CN116376247A - Modified plant fiber biodegradable composite material and preparation method thereof - Google Patents
Modified plant fiber biodegradable composite material and preparation method thereof Download PDFInfo
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- CN116376247A CN116376247A CN202310393595.0A CN202310393595A CN116376247A CN 116376247 A CN116376247 A CN 116376247A CN 202310393595 A CN202310393595 A CN 202310393595A CN 116376247 A CN116376247 A CN 116376247A
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- plant fiber
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- fiber
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
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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
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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
- D06M2101/06—Vegetal fibres cellulosic
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a modified plant fiber biodegradable composite material in the field of composite materials and a preparation method thereof, wherein the modified plant fiber biodegradable composite material comprises the following components in percentage by mass: 10% -30% of plant fiber; 70% -90% of a bio-based resin substrate; 0.1% -1% of a bio-based modifier; 0.01 to 0.1 per mill of initiator; according to the invention, the biological-based compound is used as a modifier, so that the interface combination of the hydrophilic plant fiber and the hydrophobic polymer material is realized, and the technical effects of improving the mechanical property and the stability of the composite material are further realized.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a modified plant fiber biodegradable composite material and a preparation method thereof.
Background
Since the advent of synthetic plastics, plastic products have rapidly developed, plastics mainly originate from non-renewable fossil energy sources, and at the same time, plastic wastes are often treated in a burning and burying manner, causing environmental problems, and along with the consumption of petroleum resources and the huge pressure brought by environmental pollution, bio-based resins synthesized from biomass raw materials have been paid attention to, for example, biodegradable polymer materials such as polylactic acid, polybutylene succinate, polybutylene terephthalate-adipate and the like have been commercially produced, but these polymer materials have the disadvantages of poor stability and higher use cost, and cannot be popularized in daily life.
In the prior art, natural plant fibers are used as reinforcing phases to replace part of matrix materials, so that the mechanical properties of the polyester materials can be improved, and the comprehensive cost is reduced; the plant fiber is a renewable resource with abundant natural sources, is obtained by bonding cellulose through hemicellulose, lignin and other substances, contains a large number of polar hydroxyl groups on the surface of the plant fiber, has good hydrophilicity on the surface of the plant fiber, has hydrophobicity on the surface of a high polymer resin material, has poor two-phase interface bonding property, modifies the surface of the plant fiber, and can improve the interface bonding between the fiber and the resin.
The existing plant fiber biodegradable composite material technology mainly has the following problems: firstly, how to improve the interfacial bonding capability between hydrophilic plant fibers and hydrophobic polymer materials, so as to improve the performance of the composite material; second, the degradation mode of the bio-composite degradation material mainly depends on the enzyme in the soil for decomposition, so that the components of the composite material need to be rapidly degraded in the soil.
Disclosure of Invention
Aiming at the situation, the invention provides a modified plant fiber biodegradable composite material and a preparation method thereof for overcoming the defects of the prior art, and aims to solve the problems.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the invention provides a modified plant fiber biodegradable composite material, which comprises the following components in parts by weight: 10-30 parts of plant fiber; 70-90 parts of a bio-based resin substrate; 0.1-1 part of biological base modifier; initiator 0.01-0.1 parts.
Further, the plant fiber comprises one or more of bamboo fiber, wheat straw, rice straw, cotton stalk, sorghum stalk, corn stalk, sisal fiber, palm fiber, jute fiber, flax fiber, rice hull, wheat hull, peanut hull and bagasse.
Further, the bio-based resin substrate comprises one or more combinations of polylactic acid (PLA), polybutylene succinate (PBS), polyglycolic acid (PGA), polyhydroxybutyrate (PHB).
PLA belongs to thermoplastic resin composite materials, is formed by polymerizing lactic acid generated by fermentation of carbohydrates such as corn, sucrose, potato and the like, has excellent mechanical property and simple degradation mechanism, and is a preferred substitute for traditional petroleum-based resin polyethylene, polystyrene and the like.
PGA is the simplest linear polyhydroxyalkanoate, the polymerization unit of PGA contains active carboxyl and hydroxyl groups, the molecular chain is easy to hydrolyze, and the degradation products are metabolic intermediates of lactic acid, glycolic acid and the like. The PGA molecular chain contains no branched chains, is regularly and densely arranged among chains, has excellent thermal stability, and has better performance indexes such as tensile strength, bending strength and the like than other common plastics, PLA and the like.
PBS can be synthesized by microbial fermentation, has regular and soft molecular chains, higher toughness, impact strength and tensile property, but has poorer thermal stability and slower degradation speed, and the composite material has good application performance only by modification.
PHAs polymer is synthesized by bacteria under the condition of sufficient carbon source, has good biodegradability, the mechanical property of the PHAs polymer is determined by factors such as the composition of a polymerized monomer, the length of a molecular chain and the like, and the short chain PHAs has higher crystallinity, large hardness and high brittleness, such as PHB.
Further, the mass ratio of the polylactic acid to the polybutylene succinate is 7:3.
Further, the mass ratio of polylactic acid to polyglycolic acid is 4:1.
Further, the bio-based modifier is obtained by modifying a bio-based epoxy compound through a metal organic framework ZIF-8.
Further, the bio-based epoxy compound is at least one of glycidyl ether pentaerythritol bis-vanillin epoxy resin (DEPVD) and cardanol epoxy resin.
Further, the preparation method of the bio-based modifier comprises the steps of dissolving a bio-based epoxy compound in deionized water, adding zinc acetate dihydrate, and uniformly stirring to obtain a precursor solution; and adding the precursor solution into an ethanol solution of 2-methylimidazole, standing, and removing redundant ethanol to obtain the bio-based modifier.
Further, the preparation method of the DEPVE specifically comprises the following steps:
(1) Adding raw materials of vanillin, pentaerythritol and cyclohexane into a three-necked bottle, carrying out reflux reaction at 110 ℃ by taking sulfanilic acid as a catalyst, removing residual catalyst after the reaction liquid is cooled slightly, and carrying out extraction purification and drying when the reaction liquid is cooled to room temperature to obtain an intermediate product;
(2) Placing the intermediate product and epoxy chloropropane in a three-necked bottle, reacting for 30min at 85 ℃ by taking tetrabutylammonium bromide as a catalyst, cooling to 50 ℃, adding sodium hydroxide solution, and extracting and purifying after the reaction is finished to obtain the product DEPVD.
Further, the initiator is at least one of ethylenediamine, hexamethylenediamine, diethylenetriamine, 2-aminodiphenyl sulfone, diaminodiphenyl methane, m-phenylenediamine, boron trifluoride ethylamine complex and boron trichloride dimethyl octylamine complex.
The invention also provides a preparation method of the modified plant fiber biodegradable composite material, which specifically comprises the following steps:
s1, cleaning plant fibers with distilled water, drying at 85 ℃ to constant weight, crushing by a crusher to obtain dry plant fiber powder, and placing the dry plant fiber powder in a drying environment for later use;
s2, placing the dried plant fiber powder into 10% sodium hydroxide solution, soaking for 1-4 hours at room temperature, and drying to obtain pretreated plant fibers;
s3, adding the bio-based modifier, acetone and ammonia water into a reaction kettle, and reacting for 0.5-2 hours at the temperature of 80-120 ℃ to obtain an activated modifier;
s4, mixing the activated modifier obtained in the step S3 and the initiator in acetone, adding the pretreated plant fiber obtained in the step S2, fully mixing, removing the acetone, and then carrying out melt blending with the bio-based resin substrate to obtain a blend.
And S5, extruding and granulating the blend obtained in the step S4, and drying and hot-pressing to obtain the modified plant fiber biodegradable composite material.
Further, in S2, the volume to mass ratio of the sodium hydroxide solution to the dried plant powder is 10-20mL:1g;
further, in S3, the volume-to-mass ratio of the ammonia water to the epoxy compound in the bio-based modifier is 10-20mL:1g;
further, in S4, the amount of the initiator is 1% -5% of the mass of the modifier;
further, in S5, the extrusion temperature is 150-200℃and the extrusion speed is 35-50r/min.
The beneficial effects obtained by the invention are as follows:
according to the invention, the plant fiber is modified by the bio-based modifier, so that the interface bonding strength between the plant fiber and the bio-based resin substrate is improved, and the mechanical property and stability of the composite material are further enhanced; the bio-based modifier is a high molecular polymer with terminal epoxy groups, can form covalent bonds with hydroxyl groups on the surface of plant fibers after ring opening to form hydroxyl groups, and forms a high molecular polymer layer on the surface of the plant fibers through self-polymerization reaction; the ZIF-8 nano particles are formed before the epoxy compound is subjected to self-polymerization, and after the epoxy compound is subjected to self-polymerization to form a coating film, a supporting structure can be formed in the coating film, so that the supporting force between interfaces is improved, the mechanical property of the composite material is improved, the main components in the plant fiber are cellulose, in addition, substances with binding effect such as hemicellulose, lignin and pectin are also used, the cellulose is only reserved in the process of preparing the composite material, and the plant fiber is soaked by sodium hydroxide, so that the contact area of surface fiber is enlarged, the hydroxyl active site is increased, and the binding capacity with a modifier is improved; the modifier is derived from biosynthesis, and epoxy groups in a molecular chain are subjected to ring opening through ammonolysis treatment, so that hydroxyl groups are exposed, covalent bonding is formed on the surface of the plant fiber more easily, and simultaneously, self-polymerization reaction is more easily carried out under the action of an initiator to form a high-molecular polymer coating layer; according to the invention, the high polymer coating layer can form interface transition between the hydrophilic plant fiber and the hydrophobic bio-based resin substrate, and the high polymer can form covalent bonds and chemical bonds with the plant fiber and the bio-based resin substrate respectively, so that the hydrophilic interface and the hydrophobic interface can be firmly combined, the problem of poor bonding property of the hydrophilic interface and the hydrophobic interface is solved, and the mechanical property and the stability of the composite material are further improved.
In addition, in the raw materials used in the invention, plant fibers, the bio-based modifier and the bio-based resin substrate are all biodegradable materials, the modifier adopts the epoxy-based polymer material of bio-based source, the degradation mode of the composite material after recovery is efficient and safe, no adverse effect exists on degradation bacteria and degradation enzymes in degradation environment in the degradation process, and the composite material has sustainable value.
Drawings
FIG. 1 is a graph showing the analysis of mechanical properties of composite materials prepared in examples and comparative examples of the present invention;
FIG. 2 is a graph showing stability analysis of composite materials prepared in examples and comparative examples according to the present invention;
FIG. 3 is a graph showing the degradation performance analysis of composite materials prepared in examples and comparative examples of the present invention;
FIG. 4 is a synthetic route diagram of modifier DEPVD in a composite according to the invention;
FIG. 5 is a microstructure of the composite material of example 1 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention; all other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the present invention. The preferred methods and materials described herein are illustrative only and should not be construed as limiting the scope of the present application.
The experimental methods in the following examples are all conventional methods unless otherwise specified; the test materials used in the examples described below, unless otherwise specified, were purchased from commercial sources.
The sources of the materials used in the invention are as follows:
polylactic acid (PLA; casNo:) is available from Nature works, inc., USA under the trade designation Ingeo3001D;
polyglycolic acid (PGA; casNo: 26009-03-0) is available from Shanghai Michelia Biochemical technologies Co., ltd under the trade designation P909206;
polyhydroxybutyrate (PHB; casNo: 26744-04-7) available from Shanghai Michelia Biochemical technologies Co., ltd., brand name P909977;
ethylenediamine (CasNo: 107-15-3) was purchased from Beijing enokiwi technologies Co., ltd under the trade designation A88878;
2-aminodiphenyl sulfone (CasNo: 4273-98-7) available from Shanghai Michelia Biochemical technologies Co., ltd., trade name P831403;
m-phenylenediamine (CasNo. 108-45-2) is commercially available from Shanghai Meilin Biochemical technologies Co., ltd, under the designation P816315;
boron trifluoride ethylamine complex (CasNo. 75-23-0) was purchased from Sigma Aldrich trade Co., ltd., trade name 292249;
cardanol epoxy resin was purchased from card Lai chemical (Zhuhai) Co., ltd, trade name NC514s, epoxy value 0.26;
zinc acetate dihydrate (CasNo: 5970-45-6) is available from Shanghai Micin Biochemical technologies Co., ltd under the trade designation Z820726;
2-methylimidazole (CasNo: 693-98-1) was purchased from Shanghai Michelia Biochemical technologies Co., ltd, trade name M813135;
vanillin (CasNo: 121-33-5) was purchased from Shanghai Michelia Biochemical technologies Co., ltd, under the trademark V820371;
pentaerythritol (CasNo: 115-77-5) was purchased from Sigma Aldrich trade Co., ltd., trade name 236241;
cyclohexane (CasNo: 110-82-7) is available from Shanghai Meilin Biochemical technologies Co., ltd, under the designation C804204;
sulfanilic acid (CasNo: 121-57-3) is purchased from Shanghai microphone Biochemical technologies Co., ltd, trade name S817820;
epichlorohydrin (CasNo: 106-89-8) was purchased from Shanghai Michelia Biochemical technologies Co., ltd, trade name E808939;
tetrabutylammonium bromide (CasNo: 115-77-5) was purchased from Shanghai Michelia Biochemical technologies Co., ltd, under the designation A93903.
Example 1
A modified plant fiber biodegradable composite material, which comprises the following components in percentage by mass: 18 parts of bamboo fiber; 87 parts of PLA; 0.8 parts of a bio-based modifier; 0.05 part of 2-amino diphenyl sulfone.
The preparation method of the DEPVD specifically comprises the following steps:
(1) Adding vanillin and pentaerythritol into a three-necked bottle according to a molar ratio of 2:1, adding 100mL of cyclohexane, adding 1g of sulfanilic acid, refluxing at 110 ℃ for 2 hours, removing residual catalyst after the reaction liquid is cooled slightly, and performing extraction purification and drying when the reaction liquid is cooled to room temperature to obtain an intermediate product;
(2) Adding the intermediate product and epoxy chloropropane into a three-necked bottle according to a molar ratio of 1:10, adding 1.5g of tetrabutylammonium bromide serving as a catalyst, reacting for 30min at 85 ℃, cooling to 50 ℃, adding a sodium hydroxide solution, reacting for 5h, and extracting and purifying to obtain a product DEPVD;
FIG. 4 is a synthetic route map of DEPVD according to this embodiment.
The preparation method of the bio-based modifier comprises the steps of dissolving 5g of DEPVD (digital physical vapor deposition) in 50ml of deionized water, adding 1.2g of zinc acetate dihydrate, and stirring for 1h at 50 ℃ to obtain a precursor solution; 3.6g of 2 methylimidazole is dissolved in 50ml of absolute ethyl alcohol, the precursor solution is added, the mixture is stirred uniformly, and after standing for 30 hours, the excessive ethyl alcohol is removed, so that the bio-based modifier is obtained.
The invention also provides a preparation method of the modified plant fiber biodegradable composite material, which specifically comprises the following steps:
s1, cleaning plant fibers with distilled water, drying at 85 ℃ to constant weight, crushing by a crusher to obtain dried bamboo fiber powder, and placing the dried bamboo fiber powder in a drying environment for later use;
s2, mixing 10% sodium hydroxide solution and dried bamboo fiber powder according to a volume-mass ratio of 20mL:1g, soaking for 4 hours at room temperature, and drying to obtain pretreated bamboo fibers;
s3, adding the bio-based modifier, acetone and ammonia water into a reaction kettle, and reacting for 1.5 hours at the temperature of 110 ℃ to obtain an activated modifier; the volume to mass ratio of ammonia to DEPVD in the bio-based modifier was 15mL:1g;
s4, mixing the activated modifier obtained in the step S3 and 2-amino diphenyl sulfone with acetone, adding the pretreated bamboo fibers obtained in the step S2, fully stirring for 2 hours, removing the acetone, and then carrying out melt blending with PLA.
S5, extruding the bamboo fiber/PLA blend at the speed of 50r/min at 170 ℃, drying and hot-pressing to obtain the modified plant fiber biodegradable composite material.
Fig. 5 is an internal morphology diagram of the composite material manufactured by the embodiment, and it can be obviously seen from the diagram that after the bamboo fiber and the PLA substrate are blended, the interface of the bamboo fiber and the PLA is fuzzy, no obvious boundary exists, the biological modifier plays a larger role in modifying the interface between the two, the hydrophilic-hydrophobic interface can be firmly combined, and the bonding strength is increased.
Example 2
A modified plant fiber biodegradable composite material, which comprises the following components in percentage by mass: 10 parts of sisal fibers; 90 parts of PLA; 0.1 part of bio-based modifier; 0.010 part of ethylenediamine.
The preparation method of the bio-based modifier comprises the steps of dissolving 5g of cardanol epoxy resin in 50ml of deionized water, adding 1.2g of zinc acetate dihydrate, and stirring for 1h at 50 ℃ to obtain a precursor solution; 3.6g of 2 methylimidazole is dissolved in 50ml of absolute ethyl alcohol, the precursor solution is added, the mixture is stirred uniformly, and after standing for 30 hours, the excessive ethyl alcohol is removed, so that the bio-based modifier is obtained.
The invention also provides a preparation method of the modified plant fiber biodegradable composite material, which specifically comprises the following steps:
s1, cleaning sisal fibers with distilled water, drying at 85 ℃ to constant weight, crushing by a crusher to obtain dry sisal fiber powder, and placing in a dry environment for later use;
s2, mixing 10% sodium hydroxide solution and dry sisal fiber powder according to a volume-mass ratio of 10mL:1g, soaking at room temperature for 2 hours, and drying to obtain pretreated sisal fibers;
s3, adding the bio-based modifier, acetone and ammonia water into a reaction kettle, and reacting for 2 hours at the temperature of 100 ℃ to obtain an activated modifier; wherein, the volume mass ratio of the ammonia water to the cardanol epoxy resin in the epoxy modifier is 20mL:1g;
s4, mixing the activated modifier obtained in the step S3 and 2-amino diphenyl sulfone with acetone, adding the pretreated sisal fiber obtained in the step S2, fully stirring for 1h, removing the acetone, and then carrying out melt blending with PLA.
S5, extruding the sisal fiber/PLA blend at the speed of 50r/min at the temperature of 150 ℃, and drying and hot-pressing to obtain the modified plant fiber biodegradable composite material.
Example 3
A modified plant fiber biodegradable composite material comprises 30 parts of wheat straw as a component in percentage by mass; 49 parts of PLA; 21 parts of PBS; 1 part of a bio-based modifier; 0.1 part of boron trifluoride ethylamine complex; the bio-based modifier was obtained according to the preparation method described in example 1;
the invention also provides a preparation method of the modified plant fiber biodegradable composite material, which specifically comprises the following steps:
s1, washing the wheat straw fiber with distilled water, drying to constant weight at 85 ℃, crushing by a crusher to obtain dried wheat straw fiber powder, and placing the dried wheat straw fiber powder in a drying environment for later use;
s2, mixing 10% sodium hydroxide solution and dry wheat straw fiber powder according to a volume-mass ratio of 15mL:1g, soaking for 1h at room temperature, and drying to obtain pretreated wheat straw fibers;
s3, adding the bio-based modifier, acetone and ammonia water into a reaction kettle, and reacting for 0.5h at 120 ℃ to obtain an activated modifier; the volume to mass ratio of ammonia to DEPVD in the bio-based modifier was 10mL:1g;
s4, mixing the activated modifier obtained in the step S3 and 2-amino diphenyl sulfone with acetone to form, adding the pretreated wheat straw fiber obtained in the step S2, fully stirring for 1.5h, removing the acetone, and then carrying out melt blending with PLA and PBS.
S5, extruding the wheat straw fiber/PLA/PBS blend at the speed of 35r/min at 180 ℃, drying and hot-pressing to obtain the modified plant fiber biodegradable composite material.
Example 4
A modified plant fiber biodegradable composite material, which comprises the following components in percentage by mass: 20 parts of bamboo fiber; 56 parts of PLA; 24 parts of PBS; DEPVD0.25 parts; 0.01 part of boron trifluoride ethylamine complex; the bio-based modifier was obtained according to the preparation method described in example 1;
the invention also provides a preparation method of the modified plant fiber biodegradable composite material, which specifically comprises the following steps:
s1, cleaning bamboo fibers with distilled water, drying at 85 ℃ to constant weight, crushing by a crusher to obtain dried bamboo fiber powder, and placing the dried bamboo fiber powder in a drying environment for later use;
s2, mixing 10% sodium hydroxide solution and dried bamboo fiber powder according to a volume-mass ratio of 20mL:1g, soaking at room temperature for 3 hours, and drying to obtain pretreated bamboo fibers;
s3, adding the bio-based modifier, acetone and ammonia water into a reaction kettle, and reacting for 2 hours at 80 ℃ to obtain an activated modifier; the volume to mass ratio of ammonia to DEPVD in the bio-based modifier was 20mL:1g;
s4, mixing the activated modifier obtained in the step S3 and 2-amino diphenyl sulfone with acetone, adding the pretreated bamboo fibers obtained in the step S2, fully stirring for 2 hours, removing the acetone, and then carrying out melt blending with PLA and PBS;
s5, extruding the bamboo fiber/PLA/PBS blend at the speed of 50r/min at the temperature of 200 ℃, drying and hot-pressing to obtain the modified plant fiber biodegradable composite material.
Example 5
A modified plant fiber biodegradable composite material, which comprises the following components in percentage by mass: 15 parts of jute fiber; 68 parts of PLA; 17 parts of PGA; 0.8 parts of a bio-based modifier; 0.04 parts of boron trifluoride ethylamine complex; the bio-based modifier was obtained according to the preparation method described in example 2;
the invention also provides a preparation method of the modified plant fiber biodegradable composite material, which specifically comprises the following steps:
s1, cleaning jute fibers with distilled water, drying at 85 ℃ to constant weight, crushing by a crusher to obtain jute plant fibers, and drying in a drying environment for later use;
s2, mixing 10% sodium hydroxide solution and dry jute fiber powder according to a volume-mass ratio of 20mL:1g, soaking for 2 hours at room temperature, and drying to obtain pretreated jute fibers;
s3, adding the bio-based modifier, acetone and ammonia water into a reaction kettle, and reacting for 2 hours at 90 ℃ to obtain an activated modifier; the volume mass ratio of the ammonia water to the cardanol epoxy resin in the bio-based modifier is 20mL:1g;
s4, mixing the activated modifier obtained in the step S3 and 2-amino diphenyl sulfone with acetone, adding the pretreated jute fiber obtained in the step S2, fully stirring for 2 hours, removing the acetone, and then carrying out melt blending with PLA and PGA.
S5, extruding the jute fiber/PLA/PGA blend at the speed of 50r/min at 160 ℃, drying and hot-pressing to obtain the modified plant fiber biodegradable composite material.
Comparative example 1
This comparative example provides a modified plant fiber composite material and a method for preparing the same, which is different from example 1 only in that the bio-based modifier is replaced with a silane coupling agent KH-570 among all components, and no initiator is contained, and the remaining components and the content of the components are the same as example 1.
Comparative example 2
This comparative example provides a plant fiber composite material and a method for producing the same, which is different from example 1 only in that, of all the components, no modifier is used, only the surface of the plant fiber is subjected to alkali treatment, and the remaining components and the content of the components are the same as example 1.
Comparative example 3
This comparative example was produced using commercially available polylactic acid by the production method as described in example 1, to obtain a polylactic acid material.
Experimental example
The experiment mainly carries out the measurement on the mechanical property, the stability and the degradation of the materials prepared by the embodiment of the invention and the comparative example.
Measurement of mechanical properties:
the performance of the material is measured according to the standard GB/T1040-2006, and the performance indexes are specifically tensile strength (MPa) and elongation at break (parts);
the above materials were subjected to performance measurements according to standard GB/T1843-2008, the performance index being in particular the impact strength (Kj/cm 2 ）。
Determination of stability properties:
the materials are subjected to performance test according to the standard GB/T19466.2-2004, wherein the performance index is specifically glass transition temperature (Tg, DEG C), and the used instrument is a differential scanning calorimeter; the experimental parameters are as follows: the initial temperature is 25 ℃, the heating speed is 1 ℃/min, and the final temperature is 100 ℃; the gas used is N2, and the gas flow rate is 10mL/min; the mass of the sample was 20mg.
Performing performance test on the material according to the standard GB/T1634.2-2019, wherein the performance index is specifically heat distortion temperature (HDT, DEG C); the experimental parameters are as follows: the liquid heat transfer medium is liquid paraffin; the initial temperature is 25 ℃, and the heating speed is 2 ℃/min; the sample size is 80mm×10mm×4mm; bending stress is 1.8Mpa; the span is 64mm.
Determination of degradation Properties:
and (3) carrying out a degradation experiment on the composite material sample by using outdoor soil, wherein the soil is natural soil in the field, the soil burial depth is about 15cm, the degradation experiment starts to buckle, a proper amount of watering is carried out every 5 days, the soil is kept moist, the sampling time is 1 time every 15 days, and the sampling is carried out twice.
Cleaning soil on the surface of a soil degradation material sample with clear water, drying in a 50 ℃ oven until the weight is constant, and calculating the weight loss rate, wherein the calculation method comprises the following steps:
in the method, in the process of the invention,
w is the weight loss rate (parts);
W I weight (g) of sample before landfill;
W F as a landfill sampleWeight of product (g).
Analysis of results
The test results of the performance of the composite material samples prepared in examples 1-5 and comparative examples 1-3 of the present invention are shown in fig. 3-5:
according to fig. 1, the surface of the plant fiber is modified by using a common silane coupling agent in comparative example 1, and the mechanical property of the composite material prepared in comparative example 1 is inferior to that of the composite material obtained in the example, and the interfacial bonding firmness of the plant fiber and the bio-based resin substrate by using the silane coupling agent is not high enough, so that the mechanical property of the material is poor; in the comparative example 2, plant fibers soaked by sodium hydroxide are directly blended with a bio-based resin substrate to obtain a composite material, and although alkali treatment can increase active sites on the surfaces of the fibers, the bonding capacity of the interface between the two is not improved, and the mechanical property of the material is poor; by combining the analysis, the modifier can effectively improve the interfacial bonding property of the plant fiber and the resin material, and the mechanical properties of the materials prepared in the examples 1-5 are enhanced compared with those of the comparative examples 1-3.
According to fig. 2, the stability of the composite materials prepared in examples 1-5 is better than that of the materials described in comparative example 3, the surface hydroxyl activity of the modifier is higher, and the modifier is combined with active sites in plant fibers and resin materials in the self-polymerization reaction process, so that free hydroxyl groups in the materials are reduced, the activity of the materials is reduced, and the technical effect of improving the stability is achieved. In the composite material, resin materials blended by a plurality of base materials can mutually compensate the defects of the materials and expose active sites of the materials, so that the effect of improving the stability of the composite material is achieved.
According to fig. 3, the materials used in the examples were added with a more biodegradable modifier, and the degradation efficiency in the soil environment was higher than that in comparative example 1. For comparative example 2, the chemical bond between the plant fiber and the degradable resin substrate contained in the material is less, and the natural plant fiber is more easily degraded in the soil environment, so that the degradation speed is faster in the first sampling and the degradation speed is slower in the second sampling by taking the resin material as the main degradation object. For the resin base material, the degradation rate of examples 3-5 was slightly faster, and blending of multiple resin materials can improve degradation efficiency.
From the experimental example data, the composite material prepared by the invention uses the bio-based modifier to modify the surface of the plant fiber, and the plant fiber is connected with the bio-based resin base material through covalent bonds and chemical bonds, so that a good interface modification effect is achieved, the bonding property of hydrophilic and hydrophobic interfaces is obviously improved, and the effects of improving the mechanical property and the stability are further achieved. From the aspect of degradation performance, the raw materials used in the invention are basically raw non-degradable materials, and after the soil is decomposed, degradation products are safe and do not cause adverse effects on degradation environment, and the degradation speed is obviously improved due to higher content of plant fiber materials.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
The invention and its embodiments have been described above with no limitation, and the invention is illustrated in the figures of the accompanying drawings as one of its embodiments, without limitation in practice. In summary, those skilled in the art, having benefit of this disclosure, will appreciate that the invention can be practiced without the specific details disclosed herein.
Claims (10)
1. A modified plant fiber biodegradable composite material is characterized in that: the composite material comprises the following components in parts by weight: 10-30 parts of plant fiber; 70-90 parts of a bio-based resin substrate; 0.1-1 part of biological base modifier; 0.01-0.1 part of initiator; the bio-based modifier is a metal organic framework ZIF-8 modified bio-based epoxy compound; the bio-based epoxy compound is at least one of glycidyl ether pentaerythritol bis-vanillin epoxy resin and cardanol epoxy resin.
2. The modified plant fiber biodegradable composite according to claim 1, characterized in that: the preparation method of the bio-based modifier comprises the steps of dissolving a bio-based epoxy compound in deionized water, adding zinc acetate dihydrate, and uniformly stirring to obtain a precursor solution; and adding the precursor solution into an ethanol solution of 2-methylimidazole, standing, and removing redundant ethanol to obtain the bio-based modifier.
3. The modified plant fiber biodegradable composite according to claim 2, characterized in that: the preparation method of the glycidyl ether pentaerythritol bis-vanillin epoxy resin comprises the following steps:
(1) Adding raw materials of vanillin, pentaerythritol and cyclohexane into a three-necked bottle, carrying out reflux reaction for 2 hours at 110 ℃ by taking sulfanilic acid as a catalyst, removing residual catalyst after the reaction liquid is cooled slightly, and carrying out extraction purification and drying when the reaction liquid is cooled to room temperature to obtain an intermediate product;
(2) Placing the intermediate product and epoxy chloropropane in a three-necked bottle, reacting for 30min at 85 ℃ by taking tetrabutylammonium bromide as a catalyst, cooling to 50 ℃ and adding sodium hydroxide solution, and extracting and purifying after the reaction is completed.
4. A modified plant fiber biodegradable composite according to claim 3, characterized in that: the plant fiber comprises one or more of bamboo fiber, wheat straw, rice straw, cotton stalk, sorghum stalk, corn straw, sisal fiber, palm fiber, jute fiber, flax fiber, rice hull, wheat hull, peanut hull and bagasse.
5. The modified plant fiber biodegradable composite according to claim 4, characterized in that: the bio-based resin substrate comprises one or more of polylactic acid, polybutylene succinate, polyglycolic acid and polyhydroxybutyrate; the mass ratio of the polylactic acid to the polybutylene succinate is 7:3; the mass ratio of polylactic acid to polyglycolic acid is 4:1.
6. The modified plant fiber biodegradable composite according to claim 5, characterized in that: the initiator is at least one of ethylenediamine, hexamethylenediamine, diethylenetriamine, 2-aminodiphenyl sulfone, diaminodiphenyl methane, m-phenylenediamine, boron trifluoride ethylamine complex and boron trichloride dimethyl octylamine complex.
7. A preparation method of a modified plant fiber biodegradable composite material is characterized by comprising the following steps: the method specifically comprises the following steps:
s1, cleaning plant fibers with distilled water, drying at 85 ℃ to constant weight, crushing by a crusher to obtain dry plant fiber powder, and placing the dry plant fiber powder in a drying environment for later use;
s2, placing the dried plant fiber powder into 10% sodium hydroxide solution, soaking for 1-4 hours at room temperature, and drying to obtain pretreated plant fibers;
s3, adding the bio-based modifier, acetone and ammonia water into a reaction kettle, and reacting for 0.5-2 hours at the temperature of 80-120 ℃ to obtain an activated modifier;
s4, mixing the activated modifier obtained in the step S3 and an initiator in acetone, adding the pretreated plant fiber obtained in the step S2, fully mixing, removing the acetone, and then carrying out melt blending with a bio-based resin substrate to obtain a blend;
and S5, extruding and granulating the blend obtained in the step S4, and drying and hot-pressing to obtain the modified plant fiber biodegradable composite material.
8. The method of preparing a composite material according to claim 7, wherein: in S2, the volume-mass ratio of the alkaline solution to the dry plant powder is 10-20 mL/1 g; in S3, the volume-mass ratio of the ammonia water to the epoxy compound in the bio-based modifier is 10-20 mL/1 g.
9. The method of preparing a composite material according to claim 8, wherein: in S4, the amount of the initiator is 1-5% of the mass of the modifier.
10. The method of preparing a composite material according to claim 9, wherein: in S5, the extrusion temperature is 150-200 ℃, and the extrusion speed is 35-50r/min.
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