CN108530927B - Preparation method of wood fiber transparent high-strength composite material - Google Patents
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Abstract
The invention relates to a preparation method of a wood fiber transparent high-strength composite material, which comprises the following steps: removing lignin in the wood matrix through chemical treatment, and then performing hydrophobic oleophilic modification treatment and drying treatment to obtain a hydrophobic oleophilic delignified wood matrix; and injecting a high molecular polymer monomer solution into the obtained hydrophobic and oleophilic delignified wood matrix by a full cell method or a half-limiting method, and then initiating a polymerization reaction of the high molecular polymer monomer in the hydrophobic and oleophilic delignified wood matrix to obtain the wood fiber transparent high-strength composite material. The composite material prepared by the invention has very high strength and good transparency.
Description
Technical Field
The invention relates to a preparation method of an organic transparent high-strength composite material, in particular to a preparation method of a wood fiber transparent high-strength composite material.
Background
The composite material of the wood fiber reinforced high molecular polymer is a novel high-performance transparent material. In 2004, professor Yano of tokyo university, japan, physically stripped a one-dimensional micron-sized cellulose microfibril cluster from wood (1 h Yano. (applied physical materials science) appl. phys. a.78(2004), 547-. In 2010, teaching of Isogai of tokyo university of japan chemically stripped with tetramethylpiperidine compounds, one-dimensional nanoscale cellulose microfibrils were stripped from wood, and the microfibrils were dispersed in water to be completely transparent, demonstrating that cellulose can be used for transparent materials ([2] a. Isogai. (nanoscale) nanoscale.3(2011) 71-85). In 2011, Yano professor of tokyo university of japan adopts lignocellulose fiber and high molecular polymer to compound, and produces a first piece of high-strength transparent paper, the visible light transmittance of the transparent paper is basically equal to that of a commercial PET film, the elastic modulus of the transparent paper is 4-5 times that of the commercial PET film, and the breaking tensile strength of the transparent paper can also reach 2-3 times that of the commercial PET film (3 h. In 2013, the Hu professor of the university of Maryland in America applies high-strength transparent paper to the field of solar cells, and finds that the high-strength transparent paper can better collect solar energy with non-vertical incidence, and the energy utilization rate of the solar cells is improved (4 L.Hu. (nano bulletin) NanoLett.14(2014) 765-773). The composite material of the cellulose fiber reinforced high molecular polymer has excellent performances of biodegradability, good transparency, high strength, small expansion coefficient and the like, and thus has been receiving wide attention since the discovery.
After wood, wood material and biomass resources are subjected to composite treatment, the carbon can be processed, fixed and packaged again, and CO is reduced in the whole processing process2Thereby reducing the "greenhouse effect", which is a contribution to the human living environment. The wood or biomass composite material not only can make high-efficiency use of low-quality wood, small-diameter wood, waste wood and agricultural residues, but also has a fresh and well-known ecological effect. Compared with the earth, the forest resources are poor, the forest coverage rate is less than 60 percent of the average time level, and the forest occupies the 130 th position in the world, so the total carbon storage amount of the forest is insufficient. Therefore, from the viewpoint of maintaining ecological balance, the cellulose fiber reinforced high molecular polymer composite material scientifically utilizes wood, reduces greenhouse effect and maintains ecological safety.
Disclosure of Invention
The invention aims to provide a preparation method of a wood fiber transparent high-strength composite material, which comprises the following steps:
removing lignin in the wood matrix through chemical treatment, and then performing hydrophobic oleophilic modification treatment and drying treatment to obtain a hydrophobic oleophilic delignified wood matrix;
and injecting a high molecular polymer monomer solution into the obtained hydrophobic and oleophilic delignified wood matrix by a full cell method or a half-limiting method, and then initiating a polymerization reaction of the high molecular polymer monomer in the hydrophobic and oleophilic delignified wood matrix to obtain the wood fiber transparent high-strength composite material.
According to the method, lignin in the wood matrix is removed by a chemical treatment mode, and then the wood matrix is subjected to hydrophobic oleophylic modification treatment and drying treatment, so that the pore structure of the wood matrix is not damaged, and meanwhile, the wood matrix is endowed with hydrophobic oleophylic performance, so that the wood matrix and most of high polymer monomer solutions have good wetting performance. And then injecting a low-viscosity high-molecular polymer monomer solution into the obtained hydrophobic and oleophilic delignified wood matrix by applying a certain external pressure through a full cell method or a half-limiting injection method, so that the high-molecular polymer monomer is distributed in the pore structure of the hydrophobic and oleophilic delignified wood matrix. And finally, initiating the high-molecular polymer monomer in the hydrophobic and oleophilic delignified wood matrix to perform in-situ polymerization reaction in a pore structure of the hydrophobic and oleophilic delignified wood matrix, and finally obtaining the wood fiber transparent high-strength composite material.
Preferably, the chemical treatment is to place the wood substrate in a chemical reagent to react for 1-10 hours at 25-100 ℃.
Preferably, the chemical agent is at least one of hydrogen peroxide, a mixed solution of sodium hypochlorite and sodium hydroxide, and perchloric acid.
Preferably, the hydrophobic oleophylic modification treatment is to immerse the chemically treated delignified wood matrix into a solution containing a modifier for reaction for 12-24 hours, wherein the concentration of the modifier in the solution containing the modifier is 0.01-0.1 mol/L. When the modifier is selected, the chemical bond between the modifier and hydroxyl on cellulose in the delignified wood matrix after chemical treatment needs to be formed, and the modifier contains hydrophobic groups, so that the delignified wood matrix has hydrophobicity and lipophilicity.
Also, preferably, the modifier is n-octadecanethiol, n-dodecanethiol, or stearic acid.
Preferably, the drying treatment is freeze drying, vacuum drying or supercritical drying. The porosity and surface chemical composition of the wood are not affected after the drying treatment.
Preferably, the full cell method comprises:
placing the hydrophobic and oleophilic delignified wood matrix in a container for vacuum treatment, adding a high molecular polymer monomer solution until the container is filled with the hydrophobic and oleophilic delignified wood matrix, and removing the vacuum;
and then pressurizing to 1-3MPa until the immersion amount of the high molecular polymer monomer solution is saturated, and recovering to normal pressure after vacuum treatment. The vacuum degree of the vacuum treatment is preferably 79 to 86kPa, and the time is preferably 15 minutes to 2 hours, more preferably 1 to 2 hours. Specifically, the hydrophobic and oleophilic delignified wood matrix is placed in a treatment tank and then subjected to vacuum treatment, wherein the vacuum degree is generally 79-86 kPa, and the treatment tank is kept for 15-60 min. After the vacuum reaches a certain degree, adding the high molecular polymer monomer solution, and keeping the vacuum degree unchanged so as to avoid uneven injection of the high molecular polymer monomer solution; and (3) after the treatment tank is filled with the high molecular polymer monomer solution, releasing the vacuum, starting pressurizing to the maximum pressure (1-3 MPa), and then keeping the maximum pressure until the immersion amount is saturated. After pressure is relieved, high molecular polymer monomer solution can be by the inside gas "recoil" that persists of a small amount of wood, with high molecular polymer monomer solution discharge back, the processing jar still need the evacuation again, fills the hole that exists in the wood through the high molecular polymer monomer solution who retrieves wood surface. Maintaining the vacuum for a period of time, and releasing the vacuum.
Preferably, the semi-limiting method is as follows: and (3) placing the hydrophobic and oleophilic delignified wood matrix into a container filled with a high molecular polymer monomer solution, pressurizing to 1-3MPa until the immersion amount of the high molecular polymer monomer solution is saturated, and recovering to normal pressure after vacuum treatment. The vacuum degree of the vacuum treatment is preferably 79 to 86kPa, and the time is preferably 15 minutes to 2 hours, more preferably 1 to 2 hours. Specifically, after the hydrophobic and oleophilic delignified wood matrix is placed in a treatment tank, the treatment tank is filled with a high molecular polymer monomer solution, the treatment tank starts to pressurize to the maximum pressure (1-3 MPa), and then the maximum pressure is maintained until the immersion amount is saturated. After pressure is relieved, high molecular polymer monomer solution can be by the inside gas "recoil" that persists of a small amount of wood, with high molecular polymer monomer solution discharge back, the processing jar still need the evacuation again, fills the hole that exists in the wood through the high molecular polymer monomer solution who retrieves wood surface. Maintaining the vacuum for a period of time, and releasing the vacuum.
Preferably, the high molecular polymer monomer solution is a methyl methacrylate solution, a bisphenol A glycidyl ether solution or a dimethyl siloxane solution.
Preferably, the high molecular polymer monomer is initiated to carry out polymerization reaction by ultraviolet irradiation or heating at 50-80 ℃; the power of the ultraviolet illumination is 10-30W, and the time is 1-3 h.
In another aspect, the invention also provides a wood fiber transparent high-strength composite material prepared according to the above method, which comprises a hydrophobic oleophylic modified delignified wood matrix and a high molecular polymer distributed in the pore structure of the hydrophobic oleophylic modified delignified wood matrix.
Preferably, the mass content of the high molecular polymer in the wood fiber transparent high-strength composite material is 30-70 wt%.
Preferably, the high molecular polymer is polymethyl methacrylate, epoxy resin or polydimethylsiloxane.
The optical transmittance of the wood fiber transparent high-strength composite material at 550nm is 75-90%.
The Young modulus of the wood fiber transparent high-strength composite material provided by the invention is 2.51 GPa-2.91 GPa, and the breaking tensile strength is 59.8 MPa-76.1 MPa.
Compared with the prior art, the wood fiber reinforced high molecular polymer composite material is obtained by adopting a high molecular polymer monomer injection method, the production process is simple, and the requirement on equipment is low. The main raw material used in the method is wood, and the method is low in cost and renewable. The prepared composite material has very high strength and good transparency.
The invention has the characteristics of no pollution, low energy consumption and low cost, and the prepared wood fiber composite material has the characteristics of good transparency, high strength, light weight and low cost, has good industrial prospect, and can be widely used in the fields of photoelectricity, biological medicine, agriculture, food, environment and the like.
Drawings
FIG. 1 is an SEM image of a willow wood fiber composite polymethyl methacrylate material in example 1;
FIG. 2 is an SEM image of willow wood fiber composite poly-bisphenol A glycidyl ether in example 2;
FIG. 3 is an SEM image of a willow wood fiber composite polymethyl methacrylate material in example 3;
FIG. 4 is an SEM image of a beech wood fiber composite polymethylmethacrylate material in example 4;
FIG. 5 is an SEM image of a basswood wood fiber composite polymethylmethacrylate material in example 5;
FIG. 6 is a graph showing the optical transmittance of the willow wood fiber composite polymethyl methacrylate material of example 1;
FIG. 7 is a graph showing the optical transmittance of willow wood fiber composite poly-bisphenol A glycidyl ether in example 2;
FIG. 8 is a graph showing the optical transmittance of the willow wood fiber composite polymethyl methacrylate material of example 3;
FIG. 9 is a graph of optical transmittance of a zelkova wood fiber composite polymethylmethacrylate material of example 4;
FIG. 10 is a graph showing the optical transmittance of a basswood wood fiber-polymethyl methacrylate composite material in example 5;
FIG. 11 is a stress-strain curve of the willow wood fiber composite polymethyl methacrylate material of example 1;
FIG. 12 is a stress-strain curve of willow wood fiber composite poly-bisphenol A glycidyl ether of example 2;
FIG. 13 is a stress-strain curve of the willow wood fiber composite polymethyl methacrylate material of example 3;
FIG. 14 is a stress-strain curve of a beech wood fiber composite polymethylmethacrylate material of example 4;
FIG. 15 is a stress-strain curve of a basswood wood fiber composite polymethylmethacrylate material in example 5;
FIG. 16 is a graph showing the optical transmittance of a basswood wood fiber composite polymethylmethacrylate material in a comparative example;
fig. 17 is a stress-strain curve of a basswood wood fiber composite polymethylmethacrylate material in a comparative example.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the invention, the wood fiber transparent high-strength composite material comprises a hydrophobic oleophilic delignified wood matrix and a high molecular polymer distributed in a pore structure of the hydrophobic oleophilic modified delignified wood matrix. The mass content of the high molecular polymer in the wood fiber transparent high-strength composite material is 30-70 wt%, and the content is changed according to different types of wood raw materials, but the wood is ensured not to have holes with the hole diameter of more than 50 nm. The high molecular polymer can be polymethyl methacrylate, epoxy resin or polydimethylsiloxane.
The invention firstly removes the lignin in the wood by chemical treatment. The delignified wood matrix is then dried by a special drying process. And finally, injecting a high molecular polymer monomer into the hydrophobic and oleophilic delignified wood matrix by a special injection method to initiate the polymerization of the high molecular polymer, thereby obtaining the wood fiber transparent high-strength composite material. The following is an exemplary illustration of the method for preparing the lignocellulosic transparent high strength composite material provided by the present invention.
The lignin in wood is removed by chemical treatment. Specifically, lignin in wood is removed by a chemical reagent soaking method, namely, a wood matrix is placed in a chemical reagent to react for 1-10 hours at 25-100 ℃ to obtain a product A. The chemical agent can be at least one selected from hydrogen peroxide, sodium hypochlorite and sodium hydroxide mixed solution or perchloric acid. Wherein the concentration of the hydrogen peroxide can be 15-30 wt%, the concentration of the perchloric acid can be 12-15 wt%, and the concentration of the sodium hypochlorite can be 3-5 wt% and the concentration of the sodium hydroxide can be 15-20 wt% in a mixed solution of the sodium hydroxide and the sodium hypochlorite.
And immersing the delignified wood matrix subjected to chemical treatment into a solution containing a modifier for reaction for 12-24 hours, wherein the concentration of the modifier in the solution containing the modifier is 0.01-0.1 mol/L. The organic solvent in the solution containing the modifier can be ethanol, isopropanol, toluene, ethyl acetate and the like. Or washing the chemically treated delignified wood matrix with the organic solvent (e.g., ethanol, isopropanol, toluene, ethyl acetate, etc.) prior to immersion in the solution containing the modifier to remove the chemical agents present in the delignified wood matrix. As an example, the product A (delignified wood matrix after chemical treatment) is washed by ethanol and soaked in an ethanol solution of a modifier for reaction for 12-24 hours, wherein the modifier is n-octadecanethiol, n-dodecanethiol or stearic acid. Then drying to obtain B product (hydrophobic and oleophilic delignified wood matrix). The drying treatment may be freeze drying, vacuum drying or supercritical drying. In particular, freeze drying, vacuum drying or supercritical drying is used without destroying the pore structure of the wood. Wherein, the vacuum drying can use a vacuum drying oven, the vacuum degree is 100Pa to 200Pa, and the temperature is 80 ℃ to 100 ℃. Supercritical drying may be performed using a supercritical carbon dioxide extraction apparatus. The freeze drying may be at-20 deg.C to-40 deg.C for 6-12 hr.
Injecting the high molecular polymer monomer solution into the product B to obtain a product C. The method of injection may be a full cell method or a semi-limiting method. The high molecular polymer monomer solution is methyl methacrylate solution, bisphenol A glycidyl ether solution or dimethyl siloxane solution, namely the high molecular polymer monomer can be methyl methacrylate, bisphenol A glycidyl ether or dimethyl siloxane. Wherein the full cell method comprises: the hydrophobic oleophilic delignified wood matrix is placed in a container (e.g., a treatment tank) for vacuum treatment, and then a high molecular polymer monomer solution is added until the container is filled, and then the vacuum is released. And then pressurizing to 1-3MPa until the immersion amount of the high molecular polymer monomer solution (the amount of the high molecular polymer monomer solution immersed into the hydrophobic and oleophilic delignified wood matrix) is saturated, and then recovering to normal pressure after vacuum treatment. As an example, placing the wood without lignin after hydrophobic oleophylic and drying treatment in a treatment tank and vacuumizing, wherein the vacuum degree is 79-86 kPa, and keeping for 15-60 min; then, after the treatment tank is filled with methyl methacrylate solution, the vacuum is released, the pressure is increased to 1-3MPa, and the pressure is maintained for 15-60 min; and after the pressure is relieved, vacuumizing the treatment tank again, keeping the vacuum for 1-2 hours, and finally relieving the vacuum, wherein the vacuum degree is 79-86 kPa. The semi-limiting method comprises the steps of putting the hydrophobic and oleophilic delignified wood matrix into a container filled with a high molecular polymer monomer solution, pressurizing to 1-3MPa until the immersion amount of the high molecular polymer monomer solution (the amount of the high molecular polymer monomer solution immersed in the hydrophobic and oleophilic delignified wood matrix) is saturated (the required time generally depends on the magnitude of applied pressure and the magnitude of the wood matrix, the time generally can be 10-60 minutes), and then recovering to normal pressure after vacuum treatment. As an example, the delignified wood after hydrophobic oleophilic and drying treatment is immersed in methyl methacrylate solution for 1-2h, pressurized to 1-3Mpa and kept for 15-60min, and then vacuumized to 79-86 kPa and kept for 1-2h and returned to normal pressure. As a detailed example, one of methyl methacrylate, bisphenol A glycidyl ether and dimethyl siloxane is injected (semi-limiting method) into a hydrophobic and oleophilic delignified wood matrix for 2h, pressurized to 3MPa for 15min, and then evacuated to 80kPa for 2h and returned to normal pressure.
And (4) initiating the polymerization of the high molecular polymer in the product C to obtain the wood fiber transparent high-strength composite material which is a finished product. The method for initiating polymerization of the high molecular polymer monomer may be heat treatment or ultraviolet treatment. Specifically, the transparent cellulose fiber reinforced composite material is obtained by heating under ultraviolet irradiation (the irradiation power can be 10-30W, and the irradiation time can be 1-3 h) or at 50-80 ℃ to initiate polymerization of the high molecular polymer, wherein the polymerization time is 6-24 h.
In the above preparation method, the raw material of the wood matrix can be selected from one of willow, basswood and beech.
As an example, (1) wood is soaked in hydrogen peroxide solution with the concentration of 30 wt% at 80 ℃ for 4-5 h. (2) And (2) cleaning the wood obtained in the step (1) by using ethanol, soaking the wood in an ethanol solution of n-octadecanethiol for reaction for 12 hours, and then drying the wood in a vacuum dryer, wherein the vacuum degree of the vacuum dryer is 100-200 Pa, the drying temperature is 80-100 ℃, and the drying time is 20-24 hours. (3) And (3) immersing the wood obtained in the step (2) into a methyl methacrylate solution for 1-2h, pressurizing to 3Mpa, keeping for 15min, and then vacuumizing to 200 Pa. (3) And heating and curing the obtained composite at 60-80 ℃ for 5h to finally obtain the wood fiber transparent high-strength composite material.
The optical transmittance of the wood fiber transparent high-strength composite material prepared by the invention at 550nm can be 75-90%. The Young modulus of the wood fiber transparent high-strength composite material can be 2.51 GPa-2.91 GPa, and the breaking tensile strength can be 59.8 MPa-76.1 MPa.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below. If not specifically stated, the high molecular polymer monomer solution of the present invention is composed entirely of polymer monomers.
Example 1
Willow (5 cm long, 5cm wide, 0.5cm thick) is soaked in 30 wt% hydrogen peroxide solution at 80 deg.C for 4 hr. The obtained delignified wood is washed by ethanol, soaked in ethanol solution of n-octadecanethiol (the concentration of the n-octadecanethiol is 0.05mol/L) for reaction for 12 hours, and dried in a vacuum drier (the vacuum degree of a vacuum drying oven is 200Pa, the drying temperature is 80 ℃, and the drying time is 20 hours). Placing the delignified wood (hydrophobic oleophilic delignified wood matrix) subjected to hydrophobic oleophilic drying treatment in a treatment tank, and vacuumizing with vacuum degree of 79kPa for 30 min. Then, the treatment tank was filled with a methyl methacrylate solution, the vacuum was released, and the pressure was increased to 1MPa for 60 minutes. When the pressure is released, the treatment tank is vacuumized again and kept at the vacuum level of 79kPa for 2h, and finally the vacuum is released. And heating and curing the obtained composite at 60 ℃ for 5h to finally obtain the willow wood fiber composite polymethyl methacrylate material, wherein the content of the polymethyl methacrylate in the composite material is 59.3 wt%.
Example 2
Willow 5cm long, 5cm wide and 0.5cm thick was soaked at 90 deg.C in a mixture of 5 wt% sodium hypochlorite and 20 wt% sodium hydroxide for 5 h. The obtained delignified wood is washed by ethanol, soaked in an ethanol solution of n-dodecyl mercaptan (the concentration of the n-dodecyl mercaptan is 0.05mol/L) for reaction for 18 hours, and dried by a supercritical carbon dioxide extraction device. Placing the wood with lignin removed after hydrophobic oleophylic and drying treatment in a treatment tank, and vacuumizing to 83kPa for 45 min. Then the treatment tank was filled with bisphenol A glycidyl ether solution, the vacuum was released, and pressurization to 3MPa was started and held for 15 min. When the pressure is released, the treatment tank is vacuumized again and kept at the vacuum degree of 83kPa for 2h, and finally the vacuum is released. And curing the obtained composite for 2 hours under the irradiation of an ultraviolet lamp with the irradiation power of 15W to finally obtain the willow wood fiber composite poly bisphenol A glycidyl ether material, wherein the content of the poly bisphenol A glycidyl ether in the composite material is 59.5 wt%.
Example 3
Willow 5cm long, 5cm wide and 0.5cm thick was soaked in a 15 wt% solution of perchloric acid at 100 deg.C for 4 h. The obtained delignified wood is washed by ethanol, soaked in ethanol solution of stearic acid (the concentration of stearic acid is 0.05mol/L) for reaction for 24 hours, and dried by a supercritical carbon dioxide extraction device. Placing the wood with lignin removed after hydrophobic oleophylic and drying treatment in a treatment tank, filling with polydimethylsiloxane solution, pressurizing to 2MPa, and maintaining for 20 min. When the pressure is released, the treatment tank is vacuumized and kept at the vacuum degree of 83kPa for 2h, and finally the vacuum is released. And curing the obtained compound at 60 ℃ for 12h to finally obtain the willow wood fiber composite polydimethylsiloxane material. The polydimethylsiloxane content of the composite material is 60.5 wt%.
Example 4
Beech 5cm long, 5cm wide and 0.5cm thick was soaked in 30 wt% aqueous hydrogen peroxide at 80 deg.C for 4 h. The obtained delignified wood was washed with ethanol, soaked in an ethanol solution of stearic acid (stearic acid concentration of 0.05mol/L) for 24h, and dried in a vacuum drier (vacuum degree of a vacuum drying oven of 200Pa, drying temperature of 80 ℃ C., drying time of 20 h). Placing the wood with lignin removed after hydrophobic oleophylic and drying treatment in a treatment tank, and vacuumizing at vacuum degree of 80kPa for 50 min. Then, the treatment tank was filled with a methyl methacrylate solution, the vacuum was released, and pressurization to 3MPa was started and the pressure was maintained for 15 min. When the pressure is released, the treatment tank is vacuumized again and kept for 1.5h, the vacuum degree is 80kPa, and finally the vacuum is released. And heating and curing the obtained compound at 60 ℃ for 5h to finally obtain the zelkova wood fiber composite polymethyl methacrylate material. The content of polymethyl methacrylate in the composite material is 37.3 wt%.
Example 5
A basswood material 5cm long, 5cm wide and 0.5cm thick is soaked in 30 wt% hydrogen peroxide solution at 80 deg.C for 4 h. The obtained delignified wood is washed by ethanol, soaked in ethanol solution of n-octadecanethiol (the concentration of the n-octadecanethiol is 0.05mol/L) for reaction for 16h, and dried in a vacuum drier (the vacuum degree of a vacuum drying oven is 200Pa, the drying temperature is 80 ℃, and the drying time is 20 h). Placing the wood with lignin removed after hydrophobic oleophylic and drying treatment in a treatment tank, and vacuumizing to a vacuum degree of 81kPa for 45 min. Then, the treatment tank was filled with a methyl methacrylate solution, the vacuum was released, and pressurization to 2MPa was started and the pressure was maintained for 20 min. When the pressure is released, the treatment tank is further vacuumized and kept at the vacuum degree of 81kPa for 1h, and finally the vacuum is released. And heating and curing the obtained compound at 60 ℃ for 5h to finally obtain the basswood wood fiber composite polymethyl methacrylate material. The content of polymethyl methacrylate in the composite material is 40.1 wt%.
Fig. 1-5 are SEM images of the lignocellulosic transparent high strength composites of examples 1, 2, 3, 4 and 5, respectively. It can be seen from FIGS. 2-6 that the high molecular weight polymer did not significantly fall off, indicating that the high molecular weight polymer had strong adhesion to the wood fibers.
Fig. 6-10 are optical transmittance curves for the lignocellulosic transparent high strength composites of examples 1, 2, 3, 4 and 5, respectively. From fig. 2-6, it can be seen that the optical transmittance of the wood fiber transparent high-strength composite material at 550nm is 75% -90%, which indicates that the wood fiber transparent high-strength composite material has very good transparency. Wherein the optical transmittance at 550nm of the wood fiber transparent high-strength composite material obtained in examples 1-5 is 85%, 82%, 75%, 90% and 79%, respectively.
Fig. 11-15 are stress-strain curves for lignocellulosic transparent high strength composites in example 1, example 2, example 3, example 4, and example 5, respectively. From FIGS. 11-15, it can be seen that the Young's modulus of the lignocellulosic transparent high-strength composite material is 2.51 GPa-2.91 GPa, and the breaking tensile strength is 59.8 MPa-76.1 MPa, which indicates that the lignocellulosic transparent high-strength composite material is a high-strength composite material. The Young's moduli of the transparent high-strength composite materials of wood fibers obtained in examples 1 to 5 were 2.55GPa, 2.65GPa, 2.77GPa, 2.91GPa, and 2.85GPa, and the tensile strengths at break were 76.1MPa, 59.8MPa, 60.1MPa, 62.9MPa, and 63.8MPa, respectively.
Comparative example (method using Lars)
A basswood 5cm long, 5cm wide and 0.5cm thick is soaked in a sodium chlorite solution with a concentration of 1 wt% at 80 deg.C (for 12h), and the delignified wood obtained is washed with ethanol and acetone respectively 3 times. Pre-polymerizing methyl methacrylate solution at 75 deg.C for 15min, placing the pre-polymerized viscous solution and delignified wood in a treatment tank, vacuumizing for 30min, releasing vacuum, maintaining for 30min, and circulating for 3 times. Finally obtaining the basswood wood fiber composite polymethyl methacrylate material. The content of polymethyl methacrylate in the composite material is 35.5 wt%.
Fig. 16 to 17 are an optical transmission curve and a stress-strain curve of the basswood wood fiber composite polymethylmethacrylate material in the comparative example, respectively. From FIGS. 16 to 17, it can be seen that the optical transmittance at 550nm of the basswood wood fiber composite polymethyl methacrylate material in the comparative example is 57%, the Young's modulus is 1.83GPa, and the breaking tensile strength is 39.6 MPa. The wood fiber composite resin material produced by the conventional method has lower optical transmittance and mechanical strength.
Claims (8)
1. The preparation method of the wood fiber transparent high-strength composite material is characterized by comprising the following steps:
placing a wood matrix in a chemical reagent, reacting for 1-10 hours at 25-100 ℃ to remove lignin in the wood matrix, then soaking the wood matrix in a solution containing a modifier, reacting for 12-24 hours, and performing hydrophobic and oleophylic modification treatment and drying treatment to obtain a hydrophobic and oleophylic delignified wood matrix, wherein the chemical reagent is at least one of a mixed solution of sodium hypochlorite and sodium hydroxide, hydrogen peroxide and perchloric acid, the modifier is n-octadecanethiol, n-dodecanethiol or stearic acid, and the concentration of the modifier in the solution containing the modifier is 0.01-0.1 mol/L;
injecting a high molecular polymer monomer solution into the obtained hydrophobic and oleophilic delignified wood matrix by a full cell method or a half-limiting injection method, and then initiating a polymerization reaction of the high molecular polymer monomer in the hydrophobic and oleophilic delignified wood matrix to obtain the wood fiber transparent high-strength composite material, wherein the high molecular polymer monomer solution is a methyl methacrylate solution, a bisphenol A glycidyl ether solution or a dimethyl siloxane solution;
the optical transmittance of the wood fiber transparent high-strength composite material at 550nm is 75-90%, the Young modulus of the wood fiber transparent high-strength composite material is 2.51-2.91 GPa, and the breaking tensile strength is 59.8-76.1 MPa.
2. The method according to claim 1, wherein the drying treatment is freeze drying, vacuum drying or supercritical drying.
3. The method according to claim 1, wherein the full cell method comprises:
placing the hydrophobic and oleophilic delignified wood matrix in a container for vacuum treatment, adding a high molecular polymer monomer solution until the container is filled with the hydrophobic and oleophilic delignified wood matrix, and removing the vacuum;
and then pressurizing to 1-3MPa until the immersion amount of the high molecular polymer monomer solution is saturated, and recovering to normal pressure after vacuum treatment.
4. The method of claim 1, wherein the semi-limiting process is: and (3) placing the hydrophobic and oleophilic delignified wood matrix into a container filled with a high molecular polymer monomer solution, pressurizing to 1-3MPa until the immersion amount of the high molecular polymer monomer solution is saturated, and recovering to normal pressure after vacuum treatment.
5. The method according to claim 3 or 4, wherein the vacuum degree of the vacuum treatment is 79 to 86kPa, and the time is 15 minutes to 2 hours.
6. The preparation method of claim 1, wherein the polymerization of the high molecular polymer monomer is initiated by ultraviolet irradiation or heating at 50 to 80 ℃; the power of the ultraviolet illumination is 10-30W, and the time is 1-3 hours.
7. A lignocellulosic transparent high-strength composite prepared according to the method of any one of claims 1 to 6, wherein the lignocellulosic transparent high-strength composite comprises a hydrophobic oleophilic delignified wood matrix and a high molecular polymer distributed in the pore structure of the hydrophobic oleophilic modified delignified wood matrix, the high molecular polymer being polymethyl methacrylate, epoxy resin or polydimethylsiloxane;
the optical transmittance of the wood fiber transparent high-strength composite material at 550nm is 75-90%, the Young modulus of the wood fiber transparent high-strength composite material is 2.51-2.91 GPa, and the breaking tensile strength is 59.8-76.1 MPa.
8. The transparent high-strength wood fiber composite material as claimed in claim 7, wherein the mass content of the polymer in the transparent high-strength wood fiber composite material is 30-70 wt%.
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| WO2008098037A2 (en) * | 2007-02-06 | 2008-08-14 | North Carolina State University | Polymer derivatives and composites from the dissolution of lignocellulosics in ionic liquids |
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