CN114145537A - Degradable bio-based shoe material and preparation method thereof - Google Patents

Degradable bio-based shoe material and preparation method thereof Download PDF

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Publication number
CN114145537A
CN114145537A CN202111469535.XA CN202111469535A CN114145537A CN 114145537 A CN114145537 A CN 114145537A CN 202111469535 A CN202111469535 A CN 202111469535A CN 114145537 A CN114145537 A CN 114145537A
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parts
degradable
vamp
driving
outsole
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CN114145537B (en
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丁德裕
吴东杰
黄娇
杨怀德
王伟强
朱惠娟
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Fujian Zhongyu New Material Technology Co ltd
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Fujian Zhongyu New Material Technology Co ltd
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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
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B23/00—Uppers; Boot legs; Stiffeners; Other single parts of footwear
    • A43B23/02—Uppers; Boot legs
    • A43B23/0205—Uppers; Boot legs characterised by the material
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43D—MACHINES, TOOLS, EQUIPMENT OR METHODS FOR MANUFACTURING OR REPAIRING FOOTWEAR
    • A43D35/00—Presses for shaping pre-existing loose soles, shoe bottoms or soles fixed to shoe bottoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • C08J9/06—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 by a chemical blowing agent
    • C08J9/10—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 by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2403/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08J2403/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)

Abstract

The invention discloses a degradable bio-based shoe material and a preparation method thereof, relating to the technical field of bio-based materials, and the key points of the technical scheme are that the degradable bio-based shoe material comprises a vamp material and a outsole material; the vamp material comprises the following components in parts by weight: 45.8-72.5 parts of bio-based polyethylene glycol succinate, 16.8-20.7 parts of terpolymer polyester, 6.3-7.6 parts of polylactic acid, 4.3-6.1 parts of porous nano hydroxyapatite and 1.6-2.2 parts of fly ash; the outsole material comprises the following components in parts by weight: 36.8-40.2 parts of ethylene-vinyl acetate copolymer, 18.6-22.4 parts of corn starch, 12-20 parts of xylitol-based polyfunctional epoxy resin, 3.6-4.5 parts of potassium carbonate, 1-1.5 parts of AC foaming agent, 0.8-1.2 parts of fly ash and 0.8-1 part of hexahydrophthalic anhydride. The invention has the advantages of high strength and wear resistance, and is suitable for natural degradation.

Description

Degradable bio-based shoe material and preparation method thereof
Technical Field
The invention relates to the technical field of bio-based materials, in particular to a degradable bio-based shoe material and a preparation method thereof.
Background
The material for shoes mainly comprises a vamp material and an outsole material. Wherein, the vamp material usually mainly comprises textile material, mesh cloth, leather, artificial leather, synthetic material, PVC, PU, nubuck, superfine fiber, natural leather and the like, so as to play the roles of beauty, wrapping and comfort; the outsole material is mainly made of various thermoplastic elastomers, polymer composites and functional materials such as rubber, PU, PVC, EVA, TPR, SBS and the like, so as to play roles of wear resistance and effective support.
Chinese patent with publication number CN113185794A discloses a high-strength wear-resistant material for rain shoes and a preparation method thereof, wherein the high-strength wear-resistant material for rain shoes comprises the following components in parts by weight: 50-85 parts of acrylate rubber, 20-40 parts of rare earth butadiene rubber, 35-60 parts of ethylene propylene diene monomer, 15-36 parts of medium and super wear-resistant carbon black, 6-14 parts of antioxidant wear-resistant filler, 5-13 parts of fluorescent composite filler, 6-12 parts of softener, 1.5-3.5 parts of vulcanizing agent, 3-6 parts of activator and 2-4 parts of anti-aging agent; the preparation method of the antioxidant wear-resistant filler comprises the following steps: according to the weight parts, 70-85 parts of vinyl ester resin, 3-6 parts of nano silicon dioxide micropowder, 8-15 parts of calcium sulfate whisker, 0.3-0.8 part of zinc stearate and 0.4-0.8 part of dibutyl hydroxy toluene are uniformly mixed, and then the mixture is extruded and granulated by a double-screw extruder.
However, the material for the high-strength wear-resistant rain shoes can not be effectively degraded although achieving the effects of high strength and wear resistance, and further causes pollution and threat to the environment after being discarded at will and cannot be effectively recycled, so that the improvement is needed.
Disclosure of Invention
Aiming at the defects in the prior art, the first object of the invention is to provide a degradable bio-based shoe material which has the effect of being suitable for natural degradation while maintaining the characteristics of high strength and wear resistance.
In order to achieve the purpose, the invention provides the following technical scheme:
a degradable bio-based shoe material comprises a vamp material and an outsole material;
the vamp material comprises the following components in parts by weight: 45.8-72.5 parts of bio-based polyethylene glycol succinate, 16.8-20.7 parts of terpolymer polyester, 6.3-7.6 parts of polylactic acid, 4.3-6.1 parts of porous nano hydroxyapatite and 1.6-2.2 parts of fly ash;
the outsole material comprises the following components in parts by weight: 36.8-40.2 parts of ethylene-vinyl acetate copolymer, 18.6-22.4 parts of corn starch, 12-20 parts of xylitol-based polyfunctional epoxy resin, 3.6-4.5 parts of potassium carbonate, 1-1.5 parts of AC foaming agent, 0.8-1.2 parts of fly ash and 0.8-1 part of hexahydrophthalic anhydride.
By adopting the technical scheme, the vamp material and the outsole material of the degradable bio-based shoe material are both made of degradable materials, and the degradable bio-based shoe material has the effect of being suitable for natural degradation while keeping the characteristics of high strength and wear resistance by combining corresponding components.
The invention is further configured to: the terpolymer polyester is shown below:
Figure BDA0003391044120000021
wherein n is 0, 2 or 4; x is more than or equal to 16 and less than or equal to 32; y is more than or equal to 53 and less than or equal to 82.
The invention is further configured to: the xylitol-based polyfunctional epoxy resin is shown as follows:
Figure BDA0003391044120000031
wherein, R is2Is epoxy group and one or two of carboxyl group and aldehyde group.
A preparation method of a degradable bio-based shoe material comprises a vamp preparation part and an outsole preparation part; the vamp preparation part comprises the following steps:
step 1, mixing: mixing 45.8-72.5 parts of bio-based polyethylene glycol succinate, 16.8-20.7 parts of terpolymer polyester, 6.3-7.6 parts of polylactic acid, 4.3-6.1 parts of porous nano hydroxyapatite and 1.6-2.2 parts of fly ash by weight to form a vamp mixture;
step 2, granulation: introducing the vamp mixture into a double-screw extruder for extruding to obtain vamp granules;
step 3, spinning: guiding the vamp granules into a spinning machine for spinning to obtain vamp fibers with the fineness of 1-2 dtex;
step 4, blank material: drafting vamp fibers under air flow, and uniformly paving and reinforcing to obtain degradable vamp fabrics;
step 5, forming: and cutting, sewing and molding the degradable vamp fabric to obtain the vamp material. By adopting the technical scheme, the method has the advantages that,
the invention is further configured to: the outsole preparation part comprises the following steps:
step 1, mixing: mixing 36.8-40.2 parts by weight of ethylene-vinyl acetate copolymer, 18.6-22.4 parts by weight of corn starch, 12-20 parts by weight of xylitol-based polyfunctional epoxy resin, 3.6-4.5 parts by weight of potassium carbonate, 1-1.5 parts by weight of AC foaming agent, 0.8-1.2 parts by weight of fly ash and 0.8-1 part by weight of hexahydrophthalic anhydride to form a master mix;
step 2, granulation: introducing the vamp mixture into a double-screw extruder for extruding to obtain vamp granules;
step 3, foaming: introducing the vamp granules into an injection foaming molding machine for foaming molding to obtain a degradable outsole blank;
step 4, baking: and baking the degradable outsole blank by using an oven to obtain a degradable outsole material, embedding the bottom of the vamp material into the degradable outsole blank while baking, and obtaining the degradable bio-based shoe.
The invention is further configured to: in step 4 of the outsole preparation part, the material combining device comprises a support chassis for placing the degradable outsole blanks and a driving operation arm for embedding vamp materials into the degradable outsole blanks, the upper side of the support chassis is matched with the bottom of the degradable outsole blanks, a support upright post for mounting and fixing and a fixed transfer post connected with the driving operation arm in an up-and-down rotating manner are arranged at the bottom of the support chassis, and the support upright post is provided with a driving mechanism for driving the driving operation arm to swing up and down.
Through adopting above-mentioned technical scheme, actuating mechanism orders about drive operation arm luffing motion when moving, and then will make drive operation arm upper end will drive vamp type material do downwards and support chassis periphery one side and remove towards, thereby imbed the vamp type material in the big end stock of degradable along the slope route, with the mode of pegging graft through the slope improve the embedded connection fixed stability of big end stock of degradable and vamp type material, because the big end stock of degradable is in toasting the operation this moment, consequently will make big end stock of degradable and vamp type material accomplish effective, stable connection structure after accomplishing the operation of toasting, and have the convenient operation's effect.
The invention is further configured to: the driving mechanism comprises a driving turntable sleeved on the supporting upright post, and the peripheral side wall of the driving turntable is provided with at least two abutting spiral outer side walls; the drive operation arm is Z form and includes from supreme operation underarm, operation linking arm and the operation upper arm that connects gradually down, the operation underarm is provided with the butt connecting hole, peg graft in the butt connecting hole have with butt spiral lateral wall butt is followed the drive butt post that butt spiral lateral wall removed, the operation linking arm be provided with fixed switching post rotates the rotation connecting hole of connecting, the operation upper arm is located the upside on support chassis is used for in the big end stock of vamp type material embedding degradable.
By adopting the technical scheme, the operation connecting arm is rotationally connected with the fixed switching column, so that the drive abutting column abutted with the abutting spiral outer side wall is driven to move towards or away from the axial lead of the drive turntable when the drive turntable does circumferential reciprocating rotation, and the drive operation arm does circumferential reciprocating swing motion by taking the fixed switching column as an axis; the operation of embedding vamp materials into the degradable outsole blanks is completed by the upper arm in the up-and-down swinging motion process, and the operation is convenient, efficient and stable while the stability of the connection structure of the vamp materials and the degradable outsole blanks is improved.
The invention is further configured to: the operation upper arm is connected with a butt drive plate which is used for contacting with the vamp material and driving the vamp material to be embedded into the degradable outsole blank, one side, far away from the driving operation arm, of the butt drive plate is provided with friction lines and is connected with a negative pressure device, one side, close to the driving operation arm, of the butt drive plate is provided with a horizontal rotating column, the upper end of the operation upper arm is provided with an operation connection hole, a swinging connection column is connected in the operation connection hole in a vertical rotating mode, two ends of the swinging connection column penetrate out of the operation connection hole and are connected with a limiting connection body, the limiting connection body is provided with a limiting connection waist-shaped groove in the length direction, and two ends of the horizontal rotating column are respectively inserted into the corresponding limiting connection waist-shaped grooves; the operating upper arm is provided with two connecting springs which are respectively positioned on the upper side and the lower side of the limiting connector, and one end, far away from the operating upper arm, of each connecting spring is fixedly connected with the butting driving plate.
By adopting the technical scheme, the friction lines on the butting driving plate play a role of improving the friction resistance with the vamp section material, and the negative pressure device is used for effectively adsorbing the vamp section material on the butting driving plate so as to realize the effect of effectively embedding the vamp section material into the degradable outsole blank; at the moment, when the upper arm is operated to do downward rotary motion, the abutting driving plate and the vamp molding material adsorbed on the abutting driving plate are driven to rotate downward, the limiting connector effectively connects the driving upper arm and the abutting driving plate, at the same time, the orientation of the butting driving plate is calibrated through the connecting spring, and when the butting driving plate drives the vamp material to be embedded into the degradable outsole blank, so that the connecting spring at the upper end is compressed and forms an elastic deformation force for resetting the abutting driving plate, the connecting spring at the lower end is compressed and forms an elastic deformation force for resetting the abutting driving plate, and the compression deformation length of the connecting spring at the upper end is less than that of the connecting spring at the lower end, therefore, when the vamp material is embedded into the degradable outsole blank, the effect of enabling the inclination angle between the vamp material and the vertical direction to be 0-4 degrees is achieved, and the stability and the strength of the connecting structure of the vamp material and the degradable outsole blank are obviously improved.
The invention is further configured to: the supporting chassis is provided with a plurality of driving limit slots which are respectively matched with the corresponding driving operation arms, the driving limit slots are connected with limit connecting straight rods arranged in the vertical direction in an inserted mode and limit inserting rods arranged in the length direction of the driving limit slots and penetrating through the limit connecting straight rods in an inserted mode, the bottoms of the limit connecting straight rods are provided with composite abutting rods abutted to the operation lower arms, abutting composite plates abutted to the degradable outsole blanks are arranged at the top ends of the limit connecting straight rods, and the abutting composite plates face one sides of the axial lead of the driving turntable and are provided with matched inclined walls matched with the corresponding positions of the degradable outsole blanks.
Through adopting above-mentioned technical scheme, when the upward swing motion is done at the drive upper arm, the swing motion of orientation support chassis is done to the drive underarm, and then will make the drive underarm promote compound butt stick and do the removal that supports the chassis towards, spacing connection straight-bar is done along the linear motion of spacing inserted bar length direction under the spacing of spacing inserted bar this moment, and the drive butt composite sheet is done and is moved in order to exert pressure to degradable outsole blank towards one side of drive carousel axial lead, make the degradable outsole blank that is in the operation of toasting combine the pressure that the butt composite sheet was exerted after by vamp type material embedding and form stable and effectual connection structure.
The invention is further configured to: the driving turntable is provided with a driving large gear, the driving large gear is meshed with a driving small gear, and the driving small gear is connected with a driving motor for driving rotation.
Through adopting above-mentioned technical scheme, driving motor drives the drive pinion rotation when moving, and then will make the transmission gear wheel rotate under the drive of drive pinion to realize the effect of reciprocating rotation drive carousel steadily.
In conclusion, the invention has the following beneficial effects: the vamp material and the outsole material are prepared by adopting corresponding components and steps, and the degradable outsole blank is connected with the vamp material under the driving of the material combining device, so that the degradable bio-based shoe material has the effect of being suitable for natural degradation while keeping the characteristics of high strength and wear resistance.
Drawings
FIG. 1 is a schematic structural view of the present embodiment;
FIG. 2 is a schematic view of an exploded structure of the present embodiment;
fig. 3 is an enlarged schematic view of a portion a of fig. 2.
Description of reference numerals: 1. a support chassis; 11. supporting the upright post; 12. fixing the switching column; 13. driving the limit slot; 2. driving the turntable; 21. a driving gearwheel; 22. abutting the spiral outer side wall; 3. driving the operating arm; 31. operating the lower arm; 311. abutting against the connecting hole; 312. driving the abutment post; 32. operating the upper arm; 321. a connecting spring; 322. operating the connecting hole; 33. operating the connecting arm; 331. rotating the connecting hole; 34. swinging the connecting column; 35. a limiting connector; 351. the limit is connected with the waist-shaped groove; 36. compounding abutting rods; 37. the limiting connection straight rod; 38. abutting against the composite board; 381. a matching inclined wall; 39. a limiting inserted rod; 4. a drive motor; 41. a drive pinion; 5. abutting against the drive plate; 51. the column is rotated horizontally.
Detailed Description
In order to make the technical solutions and advantages of the present invention clearer, the present invention will be described in further detail with reference to the accompanying drawings, and it is obvious that the described embodiments are only a part of the embodiments of the present application, not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
It should be mentioned that the biodegradability test employed is a test of 3 months duration under microbiological conditions of controlled temperature 50 ℃, humidity 98% and composting and is divided by the degree of decomposition from 0 to 100% into 1 to 10, of which 10 is a degree of decomposition of 90 to 100%.
The following is a detailed description of the degradable bio-based shoe material and the manufacturing method thereof according to the embodiment of the present invention:
a degradable bio-based shoe material comprises a vamp material and an outsole material.
The vamp material comprises the following components in parts by weight: 45.8-72.5 parts of bio-based polyethylene glycol succinate, 16.8-20.7 parts of terpolymer polyester, 6.3-7.6 parts of polylactic acid, 4.3-6.1 parts of porous nano hydroxyapatite and 1.6-2.2 parts of fly ash;
the terpolymer polyester is shown below:
Figure BDA0003391044120000091
wherein n is 0, 2 or 4; x is more than or equal to 16 and less than or equal to 32; y is more than or equal to 53 and less than or equal to 82.
The outsole material comprises the following components in parts by weight: 36.8-40.2 parts of ethylene-vinyl acetate copolymer, 18.6-22.4 parts of corn starch, 12-20 parts of xylitol-based polyfunctional epoxy resin, 3.6-4.5 parts of potassium carbonate, 1-1.5 parts of AC foaming agent, 0.8-1.2 parts of fly ash and 0.8-1 part of hexahydrophthalic anhydride.
The xylitol-based polyfunctional epoxy resin is shown below:
Figure BDA0003391044120000092
wherein, R is2Is epoxy group and one or two of carboxyl group and aldehyde group.
Therefore, the vamp material and the outsole material of the degradable bio-based shoe material are both made of degradable materials, and the degradable bio-based shoe material has the effect of being suitable for natural degradation while keeping the characteristics of high strength and wear resistance by combining corresponding components.
A preparation method of a degradable bio-based shoe material comprises a vamp preparation part and an outsole preparation part.
The vamp preparation part comprises the following steps:
step 1, mixing: mixing 45.8-72.5 parts of bio-based polyethylene glycol succinate, 16.8-20.7 parts of terpolymer polyester, 6.3-7.6 parts of polylactic acid, 4.3-6.1 parts of porous nano hydroxyapatite and 1.6-2.2 parts of fly ash by weight to form a vamp mixture;
step 2, granulation: introducing the vamp mixture into a double-screw extruder for extruding to obtain vamp granules;
step 3, spinning: guiding the vamp granules into a spinning machine for spinning to obtain vamp fibers with the fineness of 1-2 dtex;
step 4, blank material: drafting vamp fibers under air flow, and uniformly paving and reinforcing to obtain degradable vamp fabrics;
step 5, forming: cutting, sewing and molding the degradable vamp fabric to obtain the vamp material
The outsole preparation part comprises the following steps:
step 1, mixing: mixing 36.8-40.2 parts by weight of ethylene-vinyl acetate copolymer, 18.6-22.4 parts by weight of corn starch, 12-20 parts by weight of xylitol-based polyfunctional epoxy resin, 3.6-4.5 parts by weight of potassium carbonate, 1-1.5 parts by weight of AC foaming agent, 0.8-1.2 parts by weight of fly ash and 0.8-1 part by weight of hexahydrophthalic anhydride to form a master mix;
step 2, granulation: introducing the vamp mixture into a double-screw extruder for extruding to obtain vamp granules;
step 3, foaming: introducing the vamp granules into an injection foaming molding machine for foaming molding to obtain a degradable outsole blank;
step 4, baking: and baking the degradable outsole blank by using an oven to obtain a degradable outsole material, embedding the bottom of the vamp material into the degradable outsole blank while baking, and obtaining the degradable bio-based shoe.
As shown in fig. 1, the material combining device comprises a support chassis 1 for placing the degradable outsole stock and a driving operation arm 3 for embedding the vamp material into the degradable outsole stock. The upper side of the supporting chassis 1 is matched with the bottom of the degradable outsole blank so as to realize effective limiting and fixing of the degradable outsole blank. Meanwhile, a support upright 11 for installation and fixation is arranged at the bottom of the support chassis 1. The supporting upright 11 is provided with a driving mechanism for driving the driving operation arm 3 to swing up and down, and the driving operation arm 3 is connected with the supporting chassis 1 in a vertical rotation manner. Wherein the support chassis 1 is provided with a fixed adapter column 12 which is connected with the driving operation arm 3 in a vertical rotating way, see fig. 2. Therefore, when the driving mechanism operates, the driving operation arm 3 is driven to swing up and down, and then the upper end of the driving operation arm 3 drives the vamp material to move downwards and towards one side of the periphery of the supporting chassis 1, so that the vamp material is embedded into the degradable outsole blank along an inclined path, the embedded connection fixing stability of the degradable outsole blank and the vamp material is improved in an inclined insertion mode, at the moment, the degradable outsole blank is in the baking operation, so that the degradable outsole blank and the vamp material can complete an effective and stable connection structure after the baking operation is completed, and the driving mechanism has the effect of convenience in operation.
It should be noted that the driving turntable 2 is provided with a driving gearwheel 21. The driving gearwheel 21 is engaged with a driving pinion 41, and the driving pinion 41 is connected with a driving motor 4 for driving rotation. Therefore, when the driving motor 4 is operated, the driving pinion 41 is driven to rotate, and the transmission gearwheel 21 is driven to rotate by the driving pinion 41, so that the effect of stably rotating the driving turntable 2 in a reciprocating manner is achieved.
As shown in fig. 2 and 3, the driving mechanism includes a driving turntable 2 sleeved on the supporting upright 11. At least two abutting spiral outer side walls 22 are provided on the outer peripheral side wall of the drive turntable 2. The abutment spiral outer side wall 22 is in the form of an archimedes spiral. The drive operation arm 3 is Z-shaped and includes an operation lower arm 31, an operation connection arm 33, and an operation upper arm 32 connected in this order from bottom to top. Here, the operation lower arm 31 is provided with an abutting connection hole 311, and a driving abutting column 312 which abuts against the abutting spiral outer side wall 22 and moves along the abutting spiral outer side wall 22 is inserted into the abutting connection hole 311. The operation connecting arm 33 is provided with a rotation connecting hole 331 rotatably connected to the fixed adaptor post 12. The upper arm 32 is operatively positioned on the upper side of the support chassis 1 and is used to embed the vamp-like material into the degradable outsole material. Because the operation connecting arm 33 is rotatably connected with the fixed adapter column 12, the drive abutting column 312 abutted with the abutting spiral outer side wall 22 is driven to move towards or away from the axial lead of the drive turntable 2 when the drive turntable 2 performs circumferential reciprocating rotation, so that the drive operating arm 3 performs circumferential reciprocating swinging motion by taking the fixed adapter column 12 as an axis; at this moment, the upper arm 32 is operated to complete the operation of embedding the vamp material into the degradable outsole blank in the up-and-down swinging movement process, and the operation is convenient, efficient and stable while the stability of the connection structure of the vamp material and the degradable outsole blank is improved.
It should be mentioned that the upper arm 32 is connected with the abutting driving plate 5 for contacting with the vamp shape and driving the vamp shape to be embedded into the degradable outsole stock. And a friction line is formed on one side of the abutting driving plate 5 far away from the driving operation arm 3 and is connected with a negative pressure device. The friction lines on the butt drive plate 5 play a role in promoting the friction resistance with the vamp section material, and the negative pressure device is used for effectively adsorbing the vamp section material on the butt drive plate 5 so as to realize the effect of effectively embedding the vamp section material into the degradable outsole blank. A horizontal rotation column 51 is provided on the side of the abutment drive plate 5 adjacent to the drive operation arm 3. The upper end of the operation upper arm 32 is provided with an operation connection hole 322. The swing post 34 is rotatably connected to the inside of the operation connection hole 322. The two ends of the swing post 34 penetrate out of the operation connecting holes 322 and are connected with the limiting connecting bodies 35. Spacing connector 35 is provided with spacing connection waist type groove 351 along length direction, and the level rotates the both ends of post 51 and pegs graft respectively in corresponding spacing connection waist type groove 351 to make the level rotate post 51 have when butt drive plate 5 pressurized have do along the effect of spacing connection waist type groove 351 length direction removal, exert the effect of steady pressure to the big end stock of degradable with promotion butt drive plate 5. Meanwhile, the operating upper arm 32 is provided with two connecting springs 321 respectively located at the upper side and the lower side of the limiting connector 35, and one end of the connecting spring 321 far away from the operating upper arm 32 is fixedly connected with the abutting driving plate 5. Therefore, when the upper arm 32 is operated to rotate downwards, the abutting driving plate 5 and the vamp material adsorbed on the abutting driving plate 5 are driven to rotate downwards, the limiting connector 35 effectively connects the driving upper arm with the abutting driving plate 5, simultaneously, the orientation of the abutting driving plate 5 is calibrated through the connecting spring 321, when the abutting driving plate 5 drives the vamp material to be embedded into the degradable outsole blank, the connecting spring 321 at the upper end is compressed to form an elastic deformation force for resetting the abutting driving plate 5, the connecting spring 321 at the lower end is compressed to form an elastic deformation force for resetting the abutting driving plate 5, the compression deformation length of the connecting spring 321 at the upper end is smaller than that of the connecting spring 321 at the lower end, so that the effect of enabling the inclination angle between the vamp material and the vertical direction to be 0-4 degrees is achieved when the vamp material is embedded into the degradable outsole blank, and the stability and the strength of the connecting structure of the vamp material and the degradable outsole blank are obviously improved.
As shown in fig. 2 and 3, the support chassis 1 is provided with a plurality of driving limit slots 13 respectively matched with the corresponding driving operation arms 3. The driving limiting slot 13 is inserted with a limiting connecting straight rod 37 arranged along the vertical direction and a limiting insertion rod 39 arranged along the length direction of the driving limiting slot 13 and penetrating through the limiting connecting straight rod 37. A composite abutting rod 36 abutting against the operation lower arm 31 is provided at the bottom of the stopper connecting straight rod 37. Wherein, the top end of the limit connecting straight rod 37 is provided with an abutting composite board 38 for abutting against the degradable outsole blank, and a matching inclined wall 381 matched with the corresponding part of the degradable outsole blank is arranged on one side of the abutting composite plate 38 facing the axial lead of the driving turntable 2, and when the upper arm is driven to do upward swinging motion, the lower arm is driven to do swinging motion towards the supporting chassis 1, so that the driving lower arm pushes the composite abutting rod 36 to move towards the supporting chassis 1, at the moment, the limiting connecting straight rod 37 makes linear movement along the length direction of the limiting inserted rod 39 under the limitation of the limiting inserted rod 39, and drives the abutting composite board 38 to move towards one side of the axial lead of the driving turntable 2 so as to apply pressure to the degradable outsole blank, so that the degradable outsole blank in the baking operation is combined with the pressure applied by the abutting composite board 38 after the vamp material is embedded to form a stable and effective connection structure.
Example one
A degradable bio-based shoe material comprises a vamp material and an outsole material.
The vamp material comprises the following components in parts by weight: 45.8 parts of bio-based polyethylene glycol succinate, 16.8 parts of terpolymer polyester, 6.3 parts of polylactic acid, 4.3 parts of porous nano hydroxyapatite and 1.6 parts of fly ash;
the terpolymer polyester is shown below:
Figure BDA0003391044120000141
wherein n is 0, 2 or 4; x is more than or equal to 16 and less than or equal to 32; y is more than or equal to 53 and less than or equal to 82.
The outsole material comprises the following components in parts by weight: 36.8 parts of ethylene-vinyl acetate copolymer, 18.6 parts of corn starch, 12 parts of xylitol-based polyfunctional epoxy resin, 3.6 parts of potassium carbonate, 1 part of AC foaming agent, 0.8 part of fly ash and 0.8 part of hexahydrophthalic anhydride.
The xylitol-based polyfunctional epoxy resin is shown below:
Figure BDA0003391044120000142
wherein, R is2Is epoxy group and one or two of carboxyl group and aldehyde group.
Therefore, the vamp material and the outsole material of the degradable bio-based shoe material are both made of degradable materials, and the degradable bio-based shoe material has the effect of being suitable for natural degradation while keeping the characteristics of high strength and wear resistance by combining corresponding components.
A preparation method of a degradable bio-based shoe material comprises a vamp preparation part and an outsole preparation part.
The vamp preparation part comprises the following steps:
step 1, mixing: mixing 45.8 parts by weight of bio-based polyethylene glycol succinate, 16.8 parts by weight of terpolymer polyester, 6.3 parts by weight of polylactic acid, 4.3 parts by weight of porous nano hydroxyapatite and 1.6 parts by weight of fly ash to form a vamp mixture;
step 2, granulation: introducing the vamp mixture into a double-screw extruder for extruding to obtain vamp granules;
step 3, spinning: guiding the vamp granules into a spinning machine for spinning to obtain vamp fibers with the fineness of 1-2 dtex;
step 4, blank material: drafting vamp fibers under air flow, and uniformly paving and reinforcing to obtain degradable vamp fabrics;
step 5, forming: cutting, sewing and molding the degradable vamp fabric to obtain the vamp material
The outsole preparation part comprises the following steps:
step 1, mixing: mixing 36.8 parts by weight of ethylene-vinyl acetate copolymer, 18.6 parts by weight of corn starch, 12 parts by weight of xylitol-based polyfunctional epoxy resin, 3.6 parts by weight of potassium carbonate, 1 part by weight of AC foaming agent, 0.8 part by weight of fly ash and 0.8 part by weight of hexahydrophthalic anhydride to form a bottom mixture;
step 2, granulation: introducing the vamp mixture into a double-screw extruder for extruding to obtain vamp granules;
step 3, foaming: introducing the vamp granules into an injection foaming molding machine for foaming molding to obtain a degradable outsole blank;
step 4, baking: and baking the degradable outsole blank by using an oven to obtain a degradable outsole material, embedding the bottom of the vamp material into the degradable outsole blank while baking, and obtaining the degradable bio-based shoe.
As shown in fig. 1, the material combining device comprises a support chassis 1 for placing the degradable outsole stock and a driving operation arm 3 for embedding the vamp material into the degradable outsole stock. The upper side of the supporting chassis 1 is matched with the bottom of the degradable outsole blank so as to realize effective limiting and fixing of the degradable outsole blank. Meanwhile, a support upright 11 for installation and fixation is arranged at the bottom of the support chassis 1. The supporting upright 11 is provided with a driving mechanism for driving the driving operation arm 3 to swing up and down, and the driving operation arm 3 is connected with the supporting chassis 1 in a vertical rotation manner. Wherein the support chassis 1 is provided with a fixed adapter column 12 which is connected with the driving operation arm 3 in a vertical rotating way, see fig. 2. Therefore, when the driving mechanism operates, the driving operation arm 3 is driven to swing up and down, and then the upper end of the driving operation arm 3 drives the vamp material to move downwards and towards one side of the periphery of the supporting chassis 1, so that the vamp material is embedded into the degradable outsole blank along an inclined path, the embedded connection fixing stability of the degradable outsole blank and the vamp material is improved in an inclined insertion mode, at the moment, the degradable outsole blank is in the baking operation, so that the degradable outsole blank and the vamp material can complete an effective and stable connection structure after the baking operation is completed, and the driving mechanism has the effect of convenience in operation.
It should be noted that the driving turntable 2 is provided with a driving gearwheel 21. The driving gearwheel 21 is engaged with a driving pinion 41, and the driving pinion 41 is connected with a driving motor 4 for driving rotation. Therefore, when the driving motor 4 is operated, the driving pinion 41 is driven to rotate, and the transmission gearwheel 21 is driven to rotate by the driving pinion 41, so that the effect of stably rotating the driving turntable 2 in a reciprocating manner is achieved.
As shown in fig. 2 and 3, the driving mechanism includes a driving turntable 2 sleeved on the supporting upright 11. At least two abutting spiral outer side walls 22 are provided on the outer peripheral side wall of the drive turntable 2. The abutment spiral outer side wall 22 is in the form of an archimedes spiral. The drive operation arm 3 is Z-shaped and includes an operation lower arm 31, an operation connection arm 33, and an operation upper arm 32 connected in this order from bottom to top. Here, the operation lower arm 31 is provided with an abutting connection hole 311, and a driving abutting column 312 which abuts against the abutting spiral outer side wall 22 and moves along the abutting spiral outer side wall 22 is inserted into the abutting connection hole 311. The operation connecting arm 33 is provided with a rotation connecting hole 331 rotatably connected to the fixed adaptor post 12. The upper arm 32 is operatively positioned on the upper side of the support chassis 1 and is used to embed the vamp-like material into the degradable outsole material. Because the operation connecting arm 33 is rotatably connected with the fixed adapter column 12, the drive abutting column 312 abutted with the abutting spiral outer side wall 22 is driven to move towards or away from the axial lead of the drive turntable 2 when the drive turntable 2 performs circumferential reciprocating rotation, so that the drive operating arm 3 performs circumferential reciprocating swinging motion by taking the fixed adapter column 12 as an axis; at this moment, the upper arm 32 is operated to complete the operation of embedding the vamp material into the degradable outsole blank in the up-and-down swinging movement process, and the operation is convenient, efficient and stable while the stability of the connection structure of the vamp material and the degradable outsole blank is improved.
It should be mentioned that the upper arm 32 is connected with the abutting driving plate 5 for contacting with the vamp shape and driving the vamp shape to be embedded into the degradable outsole stock. And a friction line is formed on one side of the abutting driving plate 5 far away from the driving operation arm 3 and is connected with a negative pressure device. The friction lines on the butt drive plate 5 play a role in promoting the friction resistance with the vamp section material, and the negative pressure device is used for effectively adsorbing the vamp section material on the butt drive plate 5 so as to realize the effect of effectively embedding the vamp section material into the degradable outsole blank. A horizontal rotation column 51 is provided on the side of the abutment drive plate 5 adjacent to the drive operation arm 3. The upper end of the operation upper arm 32 is provided with an operation connection hole 322. The swing post 34 is rotatably connected to the inside of the operation connection hole 322. The two ends of the swing post 34 penetrate out of the operation connecting holes 322 and are connected with the limiting connecting bodies 35. Spacing connector 35 is provided with spacing connection waist type groove 351 along length direction, and the level rotates the both ends of post 51 and pegs graft respectively in corresponding spacing connection waist type groove 351 to make the level rotate post 51 have when butt drive plate 5 pressurized have do along the effect of spacing connection waist type groove 351 length direction removal, exert the effect of steady pressure to the big end stock of degradable with promotion butt drive plate 5. Meanwhile, the operating upper arm 32 is provided with two connecting springs 321 respectively located at the upper side and the lower side of the limiting connector 35, and one end of the connecting spring 321 far away from the operating upper arm 32 is fixedly connected with the abutting driving plate 5. Therefore, when the upper arm 32 is operated to rotate downwards, the abutting driving plate 5 and the vamp material adsorbed on the abutting driving plate 5 are driven to rotate downwards, the limiting connector 35 effectively connects the driving upper arm with the abutting driving plate 5, simultaneously, the orientation of the abutting driving plate 5 is calibrated through the connecting spring 321, when the abutting driving plate 5 drives the vamp material to be embedded into the degradable outsole blank, the connecting spring 321 at the upper end is compressed to form an elastic deformation force for resetting the abutting driving plate 5, the connecting spring 321 at the lower end is compressed to form an elastic deformation force for resetting the abutting driving plate 5, the compression deformation length of the connecting spring 321 at the upper end is smaller than that of the connecting spring 321 at the lower end, so that the effect of enabling the inclination angle between the vamp material and the vertical direction to be 0-4 degrees is achieved when the vamp material is embedded into the degradable outsole blank, and the stability and the strength of the connecting structure of the vamp material and the degradable outsole blank are obviously improved.
As shown in fig. 2 and 3, the support chassis 1 is provided with a plurality of driving limit slots 13 respectively matched with the corresponding driving operation arms 3. The driving limiting slot 13 is inserted with a limiting connecting straight rod 37 arranged along the vertical direction and a limiting insertion rod 39 arranged along the length direction of the driving limiting slot 13 and penetrating through the limiting connecting straight rod 37. A composite abutting rod 36 abutting against the operation lower arm 31 is provided at the bottom of the stopper connecting straight rod 37. Wherein, the top end of the limit connecting straight rod 37 is provided with an abutting composite board 38 for abutting against the degradable outsole blank, and a matching inclined wall 381 matched with the corresponding part of the degradable outsole blank is arranged on one side of the abutting composite plate 38 facing the axial lead of the driving turntable 2, and when the upper arm is driven to do upward swinging motion, the lower arm is driven to do swinging motion towards the supporting chassis 1, so that the driving lower arm pushes the composite abutting rod 36 to move towards the supporting chassis 1, at the moment, the limiting connecting straight rod 37 makes linear movement along the length direction of the limiting inserted rod 39 under the limitation of the limiting inserted rod 39, and drives the abutting composite board 38 to move towards one side of the axial lead of the driving turntable 2 so as to apply pressure to the degradable outsole blank, so that the degradable outsole blank in the baking operation is combined with the pressure applied by the abutting composite board 38 after the vamp material is embedded to form a stable and effective connection structure.
Through detection, the peel strength of the degradable bio-based shoe material in the first embodiment is 120N/cm3Tensile strength of 462N/cm3The biodegradation performance of the vamp material is 8, and the biodegradation performance of the outsole material is 9.
Example two
The difference between the second embodiment and the first embodiment is that the vamp material in the second embodiment comprises the following components in parts by weight: 58.6 parts of bio-based polyethylene glycol succinate, 18.6 parts of terpolymer polyester, 6.9 parts of polylactic acid, 5.2 parts of porous nano hydroxyapatite and 1.9 parts of fly ash;
the terpolymer polyester is shown below:
Figure BDA0003391044120000201
wherein n is 0, 2 or 4; x is more than or equal to 16 and less than or equal to 32; y is more than or equal to 53 and less than or equal to 82.
The outsole material comprises the following components in parts by weight: 38.2 parts of ethylene-vinyl acetate copolymer, 20 parts of corn starch, 16 parts of xylitol-based polyfunctional epoxy resin, 4 parts of potassium carbonate, 1.3 parts of AC foaming agent, 1 part of fly ash and 0.9 part of hexahydrophthalic anhydride.
The xylitol-based polyfunctional epoxy resin is shown below:
Figure BDA0003391044120000202
wherein, R is2Is epoxy group and one or two of carboxyl group and aldehyde group.
Therefore, the vamp material and the outsole material of the degradable bio-based shoe material are both made of degradable materials, and the degradable bio-based shoe material has the effect of being suitable for natural degradation while keeping the characteristics of high strength and wear resistance by combining corresponding components.
A preparation method of a degradable bio-based shoe material comprises a vamp preparation part and an outsole preparation part.
The vamp preparation part comprises the following steps:
step 1, mixing: 58.6 parts of bio-based polyethylene glycol succinate, 18.6 parts of terpolymer polyester, 6.9 parts of polylactic acid, 5.2 parts of porous nano hydroxyapatite and 1.9 parts of fly ash are mixed according to parts by weight to form a vamp mixture;
step 2, granulation: introducing the vamp mixture into a double-screw extruder for extruding to obtain vamp granules;
step 3, spinning: guiding the vamp granules into a spinning machine for spinning to obtain vamp fibers with the fineness of 1-2 dtex;
step 4, blank material: drafting vamp fibers under air flow, and uniformly paving and reinforcing to obtain degradable vamp fabrics;
step 5, forming: cutting, sewing and molding the degradable vamp fabric to obtain the vamp material
The outsole preparation part comprises the following steps:
step 1, mixing: mixing 38.2 parts by weight of ethylene-vinyl acetate copolymer, 20 parts by weight of corn starch, 16 parts by weight of xylitol-based polyfunctional epoxy resin, 4 parts by weight of potassium carbonate, 1.3 parts by weight of AC foaming agent, 1 part by weight of fly ash and 0.9 part by weight of hexahydrophthalic anhydride to form a master batch;
step 2, granulation: introducing the vamp mixture into a double-screw extruder for extruding to obtain vamp granules;
step 3, foaming: introducing the vamp granules into an injection foaming molding machine for foaming molding to obtain a degradable outsole blank;
step 4, baking: and baking the degradable outsole blank by using an oven to obtain a degradable outsole material, embedding the bottom of the vamp material into the degradable outsole blank while baking, and obtaining the degradable bio-based shoe.
The peel strength of the degradable bio-based shoe material of the second embodiment is 129N/cm3Tensile strength of 486N/cm3The biodegradable performance of the vamp material is 8, largeThe biodegradability of the base material is 9.
EXAMPLE III
The difference between the third embodiment and the first embodiment is that the vamp material in the third embodiment comprises the following components in parts by weight: 72.5 parts of bio-based polyethylene glycol succinate, 20.7 parts of terpolymer polyester, 7.6 parts of polylactic acid, 6.1 parts of porous nano hydroxyapatite and 2.2 parts of fly ash;
the terpolymer polyester is shown below:
Figure BDA0003391044120000221
wherein n is 0, 2 or 4; x is more than or equal to 16 and less than or equal to 32; y is more than or equal to 53 and less than or equal to 82.
The outsole material comprises the following components in parts by weight: 40.2 parts of ethylene-vinyl acetate copolymer, 22.4 parts of corn starch, 20 parts of xylitol-based polyfunctional epoxy resin, 4.5 parts of potassium carbonate, 1.5 parts of AC foaming agent, 1.2 parts of fly ash and 1 part of hexahydrophthalic anhydride.
The xylitol-based polyfunctional epoxy resin is shown below:
Figure BDA0003391044120000222
wherein, R is2Is epoxy group and one or two of carboxyl group and aldehyde group.
Therefore, the vamp material and the outsole material of the degradable bio-based shoe material are both made of degradable materials, and the degradable bio-based shoe material has the effect of being suitable for natural degradation while keeping the characteristics of high strength and wear resistance by combining corresponding components.
A preparation method of a degradable bio-based shoe material comprises a vamp preparation part and an outsole preparation part.
The vamp preparation part comprises the following steps:
step 1, mixing: mixing 72.5 parts by weight of bio-based polyethylene glycol succinate, 20.7 parts by weight of terpolymer polyester, 7.6 parts by weight of polylactic acid, 6.1 parts by weight of porous nano hydroxyapatite and 2.2 parts by weight of fly ash to form a vamp mixture;
step 2, granulation: introducing the vamp mixture into a double-screw extruder for extruding to obtain vamp granules;
step 3, spinning: guiding the vamp granules into a spinning machine for spinning to obtain vamp fibers with the fineness of 1-2 dtex;
step 4, blank material: drafting vamp fibers under air flow, and uniformly paving and reinforcing to obtain degradable vamp fabrics;
step 5, forming: cutting, sewing and molding the degradable vamp fabric to obtain the vamp material
The outsole preparation part comprises the following steps:
step 1, mixing: mixing 40.2 parts by weight of ethylene-vinyl acetate copolymer, 22.4 parts by weight of corn starch, 20 parts by weight of xylitol-based polyfunctional epoxy resin, 4.5 parts by weight of potassium carbonate, 1.5 parts by weight of AC foaming agent, 1.2 parts by weight of fly ash and 1 part by weight of hexahydrophthalic anhydride to form a sole mixture;
step 2, granulation: introducing the vamp mixture into a double-screw extruder for extruding to obtain vamp granules;
step 3, foaming: introducing the vamp granules into an injection foaming molding machine for foaming molding to obtain a degradable outsole blank;
step 4, baking: and baking the degradable outsole blank by using an oven to obtain a degradable outsole material, embedding the bottom of the vamp material into the degradable outsole blank while baking, and obtaining the degradable bio-based shoe.
Through detection, the peel strength of the degradable bio-based shoe material of the third embodiment is 141N/cm3Tensile strength of 512N/cm3The biodegradation performance of the vamp material is 8, and the biodegradation performance of the outsole material is 9.
In conclusion, the vamp material and the outsole material are prepared by adopting corresponding components and steps, when the bio-based polyethylene glycol succinate, the terpolymer polyester, the polylactic acid, the porous nano hydroxyapatite and the fly ash are mixed to prepare the vamp material, the vamp material has a degradable function, the terpolymer polyester is used for connecting the bio-based polyethylene glycol succinate and the polylactic acid, and the effects of improving the strength and the wear resistance are realized under the reinforcement of the porous nano hydroxyapatite and the fly ash; when ethylene vinyl acetate copolymer, corn starch, xylitol-based multifunctional epoxy resin, potassium carbonate, an AC foaming agent, fly ash and hexahydrophthalic anhydride are mixed to prepare the outsole material, the outsole material has a degradable function, and simultaneously, the xylitol-based multifunctional epoxy resin with one or two of epoxy groups, carboxyl groups and aldehyde groups is combined with the ethylene vinyl acetate copolymer and the corn starch, the strength and wear resistance improvement effects are realized under the reinforcement of the fly ash and the hexahydrophthalic anhydride, and the connection of the degradable outsole blank and a vamp material is completed under the drive of a material combining device, so that the degradable bio-based shoe material has the effect of being suitable for natural degradation while maintaining the characteristics of high strength and wear resistance.
References in this application to "first," "second," "third," "fourth," etc., if any, are intended to distinguish between similar elements and not necessarily to describe a particular order or sequence. It will be appreciated that the data so used may be interchanged under appropriate circumstances such that the embodiments described herein may be practiced otherwise than as specifically illustrated or described herein. Furthermore, the terms "comprises" and "comprising," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, or apparatus.
It should be noted that the descriptions in this application referring to "first", "second", etc. are for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In addition, technical solutions between various embodiments may be combined with each other, but must be realized by a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present application.
The principle and the implementation of the present application are explained herein by applying specific examples, and the above description of the embodiments is only used to help understand the method and the core idea of the present application; meanwhile, for a person skilled in the art, according to the idea of the present application, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present application.

Claims (10)

1. A degradable bio-based shoe material is characterized in that: comprises a vamp material and an outsole material;
the vamp material comprises the following components in parts by weight: 45.8-72.5 parts of bio-based polyethylene glycol succinate, 16.8-20.7 parts of terpolymer polyester, 6.3-7.6 parts of polylactic acid, 4.3-6.1 parts of porous nano hydroxyapatite and 1.6-2.2 parts of fly ash;
the outsole material comprises the following components in parts by weight: 36.8-40.2 parts of ethylene-vinyl acetate copolymer, 18.6-22.4 parts of corn starch, 12-20 parts of xylitol-based polyfunctional epoxy resin, 3.6-4.5 parts of potassium carbonate, 1-1.5 parts of AC foaming agent, 0.8-1.2 parts of fly ash and 0.8-1 part of hexahydrophthalic anhydride.
2. The degradable bio-based shoe material of claim 1 wherein said terpolymer polyester is as follows:
Figure FDA0003391044110000011
wherein n is 0, 2 or 4; x is more than or equal to 16 and less than or equal to 32; y is more than or equal to 53 and less than or equal to 82.
3. The degradable bio-based shoe material of claim 1, wherein said xylitol-based polyfunctional epoxy resin is as follows:
Figure FDA0003391044110000012
wherein, R is2Is epoxy group and one or two of carboxyl group and aldehyde group.
4. A preparation method of a degradable bio-based shoe material is characterized by comprising the following steps: comprises a vamp preparation part and an outsole preparation part; the vamp preparation part comprises the following steps:
step 1, mixing: mixing 45.8-72.5 parts of bio-based polyethylene glycol succinate, 16.8-20.7 parts of terpolymer polyester, 6.3-7.6 parts of polylactic acid, 4.3-6.1 parts of porous nano hydroxyapatite and 1.6-2.2 parts of fly ash by weight to form a vamp mixture;
step 2, granulation: introducing the vamp mixture into a double-screw extruder for extruding to obtain vamp granules;
step 3, spinning: guiding the vamp granules into a spinning machine for spinning to obtain vamp fibers with the fineness of 1-2 dtex;
step 4, blank material: drafting vamp fibers under air flow, and uniformly paving and reinforcing to obtain degradable vamp fabrics;
step 5, forming: and cutting, sewing and molding the degradable vamp fabric to obtain the vamp material.
5. The method for preparing a degradable bio-based shoe material as set forth in claim 4, wherein the outsole preparation part comprises the steps of:
step 1, mixing: mixing 36.8-40.2 parts by weight of ethylene-vinyl acetate copolymer, 18.6-22.4 parts by weight of corn starch, 12-20 parts by weight of xylitol-based polyfunctional epoxy resin, 3.6-4.5 parts by weight of potassium carbonate, 1-1.5 parts by weight of AC foaming agent, 0.8-1.2 parts by weight of fly ash and 0.8-1 part by weight of hexahydrophthalic anhydride to form a master mix;
step 2, granulation: introducing the vamp mixture into a double-screw extruder for extruding to obtain vamp granules;
step 3, foaming: introducing the vamp granules into an injection foaming molding machine for foaming molding to obtain a degradable outsole blank;
step 4, baking: and baking the degradable outsole blank through an oven to obtain a degradable outsole material, and embedding the bottom of the degradable vamp fabric into the degradable outsole blank by adopting a material combining device while baking to obtain the degradable bio-based shoe.
6. The method for preparing the degradable bio-based shoe material of claim 5, wherein the method comprises the following steps: in the step 4 of the outsole preparation part, the material combining device comprises a support chassis (1) for placing the degradable outsole blanks and a driving operation arm (3) for embedding vamp materials into the degradable outsole blanks, the upper side of the support chassis (1) is matched with the bottom of the degradable outsole blanks, a support upright post (11) for mounting and fixing and a fixed switching post (12) which is connected with the driving operation arm (3) in a vertical rotating manner are arranged at the bottom of the support chassis (1), and the support upright post (11) is provided with a driving mechanism for driving the driving operation arm (3) to swing up and down.
7. The method for preparing the degradable bio-based shoe material according to claim 6, wherein the method comprises the following steps: the driving mechanism comprises a driving turntable (2) sleeved on the supporting upright post (11), and at least two abutting spiral outer side walls (22) are arranged on the peripheral side wall of the driving turntable (2); drive operation arm (3) are the Z form and include from supreme operation underarm (31), operation linking arm (33) and the operation upper arm (32) that connect gradually down, operation underarm (31) are provided with butt connecting hole (311), peg graft in butt connecting hole (311) with butt spiral lateral wall (22) butt is followed drive butt post (312) that butt spiral lateral wall (22) removed, operation linking arm (33) be provided with fixed changeover post (12) rotate rotation connecting hole (331) of being connected, operation upper arm (32) are located the upside of support chassis (1) is used for imbedding the vamp type material in the degradable outsole stock.
8. The method for preparing the degradable bio-based shoe material of claim 7, wherein the method comprises the following steps: the upper operating arm (32) is connected with a butting driving plate (5) which is used for contacting with the vamp material and driving the vamp material to be embedded into the degradable outsole blank, one side of the abutting driving plate (5) far away from the driving operation arm (3) is provided with a friction line and is connected with a negative pressure device, a horizontal rotating column (51) is arranged on one side of the abutting driving plate (5) close to the driving operation arm (3), an operation connecting hole (322) is arranged at the upper end of the operation upper arm (32), a swing connecting column (34) is connected in the operation connecting hole (322) in a vertical rotating way, two ends of the swing connecting column (34) penetrate out of the operation connecting hole (322) and are connected with a limiting connecting body (35), the limiting connecting body (35) is provided with a limiting connecting waist-shaped groove (351) along the length direction, two ends of the horizontal rotating column (51) are respectively inserted into the corresponding limit connecting waist-shaped grooves (351); the operation upper arm (32) is provided with two connecting springs (321) which are respectively positioned at the upper side and the lower side of the limiting connecting body (35), and one end, far away from the operation upper arm (32), of each connecting spring (321) is fixedly connected with the abutting driving plate (5).
9. The method for preparing the degradable bio-based shoe material of claim 8, wherein the method comprises the following steps: support chassis (1) be provided with a plurality ofly respectively with corresponding drive spacing slot (13) that drive operation arm (3) match, the spacing straight-bar (37) of connecting and following that set up along vertical direction are pegged graft to drive spacing slot (13) length direction sets up and runs through spacing inserted bar (39) of spacing connecting straight-bar (37), the bottom of spacing connecting straight-bar (37) be provided with compound butt stick (36) of operation underarm (31) butt, the top of spacing connecting straight-bar (37) is provided with butt composite sheet (38) that are used for with the butt of degradable outsole stock butt, butt composite sheet (38) orientation one side of drive carousel (2) axial lead is provided with the matching inclined wall (381) that matches with the corresponding position of degradable outsole stock.
10. The method for preparing the degradable bio-based shoe material of claim 8, wherein the method comprises the following steps: the driving turntable (2) is provided with a driving large gear (21), the driving large gear (21) is meshed with a driving small gear (41), and the driving small gear (41) is connected with a driving rotating driving motor (4).
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