CN115418014A - High-strength wood-based transparent plastic film and preparation method thereof - Google Patents
High-strength wood-based transparent plastic film and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of processing and preparation of green environment-friendly functional materials, and particularly discloses a high-strength wood-based transparent plastic film and a preparation method thereof, wherein the preparation method comprises the following steps: mixing choline chloride and oxalic acid dihydrate, heating and dissolving, and adding poplar powder to obtain a basic solution; heating and stirring the basic solution to obtain viscous liquid, diluting the viscous liquid by using distilled water, filtering and washing the viscous liquid to obtain solid A, dispersing the solid A in the distilled water to obtain dispersion liquid, sequentially adding sodium chlorite and acetic acid into the dispersion liquid, heating and stirring the dispersion liquid, and filtering and washing the dispersion liquid to obtain solid B; preparing the solid B into water-dispersed slurry, then carrying out ultrasonic crushing to obtain mixed liquor, adding PVA into the mixed liquor, heating and stirring to obtain wood-based slurry; pouring the wood-based slurry into a mould, drying and curing to obtain the CNF @ PVA wood-based transparent plastic film. The high-strength wood-based transparent plastic film disclosed by the invention has the advantages of improving the mechanical property, light transmittance, degradability, mechanical stability and flexibility of the wood-based film.
Description
Technical Field
The invention relates to the technical field of processing and preparation of green environment-friendly functional materials, in particular to a high-strength wood-based transparent plastic film and a preparation method thereof.
Background
Plastic waste is increasingly moving from land to sea and accumulating in the food chain, posing a great threat to the environment and human health, which indicates an urgent need to make an eco-friendly, biodegradable alternative.
Biomass-derived renewable and biodegradable materials are attractive candidates for replacing non-biodegradable petrochemical plastics, and the development of transparent plastic films with excellent mechanical properties from wood materials is of great significance, and wood-based transparent films also have great potential in replacing traditional non-degradable plastic films.
The invention patent of application No. 202110004238.1 discloses a method for preparing biodegradable transparent film by using waste woody biomass, which comprises the steps of cleaning, drying and crushing the waste woody biomass into powder, extracting and dewaxing by absolute ethyl alcohol, mixing with methanesulfonic acid aqueous solution for prehydrolysis after drying, filtering, washing and drying, and then mixing with alkaline Na 2 SO 3 Mixing, reacting, filtering, washing and drying to obtain cellulose; then adding a mixture of acetic acid and acetic anhydride, carrying out oil bath heating reaction by taking sulfuric acid as a catalyst, then centrifuging, adding water into supernate to separate out precipitate, filtering, washing and drying, and partially hydrolyzing to obtain cellulose acetate; mixing the solution with a plasticizer, an anti-reflection agent and a solvent, stirring, standing and defoaming to obtain a cellulose acetate transparent solution; forming a film by a dry phase inversion technology after coating a template; and (4) stripping the film from the template to obtain the cellulose acetate transparent film product. The invention patent with the application number of 201310359628.6 discloses a preparation method of a lignocellulose nanofiber/acrylic resin composite film, which is prepared by chemically pre-preparingTreating to remove lignin and most hemicellulose in the wood fiber; by means of the combined treatment of mechanical grinding treatment preparation and high-intensity ultrasonic treatment/grinding/high-pressure homogenization, the prepared lignocellulose nanofibers have high length-diameter ratio and a net structure. The invention patent with application number 202110544354.2 discloses a method for preparing a nano cellulose-based plastic film, which comprises the steps of taking cellulose in natural high molecular compound lignocellulose biomass as a raw material, firstly obtaining nano cellulose through acid treatment, then carrying out graft modification or obtaining modified nano cellulose, then mixing the modified nano cellulose and biodegradable plastic, and finally dripping a mixed system into distilled water to instantly obtain the plastic film with good spreading and uniform thickness. It follows that wood-based transparent films exhibit great potential in replacing traditional non-degradable plastic films.
However, in the related art, the mechanical properties, light transmittance, degradability, mechanical stability and flexibility of the wood-based transparent film need to be improved, the preparation method is complex in process, the preparation method needs to be carried out under the conditions of high temperature and high pressure, the reaction conditions are harsh, and the energy consumption is high.
Disclosure of Invention
The invention provides a high-strength wood-based transparent plastic film and a preparation method thereof, aiming at improving the mechanical property, light transmittance, degradability, mechanical stability and flexibility of the wood-based transparent film.
In a first aspect, the invention provides a preparation method of a high-strength wood-based transparent plastic film, which is realized by adopting the following technical scheme:
a preparation method of a high-strength wood-based transparent plastic film comprises the following steps:
the method comprises the following steps: mixing choline chloride and oxalic acid dihydrate at a molar ratio of 1: 1 (2), heating to dissolve the mixture into a transparent solution, and adding poplar wood powder into the transparent solution to obtain a basic solution, wherein the total mass ratio of the poplar wood powder to the choline chloride to the oxalic acid dihydrate is 1: 15 (20); stirring the base solution for 2h at 100-120 ℃ to obtain viscous liquid, and mixing the viscous liquid and distilled water according to the volume ratio of 1: 8 to obtain prefabricated liquid;
step two: filtering the preformed liquid to obtain a solid substance, washing the solid substance to obtain a solid A, dispersing the solid A in distilled water to obtain a dispersion liquid, and sequentially adding 23 g of sodium chlorite and 0.5.5 mL of acetic acid into 100-200 mL of the dispersion liquid to obtain a preformed mixed liquid; stirring the prefabricated mixed solution at 100 ℃ for 5-6 h, filtering, and washing with distilled water for multiple times to obtain a solid B;
step three: preparing the solid B into water-dispersed slurry, carrying out ultrasonic crushing for 15-30 min to obtain mixed solution, adding 0.5-1 g of PVA into 100-200 mL of the mixed solution, and continuously stirring for 30-60 min at the temperature of 95 ℃ to obtain wood-based slurry; pouring the wood-based slurry into a mould, drying and curing to obtain the CNF @ PVA wood-based transparent plastic film.
Further, in the first step, the heating dissolution temperature is 100 ℃.
Further, in the second step, the concentration of the solid A in the dispersion liquid is 15-20 mg/mL.
Furthermore, in the second step, the washing times of the distilled water are 4-6.
Further, in the third step, the concentration of the solid B in the water dispersion slurry is 15-20 mg/mL.
Further, in the third step, the drying and curing temperature is 45-60 ℃, and the drying and curing time is 10-14 h.
In a second aspect, the invention provides a high-strength wood-based transparent plastic film, which is realized by adopting the following technical scheme.
A high-strength wood-based transparent plastic film is prepared by the preparation method.
Further, the PVA is filled in the gaps of the internal structure of the wood-based transparent plastic film.
Compared with the prior art, the invention has the following technical effects:
the invention adopts the deep cosolvent consisting of choline chloride and oxalic acid dihydrate, can effectively decompose wood by destroying hydrogen bonds among cellulose fibers and dissolving lignin, dissolve lignin and hemicellulose, and remove the close directional arrangement state of the cellulose. And further removing impurities such as lignin, hemicellulose and the like by chlorination process treatment to obtain the cellulose micro-nanofiber with carbonyl introduced on the surface. And then the cellulose micro-nano fiber can be converted into a wood-based film with excellent mechanical property.
The main raw material used by the invention is poplar powder, which can be obtained in large quantity from the nature, and the poplar powder has low price and wide obtaining path and is a typical sustainable resource. The wood-based film with excellent mechanical properties can be obtained by adopting simple DES co-dissolution and processing methods such as ultrasonic dispersion and blending, and the like.
The cellulose micro-nano fiber provided by the invention has hydrophilic side chains, so that the cellulose micro-nano fiber is easy to establish interaction with other surfaces, and the interaction of the internal structure of the film through hydrogen bonds is facilitated, and the mechanical strength of the wood-based film is enhanced.
According to the invention, PVA is used as a bonding agent, so that the bonding force between cellulose micro-nanofibers can be effectively enhanced, the surface hydrophilicity of the cellulose micro-nanofibers is inhibited, the interaction force between the micro-nanofibers is enhanced, and the stability of the cellulose micro-nanofibers in a solvent is facilitated; in addition, compared with the traditional plastic, the PVA has better degradability, and more importantly, the PVA is adopted to fill the gaps of the internal structure of the wood-based plastic film, so that the tensile strength and the elastic modulus of the composite film are increased, and the composite film has excellent light transmittance.
In summary, the poplar powder adopted by the preparation method of the high-strength wood-based transparent plastic film is green, environment-friendly and pollution-free, is a typical green and environment-friendly sustainable resource, has huge reserves in nature, has simple whole preparation process and does not need harsh conditions, and the prepared wood-based transparent plastic film has excellent mechanical properties, high light transmittance, degradability, mechanical stability and flexibility and can be a potential substitute for agricultural mulching films and various plastic products; the wood-based transparent plastic film belongs to a green pollution-free bio-based composite material, meets the requirement of environmental protection, and has good environmental compatibility.
Drawings
FIG. 1 is an infrared spectrum of a CNF @ PVA film produced in example 1 of the present invention.
FIG. 2 is a photograph showing flexibility and light transmittance of the CNF @ PVA film prepared in example 1 of the present invention.
FIG. 3 is a tensile stress-strain graph of a CNF @ PVA film prepared in example 1 of the present invention.
FIG. 4 is a graph showing tensile modulus and flexibility data of CNF @ PVA films prepared in example 2 of the present invention.
FIG. 5 is a graph of the coefficient of friction of the CNF @ PVA film prepared in example 2 of the present invention.
FIG. 6 is a surface topography before and after abrasion of the CNF @ PVA film prepared in example 2 of the present invention.
Detailed Description
The following examples are given to further illustrate the present invention in detail, and specifically are given by the following examples: the following examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer, and the starting materials used in the following examples are available from ordinary commercial sources unless otherwise specified.
Examples
Example 1
A preparation method of a high-strength wood-based transparent plastic film comprises the following steps:
step 1: mixing 14g choline chloride and 12.7g oxalic acid dihydrate, fully dissolving at 100 ℃ to form a transparent solution, adding 1.7g poplar powder, fully stirring at 120 ℃ for 2 hours to obtain a viscous liquid, and mixing the viscous liquid and distilled water according to the volume ratio of 1: 8 to obtain a prefabricated liquid;
step 2: filtering the preformed liquid to obtain a solid substance, washing the solid substance to obtain a solid A, dispersing the solid A in 150mL of distilled water to obtain a dispersion liquid with the concentration of the solid A being 15mg/mL, and sequentially adding 2g of sodium chlorite and 0.5mL of acetic acid into 100mL of the dispersion liquid to obtain a preformed mixed liquid; stirring the prefabricated mixed solution at 120 ℃ for 5 hours, filtering, and washing with distilled water for 4 times to obtain a solid B;
and step 3: dispersing the solid B in 100mL of distilled water to prepare water-dispersed slurry with the solid B concentration of 15mg/mL, carrying out ultrasonic crushing on the water-dispersed slurry for 30min to obtain mixed solution, adding 1g of PVA into 100mL of the mixed solution, and continuously stirring at the temperature of 95 ℃ for 60min until the PVA is completely dissolved to obtain wood-based slurry; pouring the wood-based slurry into a mould, and drying and curing for 14h at 45 ℃ to obtain the CNF @ PVA wood-based transparent plastic film.
Example 2
A preparation method of a high-strength wood-based transparent plastic film comprises the following steps:
step 1: mixing 14g of choline chloride and 12.7g of oxalic acid dihydrate, fully dissolving at 100 ℃ to form a transparent solution, adding 1.7g of poplar powder, fully stirring at 120 ℃ for 2 hours to obtain a viscous liquid, and mixing the viscous liquid and distilled water according to the volume ratio of 1: 14 to obtain a prefabricated liquid;
step 2: filtering the preformed liquid to obtain a solid substance, washing the solid substance to obtain a solid A, dispersing the solid A in 100mL of distilled water to obtain a dispersion liquid with the concentration of the solid A being 20mg/mL, and sequentially adding 2g of sodium chlorite and 0.5mL of acetic acid into 100mL of the dispersion liquid to obtain a preformed mixed liquid; stirring the prefabricated mixed solution at 100 ℃ for 6 hours, filtering, and washing with distilled water for 6 times to obtain a solid B;
and 3, step 3: dispersing the solid B in 100mL of distilled water to prepare water-dispersed slurry with the solid B concentration of 20mg/mL, carrying out ultrasonic crushing on the water-dispersed slurry for 15min to obtain mixed solution, adding 0.5g of PVA into the 100mL of mixed solution, and continuously stirring at the temperature of 95 ℃ for 30min until the PVA is completely dissolved to obtain wood-based slurry; pouring the wood-based slurry into a mould, and drying and curing for 10h at 60 ℃ to obtain the CNF @ PVA wood-based transparent plastic film.
Example 3
A preparation method of a high-strength wood-based transparent plastic film comprises the following steps:
step 1: mixing 15g of choline chloride and 15g of oxalic acid dihydrate, fully dissolving at 100 ℃ to form a transparent solution, adding 2g of poplar powder, fully stirring at 110 ℃ for 3 hours to obtain a viscous liquid, and mixing the viscous liquid and distilled water according to the volume ratio of 1: 14 to obtain a prefabricated liquid;
step 2: filtering the preformed liquid to obtain a solid substance, washing the solid substance to obtain a solid A, dispersing the solid A in 200mL of distilled water to obtain a dispersion liquid with the concentration of the solid A being 18mg/mL, and sequentially adding 3g of sodium chlorite and 1.5mL of acetic acid into 100mL of the dispersion liquid to obtain a preformed mixed liquid; stirring the prefabricated mixed solution at 120 ℃ for 5 hours, filtering, and washing with distilled water for 5 times to obtain a solid B;
and step 3: dispersing the solid B in 200mL of distilled water to prepare water-dispersed slurry with the solid B concentration of 18mg/mL, carrying out ultrasonic crushing on the water-dispersed slurry for 30min to obtain mixed solution, adding 1g of PVA into the 200mL of mixed solution, and continuously stirring at the temperature of 95 ℃ for 60min until the PVA is completely dissolved to obtain wood-based slurry; pouring the wood-based slurry into a mould, and drying and curing for 12h at 50 ℃ to obtain the CNF @ PVA wood-based transparent plastic film.
Example 4
A preparation method of a high-strength wood-based transparent plastic film comprises the following steps:
step 1: mixing 140g of choline chloride and 252g of oxalic acid dihydrate, fully dissolving at 100 ℃ to form a transparent solution, adding 19.6g of poplar powder, fully stirring at 110 ℃ for 4 hours to obtain a viscous liquid, and mixing the viscous liquid and distilled water according to the volume ratio of 1: 12 to obtain a prefabricated liquid;
and 2, step: filtering the preformed liquid to obtain a solid substance, washing the solid substance to obtain a solid A, dispersing the solid A in 200mL of distilled water to obtain a dispersion liquid with the concentration of the solid A being 15mg/mL, and sequentially adding 2.5g of sodium chlorite and 1mL of acetic acid into 100mL of the dispersion liquid to obtain a preformed mixed liquid; stirring the prefabricated mixed solution at 100 ℃ for 6 hours, filtering, and washing with distilled water for 6 times to obtain a solid B;
and 3, step 3: dispersing the solid B in 150mL of distilled water to prepare water-dispersed slurry with the solid B concentration of 15mg/mL, carrying out ultrasonic crushing on the water-dispersed slurry for 30min to obtain mixed solution, adding 0.8g of PVA into the 150mL of mixed solution, and continuously stirring at the temperature of 95 ℃ for 60min until the PVA is completely dissolved to obtain wood-based slurry; pouring the wood-based slurry into a mould, and drying and curing for 12h at 50 ℃ to obtain the CNF @ PVA wood-based transparent plastic film.
FIG. 1 shows C prepared in example 1Infrared spectrogram of NF @ PVA film. The infrared spectrogram of the wood-based plastic CNF @ PVA is basically the same as the peak appearance condition of the pure micro-nano cellulose film CNF, but is 908cm -1 The absorption peak is enhanced, and 3305cm is simultaneously generated due to the introduction of PVA -1 The absorption peak corresponding to-OH is enhanced.
Referring to FIG. 1, it is an infrared spectrum of a CNF @ PVA film prepared in example 1. The infrared spectrogram of the wood-based plastic CNF @ PVA is basically the same as the peak appearance condition of the pure micro-nano cellulose film CNF, but the peak appearance condition is 908cm -1 The absorption peak is enhanced, and 3305cm is simultaneously generated due to the introduction of PVA -1 The absorption peak corresponding to-OH is enhanced.
Referring to FIG. 2, it is a photograph showing flexibility and light transmittance of the CNF @ PVA film prepared in example 1. The cnf @ pva film has excellent flexibility and light transmittance, and can be arbitrarily bent without breaking and breaking. Further, the letters written on the paper could be observed through the CNF @ PVA film.
Referring to FIG. 3, it is a tensile stress-strain graph of the CNF @ PVA film prepared in example 1. The maximum tensile strength of the CNF @ PVA film can reach 209.5MPa, and anisotropy of mechanical properties of the wood material is eliminated, which is mainly due to the mutual winding of the cellulose micro-nano fibers and strong interaction formed by hydrogen bonds, and the bonding effect of the PVA between the micro-nano cellulose cross-linked networks.
Referring to FIG. 4, there is shown a graph of tensile modulus and flexibility data for the CNF @ PVA film prepared in example 2. The tensile modulus of the material reaches 12.6GPa, and the flexibility reaches 5.39MJ/m 3 The mechanical properties are significantly enhanced.
Referring to FIG. 5, there is shown a friction coefficient graph of the CNF @ PVA film prepared in example 2. Due to mutual entanglement and strong interaction of the cellulose micro-nano fibers, the CNF @ PVA film can bear a large amount of external load, the self-reinforcing and antifriction and wear-resistant effects of the friction coupling interface are realized, and the friction coefficient is very stable.
Referring to FIG. 6, it is a surface topography before and after abrasion of the CNF @ PVA film prepared in example 2. The morphology difference of the CNF @ PVA film before and after friction is not large, and obvious grinding marks are hardly observed, so that the excellent mechanical stability of the wood-based film prepared by the method is further illustrated.
Claims (8)
1. The preparation method of the high-strength wood-based transparent plastic film is characterized by comprising the following steps of:
the method comprises the following steps: mixing choline chloride and oxalic acid dihydrate at a molar ratio of 1: 1 (2), heating to dissolve the mixture into a transparent solution, and adding poplar wood powder into the transparent solution to obtain a basic solution, wherein the total mass ratio of the poplar wood powder to the choline chloride to the oxalic acid dihydrate is 1: 15 (20); stirring the base solution for 2h at 100-120 ℃ to obtain viscous liquid, and mixing the viscous liquid and distilled water according to the volume ratio of 1: 8 to obtain prefabricated liquid;
step two: filtering the preformed liquid to obtain a solid substance, washing the solid substance to obtain a solid A, dispersing the solid A in distilled water to obtain a dispersion liquid, and sequentially adding 23 g of sodium chlorite and 0.5.5 mL of acetic acid into 100-200 mL of the dispersion liquid to obtain a preformed mixed liquid; stirring the prefabricated mixed solution at 100 ℃ for 5-6 h, filtering, and washing with distilled water for multiple times to obtain a solid B;
step three: preparing the solid B into water-dispersed slurry, carrying out ultrasonic crushing for 15-30 min to obtain mixed solution, adding 0.5-1 g of PVA into 100-200 mL of the mixed solution, and continuously stirring for 30-60 min at the temperature of 95 ℃ to obtain wood-based slurry; pouring the wood-based slurry into a mould, drying and curing to obtain the CNF @ PVA wood-based transparent plastic film.
2. The method for preparing a high-strength wood-based transparent plastic film according to claim 1, wherein the method comprises the following steps: in the first step, the heating and dissolving temperature is 100 ℃.
3. The method for preparing a high-strength wood-based transparent plastic film according to claim 1, wherein the method comprises the following steps: in the second step, the concentration of the solid A in the dispersion liquid is 15-20 mg/mL.
4. The method for preparing a high-strength wood-based transparent plastic film according to claim 1, wherein the method comprises the following steps: in the second step, the washing times of the distilled water are 4-6.
5. The method for preparing a high-strength wood-based transparent plastic film as claimed in claim 1, wherein in the third step, the concentration of the solid B in the aqueous dispersion slurry is 15-20 mg/mL.
6. The method for preparing a high-strength wood-based transparent plastic film as claimed in claim 1, wherein in the third step, the drying and curing temperature is 45-60 ℃ and the drying and curing time is 10-14 h.
7. A high-strength wood-based transparent plastic film is characterized in that: prepared by the preparation method of any one of claims 1 to 6.
8. A high strength wood-based transparent plastic film according to claim 7, wherein: the PVA is filled in the gaps of the internal structure of the wood-based transparent plastic film.
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| CN116515146A (en) * | 2023-05-06 | 2023-08-01 | 陕西科技大学 | Multifunctional film material with cellulose/graphene-Mxene hybrid interweaving structure and preparation method thereof |
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| CN114015072A (en) * | 2021-11-25 | 2022-02-08 | 陕西科技大学 | High-wear-resistance lignocellulose-based friction material derived from waste wood and preparation method thereof |
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| CN114015072A (en) * | 2021-11-25 | 2022-02-08 | 陕西科技大学 | High-wear-resistance lignocellulose-based friction material derived from waste wood and preparation method thereof |
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| CN116515146A (en) * | 2023-05-06 | 2023-08-01 | 陕西科技大学 | Multifunctional film material with cellulose/graphene-Mxene hybrid interweaving structure and preparation method thereof |
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