CA2435765A1 - Furan polymer impregnated wood - Google Patents
Furan polymer impregnated wood Download PDFInfo
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- CA2435765A1 CA2435765A1 CA002435765A CA2435765A CA2435765A1 CA 2435765 A1 CA2435765 A1 CA 2435765A1 CA 002435765 A CA002435765 A CA 002435765A CA 2435765 A CA2435765 A CA 2435765A CA 2435765 A1 CA2435765 A1 CA 2435765A1
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- wood
- curing
- furan polymer
- polymer impregnated
- further compound
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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
- B27K3/15—Impregnating involving polymerisation including use of polymer-containing impregnating agents
- B27K3/156—Combined with grafting onto wood fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/092—Polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/02—Condensation polymers of aldehydes or ketones only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/14—Furfuryl alcohol polymers
Abstract
A furan polymer impregnated wood which comprises wood impregnated with a polymerizable furfural alcohol monomer solution containing at least water, stabilizers, and furfuryl alcohol, and at least one further compound selecte d from the group consisting of anhydrides, acids and combinations thereof is described. A method for preparing a furan polymer impregnated wood and uses thereof is also described.
Description
Furan polymer impregnated wood The invention described herein relates to a furan polymer impregnated wood which is uniform in colour and density throughout the treated zone. In order to obtain the polymer impregnated wood, a parent wood has been impregnated with a polymerizable furfural alcohol monomer solution containing at least water, stabilizers, and furfuryl alcohol, and at least one further compound. The invention also relates to a method for preparing a furan polymer impregnated wood and uses thereof.
Currently, wood is chemically preserved (protected from biodeterioration) mainly 1o by using toxic preservatives. Most of these preservatives also have toxicity to other organisms in the environment, including humans. Even if they are well-fixed in wood, their presence presents a problem for end-of use. Two approaches which are designed to use more environmentally-friendly chemicals are i) use of water-soluble salts which have low toxicity and ii) use of non-toxic chemicals which is react with and alter the wood cell walls, making them less susceptible to biodeterioration.
Approach i) has the drawback that such salts usually leach out of wood in contact with water, limiting their usefulness. Boron and copper compounds have been used in this way. They have the advantage that some such salts act as fire retardants as 2o well as reducing biodeterioration.
An example of approach ii) is the subject of a previous invention disclosed by Schneider (NO-A-20005137) based on furfuryl alcohol (FA) treating formulations.
This previous invention used an undiluted treating solution, and treated the wood 25 to high levels of retention. For woods with specific gravity near 0.30 (such as pine), the retention of chemical may approach 200% of the weight of the dry wood.
For denser woods (about 0.60 specific gravity, such as maple and beech) retention can be in the 100% range. This level of retention has been shown to give excellent protection from biodeterioration, high dimensional stability in varying moisture 3o conditions and an increase in most mechanical properties, particularly hardness.
The main disadvantage with this treatment is the large amount of chemical used and the resulting cost.
Furfuryl alcohol is highly water soluble and therefore easily forms a uniform 35 solution with water which can be used to impregnate wood. Therefore, FA
impregnating solutions containing different amounts of water are easily made.
However, there are things which must be overcome before a useful wood polymer composite can be made. First, after being impregnated into wood, the solution must
Currently, wood is chemically preserved (protected from biodeterioration) mainly 1o by using toxic preservatives. Most of these preservatives also have toxicity to other organisms in the environment, including humans. Even if they are well-fixed in wood, their presence presents a problem for end-of use. Two approaches which are designed to use more environmentally-friendly chemicals are i) use of water-soluble salts which have low toxicity and ii) use of non-toxic chemicals which is react with and alter the wood cell walls, making them less susceptible to biodeterioration.
Approach i) has the drawback that such salts usually leach out of wood in contact with water, limiting their usefulness. Boron and copper compounds have been used in this way. They have the advantage that some such salts act as fire retardants as 2o well as reducing biodeterioration.
An example of approach ii) is the subject of a previous invention disclosed by Schneider (NO-A-20005137) based on furfuryl alcohol (FA) treating formulations.
This previous invention used an undiluted treating solution, and treated the wood 25 to high levels of retention. For woods with specific gravity near 0.30 (such as pine), the retention of chemical may approach 200% of the weight of the dry wood.
For denser woods (about 0.60 specific gravity, such as maple and beech) retention can be in the 100% range. This level of retention has been shown to give excellent protection from biodeterioration, high dimensional stability in varying moisture 3o conditions and an increase in most mechanical properties, particularly hardness.
The main disadvantage with this treatment is the large amount of chemical used and the resulting cost.
Furfuryl alcohol is highly water soluble and therefore easily forms a uniform 35 solution with water which can be used to impregnate wood. Therefore, FA
impregnating solutions containing different amounts of water are easily made.
However, there are things which must be overcome before a useful wood polymer composite can be made. First, after being impregnated into wood, the solution must
2 be polymerized to be useful. Second, the polymerization must occur in wet or dry wood. Third, the polymerization must occur at fairly low temperatures.
Chemical initiators therefore must be added to the FA to make it polymerize in the desired temperature range and in wet or dry wood. How to initiate FA and make it polymerize in the desired temperature range is known from NO-A-20005137.
However, the initiated FA from that technology does not mix well with water.
Combing them causes the mixtures to separate into two components which cannot be uniformly impregnated into wood.
to One object of the invention is to provide a furan polymer impregnated wood by altering the wood cell wall with the same chemical monomer as that disclosed in NO-A-20005137 but using smaller amounts of chemical.
15 Another obj ect of the invention is to provide a uniform distribution of the chemicals in the furan polymer impregnated wood which causes uniform colour and density throughout the treated zone, by using water as an environmentally-friendly and production-friendly diluent which would permit uniform but low retention of active chemical in the treated zone of the wood.
2o Still another object of the invention is to provide a furan polymer impregnated wood having improved properties as regards dimensional stability, rot resistance, i.a.
According to the present invention, the foregoing and other objects are attained by a product, method and uses thereof as disclosed in the patent claims.
25 In one embodiment of this invention, there is provided a furan polymer impregnated wood, characterized by wood impregnated with a polymerizable furfural alcohol monomer solution containing at least water, stabilizers, furfuryl alcohol, and one further compound selected from malefic anhydride, phthalic anhydride, malefic acid, malic acid, phthalic acid, and combinations thereof.
3o In another embodiment of this invention, there is provided a method for preparing a furan polymer impregnated wood, characterized in that the wood is impregnated by one impregnation step with polymerizable furfural alcohol monomer solution containing at least water, stabilizers, and furfuryl alcohol, and at least one further compound selected from the group consisting of anhydrides, acids and 35 combinations thereof, followed by a curing step.
In still another embodiment of the invention, there is provided use of a furan polymer impregnated wood according to any of claims 1 to 7 or as manufactured
Chemical initiators therefore must be added to the FA to make it polymerize in the desired temperature range and in wet or dry wood. How to initiate FA and make it polymerize in the desired temperature range is known from NO-A-20005137.
However, the initiated FA from that technology does not mix well with water.
Combing them causes the mixtures to separate into two components which cannot be uniformly impregnated into wood.
to One object of the invention is to provide a furan polymer impregnated wood by altering the wood cell wall with the same chemical monomer as that disclosed in NO-A-20005137 but using smaller amounts of chemical.
15 Another obj ect of the invention is to provide a uniform distribution of the chemicals in the furan polymer impregnated wood which causes uniform colour and density throughout the treated zone, by using water as an environmentally-friendly and production-friendly diluent which would permit uniform but low retention of active chemical in the treated zone of the wood.
2o Still another object of the invention is to provide a furan polymer impregnated wood having improved properties as regards dimensional stability, rot resistance, i.a.
According to the present invention, the foregoing and other objects are attained by a product, method and uses thereof as disclosed in the patent claims.
25 In one embodiment of this invention, there is provided a furan polymer impregnated wood, characterized by wood impregnated with a polymerizable furfural alcohol monomer solution containing at least water, stabilizers, furfuryl alcohol, and one further compound selected from malefic anhydride, phthalic anhydride, malefic acid, malic acid, phthalic acid, and combinations thereof.
3o In another embodiment of this invention, there is provided a method for preparing a furan polymer impregnated wood, characterized in that the wood is impregnated by one impregnation step with polymerizable furfural alcohol monomer solution containing at least water, stabilizers, and furfuryl alcohol, and at least one further compound selected from the group consisting of anhydrides, acids and 35 combinations thereof, followed by a curing step.
In still another embodiment of the invention, there is provided use of a furan polymer impregnated wood according to any of claims 1 to 7 or as manufactured
3 according to any of claims 8 to 12.
Two keys to the invention are 1) the use of one or more chemicals acting as new initiators and 2) the use of stabilizers which allows the initiated monomer to be water soluble. The initiators have similar affinity for wood as furfuryl alcohol and therefore enter the wood and remain in solution as deeply as it penetrates.
Wherever the solution penetrates, it is polymerizable. The initiators are selected from any anhydride-containing compound as well as acids selected from the group of malefic acid, malic acid, phthalic acid, and stearic acid. However, preferably a compound selected from malefic anhydride, malic anhydride, phthalic anhydride to and combinations thereof is used. More preferably, malefic anhydride or phthalic anhydride or a combination thereof is used, most preferably malefic anhydride or phthalic anhydride. The stabilizers are borax and lignosulfonic acids. To make a treating solution, at least one of the initiators, preferably one of these initiators only, and both of the stabilizers are dissolved in water. Furfuryl alcohol is then added, forming a solution which has several months useful life at room temperature.
If limited surface impregnation or end-grain penetration is needed, brushing, rolling, spraying or soalcing can be used.
For easily impregnable woods, when deep penetration is needed, vacuum only may 2o be used. For deep and uniform penetration, there are three options: a) pressure alone (1 to 10 bar), b) vacuum followed by pressure (full cell process), c) atmospheric or low (1 bar) pressure followed by pressure and then final vacuum (empty-cell process).
For difficult-to-penetrate woods like spruce, an oscillating pressure method may be used.
Times of all of these processes depend upon many factors, including capability of equipment, size of wood, species of wood and penetration desired.
Impregnation method generally used (full cell process) in accordance with the present invention will depend on treatment loading desired, such as follows:
3o i) loading vessel with wood and securing the load so it will not float (if using air pressure, i.e., not a fluid pressure pump system), ii) closing door and drawing an appropriate partial vacuum, iii) filling the vessel with the treating solution, iv) pressurizing the submerged wood to a pressure in the range of 7 to 10 bar (100-150 psi) depending on wood species or other factors. Pressurizing for 30 to 60 min.,
Two keys to the invention are 1) the use of one or more chemicals acting as new initiators and 2) the use of stabilizers which allows the initiated monomer to be water soluble. The initiators have similar affinity for wood as furfuryl alcohol and therefore enter the wood and remain in solution as deeply as it penetrates.
Wherever the solution penetrates, it is polymerizable. The initiators are selected from any anhydride-containing compound as well as acids selected from the group of malefic acid, malic acid, phthalic acid, and stearic acid. However, preferably a compound selected from malefic anhydride, malic anhydride, phthalic anhydride to and combinations thereof is used. More preferably, malefic anhydride or phthalic anhydride or a combination thereof is used, most preferably malefic anhydride or phthalic anhydride. The stabilizers are borax and lignosulfonic acids. To make a treating solution, at least one of the initiators, preferably one of these initiators only, and both of the stabilizers are dissolved in water. Furfuryl alcohol is then added, forming a solution which has several months useful life at room temperature.
If limited surface impregnation or end-grain penetration is needed, brushing, rolling, spraying or soalcing can be used.
For easily impregnable woods, when deep penetration is needed, vacuum only may 2o be used. For deep and uniform penetration, there are three options: a) pressure alone (1 to 10 bar), b) vacuum followed by pressure (full cell process), c) atmospheric or low (1 bar) pressure followed by pressure and then final vacuum (empty-cell process).
For difficult-to-penetrate woods like spruce, an oscillating pressure method may be used.
Times of all of these processes depend upon many factors, including capability of equipment, size of wood, species of wood and penetration desired.
Impregnation method generally used (full cell process) in accordance with the present invention will depend on treatment loading desired, such as follows:
3o i) loading vessel with wood and securing the load so it will not float (if using air pressure, i.e., not a fluid pressure pump system), ii) closing door and drawing an appropriate partial vacuum, iii) filling the vessel with the treating solution, iv) pressurizing the submerged wood to a pressure in the range of 7 to 10 bar (100-150 psi) depending on wood species or other factors. Pressurizing for 30 to 60 min.,
4 v) after sufficient time under pressure, reducing pressure to 2 or 3 bar, and expelling the treating fluid with remaining pressure, vi) drawing a full vacuum in the treating vessel and holding for about 15 min., vii) releasing vacuum and pressurizing to 2 bar, viii) expelling the treating fluid (that was removed from cell lumens in step iv), ix) releasing all pressure, opening door and removing treated wood to curing area.
Wood moisture content must be below fiber saturation point (about 30% MC) in the zone to be treated. The further below, the more chemical which can be to impregnated. If a specific target amount of chemical is required, the moisture content of the wood and the amount of solution impregnated must be taken into account and the concentration of the treating chemical adjusted accordingly.
The treating solution is mixed and may contain, based on the weight of a given amount of water: borax (3%), malefic anhydride (2,3%), sodium salt of ligno-15 sulfonic acid (5,5%), and furfuryl alcohol (30,0%).
The mixing operation is started by heating the water to approximately 60°C to facilitate the addition of borax, malefic anhydride and lignosulfonic acid components. When these solid additives are fully dissolved in the water, the solution is cooled to 20-25°C and then the furfuryl alcohol is blended in with 2o stirring, and is stored at a temperature of 15-20°C.
The curing can take place at a range of temperatures, starting at from about 25°C to about 140°C. The lower temperatures (below about 40°C) require a long time to cure (days or weeks). From about 70°C to about 100°C the curing time is hours.
Above 100°C makes times even shorter but conditions are difficult because rapid 25 drying can occur and break the wood.
In accordance with the present invention steam or hot, humid air curing in the temperature range of about 70-100°C works well at a fixed temperature within the range. Also, temperature can be increased as curing and drying proceeds.
Essentially, this is conventional temperature kiln drying operation. Curing and 3o drying in hot oil also works well at temperatures from 70 to 120°C, either a fixed temperature within the range or by increasing temperature within the range as curing and drying proceeds. The furfuryl alcohol will cure readily in this temperature range with the furfuryl alcohol/initiator ratio used. Material 10 to 20 mm thick will cure in just two or three hours, but drying to final moisture content 35 takes longer.
The starting material is a woody material, usually lumber, which includes plank (thick lumber), but can also be wood composites such as oriented strand board and particle board. Woody materials of any dimensions can be utilized.
The length of the woody materials is important since the treating solution travels very fast along the length but very slow across the cross-section. With permeable
Wood moisture content must be below fiber saturation point (about 30% MC) in the zone to be treated. The further below, the more chemical which can be to impregnated. If a specific target amount of chemical is required, the moisture content of the wood and the amount of solution impregnated must be taken into account and the concentration of the treating chemical adjusted accordingly.
The treating solution is mixed and may contain, based on the weight of a given amount of water: borax (3%), malefic anhydride (2,3%), sodium salt of ligno-15 sulfonic acid (5,5%), and furfuryl alcohol (30,0%).
The mixing operation is started by heating the water to approximately 60°C to facilitate the addition of borax, malefic anhydride and lignosulfonic acid components. When these solid additives are fully dissolved in the water, the solution is cooled to 20-25°C and then the furfuryl alcohol is blended in with 2o stirring, and is stored at a temperature of 15-20°C.
The curing can take place at a range of temperatures, starting at from about 25°C to about 140°C. The lower temperatures (below about 40°C) require a long time to cure (days or weeks). From about 70°C to about 100°C the curing time is hours.
Above 100°C makes times even shorter but conditions are difficult because rapid 25 drying can occur and break the wood.
In accordance with the present invention steam or hot, humid air curing in the temperature range of about 70-100°C works well at a fixed temperature within the range. Also, temperature can be increased as curing and drying proceeds.
Essentially, this is conventional temperature kiln drying operation. Curing and 3o drying in hot oil also works well at temperatures from 70 to 120°C, either a fixed temperature within the range or by increasing temperature within the range as curing and drying proceeds. The furfuryl alcohol will cure readily in this temperature range with the furfuryl alcohol/initiator ratio used. Material 10 to 20 mm thick will cure in just two or three hours, but drying to final moisture content 35 takes longer.
The starting material is a woody material, usually lumber, which includes plank (thick lumber), but can also be wood composites such as oriented strand board and particle board. Woody materials of any dimensions can be utilized.
The length of the woody materials is important since the treating solution travels very fast along the length but very slow across the cross-section. With permeable
5 woods like beech and birch, the uniformity of treatment is determined by how well the treating solution remains uniform as it travels along the length. When impregnation is complete, the permeable woody material formed by this method has uniform properties throughout. Colour, resistance to moisture and deterioration and mechanical properties are consistent throughout. The properties and colour of to individual pieces of lumber treated this way depend upon the loading of polymer achieved. Different species of wood, and even different boards of the same species, may impregnate differently. However, resistance to moisture and deterioration are little affected by loading.
Woody material, including cheap types and scrap material, can be used to produce noble wood products such as imitation teak, mahogany, and others, and also provide them with novel properties lilce water resistance and simpler and reduced maintenance requirements.
The following examples will further illustrate the invention.
Attempts were made to change the initiator types and amounts to obtain a combination that would result in a water-soluble, curable mixture with a useful shelf life. After many trials, two things became apparent:
1. Malefic anhydride (MA) was the best polymerization initiator. It is also a desirable component because it is thought to act as a bonding agent to wood.
2. Stabilizers were needed to lceep the mixture uniform. Otherwise, it separated into two components and one settled to the bottom.
3. The pH must be near neutral for a uniform, stable mixture to be formed and maintained.
4. The pH must be on the acid side for curing to occur.
Surfactants and compatibilizers were tried as stabilizers. Borax (sodium tetraborate decahydrate) made homogeneous mixtures that penetrated wood well, and therefore became one of the stabilizers of choice. In some mixtures, stronger buffering to control pH using other compounds, such as sodium hydroxide, helped in maintaining a uniform mixture. Such compounds must maintain their buffering capacity until after the wood is impregnated. Then it is necessary for the pH
to drop to facilitate curing.
Woody material, including cheap types and scrap material, can be used to produce noble wood products such as imitation teak, mahogany, and others, and also provide them with novel properties lilce water resistance and simpler and reduced maintenance requirements.
The following examples will further illustrate the invention.
Attempts were made to change the initiator types and amounts to obtain a combination that would result in a water-soluble, curable mixture with a useful shelf life. After many trials, two things became apparent:
1. Malefic anhydride (MA) was the best polymerization initiator. It is also a desirable component because it is thought to act as a bonding agent to wood.
2. Stabilizers were needed to lceep the mixture uniform. Otherwise, it separated into two components and one settled to the bottom.
3. The pH must be near neutral for a uniform, stable mixture to be formed and maintained.
4. The pH must be on the acid side for curing to occur.
Surfactants and compatibilizers were tried as stabilizers. Borax (sodium tetraborate decahydrate) made homogeneous mixtures that penetrated wood well, and therefore became one of the stabilizers of choice. In some mixtures, stronger buffering to control pH using other compounds, such as sodium hydroxide, helped in maintaining a uniform mixture. Such compounds must maintain their buffering capacity until after the wood is impregnated. Then it is necessary for the pH
to drop to facilitate curing.
6 The effects of varying MA initiator and borax stabilizer in the mixture on some physical properties of wood treated with them are given in Table 1.
Table 1. Monomer mixture concentrations and effects on wood properties.
Treating Cured formulation material added % % % %
based swell wt water ASE
on increase swell solution FA MA BoraxTotalPineBeechPineBeechPineBeechPineBeech Water 0 0 0 0 1.7 2.2 -0.8-0.4 9.8 17 0 0 4.81.9 1.9 8.3 2.4 2.9 NA NA 8.6 76 72 6 9.12.7 2.7 13.83.0 3.6 8.2 6.3 7.3 15 26 12 16.73.2 3.2 21.94.2 6.0 14.010.2 6.8 14 31 18 23.13.7 3.7 28.65.7 7.0 20.514.6 6.3 12 36 29 23.15.1 5.1 30.65.7 7.0 NA NA NA NA 36 29 28.64.1 4.1 34.26.9 7.1 26.917.6 4.6 13 53 24 33.34.5 4.5 39.05.5 7.-3 30.916.1 5.5 11 44 35 Initiated93.96.5 0 NA 8.1 11.5 57.436.3 4.1 7 58 59 FA
Note:
Italic values are interpolated or calculated from interpolated values.
Percent swell is the remaining swelling after curing.
Percerat weight increase is after curing.
Water swell is maximum swelling in liquid water at 23~C
and the ASE
is anti-swell efficiency or percent retardation of swelling of the cured material in liquid water (based on the water swelling data).
To be useful, the mixture must impregnate and then cure throughout the wood, giving a uniform product. The monomer mixture containing 23.1 % FA, and 5.1 to each of MA and borax was selected for a uniformity-of treating trial. The results are given in Table 2.
Table 2. Results treating samples for uniformity.
Scots pine samples Sample% soln % poly Wt Wt % solids uptake uptake soln poly 1 146.2 37.9 14.58 3.78 20.6 2 138.8 38.0 14.69 4.02 21.5 3 151.0 38.9 14.92 3.84 20.5 4 147.0 41.7 14.67 4.16 22.1 152.1 38.3 15.00 3.78 20.1 6 140.4 41.2 14.59 4.28 22.7
Table 1. Monomer mixture concentrations and effects on wood properties.
Treating Cured formulation material added % % % %
based swell wt water ASE
on increase swell solution FA MA BoraxTotalPineBeechPineBeechPineBeechPineBeech Water 0 0 0 0 1.7 2.2 -0.8-0.4 9.8 17 0 0 4.81.9 1.9 8.3 2.4 2.9 NA NA 8.6 76 72 6 9.12.7 2.7 13.83.0 3.6 8.2 6.3 7.3 15 26 12 16.73.2 3.2 21.94.2 6.0 14.010.2 6.8 14 31 18 23.13.7 3.7 28.65.7 7.0 20.514.6 6.3 12 36 29 23.15.1 5.1 30.65.7 7.0 NA NA NA NA 36 29 28.64.1 4.1 34.26.9 7.1 26.917.6 4.6 13 53 24 33.34.5 4.5 39.05.5 7.-3 30.916.1 5.5 11 44 35 Initiated93.96.5 0 NA 8.1 11.5 57.436.3 4.1 7 58 59 FA
Note:
Italic values are interpolated or calculated from interpolated values.
Percent swell is the remaining swelling after curing.
Percerat weight increase is after curing.
Water swell is maximum swelling in liquid water at 23~C
and the ASE
is anti-swell efficiency or percent retardation of swelling of the cured material in liquid water (based on the water swelling data).
To be useful, the mixture must impregnate and then cure throughout the wood, giving a uniform product. The monomer mixture containing 23.1 % FA, and 5.1 to each of MA and borax was selected for a uniformity-of treating trial. The results are given in Table 2.
Table 2. Results treating samples for uniformity.
Scots pine samples Sample% soln % poly Wt Wt % solids uptake uptake soln poly 1 146.2 37.9 14.58 3.78 20.6 2 138.8 38.0 14.69 4.02 21.5 3 151.0 38.9 14.92 3.84 20.5 4 147.0 41.7 14.67 4.16 22.1 152.1 38.3 15.00 3.78 20.1 6 140.4 41.2 14.59 4.28 22.7
7 165.3 48.3 15.44 4.51 22.6
8 147.9 41.6 14.89 4.19 22.0
9 143.9 40.4 14.95 4.20 21.9 148.9 44.0 14.71 4.35 22.8 148.2 41.0 14.84 4.11 21.T
Beech samples Sample% soln % poly Wt Wt No. uptake uptake soln poly 1 115.8 25.1 14.363.11 2 118.2 25.6 14.243.09 3 121.6 26.4 14.493.14 4 113.9 24.7 14.213.08 114.5 24.8 14.283.10 6 112.3 24.3 14.093.05 7 122.3 26.5 14.603.16 8 111.4 24.1 14.303.10 9 130.9 28.4 14.933.24 127.7 27.7 14.953.24 118.8 25.8 14.453.13 Note: Weiglat is in grams, soln is solz~tion (while still liguid) poly is polymer (after curing) and percent solids is the solution converted to polymer.
The concentration study showed that the solution introduced into wood at concentrations between about 8% and 39% progressively increase wood dimensions at impregnation, polymer loading and antiswell efficiency. The values for the concentration chosen for further worlc (31%) and the highest concentration water solution tested (39%) are compared to values for undiluted, initiated FA
in Table 3.
to Table 3. Relationship between maximum values (94% FA solution) and diluted (31% and 39% solution) values of wood properties.
Percent of maximum (94%
FA) Pine Beech soln Swell PolymerASE Swell PolymerASE
I
These results show that for about 30% of the amount of polymer in wood that a full load would give results in material that has 60% of the resistance to swelling for a lower density wood (pine) and about 50% for a higher density wood (beech).
Therefore the polymer present in the wood is more effective in preventing swelling than its amount would first suggest.
Decay resistance The main reason for treating wood with this technology is to make it resistant to biodeterioration, especially decay caused by wood-rotting fungi. To test decay resistance, samples 50 mm long and 15 mm by 25 mm in cross section were treated with a solution concentration of 23.1 % FA, and 5.1 % each of MA and borax.
They were then exposed to various brown and white rot fungi according to European Standard EN113. Test results are given in Table 4.
to Table 4. Decay test results Pine samples Fungus Coniofora Poiia Gleophyllum Trametes puteav~a placenta t~~abeum vefsicolor wt 1.5 2.0 4.2 0.3 loss 5.7 -3.7 5.7 -1.4 5.3 2.4 1.2 1.6 6.6 -5.0 0.6 -1.3 0.1 2.0 -2.0 0.9 0.8 -3.1 -3.8 1.7 1.3 2.2 0.9 -5.1 0.8 -5.8 0.8 1.2 Average 2. -1.1 1. -0.3 Overall 0.6 average Beech samples Fungus Co~iofo~a Po~ia Gleophyllum Ti puteana placenta t~abeum ametes ve~sicolo~
wt 0.5 6.0 0.9 7.5 loss 2.4 3.1 4.8 3.7 -2.1 3.8 5.9 3.5 2.3 5.1 3.4 1.7 1.0 -1.6 -2.9 0.1 1.7 0.5 -1.3 0.3 2.5 0.2 0.4 1.1 5.8 2.9 -1.3 -1.8 Average 1. 2. S 1.2 2. 0 Overall 1.9 average The weight loss values for each fungus and both species allows the treated wood to be classed as «highly resistant» to decay according to Standard EN 113.
The solution of about 30% concentration was found to provide moisture and decay protection to the wood. However, other concentrations will also provide improved properties. To protect the ranges expected to be useful, the following water solution percentage limits are suggested:
FA MA Borax NaOH
Lower Upper Lower Upper Lower Upper Lower Upper
Beech samples Sample% soln % poly Wt Wt No. uptake uptake soln poly 1 115.8 25.1 14.363.11 2 118.2 25.6 14.243.09 3 121.6 26.4 14.493.14 4 113.9 24.7 14.213.08 114.5 24.8 14.283.10 6 112.3 24.3 14.093.05 7 122.3 26.5 14.603.16 8 111.4 24.1 14.303.10 9 130.9 28.4 14.933.24 127.7 27.7 14.953.24 118.8 25.8 14.453.13 Note: Weiglat is in grams, soln is solz~tion (while still liguid) poly is polymer (after curing) and percent solids is the solution converted to polymer.
The concentration study showed that the solution introduced into wood at concentrations between about 8% and 39% progressively increase wood dimensions at impregnation, polymer loading and antiswell efficiency. The values for the concentration chosen for further worlc (31%) and the highest concentration water solution tested (39%) are compared to values for undiluted, initiated FA
in Table 3.
to Table 3. Relationship between maximum values (94% FA solution) and diluted (31% and 39% solution) values of wood properties.
Percent of maximum (94%
FA) Pine Beech soln Swell PolymerASE Swell PolymerASE
I
These results show that for about 30% of the amount of polymer in wood that a full load would give results in material that has 60% of the resistance to swelling for a lower density wood (pine) and about 50% for a higher density wood (beech).
Therefore the polymer present in the wood is more effective in preventing swelling than its amount would first suggest.
Decay resistance The main reason for treating wood with this technology is to make it resistant to biodeterioration, especially decay caused by wood-rotting fungi. To test decay resistance, samples 50 mm long and 15 mm by 25 mm in cross section were treated with a solution concentration of 23.1 % FA, and 5.1 % each of MA and borax.
They were then exposed to various brown and white rot fungi according to European Standard EN113. Test results are given in Table 4.
to Table 4. Decay test results Pine samples Fungus Coniofora Poiia Gleophyllum Trametes puteav~a placenta t~~abeum vefsicolor wt 1.5 2.0 4.2 0.3 loss 5.7 -3.7 5.7 -1.4 5.3 2.4 1.2 1.6 6.6 -5.0 0.6 -1.3 0.1 2.0 -2.0 0.9 0.8 -3.1 -3.8 1.7 1.3 2.2 0.9 -5.1 0.8 -5.8 0.8 1.2 Average 2. -1.1 1. -0.3 Overall 0.6 average Beech samples Fungus Co~iofo~a Po~ia Gleophyllum Ti puteana placenta t~abeum ametes ve~sicolo~
wt 0.5 6.0 0.9 7.5 loss 2.4 3.1 4.8 3.7 -2.1 3.8 5.9 3.5 2.3 5.1 3.4 1.7 1.0 -1.6 -2.9 0.1 1.7 0.5 -1.3 0.3 2.5 0.2 0.4 1.1 5.8 2.9 -1.3 -1.8 Average 1. 2. S 1.2 2. 0 Overall 1.9 average The weight loss values for each fungus and both species allows the treated wood to be classed as «highly resistant» to decay according to Standard EN 113.
The solution of about 30% concentration was found to provide moisture and decay protection to the wood. However, other concentrations will also provide improved properties. To protect the ranges expected to be useful, the following water solution percentage limits are suggested:
FA MA Borax NaOH
Lower Upper Lower Upper Lower Upper Lower Upper
Claims (12)
1. A furan polymer impregnated wood, characterized by wood impregnated with a polymerizable furfural alcohol monomer solution containing water, stabilizers of borax and sodium salts of lignosulfonic acids, furfuryl alcohol, and at least one further compound selected from maleic anhydride, phthalic anhydride, maleic acid, malic acid, phthalic acid, and combinations thereof.
2. The furan polymer impregnated wood of claim 1, characterized in that said one further compound is maleic anhydride.
3. The furan polymer impregnated wood of claim 1, characterized in that said one further compound is phthalic anhydride.
4. The furan polymer impregnated wood of claim 1, characterized in that said one further compound is maleic acid.
5. The furan polymer impregnated wood of claim 1, characterized in that said one further compound is malic acid.
6. The furan polymer impregnated wood of claim 1, characterized in that said one further compound is phthalic acid.
7. A method for preparing a furan polymer impregnated wood, characterized in that the wood is impregnated by one impregnation step with polymerizable furfural alcohol monomer solution containing water, stabilizers of borax and sodium salts of lignosulfonic acids, furfuryl alcohol, and at least one further compound selected from maleic anhydride, phthalic anhydride, maleic acid, malic acid, phthalic acid, and combinations thereof, followed by a curing step.
8. The method of claim 7, characterized in.that said curing is performed by use of a temperature in the range of from about 70 to about 140°C.
9. The method of claim 8, characterized in that said curing requires conventional kiln drying using the normal temperature schedules for drying untreated, green lumber of the same size and species as the impregnated material, with temperatures at the beginning of curing about 70°C and at the end about 80°C, with a final post-curing step between 100 to 120°C for material with maximum hardness and dryness.
10. The method of claim 9, characterized in that said curing and drying can be accomplished using high-temperature kiln schedules in the 80 to 120°C
temperature range.
temperature range.
11 11. The method of claim 10, characterized in that curing is performed by submerging the treated material in hot oil, preferably 80 to 120°C, with the temperature either fixed or starting lower in the range and increasing as curing and drying proceeds.
12. Use of a furan polymer impregnated wood as prepared according to claims 7 to 11, as building parts (facia, cornice, siding, sills, frames, millwork), boat parts (frames, planking, decks), marine items (docks, piers, lobster traps, weir poles), outdoor items (furniture, decks, railings and stairs, walkways, boardwalks, playground equipment), bridge parts (beams, railings, decking), railway sleepers, cooling tower slats, utility poles, heavy timbers, fenceposts, stakes, highway items (guard rail posts, guard rail plates, sign posts, light poles) and container (tanks, buckets.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NO20010558 | 2001-02-01 | ||
| NO20010558A NO313273B1 (en) | 2001-02-01 | 2001-02-01 | Furan polymer-impregnated wood, method of manufacture and uses thereof |
| PCT/NO2002/000043 WO2002060660A1 (en) | 2001-02-01 | 2002-02-01 | Furan polymer impregnated wood |
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| Publication Number | Publication Date |
|---|---|
| CA2435765A1 true CA2435765A1 (en) | 2002-08-08 |
| CA2435765C CA2435765C (en) | 2013-08-06 |
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| CA2435765A Expired - Lifetime CA2435765C (en) | 2001-02-01 | 2002-02-01 | Furan polymer impregnated wood |
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|---|---|
| US (2) | US7008984B2 (en) |
| EP (1) | EP1368167B1 (en) |
| JP (1) | JP4190885B2 (en) |
| CN (1) | CN1328024C (en) |
| AP (1) | AP1558A (en) |
| AT (1) | ATE279308T1 (en) |
| AU (1) | AU2002230310B2 (en) |
| BR (1) | BR0206876B1 (en) |
| CA (1) | CA2435765C (en) |
| DE (1) | DE60201584T2 (en) |
| EE (1) | EE05266B1 (en) |
| ES (1) | ES2230473T3 (en) |
| MX (1) | MXPA03006848A (en) |
| NO (1) | NO313273B1 (en) |
| NZ (1) | NZ527842A (en) |
| PL (1) | PL202785B1 (en) |
| PT (1) | PT1368167E (en) |
| RU (1) | RU2276010C2 (en) |
| WO (1) | WO2002060660A1 (en) |
| ZA (1) | ZA200306780B (en) |
Families Citing this family (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NO313183B1 (en) * | 2000-10-12 | 2002-08-26 | Marc Schneider | Furan polymer-impregnated wood, method of preparation and use thereof |
| NO318254B1 (en) | 2002-07-26 | 2005-02-21 | Wood Polymer Technologies Asa | Furan polymer-impregnated wood, process for making same and using same |
| NO318253B1 (en) | 2002-07-26 | 2005-02-21 | Wood Polymer Technologies Asa | Furan polymer-impregnated wood, process for making same and using same |
| AU2003903242A0 (en) * | 2003-06-25 | 2003-07-10 | The University Of Melbourne | Process for the treatment of wood |
| NO321301B1 (en) * | 2003-08-15 | 2006-04-18 | Wood Polymer Technologies Asa | Formulation for treating wood, including a mixture of solutions containing styrene and furfuryl alcohol, and processes for the preparation and use thereof |
| US8167045B2 (en) * | 2003-08-26 | 2012-05-01 | Halliburton Energy Services, Inc. | Methods and compositions for stabilizing formation fines and sand |
| US7766099B2 (en) * | 2003-08-26 | 2010-08-03 | Halliburton Energy Services, Inc. | Methods of drilling and consolidating subterranean formation particulates |
| WO2005115705A1 (en) * | 2004-05-31 | 2005-12-08 | Sumitomo Forestry Co., Ltd. | Particle board manufacturing method |
| NZ551766A (en) * | 2006-12-04 | 2009-05-31 | Zelam Ltd | Use of a wood modifying composition which comprises a hydrophilic prepolymer and a crosslinking agent |
| EP1946900A1 (en) * | 2006-12-15 | 2008-07-23 | Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO | Treatment of wood |
| JP5202840B2 (en) * | 2006-12-27 | 2013-06-05 | 株式会社ザイエンス | Method for preserving wood-based materials |
| AP2009005063A0 (en) * | 2007-05-11 | 2009-12-31 | Kebony Asa | Modified wood and method for producing modified wood |
| US20090004495A1 (en) * | 2007-06-29 | 2009-01-01 | Marc Henry Schneider | High weight percent gain (WPG) furfural-urea modification of wood |
| US20090143537A1 (en) * | 2007-11-29 | 2009-06-04 | Marc Henry Schneider | Melt-polymerization surface reinforcement and hardening of wood, wood products and other porous materials using oligimer and polymer solutes in polymerizable monomer solvent |
| US8125761B2 (en) * | 2008-02-22 | 2012-02-28 | Industrial Technology Research Institute | Capacitor devices with co-coupling electrode planes |
| GB0906146D0 (en) | 2009-04-09 | 2009-05-20 | Kebony Asa | Apparatus and operating systems for manufacturing impregnated wood |
| GB0906989D0 (en) * | 2009-04-23 | 2009-06-03 | Kebony Asa | Decking |
| GB201008464D0 (en) | 2010-05-20 | 2010-07-07 | Kebony Asa | Process for polymer impregnating wood |
| DE102011104025A1 (en) | 2010-06-11 | 2011-12-15 | Technische Universität Dresden | Method for modification of wood or wood materials, involves subjecting wood of chemical and thermal treatment, where same strength properties in thermal untreated wood are achieved during reduced emission at volatile organic components |
| KR101024070B1 (en) | 2010-09-13 | 2011-03-22 | 주식회사 에코웰 | Wood modification composition and modified wood prepared therefrom |
| SE535622C2 (en) * | 2010-11-29 | 2012-10-16 | Organowood Ab | Environmentally friendly wood treatment process |
| CN202381966U (en) | 2011-05-03 | 2012-08-15 | 科博尼Asa | Deck or floor |
| CN109465942B (en) * | 2018-10-19 | 2022-06-07 | 湖南桃花江竹材科技股份有限公司 | Three-dimensional stereo surface high-strength bamboo composite material and manufacturing method thereof |
| CN109333719B (en) * | 2018-10-25 | 2021-01-05 | 北京林业大学 | Furfuryl alcohol resin wood modifier and preparation method and application thereof |
| CN109531747B (en) * | 2018-12-20 | 2020-07-14 | 中国林业科学研究院木材工业研究所 | Preparation method of nano-material toughened furfuryl alcohol wood |
| JP7116404B2 (en) * | 2019-04-27 | 2022-08-10 | 株式会社テオリアランバーテック | Method for producing furan polymer impregnated wood |
| JP7116403B2 (en) * | 2019-04-27 | 2022-08-10 | 株式会社テオリアランバーテック | Method for producing furan polymer impregnated wood |
| EP3882328A1 (en) | 2020-03-18 | 2021-09-22 | Kebony AS | Modified wood, modification solution, method of modification and use thereof |
| CA3187354A1 (en) * | 2020-07-29 | 2022-02-03 | Furanwood Co., Ltd. | Method for producing modified wood-based material, furan derivative resinification solution, and modified wood-based material |
| CN114505935A (en) * | 2020-11-16 | 2022-05-17 | 深圳碳十四科技创新有限公司 | Preparation method of multifunctional micro-nano structure modified wood |
| WO2023145902A1 (en) * | 2022-01-28 | 2023-08-03 | 富士岡山運搬機株式会社 | Method for producing modified wooden material, 5-hmf resinification solution, and modified wooden material |
| NO20220354A1 (en) | 2022-03-23 | 2023-09-25 | Kebony As | Polymerizable solution for obtaining a furan polymer impregnated material |
| CN115070890B (en) * | 2022-07-07 | 2023-07-21 | 南京林业大学 | Dehydration reinforcement treatment method for saturated wooden cultural relics |
Family Cites Families (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US209450A (en) * | 1878-10-29 | Improvement in water-proof cloth | ||
| US2947648A (en) * | 1955-12-21 | 1960-08-02 | Dow Chemical Co | Resinification of wood |
| US2909450A (en) | 1956-06-27 | 1959-10-20 | Koppers Co Inc | Impregnating solutions and method of impregnation therewith |
| US3622380A (en) * | 1969-02-18 | 1971-11-23 | Universal Oil Prod Co | Coloring solution and use thereof |
| US3697575A (en) * | 1969-12-22 | 1972-10-10 | Basf Ag | Boric acid esters of 2-vinylthioethanol |
| US3943084A (en) * | 1972-07-19 | 1976-03-09 | Chevron Research Company | Method for delaying the setting of and acid-settable liquid in a terrestrial zone |
| US4015995A (en) * | 1973-11-23 | 1977-04-05 | Chevron Research Company | Method for delaying the setting of an acid-settable liquid in a terrestrial zone |
| DE3504898A1 (en) * | 1985-02-13 | 1986-08-14 | Rütgerswerke AG, 6000 Frankfurt | METHOD FOR RETURNING WOOD AND USE OF THE RETURNED WOOD |
| US4735974A (en) * | 1985-12-13 | 1988-04-05 | Union Carbide Corporation | Binder system for castable ceramics |
| US5002981A (en) * | 1988-12-07 | 1991-03-26 | Ucar Carbon Technology Corporation | High strength carbonaceous cement |
| US5714507A (en) * | 1994-07-01 | 1998-02-03 | Janssen Pharmaceutica, N.V. | Synergistic compositions containing metconazole and another triazole |
| WO1996013468A1 (en) * | 1994-10-31 | 1996-05-09 | Tower Technologies (Proprietary) Limited | Method of preparing an exfoliated vermiculite for the manufacture of a finished product |
| US6051096A (en) * | 1996-07-11 | 2000-04-18 | Nagle; Dennis C. | Carbonized wood and materials formed therefrom |
| US6875727B2 (en) * | 1997-12-23 | 2005-04-05 | Syngenta Crop Protection, Inc. | Use of macrolides in pest control |
| MY151096A (en) * | 1998-06-26 | 2014-04-15 | Sumitomo Chemical Co | Processed lumber material |
| US6558784B1 (en) * | 1999-03-02 | 2003-05-06 | Adc Composites, Llc | Composite footwear upper and method of manufacturing a composite footwear upper |
| GB9915630D0 (en) * | 1999-07-05 | 1999-09-01 | Shafaei Manoochehr | Non-inflammable matter |
| NO313183B1 (en) * | 2000-10-12 | 2002-08-26 | Marc Schneider | Furan polymer-impregnated wood, method of preparation and use thereof |
| NO318253B1 (en) * | 2002-07-26 | 2005-02-21 | Wood Polymer Technologies Asa | Furan polymer-impregnated wood, process for making same and using same |
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| EP1368167B1 (en) | 2004-10-13 |
| RU2276010C2 (en) | 2006-05-10 |
| US20020192400A1 (en) | 2002-12-19 |
| JP2004520199A (en) | 2004-07-08 |
| CN1328024C (en) | 2007-07-25 |
| NO20010558D0 (en) | 2001-02-01 |
| BR0206876B1 (en) | 2013-09-10 |
| DE60201584T2 (en) | 2005-11-10 |
| CN1489512A (en) | 2004-04-14 |
| NZ527842A (en) | 2004-08-27 |
| AP1558A (en) | 2006-01-24 |
| AU2002230310B2 (en) | 2005-04-21 |
| EE200300352A (en) | 2003-10-15 |
| PL202785B1 (en) | 2009-07-31 |
| US20060094801A1 (en) | 2006-05-04 |
| PT1368167E (en) | 2005-02-28 |
| EE05266B1 (en) | 2010-02-15 |
| CA2435765C (en) | 2013-08-06 |
| ES2230473T3 (en) | 2005-05-01 |
| ATE279308T1 (en) | 2004-10-15 |
| MXPA03006848A (en) | 2004-05-14 |
| AP2003002851A0 (en) | 2003-09-30 |
| WO2002060660A1 (en) | 2002-08-08 |
| NO20010558L (en) | 2002-08-02 |
| US7008984B2 (en) | 2006-03-07 |
| EP1368167A1 (en) | 2003-12-10 |
| RU2003126439A (en) | 2005-03-10 |
| DE60201584D1 (en) | 2004-11-18 |
| JP4190885B2 (en) | 2008-12-03 |
| PL362439A1 (en) | 2004-11-02 |
| ZA200306780B (en) | 2004-08-30 |
| BR0206876A (en) | 2004-01-20 |
| NO313273B1 (en) | 2002-09-09 |
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