CN110698825A - Process for preparing high-toughness biodegradable composite material by utilizing loofah sponge fibers and PLA - Google Patents
Process for preparing high-toughness biodegradable composite material by utilizing loofah sponge fibers and PLA Download PDFInfo
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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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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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/395—Isocyanates
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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
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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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
- C08L2205/16—Fibres; Fibrils
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
Abstract
The invention discloses a process for preparing a high-toughness biodegradable composite material by utilizing loofah sponge fibers and PLA (polylactic acid). Dry loofah sponge is cleaned and then dried and crushed, the crushed loofah sponge dry fibers are placed in a reaction bottle, and NaOH solution and H are added2O2Carrying out reflux treatment in a solution reflux device, then adding an HCl solution, adding amino acid ester, and continuing reflux reaction; performing suction filtration, cleaning the treated loofah sponge with pure water, and placing the loofah sponge in a vacuum drying oven to be dried to constant weight for later use; mixing dried modified retinervus Luffae fructus and poly L-lactic acid in a mixer, drying, adding into an extruder, melt blending, extruding, cooling, and granulatingAnd then obtaining the composite material. The process can improve the heat-resistant temperature of the loofah sponge fiber, can be used for preparing biodegradable composite materials, and improves the degradation performance and toughness of the composite materials.
Description
Technical Field
The invention relates to preparation of a biodegradable composite material, in particular to a process for preparing a high-toughness biodegradable composite material by utilizing loofah sponge fibers and PLA.
Background
The loofah sponge is a plant fiber, wherein the content of alpha-cellulose is 61.3 percent, the loofah sponge is higher than that of common wood, is similar to that of hemp plants, has higher strength and toughness of the fiber, is rich in source and low in price, and is a good plant fiber resource. In recent years, researches mainly focus on daily necessities, and in recent years, researches on toughening modification by adding the vegetable sponge modifier into other materials are increasing, but the vegetable sponge modifier is single in type and lacks of new modifiers, so that the popularization and application of cheap plant cellulose in polylactic acid modification are limited. Polylactic acid can be obtained from starch extracted from plant resources, and is widely researched due to good biodegradability and processing universality (processing technologies such as film blowing, film drawing, injection molding and extrusion can be used), but the application of the polylactic acid is greatly limited due to poor toughness, low notch impact strength and low elongation at break of the polylactic acid; therefore, the toughening modification of polylactic acid is still a great research difficulty and hot spot.
CN101177523 discloses a method for preparing a polylactic acid composite material by using modified loofah sponge, the used loofah sponge modifier is a silane coupling agent, which can effectively improve the problem of poor compatibility between loofah sponge and polylactic acid, but the silane coupling agent is not degradable, and the prepared composite material still faces the problem of difficult degradation, which is not beneficial to environmental protection. CN106589869 discloses a preparation method of a plant fiber reinforced polylactic acid composite material, but uses a highly toxic chemical 2, 4-toluene diisocyanato as a plant fiber modifier.
Disclosure of Invention
The invention aims to provide a process for preparing a high-toughness biodegradable composite material by utilizing loofah sponge fibers and PLA, which has a reasonable process and is environment-friendly.
The technical scheme of the invention is that a process for preparing a high-toughness biodegradable composite material by using loofah sponge fibers and PLA is characterized in that: (1) cleaning dried retinervus Luffae fructus, drying, pulverizing, placing pulverized retinervus Luffae fructus dry fiber in a reaction bottle, adding NaOH solution and H2O2Carrying out reflux treatment in a solution reflux device, then adding an HCl solution, washing with hydrochloric acid until the pH value of the detected mother liquor is 7.0 +/-0.2, and adding amino acid ester to continue reflux reaction; performing suction filtration, cleaning the treated loofah sponge with pure water, and placing the loofah sponge in a vacuum drying oven to be dried to constant weight for later use; (2) and (2) taking the dried modified loofah sponge and the poly-L-lactic acid, uniformly mixing in a mixer, drying the mixture, adding the dried mixture into an extruder, carrying out melt blending, and carrying out extrusion, cooling and grain cutting to obtain the composite material.
The concentration of the dilute NaOH solution is as follows: 0.05mol/L-0.5mol/L, H2O2The concentration of the solution was: 5 to 20 percent of the hydrochloric acid is refluxed, and then the concentration of the added dilute hydrochloric acid is as follows: 0.05mol/L-0.5 mol/L.
The selected polylactic acid is L-type polylactic acid, the purity is more than or equal to 85 percent, and the molecular weight is 5-30 ten thousand.
Vacuum drying treatment is carried out for 24 hours in a vacuum drying oven at 40 ℃;
mixing polylactic acid and modified loofah sponge in a mass ratio of: 1:9-9:1.
The amino acid ester is selected from amino acid methyl ester and amino acid ethyl ester.
Synthesis of amino acid ester: taking amino acid ester hydrochloride, and reacting with triphosgene under the action of a nucleophilic reagent such as pyridine to obtain amino acid ester isocyanate (AADI). The method is a method known and commonly used in the art. The long chain amino acid ester isocyanates that can be prepared by this method include, but are not limited to: lysine methyl ester isocyanate, lysine ethyl ester isocyanate, glutamic acid dimethyl ester isocyanate, leucine methyl ester isocyanate, valine methyl ester isocyanate, aspartic acid methyl ester isocyanate and arginine methyl ester isocyanate.
The used amino acid is selected from one or more of long-chain aliphatic amino acids such as valine, leucine, aspartic acid, glutamic acid, lysine, arginine and the like or derivatives thereof, the amino acid or the derivatives thereof do not contain a benzene ring structure, and the amino acid or the derivatives thereof are introduced into the material as degradable materials so as to achieve the purpose of introducing a flexible degradable chain segment into the material.
The isocyanate group (-N = C = O) in the amino acid group isocyanate has higher activity, is very easy to react with active hydroxyl group (-OH) in the loofah sponge, the toxicity of a reaction product is low, the main molecular chain is a flexible chain, the compatibility between the loofah sponge fiber and the polylactic acid can be improved by utilizing the characteristic that the isocyanate prepared from the aliphatic amino acid is used, and meanwhile, the toughness of the chain segment is improved by introducing the aliphatic chain amino acid and the isocyanate thereof. Comprises two modification processes: amino acid ester isocyanate modified loofah sponge fiber and modification of polylactic acid by the loofah sponge fiber. The loofah serving as the plant fiber containing the active reactive group can be used as a main body of the degradable material and is combined with other partial materials to carry out comprehensive modification to prepare the high-toughness degradable material.
The invention has the beneficial effects that: the process can improve the heat-resistant temperature of the loofah sponge fiber, can be used for preparing biodegradable composite materials, and improves the degradation performance and toughness of the composite materials.
Detailed Description
In order to make the object and technical solution of the present invention more apparent, the present invention will be described in detail with reference to the following embodiments. It should be understood that the detailed description and specific examples, while indicating the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
The preparation method of the composite material prepared by blending the modified loofah sponge and the polylactic acid comprises the following specific steps:
(1) preparing lysine methyl ester isocyanate modified loofah sponge:
cleaning dried retinervus Luffae fructus, drying in vacuum drying oven at 80 deg.C to constant weight, pulverizing in pulverizer, sieving with 100 mesh sieve, placing 10 parts of pulverized retinervus Luffae fructus dry fiber in reaction bottle, adding 0.1mol/L NaOH solution 70Parts, 10% of H2O2And refluxing 20 parts of the solution in a refluxing device for 4 hours, then adding HCl solution to neutralize redundant alkali, washing with 0.1mol/L hydrochloric acid until the pH value of the detected mother liquor is 7.0 +/-0.2, adding 15 parts of lysine ethyl ester isocyanate, and continuing refluxing for 4 hours. And (4) carrying out suction filtration, washing with pure water, and then placing in a vacuum drying oven at 80 ℃ for drying to constant weight for later use.
(2) Blending of modified loofah sponge fiber and polylactic acid
And (2) uniformly mixing 10 parts of dried modified loofah sponge and 90 parts of poly-L-lactic acid with the weight average molecular weight of 10 ten thousand in a mixer to obtain a dry mixed material with the weight ratio of 1:9 (w: w), adding the dry mixed material into an extruder for melt blending at the temperature of 170 ℃, extruding, cooling and granulating to obtain a composite material, and carrying out other molding processing processes on the obtained composite material slices.
Mechanical property detection results of materials prepared from raw materials with different proportions (1)
| Sample name | Tensile strength/MPa | Elongation at break/% |
| PLA | 60.1±0.5 | 13.5±2.3 |
| Lysine methyl ester isocyanate modified loofah/PLA-1: 9 (w: w) | 81.2±0.5 | 23.3±2.1 |
| Lysine methyl ester isocyanate modified loofah/PLA-3: 7 (w: w) | 82.1±0.6 | 23.9±1.7 |
| Lysine methyl ester isocyanate modified loofah/PLA-5: 5 (w: w) | 85.3±0.3 | 23.8±1.6 |
| Lysine methyl ester isocyanate modified loofah/PLA-7: 3 (w: w) | 82.1±0.3 | 23.5±1.3 |
| Lysine methyl ester isocyanate modified loofah/PLA-9: 1 (w: w) | 83.3±0.5 | 23.7±1.5 |
Example 2
The preparation method of the composite material prepared by blending the modified loofah sponge and the polylactic acid comprises the following specific steps:
(1) preparing lysine ethyl ester isocyanate modified loofah sponge:
cleaning dried retinervus Luffae fructus, drying at 80 deg.C in vacuum drying oven to constant weight, pulverizing in pulverizer, sieving with 100 mesh sieve, placing 10 parts of pulverized retinervus Luffae fructus dry fiber in reaction bottle, adding 0.1mol/L NaOH solution 70 parts and 10% H2O2And refluxing 20 parts of the solution in a refluxing device for 4 hours, then adding HCl solution to neutralize redundant alkali, washing with 0.1mol/L hydrochloric acid until the pH value of the detected mother liquor is 7.0 +/-0.2, adding 15 parts of lysine ethyl ester isocyanate, and continuing refluxing for 4 hours. And (4) carrying out suction filtration, washing with pure water, and then placing in a vacuum drying oven at 80 ℃ for drying to constant weight for later use.
(2) Blending of modified loofah sponge fiber and polylactic acid
And (2) uniformly mixing 30 parts of dried modified loofah sponge and 70 parts of poly-L-lactic acid with the weight average molecular weight of 10 ten thousand in a mixer to obtain a dry mixture of 3:7 (w: w), adding the dry mixture into an extruder for melt blending at the temperature of 160 ℃, extruding, cooling and granulating to obtain a composite material, and carrying out other molding processing processes on the obtained composite material slices.
Mechanical property detection results of materials prepared from raw materials with different proportions (2)
| Sample name | Tensile strength/MPa | Elongation at break/% |
| PLA | 60.1±0.5 | 13.5±2.3 |
| Lysine ethyl ester isocyanate modified loofah/PLA-1: 9 (w: w) | 87.2±0.5 | 23.8±1.1 |
| Lysine ethyl ester isocyanate modified loofah/PLA-3: 7 (w: w) | 88.1±0.6 | 24.0±2.6 |
| Lysine ethyl ester isocyanate modified loofah/PLA-5: 5 (w: w) | 88.3±0.3 | 23.9±1.2 |
| Lysine ethyl ester isocyanate modified loofah/PLA-7: 3 (w: w) | 88.1±0.3 | 24.4±1.7 |
| Lysine ethyl ester isocyanate modified loofah/PLA-9: 1 (w: w) | 89.3±0.5 | 24.5±1.8 |
Example 3
The preparation method of the composite material prepared by blending the modified loofah sponge and the polylactic acid comprises the following specific steps:
(1) preparing dimethyl glutamate isocyanate modified loofah sponge:
cleaning dried retinervus Luffae fructus, drying at 80 deg.C in vacuum drying oven to constant weight, pulverizing in pulverizer, sieving with 100 mesh sieve, placing 10 parts of pulverized retinervus Luffae fructus dry fiber in reaction bottle, adding 0.1mol/L NaOH solution 70 parts and 10% H2O2And refluxing 20 parts of the solution in a refluxing device for 4 hours, then adding HCl solution to neutralize redundant alkali, washing with 0.1mol/L hydrochloric acid until the pH value of the detected mother liquor is 7.0 +/-0.2, adding 15 parts of dimethyl glutamate isocyanate, and continuing refluxing for 4 hours. And (4) carrying out suction filtration, washing with pure water, and then placing in a vacuum drying oven at 80 ℃ for drying to constant weight for later use.
(2) Blending of modified loofah sponge fiber and polylactic acid
And (2) uniformly mixing 30 parts of dried modified loofah sponge and 70 parts of poly-L-lactic acid with the weight average molecular weight of 10 ten thousand in a mixer to obtain a dry mixture of 3:7 (w: w), adding the dry mixture into an extruder for melt blending at the temperature of 150 ℃, extruding, cooling and granulating to obtain a composite material, and performing other molding processing processes on the obtained composite material master batch.
Mechanical property detection results of materials prepared from raw materials with different proportions (3)
| Sample numbering | Tensile strength/MPa | Elongation at break/% |
| PLA | 60.1±0.5 | 13.5±2.3 |
| Dimethyl glutamate isocyanate modified loofah/PLA-1: 9 (w: w) | 75.2±0.5 | 23.7±1.1 |
| Dimethyl glutamate isocyanate modified loofah/PLA-3: 7 (w: w) | 75.1±0.6 | 23.8±1.6 |
| Dimethyl glutamate isocyanate modified loofah/PLA-5: 5 (w: w) | 76.3±0.3 | 22.9±2.2 |
| Dimethyl glutamate isocyanate modified loofah/PLA-7: 3 (w: w) | 77.5±0.3 | 23.4±1.8 |
| Dimethyl glutamate isocyanate modified loofah/PLA-9: 1 (w: w) | 77.3±0.5 | 23.5±1.7 |
Example 4
The preparation method of the composite material prepared by blending the modified loofah sponge and the polylactic acid comprises the following specific steps:
(1) preparing leucine methyl ester isocyanate modified loofah sponge:
cleaning dried retinervus Luffae fructus, drying at 80 deg.C in vacuum drying oven to constant weight, pulverizing in pulverizer, sieving with 100 mesh sieve, placing 10 parts of pulverized retinervus Luffae fructus dry fiber in reaction bottle, adding 0.1mol/L NaOH solution 70 parts and 10% H2O2And refluxing 20 parts of the solution in a refluxing device for 4 hours, then adding HCl solution to neutralize redundant alkali, washing with 0.1mol/L hydrochloric acid until the pH value of the detected mother liquor is 7.0 +/-0.2, adding 15 parts of leucine methyl ester isocyanate, and continuing refluxing for 4 hours. And (4) carrying out suction filtration, washing with pure water, and then placing in a vacuum drying oven at 80 ℃ for drying to constant weight for later use.
(2) Blending of modified loofah sponge fiber and polylactic acid
And (2) uniformly mixing 50 parts of dried modified loofah sponge and 50 parts of poly-L-lactic acid with the weight average molecular weight of 10 ten thousand in a mixer to obtain a dry mixture with the weight ratio of 5:5 (w: w), adding the dry mixture into an extruder for melt blending at the temperature of 180 ℃, extruding, cooling and granulating to obtain a composite material, and carrying out other molding processing processes on the obtained composite material slices.
Mechanical property detection results of materials prepared from raw materials with different proportions (4)
| Sample name | Tensile strength/MPa | Elongation at break/% |
| PLA | 60.1±0.5 | 13.5±2.3 |
| Leucine methyl ester isocyanate modified loofah/PLA-1: 9 (w: w) | 69.2±0.6 | 21.3±1.9 |
| Leucine methyl ester isocyanate modified loofah/PLA-3: 7 (w: w) | 68.1±0.7 | 21.4±1.9 |
| Leucine methyl ester isocyanate modified loofah/PLA-5: 5 (w: w) | 71.3±1.3 | 20.8±2.1 |
| Leucine methyl ester isocyanate modified loofah/PLA-7: 3 (w: w) | 70.5±1.2 | 21.1±2.5 |
| Leucine methyl ester isocyanate modified loofah/PLA-9: 1 (w: w) | 70.8±0.3 | 20.9±2.8 |
Example 5
The preparation method of the composite material prepared by blending the modified loofah sponge and the polylactic acid comprises the following specific steps:
(1) preparing valine methyl ester isocyanate modified loofah sponge:
cleaning dried retinervus Luffae fructus, drying at 80 deg.C in vacuum drying oven to constant weight, pulverizing in pulverizer, sieving with 100 mesh sieve, placing 10 parts of pulverized retinervus Luffae fructus dry fiber in reaction bottle, adding 0.1mol/L NaOH solution 70 parts and 10% H2O2And refluxing 20 parts of the solution in a refluxing device for 4 hours, then adding HCl solution to neutralize redundant alkali, washing with 0.1mol/L hydrochloric acid until the pH value of the detected mother liquor is 7.0 +/-0.2, adding 15 parts of valine methyl ester isocyanate, and continuing refluxing for 4 hours. And (4) carrying out suction filtration, washing with pure water, and then placing in a vacuum drying oven at 80 ℃ for drying to constant weight for later use.
(2) Blending of modified loofah sponge fiber and polylactic acid
Taking 70 parts of dried modified loofah sponge and 30 parts of poly-L-lactic acid with the weight average molecular weight of 10 ten thousand, uniformly mixing in a mixer to obtain a dried mixture of 7:3 (w: w), adding the dried mixture into an extruder, carrying out melt blending at the temperature of 190 ℃, extruding, cooling and granulating to obtain a composite material, and carrying out other molding processing processes on the obtained composite material slices.
Mechanical property detection results of materials prepared from raw materials with different proportions (5)
| Sample name | Tensile strength/MPa | Elongation at break/% |
| PLA | 60.1±0.5 | 13.5±2.3 |
| Valine methyl ester isocyanate modified loofah/PLA-1: 9 (w: w) | 70.2±1.3 | 22.3±2.1 |
| Valine methyl ester isocyanate modified loofah/PLA-3: 7 (w: w) | 71.1±2.5 | 21.9±1.7 |
| Valine methyl ester isocyanate modified loofah sponge/PLA-5: 5 (w: w) | 73.3±2.3 | 20.8±2.6 |
| Valine methyl ester isocyanate modified loofah sponge/PLA-7: 3 (w: w) | 72.3±2.1 | 21.9±1.7 |
| Valine methyl ester isocyanate modified loofah/PLA-9: 1 (w: w) | 72.3±2.1 | 20.8±2.6 |
Example 6
The preparation method of the composite material prepared by blending the modified loofah sponge and the polylactic acid comprises the following specific steps:
(1) preparing methyl aspartate isocyanate modified loofah sponge:
cleaning dried retinervus Luffae fructus, drying at 80 deg.C in vacuum drying oven to constant weight, pulverizing in pulverizer, sieving with 100 mesh sieve, placing 10 parts of pulverized retinervus Luffae fructus dry fiber in reaction bottle, adding 0.1mol/L NaOH solution 70 parts and 10% H2O2And refluxing 20 parts of the solution in a refluxing device for 4 hours, then adding HCl solution to neutralize redundant alkali, washing with 0.1mol/L hydrochloric acid until the pH value of the detected mother liquor is 7.0 +/-0.2, adding 15 parts of aspartic acid methyl ester isocyanate, and continuing refluxing for 4 hours. Suction filtering, washing with pure water, vacuum drying at 80 deg.CDrying in a box to constant weight for later use.
(2) Blending of modified loofah sponge fiber and polylactic acid
And (2) uniformly mixing 90 parts of dried modified loofah sponge and 10 parts of poly-L-lactic acid with the weight average molecular weight of 10 ten thousand in a mixer to obtain a dried mixture of 9:1 (w: w), adding the mixture into an extruder to perform melt blending at the temperature of 170 ℃, extruding, cooling and granulating to obtain a composite material, and performing other molding processing processes on the obtained composite material slices.
Results of mechanical property tests of materials prepared from raw materials with different proportions (6)
| Sample name | Tensile strength/MPa | Elongation at break/% |
| PLA | 60.1±0.5 | 13.5±2.3 |
| Methyl aspartate isocyanate modified loofah/PLA-1: 9 (w: w) | 70.8±1.2 | 22.3±3.1 |
| Methyl aspartate isocyanate modified loofah sponge/PLA-3: 7 (w: w) | 68.9±1.6 | 20.9±3.7 |
| Methyl aspartate isocyanate modified loofah/PLA-5: 5 (w: w) | 75.3±0.3 | 22.8±2.5 |
| Methyl aspartate isocyanate modified loofah/PLA-7: 3 (w: w) | 72.3±0.3 | 23.3±4.1 |
| Methyl aspartate isocyanate modified loofah/PLA-9: 1 (w: w) | 72.8±0.3 | 23.9±3.7 |
Example 7
The preparation method of the composite material prepared by blending the modified loofah sponge and the polylactic acid comprises the following specific steps:
(1) preparing arginine methyl ester isocyanate modified loofah sponge:
cleaning dried retinervus Luffae fructus, drying at 80 deg.C in vacuum drying oven to constant weight, pulverizing in pulverizer, sieving with 100 mesh sieve, placing 10 parts of pulverized retinervus Luffae fructus dry fiber in reaction bottle, adding 0.1mol/L NaOH solution 70 parts and 10% H2O2And refluxing 20 parts of the solution in a refluxing device for 4 hours, then adding HCl solution to neutralize redundant alkali, washing with 0.1mol/L hydrochloric acid until the pH value of the detected mother liquor is 7.0 +/-0.2, adding 15 parts of arginine methyl ester isocyanate, and continuing refluxing for 4 hours. And (4) carrying out suction filtration, washing with pure water, and then placing in a vacuum drying oven at 80 ℃ for drying to constant weight for later use.
(2) Blending of modified loofah sponge fiber and polylactic acid
And (2) uniformly mixing 10 parts of dried modified loofah sponge and 90 parts of poly-L-lactic acid with the weight average molecular weight of 10 ten thousand in a mixer to obtain a dry mixed material with the weight ratio of 1:9 (w: w), adding the dry mixed material into an extruder for melt blending at the temperature of 180 ℃, extruding, cooling and granulating to obtain a composite material, and carrying out other molding processing processes on the obtained composite material slices.
Mechanical property test results of materials prepared from raw materials with different proportions (7)
| Sample name | Tensile strength/MPa | Elongation at break/% |
| PLA | 60.1±0.5 | 13.5±2.3 |
| Arginine methyl ester isocyanate modified loofah/PLA-1: 9 (w: w) | 75.1±0.5 | 24.2±2.4 |
| Arginine methyl ester isocyanate modified loofah/PLA-3:7（w:w） | 75.3±0.6 | 24.9±2.7 |
| Arginine methyl ester isocyanate modified loofah/PLA-5: 5 (w: w) | 76.2±0.3 | 23.5±2.3 |
| Arginine methyl ester isocyanate modified loofah/PLA-7: 3 (w: w) | 76.6±0.3 | 24.7±3.3 |
| Arginine methyl ester isocyanate modified loofah/PLA-9: 1 (w: w) | 74.7±0.3 | 24.5±2.5 |
The above examples are merely illustrative for clarity and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. It is not necessary or necessary to exhaustively enumerate all embodiments herein, and obvious variations or modifications can be made without departing from the scope of the invention.
Claims (6)
1. A process for preparing a high-toughness biodegradable composite material by utilizing loofah sponge fibers and PLA is characterized by comprising the following steps of: (1) cleaning dried retinervus Luffae fructus, drying, pulverizing, placing pulverized retinervus Luffae fructus dry fiber in a reaction bottle, adding NaOH solution and H2O2Carrying out reflux treatment in a solution reflux device, then adding an HCl solution, washing with hydrochloric acid until the pH value of the detected mother liquor is 7.0 +/-0.2, and adding amino acid ester to continue reflux reaction; performing suction filtration, cleaning the treated loofah sponge with pure water, and placing the loofah sponge in a vacuum drying oven to be dried to constant weight for later use; (2) and (2) taking the dried modified loofah sponge and the poly-L-lactic acid, uniformly mixing in a mixer, drying the mixture, adding the dried mixture into an extruder, carrying out melt blending, and carrying out extrusion, cooling and grain cutting to obtain the composite material.
2. A process as claimed in claim 1A process for preparing a high-toughness biodegradable composite material by utilizing loofah sponge fibers and PLA is characterized by comprising the following steps of: the concentration of the dilute NaOH solution is as follows: 0.05mol/L-0.5mol/L, H2O2The concentration of the solution was: 5 to 20 percent of the hydrochloric acid is refluxed, and then the concentration of the added dilute hydrochloric acid is as follows: 0.05mol/L-0.5 mol/L.
3. The process for preparing high-toughness biodegradable composite material using loofah sponge fiber and PLA according to claim 1, wherein: the selected polylactic acid is L-type polylactic acid, the purity is more than or equal to 85 percent, and the molecular weight is 5-30 ten thousand.
4. The process for preparing high-toughness biodegradable composite material using loofah sponge fiber and PLA according to claim 1, wherein: vacuum drying treatment is carried out in a vacuum drying oven at 40 ℃ for 24 h.
5. The process for preparing high-toughness biodegradable composite material using loofah sponge fiber and PLA according to claim 1, wherein: mixing polylactic acid and modified loofah sponge in a mass ratio of: 1:9-9:1.
6. The process for preparing high-toughness biodegradable composite material using loofah sponge fiber and PLA according to claim 1, wherein: the amino acid ester is selected from amino acid methyl ester and amino acid ethyl ester.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113773637A (en) * | 2021-09-03 | 2021-12-10 | 安徽农业大学 | Loofah sponge for flatulence, preparation and application thereof and pillow |
| CN113801447A (en) * | 2021-09-29 | 2021-12-17 | 广西大学 | Preparation method of toughened and reinforced polylactic acid composite material |
| CN116948372A (en) * | 2023-05-29 | 2023-10-27 | 丽的包装(广东)有限公司 | Degradable traditional Chinese medicine packaging material and preparation method thereof |
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| CN101177523A (en) * | 2007-10-16 | 2008-05-14 | 上海大学 | Polylactic acid/vegetable sponge fiber composite material and method for making same |
| CN102585464A (en) * | 2011-12-31 | 2012-07-18 | 清华大学深圳研究生院 | Polylactic acid (PLA)/polybutylene succinate (PBS)/bamboo powder composite material and preparation method thereof |
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| CN101177523A (en) * | 2007-10-16 | 2008-05-14 | 上海大学 | Polylactic acid/vegetable sponge fiber composite material and method for making same |
| CN102585464A (en) * | 2011-12-31 | 2012-07-18 | 清华大学深圳研究生院 | Polylactic acid (PLA)/polybutylene succinate (PBS)/bamboo powder composite material and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113773637A (en) * | 2021-09-03 | 2021-12-10 | 安徽农业大学 | Loofah sponge for flatulence, preparation and application thereof and pillow |
| CN113773637B (en) * | 2021-09-03 | 2022-11-15 | 安徽农业大学 | Loofah sponge for flatulence, preparation and application thereof and pillow |
| CN113801447A (en) * | 2021-09-29 | 2021-12-17 | 广西大学 | Preparation method of toughened and reinforced polylactic acid composite material |
| CN116948372A (en) * | 2023-05-29 | 2023-10-27 | 丽的包装(广东)有限公司 | Degradable traditional Chinese medicine packaging material and preparation method thereof |
| CN116948372B (en) * | 2023-05-29 | 2024-01-23 | 丽的包装(广东)有限公司 | Degradable traditional Chinese medicine packaging material and preparation method thereof |
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