CN113278267B - Wood-like completely biodegradable composite material and preparation method and application thereof - Google Patents
Wood-like completely biodegradable composite material and preparation method and application thereof Download PDFInfo
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- CN113278267B CN113278267B CN202110770905.7A CN202110770905A CN113278267B CN 113278267 B CN113278267 B CN 113278267B CN 202110770905 A CN202110770905 A CN 202110770905A CN 113278267 B CN113278267 B CN 113278267B
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
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Abstract
The invention discloses a wood-like completely biodegradable composite material and a preparation method and application thereof; the composite material comprises the following raw material components in parts by weight: 50-90 parts of poly (butylene succinate) resin and 10-50 parts of biologically crushed straw powder; wherein the biological pulverized straw powder is the tenebrio molitor feces obtained after the tenebrio molitor gnaws the straws. The invention solves the problems of straw crushing, composite material compatibility and the like in the production of straw/PBS composite materials.
Description
Technical Field
The invention belongs to the technical field of biodegradable materials, and particularly relates to a wood-like completely biodegradable composite material as well as a preparation method and application thereof.
Background
The polybutylene succinate (PBS) resin is milk white, odorless and tasteless, is easily decomposed and metabolized by various microorganisms or enzymes in animals and plants in the nature, is finally decomposed into carbon dioxide and water, and is a typical completely biodegradable polymer material. PBS has good biocompatibility and biological absorbability and the density is 1.26g/cm 3 The melting point is 114 ℃, and the crystallinity is between 30 and 45 percent according to the difference of molecular weight and molecular weight distribution. The PBS has a polymer with good biodegradability, compared with biodegradable plastics such as polylactic acid, polyhydroxyalkanoate, polycaprolactone and the like, the PBS has relatively low price, excellent mechanical property and good heat resistance, the heat distortion temperature is close to 100 ℃, and the PBS is a biodegradable plastic grinding plastic at home and abroadThe emphasis of hair.
In recent years, PBS with good comprehensive performance has rapidly become a research hotspot of general completely biodegradable plastics which can be widely popularized and applied. However, the high cost of PBS production severely limits its development and widespread use. Under the background, the cheap straw fiber with short regeneration period enters the visual field of researchers, the treated straw fiber is used as a reinforcing material to prepare the biodegradable straw/PBS composite material, the composite material combines the advantages of the PBS and the straw fiber, the cost of the product is greatly reduced, and the composite material has very important significance for solving the problem of energy shortage and environmental pollution.
However, the crushing treatment of the straw in the prior art has many problems, for example, the uniformity and fine crushing of the straw powder cannot be guaranteed by mechanical crushing, and the field dust is large during crushing, and the explosion risk exists in serious cases. In addition, the straw is a natural biomass raw material, contains a large amount of cellulose and lignin, is directly crushed and then is used for preparing the straw/PBS composite material, and the effect of increasing the performance of the PBS is difficult to achieve due to poor compatibility between the straw powder and the PBS. In addition, the straws also contain moisture, fat, starch, protein and some small molecular substances, the substances are very easy to volatilize or deteriorate, and if the straws are directly mixed with PBS without treatment, the problem of unstable performance of the composite material can be caused.
Disclosure of Invention
The invention aims to provide a wood-like completely biodegradable composite material and a preparation method and application thereof, and solves the problems of straw crushing and straw powder components and compatibility in the production of straw/PBS composite materials.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention discloses a wood-like completely biodegradable composite material, which comprises the following raw material components in parts by weight: 50-90 parts of poly (butylene succinate) resin and 10-50 parts of biologically crushed straw powder; wherein the biological pulverized straw powder is the tenebrio molitor manure obtained after the tenebrio molitor gnaws the straw.
As a preferred technical scheme, the straws are ensilaged straws.
As a preferable technical scheme, wheat bran is also mixed in the straws.
As a preferable technical scheme, the composite material also comprises the following raw material components in parts by weight: 1-5 parts of natural reinforced fiber.
As a preferred technical scheme, the natural reinforced fibers are one or more of white hemp filaments, sisal hemp filaments and raffia filaments.
As a preferred technical scheme, the particle size of the biological crushed straw powder is 40-60 meshes.
The invention also discloses a preparation method of the wood-like completely biodegradable composite material, which comprises the following steps:
(1) Feeding the flour weevil with straws, and collecting flour weevil manure obtained after the flour weevil gnaws the straws to obtain biological crushed straw powder;
(2) And blending the biological crushed straw powder and the poly (butylene succinate) resin, and then adding the mixture into an extruder to extrude and granulate to obtain the composite material.
The invention also discloses application of the wood-like completely biodegradable composite material in preparation of wood-like products.
The beneficial effects of the invention are as follows: the invention applies biological crushing as a brand new crushing mode to the production of composite materials, and takes the yellow mealworm feces obtained after yellow mealworms gnaw straws as biological crushed straw powder, and has the advantages of the following four aspects:
1. on the first hand, the biologically crushed straw is crushed more uniformly without the risk of dust and explosion.
2. In the second aspect, the flour weevil has biological selectivity to the straws, digests the grease layer on the surface of the straws to make the surface of the straw powder rough, improves the compatibility between the straw powder and the PBS, and simultaneously, the biological crushed straw powder also retains most of cellulose and lignin in the straws, so that the straw powder still has the capability of increasing the performance of the PBS.
3. In the third aspect, the biologically crushed straw powder has micropores, and the air permeability and the degradability of the biologically crushed straw powder are further improved after the biologically crushed straw powder is used for preparing a product from the composite material.
4. In the fourth aspect, the flour weevil has the biological dehydration function, and the flour weevil manure obtained after the flour weevil gnaws the straws is used as the biological crushed straw powder, so that the drying process of the straws can be omitted.
Drawings
In order to make the object, technical scheme and beneficial effect of the invention more clear, the invention provides the following drawings for explanation:
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a performance test bar;
FIG. 3 shows the results of hardness testing;
FIG. 4 shows the results of the impact strength test;
FIG. 5 shows the results of the flexural strength test;
FIG. 6 shows the results of outdoor degradation tests;
FIG. 7 shows the indoor degradation performance test results;
fig. 8 is a wood-like product (wooden comb).
Detailed Description
The present invention is further described below with reference to specific examples so that those skilled in the art can better understand the present invention and can practice the present invention, but the examples are not intended to limit the present invention.
FIG. 1 is a process flow diagram of the present invention, according to the process flow of FIG. 1, the following experiments were performed:
1. the raw material ratio is as follows:
taking 200g of mixed material as an example, the raw material formula is as follows, in the table, the raw material crushed straw powder is tenebrio molitor dung obtained after the tenebrio molitor gnaws the straw, and the natural reinforced fibers are respectively white hemp silk, sisal hemp silk and raffia silk:
| proportion of prefabrication | PBS addition amount (g) | Adding amount (g) of the bio-pulverized straw powder | Natural reinforcing fiber addition amount (g) |
| 10％ | 180 | 20 | |
| 20％ | 160 | 40 | |
| 30％ | 140 | 60 | |
| 40％ | 120 | 80 | |
| 50％ | 100 | 100 | |
| 10％ | 180 | 20 | 4 |
| 20％ | 160 | 40 | 4 |
| 30％ | 140 | 60 | 4 |
| 40％ | 120 | 80 | 4 |
| 50％ | 100 | 100 | 4 |
2. The raw materials in various proportions are respectively added into a double-screw extruder for granulation. The parameters of the twin-screw extruder are as follows:
3. after granulation was completed, dumbbell-shaped bars were injection molded using an injection molding machine for testing, as shown in FIG. 2. Parameters of the injection molding machine: injection molding temperature: 125 ℃, mold temperature: 80 ℃ and the charging amount: 10 g/bar, dwell time: 15s.
4. And (3) performance testing:
1. the hardness test results are shown in fig. 3, and it can be seen from the figure that the hardness of the blended material after adding the bio-pulverized straw powder is higher than that of pure PBS, and the hardness of the material tends to slightly increase with the increase of the amount of the bio-pulverized straw powder. The reason is that the hardness of the biological crushed straw powder is higher than that of PBS, and the surface of the biological crushed straw powder is carbonized at high temperature, so that the hardness of the biological crushed straw powder is further increased. The higher the content of the biologically crushed straw powder in the composite material is, the more obvious the hardness of the biologically crushed straw powder is increased after high-temperature treatment.
2. The impact strength test result is shown in fig. 4, and it can be seen from the figure that when the addition amount of the bio-pulverized straw powder is between 10% and 30%, the overall impact strength of the material is obviously superior to that of pure PBS, and with the increase of the addition amount of the bio-pulverized straw powder, the impact strength of the material has the phenomenon of rising first and then falling, and reaches the highest point when the addition amount is between 20% and 30%. This is because the bio-pulverized straw powder itself is a porous material, and absorbs a part of the impact energy when being impacted, resulting in an increase in the impact strength of the composite material. The high tenacity of the fibers allows the impact strength of the composite to change more gradually after the fibers are added.
3. The bending strength test result is shown in fig. 5, and it can be seen from the figure that the bending performance of the blended material is better than that of pure PBS when the addition amount of the bio-pulverized straw powder is 10% -30%, and reaches the highest point when the addition amount is 20%, the optimal bending performance can reach 39.26MPa, and is improved by 15.6% compared with that of pure PBS. The mass fraction of the bio-crushed straw powder is less than 20%, and the PBS can effectively coat the bio-crushed straw powder so that the bio-crushed straw powder is uniformly distributed in the PBS and bears bending load; when the mass fraction of the bio-crushed straw powder is more than 20%, the bending strength of the composite material shows a descending trend, which shows that when the bio-crushed straw powder is dominant in the material, the composite material shows brittleness, so that the bending stress bearing limit of the composite material is reduced.
4. The results of the outdoor degradation performance test (buried method) are shown in fig. 6, and the results of the indoor degradation performance test (buried method) are shown in fig. 7, and it can be seen from the figure that the degradation performance of all the blended materials is much higher than that of pure PBS. And the degradation performance of the composite material is better and better along with the increase of the mass fraction of the biologically crushed straw powder. When the mass fraction of the biological straw powder is 50%, the degradation rates of the four composite materials are all over 45%, and the degradation rate of pure PBS is only 5%. This is because the raw crushed straw powder contains a large amount of coarse fibers and voids, which are more easily decomposed and digested by microorganisms than PBS. The composite material can be decomposed in a shorter time. It can also be seen that the addition of a small amount of natural reinforcing fibers does not affect the degradation properties of the composite.
As can be seen from comparing fig. 6 and 7, the outdoor degradation efficiency of the composite material is higher than that of the indoor degradation, which may be because the outdoor sufficient light source gives better survival conditions for the microorganisms, or the indoor closed environment limits the survival and proliferation of the microorganisms.
The composite material obtained above can be used to prepare a wood-like product, such as a wood comb as shown in fig. 8.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitutions or changes made by the person skilled in the art on the basis of the present invention are all within the protection scope of the present invention. The protection scope of the invention is subject to the claims.
Claims (8)
1. A wood-like completely biodegradable composite material is characterized in that: the composite material comprises the following raw material components in parts by weight: 50-90 parts of poly (butylene succinate) resin and 10-50 parts of biologically crushed straw powder; wherein the biological pulverized straw powder is the tenebrio molitor feces obtained after the tenebrio molitor gnaws the straws.
2. The wood-like fully biodegradable composite according to claim 1, characterized in that: the straw is ensiled straw.
3. The wood-like fully biodegradable composite according to claim 1, characterized in that: wheat bran is also mixed in the straws.
4. The wood-like fully biodegradable composite according to claim 1, characterized in that: the composite material also comprises the following raw material components in parts by weight: 1-5 parts of natural reinforced fiber.
5. The wood-like fully biodegradable composite according to claim 4, characterized in that: the natural reinforced fiber is one or more of white hemp, sisal hemp and raffia.
6. The wood-like fully biodegradable composite according to any one of claims 1 to 5, characterized in that: the grain diameter of the biological crushed straw powder is 40-60 meshes.
7. The method for preparing a wood-like completely biodegradable composite material as set forth in any one of claims 1 to 6, characterized in that: the method comprises the following steps:
(1) Feeding the flour weevil with straws, and collecting flour weevil manure obtained after the flour weevil gnaws the straws to obtain biological crushed straw powder;
(2) And blending the biological crushed straw powder and the poly (butylene succinate) resin, and then adding the mixture into an extruder for extrusion and granulation to obtain the composite material.
8. Use of the wood-like fully biodegradable composite according to any one of claims 1 to 6 for the preparation of wood-like products.
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