CN115975361A - Colored polylactic acid composite material for shoe uppers - Google Patents
Colored polylactic acid composite material for shoe uppers Download PDFInfo
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- CN115975361A CN115975361A CN202310057798.2A CN202310057798A CN115975361A CN 115975361 A CN115975361 A CN 115975361A CN 202310057798 A CN202310057798 A CN 202310057798A CN 115975361 A CN115975361 A CN 115975361A
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 40
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 239000001913 cellulose Substances 0.000 claims abstract description 36
- 229920002678 cellulose Polymers 0.000 claims abstract description 36
- 239000003607 modifier Substances 0.000 claims abstract description 34
- 229920001661 Chitosan Polymers 0.000 claims abstract description 33
- 239000000835 fiber Substances 0.000 claims abstract description 33
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 33
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 33
- 239000002159 nanocrystal Substances 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims description 32
- 239000002775 capsule Substances 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 25
- 241001474374 Blennius Species 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 238000009987 spinning Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000839 emulsion Substances 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 7
- 239000000648 calcium alginate Substances 0.000 claims description 7
- 235000010410 calcium alginate Nutrition 0.000 claims description 7
- 229960002681 calcium alginate Drugs 0.000 claims description 7
- 239000001110 calcium chloride Substances 0.000 claims description 7
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 7
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 5
- 239000003995 emulsifying agent Substances 0.000 claims description 5
- 239000000661 sodium alginate Substances 0.000 claims description 5
- 235000010413 sodium alginate Nutrition 0.000 claims description 5
- 229940005550 sodium alginate Drugs 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- LYFQZBRXUFXPSD-UHFFFAOYSA-H cerium(3+) dioxido-oxo-phenyl-lambda5-phosphane Chemical compound [Ce+3].[Ce+3].[O-]P([O-])(=O)c1ccccc1.[O-]P([O-])(=O)c1ccccc1.[O-]P([O-])(=O)c1ccccc1 LYFQZBRXUFXPSD-UHFFFAOYSA-H 0.000 claims description 3
- 230000001112 coagulating effect Effects 0.000 claims description 3
- 239000004595 color masterbatch Substances 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 239000002667 nucleating agent Substances 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- PREGVUDYTQAQOA-UHFFFAOYSA-H dioxido-oxo-phenyl-lambda5-phosphane lanthanum(3+) Chemical compound C1=CC=C(C=C1)P(=O)([O-])[O-].C1=CC=C(C=C1)P(=O)([O-])[O-].C1=CC=C(C=C1)P(=O)([O-])[O-].[La+3].[La+3] PREGVUDYTQAQOA-UHFFFAOYSA-H 0.000 claims description 2
- 230000001804 emulsifying effect Effects 0.000 claims description 2
- 238000004804 winding Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 239000006185 dispersion Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229920001046 Nanocellulose Polymers 0.000 description 2
- 230000006179 O-acylation Effects 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 230000006196 deacetylation Effects 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- REEZZSHJLXOIHL-UHFFFAOYSA-N octanoyl chloride Chemical compound CCCCCCCC(Cl)=O REEZZSHJLXOIHL-UHFFFAOYSA-N 0.000 description 1
- 125000005543 phthalimide group Chemical group 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000052 poly(p-xylylene) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Landscapes
- Biological Depolymerization Polymers (AREA)
Abstract
The invention discloses a colored polylactic acid composite material for vamps, which is improved in component composition, wherein cellulose nanocrystals and a rare earth heat-resistant modifier are added into polylactic acid, and the addition modes of the cellulose nanocrystals and the rare earth heat-resistant modifier are improved, so that the compatibility of O-acylated chitosan and the polylactic acid is improved, and the dispersion of the cellulose nanocrystals and the rare earth heat-resistant modifier in the polylactic acid is more uniform; the mechanical property, heat resistance and other properties of the material are promoted through the fiber body and the net structure in the polylactic acid, the heat resistance and mechanical property of the polylactic acid composite material are obviously improved, and the material is degradable and more environment-friendly.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a colored polylactic acid composite material for vamps.
Background
Polylactic acid is a more important one of a plurality of biodegradable materials, has excellent mechanical properties and thermoplasticity, is a well-known green polymer material, and is widely applied to shoes, clothes, vehicle decorations, clinics and the like. However, the polylactic acid has low heat distortion temperature which is only 50-60 ℃, and a sample prepared from the pure lactic acid is easy to deform due to temperature change, so that the popularization and the application of the polylactic acid in the field of materials are greatly limited.
In contrast, the main improvement means in the market at present include graft modification of polylactic acid, multi-blending with other materials, and enhancing the performance of polylactic acid through fillers, and taking fillers as an example, the fillers disclosed at present include fibers, talcum powder, nanocellulose, montmorillonite, carbon nanotubes, and the like, such as nanocellulose, fibers, and the like, and because the compatibility with polylactic acid is poor, aggregation and aggregation are likely to occur in the melting processing procedure, and overall, the improvement of the heat distortion temperature cannot meet the application requirements, and needs to be improved.
Disclosure of Invention
In order to solve at least one technical defect, the invention provides the following technical scheme:
the application document discloses a colored polylactic acid composite material for vamps, which comprises the following components in mass: 84-90% of polylactic acid particles, 0.3-0.6% of nucleating agent, 0.5-1.0% of compatilizer, 2-3% of seaweed composite fiber, 5-10% of capsule particles and 2-3% of color master batch;
the seaweed composite fiber is a composite fiber prepared from O-acylated chitosan, calcium alginate, cellulose nanocrystals and a rare earth heat-resistant modifier, wherein the mass ratio of the O-acylated chitosan, the calcium alginate, the cellulose nanocrystals to the rare earth heat-resistant modifier in the seaweed composite fiber is (0.3-0.5): 0.1-0.2;
the capsule particles take O-acylated chitosan and cellulose nanocrystals as wall materials and rare earth heat-resistant modifiers as cores, and the mass ratio of the O-acylated chitosan, the cellulose nanocrystals and the rare earth heat-resistant modifiers in the capsule particles is as follows: 1-1.5:3-4:0.6-1.
The scheme improves the component composition, adds the cellulose nanocrystalline and the rare earth heat-resistant modifier into the polylactic acid, and improves the adding modes of the cellulose nanocrystalline and the rare earth heat-resistant modifier, wherein the first mode is as follows: the cellulose nanocrystal and the O-acylated chitosan are used as wall materials to coat the core body rare earth heat-resistant modifier to form capsule particles, and the O-acylated chitosan improves the compatibility with polylactic acid and is beneficial to more uniform dispersion of the cellulose nanocrystal and the rare earth heat-resistant modifier in the polylactic acid; the second method comprises the following steps: calcium alginate is used as a main fiber material, cellulose nanocrystals and a rare earth heat-resistant modifier are compounded to form fibers, O-acylated chitosan is used for coating the surface layer to form the composite fibers, the compatibility of the fibers in polylactic acid is improved by the O-acylated chitosan, and the mechanical property, the heat resistance and other properties of the material are improved by a fiber body and a net structure in the polylactic acid. The polylactic acid composite material prepared by the scheme has obviously improved heat resistance and mechanical properties, is degradable and is more environment-friendly.
Further, the preparation method of the seaweed composite fiber comprises the following steps: adding sodium alginate into the cellulose nanocrystalline solution, stirring to form a mixed solution, spraying the mixed solution into a calcium chloride coagulating bath containing a rare earth modifier for gelling, drawing and winding spinning, coating the obtained spinning with the solution of O-acylated chitosan, drying, and cutting to obtain the composite fiber.
According to the scheme, sodium alginate and a cellulose nanocrystalline solution are mixed and stirred to form a uniform mixed solution, then the uniform mixed solution is sprayed to calcium chloride containing a rare earth modifier for gelation reaction, after spinning is drawn, the obtained spinning can be placed in an O-acylation chitosan solution, then the O-acylation chitosan solution is drawn out and dried, and the dried fiber is cut to obtain the composite fiber.
Further, the preparation method of the capsule particle comprises the following steps: placing a rare earth modifier and an emulsifier in a solution of O-acylated chitosan, stirring and emulsifying to obtain a mixed emulsion, adding the mixed emulsion into a cellulose nanocrystal solution, stirring, adding a curing agent for curing, and separating and drying capsule particles formed by curing.
The preparation method comprises the steps of presetting a rare earth modifier and an emulsifier in a solution of O-acylated chitosan, adding a cellulose nanocrystal solution into a mixed emulsion obtained after stirring, forming a wall material by the O-acylated chitosan and the cellulose nanocrystal under the action of a curing agent, coating the rare earth modifier to form capsule particles, then performing separation treatment by means of centrifugation, suction filtration, washing and the like, drying to obtain the capsule particles, wherein the O-acylated chitosan is helpful for uniform dispersion of the capsule particles in polylactic acid, and the core body is wrapped to be simultaneously helpful for uniform dispersion of the rare earth heat-resistant modifier in the polylactic acid, so that excellent mechanical property of the heat-resistant modifier is realized in a small amount.
Further, the cellulose nanocrystal is added into water, and is heated and dissolved under the water bath condition to form a cellulose nanocrystal solution, so that the cellulose nanocrystal solution is convenient to dissolve.
Furthermore, the rare earth heat-resistant modifier is subjected to coupling modification to participate in the preparation of the seaweed composite fiber or capsule particles, and is beneficial to improving the dispersibility.
Furthermore, the rare earth heat-resistant modifier is one or more of lanthanum phenylphosphonate or cerium phenylphosphonate, and the heat-resistant effect is good.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention improves the component composition and the adding form of the components of the polylactic acid composite material, greatly improves the heat resistance of the polylactic acid, synchronously improves the mechanical property, and is degradable and more environment-friendly.
Detailed Description
The present invention is further illustrated by the following examples.
The following preparation examples were prepared using the following raw materials;
polylactic acid Particles (PLA): the molecular weight is 10-20 ten thousand;
color master batch: 46% of polylactic acid, 52% of phthalocyanine blue and 2% of dispersant EBS;
the nucleating agent is phthalimide;
the compatilizer is ethylene-vinyl acetate copolymer;
rare earth heat-resistant modifier: commercially available cerium phenylphosphonate;
cellulose Nanocrystals (CNC): preparing a commercially available sulfuric acid acidolysis method;
sodium alginate: is sold on the market;
calcium chloride: is sold on the market;
and (3) chitosan: m w ：3.0×10 3 Da, deacetylation degree of 85%;
emulsifier: commercial tween;
curing agent: ethylene glycol;
o-acylated chitosan: under the ice bath condition, adding the chitosan with the preset weight into 5 times of methane sulfonic acid solution, stirring for 2h, slowly dropwise adding 10ml of octanoyl chloride, continuously stirring for 2h, blind-standing at minus 25 ℃ for 48h, adding ice water, unfreezing and suction-filtering, pouring a filter cake into ice water, regulating the pH value to 7.0 by ammonia water, filtering and repeatedly neutralizing twice, washing the filter cake by methanol and hot water to obtain a primary product, dissolving the primary product into chloroform, filtering and concentrating the filtrate, adding methanol into a concentrated solution to obtain a precipitate, and filtering the precipitate to obtain a filter cake, namely the O-acylated chitosan, which is confirmed to be the required acylated product by infrared and nuclear magnetism;
seaweed composite fibers: placing cellulose nanocrystalline with preset weight in 10 times of water, and stirring for 3h under the water bath condition of 40-70 ℃ to obtain cellulose nanocrystalline solution;
adding sodium alginate with a preset weight into the cellulose nanocrystal solution, and uniformly stirring to form a mixed solution;
spraying the mixed solution into a calcium chloride coagulating bath (the concentration of calcium chloride is 3%) containing a rare earth modifier (with silane 570 coupling agent with the concentration of 3% being soaked) with a wet spinning mode to coagulate and draw and wind the spun yarn, then washing the obtained spun yarn with deionized water, immersing the spun yarn into a chloroform solution (the concentration of the calcium chloride is 10%) of O-acylated chitosan, then extracting and drying the spun yarn to form a composite fiber (the diameter is about 0.7 mu m) with the O-acylated chitosan as a surface layer and the cellulose nanocrystal and calcium alginate as a core, and cutting the composite fiber into 0.8-1.2mm for later use, wherein the mass ratio of the O-acylated chitosan, the calcium alginate, the cellulose nanocrystal and the rare earth heat-resistant modifier in the composite fiber is detected to be 0.3.
Capsule particle: o-acylated chitosan in a predetermined weight was dissolved in a 1% acetic acid solution in an amount of 10 times the weight thereof, stirred at 45 ℃ for 2 hours, and then filtered through a 0.2 μm microporous membrane to obtain a chitosan solution.
Adding a predetermined weight of rare earth modifier (silane 570 coupling agent with the soaking concentration of 3%) and an emulsifier into the chitosan solution, and uniformly stirring to obtain a mixed emulsion.
Dropwise adding the mixed emulsion into cellulose nanocrystal solution (prepared as above) with equal weight, stirring for 3h at 50 ℃, adding glycol with 1/10 weight of the mixed emulsion for curing, stirring for 2h at 40 ℃, centrifuging, filtering, washing at room temperature, neutralizing with ammonia water for multiple times, washing again and drying to obtain capsule particles, observing the capsule particles to be nano-scale by an electron microscope, wherein the range of the capsule particles is basically 200-400nm, and the mass ratio of O-acylated chitosan, cellulose nanocrystal and rare earth heat-resistant modifier in the capsule particles is as follows: 1:4:0.7.
the following examples show the ratio of the components of the preparation materials in table 1, the preparation methods in the examples are consistent, the preparation methods in the examples can be realized by referring to the conventional polylactic acid melt spinning process, and the mixing sequence is not particularly limited and is not repeated.
TABLE 1
Note: the above numerical units are mass percentages.
Comparative example 1
The spinning preparation method is consistent with the embodiment, and the difference is that: the molding of the seaweed composite fiber and the capsule particle is avoided, and all the components for forming the seaweed composite fiber and the capsule particle are independently added.
Comparative example 2
The spinning preparation method is consistent with the embodiment, and the difference is that: the molding of the seaweed composite fiber is avoided, and all components forming the seaweed composite fiber are independently added.
Comparative example 3
The spinning preparation method is consistent with the embodiment, and the difference is that: forming the capsule-free particles, and independently adding all the components for forming the capsule particles.
Comparative example 4
The spinning preparation method is consistent with the embodiment, and the components are different from the embodiment 3 in that: the capsule particles account for 17% by mass, and the corresponding polylactic acid particles account for 80% by mass.
The products prepared in the above examples and comparative examples were tested, including DSC apparatus, standing in boiling water test, and mechanical properties, as shown in Table 2.
TABLE 2
As can be seen from Table 2, the samples prepared in the examples of the present invention have improved properties such as tensile strength, and have a significant increase in heat distortion temperature, while the samples prepared in the examples of the present invention have a large difference in heat distortion temperature.
According to microscopic observation of an electron microscope, the fibers, capsule particles and the like in the spinning are relatively uniformly dispersed, and the infrared spectrum shows that characteristic peaks such as O-H, C = O and the like which show hydrogen bond bonding are obviously wide in peak width, strong in peak strength and the like, so that the composite fibers, the capsule particles and the like are presumed to be more tightly bonded with polylactic acid through the action of hydrogen bonds and the like, the compatibility is improved, and the corresponding mechanical property, heat resistance and the like are improved.
The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-mentioned embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (6)
1. The colored polylactic acid composite material for the shoe upper is characterized by comprising the following components in parts by mass: 84-90% of polylactic acid particles, 0.3-0.6% of nucleating agent, 0.5-1.0% of compatilizer, 2-3% of seaweed composite fiber, 5-10% of capsule particles and 2-3% of color master batch;
the seaweed composite fiber is a composite fiber prepared from O-acylated chitosan, calcium alginate, cellulose nanocrystals and a rare earth heat-resistant modifier, wherein the mass ratio of the O-acylated chitosan, the calcium alginate, the cellulose nanocrystals to the rare earth heat-resistant modifier in the seaweed composite fiber is (0.3-0.5): 0.1-0.2;
the capsule particles take O-acylated chitosan and cellulose nanocrystals as wall materials and a rare earth heat-resistant modifier as a core, and the mass ratio of the O-acylated chitosan to the cellulose nanocrystals to the rare earth heat-resistant modifier in the capsule particles is as follows: 1-1.5:3-4:0.6-1.
2. The colored polylactic acid composite material for shoe uppers according to claim 1, characterized in that: the preparation method of the seaweed composite fiber comprises the following steps: adding sodium alginate into the cellulose nanocrystalline solution, stirring to form a mixed solution, spraying the mixed solution into a calcium chloride coagulating bath containing a rare earth modifier for gelling, drawing and winding spinning, coating the obtained spinning with the solution of O-acylated chitosan, drying, and cutting to obtain the composite fiber.
3. The colored polylactic acid composite material for an upper according to claim 1, wherein: the preparation method of the capsule particle comprises the following steps: placing a rare earth modifier and an emulsifier in an acetic acid solution of O-acylated chitosan, stirring and emulsifying to obtain a mixed emulsion, adding the mixed emulsion into a cellulose nanocrystal solution, stirring, adding a curing agent for curing, and separating and drying capsule particles formed by curing.
4. A coloured polylactic acid composite material for shoe uppers according to claim 2 or 3, characterized in that: and adding the cellulose nanocrystal into water, and heating and dissolving under a water bath condition to form a cellulose nanocrystal solution.
5. A coloured polylactic acid composite material for shoe uppers according to claim 2 or 3, characterized in that: the rare earth heat-resistant modifier is used for coupling modification and participating in the preparation of seaweed composite fibers or capsule particles.
6. The colored polylactic acid composite material for shoe uppers according to claim 1, characterized in that: the rare earth heat-resistant modifier is one or more of lanthanum phenylphosphonate or cerium phenylphosphonate.
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| CN202310057798.2A CN115975361B (en) | 2023-01-16 | 2023-01-16 | Colored polylactic acid composite material for vamp |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310057798.2A CN115975361B (en) | 2023-01-16 | 2023-01-16 | Colored polylactic acid composite material for vamp |
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| CN115975361B CN115975361B (en) | 2024-05-28 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117384469A (en) * | 2023-10-16 | 2024-01-12 | 台州天奇鞋业股份有限公司 | Breathable wear-resistant vamp material and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105153659A (en) * | 2015-10-16 | 2015-12-16 | 深圳市绿意包装有限公司 | Heat resistant polylactic acid composite material and preparation method thereof |
| CN105885367A (en) * | 2014-12-12 | 2016-08-24 | 允友成(宿迁)复合新材料有限公司 | Cellulose nano fiber/polylactic acid composite material and preparation method thereof |
| CN109486139A (en) * | 2018-11-14 | 2019-03-19 | 江苏省农业科学院 | Environment-friendly toughened nano-cellulose-polylactic acid biodegradation material and preparation method thereof |
| CN110818920A (en) * | 2019-11-15 | 2020-02-21 | 东北林业大学 | Cellulose nanocrystal/polylactic acid composite material and preparation method and application thereof |
| CN112981704A (en) * | 2021-03-18 | 2021-06-18 | 徐州工牛高新材料有限公司 | High-strength polylactic acid-based electrospun nanofiber membrane and preparation method thereof |
| CN114181504A (en) * | 2021-12-23 | 2022-03-15 | 安徽英特力工业工程技术有限公司 | Method for preparing polylactic acid by using modified cellulose nanocrystals |
| CN115433442A (en) * | 2022-10-18 | 2022-12-06 | 扬州大学 | Biodegradable tough composite material and preparation method thereof |
-
2023
- 2023-01-16 CN CN202310057798.2A patent/CN115975361B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105885367A (en) * | 2014-12-12 | 2016-08-24 | 允友成(宿迁)复合新材料有限公司 | Cellulose nano fiber/polylactic acid composite material and preparation method thereof |
| CN105153659A (en) * | 2015-10-16 | 2015-12-16 | 深圳市绿意包装有限公司 | Heat resistant polylactic acid composite material and preparation method thereof |
| CN109486139A (en) * | 2018-11-14 | 2019-03-19 | 江苏省农业科学院 | Environment-friendly toughened nano-cellulose-polylactic acid biodegradation material and preparation method thereof |
| CN110818920A (en) * | 2019-11-15 | 2020-02-21 | 东北林业大学 | Cellulose nanocrystal/polylactic acid composite material and preparation method and application thereof |
| CN112981704A (en) * | 2021-03-18 | 2021-06-18 | 徐州工牛高新材料有限公司 | High-strength polylactic acid-based electrospun nanofiber membrane and preparation method thereof |
| CN114181504A (en) * | 2021-12-23 | 2022-03-15 | 安徽英特力工业工程技术有限公司 | Method for preparing polylactic acid by using modified cellulose nanocrystals |
| CN115433442A (en) * | 2022-10-18 | 2022-12-06 | 扬州大学 | Biodegradable tough composite material and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117384469A (en) * | 2023-10-16 | 2024-01-12 | 台州天奇鞋业股份有限公司 | Breathable wear-resistant vamp material and preparation method thereof |
| CN117384469B (en) * | 2023-10-16 | 2024-05-07 | 台州天奇鞋业股份有限公司 | Breathable wear-resistant vamp material and preparation method thereof |
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