阅读说明：本技术 一种糠醇改性液及其制备方法与应用 (Furfuryl alcohol modified liquid and preparation method and application thereof ) 是由 曹金珍 张亮亮 薛静 张润华 冉阳杨 张少迪 张明昌 王望 彭尧 于 2021-08-27 设计创作，主要内容包括：本发明提供一种糠醇改性液及其制备方法与应用。所述糠醇改性液含有催化剂；所述催化剂包括硼系化合物和磷系化合物；所述硼系化合物选自硼酸、磷酸硼、硼酸锌中的一种或多种；所述磷系化合物选自磷酸氢二铵、磷酸二氢铵、植酸中的一种或多种。该糠醇改性液贮存稳定性好,将其用于木材改性中,可得到尺寸稳定性、阻燃性和耐腐性俱佳的改性木材,实现了糠醇改性技术的低增重、高性能,达到了一剂多效的要求。(The invention provides a furfuryl alcohol modified liquid and a preparation method and application thereof. The furfuryl alcohol modified solution contains a catalyst; the catalyst comprises a boron compound and a phosphorus compound; the boron compound is selected from one or more of boric acid, boron phosphate and zinc borate; the phosphorus compound is selected from one or more of diammonium hydrogen phosphate, ammonium dihydrogen phosphate and phytic acid. The furfuryl alcohol modified liquid has good storage stability, and when the furfuryl alcohol modified liquid is used for modifying wood, modified wood with good dimensional stability, flame retardance and corrosion resistance can be obtained, so that the low weight increment and high performance of a furfuryl alcohol modification technology are realized, and the requirement of one agent for multiple effects is met.)

1. A furfuryl alcohol-modified liquid is characterized by containing a catalyst;

the catalyst comprises a boron compound and a phosphorus compound; the boron compound is selected from one or more of boric acid, boron phosphate and zinc borate; the phosphorus compound is selected from one or more of diammonium hydrogen phosphate, ammonium dihydrogen phosphate and phytic acid.

2. The furfuryl alcohol-modified liquid according to claim 1, wherein the catalyst is any one of the following:

(1) a mixture of boron phosphate and ammonium dihydrogen phosphate;

(2) a mixture of zinc borate and phytic acid;

(3) a mixture of boric acid and ammonium dihydrogen phosphate.

3. The furfuryl alcohol-modified liquid according to claim 1 or 2, wherein the mass ratio of the boron-based compound to the phosphorus-based compound is 1 to 5: 0.2 to 1, preferably 1 to 4: 0.2 to 0.8, and more preferably 2 to 4: 0.4 to 0.8.

4. The furfuryl alcohol-modified liquid according to claim 1 or 2, comprising, by mass, 10 to 30% of furfuryl alcohol, 1 to 5% of a boron-based compound, 0.2 to 1% of a phosphorus-based compound, and the balance being a solvent;

preferably, the solvent comprises 10 to 20 percent of furfuryl alcohol, 1 to 4 percent of boron compound, 0.2 to 0.8 percent of phosphorus compound and the balance of solvent;

further preferably, the solvent contains 10 to 15% of furfuryl alcohol, 2 to 4% of a boron compound, 0.4 to 0.8% of a phosphorus compound, and the balance being a solvent.

5. The furfuryl alcohol-modified liquid according to any one of claims 1 to 4, wherein the solvent is water.

6. A process for producing a furfuryl alcohol-modified liquid according to any one of claims 1 to 5, characterized by comprising the steps of:

dissolving the catalyst in a solvent at 30-35 ℃ to obtain a mixed solution;

and mixing the mixed solution with furfuryl alcohol to obtain the furfuryl alcohol modified solution.

7. Use of the furfuryl alcohol-modified liquid of any one of claims 1 to 5 or prepared by the process of claim 6 for the modification of wood; preferably, the wood is poplar, fir, eucalyptus or pine.

8. A method for preparing furfuryl alcohol modified wood, comprising: modifying wood by using the furfuryl alcohol-modified liquid according to any one of claims 1 to 5 or the furfuryl alcohol-modified liquid prepared by the preparation method according to claim 6; preferably, the modification is a modification treatment by the full cell method.

9. The method for producing furfuryl alcohol-modified wood according to claim 8, comprising the steps of:

(1) placing wood in a vacuum degree of-0.05 to-0.1 MPa for vacuum treatment for 30 to 60min, introducing the furfuryl alcohol modified liquid of any one of claims 1 to 5 or the furfuryl alcohol modified liquid prepared by the preparation method of claim 6, and performing pressure treatment for 60 to 120min under the pressure of 0.5 to 1.0 MPa;

(2) immobilization: taking out the treated wood, sealing the wood by using a film, standing the wood for 1 to 3 days at normal temperature, then air-drying the wood for 1 to 5 days, sealing the wood by using a heat-resistant material, and curing the wood for 1 to 8 hours at the temperature of 100 to 130 ℃;

(3) and (3) drying: removing the sealed package, and drying for 24-48 h at 40-80 ℃.

10. The method for producing furfuryl alcohol-modified wood according to claim 8 or 9, comprising the steps of:

(1) placing wood in a vacuum degree of-0.75 to-0.1 MPa for vacuum treatment for 45 to 60min, introducing the furfuryl alcohol modified liquid according to any one of claims 1 to 5 or the furfuryl alcohol modified liquid prepared by the preparation method according to claim 6 into a reaction kettle, and performing pressure treatment for 90 to 120min under the pressure of 0.5 to 0.75 MPa;

(2) immobilization: taking out the treated wood, sealing the wood by using a film, standing the wood for 1 to 3 days at normal temperature, then air-drying the wood for 2 to 4 days, sealing the wood by using a heat-resistant material, and curing the wood for 4 to 8 hours at the temperature of 100 to 120 ℃;

(3) and (3) drying: removing the sealing package, and drying for 36-48 h at the temperature of 60-80 ℃.

Technical Field

The invention belongs to the technical field of wood processing, and particularly relates to a furfuryl alcohol modified liquid as well as a preparation method and application thereof.

Background

With the advance of carbon neutralization, the demand of the society on wood is continuously increased, and the wood of the artificial forest becomes an important way for increasing carbon sink resources and relieving the contradiction between supply and demand of the wood. The problems of soft, easy deformation, flammability, easy decay and the like of the artificial forest wood generally exist, so that the modification of the artificial forest wood to improve the dimensional stability, the flame retardance and the corrosion resistance of the artificial forest wood is an important means for improving the added value of the wood and prolonging the service life of the wood.

The wood furfuryl alcohol modification technology is a chemical modification technology that furfuryl alcohol micromolecules are soaked in wood, and are subjected to polycondensation and filling wood pores under the action of an acid catalyst. The size stability, durability and other properties of the modified wood are obviously improved, the color of the wood is deepened, and the wood can imitate rare hard broad-leaved wood.

Chinese patent application 201811252454.2 discloses a furfuryl alcohol resin wood modifier with good waterproof, moisture-resistant and impact-resistant properties, which comprises the following components: 10-50% of furfuryl alcohol, 2-5% of polyvinyl alcohol, 0.3-23% of a catalyst, 1-4% of a stabilizer and 40-85% of a solvent. The wood modifier takes maleic anhydride, sulfuric acid or citric acid as a catalyst, takes polyvinyl alcohol 300 as a functional modifier, and combines sodium tetraborate or ammonium bicarbonate as a stabilizer to prepare the polyvinyl alcohol/furfuryl alcohol mixed modifier, so that the modified wood has good dimensional stability and excellent impact toughness, the service life of the modified material is prolonged, and the utilization rate of the furfuryl alcohol modified material is improved. The Chinese patent application 201710772170.5 provides a preparation method of reinforced and flame-retardant modified wood based on environment-friendly resin, wherein 20-40% of furfuryl alcohol is used as a resin modifier, 1-7% of ammonium dihydrogen phosphate is added to be used as a flame retardant, maleic anhydride is used as a catalyst, and ethanol and water are used as solvents to prepare an organic-inorganic composite wood modification solution, so that the performances of the wood, such as dimensional stability, density, bending elastic modulus, and pressure resistance along grain, are remarkably improved, meanwhile, the wood is endowed with better flame retardance, the application range of the wood is widened, and high value-added utilization of the wood is realized.

Acidic catalysts currently used, such as oxalic acid, maleic anhydride, etcMineral acids such as acid, phosphoric acid and sulfuric acid, Lewis acids such as zinc chloride and titanium chloride, iodine and the like cannot meet the requirements of low cost and high performance, and meanwhile, the catalysts are violent in reaction and single in function, and cannot be used for further improving the flame retardant performance and the biological deterioration resistance of the wood in cooperation with the furfuryl alcohol resin.

In addition, in order to maintain excellent size stability, mechanical property, biological deterioration resistance and other properties of the furfuryl alcohol modified material, the traditional furfuryl alcohol resin wood modified liquid has higher concentration of furfuryl alcohol and large wood weight gain rate, so that the popularization cost of the furfuryl alcohol modified material is increased; in addition, the traditional furfuryl alcohol resin wood modification liquid has the problems of poor storage stability, difficult recycling after use and the like, and limits the further development of the furfuryl alcohol resin modification technology. Therefore, finding an acid catalyst which is mild in catalysis and one agent of the acid catalyst has multiple effects is a research direction with important application value in the wood furfuryl alcohol modification technology.

Disclosure of Invention

The invention provides a furfuryl alcohol modified liquid, a preparation method and application thereof, wherein the furfuryl alcohol modified liquid adopts boron/phosphorus functional inorganic substances as a catalyst, is prepared according to a certain proportion and has good storage stability, and can be used for wood modification to obtain modified wood with good dimensional stability, flame retardance and corrosion resistance, so that the low weight gain and high performance of a furfuryl alcohol modification technology are realized, and the requirement of one agent for multiple effects is met.

Specifically, the invention provides the following technical scheme:

a furfuryl alcohol-modified liquid containing a catalyst;

the catalyst comprises a boron compound and a phosphorus compound; the boron compound is selected from one or more of boric acid, boron phosphate and zinc borate; the phosphorus compound is selected from one or more of diammonium hydrogen phosphate, ammonium dihydrogen phosphate and phytic acid.

The acid catalyst in the furfuryl alcohol modified liquid can effectively catalyze the polycondensation and solidification of furfuryl alcohol in wood, so that a hydrophobic three-dimensional net structure is formed, and the dimensional stability of the wood is improved. The furfuryl alcohol modified solution is a catalyst obtained by compounding a boron compound and a phosphorus compound, has excellent storage stability on the premise of ensuring the catalytic efficiency, and simultaneously improves the flame retardance and corrosion resistance of wood modified by the furfuryl alcohol modified solution.

In a preferred embodiment, the catalyst is any one of the following:

(1) a mixture of boron phosphate and ammonium dihydrogen phosphate;

(2) a mixture of zinc borate and phytic acid;

(3) a mixture of boric acid and ammonium dihydrogen phosphate.

In a preferred embodiment, the mass ratio of the boron compound to the phosphorus compound is 1 to 5: 0.2 to 1, more preferably 1 to 4: 0.2 to 0.8, and more preferably 2 to 4: 0.4 to 0.8. The boron compound and the phosphorus compound are mixed at a specific mass concentration to be used as a catalyst, so that the storage stability of the modified liquid is more excellent.

In a preferred embodiment, the furfuryl alcohol-modified liquid comprises, by mass, 10-30% of furfuryl alcohol, 1-5% of a boron compound, 0.2-1% of a phosphorus compound, and the balance of a solvent.

In a more preferred embodiment, the furfuryl alcohol-modified liquid comprises, by mass, 10 to 20% of furfuryl alcohol, 1 to 4% of a boron compound, 0.2 to 0.8% of a phosphorus compound, and the balance of a solvent.

In a further preferred embodiment, the furfuryl alcohol-modified liquid comprises, by mass, 10-15% of furfuryl alcohol, 2-4% of a boron compound, 0.4-0.8% of a phosphorus compound, and the balance of a solvent.

In a preferred embodiment, the solvent is water.

The invention also provides a preparation method of the furfuryl alcohol modified liquid, which comprises the following steps:

dissolving the catalyst in a solvent at 30-35 ℃ to obtain a mixed solution;

and mixing the mixed solution with furfuryl alcohol to obtain the furfuryl alcohol modified solution.

The invention also protects the application of the furfuryl alcohol modified liquid or the furfuryl alcohol modified liquid prepared by the preparation method in wood modification; preferably, the wood is poplar, fir, eucalyptus or pine.

The invention also provides a preparation method of the furfuryl alcohol modified wood, which comprises the following steps: modifying wood by using the furfuryl alcohol modified liquid or the furfuryl alcohol modified liquid prepared by the preparation method; preferably, the modification is a modification treatment by the full cell method.

In a preferred embodiment, the preparation method comprises the steps of:

(1) placing the wood in a vacuum degree of-0.05 to-0.1 MPa for vacuum treatment for 30 to 60min, introducing the furfuryl alcohol modified liquid or the furfuryl alcohol modified liquid prepared by the preparation method, and performing pressurization treatment for 60 to 120min under the pressure of 0.5 to 1.0 MPa;

(2) immobilization: taking out the treated wood, sealing the wood by using a film, standing the wood for 1 to 3 days at normal temperature, then air-drying the wood for 1 to 5 days, sealing the wood by using a heat-resistant material, and curing the wood for 1 to 8 hours at the temperature of 100 to 130 ℃;

(3) and (3) drying: removing the sealed package, and drying for 24-48 h at 40-80 ℃.

Through the vacuum pressure impregnation, curing and drying process, the furfuryl alcohol resin and the boron/phosphorus functional inorganic substance can be fixed in the wood cell wall, and the loss resistance of the functional inorganic substance is improved.

In a further preferred embodiment, the preparation process comprises the steps of:

(1) placing the wood in a vacuum degree of-0.75 to-0.1 MPa for vacuum treatment for 45 to 60min, introducing the furfuryl alcohol modified liquid or the furfuryl alcohol modified liquid prepared by the preparation method into a reaction kettle, and pressurizing for 90 to 120min under the pressure of 0.5 to 0.75 MPa;

(2) immobilization: taking out the treated wood, sealing the wood by using a film, standing the wood for 1 to 3 days at normal temperature, then air-drying the wood for 2 to 4 days, sealing the wood by using a heat-resistant material, and curing the wood for 4 to 8 hours at the temperature of 100 to 120 ℃;

(3) and (3) drying: removing the sealing package, and drying for 36-48 h at the temperature of 60-80 ℃.

The invention has the following beneficial effects:

(1) according to the invention, the furfuryl alcohol modified liquid with good storage stability is prepared by compounding a boron compound and a phosphorus compound as a catalyst, and wood is treated by a vacuum pressurization impregnation process so as to realize cell wall modification, thereby improving the dimensional stability, the flame retardance and the corrosion resistance of the wood, realizing multiple effects of one agent, and being beneficial to further popularization of the technology in the fields of buildings and outdoor building materials.

(2) In the furfuryl alcohol modified liquid provided by the invention, the boron compound and the phosphorus compound are used as catalysts to catalyze furfuryl alcohol to be cured in wood, and are also used as wood protective agents to endow the wood with excellent flame-retardant smoke-inhibiting performance and corrosion resistance, and meanwhile, the furfuryl alcohol resin can effectively slow down the loss of the boron compound and the phosphorus compound due to the wrapping effect of the furfuryl alcohol resin on the agents.

(3) The furfuryl alcohol modification liquid provided by the invention has the advantages of low raw material cost, simple preparation method, capability of being separated, recovered and recycled, and suitability for large-scale industrial application.

Drawings

FIG. 1 is a graph showing the results of a one-week standing comparison of the furfuryl alcohol-modified liquid (FA-BA/ADP) obtained in example 4 and the furfuryl alcohol-modified liquid (FA-MA) obtained in comparative example 3.

FIG. 2 is a graph showing the change in boron content in the run-off experiments for the furfuryl alcohol modified wood obtained in example 4 and the furfuryl alcohol modified wood obtained in comparative example 2.

FIG. 3 is a graph of the change in phosphorus content in the run-off experiments for furfuryl alcohol modified wood from example 4 and furfuryl alcohol modified wood from comparative example 2.

FIG. 4 is a cross-sectional electron micrograph and a power spectrum of furfuryl alcohol-modified wood obtained in example 4.

FIG. 5 is a comparison of the char yield of cone calorimetry experiments for the material obtained in comparative example 1 and the furfuryl alcohol-modified wood obtained in example 4.

FIG. 6 is a comparison of the white rot and brown rot resistance of the material obtained in comparative example 1 and the furfuryl alcohol-modified wood obtained in comparative example 3 and example 4 before the run-off test.

Detailed Description

The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications.

In the following examples, the equipment and the like used are not shown to manufacturers, and are all conventional products available from regular vendors. The process is conventional unless otherwise specified, and the starting materials are commercially available from the open literature.

The specific method for preparing furfuryl alcohol resin modified wood in the following examples and comparative examples is as follows:

the wood is modified by adopting a vacuum pressure impregnation treatment process: regularly placing the wood test piece in an impregnation tank, performing vacuum treatment at a relative vacuum degree of-0.75 MPa for 45 min; injecting furfuryl alcohol modified solution, relieving vacuum, pressurizing to relative pressure of 0.5MPa, and maintaining pressure for 90 min; and releasing the pressure, taking out the wood test piece, sealing the wood test piece by using a preservative film, standing the wood test piece for 2 days at room temperature, and removing the preservative film after the furfuryl alcohol is fully diffused in the wood. Air-drying the test piece for 2 days, sealing the test piece by using aluminum foil paper, curing the test piece in a 105 ℃ forced air drying oven for 8 hours, and removing the tin foil paper after the furfuryl alcohol resin is completely cured; and finally drying in a forced air drying oven at 80 ℃ for 48 hours to obtain the product.

Example 1

Putting 810mL of distilled water into a 2L glass beaker, preheating to 35 ℃, then sequentially and slowly adding 32g of boron phosphate and 8g of phytic acid, stirring for 10min by using a magnetic stirrer until the solid is completely dissolved to obtain a clear, transparent and uniform solution, cooling the mixed solution to room temperature, slowly adding 150g of furfuryl alcohol, and magnetically stirring for 10min to obtain a furfuryl alcohol modified solution.

The furfuryl alcohol modified liquid prepared above was used to prepare a standard specimen of the furfuryl alcohol resin modified wood of example 1.

Example 2

818mL of distilled water is put into a 2L glass beaker and preheated to 35 ℃, then 24g of boron phosphate and 8g of ammonium dihydrogen phosphate are slowly added in sequence, a magnetic stirrer is used for stirring for 10min until the solid is completely dissolved to obtain a clear, transparent and uniform solution, 150g of furfuryl alcohol is slowly added after the mixed solution is cooled to room temperature, and magnetic stirring is carried out for 10min to obtain the furfuryl alcohol modified solution.

The furfuryl alcohol resin modified wood standard test piece of example 2 was prepared using the furfuryl alcohol modified liquid prepared above.

Example 3

Putting 810mL of distilled water into a 2L glass beaker, preheating to 35 ℃, then sequentially and slowly adding 32g of zinc borate and 8g of phytic acid, stirring for 10min by using a magnetic stirrer until the solid is completely dissolved to obtain a clear, transparent and uniform solution, cooling the mixed solution to room temperature, slowly adding 150g of furfuryl alcohol, and magnetically stirring for 10min to obtain a furfuryl alcohol modified solution.

The furfuryl alcohol resin modified wood standard test piece of example 3 was prepared using the furfuryl alcohol modified liquid prepared above.

Example 4

Putting 810mL of distilled water into a 2L glass beaker, preheating to 35 ℃, then sequentially and slowly adding 32g of boric acid and 8g of ammonium dihydrogen phosphate, stirring for 10min by using a magnetic stirrer until the solid is completely dissolved to obtain a clear, transparent and uniform solution, slowly adding 150g of furfuryl alcohol after the mixed solution is cooled to room temperature, and magnetically stirring for 10min to obtain the furfuryl alcohol modified solution.

The furfuryl alcohol resin modified wood standard test piece of example 4 was prepared using the furfuryl alcohol modified liquid prepared above.

FIG. 4 is a cross-sectional electron micrograph and a power spectrum of furfuryl alcohol-modified wood obtained in example 4.

Comparative example 1

The material (untreated wood) was dried at 80 ℃ for 48 hours to prepare standard wood specimens.

Comparative example 2

960mL of distilled water is put into a 2L glass beaker and preheated to 35 ℃, then 32g of boric acid and 8g of ammonium dihydrogen phosphate are sequentially and slowly added, a magnetic stirrer is used for stirring for 10min until the solid is completely dissolved to obtain a clear, transparent and uniform solution, and the modified solution is obtained after the mixed solution is cooled to room temperature.

The modified wood standard test piece of comparative example 2 was prepared using the modified solution prepared above.

Comparative example 3

818mL of distilled water is put into a 2L glass beaker and preheated to 35 ℃, then 32g of maleic anhydride is slowly added, a magnetic stirrer is used for stirring for 10min until the solid is completely dissolved to obtain a clear, transparent and uniform solution, 150g of furfuryl alcohol is slowly added after the mixed solution is cooled to room temperature, and the magnetic stirring is carried out for 10min to obtain the traditional furfuryl alcohol modified solution.

The standard test piece of the conventional furfuryl alcohol resin modified wood of comparative example 3 was prepared using the conventional furfuryl alcohol-modified liquid prepared above.

Experimental example 1

The modified liquids prepared in examples 1 to 4 and comparative example 3 were left at room temperature for seven days, and the delamination (storage stability) of the modified liquids was observed on days 1, 3 and 7, respectively, and the results are shown in Table 1.

Table 1 shows the solution separation after the modification solution was allowed to stand for one week.

FIG. 1 is a graph showing the comparison of the effects of furfuryl alcohol-modified liquid (FA-BA/ADP) obtained in example 4 and furfuryl alcohol-modified liquid (FA-MA) obtained in comparative example 3 after standing for one week, and it can be seen from FIG. 1 that the furfuryl alcohol-modified liquid obtained in example 4 is transparent and has no distinct layering, and the stability of the furfuryl alcohol-modified liquid is significantly better than that of the furfuryl alcohol-modified liquid obtained in comparative example 3.

Experimental example 2

The modified solutions prepared in examples 1 to 4 and comparative example 3 were cyclically impregnated into wood three times in one week, and the weight gain of the modified wood was recorded, with the results shown in table 2.

As can be seen from table 2, after the furfuryl alcohol-modified liquids prepared in examples 1 to 4 and comparative example 3 were respectively impregnated into wood on the first day, the third day and the seventh day, compared with the conventional furfuryl alcohol-modified liquid circulation of comparative example 3, the waste liquid obtained by treating wood with the furfuryl alcohol-modified liquid prepared in example 4 by using a boric acid and ammonium dihydrogen phosphate compound system as a catalyst can be recycled at least three times within one week, and the weight gain of the modified wood is relatively stable without adding a supplementary liquid, i.e., the furfuryl alcohol-modified liquid of example 4 has excellent storage stability.

TABLE 2 weight gain of furfuryl alcohol modified liquor recycle impregnated wood

Note: the data in table 2 are the mean and standard deviation of 6 replicates.

Experimental example 3

Modified wood prepared in example 4 and comparative example 2 was subjected to a leaching experiment with reference to AWPAE11-06 Standard method for testing the leaching of Wood preservatives, and the boron and phosphorus content of the leaching solution was determined using ICP-ASE.

The modified wood prepared in example 4 and comparative example 2 was subjected to a leaching experiment in a room temperature environment, and leaching solutions were collected at 6h, 24h, 48h, 96h, 144h, 192h and 336h, respectively, and the content changes of boron and phosphorus in the leaching solutions are shown in fig. 2 and 3, respectively. As can be seen from fig. 2 to 3, compared with the wood obtained by singly modifying the boron-phosphorus compound catalyst in the comparative example 2, the furfuryl alcohol resin modified material in the example 4 has the advantages that the loss speed of boron and phosphorus is obviously slowed down in a severe loss experiment, the loss resistance of boron and phosphorus is improved, and the superior performance of the furfuryl alcohol modified wood based on the boron-phosphorus compound catalyst can be maintained for a longer time.

Experimental example 4

With reference to ISO5660-1:2015 "flame reaction test-heat release, smoke yield and mass loss rate, part 1: heat release rate (cone calorimeter method) the modified wood prepared in example 4 and comparative examples 1 to 3 was subjected to a combustion performance test.

Data of cone calorimetry experiments of the materials or modified woods prepared in example 4 and comparative examples 1 to 3 are shown in table 3. As can be seen from Table 3, the total heat release amount of the furfuryl alcohol-modified wood obtained in example 4 using the boric acid and ammonium dihydrogen phosphate complex system as the catalyst was 87.35MJ/m, respectively, as compared with the material of comparative example 1 and the conventional furfuryl alcohol resin-modified wood of comparative example 3²And 93.12MJ/m²Reduced to 54.7MJ/m²The maximum amplitude reduction reaches 41.26%; the total smoke generation is respectively 351.00m²And 517.01MJ/m²Reduced to 11.65MJ/m²The maximum reduction amplitude reaches 97.75 percent, which shows that the boron-phosphorus compound catalyst can obviously improve the flame-retardant and smoke-suppression effects of the furfuryl alcohol modified wood.

TABLE 3 comparison of data results from cone calorimetry tests

Note: the data in table 3 are the mean and standard deviation of 3 replicates.

FIG. 5 is a comparison of the carbon residue after cone calorimetry test of the material prepared in comparative example 1 and the furfuryl alcohol-modified wood prepared in Experimental example 4. from FIG. 5, it can be seen that the carbon residue of the material after burning is very small, and only white ash residue remains, whereas the carbon residue of the furfuryl alcohol-modified wood in example 4 is significantly increased, the carbon layer structure is relatively complete, and the surface has no ash.

Experimental example 5

The modified wood materials prepared in example 4 and comparative examples 1 to 2 were subjected to white rot and brown rot resistance tests before and after the loss test (see example 3 for details of the loss test) with reference to AWPA E10-12 "standard test method for testing wood preservatives by laboratory soil wood block culture method", and the results are shown in table 4.

As can be seen from Table 4, the material of comparative example 1 was subjected to the corrosion resistance test before and after running off, and the mass loss was high. Before run-off, the furfuryl alcohol resin modified wood of comparative example 2 and example 4 had very low mass loss and the modification process was effective. After the loss experiment, the mass loss of the comparative example 2 is close to that of the raw materials, the mass loss is high, the fact that boron is completely leached out and has no corrosion prevention effect is shown, and the furfuryl alcohol resin modified wood of the example 4 still has good corrosion resistance. In addition, it can be found that the weight loss ratio of the conventional furfuryl alcohol resin modifier of comparative example 3 after running off is lower than that of the furfuryl alcohol resin modifier of comparative example 4 using the boric acid/ammonium dihydrogen phosphate complex system as a catalyst, because boron runs off a lot in a long and severe run-off experiment, and the protection effect is mainly provided by the furfuryl alcohol resin.

TABLE 4 weight loss data of material and modified wood before and after loss and after decay resistance test

Note: the data in Table 4 are the mean and standard deviation of 6 replicates

FIG. 6 is a comparison of the white rot resistance and brown rot resistance of the material obtained in comparative example 1 and the furfuryl alcohol modified wood obtained in comparative example 3 and example 4 before the loss test, and as can be seen from FIG. 6, the material surface is covered with a large amount of hyphae and shows good biological activity; the traditional furfuryl alcohol resin modified wood of comparative example 3 covers part of hypha on the surface, which shows that the furfuryl alcohol resin has no obvious toxic action on fungi; the furfuryl alcohol resin modified wood surface of example 4 was covered with sterile threads, which showed inhibitory effect of boron on fungi.

In conclusion, the invention takes the catalytic system of furfuryl alcohol polycondensation and solidification as a breakthrough point, selects the specific boron compound and the phosphorus compound, and adjusts the proportion of the boron compound and the phosphorus compound to prepare the boron/phosphorus composite catalyst, thereby not only maintaining the good storage stability of the furfuryl alcohol modified solution, but also obviously improving the size stability, the flame retardance and the corrosion resistance of the wood under the condition of efficiently catalyzing the furfuryl alcohol to polymerize in situ in the wood, greatly improving the high added value of the artificial forest wood, and widening the application range of the artificial forest wood.

Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.