CN117384469B - Breathable wear-resistant vamp material and preparation method thereof - Google Patents
Breathable wear-resistant vamp material and preparation method thereof Download PDFInfo
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- CN117384469B CN117384469B CN202311334558.9A CN202311334558A CN117384469B CN 117384469 B CN117384469 B CN 117384469B CN 202311334558 A CN202311334558 A CN 202311334558A CN 117384469 B CN117384469 B CN 117384469B
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- 239000000463 material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 49
- 229920000728 polyester Polymers 0.000 claims abstract description 27
- 239000007822 coupling agent Substances 0.000 claims abstract description 25
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- 239000011256 inorganic filler Substances 0.000 claims abstract description 13
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 13
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 7
- 239000004743 Polypropylene Substances 0.000 claims abstract description 7
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 7
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 7
- 229920001194 natural rubber Polymers 0.000 claims abstract description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 7
- -1 polypropylene Polymers 0.000 claims abstract description 7
- 229920001155 polypropylene Polymers 0.000 claims abstract description 7
- 229920005989 resin Polymers 0.000 claims abstract description 7
- 239000011347 resin Substances 0.000 claims abstract description 7
- 239000008117 stearic acid Substances 0.000 claims abstract description 7
- 239000011787 zinc oxide Substances 0.000 claims abstract description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 98
- 239000005543 nano-size silicon particle Substances 0.000 claims description 61
- 238000002156 mixing Methods 0.000 claims description 42
- 238000001035 drying Methods 0.000 claims description 41
- 235000012239 silicon dioxide Nutrition 0.000 claims description 37
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 36
- 238000003756 stirring Methods 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 229910000281 calcium bentonite Inorganic materials 0.000 claims description 30
- 239000000835 fiber Substances 0.000 claims description 25
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 24
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 18
- 229920001577 copolymer Polymers 0.000 claims description 18
- 239000000839 emulsion Substances 0.000 claims description 18
- 238000001694 spray drying Methods 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 229910000278 bentonite Inorganic materials 0.000 claims description 12
- 239000000440 bentonite Substances 0.000 claims description 12
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 150000001282 organosilanes Chemical group 0.000 claims description 12
- 239000004744 fabric Substances 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 238000010306 acid treatment Methods 0.000 claims description 6
- 238000000889 atomisation Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical group COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 238000009940 knitting Methods 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 239000012188 paraffin wax Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 238000007493 shaping process Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 claims description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000009941 weaving Methods 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 12
- 238000009835 boiling Methods 0.000 description 9
- 230000035699 permeability Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- A—HUMAN NECESSITIES
- A43—FOOTWEAR
- A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
- A43B1/00—Footwear characterised by the material
- A43B1/02—Footwear characterised by the material made of fibres or fabrics made therefrom
- A43B1/04—Footwear characterised by the material made of fibres or fabrics made therefrom braided, knotted, knitted or crocheted
-
- 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
-
- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04B—KNITTING
- D04B1/00—Weft knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
- D04B1/14—Other fabrics or articles characterised primarily by the use of particular thread materials
- D04B1/16—Other fabrics or articles characterised primarily by the use of particular thread materials synthetic threads
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04B—KNITTING
- D04B21/00—Warp knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/04—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyesters, e.g. polyethylene terephthalate [PET]
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a breathable wear-resistant vamp material and a preparation method thereof, which relate to the technical field of vamp materials and are prepared from the following components: the composite modified polyester chip, inorganic filler, coupling agent, dispersing agent, zinc oxide, polypropylene resin, natural rubber and stearic acid; the invention provides a breathable wear-resistant vamp material, which has excellent breathability and wear resistance.
Description
Technical Field
The invention belongs to the field of vamp materials, and in particular relates to a breathable wear-resistant vamp material and a preparation method thereof.
Background
Shoes, which are articles worn on the feet to prevent the feet from being damaged, are mostly grass shoes and cloth shoes in the early stage of human civilization, and are widely used in leather shoes, sport shoes, casual shoes and high-heeled shoes nowadays.
For some most shoes, the breathability of the shoe, and the surface abrasion resistance are directly related to the comfort and the service life of the shoe.
For the air permeability of shoes, this directly receives the influence of vamp material, that is, the air permeability of vamp material directly relates to the air permeability of shoes, and good air permeability can keep the shoes dry, can wear more comfortablely, and to the wearability of vamp, this directly relates to the life of shoes again, and the shoes that the vamp material that wearability is relatively poor makes can lead to the fact the vamp to damage owing to long-time friction and wear to unable continue to use.
Many of the existing shoes are made of polyester material directly, however, the wear resistance of the sole made of polyester material is relatively general.
Accordingly, there is a need for further improvements in the art.
Disclosure of Invention
The invention aims to provide a breathable wear-resistant vamp material, which aims to solve the defects in the prior art.
The technical scheme adopted by the invention is as follows:
the breathable wear-resistant vamp material is prepared from the following components in parts by weight: 55-60 parts of composite modified polyester chips, 20-25 parts of inorganic filler, 1.2-1.6 parts of coupling agent, 1-2 parts of dispersing agent, 2-3 parts of zinc oxide, 5-8 parts of polypropylene resin, 2-4 parts of natural rubber and 1.5-1.8 parts of stearic acid.
As a further technical scheme: the inorganic filler is as follows: bentonite;
wherein the bentonite is calcium bentonite;
Wherein, the calcium bentonite is subjected to acid treatment:
Uniformly dispersing the calcium bentonite into deionized water, stirring and mixing uniformly, adding sulfuric acid solution, stirring and mixing for 1 hour, filtering, washing to be neutral, and drying to constant weight;
wherein, the mixing mass ratio of the calcium bentonite to the deionized water is 1:15-20;
The mass ratio of the calcium bentonite to the sulfuric acid solution is 10:1-3;
the mass fraction of the sulfuric acid solution is 5%.
As a further technical scheme: the preparation method of the composite modified polyester chip comprises the following steps:
(1) Firstly, uniformly dispersing nano silicon dioxide into deionized water to obtain nano silicon dioxide dispersion liquid;
(2) Firstly, preparing ammonia water, and then adjusting the pH of the prepared ammonia water to 10.0;
(3) Adding vinyl acetate copolymer emulsion into the nano silicon dioxide dispersion liquid with the pH adjusted, heating to 80 ℃ at the heating rate of 5 ℃/s, preserving heat and stirring for 1 hour, wherein the stirring speed is 1000r/min, and then performing spray drying to obtain composite nano silicon dioxide;
(4) Sequentially adding the composite nano silicon dioxide, polyethylene glycol terephthalate and p-aminobenzene sulfonamide into an extruder according to the mass ratio of 4-6:55:1.2-1.6 for melt extrusion granulation to obtain the composite nano silicon dioxide;
wherein, the extruder is a double-screw extruder;
The length-diameter ratio of the twin-screw extruder is 16:1, and the temperature of the machine head is 200 ℃.
As a further technical scheme: the nano silicon dioxide dispersion liquid in the step (1) is formed by mixing nano silicon dioxide and deionized water according to the mass ratio of 1-2:20 at normal temperature;
Wherein, stirring is carried out for 20min at a rotating speed of 3000r/min during mixing.
As a further technical scheme: and (3) the mass fraction of the ammonia water in the step (2) is 15%.
As a further technical scheme: the mixing mass ratio of the vinyl acetate copolymer emulsion to the nano silicon dioxide dispersion liquid in the step (3) is 1:4-5;
wherein the solid content of the vinyl acetate copolymer emulsion is 30.5%.
As a further technical scheme: the spray drying in the step (3) adopts a pressure spray drying method:
The high-pressure pump is adopted to carry out atomization treatment at 185-190 atm, and then drying is carried out.
As a further technical scheme: the coupling agent is an organosilane coupling agent;
wherein the organosilane coupling agent is vinyltris (beta-methoxyethoxy) silane;
The dispersing agent is microcrystalline paraffin.
A method for preparing an air-permeable wear-resistant vamp material, which comprises the following steps:
(1) Weighing the raw materials of the components according to the weight portions;
(2) Sequentially adding the obtained components into a drying oven, and drying to obtain a dried material;
(3) Adding the dried material into a mixer, stirring and mixing uniformly, adding the uniformly mixed raw materials into an extruder for melting, spraying through a spinneret plate, and cooling and shaping to obtain composite fibers;
(5) And weaving the composite fiber into cloth by a knitting machine to obtain the required vamp material.
As a further technical scheme, the drying temperature in the drying oven is 60 ℃, and the drying time is 10 hours.
The beneficial effects are that:
The invention provides a breathable wear-resistant vamp material, which has excellent breathability and wear resistance.
According to the invention, the crystallization performance and heat resistance of polyester can be greatly enhanced by adding the composite nano silicon dioxide, and the interface compatibility between the obtained composite nano silicon dioxide and polyester can be greatly improved by modifying and compounding the nano silicon dioxide, so that the wear resistance and heat resistance of the finished vamp material can be better improved.
After the composite nano silicon dioxide is introduced, the basic crystal structure of the polyester is not changed, so that the integrality of the crystal structure of the polyester can be ensured, meanwhile, the composite nano silicon dioxide also plays a role of a nucleating agent, and the macromolecular chains of the polyester are heterogeneous nucleated by taking the nano silicon dioxide as a center and orderly arranged into crystal lattices, so that the crystallization rate of the polyester can be remarkably improved, the crystallization performance of the polyester is further improved, and the heat resistance and the wear resistance of the polyester can be remarkably improved.
The heat resistance is improved, the heat shrinkage of vamp materials can be reduced, the wear resistance is improved, the manufactured shoe surface is more wear-resistant, and the service life is greatly prolonged.
The vamp material made in the form of the woven cloth has better air permeability compared with the complete fabric, and can have better elasticity, better adaptability and improved comfort of the manufactured shoes.
Drawings
FIG. 1 is a bar graph of boiling water shrinkage for the fiber samples of the examples and comparative examples.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The following are specific examples:
Example 1
The breathable wear-resistant vamp material is prepared from the following components in parts by weight: 55 parts of composite modified polyester chips, 20 parts of inorganic filler, 1.2 parts of coupling agent, 1 part of dispersing agent, 2 parts of zinc oxide, 5 parts of polypropylene resin, 2 parts of natural rubber and 1.5 parts of stearic acid.
The inorganic filler is as follows: bentonite;
wherein the bentonite is calcium bentonite;
Wherein, the calcium bentonite is subjected to acid treatment:
Uniformly dispersing the calcium bentonite into deionized water, stirring and mixing uniformly, adding sulfuric acid solution, stirring and mixing for 1 hour, filtering, washing to be neutral, and drying to constant weight;
wherein, the mixing mass ratio of the calcium bentonite to the deionized water is 1:15;
The mass ratio of the calcium bentonite to the sulfuric acid solution is 10:1;
the mass fraction of the sulfuric acid solution is 5%.
The preparation method of the composite modified polyester chip comprises the following steps:
(1) Firstly, uniformly dispersing nano silicon dioxide into deionized water to obtain nano silicon dioxide dispersion liquid; the nano silicon dioxide dispersion liquid is formed by mixing nano silicon dioxide and deionized water according to the mass ratio of 1:20 at normal temperature;
Wherein, stirring is carried out for 20min at a rotating speed of 3000r/min during mixing.
(2) Firstly, preparing ammonia water, and then adjusting the pH of the prepared ammonia water to 10.0; the mass fraction of the ammonia water is 15%.
(3) Adding vinyl acetate copolymer emulsion into the nano silicon dioxide dispersion liquid with the pH adjusted, heating to 80 ℃ at the heating rate of 5 ℃/s, preserving heat and stirring for 1 hour, wherein the stirring speed is 1000r/min, and then performing spray drying to obtain composite nano silicon dioxide; the mixing mass ratio of the vinyl acetate copolymer emulsion to the nano silicon dioxide dispersion liquid is 1:4;
wherein the solid content of the vinyl acetate copolymer emulsion is 30.5%.
The spray drying adopts a pressure spray drying method:
the high-pressure pump is adopted to carry out atomization treatment at 185 atmospheric pressure, and then drying is carried out.
(4) Sequentially adding the composite nano silicon dioxide, polyethylene glycol terephthalate and p-aminobenzene sulfonamide into an extruder according to the mass ratio of 4:55:1.2 for melt extrusion granulation to obtain the composite nano silicon dioxide;
wherein, the extruder is a double-screw extruder;
The length-diameter ratio of the twin-screw extruder is 16:1, and the temperature of the machine head is 200 ℃.
The coupling agent is an organosilane coupling agent;
wherein the organosilane coupling agent is vinyltris (beta-methoxyethoxy) silane;
The dispersing agent is microcrystalline paraffin.
A method for preparing an air-permeable wear-resistant vamp material, which comprises the following steps:
(1) Weighing the raw materials of the components according to the weight portions;
(2) Sequentially adding the obtained components into a drying oven, and drying to obtain a dried material;
(3) Adding the dried material into a mixer, stirring and mixing uniformly, adding the uniformly mixed raw materials into an extruder for melting, spraying through a spinneret plate, and cooling and shaping to obtain composite fibers;
(5) Weaving the composite fiber into cloth by a knitting machine to obtain the required vamp material; the drying temperature in the drying oven is 60 ℃ and the drying time is 10 hours.
Example 2
The breathable wear-resistant vamp material is prepared from the following components in parts by weight: 58 parts of composite modified polyester chips, 22 parts of inorganic filler, 1.5 parts of coupling agent, 1.2 parts of dispersing agent, 2.6 parts of zinc oxide, 6 parts of polypropylene resin, 2.5 parts of natural rubber and 1.8 parts of stearic acid.
The inorganic filler is as follows: bentonite;
wherein the bentonite is calcium bentonite;
Wherein, the calcium bentonite is subjected to acid treatment:
Uniformly dispersing the calcium bentonite into deionized water, stirring and mixing uniformly, adding sulfuric acid solution, stirring and mixing for 1 hour, filtering, washing to be neutral, and drying to constant weight;
Wherein, the mixing mass ratio of the calcium bentonite to the deionized water is 1:16;
The mass ratio of the calcium bentonite to the sulfuric acid solution is 10:2;
the mass fraction of the sulfuric acid solution is 5%.
The preparation method of the composite modified polyester chip comprises the following steps:
(1) Firstly, uniformly dispersing nano silicon dioxide into deionized water to obtain nano silicon dioxide dispersion liquid; the nano silicon dioxide dispersion liquid is formed by mixing nano silicon dioxide and deionized water according to the mass ratio of 1.5:20 at normal temperature;
Wherein, stirring is carried out for 20min at a rotating speed of 3000r/min during mixing.
(2) Firstly, preparing ammonia water, and then adjusting the pH of the prepared ammonia water to 10.0; the mass fraction of the ammonia water is 15%.
(3) Adding vinyl acetate copolymer emulsion into the nano silicon dioxide dispersion liquid with the pH adjusted, heating to 80 ℃ at the heating rate of 5 ℃/s, preserving heat and stirring for 1 hour, wherein the stirring speed is 1000r/min, and then performing spray drying to obtain composite nano silicon dioxide; the mixing mass ratio of the vinyl acetate copolymer emulsion to the nano silicon dioxide dispersion liquid is 1:4.5;
wherein the solid content of the vinyl acetate copolymer emulsion is 30.5%.
The spray drying adopts a pressure spray drying method:
the high-pressure pump is adopted to carry out atomization treatment at 189 atm, and then drying is carried out.
(4) Sequentially adding the composite nano silicon dioxide, polyethylene glycol terephthalate and p-aminobenzene sulfonamide into an extruder according to the mass ratio of 4.5:55:1.5 for melt extrusion granulation to obtain the composite nano silicon dioxide;
wherein, the extruder is a double-screw extruder;
The length-diameter ratio of the twin-screw extruder is 16:1, and the temperature of the machine head is 200 ℃.
The coupling agent is an organosilane coupling agent;
wherein the organosilane coupling agent is vinyltris (beta-methoxyethoxy) silane;
The dispersing agent is microcrystalline paraffin.
A method for preparing an air-permeable wear-resistant vamp material, which comprises the following steps:
(1) Weighing the raw materials of the components according to the weight portions;
(2) Sequentially adding the obtained components into a drying oven, and drying to obtain a dried material;
(3) Adding the dried material into a mixer, stirring and mixing uniformly, adding the uniformly mixed raw materials into an extruder for melting, spraying through a spinneret plate, and cooling and shaping to obtain composite fibers;
(5) Weaving the composite fiber into cloth by a knitting machine to obtain the required vamp material; the drying temperature in the drying oven is 60 ℃ and the drying time is 10 hours.
Example 3
The breathable wear-resistant vamp material is prepared from the following components in parts by weight: 58 parts of composite modified polyester chips, 22 parts of inorganic filler, 1.4 parts of coupling agent, 1.5 parts of dispersing agent, 2.2 parts of zinc oxide, 7 parts of polypropylene resin, 3 parts of natural rubber and 1.6 parts of stearic acid.
The inorganic filler is as follows: bentonite;
wherein the bentonite is calcium bentonite;
Wherein, the calcium bentonite is subjected to acid treatment:
Uniformly dispersing the calcium bentonite into deionized water, stirring and mixing uniformly, adding sulfuric acid solution, stirring and mixing for 1 hour, filtering, washing to be neutral, and drying to constant weight;
Wherein, the mixing mass ratio of the calcium bentonite to the deionized water is 1:18;
The mass ratio of the calcium bentonite to the sulfuric acid solution is 10:2;
the mass fraction of the sulfuric acid solution is 5%.
The preparation method of the composite modified polyester chip comprises the following steps:
(1) Firstly, uniformly dispersing nano silicon dioxide into deionized water to obtain nano silicon dioxide dispersion liquid; the nano silicon dioxide dispersion liquid is formed by mixing nano silicon dioxide and deionized water according to the mass ratio of 1.5:20 at normal temperature;
Wherein, stirring is carried out for 20min at a rotating speed of 3000r/min during mixing.
(2) Firstly, preparing ammonia water, and then adjusting the pH of the prepared ammonia water to 10.0; the mass fraction of the ammonia water is 15%.
(3) Adding vinyl acetate copolymer emulsion into the nano silicon dioxide dispersion liquid with the pH adjusted, heating to 80 ℃ at the heating rate of 5 ℃/s, preserving heat and stirring for 1 hour, wherein the stirring speed is 1000r/min, and then performing spray drying to obtain composite nano silicon dioxide; the mixing mass ratio of the vinyl acetate copolymer emulsion to the nano silicon dioxide dispersion liquid is 1:4.5;
wherein the solid content of the vinyl acetate copolymer emulsion is 30.5%.
The spray drying adopts a pressure spray drying method:
The high-pressure pump is adopted to carry out atomization treatment at the pressure of 186 atm, and then drying is carried out.
(4) Sequentially adding the composite nano silicon dioxide, polyethylene glycol terephthalate and p-aminobenzene sulfonamide into an extruder according to the mass ratio of 5:55:1.4 for melt extrusion granulation to obtain the composite nano silicon dioxide;
wherein, the extruder is a double-screw extruder;
The length-diameter ratio of the twin-screw extruder is 16:1, and the temperature of the machine head is 200 ℃.
The coupling agent is an organosilane coupling agent;
wherein the organosilane coupling agent is vinyltris (beta-methoxyethoxy) silane;
The dispersing agent is microcrystalline paraffin.
A method for preparing an air-permeable wear-resistant vamp material, which comprises the following steps:
(1) Weighing the raw materials of the components according to the weight portions;
(2) Sequentially adding the obtained components into a drying oven, and drying to obtain a dried material;
(3) Adding the dried material into a mixer, stirring and mixing uniformly, adding the uniformly mixed raw materials into an extruder for melting, spraying through a spinneret plate, and cooling and shaping to obtain composite fibers;
(5) Weaving the composite fiber into cloth by a knitting machine to obtain the required vamp material; the drying temperature in the drying oven is 60 ℃ and the drying time is 10 hours.
Example 4
The breathable wear-resistant vamp material is prepared from the following components in parts by weight: 60 parts of composite modified polyester chips, 25 parts of inorganic filler, 1.6 parts of coupling agent, 2 parts of dispersing agent, 3 parts of zinc oxide, 8 parts of polypropylene resin, 4 parts of natural rubber and 1.8 parts of stearic acid.
The inorganic filler is as follows: bentonite;
wherein the bentonite is calcium bentonite;
Wherein, the calcium bentonite is subjected to acid treatment:
Uniformly dispersing the calcium bentonite into deionized water, stirring and mixing uniformly, adding sulfuric acid solution, stirring and mixing for 1 hour, filtering, washing to be neutral, and drying to constant weight;
Wherein, the mixing mass ratio of the calcium bentonite to the deionized water is 1:20;
the mass ratio of the calcium bentonite to the sulfuric acid solution is 10:3;
the mass fraction of the sulfuric acid solution is 5%.
The preparation method of the composite modified polyester chip comprises the following steps:
(1) Firstly, uniformly dispersing nano silicon dioxide into deionized water to obtain nano silicon dioxide dispersion liquid; the nano silicon dioxide dispersion liquid is formed by mixing nano silicon dioxide and deionized water according to the mass ratio of 2:20 at normal temperature;
Wherein, stirring is carried out for 20min at a rotating speed of 3000r/min during mixing.
(2) Firstly, preparing ammonia water, and then adjusting the pH of the prepared ammonia water to 10.0; the mass fraction of the ammonia water is 15%.
(3) Adding vinyl acetate copolymer emulsion into the nano silicon dioxide dispersion liquid with the pH adjusted, heating to 80 ℃ at the heating rate of 5 ℃/s, preserving heat and stirring for 1 hour, wherein the stirring speed is 1000r/min, and then performing spray drying to obtain composite nano silicon dioxide; the mixing mass ratio of the vinyl acetate copolymer emulsion to the nano silicon dioxide dispersion liquid is 1:5;
wherein the solid content of the vinyl acetate copolymer emulsion is 30.5%.
The spray drying adopts a pressure spray drying method:
The high-pressure pump is adopted to carry out atomization treatment at the pressure of 190 atm, and then the mixture is dried.
(4) Sequentially adding the composite nano silicon dioxide, polyethylene glycol terephthalate and p-aminobenzene sulfonamide into an extruder according to the mass ratio of 6:55:1.6 for melt extrusion granulation to obtain the composite nano silicon dioxide;
wherein, the extruder is a double-screw extruder;
The length-diameter ratio of the twin-screw extruder is 16:1, and the temperature of the machine head is 200 ℃.
The coupling agent is an organosilane coupling agent;
wherein the organosilane coupling agent is vinyltris (beta-methoxyethoxy) silane;
The dispersing agent is microcrystalline paraffin.
A method for preparing an air-permeable wear-resistant vamp material, which comprises the following steps:
(1) Weighing the raw materials of the components according to the weight portions;
(2) Sequentially adding the obtained components into a drying oven, and drying to obtain a dried material;
(3) Adding the dried material into a mixer, stirring and mixing uniformly, adding the uniformly mixed raw materials into an extruder for melting, spraying through a spinneret plate, and cooling and shaping to obtain composite fibers;
(5) Weaving the composite fiber into cloth by a knitting machine to obtain the required vamp material; the drying temperature in the drying oven is 60 ℃ and the drying time is 10 hours.
Comparative example 1:
based on the embodiment 1, the composite modified polyester chip is replaced by an unmodified polyester chip, and the rest technical schemes are unchanged.
Comparative example 2:
Based on the embodiment 1, the composite modified polyester chip is replaced by an equivalent amount of physical mixture of nano silicon dioxide and the polyester chip, and the rest technical schemes are unchanged.
Experiment
The fibers of the examples and comparative examples were subjected to a boiling water shrinkage test
The boiling water shrinkage rate reflects the structural order of the fiber, characterizes the stability of the fiber size, changes the length of the fiber after the fiber is treated in boiling water at 100 ℃ for 30min, and divides the change of the contracted or elongated filaments by the percentage of the original filament length to obtain the boiling water shrinkage rate of the fiber;
TABLE 1
| Shrinkage in boiling water% | |
| Example 1 | 1.27 |
| Example 2 | 1.20 |
| Example 3 | 1.25 |
| Example 4 | 1.26 |
| Comparative example 1 | 4.58 |
| Comparative example 2 | 4.04 |
As can be seen from Table 1, the raw material fibers of the present invention have lower boiling water shrinkage, and the vamp material prepared from the raw material fibers have lower boiling water shrinkage.
Fibers from examples and comparative examples were tested by XQ-1A yarn extensometer as shown in Table 2:
TABLE 2
| Breaking strength CN/dtex | |
| Example 1 | 2.6 |
| Example 2 | 2.9 |
| Example 3 | 2.4 |
| Example 4 | 2.5 |
| Comparative example 1 | 1.2 |
| Comparative example 2 | 1.8 |
As can be seen from Table 2, the raw material fiber prepared by the invention has higher breaking strength, and the mechanical properties of vamp materials prepared by the raw material fiber can be obviously improved.
Wear-resisting instrument with hem grinds function. The width of the edge folding grinding clamp is 1 plus or minus 0.1 mm, the reciprocating speed is 150 plus or minus 5 times/min, and the stroke is 20 plus or minus 2 mm; the test bed moves reciprocally for 150 times, and the edge folding grinding clamp just rotates around the center of the test bed for one circle; friction pressure pressurizing weight (500±5) g:
recording the accumulated friction times before each sample is damaged as wear-resistant times;
TABLE 3 Table 3
| Number of wear-resistant times/times | |
| Example 1 | 5526 |
| Example 2 | 5598 |
| Example 3 | 5563 |
| Example 4 | 5517 |
| Comparative example 1 | 3764 |
| Comparative example 2 | 3985 |
As can be seen from Table 3, the vamp material prepared by the method has higher wear resistance.
FIG. 1 is a bar graph of boiling water shrinkage for the fiber samples of the examples and comparative examples.
The foregoing description of the preferred embodiments of the invention should not be taken as limiting the scope of the invention, which is defined by the appended claims, but rather by the description of the preferred embodiments, all changes and modifications that come within the meaning and range of equivalency of the claims are intended to be embraced therein.
Claims (9)
1. A breathable wear-resistant upper material, characterized in that: the coating is prepared from the following components in parts by weight: 55-60 parts of composite modified polyester chips, 20-25 parts of inorganic filler, 1.2-1.6 parts of coupling agent, 1-2 parts of dispersing agent, 2-3 parts of zinc oxide, 5-8 parts of polypropylene resin, 2-4 parts of natural rubber and 1.5-1.8 parts of stearic acid;
the preparation method of the composite modified polyester chip comprises the following steps:
(1) Firstly, uniformly dispersing nano silicon dioxide into deionized water to obtain nano silicon dioxide dispersion liquid;
(2) Firstly, preparing ammonia water, and then adjusting the pH of the prepared ammonia water to 10.0;
(3) Adding vinyl acetate copolymer emulsion into the nano silicon dioxide dispersion liquid with the pH adjusted, heating to 80 ℃ at the heating rate of 5 ℃/s, preserving heat and stirring for 1 hour, wherein the stirring speed is 1000r/min, and then performing spray drying to obtain composite nano silicon dioxide; the mixing mass ratio of the vinyl acetate copolymer emulsion to the nano silicon dioxide dispersion liquid is 1:4-5; the solid content of the vinyl acetate copolymer emulsion is 30.5%;
(4) Sequentially adding the composite nano silicon dioxide, polyethylene glycol terephthalate and p-aminobenzene sulfonamide into an extruder according to the mass ratio of 4-6:55:1.2-1.6 for melt extrusion granulation to obtain the composite nano silicon dioxide;
wherein, the extruder is a double-screw extruder;
The length-diameter ratio of the twin-screw extruder is 16:1, and the temperature of the machine head is 200 ℃.
2. A breathable wear-resistant upper material according to claim 1, characterized in that: the inorganic filler is as follows: bentonite;
wherein the bentonite is calcium bentonite;
Wherein, the calcium bentonite is subjected to acid treatment:
Uniformly dispersing the calcium bentonite into deionized water, stirring and mixing uniformly, adding sulfuric acid solution, stirring and mixing for 1 hour, filtering, washing to be neutral, and drying to constant weight;
wherein, the mixing mass ratio of the calcium bentonite to the deionized water is 1:15-20;
The mass ratio of the calcium bentonite to the sulfuric acid solution is 10:1-3;
the mass fraction of the sulfuric acid solution is 5%.
3. A breathable wear-resistant upper material according to claim 1, characterized in that: the nano silicon dioxide dispersion liquid in the step (1) is formed by mixing nano silicon dioxide and deionized water according to the mass ratio of 1-2:20 at normal temperature;
Wherein, stirring is carried out for 20min at a rotating speed of 3000r/min during mixing.
4. A breathable wear-resistant upper material according to claim 1, characterized in that: and (3) the mass fraction of the ammonia water in the step (2) is 15%.
5. A breathable wear-resistant upper material according to claim 1, characterized in that: the spray drying in the step (3) adopts a pressure spray drying method:
The high-pressure pump is adopted to carry out atomization treatment at 185-190 atm, and then drying is carried out.
6. A breathable wear-resistant upper material according to claim 1, characterized in that: the coupling agent is an organosilane coupling agent;
The dispersing agent is microcrystalline paraffin.
7. A breathable wear-resistant upper material according to claim 1, characterized in that: the organosilane coupling agent is vinyltris (beta-methoxyethoxy) silane.
8. A method for preparing a breathable wear-resistant upper material according to claim 1, characterized in that: the method comprises the following steps:
(1) Weighing the raw materials of the components according to the weight portions;
(2) Sequentially adding the obtained components into a drying oven, and drying to obtain a dried material;
(3) Adding the dried material into a mixer, stirring and mixing uniformly, adding the uniformly mixed raw materials into an extruder for melting, spraying through a spinneret plate, and cooling and shaping to obtain composite fibers;
(4) And weaving the composite fiber into cloth by a knitting machine to obtain the required vamp material.
9. The method for preparing a breathable and wear-resistant upper material according to claim 8, wherein the drying temperature in the drying oven is 60 ℃ and the drying time is 10 hours.
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