CN114145537B - Degradable bio-based material for shoes and preparation method thereof - Google Patents

Degradable bio-based material for shoes and preparation method thereof Download PDF

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Publication number
CN114145537B
CN114145537B CN202111469535.XA CN202111469535A CN114145537B CN 114145537 B CN114145537 B CN 114145537B CN 202111469535 A CN202111469535 A CN 202111469535A CN 114145537 B CN114145537 B CN 114145537B
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China
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parts
degradable
vamp
outsole
driving
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CN114145537A (en
Inventor
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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Publication of CN114145537A publication Critical patent/CN114145537A/en
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Classifications

    • 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

Abstract

The invention discloses a degradable bio-based shoe material and a preparation method thereof, relating to the technical field of bio-based materials, wherein the technical scheme is characterized by comprising vamp materials and outsole materials; 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 large substrate 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 material for shoes and preparation method thereof
Technical Field
The invention relates to the technical field of biological base materials, in particular to a degradable biological base material for shoes and a preparation method thereof.
Background
The shoe material mainly comprises vamp materials and outsole materials. Wherein, the vamp material is mainly made of textile materials, mesh fabrics, leather, artificial leather, synthetic materials, PVC, PU, cowhells, superfine fibers, natural leather and the like, so as to play roles of beautiful appearance, wrapping and comfort; the base material is mainly made of various thermoplastic elastomers such as rubber, PU, PVC, EVA, TPR, SBS and the like, high polymer composite materials and functional materials, so as to play roles of wear resistance and effective support.
The Chinese patent with publication number of 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 rubber, 15-36 parts of medium 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 active agent and 2-4 parts of antioxidant; the preparation method of the antioxidant wear-resistant filler comprises the following steps: according to the weight portions, 70 to 85 portions of vinyl ester resin, 3 to 6 portions of nanometer silica micropowder, 8 to 15 portions of calcium sulfate whisker, 0.3 to 0.8 portion of zinc stearate and 0.4 to 0.8 portion of dibutyl hydroxy toluene are evenly mixed, extruded and granulated by a double screw extruder.
However, although the high-strength wear-resistant material for the rain shoes achieves the high strength and wear-resistant effect, the material cannot be effectively degraded, and further, pollution and threat are caused to the environment after being discarded at will and when the material cannot be effectively recycled, so that the material needs to be improved.
Disclosure of Invention
In view of the shortcomings of the prior art, a first object of the present invention is to provide a degradable bio-based material for shoes, which has an effect suitable for natural degradation while maintaining high strength and wear resistance.
In order to achieve the above purpose, the present invention provides the following technical solutions:
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 large substrate 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 large substrate material of the degradable bio-based shoe material are both composed of degradable materials, and the effect of being suitable for natural degradation while maintaining the characteristics of high strength and wear resistance is realized by combining the corresponding components.
The invention is further provided with: the terpolymer polyesters are shown below:
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 provided with: the xylitol-based multifunctional epoxy resin is as follows:
wherein the R is 2 Is epoxy group and one or two of carboxyl and aldehyde groups.
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: 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 are mixed to form a vamp mixture;
step 2, granulating: introducing the vamp mixture into a double-screw extruder for extrusion to obtain vamp granules;
Step 3, spinning: introducing vamp granules into a spinning machine for spinning to obtain vamp fibers with fineness of 1-2 dtex;
step 4, blank: drawing vamp fibers under air flow, and uniformly paving and reinforcing to obtain degradable vamp fabrics;
step 5, molding: and cutting and sewing the degradable vamp fabric to form the vamp material. By adopting the technical proposal, the utility model has the advantages that,
the invention is further provided with: 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 multifunctional 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 an outsole mixture;
step 2, granulating: introducing the vamp mixture into a double-screw extruder for extrusion to obtain vamp granules;
step 3, foaming: introducing vamp granules into an injection foaming molding machine for foaming molding to obtain degradable outsole blanks;
step 4, baking: and baking the degradable outsole blank by a baking oven to obtain the degradable outsole blank, and embedding the bottom of the vamp type blank into the degradable outsole blank while baking to obtain the degradable bio-based shoe.
The invention is further provided with: in step 4 of the outsole preparation part, the material combining device comprises a supporting chassis for placing the degradable outsole blank and a driving operation arm for embedding the vamp type material into the degradable outsole blank, wherein the upper side of the supporting chassis is matched with the bottom of the degradable outsole blank, a supporting upright column for mounting and fixing and a fixed switching column connected with the driving operation arm in an up-and-down rotation mode are arranged at the bottom of the supporting chassis, and the supporting upright column 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 the drive operating arm up-and-down swing when the operation, and then will make the drive operating arm upper end will drive the vamp molding material and do downwards and move towards supporting chassis periphery one side to in embedding degradable big end molding material along the slope route with the vamp molding material, with the embedded fixed stability of being connected of mode improvement degradable big end molding material and vamp molding material through the slope grafting, because degradable big end molding material is in the operation of toasting this moment, will be in the degradable big end molding material of messenger and vamp molding material completion effective, stable connection structure after accomplishing the operation of toasting, and have the effect of simple operation.
The invention is further provided with: the driving mechanism comprises a driving turntable sleeved on the supporting upright post, and at least two abutting spiral outer side walls are arranged on the outer peripheral side wall of the driving turntable; the operation arm is Z-shaped and comprises an operation lower arm, an operation connecting arm and an operation upper arm which are sequentially connected from bottom to top, the operation lower arm is provided with an abutting connection hole, a driving abutting column which abuts against the outer side wall of the abutting spiral and moves along the outer side wall of the abutting spiral is inserted into the abutting connection hole, the operation connecting arm is provided with a rotation connecting hole which is rotationally connected with the fixed switching column, and the operation upper arm is positioned on the upper side of the supporting chassis and used for embedding vamp-shaped materials into degradable outsole blanks.
By adopting the technical scheme, the operation connecting arm is rotationally connected with the fixed switching column, so that the driving abutting column abutting against the outer side wall of the abutting spiral is driven to move towards or away from the axial line of the driving turntable when the driving turntable performs circumferential reciprocating rotation, and the driving operation arm performs circumferential reciprocating swinging movement by taking the fixed switching column as an axis; at the moment, the upper arm is operated to complete the operation of embedding the vamp-shaped material into the degradable outsole blank in the up-and-down swinging movement process, and the connecting structure stability of the vamp-shaped material and the degradable outsole blank is improved, and meanwhile, the connecting structure has the effects of convenience, high efficiency and stability in operation.
The invention is further provided with: the upper operating arm is connected with an abutting driving plate which is used for contacting with vamp-shaped materials and driving the vamp-shaped materials to be embedded into degradable outsole blanks, friction lines are formed on one side, away from the driving operating arm, of the abutting driving plate and connected with a negative pressure device, a horizontal rotating column is arranged on one side, close to the driving operating arm, of the abutting driving plate, an operation connecting hole is formed in the upper end of the upper operating arm, a swinging connecting column is connected in the operation connecting hole in a vertical rotating mode, two ends of the swinging connecting column penetrate out of the operation connecting hole and are connected with limiting connectors, limiting connecting waist-shaped grooves are formed in the limiting connectors along the length direction, and two ends of the horizontal rotating column are respectively spliced in the corresponding limiting connecting waist-shaped grooves; the upper operation arm is provided with two connecting springs which are respectively positioned at the upper side and the lower side of the limiting connector, and one end, far away from the upper operation arm, of the connecting springs is fixedly connected with the abutting driving plate.
By adopting the technical scheme, the friction lines on the abutting driving plate play a role in improving friction resistance with the vamp type material, and the negative pressure device is used for effectively adsorbing the vamp type material on the abutting driving plate so as to realize the effect of effectively embedding the vamp type material into the degradable outsole blank; at this time, when the upper arm is operated to do the downward rotation motion, will drive the upper arm and adsorb the vamp type material of butt drive plate and rotate downwards, the spacing connector is when effectively connecting drive upper arm and butt drive plate, calibrate the orientation of butt drive plate through the connecting spring, and when the butt drive plate drives vamp type material embedding degradable big end stock, make the connecting spring compression that is located the upper end and form the elastic deformation power that will butt drive plate reset, the connecting spring compression that is located the lower extreme and form the elastic deformation power that will butt drive plate reset, and the compression deformation length of connecting spring that is located the upper end is less than the compression deformation length of connecting spring that is located the lower extreme, thereby reach the effect that makes vamp type material and vertical direction's inclination be 0-4 when vamp type material embedding degradable big end stock, and show promotion vamp type material and degradable big end stock's connection structure stability and intensity.
The invention is further provided with: the support chassis is provided with a plurality of drive spacing slots that match with corresponding drive operating arm respectively, drive spacing slot peg graft have along the spacing connection straight-bar of vertical direction setting and follow drive spacing slot length direction sets up and runs through spacing inserted bar of spacing connection straight-bar, the bottom of spacing connection straight-bar be provided with the compound butt stick of operation lower arm butt, the top of spacing connection straight-bar is provided with the butt composite sheet that is used for with degradable outsole stock butt, the butt composite sheet orientation one side of drive carousel axial lead is provided with the matching inclined wall that matches with the corresponding position of degradable outsole stock.
Through adopting above-mentioned technical scheme, when the drive upper arm is done orientation wobbling motion, the drive lower arm is done orientation and is supported the wobbling motion of chassis, and then will make the drive lower arm promote compound butt stick and do the removal towards supporting the chassis, spacing connection straight-bar is done the linear movement along the length direction of spacing peg graft under the spacing of spacing peg at this moment, and the drive butt composite sheet is done and is moved in order to exert pressure to degradable big end stock towards one side of drive carousel axial lead, make the degradable big end stock that is in the baking operation combine the pressure that the butt composite sheet applyed after being embedded by vamp type material and form stable and effectual connection structure.
The invention is further provided with: the driving turntable is provided with a transmission large gear, the transmission 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, drive pinion rotates when driving motor operates, and then will make the drive gear wheel rotate under the drive of drive pinion to realize the effect of the reciprocal drive carousel that rotates steadily.
In summary, 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 and the vamp material are connected under the driving of the material mixing device, so that the degradable bio-based shoe material has the effects 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 diagram of an explosive structure of the present embodiment;
fig. 3 is an enlarged schematic view of the portion a in fig. 2.
Reference numerals illustrate: 1. a support chassis; 11. a support column; 12. fixing the transfer column; 13. driving the limiting slot; 2. driving a turntable; 21. a transmission gearwheel; 22. abutting against the outer side wall of the spiral; 3. driving the operating arm; 31. operating the lower arm; 311. abutting the connecting hole; 312. driving the abutment post; 32. operating the upper arm; 321. a connecting spring; 322. an operation connection hole; 33. operating the connecting arm; 331. rotating the connecting hole; 34. swinging the connecting column; 35. a limit connector; 351. the limiting part is connected with the waist-shaped groove; 36. a composite abutment rod; 37. the limit is connected with the straight rod; 38. abutting against the composite board; 381. matching the inclined walls; 39. a limit inserted link; 4. a driving motor; 41. a drive pinion; 5. abutting against the driving plate; 51. the column is rotated horizontally.
Detailed Description
In order to make the technical solution and advantages of the present application more apparent, the present application will be described in more detail below with reference to the accompanying drawings, wherein it is apparent that the embodiments described are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
It should be mentioned that the biodegradability test employed is carried out for a period of 3 months under microbiological conditions with a control temperature of 50 ℃, a humidity of 98% and composting, and is divided by a degree of decomposition from 0 to 100% into 1 to 10, where 10 is the degree of decomposition from 90 to 100%.
The degradable bio-based shoe material and the manufacturing method thereof according to the embodiment of the application are specifically described below:
a degradable bio-based shoe material comprises vamp materials and outsole materials.
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 polyesters are shown below:
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 large substrate 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 multifunctional epoxy resin is shown below:
wherein the R is 2 Is epoxy group and one or two of carboxyl and aldehyde groups.
Therefore, the vamp material and the large substrate material of the degradable bio-based shoe material are both composed of degradable materials, and the effect of being suitable for natural degradation while maintaining the characteristics of high strength and wear resistance is realized by combining the corresponding components.
A preparation method of a degradable bio-based shoe material comprises an vamp preparation part and an outsole preparation part.
The vamp preparation part comprises the following steps:
step 1, 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 are mixed to form a vamp mixture;
Step 2, granulating: introducing the vamp mixture into a double-screw extruder for extrusion to obtain vamp granules;
step 3, spinning: introducing vamp granules into a spinning machine for spinning to obtain vamp fibers with fineness of 1-2 dtex;
step 4, blank: drawing vamp fibers under air flow, and uniformly paving and reinforcing to obtain degradable vamp fabrics;
step 5, molding: cutting and sewing the degradable vamp fabric to form 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 multifunctional 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 an outsole mixture;
step 2, granulating: introducing the vamp mixture into a double-screw extruder for extrusion to obtain vamp granules;
step 3, foaming: introducing vamp granules into an injection foaming molding machine for foaming molding to obtain degradable outsole blanks;
step 4, baking: and baking the degradable outsole blank by a baking oven to obtain the degradable outsole blank, and embedding the bottom of the vamp type blank into the degradable outsole blank while baking to obtain the degradable bio-based shoe.
As shown in fig. 1, the material combining device comprises a supporting chassis 1 for placing the degradable outsole blank and a driving operation arm 3 for embedding the vamp type material into the degradable outsole blank. The upper side of the supporting chassis 1 is matched with the bottom of the degradable outsole blank so as to realize effective limit and fixation of the degradable outsole blank. At the same time, a support column 11 for mounting and fixing is provided 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 an up-down rotation manner. Wherein the supporting chassis 1 is provided with a fixed adapter column 12 which is connected with the driving operation arm 3 in a vertical rotation way, see fig. 2. Therefore, when the driving mechanism operates, the driving operation arm 3 is driven to swing up and down, so that the upper end of the driving operation arm 3 drives the vamp type material to move downwards and towards one side of the periphery of the supporting chassis 1, and the vamp type material is embedded into the degradable outsole type material along an inclined path, so that the embedded connection stability of the degradable outsole type material and the vamp type material is improved in an inclined inserting manner, and at the moment, the degradable outsole type material is in baking operation, so that the degradable outsole type material and the vamp type material can be in an effective and stable connection structure after the baking operation is finished, and the effect of convenience in operation is achieved.
The drive turntable 2 is provided with a transmission gearwheel 21. The drive pinion 41 is meshed with the transmission pinion 21, and the drive motor 4 for driving rotation is connected to the drive pinion 41. Therefore, the drive pinion 41 is driven to rotate when the drive motor 4 is operated, and the transmission large gear 21 is rotated by the drive of the drive pinion 41, thereby achieving the effect of stably reciprocating the drive turntable 2.
As shown in fig. 2 and 3, the driving mechanism comprises a driving turntable 2 sleeved on a supporting upright 11. At least two abutment screw outer side walls 22 are provided on the outer peripheral side walls of the drive turntable 2. The abutment screw outer wall 22 has an archimedes screw shape. The driving operation arm 3 is Z-shaped and includes an operation lower arm 31, an operation connection arm 33, and an operation upper arm 32 which are connected in this order from bottom to top. The operation lower arm 31 is provided with an abutment connection hole 311, and a driving abutment post 312 which abuts against the abutment screw outer side wall 22 and moves along the abutment screw outer side wall 22 is inserted into the abutment connection hole 311. The operation connection arm 33 is provided with a rotation connection hole 331 rotatably connected to the fixed switching post 12. An upper arm 32 is operated to be located on the upper side of the support chassis 1 and is used to embed the vamp form into the degradable outsole stock. Because the operation connecting arm 33 is rotationally connected with the fixed switching post 12, when the driving turntable 2 performs circumferential reciprocating rotation, the driving abutting post 312 abutting against the abutting spiral outer side wall 22 is driven to perform movement towards or away from the axial line of the driving turntable 2, so that the driving operation arm 3 performs circumferential reciprocating swinging movement taking the fixed switching post 12 as an axis; at this time, the operation of embedding the vamp-shaped material into the degradable outsole blank is completed in the up-and-down swinging movement process of the upper arm 32, and the connecting structure stability of the vamp-shaped material and the degradable outsole blank is improved, and meanwhile, the upper arm has the effects of convenience, high efficiency and stability in operation.
It should be mentioned that the upper arm 32 is operatively connected to an abutment drive plate 5 for contacting the vamp material and driving the embedding of the vamp material into the degradable outsole blank. The side of the abutting driving plate 5 far away from the driving operation arm 3 is provided with friction lines and is connected with a negative pressure device. The friction lines on the abutting driving plate 5 play a role in improving friction resistance with vamp type materials, and the negative pressure device is used for effectively adsorbing the vamp type materials on the abutting driving plate 5 so as to achieve the effect of effectively embedding the vamp type materials into the degradable outsole blank. A horizontal rotation column 51 is provided on the side of the abutment drive plate 5 close to the drive operation arm 3. The upper end of the operation upper arm 32 is provided with an operation coupling hole 322. The swing post 34 is rotatably connected up and down in the operation connecting hole 322. Both ends of the swing post 34 penetrate out of the operation connecting hole 322 and are connected with a limit connector 35. The limiting connector 35 is provided with a limiting connection waist-shaped groove 351 along the length direction, and two ends of the horizontal rotating column 51 are respectively inserted into the corresponding limiting connection waist-shaped groove 351, so that the horizontal rotating column 51 has the effect of moving along the length direction of the limiting connection waist-shaped groove 351 when the abutting driving plate 5 is pressed, and the effect of applying stable pressure to the degradable outsole blank by the abutting driving plate 5 is improved. Meanwhile, the upper operating arm 32 is provided with two connecting springs 321 respectively positioned 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 upper operating arm 32 is fixedly connected with the abutting driving plate 5. Therefore, when the upper arm 32 is operated to perform a downward rotation motion, the abutting driving plate 5 and the vamp molding material adsorbed on the abutting driving plate 5 are driven to rotate downward, the limiting connector 35 effectively connects the upper arm and 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 molding material to be embedded into the degradable outsole molding material, the connecting spring 321 at the upper end compresses and forms an elastic deformation force for resetting the abutting driving plate 5, the connecting spring 321 at the lower end compresses and forms an elastic deformation force for resetting the abutting driving plate 5, and the compression deformation length of the connecting spring 321 at the upper end is smaller than the compression deformation length of the connecting spring 321 at the lower end, so that the effect that the inclination angle between the vamp molding material and the vertical direction is 0-4 degrees is achieved when the vamp molding material is embedded into the degradable outsole molding material, and the connection structure stability and strength of the vamp molding material and the degradable outsole molding material are obviously improved.
As shown in fig. 2 and 3, the support chassis 1 is provided with a plurality of drive limit slots 13 respectively matched with the corresponding drive 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 inserting rod 39 arranged along the length direction of the driving limiting slot 13 and penetrating through the limiting connecting straight rod 37. A composite abutment bar 36 abutting against the operation lower arm 31 is provided at the bottom of the limit connection straight bar 37. Wherein, the top end of the limit connection straight rod 37 is provided with an abutting composite board 38 for abutting against the degradable outsole blank, and one side of the abutting composite board 38 facing the axis of the driving turntable 2 is provided with a matching inclined wall 381 matching with the corresponding part of the degradable outsole blank, when the driving upper arm swings upwards, the driving lower arm swings towards the supporting chassis 1, and the driving lower arm pushes the composite abutting rod 36 to move towards the supporting chassis 1, at this time, the limit connection straight rod 37 moves linearly along the length direction of the limit inserted rod 39 under the limit of the limit inserted rod 39, and the abutting composite board 38 moves towards one side of the axis of the driving turntable 2 to apply pressure to the degradable outsole blank, so that the degradable outsole blank in baking operation forms a stable and effective connection structure by combining the pressure applied by the abutting composite board 38 after being embedded by the vamp type material.
Example 1
A degradable bio-based shoe material comprises vamp materials and outsole materials.
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 polyesters are shown below:
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 large substrate 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 multifunctional epoxy resin is shown below:
wherein the R is 2 Is epoxy group and one or two of carboxyl and aldehyde groups.
Therefore, the vamp material and the large substrate material of the degradable bio-based shoe material are both composed of degradable materials, and the effect of being suitable for natural degradation while maintaining the characteristics of high strength and wear resistance is realized by combining the corresponding components.
A preparation method of a degradable bio-based shoe material comprises an vamp preparation part and an outsole preparation part.
The vamp preparation part comprises the following steps:
step 1, mixing: 45.8 parts of bio-based polyethylene 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 are mixed to form a vamp mixture;
step 2, granulating: introducing the vamp mixture into a double-screw extruder for extrusion to obtain vamp granules;
step 3, spinning: introducing vamp granules into a spinning machine for spinning to obtain vamp fibers with fineness of 1-2 dtex;
step 4, blank: drawing vamp fibers under air flow, and uniformly paving and reinforcing to obtain degradable vamp fabrics;
step 5, molding: cutting and sewing the degradable vamp fabric to form 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 multifunctional 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 an outsole mixture;
step 2, granulating: introducing the vamp mixture into a double-screw extruder for extrusion to obtain vamp granules;
Step 3, foaming: introducing vamp granules into an injection foaming molding machine for foaming molding to obtain degradable outsole blanks;
step 4, baking: and baking the degradable outsole blank by a baking oven to obtain the degradable outsole blank, and embedding the bottom of the vamp type blank into the degradable outsole blank while baking to obtain the degradable bio-based shoe.
As shown in fig. 1, the material combining device comprises a supporting chassis 1 for placing the degradable outsole blank and a driving operation arm 3 for embedding the vamp type material into the degradable outsole blank. The upper side of the supporting chassis 1 is matched with the bottom of the degradable outsole blank so as to realize effective limit and fixation of the degradable outsole blank. At the same time, a support column 11 for mounting and fixing is provided 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 an up-down rotation manner. Wherein the supporting chassis 1 is provided with a fixed adapter column 12 which is connected with the driving operation arm 3 in a vertical rotation way, see fig. 2. Therefore, when the driving mechanism operates, the driving operation arm 3 is driven to swing up and down, so that the upper end of the driving operation arm 3 drives the vamp type material to move downwards and towards one side of the periphery of the supporting chassis 1, and the vamp type material is embedded into the degradable outsole type material along an inclined path, so that the embedded connection stability of the degradable outsole type material and the vamp type material is improved in an inclined inserting manner, and at the moment, the degradable outsole type material is in baking operation, so that the degradable outsole type material and the vamp type material can be in an effective and stable connection structure after the baking operation is finished, and the effect of convenience in operation is achieved.
The drive turntable 2 is provided with a transmission gearwheel 21. The drive pinion 41 is meshed with the transmission pinion 21, and the drive motor 4 for driving rotation is connected to the drive pinion 41. Therefore, the drive pinion 41 is driven to rotate when the drive motor 4 is operated, and the transmission large gear 21 is rotated by the drive of the drive pinion 41, thereby achieving the effect of stably reciprocating the drive turntable 2.
As shown in fig. 2 and 3, the driving mechanism comprises a driving turntable 2 sleeved on a supporting upright 11. At least two abutment screw outer side walls 22 are provided on the outer peripheral side walls of the drive turntable 2. The abutment screw outer wall 22 has an archimedes screw shape. The driving operation arm 3 is Z-shaped and includes an operation lower arm 31, an operation connection arm 33, and an operation upper arm 32 which are connected in this order from bottom to top. The operation lower arm 31 is provided with an abutment connection hole 311, and a driving abutment post 312 which abuts against the abutment screw outer side wall 22 and moves along the abutment screw outer side wall 22 is inserted into the abutment connection hole 311. The operation connection arm 33 is provided with a rotation connection hole 331 rotatably connected to the fixed switching post 12. An upper arm 32 is operated to be located on the upper side of the support chassis 1 and is used to embed the vamp form into the degradable outsole stock. Because the operation connecting arm 33 is rotationally connected with the fixed switching post 12, when the driving turntable 2 performs circumferential reciprocating rotation, the driving abutting post 312 abutting against the abutting spiral outer side wall 22 is driven to perform movement towards or away from the axial line of the driving turntable 2, so that the driving operation arm 3 performs circumferential reciprocating swinging movement taking the fixed switching post 12 as an axis; at this time, the operation of embedding the vamp-shaped material into the degradable outsole blank is completed in the up-and-down swinging movement process of the upper arm 32, and the connecting structure stability of the vamp-shaped material and the degradable outsole blank is improved, and meanwhile, the upper arm has the effects of convenience, high efficiency and stability in operation.
It should be mentioned that the upper arm 32 is operatively connected to an abutment drive plate 5 for contacting the vamp material and driving the embedding of the vamp material into the degradable outsole blank. The side of the abutting driving plate 5 far away from the driving operation arm 3 is provided with friction lines and is connected with a negative pressure device. The friction lines on the abutting driving plate 5 play a role in improving friction resistance with vamp type materials, and the negative pressure device is used for effectively adsorbing the vamp type materials on the abutting driving plate 5 so as to achieve the effect of effectively embedding the vamp type materials into the degradable outsole blank. A horizontal rotation column 51 is provided on the side of the abutment drive plate 5 close to the drive operation arm 3. The upper end of the operation upper arm 32 is provided with an operation coupling hole 322. The swing post 34 is rotatably connected up and down in the operation connecting hole 322. Both ends of the swing post 34 penetrate out of the operation connecting hole 322 and are connected with a limit connector 35. The limiting connector 35 is provided with a limiting connection waist-shaped groove 351 along the length direction, and two ends of the horizontal rotating column 51 are respectively inserted into the corresponding limiting connection waist-shaped groove 351, so that the horizontal rotating column 51 has the effect of moving along the length direction of the limiting connection waist-shaped groove 351 when the abutting driving plate 5 is pressed, and the effect of applying stable pressure to the degradable outsole blank by the abutting driving plate 5 is improved. Meanwhile, the upper operating arm 32 is provided with two connecting springs 321 respectively positioned 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 upper operating arm 32 is fixedly connected with the abutting driving plate 5. Therefore, when the upper arm 32 is operated to perform a downward rotation motion, the abutting driving plate 5 and the vamp molding material adsorbed on the abutting driving plate 5 are driven to rotate downward, the limiting connector 35 effectively connects the upper arm and 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 molding material to be embedded into the degradable outsole molding material, the connecting spring 321 at the upper end compresses and forms an elastic deformation force for resetting the abutting driving plate 5, the connecting spring 321 at the lower end compresses and forms an elastic deformation force for resetting the abutting driving plate 5, and the compression deformation length of the connecting spring 321 at the upper end is smaller than the compression deformation length of the connecting spring 321 at the lower end, so that the effect that the inclination angle between the vamp molding material and the vertical direction is 0-4 degrees is achieved when the vamp molding material is embedded into the degradable outsole molding material, and the connection structure stability and strength of the vamp molding material and the degradable outsole molding material are obviously improved.
As shown in fig. 2 and 3, the support chassis 1 is provided with a plurality of drive limit slots 13 respectively matched with the corresponding drive 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 inserting rod 39 arranged along the length direction of the driving limiting slot 13 and penetrating through the limiting connecting straight rod 37. A composite abutment bar 36 abutting against the operation lower arm 31 is provided at the bottom of the limit connection straight bar 37. Wherein, the top end of the limit connection straight rod 37 is provided with an abutting composite board 38 for abutting against the degradable outsole blank, and one side of the abutting composite board 38 facing the axis of the driving turntable 2 is provided with a matching inclined wall 381 matching with the corresponding part of the degradable outsole blank, when the driving upper arm swings upwards, the driving lower arm swings towards the supporting chassis 1, and the driving lower arm pushes the composite abutting rod 36 to move towards the supporting chassis 1, at this time, the limit connection straight rod 37 moves linearly along the length direction of the limit inserted rod 39 under the limit of the limit inserted rod 39, and the abutting composite board 38 moves towards one side of the axis of the driving turntable 2 to apply pressure to the degradable outsole blank, so that the degradable outsole blank in baking operation forms a stable and effective connection structure by combining the pressure applied by the abutting composite board 38 after being embedded by the vamp type material.
The peel strength of the degradable bio-based shoe material of example one was detected to be 120N/cm 3 The breaking strength is 462N/cm 3 The 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 polyesters are shown below:
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 large substrate 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 multifunctional epoxy resin is shown below:
wherein the R is 2 Is epoxy group and one or two of carboxyl and aldehyde groups.
Therefore, the vamp material and the large substrate material of the degradable bio-based shoe material are both composed of degradable materials, and the effect of being suitable for natural degradation while maintaining the characteristics of high strength and wear resistance is realized by combining the corresponding components.
A preparation method of a degradable bio-based shoe material comprises an 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 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, granulating: introducing the vamp mixture into a double-screw extruder for extrusion to obtain vamp granules;
step 3, spinning: introducing vamp granules into a spinning machine for spinning to obtain vamp fibers with fineness of 1-2 dtex;
step 4, blank: drawing vamp fibers under air flow, and uniformly paving and reinforcing to obtain degradable vamp fabrics;
step 5, molding: cutting and sewing the degradable vamp fabric to form the vamp material
The outsole preparation part comprises the following steps:
step 1, mixing: 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 are mixed to form an outsole mixture;
Step 2, granulating: introducing the vamp mixture into a double-screw extruder for extrusion to obtain vamp granules;
step 3, foaming: introducing vamp granules into an injection foaming molding machine for foaming molding to obtain degradable outsole blanks;
step 4, baking: and baking the degradable outsole blank by a baking oven to obtain the degradable outsole blank, and embedding the bottom of the vamp type blank into the degradable outsole blank while baking to obtain the degradable bio-based shoe.
The peel strength of the degradable bio-based footwear material of example two was detected to be 129N/cm 3 The breaking strength is 486N/cm 3 The biodegradation performance of the vamp material is 8, and the biodegradation performance of the outsole 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 polyesters are shown below:
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 large substrate 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 multifunctional epoxy resin is shown below:
wherein the R is 2 Is epoxy group and one or two of carboxyl and aldehyde groups.
Therefore, the vamp material and the large substrate material of the degradable bio-based shoe material are both composed of degradable materials, and the effect of being suitable for natural degradation while maintaining the characteristics of high strength and wear resistance is realized by combining the corresponding components.
A preparation method of a degradable bio-based shoe material comprises an vamp preparation part and an outsole preparation part.
The vamp preparation part comprises the following steps:
step 1, mixing: 72.5 parts of bio-based polyethylene 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 are mixed to form a vamp mixture;
step 2, granulating: introducing the vamp mixture into a double-screw extruder for extrusion to obtain vamp granules;
step 3, spinning: introducing vamp granules into a spinning machine for spinning to obtain vamp fibers with fineness of 1-2 dtex;
step 4, blank: drawing vamp fibers under air flow, and uniformly paving and reinforcing to obtain degradable vamp fabrics;
Step 5, molding: cutting and sewing the degradable vamp fabric to form 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 multifunctional 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 an outsole mixture;
step 2, granulating: introducing the vamp mixture into a double-screw extruder for extrusion to obtain vamp granules;
step 3, foaming: introducing vamp granules into an injection foaming molding machine for foaming molding to obtain degradable outsole blanks;
step 4, baking: and baking the degradable outsole blank by a baking oven to obtain the degradable outsole blank, and embedding the bottom of the vamp type blank into the degradable outsole blank while baking to obtain the degradable bio-based shoe.
The degradable bio-based shoe of example three was testedThe peel strength of the material is 141N/cm 3 The breaking strength is 512N/cm 3 The biodegradation performance of the vamp material is 8, and the biodegradation performance of the outsole material is 9.
In summary, 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 and the vamp material is prepared, the vamp material has a degradable function, and meanwhile, the bio-based polyethylene glycol succinate and the polylactic acid are connected by the terpolymer polyester, and the effects of improving the strength and improving the wear resistance are realized under the reinforcement of the porous nano hydroxyapatite and the fly ash; when the ethylene-vinyl acetate copolymer, the corn starch, the xylitol-based multifunctional epoxy resin, the potassium carbonate, the AC foaming agent, the fly ash and the hexahydrophthalic anhydride are mixed and the outsole material is prepared, the outsole material has a degradable function, 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 improvement and the wear resistance improvement effect are realized under the reinforcement of the fly ash and the hexahydrophthalic anhydride, and the connection of the degradable outsole blank and the vamp material is completed under the driving of a 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.
The references to "first," "second," "third," "fourth," etc. (if present) are used to distinguish similar objects from each other and are not necessarily used to describe a particular order or sequence. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments described herein may be implemented in other sequences than those illustrated or otherwise described herein. Furthermore, the terms "comprises," "comprising," and "having," 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 or inherent to such process, method, or apparatus.
It should be noted that the description of "first", "second", etc. in this disclosure is for descriptive purposes only and is not to be construed as indicating or implying a relative importance or implying an indication of the number of technical features being indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present application.
The principles and embodiments of the present application have been described herein with reference to specific examples, the description of which is intended only to assist in understanding the methods of the present application and the core ideas thereof; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present application, the present description should not be construed as limiting the present application in view of the above.

Claims (9)

1. A degradable bio-based footwear material, characterized by: comprises vamp materials and outsole materials;
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 large substrate 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. A degradable biobased shoe material according to claim 1, wherein said terpolymer polyester is as follows:
；
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 footwear material according to claim 1, wherein the xylitol-based multifunctional epoxy resin is as follows:
；
wherein the R is 2 Is epoxy group and one or two of carboxyl and aldehyde groups.
4. A preparation method of a degradable bio-based shoe material is characterized by comprising the following steps: comprises an vamp preparation part and an outsole preparation part; the vamp preparation part comprises the following steps:
step 1, 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 are mixed to form a vamp mixture;
step 2, granulating: introducing the vamp mixture into a double-screw extruder for extrusion to obtain vamp granules;
step 3, spinning: introducing vamp granules into a spinning machine for spinning to obtain vamp fibers with fineness of 1-2 dtex;
step 4, blank: drawing vamp fibers under air flow, and uniformly paving and reinforcing to obtain degradable vamp fabrics;
step 5, molding: cutting and sewing the degradable vamp fabric to form a 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 multifunctional 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 an outsole mixture;
step 2, granulating: introducing the outsole mixture into a double-screw extruder for extrusion to obtain outsole granules;
step 3, foaming: introducing the outsole granules into an injection foaming molding machine for foaming molding to obtain degradable outsole blanks;
step 4, baking: and baking the degradable outsole blank by a baking oven to obtain the degradable outsole blank, and embedding the bottom of the degradable vamp fabric into the degradable outsole blank by a material combining device while baking to obtain the degradable bio-based shoe.
5. The method for preparing the degradable bio-based shoe material according to claim 4, wherein: in step 4 of the outsole preparation part, the material combining device comprises a supporting base plate (1) for placing a degradable outsole blank and a driving operation arm (3) for embedding an vamp type material into the degradable outsole blank, the upper side of the supporting base plate (1) is matched with the bottom of the degradable outsole blank, a supporting stand column (11) for installing and fixing and a fixed switching column (12) connected with the driving operation arm (3) in an up-and-down rotation mode are arranged at the bottom of the supporting base plate (1), and a driving mechanism for driving the driving operation arm (3) to swing up and down is arranged on the supporting stand column (11).
6. The method for preparing the degradable bio-based shoe material according to claim 5, 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 outer peripheral side walls of the driving turntable (2); the driving operation arm (3) is Z-shaped and comprises an operation lower arm (31), an operation connecting arm (33) and an operation upper arm (32) which are sequentially connected from bottom to top, the operation lower arm (31) is provided with an abutting connection hole (311), a driving abutting column (312) which abuts against 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 connection hole (331) which is rotationally connected with the fixed switching column (12), and the operation upper arm (32) is positioned on the upper side of the supporting chassis (1) and used for embedding vamp-shaped materials into degradable outsole blanks.
7. The method for preparing the degradable bio-based shoe material according to claim 6, wherein: the upper operating arm (32) is connected with a butt driving plate (5) which is used for being in contact with vamp-shaped materials and driving the vamp-shaped materials to be embedded into degradable outsole blanks, friction lines are formed on one side, away from the driving operating arm (3), of the butt driving plate (5) and connected with a negative pressure device, a horizontal rotating column (51) is arranged on one side, close to the driving operating arm (3), of the butt driving plate (5), an operation connecting hole (322) is formed in the upper end of the upper operating arm (32), a swing connecting column (34) is connected in the operation connecting hole (322) in a vertical rotating mode, two ends of the swing connecting column (34) penetrate out of the operation connecting hole (322) and are connected with limiting connecting bodies (35), limiting connecting waist-shaped grooves (351) are formed in the length direction of the limiting connecting bodies (35), and two ends of the horizontal rotating column (51) are respectively inserted into the corresponding limiting waist-shaped grooves (351); the upper operating arm (32) is provided with two connecting springs (321) which are respectively positioned on the upper side and the lower side of the limiting connector (35), and one end, far away from the upper operating arm (32), of the connecting springs (321) is fixedly connected with the abutting driving plate (5).
8. The method for preparing the degradable bio-based shoe material according to claim 7, wherein: the supporting chassis (1) is provided with a plurality of drive limiting slots (13) that respectively match with corresponding drive operation arm (3), drive limiting slots (13) are pegged graft have along spacing connection straight-bar (37) of vertical direction setting and are followed drive limiting slots (13) length direction sets up and runs through spacing inserted bar (39) of spacing connection straight-bar (37), the bottom of spacing connection straight-bar (37) be provided with compound butt stick (36) of operation lower arm (31) butt, the top of spacing connection straight-bar (37) is provided with butt composite sheet (38) that are used for with degradable big end 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 big end stock.
9. The method for preparing the degradable bio-based shoe material according to claim 7, wherein: the driving turntable (2) is provided with a transmission large gear (21), the transmission large gear (21) is meshed with a driving small gear (41), and the driving small gear (41) is connected with a driving motor (4) for driving and rotating.
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