirring process, and then taking out materials in the stirrer and placing the materials into a double-screw extruder to generate P4U master batch;
the step S12 includes the steps of:
s121, raw rubber refining: the thermosetting phenolic resin, the epoxy resin and the perchloroethylene resin are sequentially put into a plasticator according to the weight parts, and raw rubber is generated after the reaction for 1h in a low-power mode of the plasticator;
s122, plasticating: after the raw rubber in the step S121 is generated, setting a plasticator to a high-power mode for quick reaction, and generating plasticated rubber after 2 hours;
the step S13 includes the following steps:
s131, breaking walls: placing the crude extract of the natural plant into a wall breaking device according to the weight parts, and carrying out wall breaking treatment on the crude extract of the natural plant at the rotating speed of 300r/s by a blade of the wall breaking device for 10min to obtain natural plant particles for later use;
s132, extracting: after the natural plant particles in the step S131 are generated, acid solvent, cellulase and chloroform are taken according to parts by weight and are placed into a wall breaking device, natural plant macromolecules are extracted after the reaction is carried out for 1 hour, and the natural plant macromolecules are ready for use;
s133, purifying: after the natural plant macromolecules in the step S132 are extracted, the materials in the wall breaking device are taken out for filtering and purifying to obtain a natural plant base material;
the acidic solvent comprises n-butanol, water and acetic acid;
the mass ratio of the n-butanol to the water to the acetic acid is 4:5:1;
the compounding agent is prepared by mixing one or more raw materials of plasticizer, anti-aging agent and anti-wear agent according to any proportion.
2. The preparation method of the P4U rubber-plastic composite foam material according to claim 1 is characterized by comprising the following raw material formula in parts by weight: 75 parts of dihydroxypolydimethylsiloxane, 22 parts of boric acid, 16 parts of simethicone, 5 parts of beta-hydroxyethyl ether, 15 parts of white carbon black, 5 parts of vinyl triethoxysilane, 4 parts of ethylene-vinyl acetate copolymer emulsion, 12 parts of thermosetting phenolic resin, 15 parts of epoxy resin, 4 parts of perchloroethylene resin, 18 parts of natural plant crude extract, 10 parts of acid solvent, 11 parts of cellulase, 7 parts of chloroform, 35 parts of foaming agent and 12 parts of compounding agent.
3. The preparation method of the P4U rubber-plastic composite foam material according to claim 1, wherein the stirring kettle is used for stirring She Zhuaisu at 100r/min in a low power mode, and the stirring kettle is used for stirring She Zhuaisu at 200r/min in a high power mode.
4. The preparation method of the P4U rubber-plastic composite foam material according to claim 1, wherein the rotation speed of blades of the internal mixer is 500r/s and the temperature is 100 degrees in a low power mode, the rotation speed of blades of the internal mixer is 800r/s and the temperature is 200 degrees in a high power mode, and the rotation speeds of two rollers of the internal mixer are 250r/s and 500r/s in a low power mode respectively.
5. The method for preparing the P4U rubber-plastic composite foam material according to claim 1, wherein the P4U rubber-plastic composite foam material is used for manufacturing soles of sports shoes.
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| JP2006328167A (en) * | 2005-05-25 | 2006-12-07 | The Eco Kk | Natural vegetable composite molding and method for producing the same |
| CN109867853A (en) * | 2019-01-30 | 2019-06-11 | 泉州匹克鞋业有限公司 | A kind of P4U rubber and plastic composite foam material and its preparation method and application |
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| CN111808358A (en) * | 2020-07-29 | 2020-10-23 | 安徽集虹材料科技有限公司 | Masterbatch processing technology of P4U material |
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| JP2006328167A (en) * | 2005-05-25 | 2006-12-07 | The Eco Kk | Natural vegetable composite molding and method for producing the same |
| CN109867853A (en) * | 2019-01-30 | 2019-06-11 | 泉州匹克鞋业有限公司 | A kind of P4U rubber and plastic composite foam material and its preparation method and application |
| CN111423653A (en) * | 2020-04-25 | 2020-07-17 | 泉州西米露新材料科技有限公司 | Natural aromatic environment-friendly EVA (ethylene-vinyl acetate) composite foaming material as well as preparation method and application thereof |
| CN111808358A (en) * | 2020-07-29 | 2020-10-23 | 安徽集虹材料科技有限公司 | Masterbatch processing technology of P4U material |
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