CN109096712B - Polylactic acid-ferroferric oxide nano composite foam material and preparation method thereof - Google Patents
Polylactic acid-ferroferric oxide nano composite foam material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a polylactic acid-ferroferric oxide nano composite foaming material, which is prepared by heating the following raw materials in parts by weight: 100 parts of polylactic acid, 1-30 parts of lactic acid graft modified nano ferroferric oxide, 1-10 parts of foaming agent and 0.1-3 parts of accelerant. The invention also discloses a preparation method of the polylactic acid-ferroferric oxide nano composite foaming material, which comprises the steps of taking polylactic acid as a matrix, taking ferroferric oxide nano particles with better microwave absorption characteristics as a microwave absorbent, grafting lactic acid or forming oligomers on the surface of the nano ferroferric oxide to improve the dispersibility of the nano particles in the matrix, preparing the polylactic acid/ferroferric oxide nano composite material by using a melt blending process, and finally heating, foaming and forming by utilizing microwave irradiation to obtain the polylactic acid-ferroferric oxide nano composite foaming material which simultaneously has good foaming effect and mechanical property.
Description
Technical Field
The invention relates to the technical field of foaming materials, in particular to a polylactic acid-ferroferric oxide nano composite foaming material and a preparation method thereof.
Background
With the increasing awareness of environmental protection, the development and application of biopolymer foam materials represented by polylactic acid are receiving increasing attention from researchers and industrial fields. Polylactic acid has the characteristics of plant raw material reproducibility and complete biodegradation, and the mechanical property of the polylactic acid can be compared with that of general high polymer materials such as polypropylene, and related products of the polylactic acid are not only widely applied to the field of biomedicine, such as sutures, tissue engineering scaffolds and the like, but also have huge application potential in the fields of daily necessities and industry.
At present, the preparation method of polylactic acid foam material mainly uses traditional thermoplastic foam preparation technology, including extrusion foaming, mold pressing foaming, injection molding foaming, high pressure batch foaming, etc., and strong shearing or long-time high temperature action is usually accompanied in the foaming process. However, polylactic acid has an aliphatic structure and is very sensitive to temperature and shear, and the polylactic acid matrix is easily significantly degraded due to overhigh processing temperature or overlong processing time, so that the mechanical property of the material is seriously reduced, and a foamed product with higher mechanical property is often difficult to obtain.
As a novel heating technology, the microwave irradiation heating technology is widely applied to the fields of chemical synthesis and polymer materials, has unique advantages in the aspects of synthesis, preparation, forming, interface compounding, foaming and the like of polymers and composite materials thereof, and particularly provides a new method for preparing the foaming material. At present, the method is mainly applied to the preparation of starch, thermosetting polymer and organic silicon foam materials. Because the dielectric constant of the thermoplastic polymer material is very low, the thermoplastic polymer material cannot generate heat energy through molecular polarization under the action of microwaves, is almost transparent to the microwaves, cannot be directly heated and foamed by the microwaves, and usually needs to be added with a certain auxiliary agent to serve as a microwave auxiliary absorbent or a heat conduction medium. Prociak et al introduced Carbon Black into thermoplastic Polymers (polypropylene and polyurethane) to enable Foaming and improved Foaming using microwave heating, but the effect was not ideal, mainly due to the non-uniform dispersion of Carbon Black in the matrix [ Prociak A, Sterzynski T, Michalowski S, Andrzejewski J.Microwave Enhanced foam of Carbon Black filed polypropylene. cellular Polymers, Vol.30, No.4,2011: 157-169./Prociak A, Michalowski S, Bak S.Thermoplastic polyurethane foam bottom microwave irradiation. Polimery,2012,57(11-12):786-790 ].
At present, few researches on heating, foaming and forming polylactic acid by microwave irradiation are carried out, and how to introduce a microwave irradiation heating technology into polylactic acid foaming and forming is a technical problem which needs to be solved urgently so as to prepare a polylactic acid foaming material with good foaming effect and excellent mechanical property.
Disclosure of Invention
The invention provides a polylactic acid-ferroferric oxide nano composite foaming material and a preparation method thereof, polylactic acid is taken as a matrix, ferroferric oxide nano particles with better microwave absorption property are taken as a microwave absorbent, lactic acid is grafted or oligomer is formed on the surface of the nano ferroferric oxide to improve the dispersibility of the nano particles in the matrix, the polylactic acid/ferroferric oxide nano composite foaming material is prepared by a melt blending process, and finally the polylactic acid-ferroferric oxide nano composite foaming material can be obtained by heating, foaming and forming by microwave irradiation, and the foaming material has good foaming effect and mechanical property.
The invention provides a polylactic acid-ferroferric oxide nano composite foaming material, which is prepared by heating the following raw materials in parts by weight: 100 parts of polylactic acid, 1-30 parts of lactic acid graft modified nano ferroferric oxide, 1-10 parts of foaming agent and 0.1-3 parts of accelerant.
Preferably, the foaming agent is an inorganic salt foaming agent, an azo foaming agent or a sulfonyl hydrazine foaming agent, or a compound thereof, and preferably is a foaming agent AC; the promoter is zinc oxide, magnesium oxide, lead oxide, stearic acid or zinc stearate, or a compound thereof, preferably zinc oxide.
The invention also provides a preparation method of the polylactic acid-ferroferric oxide nano composite foam material, which comprises the following steps:
s1, mixing 0.5-10 parts by weight of nano ferroferric oxide, 25-500 parts by weight of lactic acid and 45-900 parts by weight of organic solvent, performing ultrasonic dispersion, heating for reflux reaction, centrifuging, filtering, washing, drying and grinding to obtain lactic acid grafted modified nano ferroferric oxide;
s2, uniformly mixing the lactic acid graft modified nano ferroferric oxide obtained in the step S1 with 84-94 parts of polylactic acid, 4-8 parts of foaming agent and 0.3-0.6 part of accelerant, feeding the mixture into a double-screw extruder for melting and blending, and then extruding and granulating to obtain an expandable polylactic acid-ferroferric oxide nano composite material;
and S3, placing the expandable polylactic acid-ferroferric oxide nano composite material obtained in the step S2 into a mold, sending the mold into a microwave reactor, carrying out microwave heating, foaming and forming, taking out, cooling and solidifying to obtain the polylactic acid-ferroferric oxide nano composite foaming material.
Preferably, the polylactic acid has a melt index of 10-20g/10min and a density of 1.25-1.30g/cm3(ii) a The particle diameter of the nano ferroferric oxide is 10-30nm, and the specific surface area is 30-40m2/g。
Preferably, in S1, the organic solvent is toluene; in S2, the foaming agent is foaming agent AC, and the accelerator is zinc oxide.
Preferably, in S1, the ultrasonic dispersion time is 0.5-1h, the heating reflux reaction temperature is 150-170 ℃, and the time is 8-12 h.
Preferably, in S2, when the lactic acid graft-modified nano ferroferric oxide is uniformly mixed with polylactic acid, a foaming agent and an accelerator, liquid paraffin is added as a binder.
Preferably, in S2, the temperatures of the sections of the twin-screw extruder are respectively: and (3) extruding at 150 ℃, 175 ℃, 180 ℃, 185 ℃ and 175 ℃, preferably, cooling with water, granulating, and drying with air blast for 20-30h to obtain the expandable polylactic acid-ferroferric oxide nano composite material.
Preferably, in S3, the mold is a polytetrafluoroethylene mold, and preferably, microwave heating is performed at 5-8 times by using microwaves with power of 300-600W, each heating is performed for 2-6min, and more preferably, ice water is used for cooling and curing, so as to obtain the polylactic acid-ferroferric oxide nanocomposite foam material.
Preferably, in S1, the nano ferroferric oxide is purified nano ferroferric oxide, and specifically, the nano ferroferric oxide is placed in absolute ethyl alcohol and stirred at a high speed for 1-2 hours, centrifuged, filtered, washed by absolute ethyl alcohol and dried to obtain the purified nano ferroferric oxide.
According to the polylactic acid-ferroferric oxide nano composite foaming material, the nano ferroferric oxide subjected to lactic acid grafting modification is added into a polylactic acid matrix, so that the formed composite material can be foamed and formed by microwave heating, and meanwhile, as the nano ferroferric oxide is subjected to grafting modification by lactic acid, the nano ferroferric oxide can be well dispersed in the polylactic acid matrix, and when microwave irradiation heating is carried out, heating points of the polylactic acid matrix are uniformly distributed by microwaves, so that the foaming effect of the polylactic acid composite material is good, and the finally obtained foaming material is uniform and fine in cells, and the mechanical properties such as compressive strength, compression modulus and the like can be remarkably improved.
Meanwhile, the preparation method of the polylactic acid-ferroferric oxide nano composite foaming material is simple in process, the polylactic acid-ferroferric oxide nano composite foaming material can be obtained by directly mixing and then heating and foaming through microwave irradiation, and the foaming material has excellent performances of biodegradability, controllable density, good mechanical property and the like.
Drawings
FIG. 1 is an SEM image of a microscopic section of the polylactic acid-ferroferric oxide nanocomposite foam material in example 1 of the invention.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
A preparation method of a polylactic acid-ferroferric oxide nano composite foaming material comprises the following steps:
s1, mixing 7 parts by weight of nano ferroferric oxide, 300 parts by weight of lactic acid and 600 parts by weight of toluene, ultrasonically dispersing for 0.5h, heating at 160 ℃ for reflux reaction for 10h, centrifuging, filtering, washing, drying and grinding to obtain lactic acid grafted modified nano ferroferric oxide, wherein the nano ferroferric oxide is purified nano ferroferric oxide, specifically, the nano ferroferric oxide is placed in absolute ethyl alcohol to be stirred at a high speed for 2h, centrifuged, filtered, washed for 4 times by the absolute ethyl alcohol and dried to obtain the purified nano ferroferric oxide;
s2, uniformly mixing the lactic acid grafted and modified nano ferroferric oxide obtained in the step S1 with 87.5 parts of polylactic acid, 5 parts of foaming agent AC and 0.5 part of accelerator zinc oxide, feeding the mixture into a double-screw extruder for melt blending, and then extruding and granulating, wherein the temperature of each section of the double-screw extruder is respectively as follows: blowing and drying at 150 ℃, 175 ℃, 180 ℃, 185 ℃ and 175 ℃ for 24 hours to obtain the expandable polylactic acid-ferroferric oxide nano composite material;
and S3, placing the expandable polylactic acid-ferroferric oxide nano composite material obtained in the step S2 in a polytetrafluoroethylene mold, feeding the material into a microwave reactor, performing microwave heating for 6 times by using microwaves with the power of 500W, performing foaming forming after heating for 3min each time, taking out, and cooling and curing by using ice water to obtain the polylactic acid-ferroferric oxide nano composite foaming material.
Example 2
A preparation method of a polylactic acid-ferroferric oxide nano composite foaming material comprises the following steps:
s1, mixing 5 parts of nano ferroferric oxide, 250 parts of lactic acid and 500 parts of toluene in parts by weight, ultrasonically dispersing for 0.5h, heating and refluxing at 160 ℃ for 10h, centrifuging, filtering, washing, drying and grinding to obtain lactic acid grafted modified nano ferroferric oxide, wherein the nano ferroferric oxide is purified nano ferroferric oxide, and specifically, the nano ferroferric oxide is placed in absolute ethyl alcohol to be stirred at a high speed for 2h, centrifuged, filtered, washed for 4 times by absolute ethyl alcohol and dried to obtain the purified nano ferroferric oxide;
s2, uniformly mixing the lactic acid grafted and modified nano ferroferric oxide obtained in the step S1 with 89.5 parts of polylactic acid, 5 parts of foaming agent AC and 0.5 part of accelerator zinc oxide, feeding the mixture into a double-screw extruder for melt blending, and then extruding and granulating, wherein the temperature of each section of the double-screw extruder is respectively as follows: blowing and drying at 150 ℃, 175 ℃, 180 ℃, 185 ℃ and 175 ℃ for 24 hours to obtain the expandable polylactic acid-ferroferric oxide nano composite material;
and S3, placing the expandable polylactic acid-ferroferric oxide nano composite material obtained in the step S2 in a polytetrafluoroethylene mold, feeding the material into a microwave reactor, performing microwave heating for 6 times by using microwaves with the power of 500W, performing foaming forming after heating for 3min each time, taking out, and cooling and curing by using ice water to obtain the polylactic acid-ferroferric oxide nano composite foaming material.
Example 3
A preparation method of a polylactic acid-ferroferric oxide nano composite foaming material comprises the following steps:
s1, mixing 1 part of nano ferroferric oxide, 50 parts of lactic acid and 90 parts of toluene in parts by weight, ultrasonically dispersing for 0.5h, heating and refluxing at 160 ℃ for 10h, centrifuging, filtering, washing, drying and grinding to obtain lactic acid grafted modified nano ferroferric oxide, wherein the nano ferroferric oxide is purified nano ferroferric oxide, and specifically, the nano ferroferric oxide is placed in absolute ethyl alcohol to be stirred at a high speed for 2h, centrifuged, filtered, washed for 4 times by absolute ethyl alcohol and dried to obtain the purified nano ferroferric oxide;
s2, uniformly mixing the lactic acid grafted and modified nano ferroferric oxide obtained in the step S1 with 93.5 parts of polylactic acid, 5 parts of foaming agent AC and 0.5 part of accelerator zinc oxide, feeding the mixture into a double-screw extruder for melt blending, and then extruding and granulating, wherein the temperature of each section of the double-screw extruder is respectively as follows: blowing and drying at 150 ℃, 175 ℃, 180 ℃, 185 ℃ and 175 ℃ for 24 hours to obtain the expandable polylactic acid-ferroferric oxide nano composite material;
and S3, placing the expandable polylactic acid-ferroferric oxide nano composite material obtained in the step S2 in a polytetrafluoroethylene mold, feeding the material into a microwave reactor, performing microwave heating for 6 times by using microwaves with the power of 500W, performing foaming forming after heating for 3min each time, taking out, and cooling and curing by using ice water to obtain the polylactic acid-ferroferric oxide nano composite foaming material.
Example 4
A preparation method of a polylactic acid-ferroferric oxide nano composite foaming material comprises the following steps:
s1, mixing 10 parts by weight of nano ferroferric oxide, 500 parts by weight of lactic acid and 900 parts by weight of ethylene glycol monomethyl ether, performing ultrasonic dispersion for 0.5h, performing heating reflux reaction at 170 ℃ for 8h, centrifuging, filtering, washing, drying and grinding to obtain lactic acid grafted modified nano ferroferric oxide, wherein the nano ferroferric oxide is purified nano ferroferric oxide, and specifically, the nano ferroferric oxide is placed in absolute ethyl alcohol to be stirred at a high speed for 2h, centrifuged, filtered, washed for 4 times by absolute ethyl alcohol and dried to obtain the purified nano ferroferric oxide;
s2, uniformly mixing the lactic acid graft modified nano ferroferric oxide obtained in the step S1 with 84 parts of polylactic acid, 8 parts of foaming agent diisopropyl azodicarboxylate and 0.3 part of magnesium oxide, feeding the mixture into a double-screw extruder for melt blending, and then extruding and granulating, wherein the temperature of each section of the double-screw extruder is respectively as follows: blowing and drying at 150 ℃, 175 ℃, 180 ℃, 185 ℃ and 175 ℃ for 30 hours to obtain the expandable polylactic acid-ferroferric oxide nano composite material;
and S3, placing the expandable polylactic acid-ferroferric oxide nano composite material obtained in the step S2 in a polytetrafluoroethylene mold, feeding the material into a microwave reactor, performing microwave heating 8 times by using microwaves with the power of 300W, performing foaming forming after heating for 6min each time, taking out, and cooling and curing by using ice water to obtain the polylactic acid-ferroferric oxide nano composite foaming material.
Example 5
A preparation method of a polylactic acid-ferroferric oxide nano composite foaming material comprises the following steps:
s1, mixing 0.5 part of nano ferroferric oxide, 25 parts of lactic acid and 45 parts of dichloromethane in parts by weight, ultrasonically dispersing for 1h, heating and refluxing at 150 ℃ for 12h, centrifuging, filtering, washing, drying and grinding to obtain lactic acid grafted modified nano ferroferric oxide, wherein the nano ferroferric oxide is purified nano ferroferric oxide, and specifically, the nano ferroferric oxide is placed in absolute ethyl alcohol to be stirred at a high speed for 1h, centrifuged, filtered, washed for 3 times by the absolute ethyl alcohol and dried to obtain the purified nano ferroferric oxide;
s2, uniformly mixing the lactic acid grafted and modified nano ferroferric oxide obtained in the step S1 with 94 parts of polylactic acid, 4 parts of sodium bicarbonate and 0.6 part of stearic acid, feeding the mixture into a double-screw extruder for melt blending, and then extruding and granulating, wherein the temperatures of all sections of the double-screw extruder are respectively as follows: drying by blowing at 150 ℃, 175 ℃, 180 ℃, 185 ℃ and 175 ℃ for 20h to obtain the expandable polylactic acid-ferroferric oxide nano composite material;
and S3, placing the expandable polylactic acid-ferroferric oxide nano composite material obtained in the step S2 in a polytetrafluoroethylene mold, feeding the material into a microwave reactor, performing microwave heating for 5 times by using microwaves with the power of 600W, performing foaming forming after heating for 2min each time, taking out, and cooling and curing by using ice water to obtain the polylactic acid-ferroferric oxide nano composite foaming material.
Example 6
A preparation method of a polylactic acid-ferroferric oxide nano composite foaming material comprises the following steps:
s1, mixing 2 parts of nano ferroferric oxide, 100 parts of lactic acid and 300 parts of tetrahydrofuran in parts by weight, ultrasonically dispersing for 0.7h, heating and refluxing at 160 ℃ for 9h, centrifuging, filtering, washing, drying and grinding to obtain lactic acid grafted modified nano ferroferric oxide, wherein the nano ferroferric oxide is purified nano ferroferric oxide, and specifically, the nano ferroferric oxide is placed in absolute ethyl alcohol to be stirred at a high speed for 1.5h, centrifuged, filtered, washed by absolute ethyl alcohol and dried to obtain purified nano ferroferric oxide;
s2, uniformly mixing the lactic acid graft modified nano ferroferric oxide obtained in the step S1 with 92 parts of polylactic acid, 6 parts of benzenesulfonyl hydrazide and 0.4 part of zinc stearate, feeding the mixture into a double-screw extruder for melt blending, and then extruding and granulating, wherein the temperature of each section of the double-screw extruder is respectively as follows: blowing and drying at 150 ℃, 175 ℃, 180 ℃, 185 ℃ and 175 ℃ for 25 hours to obtain the expandable polylactic acid-ferroferric oxide nano composite material;
and S3, placing the expandable polylactic acid-ferroferric oxide nano composite material obtained in the step S2 in a polytetrafluoroethylene mold, feeding the material into a microwave reactor, performing microwave heating 7 times by adopting microwaves with the power of 400W, performing foaming forming after heating for 5min each time, taking out, and cooling and curing by adopting ice water to obtain the polylactic acid-ferroferric oxide nano composite foaming material.
Example 7
A preparation method of a polylactic acid-ferroferric oxide nano composite foaming material comprises the following steps:
s1, mixing 7 parts by weight of nano ferroferric oxide, 300 parts by weight of lactic acid and 600 parts by weight of dimethylbenzene, ultrasonically dispersing for 0.8h, heating at 160 ℃ for reflux reaction for 10h, centrifuging, filtering, washing, drying and grinding to obtain lactic acid grafted modified nano ferroferric oxide, wherein the nano ferroferric oxide is purified nano ferroferric oxide, specifically, the nano ferroferric oxide is placed in absolute ethyl alcohol to be stirred at a high speed for 1h, centrifuged, filtered, washed by the absolute ethyl alcohol and dried to obtain the purified nano ferroferric oxide;
s2, uniformly mixing the lactic acid graft modified nano ferroferric oxide obtained in the step S1 with 87.5 parts of polylactic acid, 5 parts of foaming agent 2, 2' -azobisisobutyronitrile and 0.5 part of accelerator lead oxide, feeding the mixture into a double-screw extruder for melt blending, and then extruding and granulating, wherein the temperature of each section of the double-screw extruder is respectively as follows: blowing and drying at 150 ℃, 175 ℃, 180 ℃, 185 ℃ and 175 ℃ for 30 hours to obtain the expandable polylactic acid-ferroferric oxide nano composite material;
and S3, placing the expandable polylactic acid-ferroferric oxide nano composite material obtained in the step S2 in a polytetrafluoroethylene mold, feeding the material into a microwave reactor, performing microwave heating 8 times by using microwaves with the power of 500W, performing foaming forming after heating for 4min each time, taking out, and cooling and curing by using ice water to obtain the polylactic acid-ferroferric oxide nano composite foaming material.
Comparative example 1
A preparation method of a polylactic acid-ferroferric oxide nano composite foaming material comprises the following steps:
s1, uniformly mixing 7 parts of nano ferroferric oxide, 87.5 parts of polylactic acid, 5 parts of foaming agent AC and 0.5 part of accelerator zinc oxide in parts by weight, feeding the mixture into a double-screw extruder for melt blending, and then extruding and granulating, wherein the temperatures of all sections of the double-screw extruder are respectively as follows: blowing and drying at 150 ℃, 175 ℃, 180 ℃, 185 ℃ and 175 ℃ for 24 hours to obtain the expandable polylactic acid-ferroferric oxide nano composite material;
and S2, placing the expandable polylactic acid-ferroferric oxide nano composite material obtained in the step S1 in a polytetrafluoroethylene mold, feeding the material into a microwave reactor, performing microwave heating for 6 times by using microwaves with the power of 500W, performing foaming forming after heating for 3min each time, taking out, and cooling and curing by using ice water to obtain the polylactic acid-ferroferric oxide nano composite foaming material.
Comparative example 2
A preparation method of a polylactic acid-ferroferric oxide nano composite foaming material comprises the following steps:
s1, uniformly mixing 5 parts of nano ferroferric oxide, 89.5 parts of polylactic acid, 5 parts of foaming agent AC and 0.5 part of accelerator zinc oxide in parts by weight, feeding the mixture into a double-screw extruder for melt blending, and then extruding and granulating, wherein the temperatures of all sections of the double-screw extruder are respectively as follows: blowing and drying at 150 ℃, 175 ℃, 180 ℃, 185 ℃ and 175 ℃ for 24 hours to obtain the expandable polylactic acid-ferroferric oxide nano composite material;
and S2, placing the expandable polylactic acid-ferroferric oxide nano composite material obtained in the step S1 in a polytetrafluoroethylene mold, feeding the material into a microwave reactor, performing microwave heating for 6 times by using microwaves with the power of 500W, performing foaming forming after heating for 3min each time, taking out, and cooling and curing by using ice water to obtain the polylactic acid-ferroferric oxide nano composite foaming material.
Comparative example 3
A preparation method of a polylactic acid-ferroferric oxide nano composite foaming material comprises the following steps:
s1, uniformly mixing 1 part of nano ferroferric oxide, 93.5 parts of polylactic acid, 5 parts of foaming agent AC and 0.5 part of accelerator zinc oxide in parts by weight, feeding the mixture into a double-screw extruder for melt blending, and then extruding and granulating, wherein the temperatures of all sections of the double-screw extruder are respectively as follows: blowing and drying at 150 ℃, 175 ℃, 180 ℃, 185 ℃ and 175 ℃ for 24 hours to obtain the expandable polylactic acid-ferroferric oxide nano composite material;
and S2, placing the expandable polylactic acid-ferroferric oxide nano composite material obtained in the step S1 in a polytetrafluoroethylene mold, feeding the material into a microwave reactor, performing microwave heating for 6 times by using microwaves with the power of 500W, performing foaming forming after heating for 3min each time, taking out, and cooling and curing by using ice water to obtain the polylactic acid-ferroferric oxide nano composite foaming material.
The foaming effect and the compression performance of the polylactic acid-ferroferric oxide nano composite foaming materials obtained in the examples and the comparative examples are respectively observed and tested, wherein,
(1) and (3) observing a foaming effect: observing the surrounding section of the foaming material by using a scanning electron microscope, counting and calculating the size of the cells by using ImageJ software, and calculating the density of the cells;
(2) and (3) testing the compression performance: the unidirectional compression performance of the cylindrical sample is tested by a WDW-50 universal electronic testing machine according to GB 8813-88, the deformation rate is 1.0mm/min, and the compression strength and the compression elastic modulus of the sample are recorded when the relative deformation is 50 percent.
The foaming characteristics and the compression properties of the polylactic acid-ferroferric oxide nanocomposite foams prepared in examples 1 to 7 and comparative examples 1 to 3 were compared as shown in table 1.
Table 1: product performance data sheet
As can be seen from Table 1, the formulation was modified with Fe without grafting3O4Comparative examples 1-3 of nanoparticles and Fe graft-modified with lactic acid3O4Examples 1 to 3 of nanoparticles, when the foaming characteristics and the compression properties of the composite foamed material obtained under the same preparation conditions were compared, it was found that the examples were significantly higher than the comparative examples in terms of both the foaming effect and the compression properties. This is mainly due to unmodified Fe3O4The nano particles are easy to agglomerate in the melt blending process and difficult to uniformly disperse in a matrix, and few foaming points are formed in the foaming process and foam holes are enlarged, so that the compression property of the nano particles is also obviously reduced.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A polylactic acid-ferroferric oxide nano composite foam material is characterized in that the preparation method of the polylactic acid-ferroferric oxide nano composite foam material comprises the following steps:
s1, mixing 0.5-10 parts by weight of nano ferroferric oxide, 25-500 parts by weight of lactic acid and 45-900 parts by weight of organic solvent, performing ultrasonic dispersion, heating for reflux reaction, centrifuging, filtering, washing, drying and grinding to obtain lactic acid grafted modified nano ferroferric oxide;
s2, uniformly mixing the lactic acid graft modified nano ferroferric oxide obtained in the step S1 with 84-94 parts of polylactic acid, 4-8 parts of foaming agent and 0.3-0.6 part of accelerant, feeding the mixture into a double-screw extruder for melting and blending, and then extruding and granulating to obtain an expandable polylactic acid-ferroferric oxide nano composite material;
and S3, placing the expandable polylactic acid-ferroferric oxide nano composite material obtained in the step S2 into a mold, sending the mold into a microwave reactor, carrying out microwave heating, foaming and forming, taking out, cooling and solidifying to obtain the polylactic acid-ferroferric oxide nano composite foaming material.
2. The polylactic acid-ferroferric oxide nanocomposite foam material according to claim 1, wherein the foaming agent is an inorganic salt foaming agent, an azo foaming agent or a sulfonyl hydrazide foaming agent, or a composite thereof; the accelerant is zinc oxide, magnesium oxide, lead oxide, stearic acid or zinc stearate, or a compound of the zinc oxide, the magnesium oxide, the lead oxide, the stearic acid or the zinc stearate.
3. The polylactic acid-ferroferric oxide nanocomposite foam material according to claim 1, wherein the foaming agent is an azo foaming agent AC; the accelerant is zinc oxide.
4. The polylactic acid-ferroferric oxide nanocomposite foam material according to claim 1, wherein the particle size of the nano ferroferric oxide is 10-30nm, and the specific surface area is 30-40m2The melt index of the polylactic acid is 10-20g/10min, and the density is 1.25-1.30g/cm3。
5. The polylactic acid-ferroferric oxide nanocomposite foam material according to claim 1 or 4, wherein in S1, the organic solvent is toluene; in S2, the foaming agent is foaming agent AC, and the accelerator is zinc oxide.
6. The polylactic acid-ferroferric oxide nanocomposite foam material according to claim 1, wherein in S1, the ultrasonic dispersion time is 0.5-1h, the heating reflux reaction temperature is 150-170 ℃, and the heating reflux reaction time is 8-12 h.
7. The polylactic acid-ferroferric oxide nanocomposite foam material according to claim 1, wherein in S2, liquid paraffin is added as a binder when the lactic acid graft modified ferroferric oxide nanocomposite foam material is uniformly mixed with polylactic acid, a foaming agent and an accelerator.
8. The polylactic acid-ferroferric oxide nanocomposite foam material according to claim 1, wherein in S2, the temperatures of each section of a twin-screw extruder are respectively as follows: extruding at 150 ℃, 175 ℃, 180 ℃, 185 ℃ and 175 ℃, cooling with water, granulating, and drying by blowing for 20-30h to obtain the expandable polylactic acid-ferroferric oxide nano composite material.
9. The polylactic acid-ferroferric oxide nanocomposite foam material according to claim 1, wherein in S3, the mold is a polytetrafluoroethylene mold, microwave heating is performed 5-8 times by using microwaves with power of 300-600W, each time is performed for 2-6min, and ice water is used for cooling and curing to obtain the polylactic acid-ferroferric oxide nanocomposite foam material.
10. The polylactic acid-ferroferric oxide nanocomposite foam material according to claim 1, wherein in S1, the nano ferroferric oxide is purified nano ferroferric oxide, and specifically, the nano ferroferric oxide is placed in absolute ethyl alcohol and stirred at a high speed for 1-2 hours, and then centrifuged, filtered, washed by the absolute ethyl alcohol and dried to obtain the purified nano ferroferric oxide.
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