Patent Application
20190233690
It is provided adhesive resin comprising unmodified chitosan and an urea-formaldehyde (UF) resin.
Urea-formaldehyde (UF) adhesives are made of unsubstituted urea and formaldehyde and are currently used as binders for manufacturing wood composites. The most common applications of UF adhesives are in the manufacture of plywood, particleboard and medium density fibreboard (MDF) for interior uses. Exterior grade panels often employ phenol-formaldehyde (PF) adhesives that meet the requirements for extreme conditions of moisture and temperature. However, the cost of PF adhesive is at least twice as much as that of UF adhesive. In order to improve bonding quality and reduce cost of plywood products, UF adhesives are usually incorporated with fillers or extenders to increase their viscosity (thickness) and reduce penetration into the wood tissue. Wheat flour is the most common extender (filler) used in the plywood manufacturing. Level of wheat flour used as an extender in UF adhesives is normally from 15% to 50% based on resin solids. Wheat flour is a main food resource of human being and the large amount of utilization of wheat flour in the wood composite industry will increase agricultural burden of earth and increase food price. In addition, high level (more than 30%) of wheat flour used in a UF resin also lowers water resistance and physical and mechanical properties of plywood products.
Wood-based composites are made of different types of wood materials glued with adhesives into structural or non-structural panels. Currently, the main types of wood adhesives used are formaldehyde-based resins, such as urea-formaldehyde (UF), phenol-formaldehyde (PF) and melamine-formaldehyde (MF) resins.
There is still a need to be provided with novel types of adhesives for green composite panel production from renewable natural resource that reduces environmental impact from composite products. It would be highly desirable to be provided with adhesives produced with low-formaldehyde or free of formaldehyde that have excellent performance and low cost.
It is provided an adhesive resin comprising unmodified chitosan; and an urea-formaldehyde (UF) resin.
In an embodiment, the adhesive resin described herein further comprises wheat flour.
In another embodiment, the adhesive resin described herein further comprises a catalyst.
In a further embodiment, the adhesive resin described herein further comprises phenol-formaldehyde (PF) or melamine-formaldehyde (MF).
In an additional embodiment, the adhesive resin described herein further comprises polyvinyl acetate (PVA) adhesives.
In an additional embodiment, the adhesive resin described herein further comprises two parts of the 2% chitosan solution (w/v) for one part of UF resin (weight to weight).
In an embodiment, the adhesive resin described herein further comprises one part (weight to weight) of 2% chitosan solution (w/v) for two parts of UF resin.
In another embodiment, the adhesive resin described herein further comprises a ratio of 1:2 or 2:1 of chitosan-UF resin.
In another embodiment, the adhesive resin described herein further comprises one part (volume to volume) of chitosan in solution (2% w/v) for three parts of a liquid UF resin.
In a further embodiment, the catalyst is NH4Cl.
In another embodiment, the chitosan is from shells of marine crustaceans or from cell wall of fungi.
In another embodiment, the crustaceans are crabs, lobsters or shrimps.
In a further embodiment, the resin comprises a viscosity of up to 900 CP.
It is also provided a plywood panel comprising the adhesive resin encompassed herein.
In an embodiment, the plywood panel comprises a strength of up to 6809 kPa.
It is further provided a particleboard comprising the adhesive resin described herein.
It is also provided a fibrous material comprising the adhesive resin described herein.
In an embodiment, the fibrous material is a paper, wood, plywood, strandboard, particleboard, fibreboard or a combination thereof.
It is further provided a method of producing an adhesive resin comprising dissolving chitosan in an acid to produce a chitosan solution; and mixing the chitosan solution to an urea-formaldehyde (UF) resin.
In an embodiment, the chitosan is dissolved in acetic acid.
In a further embodiment, 2% (w/v) of chitosan is dissolved in 2-10% (v/v) 1N acetic acid aqueous solution (in other word, 2% of chitosan is dissolved in ˜0.1%-0.6% acetic acid aqueous solution (w/v)).
Reference will now be made to the accompanying drawings.
In accordance with the present invention, there is provided adhesive resin comprising unmodified chitosan and a urea-formaldehyde (UF) resin.
It is disclosed a chitosan-reinforced urea-formaldehyde (UF) adhesive for bonding wood-based composites, such as plywood and particleboard, or other fibrous materials and the method of producing the adhesives. The adhesives described herein are produced by mixing a chitosan containing raw material and a urea-formaldehyde resin to produce wood composite adhesive resins with desirable viscosity, improved bonding quality and better water resistance for reduced resin consumption of composite panel manufacturing.
The glue formulation encompassed herein for plywood comprises:
In an embodiment, the adhesive resin described herein can further comprise phenol-formaldehyde (PF) or melamine-formaldehyde (MF).
In another embodiment, the adhesive resin described herein can further comprise polyvinyl acetate (PVA) adhesives.
Referring now to
The method (1) for producing an adhesive resin starts with providing a chitosan containing raw material (2).
Chitosan is an amino polysaccharide deacetylated from chitin, which is naturally occurring in large amount in shells of marine crustaceans such as crabs and shrimps and in cell wall of fungi. The chemical structure of chitosan consists of β-1,4-linked D-glucosamine residues with a number of randomly located N-acetyl-glucosamine. Chitosan is an amino polysaccharide obtained by partial to substantial alkaline N-deacetylation of chitin also named poly(N-acetyl-D-glucosamine), which is a naturally occurring biopolymer found in exoskeleton of crustaceans, such as shrimp, crab and lobster shells. Chitosan contains free amine (—NH2) groups and may be characterized by the proportion of N-acetyl-D-glucosamine units and D-glucosamine units, which is expressed as the degree of deacetylation (DDA) of the fully acetylated polymer chitin. The properties of chitosan, such as the solubility and the viscosity, are influenced by the degree of deacetylation (DDA), which represents the percentage of deacetylated monomers, and the average molecular weight (Mw).
Chitosan is soluble in weakly acidic aqueous solutions and presents in a cationic polyelectrolyte form, which creates the possibility for interactions with negatively charged molecules. In other words, chitosan possesses adhesive properties.
Chitosan has received much attention as a potential polysaccharide resource in various fields, and it has been studied extensively for medical and industrial applications.
The chitosan raw material (2) is dissolved/solubilized (10) in an acid (4) to produce a chitosan solution (12). In an embodiment, chitosan is solubilized in for example 2-10% (w/v) 1N acetic acid (˜0.1%-0.6% acetic acid aqueous solution). Chitosan can be dissolved in the acid aqueous solution with gentle stirring. In an embodiment, 2% (w/v) of chitosan is dissolved in 2-10% (v/v) 1N acetic acid (˜0.1%-0.6% acetic acid aqueous solution). Vigorous stirring produced many small bubbles in the solution, and these bubbles required minimal 12 hours to be settled down.
The chitosan solution (12) is then added and mixed (20) to a urea-formaldehyde (UF) resin (14) to produce a chitosan-reinforced urea-formaldehyde adhesive (22).
In an embodiment, two parts of the 2% chitosan solution can be added to one part of a UF resin (weight to weight). In another embodiment, one part (weight to weight) of the 2% chitosan solution can be added to two parts of a UF resin.
Exoskeletons of crustaceans, such shrimp, crab and lobster shells are usually the source of commercial chitosan. In a preferred embodiment the chitosan containing starting material encompassed herein derives from a marine source such as shrimp or crustacean shells or fungi.
Dutkiewicz et al. (1984, J. Appl. Polym. Sci., 29: 45-55) describes methods of mixing several polymers as formaldehyde scavengers into to a urea-formaldehyde (UF) resin for reducing formaldehyde emission from the cured resin. Among disclosed formaldehyde scavengers, polymethacrylamide and chitosan did not inhibit formaldehyde release compared to other three investigated.
Verville et al. (U.S. Pat. No. 8,747,539) disclosed an hydrolyzed chitosan as an adhesive for making wood-based composite panels. The chitosan is hydrolyzed by acid for 8-12 hours before usage. The adhesive is reinforced by a crosslinking agent which is chosen from phenylglyoxal, hexylglyoxal, benzoquinone, t-butylbenzoquinone, and mixtures thereof, in which ratio of crosslinking agent to chitosan is about 1:15-30.
U.S. Pat. No. 8,562,731 discloses a fungal modified chitosan-based adhesive for binding a fibrous material and the method of producing the adhesive. It is disclosed the modification of chitosan with a biological approach for wood adhesive application. This patent also revealed that bio-modified chitosan can be used to enhance the bond quality of UF and PF resins to make them stronger binders for manufacturing wood composites.
The present disclosure includes a method to formulate unmodified chitosan as an enhancer in urea-formaldehyde (UF) resins and a production process for manufacturing plywood panels with chitosan-reinforced UF resins.
It is provided methods and manufacturing process using a small amount of chitosan (less than 1%) in a UF resin to replace wheat flour as an extender for increasing resin viscosity (thickening) and reducing extensive resin consumption.
Accordingly, by the process described herein, the water resistance and bonding properties of wood composite products is increased, allowing the use of such product in potential humid environmental conditions, such as flooring.
As shown hereinbelow, the strength of 2-ply plywood panels made with the UF resin at different spread rates were between 3591 to 4479 kPa. The strength of the panels made with the chitosan-reinforced UF resin at the ratio of 1:2 of 2% chitosan solution to the UF resin with similar spread rates as the UF resin increased to 5235-6547 kPa. Whereas the strength of the panels made with the chitosan-reinforced UF resin at the ratio of 2:1 of 2% chitosan solution to the UF resin with half of spread rates as the UF resin further increased to 5632-6809 kPa.
Under wet conditions, the strength of 2-ply plywood panels made with the UF resin at different spread rates was low; between 1599 and 2311 kPa. The strength of the panels made with the chitosan-reinforced UF resin at the ratio of 1:2 of 2% chitosan solution to the UF resin with similar spread rates as the UF resin increased to 4375-5456 kPa. The strength of the panels made with the chitosan-reinforced UF resin at the ratio of 2:1 of 2% chitosan solution to the UF resin with half of spread rates as UF resin reached to 3782-5088 kPa. Accordingly, the water resistance of the UF resin is much improved by after chitosan incorporated in it.
By adding chitosan in UF resins, the viscosity of the resin mixtures is significantly increased. The water resistance of the UF resin is also improved by adding chitosan inside the formulations.
As disclosed herein, a small quantity of chitosan solution with a 2% concentration was added into a commercial urea-formaldehyde (UF) resin via post-blending to improve its tacking property in the manufacture of particleboard. Good initial adhesion (tack) of urea-formaldehyde (UF) resin is important for keeping the mat integrity during forming and transportation to the hot press, while poor tacking of UF resin normally results in increased rejection rate of panels because of surface cracks. It was found that adding 1 part of 2% chitosan solution into 3 parts of liquid UF resin, corresponding to 0.66 wt % solid chitosan in the liquid resin, can improve the resin tack by 28% in terms of particleboard mat falling distance.
Panels made of UF resin plus 0.99% chitosan powder and 1% catalyst (NH4Cl) as face resin and UF resin plus 0.95% chitosan powder and 2% catalyst (NH4Cl) as core resin have the best physical and mechanical properties and lowest rates of water absorption and thickness swelling.
Accordingly, it is described the use of unmodified chitosan to reinforce commercial UF resins designed for plywood panels and particleboard, respectively. As shown herein it improves UF resin bond strength and durability in plywood manufacturing; improves UF resin bond strength and durability in particleboard manufacturing; and improves UF resin tack property in particleboard manufacturing.
The present disclosure will be more readily understood by referring to the following examples which are given to illustrate the invention rather than to limit its scope.
The chitosan used in this test was obtained from Marinard Biotech of Rivière-au-Renard, Quebec. The characteristics of this product are shown in Table 1.
Chitosan appears as white flakes and is soluble in dilute acids such as acetic acid or formic acid. Most literatures recorded that chitosan is soluble in 1% (w/v) acetic acid. However, different concentrations of the acids will affect the pH, solubility and viscosity of chitosan solution. In order to find a best concentration of the acid that could produce a suitable chitosan solution, a series of dilutions from 1N acetic acid solution, i.e. 1%, 2%, 4%, 6%, 8% and 10% (v/v), were made with sterile distilled water. The different concentrations of chitosan in the acid solutions were prepared by 1%, 2% and 4% (w/v), and the chitosan solutions were stirred with or without heating for 30 min.
The results of this test showed that 1% (v/v) of 1N acetic acid (˜0.06% acetic acid aqueous solution) was unable to dissolve chitosan, and 2-4% (v/v) of the acid (˜0.1%-0.3% acetic acid aqueous solution) partially dissolved chitosan to form a milky solution. The solution of 6% (v/v) 1N acetic acid (˜0.4% acetic acid aqueous solution) was able to totally dissolve 2% of chitosan (w/v), and 8-10% (v/v) of the acid (˜0.5%-0.6% acetic acid aqueous solution) dissolved 4% of chitosan (w/v). A clear transparent chitosan liquid could be produced with 10% (v/v) of 1N acetic acid aqueous solution (˜0.6% acetic acid aqueous solution). Heat did not help to dissolve chitosan, but a gentle stirring was required. Vigorous stirring produced many small bubbles in the solution, and these bubbles required minimal 12 hours to be settled down.
The pH and viscosity of chitosan solution made with 10% (v/v) of 1N acetic acid (˜0.6% acetic acid aqueous solution as medium increased along with the increase of chitosan content in the solution. At room temperature (around 20° C.), the pH of 1% of chitosan solution (w/v) was 3.97 with a viscosity of 300 cps, whereas that of 2% of chitosan solution (w/v) was 4.77 with a viscosity of 2300 cps, and that of 4% (w/v) of chitosan solution was 5.53 with an immeasurable viscosity (Table 2).
The UF resin solid content is 66.8% with a pH of 6.95.
Two types of chitosan-reinforced urea-formaldehyde adhesive mixtures were prepared with chitosan solution and a urea-formaldehyde resin as described above.
The changes in pH and viscosity of UF resin were observed after mixing with chitosan solution (Table 3). The pH of the 2% chitosan solution (w/v) was 4.77, whereas that of UF resin was 6.95. After adding one part of the 2% chitosan solution to two parts of the UF resin, the pH decreased to 5.33. Contrary to pH, after adding one part of the 2% chitosan solution to two parts of the UF resin, the viscosity increased from 230 CP to about 900 CP.
Yellow birch veneer strips (1.5 mm thick×148 mm wide×313 mm long) were cut from fresh yellow birch logs with the long direction being parallel to the wood grains. Two pieces of the veneer strips were brushed with an adhesive mix based on the resin solids content, and different spread rates were applied to make 2-ply plywood panels under conditions shown in Table 4. The 2 plies were stacked together after a proper open assembly time and then hot-pressed at 140° C. for 3 minutes. The applied pressure to veneer strips was 1500 kPa (Table 5). After manufacturing, the panels were conditioned at 21° C. and 50% relative humidity (RH) until reaching equilibrium moisture content (EMC). These 2-ply plywood samples were then cut into testing specimens (25 mm wide×80 mm long) for lap-shear test. The lap-shear strengths of these samples were determined by a MTS Alliance RT/50 testing machine with a crosshead speed of 1 mm per minute according to the standard method of CSA 0112.0, in both dry and wet conditions. For the wet test condition, specimens were soaked in tap water for 48 hours at room temperature, and then tested according to the same lap-shear method. Twelve specimens cut from 2 plywood samples were tested for each resin system, and the shear strength of plywood samples made with each resin system was obtain from an average of the 12 specimens tested.
The dry and wet lap-shear strengths of 2-ply plywood panels made with lower and higher glue spread rates are summarized in Table 6 and Table 7 and
Under the dry conditions, the strength of 2-ply plywood panels made with the UF resin at different spread rates were between 3591 and 4479 kPa (Table 6). The strength of the panels made with the chitosan-reinforced UF resin at the ratio of 1:2 with similar spread rates as the UF resin increased to 5235-6547 kPa. Whereas the strength of the panels made with the chitosan-reinforced UF resin at the ratio of 2:1 with half of spread rates as the UF resin further increased to 5632-6809 kPa.
Under the wet conditions, the strength of 2-ply plywood panels made with the UF resin at different spread rates was low; between 1599 and 2311 kPa (Table 7). The strength of the panels made with the chitosan-reinforced UF resin at the ratio of 1:2 with similar spread rates as the UF resin increased to 4375-5456 kPa. The strength of the panels made with the chitosan-reinforced UF resin at the ratio of 2:1 with half of spread rates as UF resin reached to 3782-5088 kPa. These data indicated that water resistance of the UF resin is much improved by after chitosan incorporated in it.
Six formulations of chitosan-reinforced urea-formaldehyde adhesive mixtures were prepared with the chitosan solution (Example I) and a urea-formaldehyde resin (Example II) as described above by adding different proportions of wheat flour and a catalyst NH4Cl inside (Table 8).
By adding chitosan in UF resins, the viscosity of the resin mixtures was significantly increased (Table 8, formulations C to F).
Yellow birch veneer strips (1.5 mm thick×120 mm wide×240 mm long) were cut from fresh yellow birch logs with the long direction being parallel to the wood grains. The resins prepared above were applied to one side of each face layer with a spread rate target at 214 g/m2. Table 9 summarizes the plywood panels manufacturing parameters. After manufacturing, the panels were conditioned at 21° C. and 50% relative humidity until consistent moisture content was reached. These 3-ply plywood samples were then cut into testing specimen size (25 mm wide×80 mm long) for plywood shear test. For each panel, the half were cut in pulled open and the other half were cut in pulled closed. Equal amount of specimens (pulled opened and pulled closed) from same panels are distributed for testing at dry and wet condition.
The 3-ply plywood were tested according to ASTM D906, and the results are summarized in Table 10 and
Spruce, pine and fir (SPF) wood particles were obtained from a local particleboard mill. A 24 in.×24 in. Viceroy Standard Press was used to press boards. Detailed information on board manufacturing conditions is presented in Table 11.
UF resin was collected from a local resin supplier, with solid content of 66.8%.
A series of particleboard panels were manufactured with use of a catalyst NH4Cl as described below:
All particleboards were conditioned at 65% RH/23° C. for more than three (3) weeks till reaching the equilibrium moisture content (EMC) and then evaluated for internal bond (IB) strength, modulus of rupture (MOR), modulus of elasticity (MOE) and thickness swelling (TS)/water absorption (WA) after soaking for 24 hours in water according to ASTM D1037-06 standard.
The test results are presented in Table 12 and
Three UF resin formulations were used for tacking evaluation in particleboard mat manufacturing:
Adhesive loading (% wt.) was 8% on a solids basis. Three layers with face and core UF (using different amounts of NH4Cl face and core layers) were made in making particleboard mat. The tack test was duplicated. The test results are present in Table 13.
It was found that adding 1 part of 2% chitosan solution into 3 parts of liquid UF resin, corresponding to 0.66 wt % solid chitosan in the liquid resin improves the resin tack by 28% in terms of increased particleboard mat falling distance (with an in-house test method for characterizing resin tacking).
While the present disclosure has been described in connection with specific embodiments thereof, it will be understood that it is capable of further modifications and this application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains and as may be applied to the essential features hereinbefore set forth, and as follows in the scope of the appended claims.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CA2017/051094 | 9/18/2017 | WO | 00 |
| Number | Date | Country | |
|---|---|---|---|
| 62398008 | Sep 2016 | US |
