CN114456560A - Multifunctional polylactic acid nano composite material with high transparency and preparation method thereof - Google Patents
Multifunctional polylactic acid nano composite material with high transparency and preparation method thereof Download PDFInfo
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- CN114456560A CN114456560A CN202210146190.2A CN202210146190A CN114456560A CN 114456560 A CN114456560 A CN 114456560A CN 202210146190 A CN202210146190 A CN 202210146190A CN 114456560 A CN114456560 A CN 114456560A
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- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 140
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 140
- 239000000463 material Substances 0.000 title claims abstract description 51
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000002073 nanorod Substances 0.000 claims abstract description 72
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 49
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 17
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 15
- 238000011049 filling Methods 0.000 claims abstract description 8
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims description 71
- 238000002844 melting Methods 0.000 claims description 35
- 230000008018 melting Effects 0.000 claims description 35
- 239000002131 composite material Substances 0.000 claims description 29
- 239000000155 melt Substances 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 11
- 238000007599 discharging Methods 0.000 claims description 8
- 239000002105 nanoparticle Substances 0.000 claims description 7
- 238000003892 spreading Methods 0.000 claims description 7
- 230000007480 spreading Effects 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims 2
- 238000011068 loading method Methods 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 15
- 238000002425 crystallisation Methods 0.000 abstract description 9
- 230000008025 crystallization Effects 0.000 abstract description 9
- 239000013078 crystal Substances 0.000 abstract description 8
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 7
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- 230000003287 optical effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 30
- 239000003795 chemical substances by application Substances 0.000 description 17
- 229920001432 poly(L-lactide) Polymers 0.000 description 17
- JVTAAEKCZFNVCJ-REOHCLBHSA-N L-lactic acid Chemical compound C[C@H](O)C(O)=O JVTAAEKCZFNVCJ-REOHCLBHSA-N 0.000 description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 14
- 239000000523 sample Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000004048 modification Effects 0.000 description 5
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- 239000002245 particle Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000002159 nanocrystal Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
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- 238000006243 chemical reaction Methods 0.000 description 2
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- 238000010586 diagram Methods 0.000 description 2
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical class 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 2
- 239000000945 filler Substances 0.000 description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- RBMHUYBJIYNRLY-UHFFFAOYSA-N 2-[(1-carboxy-1-hydroxyethyl)-hydroxyphosphoryl]-2-hydroxypropanoic acid Chemical compound OC(=O)C(O)(C)P(O)(=O)C(C)(O)C(O)=O RBMHUYBJIYNRLY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
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- 230000005764 inhibitory process Effects 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
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- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001434 poly(D-lactide) Polymers 0.000 description 1
- 229920000052 poly(p-xylylene) Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- 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
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- 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
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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Abstract
The invention discloses a multifunctional polylactic acid nano composite material with high transparency and a preparation method thereof. Comprises polylactic acid and boehmite nano-rods. The multifunctional polylactic acid nano composite material comprises polylactic acid and modified boehmite nano rods; the modified boehmite nanorods are modified with epoxy groups on the surface and grafted with polylactic acid molecular chains through ring-opening reaction. The polylactic acid nano composite material has good optical property, mechanical property, heat resistance and flame retardant property. The high-filling nano rod causes the limitation of the crystallization space in the polylactic acid matrix, the introduction of the nano rod promotes the nucleation of the polylactic acid, but the growth of polylactic acid crystals is inhibited, the high transparency of the material is kept, the modulus of the polylactic acid nano composite material is enhanced by the addition of the nano rod, the ductility and the toughness are greatly improved, the heat resistance of the material is further improved, and the material has certain dimensional stability at high temperature.
Description
Technical Field
The invention belongs to the field of high polymer materials, relates to a multifunctional polylactic acid nano composite material with high transparency and a preparation method thereof, and particularly relates to a multifunctional polylactic acid nano composite material obtained by modifying nano particles and reactively blending and a preparation method thereof.
Background
It is well known that polylactic acid is the most widely studied and applied biodegradable green polymer at present. It not only has good mechanical properties (high modulus and high strength), biocompatibility, high transparency and easy processing, but also is more environment-friendly than the traditional petroleum-based polymer in the production process, so that the polymer is widely applied to the aspects of packaging, textile and biomedicine. But as a biodegradable thermoplastic material it is susceptible to degradation during processing and thus loss of mechanical properties. In addition, polylactic acid has some serious disadvantages, such as high brittleness, poor toughness, low impact strength, poor ductility, low crystallization rate, poor heat resistance, low heat distortion temperature, etc., which affect the processing conditions of polylactic acid and limit the application of polylactic acid. Therefore, in order to expand the application range of polylactic acid, it is necessary to modify polylactic acid to improve the performance of the material.
At present, there are many methods for modifying polylactic acid using inorganic fillers and fibers as a compatibilizer. Compared with other fillers, the nano particles have the characteristics of small volume and high surface area, so that the nano composite material can improve better mechanical property under the same addition amount. The Ming Wang et al successfully prepares the PLLA/multi-walled carbon nanotube nanocomposite material with the isolation structure by utilizing two PLLAs with different viscosities and crystallinities, the intensive distribution of the multi-walled carbon nanotubes in the L-PLLA phase and the continuous L-PLANT network formed by the isolation structure enable the material to show high conductivity, ultralow permeation threshold and high performance electromagnetic interference shielding effectiveness, and the Young modulus, the tensile strength and the elongation at break are improved. Jinping Qu et al prepared PLLA/Organically Modified Montmorillonite (OMMT) nanocomposites with different OMMT concentrations using an extruder, found that the rheological properties and modulus of the material are significantly enhanced, and the addition of OMMT nanoparticles increases the crystallinity of the PLLA matrix. Jacques Lemaitre et al prepared a compact PLLA/nano-hydroxyapatite composite material using a hot pressing method, and found that increasing the concentration of nano-hydroxyapatite increased the Young's modulus and mechanical strength of the composite material while maintaining the particle size and degree of dispersion, and at the same time, the failure mechanism of the material changed from plastic to brittle. Long Jiang et al first adsorbed and modified the surfaces of calcium carbonate and montmorillonite, improved the affinity of two kinds of particles with polylactic acid, made the particles obtain good dispersion in the polymer matrix, and realized the enhancement and toughening modification to polylactic acid. Jean-Jacques Robin et al grafted PLLA molecular chains onto Cellulose Nanocrystals (CNC) to obtain a PLLA-based nanocomposite grafted with nanocrystals (PLLA/PLLA-g-CNCs), which has significantly enhanced crystallinity and mechanical properties due to the interaction between the cellulose nanocrystals and PLLA, compared to the ungrafted one. Changren Zhou et al prepared g-CHW/PLLA nanocomposites by solution casting, and compared to unmodified CHW/PLLA materials, g-CHWs were better dispersed throughout the matrix than CHWs, with greater improvements in tensile strength, tensile modulus and energy at break. Dong Keun Han et al prepared two surface modifications nMH with oligomeric lactic acid, and the addition of modified nMH not only improved the mechanical properties, but also improved the uniformity of the magnesium hydroxide particles in the PLLA matrix due to the increased interfacial interactions. Surface modified nMH successfully improved the physical and biological properties of the PLLA/nMH composite compared to the unmodified control sample.
However, in most work, transparency of PLLA materials is often sacrificed in order to obtain excellent mechanical properties. In addition, the poor heat resistance of the polylactic acid composite material is still a problem to be solved urgently. Therefore, the present invention is still a difficult task to prepare a multifunctional PLLA nanocomposite material having excellent transparency, ductility, toughness, rigidity, heat resistance, flame retardancy and complete biodegradability while maintaining good dispersibility of the filler.
According to the invention, a boehmite nanorod is synthesized by a hydrothermal method, surface modification and modification are carried out on the boehmite nanorod to modify an epoxy group, and then the polylactic acid nanocomposite with high transparency and versatility is prepared by a melt blending method. The epoxy groups on the nanorods can be grafted with polylactic acid molecular chains through ring-opening reaction in the process of melt blending, so that the polylactic acid molecular chains are uniformly dispersed in a polylactic acid matrix, and because the high-filled nanorods cause the limitation of crystallization space in the polylactic acid matrix, although the introduction of the nanorods promotes the nucleation of polylactic acid, the growth of polylactic acid crystals is inhibited, and the high transparency of the material is maintained; in addition, the nucleation of the polylactic acid matrix is promoted by increasing the content of the nano rods, and a good interface is formed between the uniformly dispersed nano rods and the polylactic acid matrix, so that the toughness, the ductility and the modulus of the material are increased. In addition, the addition of the boehmite nano-rods with high filling amount also endows the material with certain flame retardant property and heat resistance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a multifunctional polylactic acid nano composite material with high transparency through a simple preparation process, and particularly provides the multifunctional polylactic acid nano composite material prepared through reactive blending under the condition of high filling amount, and the multifunctional polylactic acid nano composite material has excellent transparency, ductility, toughness, rigidity, heat resistance and flame resistance and is completely biodegradable, so that the multifunctional polylactic acid nano composite material has important application significance in the field of preparing multifunctional biodegradable materials.
The purpose of the invention is realized by the following technical scheme:
a multifunctional polylactic acid nano composite material with high transparency is a blend and comprises polylactic acid and modified boehmite nanorods;
the surface of the modified boehmite nanorod is modified with an epoxy group; the epoxy groups on the surface of the modified boehmite nanorod can be grafted with polylactic acid molecular chains through a ring-opening reaction.
The modified boehmite nanorods account for 1-50 wt% of the total filling amount of the polylactic acid composite material.
Preferably, the modified boehmite nanorods are obtained by modifying epoxy groups on the surfaces of the boehmite nanorods through a silane coupling agent Kh 560.
Preferably, the boehmite nanorods are rod-shaped nanoparticles with the diameter of 5-20nm and the length of 60-100 nm.
Preferably, in the technical scheme, the grafting ratio of the epoxy group in the modified boehmite nanorod is 4-7.4%, and more preferably is 7.4%.
Preferably, the modified boehmite nanorods account for 1 wt% -30 wt% of the total filling amount of the polylactic acid composite material.
Preferably, the polylactic acid is a levorotatory polylactic acid or a dextrorotatory polylactic acid.
Another object of the present invention is to provide a method for preparing the above multifunctional polylactic acid nanocomposite sheet, comprising the steps of;
step (1): vacuum drying polylactic acid at 60-120 deg.C for more than 12 hr;
step (2): dissolving polylactic acid and the modified boehmite nanorods in a solvent according to a certain proportion for dispersion, then spreading a film, and drying for more than 12 hours;
and (3): adding the dried film paving sample into a melting and mixing device, and melting and mixing at 180-210 ℃ to obtain a product 1;
and (4): discharging the product 1 from the melt mixing equipment, cooling to normal temperature, uniformly mixing with polylactic acid, adding into the melt mixing equipment, and carrying out melt mixing at 180-210 ℃ to obtain a product 2 with the mass content of the modified boehmite nanorods being 1-50 wt%;
and (5): the product 2 was melt-tableted and then water-cooled to prepare a sheet having a thickness of 0.1 to 0.5 mm.
Preferably, the mass ratio of the polylactic acid to the modified boehmite nanorods in the step (2) is 3: 1.
Preferably, in the above technical means, the solvent in the step (2) is chloroform.
As the technical scheme, the melting and mixing device in the steps (3) and (4) is preferably an internal mixer, the rotor speed is 50rpm/min, and the melting and mixing time is 10 min.
Preferably, the temperature of the melting and tabletting in the step (5) is 190-220 ℃, the pressure is 10-30MPa, and the dwell time is 3-8 min. More preferably, the temperature of the melt tabletting in the step (5) is 200 ℃, the pressure is 10MPa, and the dwell time is 6 min.
It is still another object of the present invention to provide a plastic article using the above multifunctional polylactic acid nanocomposite.
The invention has the beneficial effects that:
the polylactic acid nano composite material sheet prepared by the method has good optical property, mechanical property, heat resistance and flame retardant property. Epoxy groups on the nanorods can be grafted with polylactic acid molecular chains through ring-opening reaction in the process of melt blending, so that the epoxy groups are uniformly dispersed in a polylactic acid matrix, and the high transparency of the material is kept due to the small size of the nanorods and the inhibition effect of the nanorods on the growth of polylactic acid spherulites; in addition, the addition of the nanorods promotes the nucleation of the polylactic acid matrix and increases the rigidity, toughness and ductility of the material. In addition, the addition of the boehmite nano-rods with high filling amount also endows the material with certain flame retardant property and heat resistance. The invention only needs common melting mixing equipment, has simple industrial preparation and provides a feasible strategy for preparing the multifunctional and high-performance high-transparency nano composite material.
Drawings
FIGS. 1(a) - (b) are the quenched cross-sectional morphologies of the composite sheets prepared in comparative example 1 and example 6, respectively.
FIGS. 2(a) - (b) are polarization microscope images of the composite material sheet prepared in comparative example 1 and example 6 at different times during melt crystallization at a temperature of 130 ℃ respectively.
FIG. 3 is a macroscopic picture of the composite sheet obtained in comparative example 1 and examples 1 to 6.
FIG. 4 is a drawing of a sheet of the composite material obtained in comparative example 1 and examples 4 to 6.
FIG. 5 is an impact diagram of composite sheets prepared in comparative example 1 and examples 3-6.
FIG. 6 is a DMA map of composite sheets made in comparative example 1 and examples 3-6.
FIGS. 7(a) - (b) are pictures of the composite sheet obtained in comparative example 1 and example 6 after the flame retardant test, respectively.
Detailed Description
In order to enhance the understanding of the present invention, the present invention will be further described in detail with reference to the following examples, which are provided for illustration only and are not intended to limit the scope of the present invention.
In the following examples and comparative examples, PLLA, which is inexpensive, was used as polylactic acid, but PDLA is also suitable.
The specific preparation process of the modified boehmite nanorods used in the following examples is as follows:
aluminum isopropoxide is used as a raw material, and a hydrothermal method is adopted to prepare the boehmite nanorod. And after the hydrothermal reaction is finished, removing acetic acid and water by rotary evaporation to obtain the boehmite nano-rod. And then, carrying out epoxy modification on the surface of the boehmite nanorod by using a silane coupling agent Kh560 to obtain a modified boehmite nanorod (AG) with the grafting rate of epoxy groups of 4-7.4%. The method comprises the specific steps of adding boehmite nanorods (5g) and a silane coupling agent Kh560(10ml) into 250ml of absolute ethyl alcohol, and carrying out ultrasonic treatment for 5min and 6 times. The reaction was transferred to a round bottom flask and refluxed at 85 ℃ for 20 h. After the reaction is finished, precipitating the product by using petroleum ether, centrifuging for 4min at the rotating speed of 5000rpm, removing the unreacted silane coupling agent, and finally obtaining the modified boehmite nanorod. And (3) characterizing epoxy groups on the surface of the modified boehmite nanorod by TGA and infrared.
Comparative example 1: polylactic acid
Step (1): drying the polylactic acid at 80 ℃ for 24 hours in vacuum;
step (2): adding 50g of polylactic acid into an internal mixer for melt mixing at 180-210 ℃, wherein the rotor speed of the internal mixer is 50rpm/min, and the melt mixing is carried out for 10min to obtain a blend;
and (3) performing melt tabletting on the obtained blend, wherein the tabletting conditions are as follows: maintaining the pressure at 10MPa and 200 ℃ for 6 min; then water cooling is carried out, and the thin slice with the thickness of 0.1-0.5mm is prepared.
Example 1
Step (1): drying the polylactic acid at 80 ℃ for 24 hours in vacuum;
step (2): dissolving polylactic acid and the modified boehmite nanorod AG in a chloroform solution according to a mass ratio of 3:1 for dispersion, then paving a film, and drying for 12 hours;
and (3): adding the dried film-paving sample into a melting and mixing device, and melting and mixing at 180-210 ℃, wherein the rotor speed of an internal mixer is 50rpm/min, and the melting and mixing time is 10min, so as to obtain a product 1;
and (4): discharging the product 1 from a melt mixing device, cooling to normal temperature, taking 2g of the product 1, uniformly mixing with 48.5g of dried polylactic acid, adding into the melt mixing device, and carrying out melt mixing at 180-210 ℃, wherein the rotor speed of an internal mixer is 50rpm/min, and the melt mixing is carried out for 10min, so as to obtain a product 2 with the mass content of 1 wt%;
and (5): and performing melt tabletting on the product 2 under the following tabletting conditions: maintaining the pressure at 10MPa and 200 ℃ for 6 min; then water cooling is carried out, and the thin slice with the thickness of 0.1-0.5mm is prepared.
Example 2
Step (1): drying the polylactic acid at 80 ℃ for 24 hours in vacuum;
step (2): dissolving polylactic acid and the modified boehmite nanorods in a chloroform solution according to the mass ratio of 3:1 for dispersion, then spreading a film, and drying for 12 hours;
and (3): adding the dried film-paving sample into a melting and mixing device, and melting and mixing at 180-210 ℃, wherein the rotor speed of an internal mixer is 50rpm/min, and the melting and mixing time is 10min, so as to obtain a product 1;
and (4): discharging the product 1 from a melt mixing device, cooling to normal temperature, taking 6g of the product 1, uniformly mixing with 45.5g of dried polylactic acid, adding into the melt mixing device, and carrying out melt mixing at 180-210 ℃, wherein the rotor speed of an internal mixer is 50rpm/min, and the melt mixing is carried out for 10min, so as to obtain a product 2 with the mass content of 3 wt%;
and (5): and (3) performing melt tabletting on the product 2, wherein the tabletting conditions are as follows: maintaining the pressure at 10MPa and 200 ℃ for 6 min; then water cooling is carried out, and the thin slice with the thickness of 0.1-0.5mm is prepared.
Example 3
Step (1): drying the polylactic acid at 80 ℃ for 24 hours in vacuum;
step (2): dissolving polylactic acid and the modified boehmite nanorods in a chloroform solution according to the mass ratio of 3:1 for dispersion, then spreading a film, and drying for 12 hours;
and (3): adding the dried film-paving sample into a melting and mixing device, and melting and mixing at 180-210 ℃, wherein the rotor speed of an internal mixer is 50rpm/min, and the melting and mixing time is 10min, so as to obtain a product 1;
and (4): discharging the product 1 from a melt mixing device, cooling to normal temperature, taking 10g of the product 1, uniformly mixing with 42.5g of dried polylactic acid, adding into the melt mixing device, and carrying out melt mixing at 180-210 ℃, wherein the rotor speed of an internal mixer is 50rpm/min, and the melt mixing is carried out for 10min, so as to obtain a product 2 with the mass content of 5 wt%;
and (5): and performing melt tabletting on the product 2 under the following tabletting conditions: maintaining the pressure at 10MPa and 200 ℃ for 6 min; then water cooling is carried out, and the thin slice with the thickness of 0.1-0.5mm is prepared.
Example 4
Step (1): drying the polylactic acid at 80 ℃ for 24 hours in vacuum;
step (2): dissolving polylactic acid and the modified boehmite nanorods in a chloroform solution according to the mass ratio of 3:1 for dispersion, then spreading a film, and drying for 12 hours;
and (3): adding the dried film-paving sample into a melting and mixing device, and melting and mixing at 180-210 ℃, wherein the rotor speed of an internal mixer is 50rpm/min, and the melting and mixing time is 10min, so as to obtain a product 1;
and (4): discharging the product 1 from a melt mixing device, cooling to normal temperature, taking 20g of the product 1, uniformly mixing with 35g of dried polylactic acid, adding into the melt mixing device, and carrying out melt mixing at 180-210 ℃, wherein the rotor speed of an internal mixer is 50rpm/min, and the melt mixing is carried out for 10min, so as to obtain a product 2 with the mass content of 10 wt%;
and (5): and performing melt tabletting on the product 2 under the following tabletting conditions: maintaining the pressure at 10MPa and 200 ℃ for 6 min; then water cooling is carried out, and the thin slice with the thickness of 0.1-0.5mm is prepared.
Example 5
Step (1): drying the polylactic acid at 80 ℃ for 24 hours in vacuum;
step (2): dissolving polylactic acid and the modified boehmite nanorods in a chloroform solution according to the mass ratio of 3:1 for dispersion, then spreading a film, and drying for 12 hours;
and (3): adding the dried film-paving sample into a melting and mixing device, and melting and mixing at 180-210 ℃, wherein the rotor speed of an internal mixer is 50rpm/min, and the melting and mixing time is 10min, so as to obtain a product 1;
and (4): discharging the product 1 from a melting and mixing device, cooling to normal temperature, taking 40g of the product 1, uniformly mixing with 20g of dried polylactic acid, adding into the melting and mixing device, and melting and mixing at 180-210 ℃, wherein the rotor speed of an internal mixer is 50rpm/min, and the melting and mixing is carried out for 10min, so as to obtain a product 2 with the mass content of 20 wt%;
and (5): and performing melt tabletting on the product 2 under the following tabletting conditions: maintaining the pressure at 10MPa and 200 ℃ for 6 min; then water cooling is carried out, and the thin slice with the thickness of 0.1-0.5mm is prepared.
Example 6
Step (1): drying the polylactic acid at 80 ℃ for 24 hours in vacuum;
step (2): dissolving polylactic acid and the modified boehmite nanorods in a chloroform solution according to the mass ratio of 3:1 for dispersion, then spreading a film, and drying for 12 hours;
and (3): adding the dried film-paving sample into a melting and mixing device, and melting and mixing at 180-210 ℃, wherein the rotor speed of an internal mixer is 50rpm/min, and the melting and mixing time is 10min, so as to obtain a product 1;
and (4): discharging the product 1 from a melting and mixing device, cooling to normal temperature, taking 60g of the product 1, uniformly mixing with 5g of dried polylactic acid, adding into the melting and mixing device, and melting and mixing at 180-210 ℃, wherein the rotor speed of an internal mixer is 50rpm/min, and the melting and mixing is carried out for 10min, so as to obtain a product 2 with the mass content of 30 wt%;
and (5): and (3) performing melt tabletting on the product 2, wherein the tabletting conditions are as follows: maintaining the pressure at 10MPa and 200 ℃ for 6 min; then water cooling is carried out, and the thin slice with the thickness of 0.1-0.5mm is prepared.
FIGS. 1(a) - (b) are the quenched cross-sectional morphologies of the composite sheets prepared in comparative example 1 and example 6, respectively.
As shown in FIG. 1, SEM analysis of example 6 (polylactic acid containing 30 wt% AG) and comparative example 1 (pure polylactic acid) shows that after the nanoparticles are added, the nanoparticles are uniformly dispersed in the polylactic acid matrix, and no obvious agglomeration phenomenon is found, which indicates that the modified boehmite nanorods have better dispersibility.
FIGS. 2(a) - (b) are polarization microscope images of the composite sheets prepared in comparative example 1 and example 6, respectively.
As shown in FIG. 2, when POM analysis was performed on example 6 (polylactic acid containing 30 wt% AG) and comparative example 1 (pure polylactic acid), it was found that melt crystallization at a temperature of 130 ℃ resulted in slow crystallization of the pure polylactic acid sample, forming large and small crystals at 120min, while the polylactic acid sample containing 30 wt% AG completely crystallized at 13min, forming small and large crystals. This is because the highly filled nanorods cause the crystallization space in the polylactic acid matrix to be limited, and even though the introduction of the nanorods promotes the nucleation of polylactic acid, the growth of polylactic acid crystals is inhibited, thereby obtaining spherulites of smaller size.
FIG. 3 is a macroscopic picture of the composite sheet obtained in comparative example 1 and examples 1 to 6.
As shown in FIG. 3, by macroscopically comparing the flakes of examples 1 to 6 with that of comparative example 1 (pure polylactic acid), it can be seen that the transparent property is better exhibited regardless of the pure polylactic acid or the nanorod-added sample. This is attributed to the fact that the epoxy groups on the nanorods can be grafted with polylactic acid molecular chains through ring-opening reaction in the process of melt blending, so that the polylactic acid molecular chains are uniformly dispersed in the polylactic acid matrix, and because the highly filled nanorods cause the crystal space in the polylactic acid matrix to be limited, even if the introduction of the nanorods promotes the nucleation of the polylactic acid, the growth of polylactic acid crystals is inhibited, the spherulite size is small, and the high transparency of the material is still maintained.
TABLE 1 light transmittance and haze of composite sheets obtained in comparative example 1 and examples 1 to 6
It is well known that pure polylactic acid crystals crystallize slowly and amorphous polylactic acid is highly transparent. While the well-crystallized polylactic acid is opaque because large spherulites are formed. Such non-uniformity typically results in reflection and refraction of light, resulting in low light transmission and high haze of the material. As shown in table 1, comparative example 1 (pure polylactic acid) has a light transmittance of 93.2% and a haze of 2.12%, and is a good transparent material. The light transmittance slightly decreases as the amount of added nanorods increases, because the addition of nanorods promotes the nucleation of polylactic acid. However, even at an extreme addition level of 30%, the light transmittance of the example 6 (polylactic acid containing 30 wt% AG) sheet was still 90% or more. Correspondingly, the haze of the composite material gradually increases with the increase of the addition amount, but the material still maintains lower haze (less than 4%) due to the uniform dispersion and smaller spherulite size of the nanorods, wherein the haze of example 6 is the highest, and is only 3.1%, and all the haze meets the use requirement of the transparent high polymer material.
FIG. 4 is a drawing of a composite sheet obtained in comparative example 1 and examples 4 to 6.
As shown in fig. 4, when the stress-strain curves of examples 4 to 6 are compared with that of comparative example 1 (pure polylactic acid), it can be seen that the pure polylactic acid sample shows a typical brittle fracture, and the elongation at break, modulus, and strength are low. With the introduction of the nano-rods, the material yields, shows completely different toughness fracture and obviously enhances the ductility. At the same time, the modulus and tensile strength of the material also gradually increase, and a higher plateau is shown with increasing addition during the yielding process, and strain hardening occurs. This is because the rigid structure of the nanorods improves the modulus of the composite. Specific data on the mechanical properties of the composites of comparative example 1 and examples 4-6 are as follows:
TABLE 2 mechanical properties of the composites of comparative example 1 and examples 4-6
As shown in Table 3, when the impact data of examples 3 to 6 were compared with that of comparative example 1 (pure polylactic acid), it can be seen that the pure polylactic acid sample showed brittle fracture in the impact test, and the impact strength of the material gradually increased with the increase of the amount of AG added, wherein the impact strength of example 5 (polylactic acid containing 20 wt% AG) was 35.8KJ/m2, which is about 17 times that of the pure polylactic acid, and showed the best toughness. Whereas example 6 (polylactic acid containing 30 wt% AG) had a material with a reduced impact strength at an extreme addition of 30%, but still higher than comparative example 1 (pure polylactic acid), about 5 times as high as pure polylactic acid.
TABLE 3 mechanical Properties of the composites of comparative example 1 and examples 3-6
FIG. 5 is an impact diagram of composite sheets prepared in comparative example 1 and examples 3-6.
FIG. 6 is a DMA map of composite sheets made in comparative example 1 and examples 3-6.
As shown in fig. 6, comparing the DMA modulus curves of examples 3 to 6 with comparative example 1 (pure polylactic acid), it can be seen that as the temperature rises, the molecular segment starts to move near Tg, the storage modulus of the material decreases, then the modulus starts to rise due to cold crystallization of polylactic acid, and as the amount of AG added increases, the modulus at the lowest point also gradually increases, which is related to the crystallinity of the material, demonstrating that the addition of AG can promote the crystallization of polylactic acid. Interestingly, the polylactic acid sample containing 30 wt% AG still maintains a certain modulus and has higher dimensional stability at 250 ℃ (far exceeding the melting point of polylactic acid).
As shown in Table 4, it was found that the storage modulus of the material also gradually increased with the increase in the amount of AG added at room temperature (25 ℃ C.). This is because the rigid structure of the nanorods increases the hardness and modulus of the material, which is consistent with the reinforcement in the stress-strain curve. In addition, as the addition amount of AG is increased, the Tg of the material is gradually reduced, because the free volume between the polylactic acid molecular chains grafted on AG is increased, so that the polylactic acid molecular chains move more easily. This also leads to the polylactic acid/AG nano composite material being easier to generate forced high elastic deformation under the action of external force, thereby leading the material to generate yield and finally show ductile fracture.
TABLE 4 DMA data for composites of comparative example 1 and examples 3-6
FIGS. 7(a) - (b) are flame retardant pictures of composite sheets prepared in comparative example 1 and example 6, respectively.
As shown in FIG. 7, when example 6 (polylactic acid containing 30 wt% AG) is compared with comparative example 1 (pure polylactic acid) in a flame retardant test, it can be found that the addition of boehmite nanorods slowed down the melting-off phenomenon of polylactic acid and formed a dense and uniform carbon layer at the ignition site in the case of high filling. This demonstrates that the addition of boehmite nanorods also imparts some flame retardancy to the material.
The above embodiments are not intended to limit the present invention, and the present invention is not limited to the above embodiments, and all embodiments are within the scope of the present invention as long as the requirements of the present invention are met.
Claims (10)
1. A multifunctional polylactic acid nano composite material with high transparency is a blend and is characterized by comprising polylactic acid and modified boehmite nanorods;
the surface of the modified boehmite nanorod is modified with an epoxy group; the epoxy groups on the surface of the modified boehmite nanorods can be grafted with polylactic acid molecular chains through a ring opening reaction;
the modified boehmite nanorods account for 1-50 wt% of the total filling amount of the polylactic acid composite material.
2. The multifunctional polylactic acid nanocomposite with high transparency according to claim 1, wherein the modified boehmite nanorods are modified with epoxy groups on the surface of the boehmite nanorods by a silane coupling agent Kh 560; the boehmite nanorods are rod-shaped nanoparticles with the diameter of 5-20nm and the length of 60-100 nm.
3. The multifunctional polylactic acid nanocomposite with high transparency according to claim 1, wherein the modified boehmite nanorods have an epoxy group grafting ratio of 4% to 7.4%.
4. The multifunctional polylactic acid nanocomposite with high transparency according to claim 1, wherein the polylactic acid is L-polylactic acid or D-polylactic acid.
5. The multifunctional polylactic acid nanocomposite with high transparency according to claim 3, wherein the modified boehmite nanorods account for 1 wt% to 30 wt% of the total loading of the polylactic acid composite.
6. A preparation method of a multifunctional polylactic acid nano composite material with high transparency is characterized by comprising the following steps;
step (1): vacuum drying polylactic acid at 60-120 deg.C for more than 12 h;
step (2): dissolving polylactic acid and the modified boehmite nanorods in a solvent according to a certain proportion for dispersion, then spreading a film, and drying for more than 12 hours; the surface of the modified boehmite nanorod is modified with an epoxy group;
and (3): adding the dried film-paving sample into a melting and mixing device, and melting and mixing at 180-210 ℃ to obtain a product 1;
and (4): discharging the product 1 from the melt mixing equipment, cooling to normal temperature, uniformly mixing with polylactic acid, adding into the melt mixing equipment, and carrying out melt mixing at 180-210 ℃ to obtain a product 2 with the mass content of the modified boehmite nanorods being 1-50 wt%;
and (5): product 2 was melt tableted.
7. The method of claim 6, wherein the mass ratio of the polylactic acid to the modified boehmite nanorods in step (2) is 3: 1.
8. The method according to claim 6, wherein the melt-kneading apparatus of the steps (3) (4) is an internal mixer, the rotor speed is 50rpm/min, and the melt-kneading time is 10 min.
9. The method according to claim 1, wherein the temperature of the melt-tableting in step (5) is 190 ℃ and 220 ℃, the pressure is 10-30MPa, and the dwell time is 3-8 min.
10. A plastic article characterized by using a multifunctional polylactic acid nanocomposite with high transparency according to any one of claims 1 to 5.
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|---|---|---|---|---|
| US20030197300A1 (en) * | 2002-04-19 | 2003-10-23 | Saint-Gobain Ceramics & Plastics, Inc. | Novel boehmite particles and polymer materials incorporating same |
| JP2009001739A (en) * | 2007-06-25 | 2009-01-08 | Nippon Zeon Co Ltd | Thermoplastic resin composition and molded product thereof |
| US20090270555A1 (en) * | 2005-10-03 | 2009-10-29 | Kri, Inc. | Functional Filler and Resin Composition Containing Same |
| CN112876826A (en) * | 2021-01-18 | 2021-06-01 | 山东科技大学 | Method for promoting polylactic acid stereo composite crystallization |
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| US20030197300A1 (en) * | 2002-04-19 | 2003-10-23 | Saint-Gobain Ceramics & Plastics, Inc. | Novel boehmite particles and polymer materials incorporating same |
| US20090270555A1 (en) * | 2005-10-03 | 2009-10-29 | Kri, Inc. | Functional Filler and Resin Composition Containing Same |
| JP2009001739A (en) * | 2007-06-25 | 2009-01-08 | Nippon Zeon Co Ltd | Thermoplastic resin composition and molded product thereof |
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