WO1998037148A2

WO1998037148A2 - Adhesive composition

Info

Publication number: WO1998037148A2
Application number: PCT/IB1998/000828
Authority: WO
Inventors: Kuo Cheng Shen
Original assignee: Kc Shen International Ltd; Kronospan GmbH
Current assignee: Kc Shen International Ltd; Kronospan GmbH
Priority date: 1997-02-20
Filing date: 1998-02-20
Publication date: 1998-08-27
Anticipated expiration: 1999-08-20
Also published as: AU7230398A; WO1998037148A3

Abstract

Adhesive composition comprising: a product produced by copolymerization of one or more phenolic compounds and one or more water-soluble carbohydrates; or a mixture comprising one or more phenolic compounds or one or more water-soluble carbohydrates, the one or more phenolic compounds being copolymerizable with the one or more water-soluble carbohydrates.

Description

Adhesive Composition

The present invention relates to the use of water soluble carbohydrates and phenolic compounds as thermosetting adhesives.

BACKGROUND

Typically, exterior grade composite and panel wood products are bonded with synthetic adhesives. Phenol-formaldehyde resin adhesives are used in more than 90 % of exterior grade composite products. However, the finite supply of fossil fuels, coupled with an increasing global demand for wood products, has created a need for an alternative, environmentally sound adhesive system based on renewable resources. At the same time, the need to produce uniform and high quality composite products from lower cost raw material such as smaller diameter logs, wood processing by-products such as sawdust and bark, and agricultural wastes, has created a need for improved bonding products and processes.

Renewable resources, such as carbohydrates and phenolics, and particularly those of a lignocellulosic nature, have been investigated as a possible source of constituents suitable in exterior grade adhesives. To date, few renewable source adhesive systems have been successfully adapted for commercial application. Generally, such adhesives do not possess adequate properties, suffering from weak bond strength and poor handling qualities, to meet the standards required of composite products. Those renewable source adhesives capable of meeting today's composite product standards are usually too expensive to compete with existing synthetic resins, often requiring extensive chemical modification and/or extremely long curing times.

Nonetheless, the components of lignocellulosic materials have been extensively studied in hopes of finding a renewable source adhesive suitable for commercial use in composite wood products. Wood, similar to other plant resources, is composed of about 45-50% cellulose, 20- 35% hemicellulose, 20-25% lignin, and 0-10% extractives. Chemically, cellulose is the main structural component of all plant cell walls, and is a linear polysaccharide built up from anhydro glucose units having the general crystalline formula (C_βH_lo0j)_n. Cellulose is the most abundant source of carbohydrates in plants. Upon acid hydrolysis cellulose converts into glucose. Hemicelluloses are a non crystalline group of heterogenous polysacharides that, next to cellulose, constitute the most abundant sources of carbohydrates in plants. Hemicellulose, associated with the cell wall, is mostly soluble in alkali and is relatively easy to degrade by an acid hydrolysis into simple sugars or sugar acids. Hemicellulose may be represented by the general formula (C₅H₈O₄)_nl

representing 5 and 6 carbon sugars such as pentosan and hexosan. Upon acid hydrolysis, hemicellulose converts into various reducing sugars.

The third major component of lignocellulose is lignin, which is phenolic in character and acts as the natural binder within the lignocellulose to cement cells together. The precursors of lignin and its formation in lignocellulosic material are still not completely understood, although recently, considerable progress has been made in this area of research. It is generally accepted that lignin is a polymeric material composed of phenolpropane units that are linked together by carbon to carbon as well as carbon to oxygen (ether) bonds.

The minor component of lignocellulose consists of extractives. All plants and agricultural vegetation contain a number of organic substances that can be extracted with organic solvents, or in some cases, with water. Among these belong aliphatic, aromatic and alicyclic compounds, hydrocarbons, alcohols, ketones, and various types of acids and phenol compounds. Furthermore, sterols, tannins, essential oils, resins, dyestuffs, proteins, wax, and some alkaloids are found.

Carbohydrates have been explored in the past as both coreactants with phenolic resin and as the sole ingredient in adhesive. Meigs (US patents 1,593,342, 1,801,053 and 1,868,216) carried out some of the early work with a phenol-carbohydrate combination. Meigs was searching for a process to produce solid, fusible, thermoset molding compounds. The reactions used both acidic and base catalysts and often introduced coreactions with aniline or aliphatic amines. In other examples, Chang and Kononenko (Sucrose-Modified Phenolic Resin as Plywood Adhesives, Adhesives Age 5(7):36-40, 1962) developed an adhesive system by coreacting sucrose in a phenol-formaldehyde resin formulation under alkaline conditions. More recently, Gibbons and Wondolowski (Can. Pat. 1,090,026) reacted carbohydrates with phenol and urea, or a diamine, in the presence of an acid catalyst to produce a fusible resin for bonding wood products. Other investigators have used acidic conditions only to produce carbohydrate-based resin. Mudde (Com Starch: A Low Cost Route to Novolac Resins. Mod Plast. 57(2): 69;74, 1980) described a method that relied on the acidic conversion of starch to 5 hydroxymethyl furfural - 2 formaldehyde for condensing with phenol in a Novolac resin. Turner et al., (Deutsch Offenlegenselrift No. 1,905,054) investigated carbohydrates, not involving phenol as a coreactant, and produced a water resistant adhesive. Turner et al. degraded pentose and hexose sugars with acid, while coreacting with such materials as formaldehyde, furfural alcohol, polyvinyl alcohol, or amines to produce a thermosetting adhesive suitable for particleboard production. As another example, Stofko (US patents 4,107,379 and 4,183,997) proposed formulations that used a variety of carbohydrates sources and reactions under acidic conditions with different modifiers to produce thermosetting water-resistant adhesives.

K.C. Shen (US Patent 5,017,319 and EU Patent 0,161,766 and specification 0492,016) converted lignocellulosic material directly into both mermosetting resin adhesive and composite products by selectively hydrolyzing and decomposing hemicellulose and/or cellulose fractions, using high pressure steam, into low molecular weight water soluble resin material including pentose and hexose sugars, sugar polymer, furfural, hydroxymethyl furfural, dehydrated carbohydrates, organic acids and other decomposition products. The water soluble resin material alone, thus produced, can be used in liquid or powder form as a thermosetting water-proof resin adhesive.

Since lignin is believed to be the natural binder within lignocellulose and is phenolic in nature, it has been extensively studied and researched in the past hundred years as a binder for lignocellulosic composite products.

In US-A-726,029, A. Classen used steam to treat saw dust with acid and then cooked the acidified saw dust under pressure at a temperature of 105 to 145 °C for 30 to 60 minutes to render the hemicellulose water soluble. After cooking, the treated mass was washed with water to remove the water solubles before drying and molding into composite products. US-A- 2,303,345 by Mason and Boehm described a process of making strong products from lignocellulosic material. Mason and Boehm employed high pressure steam to separate lignin from lignocellulosic material for bonding. In their process, the hemicellulose was hydrolysed into water solubles and removed from the treated lignocellulose before the fibres and lignins were made into hardboard. Under high temperature and pressure lignins were melted as a binder to cement fibers into a high density hardboard. The water solubles, consisting mainly of reducing sugars, were concentrated into wood molasses commonly used in animal fodder. Although the well-known Masonite process of making hardboard, using natural lignin as binder, has been in commercial production since the 1930s in USA and other countries, it is now an industry in decline due to inefficiencies and environmental concerns about the enormous quantities of waste water.

Other investigators have used lignin from the pulping industry in combination with phenol formaldehyde resin to form copolymer resin adhesives. In US-A-2,786,008, R. Herschler incorporated ammonium based spent sulfite liquor, or lignosulfonates, a by-product of sulfϊte pulping industry, into an acid tolerant thermosetting phenol-aldehyde resin for bonding plywood and fibreboard. In UK-A1, 4044,536, K. Forss proposed a system of incorporating high molecular weight lignins, fractionated from lignosulfonates, into a phenol formaldehyde resin to yield a copolymer thermosetting adhesive for bonding plywood and fibreboard. In sulfite pulping, both lignin and hemicellulose fractions are solubilized during acidic cooking and washed off as spent sulfite liquor effluent. In the past, this waste material was discharged into rivers and streams causing severe water pollution. Today, pulp mills in North America are equipped to recover the waste liquor and use it for boiler fuel. A very small fraction of the spent sulfite liquor is processed into useful products for industrial application.

US-A4, 193,814, issued to K.C. Shen, describes a method of using calcium, sodium, magnesium and ammonium based spent sulfite liquor, or lignosulfonates as a thermosetting adhesive for bonding wood composite products. This process involved treating the spent sulfite liquor with sulfuric acid to activate the lignosulfonic acids and convert the spent sulfite liquor into a highly acidic thermosetting adhesive. Further, in US-A4,265,845 K.C. Shen et al. discovered that ammonium based spent sulfite liquor, without any modification or addition of chemicals, could be thermoset to yield a water-proof bond. Fractionation of the spent sulfite liquor to contain a high proportion of the low molecular weight fraction of carbohydrates further improved the adhesive quality. However, the improved spent sulfite liquor adhesive still required high press temperature and long press time to thermoset or cure into a waterproof bond. Trees contain about 15 - 20 % by weight of bark. Therefore the wood processing industry generates enormous amounts of bark as waste which at present are simply being used as boiler fuel having a very low economic value. The barks of various trees and certain agricultural wastes contain organic extracts of which phenolic compounds are the major constituents. These extracted phenolic compounds constitute the starting material for the production of adhesives and are available from the wood industry's own resources and from agricultural resources. A waste material itself, bark is generally a much richer source than wood for quantity and complexity of extracts, the most important being monomeric polyphenol or flavonoid compounds, and polymeric phenolics, such as tannins, phlobophenes and phenolic acids with a minor portion of non-tannin fraction consisting mainly of sugars and gums. There is no real difference between phenols and tannins since both are phenolic in character. There are two types of tannins: condensed and hydrolyzable. Condensed tannins, using phenolic components from bark and wood extract or from certain agricultural residues, with the addition of formaldehyde, have been used from time to time as a resin adhesives for bonding plywood and particleboard. Tannin extractives from the bark of Acacia (wattle of mimosa bark extract) and the wood of Quebracho, typically fortified with a small portion of synthetic phenol-formaldehyde resin, have been used in the commercial production of exterior grade plywood and particleboard in certain countries. However, there are practical and cost limitations associated with the use of tannin adhesives, which have restricted their application for wider commercial use.

It is well known that carbohydrate and lignin based adhesives have not achieved commercial success due to some fundamental flaws, such as high acidity, slow curing rates/longer press times, and low tolerance to high moisture content during processing. Similarly, tannin- formaldehyde adhesives suffer from a variety of shortcomings, such as weak cohesive strength, short pot-life, pre-cure and high viscosity. These problems not only affect bonding qualities, but also pose difficulties in production, processing and handling.

It has now been discovered, unexpectedly and surprisingly, that mixtures of carbohydrates and phenolic compounds, both derived from lignocellulosic vegetation, used as thermosetting copolymer adhesives have unexpected advantages, overcoming most of the problems usually associated with carbohydrate, lignin and tannin adhesives respectively. For instance, it is well known that tannin formaldehyde resin adhesive can be more reactive at certain pH levels, ranging from very acidic to very alkaline conditions. However, this potential has not been fully realized m practical terms. because the specific pH of existing formulations of tannin- formaldehyde adhesive usually results a very short pot life and consequently, the adhesivecannot have any practical application. However, by incorporating carbohydrates into the tannin-carbohydrate formaldehyde copolymer resin adhesive, the copolymer adhesive can be tailored to any desired pH range, from very acidic to very alkaline conditions to achieve the maximum reactivity without suffering from a short pot life.

The conventional teaching is that the non tannin fraction, consisting mainly of sugars and high molecular weight gums, cannot participate in resin formation with formaldehyde. Sugars reduced the strength and water resistance of the bonded composite in proportion to the amount added. The addition of carbohydrates is detrimental to the overall bonding quality of tannin- formaldehyde adhesives (see Pizzi, A., "Tannin Based Wood Adhesives", at p. 215, Wood Adhesives: Chemistry and Technology, Marcel Dekker, (New York: 1983) and Hemingway et al., "Condensed Tannin: Problems and Prospects for their Extended Use in Wood Adhesives" at p. 164 Wood Adhesives in 1985: Status and Needs: Proceedings of a conference sponsored by the Forest Products Laboratory, USDA, in cooperation with the Forest Products Research Society). Further, "carbohydrate impurities are particularly undesirable, so investigators over the years have usually expended much effort in trying to find a particular plant species that would yield an extract high in tannin content and low in the offending carbohydrate "contaminates"." (Hugert, H.L. Chapter 12 "Condensed Tannin in Adhesives—Introduction and Historical Perspective. Adhesives from Renewable Resources. American Chemical Society (1989).

It has now been found, however, that copolymer adhesives of carbohydrates, lignin and tannins alleviate common problems inherent to carbohydrates, lignin and tannin-formaldehyde based resins, namely as high acidity, slow curing, low cohesive strength, short pot life, high viscosity and pre-curing. In short, contrary to conventional teachings, the correct combination of carbohydrates, lignin and tannin sufficiently enhances physical properties so that these copolymer adhesives may be used for commercial applications. Furthermore carbohydrates in the form of sugars, molasses, black liquor and spent sulfite liquor or lignosulfonate, which are waste by-products from the hardboard and pulping industries, respectively, can be incorporated into the copolymer resin system, thus, not only improving the physical properties of such resins, but also rendering their production moreeconomically efficient and environmentally attractive. Renewable source thermosetting adhesives entirely based on lignocellulose vegetation offer permanent solutions to the wood industry. Although tannins are relatively expensive and limited in production quantity - 400,000 tons per year worldwide for condensed tannins, a thermosetting adhesive consisting of a minor portion of tannin and a major portion of carbohydrates and lignins would provide a significant economic advantage to the wood industry. The lower cost adhesives will allow for the application of higher resin content to produce new and/or better quality composite products.

In one aspect the invention provides: an adhesive composition comprising a product produced by copolymerization of one or more phenolic compounds and one or more water-soluble carbohydrates; or a mixture comprising one or more phenolic compounds or one or more water soluble carbohydrates, the one or more phenolic compounds being copolymerizable with the one or more water soluble carbohydrates.

It may be preferable that the carbohydrates comprise reducing sugars or other reducing carbohydrates.

The phenolic compounds may be provided by extract of bark, wood, leaves, fruit skin and seed hulls.

The copolymerization may be effected by means of an aldehyde, which is believed to act as a cross-linking agent.

The invention is illustrated by the following examples:

Example 1

Chfps made from pine were pre-hydrolyzed with sulfuric acid at a concentration 0.05 % based on dry wood at a temperature of 200 °C for 3 min. For this purpose the chips were sprayed with sulfuric acid solution and treated with pressurized steam at 200 °C. After treatment the chips were dried and glued with tannin formaldehyde resin at a level of 10 % resin based on dry wood to a particle board with a density of 0.7 g/cm3. For comparison particle boards were made from the same raw material without acid treatment. Boards treated with acid showed lower thickness swelling and better dimensional stability compared to those prepared without acid treatment.

Example 2

This example describes the use of bark extract from Western hemlock in combination with black liquor, a by-product from a wet process hardboard mill, for bonding particleboard.

Hemlock bark was dried to a moisture content (M.C.) of less than 5 % and hammer milled into fine particles, passing 1 mm mesh screen. Ten kg bark particles were mixed with hot water to which about 2 % of sodium carbonate was added as extractant. The bark slurry was vigorously stirred in hot water (70-80 °C) for about 45 minutes and filtered. The extract was mixed with 0.3 % sodium sulfite based on oven dry (O.D.) weight of bark particles and evaporated under vacuum to a concentration of about 38 % solids. The yield of extract solids was about 16.6 % of the original O.D. bark weight. The polyphenolic content in the extract was determined to be about 10.2 % based on the original O.D. bark particle weight. The black liquor, a wood molasses and by-product from a wet process hardboard mill, consisted mainly of reducing sugars derived from hemicellulose hydrolysis. Hydrolysis of hemicelluloses yield a mixture of D-glucose, D-mannose, D-xylose, D-galactose, L-arabinose, and small amounts of sugar acids. The solids content of the black liquor was about 52 % with a pH of 4.2.

Forty-five parts by solids weight of the hemlock bark extract was mixed with forty-five parts of the black liquor solids and ten parts of 95 % paraformaldehyde powder to formulate a copolymer resin adhesive for making pine planer shavings boards. This liquid copolymer resin adhesive had a solids content of 50 %, having a pH of 4.8 and a viscosity of 387 cps (Brookfield, 25°C). Dry pine shavings were sprayed with 10 % copolymer liquid resin based on O.D. weight of pine shavings. After spraying, the resinated shavings were hand felted into a homogeneous mat. The mat was pressed at platen temperature of 220 °C, under an initial pressure of 30 kg/m² for 5 minutes to produce a 12 mm thick board (650 x 650 mm) having a density of about 740 kg/m³. Test results are listed in Table 1. Table 1. Properties of 12 mm shaving board bonded with 10 % copolymer resin adhesive.

Density MOR ( Pa) MOE IB Swelling (%) Q M³) dry_ boil (GPa) ( Pa) Soak Boil

757 19.3 9.7 37.2 580 8.5 32.7

CAN0188.2-M78 17.2 5.0 25.0 500

Example 3'

This example demonstrates the use of water soluble resin material derived from hydrolyzed pine sawdust and modified with hemlock bark extract and formaldehyde to formulate a copolymer adhesive for bonding particleboard. Wet pine sawdust was first impregnated with 0.2 % sulphuric acid in dilute solution and steamed at 10.5 bar (186 °C) for 30 minutes. The steamed hydrolysed sawdust was eluted with hot water and the solution was evaporated under vacuum to a concentration of about 50 % solids with a pH of 3.5. The yield of water solubles was about 17 % solids based on the original OD weight of pine sawdust. This water soluble low molecular weight resin material derived from hemicellulose hydrolysis consisted of pentose and hexose sugars, sugar polymer, furfural, hexamethyl furfural, dehydrated carbohydrates, organic acids and other decomposition products, with a small portion of lignin decomposition products. This carbohydrate based resin adhesive can be thermoset to produce a water-proof bond, but required higher pressing temperature and longer pressing time. This carbohydrate based liquid resin was mixed with liquid hemlock bark extract (the same material as used in Example 1) and 95 % paraformaldehyde powder at a ratio of 50:40:10 based on OD weight of these components. The copolymer adhesive had a pH of 3.9, viscosity of 250 cps and was ready for spraying to pine wood particles for making a 3-layer exterior grade particleboard.

Dry fine pine particles of less than 20 mesh size were sprayed with 12 %, by weight of the liquid copolymer adhesive based on oven dry weight of pine particles. The large size core particles, larger than 20 mesh and smaller 1han 4 mesh, were sprayed with 8 % of the mixed adhesive. The resinated face particles had a moisture content of about 15 - 18% and the core particles had a moisture content of about 8 - 12 %. A 3-layer construction particleboard (450 x 350 x 16 mm) was formed with 50 % fine particles for the face layers and 50 % large particles for the core layer. The mat was pressed at 210 °C under an initial pressure of 30 kg/M³.

Under the same condition two boards bonded with the water soluble carbohydrates resin were produced with much longer press times of 10 & 12 minutes respectively. As can be seen from Table 2 board bonded with the copolymer adhesive required only 4 minutes to thermoset while board bonded with water soluble carbohydrates based adhesive took 12 minutes to produce a boil resistant bond. The board bonded with the copolymer adhesive was less odourous and had a lighter colour than the board bonded with water soluble carbohydrates.

Table 2. Properties of 16 mm particleboards bonded with copolymer adhesive and carbohydrate based adhesive

Board ID Press time Density OR ( Pa) OE IB 24 hr adhesive (min) (kg/IvO dry boil (GPa) (kPa) Swell (%)

Copolymer 4 786 17.6 9.2 37.2 560 8.2

Carbo- 10 782 17.5 3.2 30.7 380 25.6 hydrate

12 779 18.2 9.8 38.4 570 7.7

CAN0188.2-M78 17.2 5.0 25.0 500

Example 4'

This example demonstrates the use of spent sulfite liquor, a waste by-product of sulfite pulping process, in combination with mimosa tannin powder, derived from black wattle bark, a commercial product from South Africa, to produce a copolymer liquid resin adhesive. This copolymer resin adhesive was used to manufacture exterior grade poplar waferboard. The spent sulfite liquor, an ammonium based lignosulfonate, was drained off from a chip digester at a Canadian pulp mill and evaporated under vacuum to a concentration of about 31 % solids content. The concentrated spent sulfite liquor consisted mainly of lignins (61 %) and reducing sugars (32 %), had a viscosity of 85 cps, and a pH of 3.9. The reducing sugars were derived from hemicellulose hydrolysis and consisted mainly of monomeric xylose, glucose, mannose, galactose. Ten parts by weight of the concentrated spent sulfite liquor was admixed with fifty parts by weight of mimosa tannin powder and then subsequently mixed with ten parts by weight of 95 % paraformaldehyde powder. The copolymer liquid resin adhesive had a solids content of about 50 %, a pH of about 4.8, and a viscosity of 378 cps. Commercial poplar wafers were sprayed with the liquid copolymer resin adhesive at a rate of 6 % solids weight based on O.D. weight of poplar wafers. In addition, 1 % by weight of molten slack wax was also sprayed onto the wafers. The resinated wafers were hand felted into mats that were hot pressed at 210 °C temperature and a pressure of 35 kg/cm², for 3, 4, and 5 minutes respectively, resulting in three waferboards of 460 X 460 x 11.1 mm, with an average density of about 680 kg/m³. The waferboards were conditioned for three days and then tested in accordance with CAN 3- 0188.0-M78 standard test method for waferboard. Test results are summarized in Table 3.

Table 3. Properties of 11.1 mm poplar waferboards bonded with 6 % copolymer liquid resin adhesive (spent sulfite liquor and tannin resin adhesive)

Board ID Press time Density MOR (MPa) MOE IB 24 hr (min) ( g/ ³) dry boil (GPa) (kPa) Swell

1 3 650 23.5 10.7 4030 440 12.6

2 4 664 24.5 12.3 4240 485 10.4

3 5 673 24.7 13.6 4380 480 9.6

CAN3-0437.0M86 17.2 8.6 3100 345 25.0

It should be noted that when the ammonium based spent sulfite liquor was used alone to bond the waferboard, a minimum press time of 10 minutes was required to cure the resin adhesive to produce a boil-proof bond. The above copolymer resin adhesive bonded waferboards surpassed the Canadian National standards for waferboards.

Example 5

This example describes the use of sugar molasses, quebracho tannin, pine bark fine powder and formalin to formulate a copolymer resin adhesive for bonding a 3-layer poplar particleboard. The sugar molasses was obtained from a beet sugar refinery with solids content of 68% and pH of 9.3. Quebracho tannin powder was dissolved into the molasses with sodium hydroxide solution to adjust the pH of the mixture to 12.6 and the solids content of 42%. To is mixture was added 10% dry weight of pine bark powder (<0.125 mm based on O.D. weight of wood particle furnish) and an equal amount of water. To this mixture 9% formaldehyde (30% solution formalin) based on solids weight of tannin powder and beet molasses was added to form a viscous liquid. This catalyzed adhesive mixture had a relatively long pot life, more man 7 hours, after the addition of formaldehyde. This resin adhesive was blended with particle furnish to contain 12% resin solids for face fumish and 10% for core fumish particles. The moisture content for the face fumish was about 28% and for the core particles, 16%. A three layer particleboard of 16mm thickness of 600mm x 600mm size was pressed at 200°C for two and a half minutes. Test results are summarized in the following table:

Table 4. Properties of 3-layer particleboard bonded with sugar molasses, quebracho tannin, pine bark powder, copolymer resin adhesive

Board ID Press Density MOR (MPa) MOE IB Swell(%) temp/time (kg m³) dry boil (MPa) (kPa) Boil/Soak

°C/min (2h)/(24h)

1 200/2.5 755 19.3 8.2 3260 850 21.5/10.2

CAN3-188.2-M78 17.2 5.0 2500 500 25.0/na

The use of pine bark powder is particularly beneficial: direct use of tannin in the pine bark as adhesive and as well as a filler, proportionally enhances bonding efficiency, reduces wood particle furnish in the particleboard and acts as a scavenger to reduce free formaldehyde

Example 6

This example describes the use of commercial sugar products in combination with western hemlock bark extract, as a thermosetting adhesive for bonding plywood. Purified granulated sugar, a disaccharide of glucose and fructose derived from sugarcane, and com syrup, consisting mainly of glucose derived from co starch, were used, respectively, in combination with western hemlock bark extract solids, to formulate copolymer adhesives. Sucrose and com syrup were separately mixed with water to obtain a solution of 50 % concentration or solids content. To each solution, 5 % ammonium sulfate powder, O.D. basis, was added. Each solution was heated to boiling point until the solution turned brownish in colour before being mixed with equal parts of western hemlock bark extract solution at 50 % solids. After mixing, 10 % by weight of 95 % paraformaldehyde powder was added to each of the copolymer adhesives, based on O.D. weight. The sucrose-phenolic copolymer liquid adhesive had a solids content of about 51.3 %, a pH of 6.8 and a viscosity of 142 cps. The com-syrup phenolic copolymer liquid adhesive had a solid content of 52.5 %, a pH of 5.6 and a viscosity of 395.

These two carbohydrates-phenolics copolymer liquid adhesives were used for bonding plywood. Fabrication of 3-ply birch plywood was performed under identical conditionzsas described in the previous Example 4. The same cycle of boiling-drying treatment was also carried out on the plywood test specimens. After 5 cyclic treatments, these plywood specimens remained intact and showed no sign of delamination along the glue lines.

Example 7

This example demonstrates the production of exterior grade medium density fiberboard (MDF) with addition of liquid mimosa tannin and formaldehyde resin in combination with the water soluble resin material (carbohydrates) already existing in the pine wood fibre, at a conventional MDF manufacturing facility. Pine wood chips, as they entered the pressurized cooker (digester), were sprayed with dilute solution of sulfuric acid (2.5 % concentration by weight) at a rate of a 0.1 % based on oven dry weight of pine chips, cooked under a steam pressure of 10.5 bar (186.5 °C) for about 10 minutes before being extruded through a disc refiner and converted into fibre. The wet pine fibre had a pH of 3.9 and contained about 16.2 % water soluble resin material derived from hemicellulose hydrolysis, resulting from the ten minute cooking. The wet fibre was men blended with liquid tannin and formaldehyde solution (20 % solids content) at a rate of 4 % based on O.D. weight of pine fibre and dried to 4 - 6 % M.C. and formed into a mat, which was pressed in a continuous press to produce an 8.5 mm MDF with a density of about 870 kg/m³. During pressing the water soluble resin material present in the fiber copolymerized in situ with the added tannin-formaldehyde resin and thermoset to form a strong bond. This 8.5 mm MDF had good physical properties suitable for all purpose interior applications. However, this 8.5 mm MDF was further given a post-heating treatment, resulting in an exterior grade, or N100 grade MDF (German standard DIN 68761). The most effective methods of carrying out the post-heating treatment were to press the freshly made MDF between two heated platens for a few minutes, or to put the MDF into a hot oven for a few hours. A full size MDF was put into a single opening press with a platen temperature maintained at 230 °C. The MDF was pressed at 2 bar of pressure to make full contact of MDF with the platens, for 3 minutes. Another MDF, while it was still hot from the continuous press, was put into an oven set at 180 °C temperature with forced circulation, for 3 hours. Test results of the controlled MDF along with post-heat treated MDF are listed in Table 5.

Table 5. Properties of 8.5 mm MDF bonded in situ with Carbohydrate and Liquid-Tannin- Formaldehyde Copolymer Adhesive

Post-heating Density MOR MOE IB (kPa) Swell (%) treatment (kg/M³) (MPa) (GPa) dry_ V- 100 24 hr soak 2 hr boil

none 882 36.2 42.6 0.95 - 8.2

post oven 876 37.3 44.7 1.05 0.36 4.3 15.6 heating (180

°C/3hr) post press 879 38.1 44.1 1.07 0.55 3.7 14.4 heating (230

°²C /3 min)

DIN 68761 0.15

Example 8

This example describes the use of a copolymer resin adhesive consisting of tannin powder, black liquor, spent sulfite liquor and 95 % paraformaldehyde powder, for bonding foundry sand. Fifty-five parts by O.D. weight of the black liquor (the same material as used in Example 1), thirty-five parts of the ammonium based lignosulfonate (the same material as used in Example 3), fifteen parts of mimosa tannin powder and thirteen and a half parts of formalin solution (37 % with 5% methanol) were put together and mixed thoroughly with addition of water to formulate a liquid resin adhesive with a solids content of about 50 %.

A 60 gram sample of the liquid adhesive was mixed with 2 kg of AFS GEN 60 sand, resulting in a resin content of 1.5 % by weight of the sand. The resin coated sand was Ihen used to produce 6.3 mm thick tensile specimen (dog bones) by heating hand rammed sand between a pair of hot plates at 250 °C for 2, 3, and 4 minutes respectively, to cure and thermoset the resin adhesive. All heated solids turned brownish in colour. Edge retention and surface definition appeared normal. Test results of tensile strengths, curing time and results from a commercial phenolic resin are summarized in Table 6.

Table 6. Tensile strength vs. curing time

Curing time Tensile strength vs. Curing time (min at 250 °C) (1.5 % copolymer adhesive)

2 645

3 686

4 722 commercial phenolic resin 700

Strength figures were the average of the two tests. Additional specimens were made one week later from the original batch of bagged resin coated sand. Tensile strengths were not changed. This indicated that the pre-mixed sand has a long shelf life. By contrast, liquid tannin formaldehyde resin used alone had a shelf life of only a few hours.

Claims

1. An adhesive composition comprising: a product produced by copolymerization of one or more phenolic compounds and one or more water-soluble carbohydrates; or a mixture comprising one or more phenolic compounds or one or more water soluble carbohydrates, the one or more phenolic compounds being copolymerizable with the one or more water soluble carbohydrates.

2. A composition according to claim 1, being in the form of an aqueous mixture.

3. A composition according to claim 1, comprising the product produced by copolymerisation or the mixture of the one or more phenolic compounds and the one or more carbohydrates and being in the form of a dry powder.

4. A composition according to any claim 1 to 3 wherein the one or more phenolic compounds are provided by extract of bark, wood or nut shells.

5. A composition according to any claim 1 to 4 wherein composition comprises tannin as a source of phenolic compounds.

6. A composition according to claim 5 wherein the tannin is derived from the bark of mimosa or hemlock or the wood of Quebracho.

7. A composition according to any of claims 1 - 6, including bark powder as a source of the phenolic compounds.

8. A composition according to any of claims 1 to 7 wherein the one or more carbohydrates are derived from lignocellulosic material.

9. A composition according to any of claims 1 to 8 wherein the one or more carbohydrates comprise sucrose, fructose and/or glucose.

10. A composition according to any claim 1 to 9 wherein the carbohydrates are derived from sugar cane, molasses, beet and/or com syrup.

11. A composition according to any of claims 1 to 10 wherein the carbohydrates are provided by black liquor from hardboard production or by other wood molasses.

12. A composition according to any of claims 1 to 11 wherein the carbohydrates are provided by hydrolysis of hemicellulose and/or cellulose in lignocellulosic material.

13. A composition according to any of claims 1 to 12 wherein the copolymerization has been effected by means, or carried out in the presence of an aldehyde, or the mixture comprises an aldehyde for effecting copolymerization of the one or more phenolic compounds and the one or more water soluble carbohydrates.

14. A composition according to claim 13 wherein the aldehyde is formaldehyde.

15. A composition according to any of claims 1 to 14 wherein the copolymerization is effected using, or the mixture comprises, at least 30 %, by weight, of the phenolic compounds and at least 30 %, by weight, of the carbohydrates, based on the total weight of the phenolic compounds and the carbohydrates.

16. A composition according to claim 1 to 15 wherein the phenolic compounds and carbohydrates are copolymerized in the presence of lignosulfonate.

17. A composition according to any of claims 1 to 16 wherein the carbohydrates and lignin are provided by ammonia based spent sulfite liquor or lignosulfonate waste by-products from pulping of wood or other lignocellulosic material.

18. A composition according to claim 16 or 17 wherein the copolymerization is effected using, or the mixture comprises, at least 30 %, by weight, of the phenolic compounds, at least 30 %, by weight, of the carbohydrates, and at most 20 %, by weight, of the lignosulfonate, based on the total weight of the phenolic compounds, the carbohydrates, and the lignosulfonate.

19. A method of producing an adhesive bond comprising applying a composition according to any of claims 1 to 18 to a surface to which the bond is to be made and applying heat and pressure to the mixture to cause the composition to thermoset or cure to form the bond.

20. A method accordmg to claim 19, for producing a composite product, wherein the bonding is effected between components of the product, the adhesive composition being applied to the components and heat and pressure being applied to the components to cause the composition to thermoset or cure to form the bond.

21. A method according to claim 19 or 20, wherein immediately after the bonding has been effected the components are subjected to further heating under reduced pressure or in the absence of pressure to improve the bonding.

22. A method according to claim 19 or 21 wherein the composite product is a wood particle board (chip board), fiberboard, waferboard or orientated strand board or plywood or other wood composite product.

23. A method according to claim 19 or 20, for bonding foundry sand to produce a coherent product of foundry sand.

24. A method for producing a chip or fiber board or other composite article by bonding particulate lignocellulosic material with an aαnesive composition comprising tannin wherein the lignocellulosic material is hydrolyzed to release one or more water- soluble carbohydrates prior to adding 1he adhesive to the lignocellulosic material.

25. A method according to claim 24, wherein the adhesive composition comprises in addition to tannin, sulfite liquor and/or monomeric sugars.