CN110757605A - Method for modifying artificial forest wood by phenol-aldehyde impregnation - Google Patents
Method for modifying artificial forest wood by phenol-aldehyde impregnation Download PDFInfo
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- CN110757605A CN110757605A CN201910934598.4A CN201910934598A CN110757605A CN 110757605 A CN110757605 A CN 110757605A CN 201910934598 A CN201910934598 A CN 201910934598A CN 110757605 A CN110757605 A CN 110757605A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/02—Processes; Apparatus
- B27K3/08—Impregnating by pressure, e.g. vacuum impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/34—Organic impregnating agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/52—Impregnating agents containing mixtures of inorganic and organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
- B27K5/001—Heating
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- Forests & Forestry (AREA)
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- Chemical And Physical Treatments For Wood And The Like (AREA)
Abstract
The invention discloses a method for modifying artificial forest wood by phenol-aldehyde impregnation, which is mainly characterized in that the artificial forest wood is subjected to respiratory cycle treatment in a mode of providing negative pressure, impregnating liquid A, applying positive pressure, discharging redundant liquid A, providing negative pressure, impregnating liquid B, applying positive pressure and discharging redundant liquid B, wherein the liquid A is a mixed liquid consisting of phenol, NaOH and water, and the liquid B is a formaldehyde solution, so that the artificial forest wood modified by phenol-aldehyde impregnation is obtained. The method provided by the invention treats the wood in an alternating circulation mode of negative pressure expiration and positive pressure inspiration by simulating a biological respiration principle, so that the impregnation property of the wood is improved bidirectionally, the impregnation effect and the uniformity are obviously improved, the reaction efficiency is high, and the performance is excellent.
Description
Technical Field
The invention belongs to the technical field of wood functional improvement, and relates to a method for impregnating and modifying artificial forest wood by phenol-aldehyde, in particular to a method for impregnating and modifying artificial forest wood by respiratory phenol-aldehyde oligomer.
Background
The area of the artificial forest in China is the first in the world, wherein eucalyptus and fir are mostly used in the south, and poplar and pine are mainly used in the north. The artificial forest wood has low density and poor material quality due to high growth speed and short felling period, and is generally used in the fields of low added value such as papermaking and artificial boards. The functional improvement of the artificial forest wood is an effective way for improving the performance and the added value of the wood. At present, the modifier is pressed into the wood mainly by adopting a pressurizing and dipping mode, so that the aim of strengthening the wood is fulfilled. However, when wood is impregnated, many organic agents are difficult to enter the wood, mainly due to the following two reasons: firstly, most of wood impregnated organic resins are reactants of 'two-step reaction-addition and polycondensation', and the molecules are subjected to polycondensation to form a macromolecular structure, so that the wood impregnated organic resins are difficult to enter the wood; secondly, the permeability is an important physical property of the wood, and can directly influence the process and effect of the impregnation modification. Researchers mainly destroy the tissue structure of wood by freezing treatment, steam explosion, microwave treatment and other methods, and further improve the permeability of the wood. However, the method has high requirements on equipment and process and is inconvenient to popularize and utilize. In view of the above circumstances, it is urgent to develop a novel method for modifying artificial forest wood.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for impregnating and modifying the wood of the artificial forest by phenol-aldehyde, which takes negative pressure (expiration) and positive pressure (inspiration) as a cycle to act on the wood alternately by simulating a biological respiration principle, has high reaction efficiency, is uniformly impregnated and has excellent performance.
In order to solve the technical problems, the invention adopts the following technical scheme.
A method for modifying artificial forest wood by phenol-aldehyde impregnation mainly comprises the steps of carrying out respiratory cycle treatment on the artificial forest wood in a mode of providing negative pressure, impregnating liquid A, applying positive pressure, discharging redundant liquid A, providing negative pressure, impregnating liquid B, applying positive pressure and discharging redundant liquid B, wherein the liquid A is a mixed liquid composed of phenol and a NaOH solution, and the liquid B is a formaldehyde solution, so that the artificial forest wood modified by phenol-aldehyde impregnation is obtained.
The method for impregnating and modifying the artificial forest wood by using the phenol-aldehyde preferably comprises the following steps:
(1) placing the artificial forest wood in a reaction container, vacuumizing to form negative pressure and maintaining the pressure to pump out air in gaps of wood cells, adding the solution A to immerse the wood, unloading the negative pressure after liquid inlet is finished, applying positive pressure and maintaining the pressure in the reaction container to fully immerse the solution A in the wood, and discharging redundant solution A;
(2) vacuumizing the reaction container with the discharged redundant liquid A to form negative pressure and maintaining the pressure, pumping out air and residual moisture in gaps of wood cell cavities, adding the liquid B to immerse the wood, unloading the negative pressure after liquid inlet is finished, applying positive pressure and maintaining the pressure in the reaction container to fully immerse the liquid B in the wood, and discharging the redundant liquid B;
(3) and (3) performing one-time breathing type circulation in the treatment process from the step (1) to the step (2), repeating the circulation for multiple times, and performing vacuum heating and curing to obtain the phenol-aldehyde impregnated and modified artificial forest wood.
In the method for impregnating and modifying the artificial forest wood by using the phenol-aldehyde, preferably, the NaOH solution is composed of NaOH and water, the mass ratio of the phenol to the NaOH to the formaldehyde solution is 185-190: 50-70: 70-117: 240-570, and the mass fraction of the formaldehyde solution (namely the formaldehyde aqueous solution) is 37%. The mass fraction of the NaOH solution is preferably 30-50%.
In the method for impregnating and modifying the artificial forest wood by using the phenol-aldehyde, the mass ratio of the phenol to the NaOH to the formaldehyde solution is preferably 188.22: 50-70: 70-117: 243.49-568.14.
In the method for impregnating and modifying the artificial forest wood by using the phenol-aldehyde, the solution A is preferably prepared by the following steps: and dissolving NaOH in water to prepare a NaOH solution, and then melting phenol and uniformly mixing with the NaOH solution to obtain solution A.
In the method for impregnating and modifying the artificial forest wood by using the phenol-aldehyde, preferably, the artificial forest wood is dried to the water content of 8-12% and then is subjected to respiratory cycle treatment.
In the method for impregnating and modifying the artificial forest wood by using the phenol-aldehyde, preferably, in the step (1), the vacuum pumping is carried out until the pressure is between-0.085 MPa and-0.1 MPa, the negative pressure is kept for 10min to 30min, the positive pressure is between 0.3MPa and 1.1MPa, and the positive pressure is kept for 30min to 50 min.
In the method for impregnating and modifying the artificial forest wood by using the phenol-aldehyde, preferably, in the step (2), the vacuum pumping is carried out until the pressure is between-0.085 MPa and-0.1 MPa, the negative pressure is kept for 10min to 30min, the positive pressure is between 0.3MPa and 1.1MPa, and the positive pressure is kept for 30min to 50 min.
In the method for impregnating and modifying the artificial forest wood by using the phenol-aldehyde, the number of the circulation in the step (3) is preferably 1 to 12; the temperature of the vacuum heating curing is 50-80 ℃, and the time of the vacuum heating curing is 6-24 h.
In the method for modifying artificial forest wood by phenol-aldehyde impregnation, the artificial forest wood preferably comprises one or more of fir, eucalyptus, pine and poplar.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a method for impregnating and modifying artificial forest wood by using respiratory phenolic aldehyde oligomer, which adopts micromolecular reaction raw materials as an impregnant, is combined with a newly designed impregnation process, improves the impregnation property of the wood in a double phase manner, obviously improves the impregnation effect and the uniformity, and solves the technical key for impregnating the artificial forest wood. Resin obtained by a two-step reaction formula (addition reaction and polycondensation reaction) is mostly used for traditional resin impregnated modified wood, but the resin forms a macromolecular structure due to the completion of polycondensation, so that the penetrability of the resin in the wood is influenced, the impregnation efficiency is low, and the uniformity is poor; the invention adopts phenol and aldehyde micromolecule raw materials to dip wood, the molecules are not condensed, and the molecular weight is smaller. The small molecule phenol-aldehyde can be easily and uniformly infiltrated into the wood, and the impregnation depth and uniformity can be obviously improved.
(2) Compared with the traditional phenolic resin impregnation modified wood, the method for impregnating and modifying the wood by using the respiratory phenol-aldehyde reduces the curing time of the phenol-aldehyde in the wood and improves the efficiency of impregnating and modifying the wood.
(3) Compared with the traditional phenolic resin impregnated modified wood, the method for strengthening the wood by using the respiratory phenol-aldehyde provided by the invention has the advantages that through the circulating action of external pressure, the modifier is pushed into the wood, meanwhile, the internal channel of the wood is effectively opened, and the impregnation degree and the uniformity of the modifier in the wood are obviously improved.
(4) The respiratory phenol-aldehyde impregnated modified wood provided by the invention can be used in the fields of furniture, floors, buildings and the like, and can even meet the requirements of modern fabricated wood structure engineering materials.
Drawings
FIG. 1 is a schematic diagram of the principle of the method for modifying artificial forest wood by phenol-aldehyde impregnation in the embodiment of the invention.
Detailed Description
The invention is further described below with reference to the drawings of the specification and to specific preferred embodiments, without thereby limiting the scope of protection of the invention.
The materials and equipment used in the following examples are commercially available.
Example 1
The method for impregnating and modifying the artificial forest wood by the phenol-aldehyde comprises the following steps as shown in figure 1:
(1) sawing fir wood into 10mm × 10mm × 200mm, and drying until water content is 12%. 50g of NaOH was dissolved in 117g of water and mixed with 188.22g of molten phenol to prepare solution A for use. The method comprises the steps of putting dried fir wood with the water content of 12% into an impregnation tank, vacuumizing the impregnation tank to-0.085 MPa, maintaining the pressure for 10min to enable air in pores of wood cells to be extracted, then starting to feed liquid, sucking a medicament liquid A into the tank through negative pressure in the tank and enabling the medicament liquid A to submerge the wood, unloading the negative pressure after the liquid A is fed, applying positive pressure of 0.5MPa into the tank, maintaining the pressure for 50min, aiming at providing thrust for the liquid A fed under the negative pressure condition to enable the wood to be completely impregnated, accelerating the impregnation speed, effectively shortening the impregnation time, and discharging redundant liquid A, wherein the redundant liquid A is discharged by utilizing the positive pressure in the tank, and when the liquid A is generally discharged, the positive pressure in the tank is already discharged.
(2) Vacuumizing the impregnation tank with the discharged liquid A to form negative pressure of-0.085 MPa, maintaining the pressure for 10min to ensure that air and residual moisture in the gaps of the wood cell cavities are filled, adding 243.49g B liquid to immerse the wood, wherein the liquid B is formaldehyde solution with the mass fraction of 37%, unloading the negative pressure after the liquid B is filled, applying positive pressure of 0.5MPa to the tank, maintaining the pressure for 50min to fully impregnate the liquid B into the wood, and discharging redundant liquid B, wherein the redundant liquid B is discharged by utilizing the positive pressure in the tank.
(3) And (3) alternately circulating the wood for 2 times by taking the negative pressure-impregnation liquid A-positive pressure-liquid A discharge-negative pressure-impregnation liquid B-positive pressure-liquid B discharge in the steps (1) to (2) as a breathing type circulation. And taking out the wood subjected to the impregnation modification, washing the surface with water, and then putting the wood into a vacuum drying oven at 50 ℃ for curing for 6 hours to obtain the phenol-aldehyde impregnation modified artificial forest wood.
Example 2
The method for impregnating and modifying the artificial forest wood by the phenol-aldehyde comprises the following steps as shown in figure 1:
(1) sawing poplar wood into 20mm × 20mm × 400mm, and drying until the water content is 10%. 60g of NaOH is dissolved in 90g of water, and the NaOH and 188.22g of phenol are melted and mixed uniformly to prepare solution A for later use. Putting dried fir wood with the water content of 10% into a dipping tank, vacuumizing the dipping tank to-0.095 MPa, maintaining the pressure for 20min, then starting to feed liquid, sucking the medicament A liquid into the tank through the negative pressure in the tank and submerging the wood, unloading the negative pressure after the A liquid is fed, applying the positive pressure of 0.9MPa into the tank, and maintaining the pressure for 40min, so that the aim of applying a thrust to the A liquid fed under the negative pressure condition is fulfilled, the wood is more completely dipped, the dipping speed is accelerated, the dipping time can be effectively shortened, and the redundant A liquid is discharged.
(2) And (3) vacuumizing the impregnation tank with the liquid A discharged to form negative pressure of-0.095 MPa, maintaining the pressure for 20min, adding 405.81g of 37 wt% formaldehyde solution of the liquid B to immerse the wood, unloading the negative pressure after the liquid B is fed, applying positive pressure of 0.9MPa to the tank, maintaining the pressure for 40min, and discharging the redundant liquid B.
(3) And (3) alternately and totally circulating the wood for 6 times by taking the negative pressure-impregnation liquid A-positive pressure-liquid A discharge-negative pressure-impregnation liquid B-positive pressure-liquid B discharge in the steps (1) to (2) as a respiratory cycle. And taking out the impregnated and modified wood, washing the surface with water, and curing in a vacuum drying oven at 70 ℃ for 18h to obtain the phenol-aldehyde impregnated and modified artificial forest wood.
Example 3
The method for impregnating and modifying the artificial forest wood by the phenol-aldehyde comprises the following steps as shown in figure 1:
(1) sawing pine wood into 40mm × 40mm × 800mm, and drying until the water content is 8%. 70g of NaOH is dissolved in 70g of water, and the NaOH and 188.22g of phenol are melted and mixed evenly to prepare solution A for later use. Putting dried fir wood with the water content of 10% into an impregnation tank, vacuumizing the impregnation tank to-0.1 MPa, maintaining the pressure for 30min, then starting to feed liquid, sucking the medicament A liquid into the tank through the negative pressure in the tank and submerging the wood, unloading the negative pressure after the A liquid is fed, applying the positive pressure of 1.1MPa into the tank, and maintaining the pressure for 30min, so that the aim of applying a thrust to the A liquid fed under the negative pressure condition is fulfilled, the wood is more completely impregnated, the impregnation speed is accelerated, and the impregnation time can be effectively shortened; the excess solution A was discharged.
(2) And (3) vacuumizing the impregnation tank with the liquid A discharged to form negative pressure of-0.1 MPa, maintaining the pressure for 30min, adding 568.14g of 37 wt% formaldehyde solution of the liquid B to immerse the wood, unloading the negative pressure after the liquid B is fed, applying positive pressure of 1.1MPa to the tank, maintaining the pressure for 30min, and discharging the redundant liquid B.
(3) The wood is alternately circulated for 12 times by taking the negative pressure-impregnation liquid A-positive pressure-discharge liquid A-negative pressure-impregnation liquid B-positive pressure-discharge liquid B as a breathing type cycle. And taking out the impregnated and modified wood, washing the surface with water, and curing in a vacuum drying oven at 70 ℃ for 24 hours to obtain the phenol-aldehyde impregnated and modified artificial forest wood.
The results of testing the properties of the above-mentioned examples 1, 2, 3 and unmodified wood are shown in table 1. As can be seen from the detection results, the wood weight and density are remarkably improved after the phenol-aldehyde modification, thereby indicating that the phenol-aldehyde is successfully impregnated into the wood. Meanwhile, the mechanical strength of the modified wood is obviously superior to that of unmodified wood, and further shows that phenol-aldehyde is successfully impregnated into the wood and undergoes polymerization and curing reaction to generate macromolecular phenolic resin, so that the wood cavity is filled, and the mechanical property of the wood is enhanced.
Table 1 phenol-aldehyde modified wood property comparison
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make many possible variations and modifications to the disclosed embodiments, or equivalent modifications, without departing from the spirit and scope of the invention, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical scheme of the present invention, unless the contents of the technical scheme of the present invention are departed from.
Claims (10)
1. A method for impregnating and modifying artificial forest wood by phenol-aldehyde is characterized in that the artificial forest wood is subjected to respiratory cycle treatment in a mode of providing negative pressure, impregnating liquid A, applying positive pressure, discharging redundant liquid A, providing negative pressure, impregnating liquid B, applying positive pressure and discharging redundant liquid B, the liquid A is a mixed liquid composed of phenol and NaOH solution, and the liquid B is formaldehyde solution, so that the artificial forest wood impregnated and modified by phenol-aldehyde is obtained.
2. The method of phenol-aldehyde impregnation of modified forest wood according to claim 1, comprising the steps of:
(1) placing the artificial forest wood in a reaction container, vacuumizing to form negative pressure and maintaining the pressure to pump out air in gaps of wood cells, adding the solution A to immerse the wood, unloading the negative pressure after liquid inlet is finished, applying positive pressure and maintaining the pressure in the reaction container to fully immerse the solution A in the wood, and discharging redundant solution A;
(2) vacuumizing the reaction container with the discharged redundant liquid A to form negative pressure and maintaining the pressure, pumping out air and residual moisture in gaps of wood cell cavities, adding the liquid B to immerse the wood, unloading the negative pressure after liquid inlet is finished, applying positive pressure and maintaining the pressure in the reaction container to fully immerse the liquid B in the wood, and discharging the redundant liquid B;
(3) and (3) performing one-time breathing type circulation in the treatment process from the step (1) to the step (2), repeating the circulation for multiple times, and performing vacuum heating and curing to obtain the phenol-aldehyde impregnated and modified artificial forest wood.
3. The method for impregnating and modifying artificial forest wood by phenol-aldehyde according to claim 1 or 2, wherein the NaOH solution is composed of NaOH and water, the mass ratio of the phenol, the NaOH, the water and the formaldehyde solution is 185-190: 50-70: 70-117: 240-570, and the mass fraction of the formaldehyde solution is 37%.
4. The method for phenol-aldehyde impregnation modification of artificial forest wood according to claim 3, wherein the mass ratio of the phenol, NaOH, water and formaldehyde solution is 188.22: 50-70: 70-117: 243.49-568.14.
5. The method for phenol-aldehyde impregnation of modified forest wood according to claim 3, wherein the solution A is prepared by: and dissolving NaOH in water to prepare a NaOH solution, and then melting phenol and uniformly mixing with the NaOH solution to obtain solution A.
6. The method for impregnating and modifying the wood of the artificial forest according to the phenol-aldehyde according to the claim 1 or 2, wherein the wood of the artificial forest is dried to the water content of 8-12% and then is subjected to the respiratory cycle treatment.
7. The method for phenol-aldehyde impregnation of modified artificial forest wood according to claim 2, wherein in the step (1), the vacuum is applied to-0.085 MPa to-0.1 MPa, the negative pressure is maintained for 10min to 30min, the positive pressure is 0.3MPa to 1.1MPa, and the positive pressure is maintained for 30min to 50 min.
8. The method for phenol-aldehyde impregnation of modified artificial forest wood according to claim 2, characterized in that, in the step (2), the vacuum is pumped to-0.085 MPa to-0.1 MPa, the negative pressure is maintained for 10min to 30min, the positive pressure is 0.3MPa to 1.1MPa, and the positive pressure is maintained for 30min to 50 min.
9. The method for phenol-aldehyde impregnation of modified forest wood according to claim 2, wherein in the step (3), the number of the cycles is 1 to 12; the temperature of the vacuum heating curing is 50-80 ℃, and the time of the vacuum heating curing is 6-24 h.
10. The method of phenol-aldehyde impregnation of modified forest wood according to claim 1 or 2, wherein the forest wood comprises one or more of fir, eucalyptus, pine and poplar.
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