CN115229919B - Flame-retardant modification method based on in-situ self-assembly of nanometer microspheres in bamboo wood by pyridine hybrid heteropoly acid - Google Patents

Flame-retardant modification method based on in-situ self-assembly of nanometer microspheres in bamboo wood by pyridine hybrid heteropoly acid Download PDF

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CN115229919B
CN115229919B CN202210884799.XA CN202210884799A CN115229919B CN 115229919 B CN115229919 B CN 115229919B CN 202210884799 A CN202210884799 A CN 202210884799A CN 115229919 B CN115229919 B CN 115229919B
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bamboo wood
flame
wood
reagent
retardant
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CN115229919A (en
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杨守禄
王忠伟
刘竹
姬宁
吴义强
卿彦
王勇
李迅
裴学喜
李丹
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GUIZHOU ACADEMY OF FORESTRY
Central South University of Forestry and Technology
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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
    • 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
    • B27K3/10—Apparatus
    • 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
    • B27K3/50—Mixtures of different organic impregnating agents
    • 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
    • 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
    • B27K2240/00—Purpose of the treatment
    • B27K2240/30—Fireproofing

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Forests & Forestry (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)

Abstract

The invention discloses a flame retardant modification method of in-situ self-assembled nano microspheres in bamboo wood based on pyridine hybrid heteropoly acid, which comprises the following steps: (1) Slowly dripping the first modifying reagent into the solvent, then putting the first modifying reagent into the bamboo wood, and carrying out pressurized impregnation in an impregnation tank to obtain pre-modified bamboo wood; the first modification reagent is one or more of 4-aminopyridine, 4-ethylpyridine, 2-hydrazinopyridine and 3-hydroxypyridine; (2) Slowly dripping a second modification reagent into the solvent, then putting the pre-modified bamboo wood into the solvent, carrying out pressure impregnation in an impregnation tank, taking out the pre-modified bamboo wood and drying the pre-modified bamboo wood to obtain the flame-retardant modified bamboo wood; the second modifying reagent is sodium phosphotungstate or sodium silicotungstate. The flame-retardant modification method is an in-situ self-assembly mode, and has the advantages that the flame retardance is realized by the cooperation of nitrogen and phosphorus, the material characteristics of the nano-scale microspheres and the introduction of the characteristics of acid and metal tungsten elements, so that the characteristics of high efficiency, low consumption, loss resistance, smoke suppression and the like of the flame retardant are greatly improved, and the flame-retardant modification effect on bamboo and wood is good.

Description

Flame-retardant modification method based on in-situ self-assembly of nanometer microspheres in bamboo wood by pyridine hybrid heteropoly acid
Technical Field
The invention belongs to the field of flame-retardant materials, and particularly relates to a method for modifying bamboo and wood.
Background
Bamboo and wood are traditional, non-toxic and harmless building materials and are widely applied to house construction and interior decoration. Because bamboo timber has the flammability, the flue gas that the burning produced often leads to the leading cause of casualties, and this has brought very big potential safety hazard for people's daily life and building fire control. Therefore, it is essential to perform fire retardant and smoke suppression treatment on wood. As is known, the addition of flame retardants is an effective way to achieve the purpose of flame retardance and smoke suppression, and most of traditional flame retardants use single flame retardants of halogen, phosphorus, nitrogen, boron and the like, and have the fatal defects of large use amount and certain pollution to the environment.
How to improve the environmental protection, low dosage and high efficiency of the flame retardant has become a research hotspot and difficulty. In order to overcome the defects of low efficiency, high dosage and environmental unfriendliness of the flame retardant, researchers at home and abroad try a plurality of physical methods and chemical methods. Researches show that the wood treated by the phosphate and the boric acid has better flame retardant property, but the using amount is still larger. The novel wood flame retardant which adopts Guanyl Urea Phosphate (GUP) and boric acid as main flame retardant active substances improves the fire resistance of the material to a great extent, but the using amount is still large. The experimental sample is injected with nano silver, copper oxide, tin oxide and cesium oxide, and the flame retardant properties of the nano silver, the copper oxide, the tin oxide and the cesium oxide are compared, and the result shows that the metal silver greatly improves the fire resistance of the material, but the flame retardant properties are still required to be further improved, and the problem of high loss exists.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings in the background technology and provide a flame-retardant modification method based on in-situ self-assembly of nanometer microspheres in bamboo wood by pyridine hybrid heteropoly acid, which has the characteristics of high efficiency, low dosage, environmental protection and flow loss resistance. In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a flame retardant modification method based on pyridine hybrid heteropoly acid in-situ self-assembly nano microspheres in bamboo wood comprises the following steps:
(1) Slowly dripping the first modifying reagent into the solvent, then putting the first modifying reagent into the bamboo wood, and carrying out pressurized impregnation in an impregnation tank to obtain pre-modified bamboo wood; the first modification reagent is one or more of 4-aminopyridine, 4-ethylpyridine, 2-hydrazinopyridine and 3-hydroxypyridine;
(2) Slowly dripping a second modification reagent into the solvent, then putting the pre-modified bamboo wood in the step (1), pressurizing and dipping the pre-modified bamboo wood in a dipping tank, taking out the pre-modified bamboo wood and drying the pre-modified bamboo wood to obtain the flame-retardant modified bamboo wood; the second modifying reagent is sodium phosphotungstate or sodium silicotungstate.
In the above flame retardant modification method, the molar ratio of the first modifying agent to the second modifying agent is preferably (1-3): 1. more preferably, the molar ratio of the first modifying agent to the second modifying agent is 1:1. the research shows that the molar ratio of the first modification reagent to the second modification reagent directly influences the shape, the diameter and the particle size of the microspheres generated in situ, and also influences the number of acid sites, thereby influencing the flame retardant effect, and the microspheres are difficult to form spheres if the molar ratio is not the above molar ratio. The preferable molar ratio is favorable for generating the nano microspheres in the bamboo wood in situ, so that the flame retardant with the best performance is obtained.
In the above flame retardant modification method, preferably, the first modifying agent is 3-hydroxypyridine, and the second modifying agent is sodium phosphotungstate. When different first modification reagents and second modification reagents grow in situ in bamboo and wood to generate microspheres, different group attributes of the different modification reagents are different, whether the reaction is finally carried out to generate the nano microspheres or not can be determined, the properties of the generated nano microspheres can be influenced, more preferably, the nano microspheres synthesized by the in-situ self-assembly of the bamboo and wood through two-step dipping reaction can be facilitated by utilizing the synergistic reaction of 3-hydroxypyridine and sodium phosphotungstate, and the product with the best flame retardant effect and the best anti-loss performance can be obtained.
In the method for modifying the flame retardance, the pressure impregnation is preferably carried out at room temperature for 7 to 8.5 hours under 1.1 to 1.3 times of atmospheric pressure. The temperature, pressure and reaction time all influence the generation of the nano microspheres and influence the morphology of the nano microspheres, the two-step pressure impregnation under the conditions, especially the control of the reaction time is beneficial to the in-situ growth of the first modification reagent and the second modification reagent in bamboo wood to generate the microspheres with the optimal morphology, and the final product has good flame retardant effect and good anti-loss performance.
In the above flame retardant modification method, preferably, when the pressure impregnation is performed in the step (2), an acid regulator is further added to adjust the pH of the solution to 2 to 4. The appearance of the microspheres generated in situ on the bamboo and wood can be controlled by adding the acid regulator, and the pH value is favorable for the formation and appearance control of the microspheres.
In the above flame retardant modification method, preferably, the acid regulator is dilute hydrochloric acid or glacial acetic acid.
In the above flame retardant modification method, preferably, the solvent is ethanol and water in a volume ratio of (6-9): 1, and (b) a mixed solution.
Research shows that nitrogen and phosphorus synergistic, multi-element and nano-scale acidic flame retardant is an effective way for solving the problems of low efficiency and high dosage. According to the invention, a self-assembly particle precursor is provided by dipping in bamboo and wood in the first step, and then nano-scale flame retardant (nano-microspheres) is generated in situ in the bamboo and wood by dipping and self-assembly in the second step. Through two-step pressure impregnation, the bamboo wood is self-assembled into nano microspheres under the electrostatic action, and the nano microspheres have the advantages of strong acidity, rich acid sites, rich N, P (or Si), W elements and nano-grade materials, so that in the combustion and oxidation process of the bamboo wood, non-combustible gas containing nitrogen micromolecules, carbon dioxide and the like is released, the acid sites are synergistically catalyzed into carbon and catalyzed into carbon to form a compact non-combustible barrier body, the flame retardant is favorable for flame retardance, the flame retardant effect is good, the W-containing elements have good smoke suppression property, the smoke suppression is favorable, and the using amount of the flame retardant can be reduced. In addition, the flame retardant material is a nano microsphere synthesized by pressurizing and dipping and in-situ self-assembly, and the nano microsphere naturally has certain adhesiveness to a substrate, contains hydrophilic OH-groups and a benzene ring-like rigid structure containing non-hydrophilic lignin, and amphiphilic substances are similar and dissolved once contacted and are not easy to fall off, so that the flame retardant material has better anti-loss capability. In addition, the whole flow of the modification process only adopts water and ethanol as solvents, so that the environment-friendly advantage is obvious.
The invention is characterized in that the invention is based on two-step dipping reaction, through specific reagent optimization and specific dipping condition optimization, the nano-microspheres synthesized by in-situ self-assembly in bamboo wood are compared with flame retardants with other loading modes and other shapes, the regular and uniform nano-microspheres generated by the invention are more beneficial to contact with substrates, the generation of reaction is further promoted, the shape of the flame retardants is more regular and uniform, the material transmission in the reaction is more beneficial, the pyrolysis reaction rate of the substrate is improved, better flame-retardant smoke-inhibiting effect is achieved, and the anti-losing performance is improved. On the whole, the nano-microspheres obtained by the two-step impregnation reaction are beneficial to improving the flame retardant property of the bamboo wood and the anti-loss property of the flame retardant.
Compared with the prior art, the invention has the advantages that:
1. the flame-retardant modification method is an in-situ self-assembly mode, a nitrogen-phosphorus (or silicon) synergistic flame-retardant mode is adopted, the nano-scale microsphere material is particularly fixed on the bamboo and wood in an amphiphilic mode, the acid characteristic and the metal tungsten element are introduced, the characteristics of high efficiency, low consumption, loss resistance, smoke suppression and the like of the flame retardant are greatly improved, and the flame-retardant modification effect on the bamboo and wood is good.
2. The modification mode of the organic-inorganic hybrid nano flame retardant has the advantages of simple modification components, convenient manufacture, relatively low production cost and environmental protection.
Drawings
In order to more clearly illustrate the embodiments or technical solutions of the present invention, the drawings used in the embodiments or technical solutions in the prior art are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a TEM image of a sample PY-PW-1 obtained in example 1.
FIG. 2 is an element distribution diagram in SEM mode of the sample PY-PW-1 obtained in example 1.
FIG. 3 is a graph showing the combustion performance of the samples obtained in the examples and the untreated samples.
Detailed Description
In order to facilitate an understanding of the invention, reference will now be made in detail to the present preferred embodiments of the invention, examples of which are illustrated in the accompanying drawings, and the scope of the invention is not limited to the specific embodiments described below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
a flame retardant modification method based on pyridine hybrid heteropoly acid in-situ self-assembly nano microspheres in wood comprises the following steps:
(1) Slowly dropping a first modifying reagent into ethanol and water according to the volume ratio of 9:1, controlling the concentration of the first modifying reagent to be 0.1mol/L, then putting the wood into an impregnation tank, and carrying out pressure impregnation (impregnating for 8 hours under 1.1 times of atmospheric pressure to submerge the wood) at room temperature to obtain pre-modified wood; the first modifying reagent is 3-hydroxypyridine;
(2) Slowly dropping sodium phosphotungstate into ethanol and water according to the volume of 9:1, adding acetic acid to adjust the pH value to 3-4, then placing the pre-modified wood in the step (1), carrying out pressure impregnation in an impregnation tank at room temperature (impregnating for 8 hours under the atmospheric pressure of 1.1 times to submerge the pre-modified wood), taking out and drying to obtain the flame-retardant modified wood, and marking as a sample PY-PW-1.
In this example, the molar ratio of 3-hydroxypyridine to sodium phosphotungstate was controlled to be 1:1.
FIG. 1 is a TEM image of the sample PY-PW-1 obtained in example 1 (the left and right images represent different characterization positions respectively), and it can be known that after wood is modified, nano particles (nano microspheres) can be self-assembled in situ in the wood, which is beneficial to improving the product performance.
FIG. 2 is an SEM pattern elemental distribution of the sample PY-PW-1 obtained in example 1, which shows that P and N elements are distributed in the cell wall and cell cavity of wood. The above results demonstrate that the modification mode of this example is not only the modification on the surface of wood, but also the modification elements can be detected in the cell wall and duct of wood. Therefore, in the embodiment, the nano microsphere flame retardant is synthesized in the wood cell wall and the conduit through in-situ self-assembly (through electrostatic interaction) by a pressurized normal-temperature two-step method, so that the flame retardant effect is good, and the anti-loss performance is good.
Example 2:
a flame retardant modification method based on pyridine hybrid heteropoly acid in-situ self-assembly nano microspheres in wood comprises the following steps:
(1) Slowly dropping a first modifying reagent into ethanol and water according to the volume ratio of 9:1, controlling the concentration of the first modifying reagent to be 0.1mol/L, then putting the wood into an impregnation tank, and carrying out pressurized impregnation (impregnating for 8 hours under 1.1 times of atmospheric pressure to submerge the wood) at room temperature to obtain pre-modified wood; the first modifying reagent is 3-hydroxypyridine;
(2) Slowly dropping sodium phosphotungstate into ethanol and water according to the volume of 9:1, adding acetic acid to adjust the pH value to 3-4, then placing the pre-modified wood in the step (1), carrying out pressure impregnation in an impregnation tank at room temperature (impregnating for 8 hours under 1.1 times of atmospheric pressure to submerge the pre-modified wood), taking out and drying to obtain the flame-retardant modified wood, and marking as a sample PY-PW-2.
In this example, the molar ratio of 3-hydroxypyridine to sodium phosphotungstate was controlled to be 2:1.
example 3:
a flame retardant modification method based on pyridine hybridized heteropoly acid in-situ self-assembly nano-microspheres in wood comprises the following steps:
(1) Slowly dropping a first modifying reagent into ethanol and water according to the volume ratio of 9:1, controlling the concentration of the first modifying reagent to be 0.1mol/L, then putting the wood into an impregnation tank, and carrying out pressurized impregnation (impregnating for 8 hours under 1.1 times of atmospheric pressure to submerge the wood) at room temperature to obtain pre-modified wood; the first modifying reagent is 3-hydroxypyridine;
(2) Slowly dropping sodium phosphotungstate into ethanol and water according to the volume of 9:1, adding acetic acid to adjust the pH value to 3-4, then placing the pre-modified wood in the step (1), carrying out pressure impregnation in an impregnation tank at room temperature (impregnating for 8 hours under 1.1 times of atmospheric pressure to submerge the pre-modified wood), taking out and drying to obtain the flame-retardant modified wood, and marking as a sample PY-PW-3.
In this example, the molar ratio of 3-hydroxypyridine to sodium phosphotungstate was controlled to be 3:1.
the samples 1 to 3 and the untreated wood (i.e., the wood obtained in step (1) of the original example 1) were subjected to the test for the loss resistance and the flame retardancy, which was measured by the Standard method for accelerated evaluation of Corrosion leaching (AWPAE 11-16) and the laboratory Standard method for measuring Wood preservative leaching Rate (GB/T29905-2013). The 6 preservative treated samples were soaked in 500mL of distilled water and continuously stirred with a magnetic stirrer. The water was changed after 6, 24, 48h, respectively, once every 48h for 14d. The W and P concentrations in the water sample were measured by ICP-OES method, and the total loss rate L was calculated by the following formula (1).
L＝(0.18×C 1 +0.18×C 2 )/(M G X 1000) x 100% formula (1)
Wherein, C 1 Is the concentration of W element, C 2 Is the concentration of the P element, M G Is the original amount retained.
The UL-94 vertical flame chamber was used for Vertical Burning Test (VBT) (FTT 0082) (sample size 125X 13 mm) with 6 samples of each composition according to ASTM d 3801. Cone Calorimeter Test (CCT) (british fire test technology limited) three samples of each component were used according to ISO5660-1 standard (sample size 100 x 5 mm) using 50 kw per square meter.
Specific performance data are shown in tables 1 and 2 below:
table 1: addition retention of nano-microspheres in sample before and after leaching
Figure BDA0003764940000000051
Table 2: results of UL-94 and Cone calorimeter processing of samples
Figure BDA0003764940000000052
As can be seen from the above tables 1 and 2, the samples obtained by the treatments in the examples have performance data obviously better than that of the untreated sample compared with that of the untreated sample, and especially the comprehensive performance data of the sample in the example 1 is the most excellent.
FIG. 3 is a graph showing the combustion performance of each sample in examples, wherein the ordinate represents the limiting oxygen index, NR represents no grade, and V-0 represents the highest grade of flame retardancy of the material, and it can be seen that the treated wood in each example exhibits excellent flame retardancy compared with the untreated wood, and the various proportions can reach the V0 grade, particularly the performance of the sample in example 1 is the most excellent.
Example 4:
the present example is different from example 1 in that 4-aminopyridine, 4-ethylpyridine, and 2-hydrazinopyridine are used in place of 3-hydroxypyridine, respectively, and the other conditions are the same as in example 1.
The performance data of example 4 using the same test method as example 1 are shown in tables 3 and 4.
Table 3: example 4 Retention of nanospheres added to the sample before and after leaching
Figure BDA0003764940000000061
Table 4: sample UL-94 of example 4 and the results of the cone calorimeter treatment of the sample
Figure BDA0003764940000000062
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Claims (7)

1. A flame retardant modification method based on pyridine hybrid heteropoly acid in-situ self-assembly nano microspheres in bamboo and wood materials is characterized by comprising the following steps:
(1) Slowly dripping the first modifying reagent into the solvent, then putting the first modifying reagent into the bamboo wood, and carrying out pressurized impregnation in an impregnation tank to obtain pre-modified bamboo wood; the first modifying reagent is 3-hydroxypyridine;
(2) Slowly dripping a second modification reagent into the solvent, then putting the pre-modified bamboo wood in the step (1), pressurizing and dipping the pre-modified bamboo wood in a dipping tank, taking out the pre-modified bamboo wood and drying the pre-modified bamboo wood to obtain the flame-retardant modified bamboo wood; the second modifying reagent is sodium phosphotungstate.
2. The method of claim 1, wherein the molar ratio of the first modifying agent to the second modifying agent is (1-3): 1.
3. the method of claim 2, wherein the molar ratio of the first modifying agent to the second modifying agent is 1:1.
4. the method of claim 1, wherein the pressure impregnation is 1.1 to 1.3 times atmospheric pressure impregnation at room temperature for 7 to 8.5 hours.
5. The method of any of claims 1-4, wherein an acid regulator is further added to adjust the pH of the solution to 2-4 during the pressure impregnation in step (2).
6. The method of claim 5, wherein the acid modifier is dilute hydrochloric acid or glacial acetic acid.
7. The method of any of claims 1 to 4, wherein the solvent is ethanol and water in a volume ratio of (6 to 9): 1, and (b) a mixed solution.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1395780A (en) * 1971-12-27 1975-05-29 Monsanto Co Flame retardant compositions
US4420542A (en) * 1982-10-25 1983-12-13 Reilly Tar & Chemical Corp. Article and method for wood preservation
US20070163465A1 (en) * 2005-12-30 2007-07-19 E.I. Dupont De Nemours & Company Metal salts of hydrolyzed olefin/maleic anhydride copolymers and their use as wood preservatives
CN102001995A (en) * 2010-11-03 2011-04-06 湖南欧亚生物有限公司 Preparation method of 2-hydroxypyridine-N-oxide
CN109176794A (en) * 2018-09-21 2019-01-11 四川大学 A kind of pair of incense wood protects the modifying agent and method of fragrant enhancing

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1395780A (en) * 1971-12-27 1975-05-29 Monsanto Co Flame retardant compositions
US4420542A (en) * 1982-10-25 1983-12-13 Reilly Tar & Chemical Corp. Article and method for wood preservation
US20070163465A1 (en) * 2005-12-30 2007-07-19 E.I. Dupont De Nemours & Company Metal salts of hydrolyzed olefin/maleic anhydride copolymers and their use as wood preservatives
CN102001995A (en) * 2010-11-03 2011-04-06 湖南欧亚生物有限公司 Preparation method of 2-hydroxypyridine-N-oxide
CN109176794A (en) * 2018-09-21 2019-01-11 四川大学 A kind of pair of incense wood protects the modifying agent and method of fragrant enhancing

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