阅读说明：本技术 木质素纳米颗粒/聚乙烯醇/壳聚糖三元复合材料及其制备方法和应用 (Lignin nanoparticle/polyvinyl alcohol/chitosan ternary composite material and preparation method and application thereof ) 是由 李静 章沈翀 曾士乂 周敏霞 程俊豪 于 2021-09-23 设计创作，主要内容包括：本发明公开了一种木质素纳米颗粒/聚乙烯醇/壳聚糖(LNP/PVA/CH)三元复合材料及其制备方法和应用,属于功能复合材料制备技术领域。本发明首先利用木质素作为原料,通过溶剂反溶剂法制备LNP,然后利用LNP与聚乙烯醇溶液与壳聚糖溶液共混,接枝改性制得LNP/PVA/CH三元复合材料；并通过涂布工艺将所述复合材料均匀涂布至原纸表面得到涂布纸。本发明基于3LNP/PVA/CH复合材料的涂布纸紫外透过率于可见光区与近紫外区总体在10％以下,且在大部分近紫外区透过率小于5％,实现了近紫外区95％的紫外光吸收；且氧指数为27％,达到了难燃的级别；10-12℃条件下贮藏新鲜草莓5天后,失重率仅为5％,因此本发明的复合材料可用于制备具有紫外屏蔽协同阻燃功能的活性复合膜、活性包装纸或纸板。(The invention discloses a lignin nanoparticle/polyvinyl alcohol/chitosan (LNP/PVA/CH) ternary composite material, and a preparation method and application thereof, and belongs to the technical field of functional composite material preparation. Firstly, preparing LNP by using lignin as a raw material through a solvent anti-solvent method, then blending LNP with a polyvinyl alcohol solution and a chitosan solution, and carrying out graft modification to prepare an LNP/PVA/CH ternary composite material; and uniformly coating the composite material on the surface of base paper by a coating process to obtain the coated paper. The ultraviolet transmittance of the coated paper based on the 3LNP/PVA/CH composite material is below 10% in the visible region and the near ultraviolet region, and the transmittance in most near ultraviolet regions is less than 5%, so that 95% of ultraviolet light absorption in the near ultraviolet region is realized; the oxygen index is 27 percent, and the flame retardant grade is achieved; after the fresh strawberries are stored for 5 days at the temperature of 10-12 ℃, the weight loss rate is only 5 percent, so that the composite material can be used for preparing an active composite film, active packaging paper or paperboard with the ultraviolet shielding synergistic flame retardant function.)

1. A preparation method of a lignin nanoparticle/polyvinyl alcohol/chitosan LNP/PVA/CH ternary composite material is characterized by comprising the following steps: the method specifically comprises the following steps:

(1) preparation of lignin nanoparticles LNP

Dissolving lignin in an ethanol aqueous solution or absolute ethanol at room temperature to obtain a lignin ethanol solution; then slowly dripping hydrochloric acid aqueous solution with the concentration of 0.1-0.5mol/L into the lignin ethanol solution at the speed of 1-10 drops/min; after the dropwise addition is finished, standing, filtering, dialyzing, diluting the mixed solution in the dialysis bag, standing, carrying out thermal evaporation or mechanical filtration, taking out the obtained product, and freeze-drying to obtain the lignin nanoparticles LNP;

(2) and (2) mixing the lignin nanoparticles, the polyvinyl alcohol PVA solution and the chitosan CH solution in the step (1) according to a ratio, uniformly stirring, and then carrying out ultrasonic treatment to obtain the lignin nanoparticle/polyvinyl alcohol/chitosan LNP/PVA/CH ternary composite material.

2. The preparation method of the lignin nanoparticle/polyvinyl alcohol/chitosan LNP/PVA/CH ternary composite material according to claim 1, characterized in that: the lignin in the step (1) is prepared by adopting the following method:

drying the crushed straws, putting the dried straws into a reaction kettle, and adding an ethanol water solution; then introducing oxygen into the reaction kettle, sealing the reaction kettle after the air above the material is completely replaced by the oxygen, and keeping introducing the oxygen; heating the reaction kettle to 70-90 ℃, and reacting for 2-3h under the condition of heat preservation; after the reaction is finished, opening a valve of the reaction kettle, and releasing pressure; after the pressure relief is finished, immediately filtering to separate the straw from the liquid; distilling the obtained liquid to obtain a lignin mixture; and finally, hydrolyzing the lignin mixture, precipitating, centrifuging, and freeze-drying the obtained precipitate to obtain the lignin.

3. The preparation method of the lignin nanoparticle/polyvinyl alcohol/chitosan LNP/PVA/CH ternary composite material according to claim 1, characterized in that: in the step (1), the dropping speed of the hydrochloric acid aqueous solution is 10 drops/min, and the concentration of the hydrochloric acid aqueous solution is 0.25 mol/L.

4. The preparation method of the lignin nanoparticle/polyvinyl alcohol/chitosan LNP/PVA/CH ternary composite material according to claim 1, characterized in that: the volume of the hydrochloric acid aqueous solution in the step (1) is the same as that of the ethanol aqueous solution or the absolute ethanol.

5. The preparation method of the lignin nanoparticle/polyvinyl alcohol/chitosan LNP/PVA/CH ternary composite material according to claim 1, characterized in that: the LNP/PVA/CH ternary composite material prepared in the step (2) comprises the following raw materials: the mass percent of the lignin nanoparticles is 1-3%, the mass percent of the CH solution is 9-10%, and the balance is PVA solution; the sum of the mass percentages of the raw material components is 100%.

6. The lignin nanoparticle/polyvinyl alcohol/chitosan LNP/PVA/CH ternary composite material prepared by the preparation method of the lignin nanoparticle/polyvinyl alcohol/chitosan LNP/PVA/CH ternary composite material according to any one of claims 1 to 5.

7. The application of the lignin nanoparticle/polyvinyl alcohol/chitosan LNP/PVA/CH ternary composite material prepared by the preparation method of any one of claims 1 to 5 in the preparation of a lignin nanoparticle-based active composite membrane or active packaging paper or paperboard.

8. A lignin nanoparticle-based active composite film with ultraviolet shielding and flame retardant functions is characterized in that: the lignin nanoparticle/polyvinyl alcohol/chitosan ternary composite material prepared by the method of any one of claims 1 to 5 is coated on the surface of a substrate and then dried to form the lignin nanoparticle/polyvinyl alcohol/chitosan ternary composite material.

9. An active packaging paper or paperboard, characterized in that: the lignin nanoparticle/polyvinyl alcohol/chitosan ternary composite material prepared by the method of any one of claims 1 to 5 is coated on the surface of a paperboard or paper base paper and then dried to form the lignin nanoparticle/polyvinyl alcohol/chitosan ternary composite material.

10. An activated wrap paper as defined in claim 9, wherein: the coating weight adopted by the coating is 5-15g/m²。

Technical Field

The invention belongs to the technical field of functional composite material preparation, and particularly relates to a lignin nanoparticle/polyvinyl alcohol/chitosan (LNP/PVA/CH) ternary composite material, a preparation method and application thereof, in particular to application in preparation of an active composite film or active packaging paper or paperboard with an ultraviolet shielding synergistic flame retardant function.

Background

Lignin is an amorphous polymer formed by connecting phenylpropane units through carbon-carbon bonds and ether bonds, and is the second largest biomass resource with the second reserves of cellulose in the plant world. As a typical biomass material, lignin is one of the few renewable resources in aromatic compounds. Lignin, as a biomass material of the second largest resource after cellulose in the plant world, produces about 5000 million tons per year worldwide, with about 10-20% lignin from agricultural residues and about 20-30% lignin from forest biomass materials, widely available and in enormous quantities. For a long time, the application of lignin as a byproduct in cellulose production in the pulping and papermaking industry has the problem of low efficiency and added value, however, the nano lignin can open up a new way for high-added-value development and application of lignin-based products. The inorganic nanoparticles which are not renewable and non-degradable can be replaced in partial fields, and meanwhile, the nano lignin particles can be functionalized to endow the nano lignin particles with specific chemical, optical, catalytic, sensing and antimicrobial properties, and the overall properties of the nano lignin particles can be maintained, so that the development of novel lignin-based natural composite materials is more possible.

As previously mentioned, nano-lignin exhibits many unique properties such as resistance to decay and biological attack, Ultraviolet (UV) absorption, high stiffness and the ability to delay and inhibit oxidation reactions. It therefore has the potential to produce high value products from large quantities of raw materials. Incorporating nanoparticles into polymers can be one way to increase their value, as current properties can be improved and new functions can be provided to the material. Although studies on lignin in terms of oxidation resistance, ultraviolet resistance, etc. have been reported, no reports have been made on the application of lignin nanoparticles to active packaging of paperboard or paper.

The present application has been made for the above reasons.

Disclosure of Invention

In view of the problems or defects of the prior art, the present invention aims to provide a lignin nanoparticle/polyvinyl alcohol/chitosan (LNP/PVA/CH) ternary composite material, a preparation method thereof and applications thereof. The preparation method comprises the steps of blending Lignin Nanoparticles (LNP), polyvinyl alcohol and chitosan, grafting and modifying to prepare a ternary composite material, and uniformly coating the ternary composite material on the surface of corrugated base paper or a paperboard through a coating process to form an LNP/PVA/CH active composite film with ultraviolet shielding synergistic flame retardant function and excellent mechanical and optical properties, so that the preparation of active packaging paper or paperboard is realized.

In order to achieve one of the above objects of the present invention, the present invention adopts the following technical solutions:

a preparation method of a lignin nanoparticle/polyvinyl alcohol/chitosan (LNP/PVA/CH) ternary composite material specifically comprises the following steps:

(1) preparation of Lignin Nanoparticles (LNP)

Dissolving lignin in an ethanol aqueous solution or absolute ethanol at room temperature to obtain a lignin ethanol solution; then slowly dripping hydrochloric acid aqueous solution with the concentration of 0.1-0.5mol/L into the lignin ethanol solution at the speed of 1-10 drops/min; after the dropwise addition is finished, standing, filtering, dialyzing, diluting the mixed solution in the dialysis bag, standing, carrying out thermal evaporation or mechanical filtration, taking out the obtained product, and freeze-drying to obtain the Lignin Nanoparticles (LNP);

(2) and (2) mixing the lignin nanoparticles, the polyvinyl alcohol (PVA) solution and the Chitosan (CH) solution in the step (1) according to a ratio, uniformly stirring, and then carrying out ultrasonic treatment to obtain the lignin nanoparticle/polyvinyl alcohol/chitosan (LNP/PVA/CH) ternary composite material.

Further, in the above technical solution, the lignin (lignin) in the step (1) is preferably prepared by the following method:

drying the crushed straws, putting the dried straws into a reaction kettle, and adding an ethanol water solution; then introducing oxygen into the reaction kettle, sealing the reaction kettle after the air above the material is completely replaced by the oxygen, and keeping introducing the oxygen; heating the reaction kettle to 70-90 ℃, and reacting for 2-3h under the condition of heat preservation; after the reaction is finished, opening a valve of the reaction kettle, and releasing pressure; after the pressure relief is finished, immediately filtering to separate the straw from the liquid; distilling the obtained liquid to obtain a lignin mixture; and finally, hydrolyzing the lignin mixture, precipitating, centrifuging, and freeze-drying the obtained precipitate to obtain the lignin.

Preferably, in the technical scheme, the mass percentage concentration of the ethanol aqueous solution is 70-90%.

Preferably, in the technical scheme, the feed liquid mass ratio of the straw to the ethanol aqueous solution is 1: 10-30.

Preferably, in the technical scheme, the straw is separated from the liquid by adopting a filtering method, and the filtering preferably adopts a 250-mesh filter screen.

In particular, in the above technical solution, the distillation is aimed at removing ethanol from the liquid.

Preferably, in the above technical solution, the hydrolysis is specifically a hydrolysis of the lignin mixture using a dilute aqueous sulfuric acid solution, wherein: the concentration of the dilute sulfuric acid aqueous solution is 2-5% by mass, and 3% by mass is more preferable.

Further, according to the technical scheme, the mass percentage concentration of the ethanol aqueous solution in the step (1) is more than or equal to 70% and less than 100%.

Further, in the above technical solution, the amount of the ethanol aqueous solution or the absolute ethanol used in step (1) may not be specifically limited, as long as the uniform dissolution of the lignin can be achieved. More preferably, the dosage ratio of the lignin to the ethanol aqueous solution or the absolute ethanol can be (1-2) parts by mass: (5-15) parts by volume, wherein: the mass portion and the volume portion are as follows: mL was used as a reference.

Further, in the above technical solution, the concentration of the lignin ethanol solution in the step (1) is preferably 0.15 g/mL.

Further, in the above technical solution, the dropping speed of the hydrochloric acid aqueous solution in the step (1) is preferably 10 drops/min, and the concentration of the hydrochloric acid aqueous solution is preferably 0.25 mol/L; the lignin nanoparticles prepared under the condition are most spherical and are distributed more uniformly, and the sizes of the particles are mostly distributed in the range of 200nm-800 nm.

Further, in the above technical solution, the volume of the hydrochloric acid aqueous solution in the step (1) is the same as the volume of the ethanol aqueous solution or the absolute ethanol.

Further, in the above technical scheme, the standing time in the step (1) is 1-3h, and preferably 2 h.

Further, in the above technical solution, the dialysis time in step (1) is 2 to 4 days, and more preferably 3 days.

Further, in the above technical scheme, the thermal evaporation method in the step (1) is preferably used for baking for 12-36h in an oven at 40-60 ℃.

Further, in the above technical solution, the mechanical filtration method in the step (1) is preferably performed by placing in a suction filtration device for suction filtration.

Further, in the above technical scheme, the LNP/PVA/CH ternary composite material prepared in step (2) comprises the following raw materials: the mass percent of the lignin nanoparticles is 1-3%, the mass percent of the CH solution is 9-10%, and the balance is PVA solution; the sum of the mass percentages of the raw material components is 100%.

Specifically, in the above technical solution, the PVA solution is composed of polyvinyl alcohol (PVA) and deionized water. More preferably, the concentration of the PVA solution is 10 to 20 g/L.

Specifically, in the technical scheme, the CH solution is composed of Chitosan (CH) and deionized water. More preferably, the concentration of the CH solution is 1-2 g/L.

The second purpose of the invention is to provide the lignin nanoparticle/polyvinyl alcohol/chitosan (LNP/PVA/CH) ternary composite material prepared by the method.

The third purpose of the invention is to provide the application of the lignin nanoparticle/polyvinyl alcohol/chitosan ternary composite material prepared by the method in preparing a lignin nanoparticle-based active composite film or active packaging paper or paperboard.

A lignin nanoparticle-based active composite membrane with an ultraviolet shielding synergistic flame retardant function is formed by coating the lignin nanoparticle/polyvinyl alcohol/chitosan ternary composite material prepared by the method on the surface of a substrate and then drying.

Further, in the above technical solution, the substrate may be glass, corrugated paper, or the like.

Further, in the above technical solution, the thickness of the active composite membrane is not limited, and composite membranes with different thicknesses can be designed according to actual functional requirements, for example, the thickness of the active composite membrane can be 1 mm.

Further, in the above technical scheme, the drying temperature is preferably 75-85 ℃, and the drying time is preferably 15-25min, more preferably 20 min.

The active packaging paper or the paper board is formed by coating the lignin nanoparticle/polyvinyl alcohol/chitosan ternary composite material prepared by the method on the surface of the paper board or paper base paper and then drying.

Further, according to the technical scheme, the coating weight adopted by the coating is 5-15g/m²。

Compared with the prior art, the invention has the following beneficial effects:

(1) the lignin is used as a raw material, the lignin nanoparticles are prepared by a solvent anti-solvent method, and then the lignin nanoparticles are introduced into the ternary composite material and prepared into a ternary composite film so as to improve the mechanical, optical, ultraviolet-shielding and flame-retardant capabilities of the ternary composite film, so that the method is the primary innovation point of the method; the invention also discloses a preparation method of the active packaging paper.

(2) The ultraviolet transmittance of the 3LNP/PVA/CH coated paper prepared by the invention is below 10% in the visible light region and the near ultraviolet region, and the transmittance in most near ultraviolet regions is less than 5%, the ultraviolet absorption of 95% in the near ultraviolet region is realized, the ultraviolet shielding effect is higher than that of other coated paper, the complementary relationship among the lignin nanoparticles, the chitosan and the polyvinyl alcohol in the ultraviolet reflection and the ultraviolet absorption is also embodied, and the effect of effectively shielding ultraviolet can be realized after the lignin nanoparticle/polyvinyl alcohol/chitosan ternary composite material is coated on the surface of a paperboard or paper.

Drawings

FIG. 1 is a micro-topography of lignin nanoparticles prepared in examples 1-3 using 0.10mol/L HCl solution at different dropping speeds; wherein: (a)1 drop/min; (b)2 drops/min; (c)10 drops/min;

FIG. 2 is a micro-topography of the lignin nanoparticles prepared in examples 4-6 using 0.25mol/L HCl solution at different dropping speeds; wherein: (a)1 drop/min; (b)2 drops/min; (c)10 drops/min;

FIG. 3 is a micro-topography of the lignin nanoparticles prepared in examples 7-8 using 0.50mol/L HCl solution at different dropping speeds; wherein: (a)1 drop/min; (b)2 drops/min;

fig. 4 is a micro-topography of a corrugating medium used in application example 1;

fig. 5 (a), (b), and (c) are microstructure morphology diagrams formed after the CH solution, the 1LNP/CH binary composite material, and the 3LNP/CH binary composite material are coated and dried on the surface of the corrugated medium in the application example, respectively;

fig. 6 (a), (b), and (c) are microstructure morphology diagrams formed after the PVA solution, the 1LNP/PVA binary composite material, and the 3LNP/PVA binary composite material are coated and dried on the surface of the corrugated medium in the application example, respectively;

in fig. 7, (a), (b), and (c) are microstructure morphology diagrams formed after the PVA/CH binary composite material, the 1LNP/PVA/CH ternary composite material, and the 3LNP/PVA/CH ternary composite material in the application example are coated and dried on the surface of the corrugated base paper, respectively;

FIG. 8 is an infrared spectrum of KBr with each component alone and mixed;

FIG. 9 is a comparative graph of ultraviolet transmittance curves of paper sheets after a 3LNP/PVA binary composite material, a 1LNP/PVA binary composite material and a PVA solution are coated and dried on the surface of corrugated medium paper in an application example respectively;

FIG. 10 is a graph comparing ultraviolet transmittance curves of a paper sheet coated and dried on the surface of a corrugated medium by using a 3LNP/CH binary composite, a 1LNP/CH binary composite and a CH solution in the application example respectively;

FIG. 11 is a comparison graph of UV transmittance curves of paper sheets coated and dried on the surface of corrugated medium by using 1LNP/PVA/CH ternary composite material, 3LNP/PVA/CH and PVA/CH in the application example respectively.

Detailed Description

The present invention will be described in further detail below with reference to examples. The present invention is implemented on the premise of the technology of the present invention, and the detailed embodiments and specific procedures are given to illustrate the inventive aspects of the present invention, but the scope of the present invention is not limited to the following embodiments.

The test methods used in the following examples are all conventional methods unless otherwise specified; the raw materials and reagents used are, unless otherwise specified, those commercially available from ordinary commercial sources.

The lignin (lignin) raw material used for preparing the lignin nanoparticles in the following examples of the present invention is prepared by referring to the method disclosed in patent CN201910435215.9 (a method for refining lignin in straw by using oxygen to catalyze ethanol and its application) previously disclosed by the inventor of the present application, example 3.

Example 1

The preparation method of the Lignin Nanoparticle (LNP) of this embodiment specifically includes the following steps:

dissolving 1.5g of lignin in 10mL of ethanol solvent to obtain a lignin ethanol solution; slowly dropwise adding 10mL of HCl solution with the concentration of 0.1mol/L to the lignin ethanol solution at the speed of 1 drop/minute, and standing for 2 hours at room temperature; filtering with Whatman 541 filter paper (pore size 0.22 μm); dialyzing in deionized water for 3 days by using an MD55 dialysis bag, and diluting the solution in the dialysis bag into 400mL of aqueous solution after the dialysis is finished; standing for one day, taking out lignin at the bottom when the lignin in the solution is deposited at the bottom, baking the obtained lignin in an oven at the temperature of 40-60 ℃ for 24 hours by using a thermal evaporation method, taking out the lignin, placing the lignin in a culture dish, placing the culture dish in a refrigerator freezing layer for freezing for half an hour to 1 hour, and finally placing the culture dish containing the lignin in a freeze dryer for freeze drying to obtain the lignin nanoparticles;

wherein: the ethanol solvent is ethanol water solution or absolute ethanol, and the mass percentage concentration of the ethanol water solution is 70-90%.

Examples 2 to 3

The preparation method of Lignin Nanoparticles (LNPs) of examples 2-3 is the same as example 1 except that: the dropping rate of the HCl solution in examples 2 to 3 was 2 drops/min and 10 drops/min.

Example 4

The preparation method of Lignin Nanoparticles (LNP) of example 4 is the same as example 1 except that: the concentration of the HCl solution in example 4 was 0.25 mol/L.

Examples 5 to 6

The preparation method of Lignin Nanoparticles (LNPs) of examples 5-6 is the same as example 4, except that: the dropping rate of the HCl solution in examples 5 to 6 was 2 drops/min and 10 drops/min.

Example 7

The preparation method of Lignin Nanoparticles (LNP) of example 7 is the same as example 1 except that: the concentration of the HCl solution in example 7 was 0.5 mol/L.

Example 8

The preparation method of Lignin Nanoparticles (LNP) of example 8 is the same as that of example 7, except that: the dropping rate of the HCl solution in example 8 was 2 drops/min.

In FIG. 1, three sets of SEM images are obtained under the condition that the magnification of a scanning electron microscope is 5000 times, and it can be seen that the nano lignin structure obtained after 0.1mol/L HCl solution is dripped has polymerization in different degrees and is not uniformly distributed, and the nano lignin particles are not spherical but are massive and rod-shaped. With the increase of the dropping speed of the HCl solution, the particle size of the nano-particles tends to decrease. However, due to the short stabilization time, there is some agglomeration of the nanoparticles. The concentration of hydrochloric acid can be properly increased, so that the obtained lignin nanoparticles are more uniformly distributed, the particle size is smaller, and the shape can be close to a spherical shape.

FIG. 2 shows that three sets of SEM images are obtained under the condition that a scanning electron microscope magnifies by 5000 times, and it can be seen that when 0.25mol/L HCl solution is used for dropwise adding lignin ethanol solution at the speed of 10 drops/min, the obtained product particles are most spherical, the distribution is more uniform, and the sizes of the particles are mostly distributed in the range of 200nm-800nm, and the lignin nanoparticles prepared under the condition are the optimal product of the invention. The obtained product dropped at the rate of 1 drop/min and at the rate of 2 drops/min was polymerized, and some of the nano lignin particles lost the spherical morphology.

In FIG. 3, three sets of SEM images are obtained under the condition that the scanning electron microscope is magnified by 10000 times, and it can be seen that the nano lignin obtained after 0.5mol/L HCl solution is dripped has the phenomena of polymerization to a certain extent and uneven distribution. With the increase of the dropping speed of the HCl solution, the particle size of the nanoparticles tends to decrease but does not show a round and smooth sphere, most of the nanoparticles are rod-shaped or irregular, and the lignin nanoparticles cannot be completely in a nanometer level.

The following methods for preparing PVA solutions and CH solutions used in examples 9 to 10 and comparative examples 1 to 5 were as follows:

the preparation method of the PVA solution comprises the following steps:

firstly weighing 1.5g of polyvinyl alcohol solid small particles, then weighing 100mL of deionized water, mixing the polyvinyl alcohol solid small particles in a beaker, putting the beaker into an ultrasonic cleaner for ultrasonic treatment for 5min, then putting the mixed solution after ultrasonic treatment into a high-temperature reaction kettle, and stirring the mixed solution at the temperature of 90 ℃ at the speed of 1000 revolutions per minute of a rotor for 3 hours to finally obtain the PVA solution.

The preparation method of the CH solution comprises the following steps:

weighing 0.15g of chitosan solid small particles, weighing 100mL of deionized water, mixing the chitosan solid small particles in a beaker, putting the beaker into an ultrasonic cleaner for ultrasonic treatment for 5min, putting the mixed solution after ultrasonic treatment into an SLP2-250 high-temperature reaction kettle, and stirring the mixed solution at the temperature of 40 ℃ at the speed of 1000 revolutions per minute of a rotor for 12 hours to finally obtain the CH solution.

Example 9

The preparation method of the lignin nanoparticle/polyvinyl alcohol/chitosan (1LNP/PVA/CH) ternary composite material of the embodiment specifically includes the following steps:

and (2) mixing 1g of the Lignin Nanoparticles (LNP) prepared in the embodiment 6, 89.1g of PVA solution and 9.9g of CH solution according to the mass ratio of 1:89.1:9.9, uniformly stirring, and putting into an ultrasonic cleaner for ultrasonic treatment for 5min to obtain the 1LNP/PVA/CH ternary composite material.

Example 10

The preparation method of the lignin nanoparticle/polyvinyl alcohol/chitosan (3LNP/PVA/CH) ternary composite material of the embodiment specifically includes the following steps:

and 3g of the Lignin Nanoparticles (LNP) prepared in the embodiment 6, 87.3g of PVA solution and 9.7g of CH solution are mixed according to the mass ratio of 3:87.3:9.7, stirred and mixed uniformly, and placed in an ultrasonic cleaner for ultrasonic treatment for 5min, so that the 3LNP/PVA/CH ternary composite material is obtained.

Comparative example 1

The preparation method of the lignin nanoparticle/polyvinyl alcohol (1LNP/PVA) binary composite material of the comparative example comprises the following steps:

and (2) mixing 1g of the Lignin Nanoparticles (LNP) prepared in the embodiment 6 and 99g of PVA solution in a mass ratio of 1:99, uniformly stirring, and putting into an ultrasonic cleaner for ultrasonic treatment for 5min to obtain the 1LNP/PVA binary composite material.

Comparative example 2

The preparation method of the lignin nanoparticle/polyvinyl alcohol (3LNP/PVA) binary composite material of the comparative example comprises the following steps:

and 3g of the Lignin Nanoparticles (LNP) prepared in the embodiment 6 and 97g of PVA solution are mixed according to the mass ratio of 3:97, stirred and uniformly mixed, and placed in an ultrasonic cleaner for ultrasonic treatment for 5min to obtain the 3LNP/PVA binary composite material.

Comparative example 3

The preparation method of the lignin nanoparticle/chitosan (1LNP/CH) binary composite material of the comparative example comprises the following steps:

and (2) mixing 1g of the Lignin Nanoparticles (LNP) prepared in the embodiment 6 and 99g of CH solution in a mass ratio of 1:99, uniformly stirring, and putting into an ultrasonic cleaner for ultrasonic treatment for 5min to obtain the (1LNP/CH) binary composite material.

Comparative example 4

The preparation method of the lignin nanoparticle/chitosan (3LNP/CH) binary composite material of the comparative example comprises the following steps:

and 3g of the Lignin Nanoparticles (LNP) prepared in the embodiment 6 and 97g of CH solution are mixed according to the mass ratio of 3:97, stirred and uniformly mixed, and placed in an ultrasonic cleaner for ultrasonic treatment for 5min to obtain the (3LNP/CH) binary composite material.

Comparative example 5

The preparation method of the polyvinyl alcohol/chitosan (PVA/CH) binary composite material of the comparative example comprises the following steps:

and (3) adding 9: 1, and putting the mixture into an ultrasonic cleaner for ultrasonic treatment for 5min to obtain the PVA/CH (90 wt% of PVA and 10 wt% of CH) binary composite material.

TABLE 1 composite materials of examples 9-10 and comparative examples 1-5, PVA solution, CH solution formulation and ingredient ratio table

Application examples

The ternary composites prepared in examples 9 to 10, the binary composites prepared in comparative examples 1 to 5, and the PVA solution and the CH solution were coated to 90g/m, respectively²The surface of the corrugated base paper is controlled to be 15g/m²And then drying the corrugated base paper at the temperature of 75-85 ℃ for 15-25min to respectively obtain PVA coated paper, CH coated paper, PVA/CH coated paper, 1LNP/CH coated paper, 3LNP/CH coated paper, 1LNP/PVA coated paper, 3LNP/PVA coated paper, 1LNP/PVA/CH coated paper and 3LNP/PVA/CH coated paper, and then respectively carrying out performance detection on the corrugated base paper and the coated papers, wherein the performance detection comprises micro-topography characterization, chemical structure, ultraviolet shielding, flame retardance, strength and fresh strawberry preservation effect.

Wherein: the stiffness test is carried out according to the GB/T2679.3-1996 standard; the whiteness test is carried out according to the GB/T24999-; the bursting strength test is carried out according to the GB/T454-2002 standard; the tensile strength test is carried out according to the GB/T453-2002 standard; the oxygen index test is referred to GB 2406.2-2009;

the specific test method of the ultraviolet shielding comprises the following steps: measuring the uvioresistant performance of the corrugated base paper and each piece of coated paper by using a Shimadzu UV-2600 ultraviolet visible spectrophotometer, scanning 5 points for each sample, and collecting the transmittance (T) of each 1nm in the wavelength range from UVB (290-320 nm) to UVA (320-400 nm) in each scanning.

The specific test method for the strawberry preservation effect comprises the following steps: fresh strawberries were weighed before the test and then reweighed after the test was completed. The mass difference between the strawberry before and after the test is divided by the mass before the test starts, namely the weight loss rate.

Firstly, micro-morphology characterization:

fig. 4 is obtained by magnifying by 500 times a scanning electron microscope, and it can be seen that the micro-topography of the corrugated base paper is disordered and complex. The waste paper fiber is used as a raw material, the fiber is disordered, and the fiber of the base paper is in planar distribution and has no three-dimensional distribution.

All three images in fig. 5 are obtained under a scanning electron microscope with a magnification of 2000 times, and from (a), we can see that after the corrugated base paper is coated by the CH solution alone, the fibers gradually assume a three-dimensional distribution, and some holes appear. From (b), we can see that some lignin nanoparticles are attached to the fiber, and enter the pores in the fiber, and are effective binding. From (c) we can see more clearly the binding of lignin nanoparticles to the fibers, and more lignin nanoparticles attached in the pores of the fibers. The binary composite system of CH and LNP is proved to be capable of effectively promoting the combination of lignin nanoparticles and fibers, thereby achieving the final purpose of us.

The three SEM images in the group of fig. 6 are all obtained under the magnification of 2000 times of a scanning electron microscope, and from the image (a), we can find that the fiber of the corrugating medium is three-dimensionally distributed after being coated with the PVA solution alone, and has a very large number of holes, and the PVA effect is more obvious compared with the single coating of the CH solution. From (b) this figure we can see that some lignin nanoparticles are attached to the fiber and many enter the pores in the fiber, and the lignin nanoparticles are well bound to the fiber. From (c), the combination of lignin nanoparticles and fibers can be seen more clearly, and more holes are generated between the fibers, and more lignin nanoparticles are attached in the holes of the fibers. The binary composite system of PVA and LNP is proved to be capable of effectively generating holes between fibers, and the lignin nanoparticles can enter the holes between the fibers, so that the combination of the lignin nanoparticles and the fibers is achieved, and meanwhile, the destruction effect of PVA on the structural connection of the fibers is verified from the microstructure, and the strength of paper sheets can be reduced. Further, the desired results can be obtained.

The three SEM images in the group of fig. 7 are all obtained under the magnification of 2000 times of scanning electron microscope, and from the image (a), we can find that the fiber distribution of the corrugated base paper after being coated by the PVA/CH binary system is less disordered on the plane, but becomes more three-dimensional, and very many holes are formed between the fibers, and the effect of the two binary mixed system on the fibers is more obvious compared with the single coating of PVA or CH. From (b), we can see that many lignin nanoparticles are attached to one fiber, and many lignin nanoparticles enter the pores in the fiber, and the lignin nanoparticles are bonded with the fiber very well. Therefore, the ternary composite system of PVA/CH/LNP can effectively improve the structure among fibers, so that the lignin nanoparticles can fully enter the holes. In the graph of (c), we can see that the lignin nanoparticles are better combined with the fibers, more holes are generated between the fibers, and almost all the lignin nanoparticles can be attached in the holes of the fibers. The ternary composite system of PVA/CH/3LNP is proved to be capable of effectively generating holes among fibers, and the lignin nanoparticles almost completely enter the holes among the fibers, so that the combination of the lignin nanoparticles and the fibers is perfectly achieved, and the desired result can be obtained.

The absorption peak of KBr in a single component can be seen from FIG. 8(a), which is a comparative group.

It can be seen from FIG. 8(b) that the peak voltage at 1650cm^-1And 1730cm^-1Absorption occurred nearby, indicating the presence of C ═ O conjugated bonds. At 3410cm^-1-3440cm^-1An absorption peak appears nearby, indicating that O-H stretching vibration exists. Upon comparing fig. 8(c), it is clear that a clear difference was observed before and after the addition of chitosan.

It can be seen from FIG. 8(d) that the distance between the first and second electrodes is 832cm^-1-840cm^-1The nearby presence of absorption indicates the presence of C-H oscillations on the aryl group and C-O deformation of the guaiacol type. Under the curve of fig. 8(e), a clear difference before and after addition of polyvinyl alcohol can be clearly observed.

It can be seen from FIG. 8(f) that the peak value is at 1500cm^-1-1600cm^-1The nearby absorption peak is the vibration absorption animal of the benzene ring skeleton and is the characteristic absorption peak of the lignin nano-particles. 1650cm^-1And 1730cm^-1Absorption occurred nearby, indicating the presence of C ═ OConjugated bonds, and at 2730cm^-1There is no absorption, indicating that the bond is a ketone bond rather than an aldehyde bond. At 1250cm^-1-1270cm^-1The absorption peak appeared indicating the presence of stretching vibration of the benzene ring-oxygen bond. In the graph of fig. 8(g), we can clearly observe the significant difference before and after addition of the lignin nanoparticles.

The groups of the ternary combinations similar to those of FIG. 8(h), FIG. 8(i) and FIG. 8(j) can observe the absorption peaks of the functional groups of the respective components.

Third, mechanical analysis

Table 2 is a comparison table of the results of measuring stiffness, whiteness, and bursting strength of the coated paper obtained by coating in the application examples. As shown in table 2, the binary mixed solution grouping force value of PVA and LNP was the largest and the binary mixed solution grouping force value of CH and LNP was the smallest, and the force values showed an increasing tendency as the content of lignin nanoparticles increased. The data performance of the torque is very similar to the force value, and the grouping torque of the binary mixed solution of PVA and LNP is the maximum, and the grouping torque of the binary mixed solution of CH and LNP is the minimum. Ternary systems do not perform as expected and exhibit smaller force and moment values. In conclusion, the addition of the lignin nanoparticles can increase the force value and the moment of the paper within a certain range. The whiteness is uniformly lower than that of the base paper. And the higher the lignin nanoparticle content, the lower its whiteness. The burst of the base paper is higher compared to the coated paper. It can also be found that the higher the lignin nanoparticle content, the lower the paper burst, while keeping the amount of other than lignin nanoparticles constant. The data are completely expected, the reason why the added lignin nanoparticles reduce the bursting strength of paper is probably that the lignin nanoparticles are natural high molecular compounds with a spatial network structure and are non-linear high molecules, the lignin nanoparticles have the functions of bonding fibers and enhancing the strength of plant tissues, and the lignin nanoparticles are hydrophobic substances and are not easy to absorb water and wet, and when the content of the lignin nanoparticles is high, the paper is fragile and not convenient for interweaving fibers. The interlacing ability between the fibers is weakened and the bursting strength is reduced.

TABLE 2 comparison table of mechanical and optical properties of corrugated base paper and paper coated and dried on the surface in application example

Fourth, ultraviolet shielding performance detection

As can be seen from FIG. 9, the PVA coated paper and the 1LNP/PVA coated paper coated and dried by the PVA solution and the 1LNP/PVA binary composite material show the fluctuation of the transmittance at 370nm, and the transmittance in the visible light region (400-460 nm) is about 20-30%. The 3LNP/PVA coated paper shows lower transmittance in the visible light region, and about 5% can be seen from FIG. 9. Compared with PVA coated paper and PVA/1LNP coated paper, the ultraviolet shielding effect is similar, but the ultraviolet transmittance at 350nm is 0, which is caused by the absorption effect of the conjugated system and the aromatic structure of the lignin nanoparticles on ultraviolet rays.

As can be seen from fig. 10, the CH coated paper and the 1LNP/CH coated paper showed the fluctuation of transmittance at 370nm and reached 60% and 54% at 350 nm. The two groups have a transmittance in the visible light region (400-460 nm) of about 15-25%. The 3LNP/CH coated paper also shows lower transmittance in a visible light region, and the transmittance is only about 3 percent as can be seen from the figure. The transmittance of the lignin nano-particles is similar to that of CH coated paper and 1LNP/CH coated paper, but the UV shielding effect starts to be shown in a near UV region (350-400 nm), and is greatly different from that of the CH coated paper and 1LNP/CH coated paper, and the UV transmittance at 350nm is 0, which is caused by the absorption effect of the conjugated system and aromatic structure of the lignin nano-particles on UV.

As can be seen from FIG. 11, the PVA/CH coated paper coated with the PVA/CH binary composite material showed strong fluctuation of transmittance at 370nm, almost reaching 80%. The transmittance in a visible light region (400 to 460nm) is about 70 to 75%. In contrast, 1LNP/PVA/CH coated paper and 3LNP/PVA/CH coated paper also showed lower transmittance in the visible region, which is only about 12% and 0%. Both of the two materials start to show strong ultraviolet shielding effect in a near ultraviolet region (350-400 nm), the ultraviolet transmittance of 3LNP/PVA/CH coated paper at 350nm is 0%, and the ultraviolet transmittance of 1LNP/PVA/CH coated paper at 350nm is as low as 5%. This is due to the absorption of ultraviolet light by the conjugated system and aromatic structure of the lignin nanoparticles.

The ultraviolet transmittance of the 3LNP/PVA/CH coated paper is below 10% in the visible light region and the near ultraviolet region, and the transmittance in most near ultraviolet regions is less than 5%, so that the ultraviolet absorption of 95% in the near ultraviolet region is realized, the ultraviolet shielding effect is higher than that of other coated paper, the complementary relationship among the lignin nanoparticles, the chitosan and the polyvinyl alcohol in the ultraviolet reflection and the ultraviolet absorption is also embodied, and the fact that the 3LNP/PVA/CH ternary composite material can effectively shield ultraviolet after being coated on the paper is demonstrated.

In summary, the following steps:

firstly, lignin is used as a raw material, a solvent anti-solvent method is used for preparing lignin nanoparticles, and the physical and chemical properties of the lignin nanoparticles are represented; the lignin nanoparticles, polyvinyl alcohol and chitosan are blended and grafted and modified to prepare a lignin nanoparticle/polyvinyl alcohol/chitosan (LNP/PVA/CH) ternary composite material; and uniformly coating the ternary composite material on the surface of the corrugated base paper by a coating process to obtain the coated paper, and detecting the ultraviolet shielding performance of the coated paper by using an ultraviolet-visible spectrophotometer.

Secondly, after the multicomponent system comprising the lignin nanoparticles, the chitosan and the polyvinyl alcohol is coated on paper, the components can be clearly found to destroy the connection among fibers to a certain extent, so that the strength of the paper sheet is reduced. The microscopic appearance can be seen visually, and the lignin nanoparticles fully enter the holes among the fibers, are effectively attached and are filled in the network structure.

The ultraviolet transmittance of the ultraviolet shielding lignin-based ternary composite coated paper of 3LNP/PVA/CH is below 10% in the visible region and the near ultraviolet region, and the transmittance in most near ultraviolet regions is less than 5%, so that the ultraviolet absorption of 95% in the near ultraviolet region is realized.

Fourthly, the whiteness and the bursting strength of the ultraviolet shielding type coating paper based on the 3LNP/PVA/CH composite material are respectively 17.9 percent and 68.7kPa, the oxygen index is 27 percent, and the weight loss rate is only 5 percent after the fresh strawberries are stored for 5 days at the temperature of 10-12 ℃. And the oxygen index of the corrugated base paper is 22%, so that the ultraviolet shielding type coating paper based on the 3LNP/PVA/CH composite material achieves the flame-retardant grade.