WO2010135833A1

WO2010135833A1 - Derivatives of native lignin, lignin-wax compositions, their preparation, and uses thereof

Info

Publication number: WO2010135833A1
Application number: PCT/CA2010/000801
Authority: WO
Inventors: Alex Berlin; Paul Mulyk
Original assignee: Lignol Innovations Ltd.
Priority date: 2009-05-28
Filing date: 2010-05-27
Publication date: 2010-12-02
Also published as: EP2435454B1; EP2435453A1; US20140346395A1; CA2798161A1; EP2435455A1; CN102459425A; EP2435456A1; BRPI1012286A2; CN102459424B; EP2435454A1; CA2798161C; US20130253075A1; CA2798256A1; CA2798158C; CA2798196A1; US20100305243A1; US20130228298A1; CA2798196C; EP2435455A4; EP2435455B1

Abstract

A wax composition comprising a lignin derivative wherein the derivative has a total hydroxyl content of from about 0.1 mmol/g to about 7 mmol/g.

Description

TITLE: DERIVATIVES OF NATIVE LIGNIN, LIGNIN-WAX COMPOSITIONS,

THEIR PREPARATION, AND USES THEREOF

FIELD

This disclosure relates to derivatives of native lignin. This disclosure further relates to wax emulsions comprising derivatives of native lignin such as, for example, those suitable for production of wood composite materials. This disclosure further relates to waxy compositions, processes for dieir preparation, and methods for their use.

BACKGROUND

Wood composites are among the world's most significant renewable materials. The most common wood composites produced today are oriented strandboard (OSB), plywood, and particle board. Waxes are commonly used in the production of wood composites. The production of wood composites generally includes the blending of dried wood strands and/or particles with a suitable oil-derived liquid wax formulation and an adhesive (resin). These materials are generally derived from non-renewable sources. The wax component may provide water repellant properties that reduce swelling of composites during periods of elevated environmental humidity. The resin components bind wood strands and/or particles to form the composite structures. The addition of wax components to the wood composites is thought to improve the mechanical and physical properties of the panels.

Generally, after blending the wood feedstock with a wax emulsion and a resin, the wood composite is formed by applying suitable pressure at elevated temperatures. Optimal application of pressure and temperature levels are determined from the specifications of the wax and resin components used, the type of composite being produced, and the tree species from which the wood fibers and/or strands and/or particles are produced. Once the wood composites are produced, a number of quality/performance characteristics are determined including, thickness swell, water adsorption, modulus of rupture, modulus of elasticity, internal bond, among others. The testing protocols for each type of wood composite have been well-defined by the respective regulatory bodies. Examples of these standards include: the Canadian Standards Association (CSA) O112.6-M1977 Phenol and Phenol-Resorcinol Resin Adhesives for Wood (High- Temperature Curing), the CSA O437.1-93 Test Methods for OSB and Waferboard, or the CSA Standard 0151-04 Canadian softwood plywood. Before the commercialization of new resin (adhesive) it is usually necessary for them to meet the established standards such as the ones listed above.

Native lignin is a naturally occurring amorphous complex cross-linked organic macro- molecule that comprises an integral component of all plant biomass. Extracting native lignin from lignocellulosic biomass during pulping generally results in lignin fragmentation into numerous mixtures of irregular components. Furthermore, the lignin fragments may react with any chemicals employed in the pulping process. Consequently, the generated lignin fractions can be referred to as lignin derivatives and/ or technical lignins. As it is difficult to elucidate and characterize such complex mixture of molecules, lignin derivatives are usually described in terms of the lignocellulosic plant material used, and the methods by which they are generated and recovered from lignocellulosic plant material, i.e. hardwood lignins, softwood lignins, and annual fibre lignins.

Given that lignin derivatives are available from renewable biomass sources there is an interest in using these derivatives in certain industrial applications. For example, lignin derivatives obtained via organosolv extraction, such as the Alcell® process (Alcell is a registered trademark of Lignol Innovations Ltd., Burnaby, BC, CA), have been used in rubber products, adhesives, resins, plastics, asphalt, cement, casting resins, agricultural products, oil-field products and as feedstocks for the production of fine chemicals. It has been suggested to use lignin- modified phenol-formaldehyde resin as an adhesive for wood composites (see, for example, US5,010,156; WO93/21260; WO94/24192).

However, large-scale commercial application of the extracted lignin derivatives, has been limited due to, for example, the inconsistency of their chemical and functional properties. This inconsistency may, for example, be due to changes in feedstock supplies and the particular extraction/generation/recovery conditions. These issues are further complicated by the complexity of the molecular structures of lignin derivatives produced by the various extraction methods and the difficulty in performing reliable routine analyses of the structural conformity and integrity of recovered lignin derivatives.

Despite the advantages of lignin, for a variety of reasons, it has not been adopted for widespread use in wood composites. For instance, it is often problematic to provide lignins that have acceptable and consistent performance characteristics. Additionally, the cost of producing and/or purifying the lignin may make it uneconomic for certain uses. Furthermore, incorporation of high levels of lignin in phenol- formaldehyde resin can lead to undesirably high end-point viscosities. SUMMARY

The present disclosure provides derivatives of native lignin having a certain hydroxyl content. Surprisingly, it has been found that consistent and predictable properties may be provided by selecting for derivatives of native lignin having certain hydroxyl contents. The present disclosure provides derivatives of native lignin having a total hydroxyl content of from about 0.1 mmol/g to about 7 mmol/g. Such lignins have surprisingly been found to have an appropriate hydrophobicity for use in the wax component in die production of wood composites.

As used herein, the term "native lignin" refers to lignin in its natural state, in plant material.

As used herein, the terms "lignin derivatives" and "derivatives of native lignin" refer to lignin material extracted from lignocellulosic biomass. Usually, such material will be a mixture of chemical compounds that are generated during the extraction process.

Some exemplary embodiments of the present disclosure relate to lignin-modifϊed wax composition, such as an emulsion or a suspension, suitable for production of composite materials exemplified by composite wood products and die like.

Some exemplary embodiments of the present disclosure relate to lignin derivatives suitable for production of lignin-modified wax compositions. Suitable lignin derivatives generally comprise lignin derivatives diat are solubilized from lignocellulosic biomass by an organosolv process.

This summary does not necessarily describe all features of the invention. Other aspects, features and advantages of the invention will be apparent to those of ordinary skill in the art upon review of the following description of specific embodiments of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

The present disclosure will be described in conjunction with reference to the following drawings, in which:

Fig. 1 is a schematic flowchart showing various exemplary embodiments of a modular biorefinery processing system for recovery of four distinct structural classes of lignin derivatives from lignocellulosic feedstocks with organic solvents; Fig. 2 is a schematic flowchart of an exemplary modular continuous counter-flow biorefinery system configured for separation and recovery of three lignin solids fractions from a lignocellulosic feedstock. DETAILED DESCRIPTION

The present disclosure provides derivatives of native ligmn having a total hydroxyl content of from about 0.1 mmol/g to about 7 mmol/g. The present ligmn derivatives may have a total hydroxyl content of from about 1 mmol/g, about 2 mmol/g, 3 5 mmol/g, 4 mmol/g, 45 mmol/g, or greater The present kgnin derivatives may have a total hydroxyl content of from about 6 8 mmol/g, about 6.7 mmol/g, about 6.6 mmol/g, about 6.5 mmol/g, or less.

The present kgnin derivatives may be used in the production of wood composite materials Examples of wood composites include low density fibreboard (LDF), medium density fibreboard (MDF), high density fibreboard (HDF), strawboard & other agricultural fibre/particle boards, oriented strand board (OSB), particle board, plywood, and the like. The present kgnin derivatives may be used in the production of wood-plastic composites.

The present ligmn derivatives may be incorporated into the wax compositions useful in the manufacture of wood composites. The present wax composition may be an emulsion, suspension, or the like. The present wax compositions preferably comprise, on the basis of the solid contents, about 50% or less, about 45% or less, about 40% or less, about 35% or less, about 30% or less, of ligmn derivative. The present wax compositions preferably comprise, on the basis of the solid contents, about 0 1 or greater, about 1% or greater, about 5% or greater, about 10% or greater, about 15% or greater, about 20% or greater, of ligmn derivative. Presently, it is common to use "slack waxes" in the manufacture of wood composites.

Slack was is a by-product of the oil refining process and, as such, is a non-renewable resource whose cost is subject to the vagaries of crude oil prices. Furthermore, changes in oil-refinery practices, such as catalytic dewaxing, are eliminating slack-wax as a by-product.

The present wax compositions may comprises a variety of waxes including, but not limited to, fossil waxes (e g. montan, ozocerite, pyropissite, and the like); non-fossil waxes such as animal or vegetable waxes (e g. bees wax, plant waxes such as carnauba or candehlla, and the like); partially synthetic waxes (e.g. alcohol waxes, wool wax, and the like), syndietic waxes (e.g. amide waxes, polyethylene waxes, Fischer-Tropsch, polyolefins, Ziegler process wax, and the like); petroleum waxes such as macro-crystalline waxes or microcrystalline waxes (e g paraffins, slack wax, slack wax raffinates, decoded slack wax, soft wax, semi-refined wax, filtered wax, fully refined wax, bright stock wax, plastic microwaxes, hard microwaxes, and the like), and combinations thereof Preferred waxes for use herein include, petroleum waxes, synthetic waxes, and combinations thereof. For example, the present wax may be a slack wax The present compositions preferably comprise, on the basis of the solid contents, about 90% or less, about 80% or less, about 70% or less, of wax The present compositions preferably comprise, on the basis of the solid contents, about 20% or greater, about 30% or greater, about 40% or greater, about 50% or greater, of wax The present compositions may comprise a variety of optional components such as, for example, water, stabilizer, emulsifϊer, and combinations thereof.

Exemplary embodiments of the present disclosure relate to lignin-modified wax emulsions suitable for production of wood composite materials such as, but not limited to, oriented strandboard (OSB), plywood, and laminated veneerlumber (LVL). For example, the present hgnin derivatives may be commingled with commercial slack wax compositions to produce lignin-modifLed slack wax emulsions. Certain exemplary kgnin-modifϊed wax emulsions may be prepared by intermixing a wax or its components widi a surface tension/interfacial tension reducing agent such as lignosulphonates, isogenic hgnin derivatives, ionogenic detergents (e.g sodium dodecyl sulfate and the like), hgnin solubilizing agents (e g. sodium hydroxide, potassium hydroxide, concentrated soda solutions), strong nitrogen bases, and the like; and the present lignin derivatives Such exemplary emulsions may comprise at least 20% replacement of solids with the hgnin derivatives The hgnin-modified wax emulsions are preferably stable and provide bonding and stability performance that is similar to commercial wax emulsions when applied to wood composites. The levels of hgnin derivatives that may be incorporated into such modified wax emulsions can be further increased by hydrophobization of the hgnin derivatives by chemical modification or by modified biomass processing conditions Such hgnin-modified wax emulsions may be suitable replacements for oil-derived slack wax compositions that are commonly used for commercial production of wood composite materials.

The present invention provides derivatives of native hgnin recovered during or after pulping of lignocellulosic feedstocks The pulp may be from any suitable hgnocellulosic feedstock including hardwoods, softwoods, annual fibres, and combinations thereof.

Hardwood feedstocks include Acacia; Afzeka; Sjnsepalum duloifiium; Albizia, Alder (e g Alnus gluttnosa, Alnus rubra); Applewood; Arbutus; Ash (e.g F nigra, F quadrangulata, F excelsior, F. penmylvamca lameolata, F. latifoka, R profunda, F. amemana); Aspen (e.g. P. grandidentata, P. tremula, P. tπmuloides), Australian Red Cedar (Toona ahatά); Ayna (Distemonanthus benthatmanus); Balsa (O chroma pyramidale), Basswood (e g T. amemana, T heterophylld); Beech (e g F sylυatica, F grandijohά); Birch; (e g. Betula popuhjolia, B. nigra, B. papynfera, B. lenta, B. alleghaniensis/B. lutea, B. pendula, B. pubescem); Blackbean, Blackwood, Bocote, Boxelder, Boxwood, Brazilwood, Bubinga; Buckeye (e g. Aesailus hippocastanum, Aesculus glabra, Aeuulm jlava/ Aesculus octandrd); Butternut; Catalpa; Cherry (e g Prunus serotina, Prunus pennsylvanua, Prunus avium); Crabwood; Chestnut; Coachwood, Cocobolo; Corkwood; Cottonwood (e g Populus balsamijera, Populus deltoides, Populus sargentu, Populus heterophylld); Cucumbertree; Dogwood (e.g. Cornus flonda, Cornus nuttallii); Ebony (e g Dwspjros kurvζii, Diospyros melanida, Diospyros crassiβora), Elm (e.g. IJlmus amencana, Ulmus procera, IJlmus thomasii, Ulmus rubra, IJlmus glabra); Eucalyptus; Greenheart; Grenadilla; Gum (e g Nyssa sylvatua, Eucalyptus globulus, Lzqmdambar styraciflua, Nyssa aquahcά), Hickory (e g Carya alba, Carya glabra, Carya ovata, Carya laaniosά), Hornbeam, Hophornbeam, Ipέ, Iroko, Ironwood (e.g Bangkirai, Carpinus tarohniana, Casuanna eqmsetijolia, Choricbangarpia subargentea, Copatfera spp , Eusideroxylon %wagen, Guajacum officinale, Guajacum sanctum, Hopea odorata, Ipe, Krugiodendron jerreum, Lyonothamnus y l onii (L. βonbundus), Mesuajema, Oka spp., Olneya tesota, Ostrya virginiana, Parrotia persica, Tabebuia serratijolid), Jacaranda; Jotoba, Lacewood; Laurel; Limba; Lignum vitae; Locust (e.g. Robinia pseudacacia, Gkditsia tnacanthos); Mahogany; Maple (e.g Acer saccharum, Acer nigrum, Acer negundo, Aur rubrum, Acer sacώannum, Acer pseudoplatanus); Meranti; Mpingo; Oak (e.g. Quercus macrocarpa, Quenus alba, Quercus stellata, Quercus bicolor, Quercus vtrginiana, Quenus michauxii, Quercus prtnus, Quercus muhlenbergii, Quenus ihrysolepis, Quenus y l rata, Quercus robur, Quercus petraea, Quercus rubra, Quenus velutina, Quercus launjoha, Quercus jalcata, Quenus nigra, Quercus phellos, Quercus texanά); Obeche, Okoume; Oregon Myrtle; California Bay Laurel; Pear; Poplar (e.g. P. balsamifera, P. nigra, Hybrid Poplar {populus X

Ramin, Red cedar; Rosewood; Sal; Sandalwood; Sassafras; Satinwood, Silky Oak; Silver Wattle, Snakewood; Sourwood; Spanish cedar, American sycamore; Teak, Walnut (e g. Juglans nigra, Juglans regiά), Willow (e.g. Salix nigra, Sahx alba); Yellow poplar (Lanodendron tulipifera); Bamboo; Palmwood; and combinations /hybrids thereof

For example, hardwood feedstocks for the present invention may be selected from Acacia, Aspen, Beech, Eucalyptus, Maple, Birch, Gum, Oak, Poplar, and combinations /hybrids thereof The hardwood feedstocks for the present invention may be selected from Populus spp. (e g. Populus tnmuloides), Eucalyptus spp. (e.g Eucaylptus globulus), Acacia spp. (e.g. Acacia dealbata), and combinations/hybrids thereof.

Softwood feedstocks include Araucaπa (e g A. cunninghamu, A. angustijoha, A. araucana), softwood Cedar (e g. Jumperus inrgimana, Thuja phcata, Thuja ocadentalis, Chamaecyparis thyoides Callitropsis nootkatensis), Cypress (e.g Chamaecyparis, Cupressus Taxodium, Cupressus an^onica,

Taxodmm dishώum, Chamaecyparis obtusa, Chamaecyparis lawsomana, Cupressus sempervtren); Rocky Mountain Douglas fir, European Yew; Fir (e g. Abies balsamea, Abies alba, Abies procera, Abies amabihs), Hemlock (e.g Tsuga canadensis, Tsuga mertensiana, Tsuga heterophylld), Kauri, Kaya, Larch (e g Lanx deadua, Lanx kaempfen, Lanx lancina, Laπx ocadentalis), Pine (e g Pinus nigra, Pinus banksiana, Pinus ωntorta, Pinus mdiata, Pinus ponderosa, Pinus resinosa, Pinus sylvestns, Pinus strobus, Pinus monticola, Pinus lambertiana, Pinus taeda, Pinus paiustm, Pinus ngida, Pinus eώinatά), Redwood, Rimu; Spruce (e.g. Picea abies, Picea manana, Picea rubens, Picea sitchensis, Puea glaucά); Sugi; and combinations/hybrids thereof. For example, softwood feedstocks which may be used herein include cedar; fir; pine, spruce; and combinations thereof. The softwood feedstocks for the present invention may be selected from loblolly pine (Pinus taeda), radiata pine, jack pine, spruce (e.g., white, interior, black), Douglas fir, Pinus silvestns, Puea abies, and combinations/hybrids thereof. The softwood feedstocks for the present invention may be selected from pine (e g. Pinus radiata, Pinus taeda); spruce, and combinations/hybrids thereof.

Annual fibre feedstocks include biomass derived from annual plants, plants which complete their growth in one growing season and therefore must be planted yearly. Examples of annual fibres include, flax, cereal straw (wheat, barley, oats), sugarcane bagasse, rice straw, corn stover, corn cobs, hemp, fruit pulp, alfa grass, switchgrass, and combinanons/hybnds thereof. Industrial residues like corn cobs, fruit peals, seeds, etc. may also be considered annual fibres since they are commonly derived from annual fibre biomass such as edible crops and fruits. For example, the annual fibre feedstock may be selected from wheat straw, corn stover, corn cobs, sugar cane bagasse, and combinations /hybrids thereof.

The derivatives of native kgnin will vary with the type of process used to separate native lignins from cellulose and other biomass constituents. Preparations very similar to native hgnin can be obtained by (1) solvent extraction of finely ground wood (milled-wood lignin, MWL) or by (2) acidic dioxane extraction (acidolysis) of wood. Derivatives of native lignin can be also isolated from biomass pre-treated using (3) steam explosion, (4) dilute acid hydrolysis, (5) ammonia fibre expansion, (6) autohydrolysis methods Derivatives of native lignin can be recovered after pulping of lignocellulosics including industrially operated kraft, soda pulping (and their modifications) or sulphite pulping. In addition, a number of various pulping methods have been developed but not industrially introduced. Among them four major "organosolv" pulping methods tend to produce highly-purified lignin mixtures. The first organosolv method uses ethanol/ solvent pulping (aka the Alcell® process); the second organosolv method uses alkaline sulphite anthraquinone methanol pulping (aka the "ASAM" process); the third organosolv process uses methanol pulping followed by methanol, NaOH, and anthraquinone pulping (aka the "OrganoceU" process); the fourth organosolv process uses acetic acid/hydrochloπc acid or formic acid pulping (aka the "Acetosolv" process). It should be noted that kraft pulping, sulphite pulping, and ASAM organosolv pulping will generate derivatives of native hgmn containing significant amounts of organically-bound sulphur which may make them unsuitable for certain uses. Acid hydrolysis, soda pulping, steam explosion, Alcell® pulping, Organocell pulping, and Acetosolv pulping will generate derivatives of native lignin that are sulphur- free or contain low amounts of inorganic sulphur

Organosolv processes, particularly the Alcell® process, tend to be less aggressive and can be used to separate highly purified lignin derivatives and other useful materials from biomass without excessively altering or damaging the native lignin building blocks Such processes can therefore be used to maximi2e the value from all the components making up the biomass. Organosolv extraction processes however typically involve extraction at higher temperatures and pressures with a flammable solvent compared to other industrial processes and thus are generally considered to be more complex and expensive.

A description of the Alcell® process can be found in US Patent 4,764,596 (herein incorporated by reference) The process generally comprises pulping or pre-treating a fibrous biomass feedstock with primarily an ethanol/water solvent solution under conditions that include: (a) 60% ethanol/40% water, (b) temperature of about 180° C to about 210° C, (c) pressure of about 20 atm to about 35 atm, and (d) a processing time of 5-120 minutes. Derivatives of native lignin are fractionated from the native lignins into the pulping kquor which also receives solubilised hemicelluloses, other carbohydrates and other extractives such as resins, organic acids, phenols, and tannins. Organosolv pulping liquors comprising the fractionated derivatives of native lignin and other extractives from the fibrous biomass feedstocks, are often called "black liquors". The organic acid and extractives released by organosolv pulping significantly acidify the black liquors to pH levels of about 5 and lower. After separation from the cellulosic pulps produced during the pulping process, die derivatives of native lignin are recovered from the black liquors by depressurization followed by flashing with cold water which will cause the fractionated derivatives of native lignin to precipitate thereby enabling their recovery by standard solids/liquids separation processes. Various disclosures exemplified by US Patent No 7,465,791 and PCT Patent Application Publication No. WO 2007/129921, describe modifications to the Alcell organosolv process for the purposes of increasing the yields of fractionated derivatives of native lignin recovered from fibrous biomass feedstocks during biorefining. Modifications to the Alcell organosolv process conditions included ad_justing: (a) ethanol concentration in the pulping liquor to a value selected from a range of 35% - 85% (w/w) ethanol, (b) temperature to a value selected from a range of 100° C to 350° C, (c) pressure to a value selected from a range of 5 atm to 35 atm, and (d) processing time to a duration from a range of 20 minutes to about 2 hours or longer, (e) hquor-to-wood ratio of 3.1 to 15.1 or higher, (f) pH of the cooking liquor from a range of 1 to 6.5 or higher if a basic catalyst is used

The present invention provides a process for producing derivatives of native lignin, said process comprising (a) pulping a fibrous biomass feedstock with an organic solvent/water solution,

(b) separating the cellulosic pulps or pre-treated substrates from the pulping liquor or pre-treatment solution,

(c) recovering derivatives of native hgnin.

The organic solvent may be selected from short chain primary and secondary alcohols, such as such as methanol, ethanol, propanol, and combinations thereof. For example, the solvent may be ethanol. The liquor solution may comprise about 20%, by weight, or greater, about 30% or greater, about 50% or greater, about 60% or greater, about 70% or greater, of ethanol.

Step (a) of the process may be earned out at a temperature of from about 100°C and greater, or about 120⁰C and greater, or about 140⁰C and greater, or about 160⁰C and greater, or about 17O⁰C and greater, or about 180⁰C and greater The process may be carried out at a temperature of from about 300⁰C and less, or about 28O⁰C and less, or about 26O⁰C and less, or about 24O⁰C and less, or about 220⁰C and less, or about 210⁰C and less, or about 205⁰C and less, or about 200⁰C and less.

Step (a) of the process may be earned out at a pressure of about 5 atm and greater, or about 10 atm and greater, or about 15 atm and greater, or about 20 atm and greater, or about 25 atm and greater, or about 30 atm and greater. The process may be earned out at a pressure of about 150 atm and less, or about 125 atm and less, or about 115 atm and less, or about 100 atm and less, or about 90 atm and less, or about 80 atm and less

The fibrous biomass may be treated with the solvent solution of step (a) for about 1 minute or more, about 5 minutes or more, about 10 minutes or more, about 15 minutes or more, about 30 minutes or more The fibrous biomass may be treated with the solvent solution of step (a) at its operating temperature for about 360 minutes or less, about 300 minutes or less, about 240 minutes or less, about 180 minutes or less, about 120 minutes or less.

The pH of the pulp liquor may, for example, be from about 1 to about 6, or from about 1 5 to about 5.5.

The weight ratio of liquor to biomass may be any suitable ratio. For example, from about 5.1 to about 15 1, from about 5.5.1 to about 10 1, from about 6:1 to about 8 1. The volume of extraction solution is from about 5 to about 10 times the volume of the biomass feedstock. For example, the volume of extraction solution may be from about 6 to about 8 times that of the biomass

The present disclosure provides a process for producing a hgnin derivative having a total hydroxyl content of about 0.1 mmol/g to about 7 mmol/g. Said process comprises: a) pulping or pre-treating a fibrous biomass feedstock in a vessel with an organic solvent/water solution to form a liquor, wherein: l. the solution comprises about 30% or greater, by weight, of organic solvent; and 11. the pH of the hquor is from about 1 to about 6; b) heating the hquor to about 100⁰C or greater; c) raising the pressure in the vessel to about 5 atm or greater; d) maintaining the elevated temperature and pressure for 1 minute or longer; e) separating the cellulosic pulps from the pulp liquor The present lignin derivatives may comprise alkoxy groups. For example, the present ϋgnin derivatives may have an alkoxy content of 2 mmol/g or less; about 1.4 mmol/g or less; about 1.2 mmol/g or less; about 1 mmol/g or less; about 0.8 mmol/g or less; about 0.7 mmol/g or less; about 0.6 mmol/g or less; about 0.5 mmol/g or less; about 0.4 mmol/g or less; about 0.3 mmol/g or less. The present lignin derivatives may have an alkoxy content of 0.001 mmol/g or greater, about 0.01 mmol/g of greater, about 0.05 mmol/g or greater, about 0.1 mmol/g or greater.

The present lignin derivatives may comprise ethoxyl groups. For example, the present lignin derivatives may have an ethoxyl content of 2 mmol/g or less; about 1.4 mmol/g or less; about 1.2 mmol/g or less; about 1 mmol/g or less; about 0.8 mmol/g or less; about 0.7 mmol/g or less; about 0.6 mmol/g or less; about 0.5 mmol/g or less; about 0.4 mmol/g or less; about 0.3 mmol/g or less. The present lignin derivatives may have an ethoxyl content of 0.001 mmol/g or greater, about 0.01 mmol/g of greater, about 0.05 mmol/g or greater, about 0.1 mmol/g or greater.

The present lignin derivatives may have any suitable phenolic hydroxyl content such as from about 2 mmol/g to about 8 mmol/g. For example, the phenolic hydroxyl content may be from about 2.5 mmol/g to about 7 mmol/g; about 3 mmol/g to about 6 mmol/g.

The present lignin derivatives may have any suitable number average molecular weight

(Mn). For example, the Mn may be from about 200 g/mol to about 3000 g/mol; about 350 g/mol to about 2000 g/mol; about 500 g/mol to about 1500 g/mol. The present hgnin derivatives may have any suitable weight average molecular weight (Mw) For example, the Mw may be from about 500 g/mol to about 5000 g/mol; about 750 g/mol to about 4000 g/mol; about 900 g/mol to about 3500 g/mol.

The present hgnin derivatives may have any suitable polydispersity (D). For example, the D may be from about 1 to about 5; from about 1 2 to about 4, from about 1 3 to about 3 5, from about 1.4 to about 3.

The present lignin derivatives are preferably hydrophobic. Hydrophobicity may be assessed using standard contact angle measurements In the case of hgnin a pellet may be formed using a FTIR KBr pellet press. Then a water droplet is added onto the pellet surface and the contact angle between the water droplet and the hgnin pellet is measured using a contact angle goniometer As the hydrophobicity of lignins increases the contact angle also increases Preferably the hgnins herein will have a contact angle of about 90° or greater. In the case of the use of kgnin in wax emulsions the lignins are preferably very hydrophobic so as to resemble paraffin and provide maximum water repellent properties As used herein the term "total hydroxyl content" refers to the quantity of hydroxyl groups in the kgnin derivatives and is the arithmetic sum of the quantity of aliphatic and phenolic hydroxyl groups (OHtot = OHaI + OHph) OHaI is the arithmetic sum of the quantity of primary and secondary hydroxyl groups (OHaI = OHpr + OHsec). The hydroxyl content can be measured by quantitative ^πC high resolution NMR spectroscopy of acetylated and non- acetylated lignin derivatives, using, for instance, 1,3,5-trioxane and tetramethyl silane (TMS) as internal reference. For the data analysis "BASEOPT" (DIGMOD set to baseopt) routine in the software package TopSpin 2.1.4 was used to predict the first FID data point back at the midpoint of ¹³C r.f. pulse in the digitally filtered data was used. For the NMR spectra recording a Bruker AVANCE II digital NMR spectrometer running TopSpin 2.1 was used. The spectrometer used a Bruker 54 mm bore Ultrashield magnet operating at 14.1 Tesla (600 13 MHz for ¹H, 15090 MHz for ^πC). The spectrometer was coupled with a Bruker QNP cryoprobe (5 mm NMR samples, ^πC direct observe on inner coil, ¹H outer coil) that had both coils cooled by helium gas to 2OK and all preamplifiers cooled to 77K for maximum sensitivity Sample temperature was maintained at 300 K±O 1 K using a Bruker BVT 3000 temperature unit and a Bruker BCU05 cooler with ca. 95% nitrogen gas flowing over the sample tube at a rate of 800 L/h

Quantification of ethoxyl groups was performed similarly to aliphatic hydroxyls quantification by high resolution ⁿC NMR spectroscopy Identification of ethoxyl groups was confirmed by 2D NMR HSQC spectroscopy 2D NMR spectra were recorded by a Bruker 700 MHz UltraShield Plus standard bore magnet spectrometer equipped with a sensitive cryogenically cooled 5mm TCI gradient probe with inverse geometry The acquisition parameters were as follow: standard Bruker pulse program hsqcergp, temperature of 298 K, a 90° pulse, 1.1 sec pulse delay (dl), and acquisition time of 60 msec. The present disclosure provides a method of producing a composite wood product, said method comprising: a. Obtaining a cellulosic fibre material; b. Obtaining an adhesive suitable for adhering the fibres of said material; c. Mixing said cellulosic material with said adhesive, forming the mixture into a suitable shape and curing; and d Applying a wax composition according to the present disclosure to the shaped article.

While the present wax compositions are useful in the production of composite wood products, they also have other utilities. For example, the present wax compositions may be used in paints/lacquers, printing inks, textiles, floor polishes/protectants, facade protection, wood/timber protection, mold release, tube drawing, agricultural uses, automotive polishes, packaging films, temporary protective coatings, food coatings, metal working, alkali stπppable coatings, anti-transpiration, paper & board (coatings/lubricants, sixing, corrugated board tteatment, transfer papers, wet-strength improvement, pπntabikty improvement), glass lubrication, glass fibre srzing, insecticide stickers, leather treatment, and the like.

All citations are herein incorporated by reference, as if each individual publication was specifically and individually indicated to be incorporated by reference herein and as though it were fully set forth herein. Citation of references herein is not to be construed nor considered as an admission that such references are prior art to the present invention. One or more currently preferred embodiments of the invention have been described by way of example The invention includes all embodiments, modifications and variations substantially as hereinbefore described and with reference to the examples and figures. It will be apparent to persons skilled in the art that a number of variations and modifications can be made without departing from the scope of the lnvenuon as defined in the claims Examples of such modrficauons include the substitution of known equivalents for any aspect of the invention in order to achieve the same result in substantially the same way.

The following examples are intended to be exemplary of the invention and are not intended to be limiting. EXAMPLES

Example 1: Preparation of lignin-modified wax emulsions using sodium hydroxide as a solubilizing agent at medium slack wax replacement levels

An exemplary lignin-modified slack wax emulsion was prepared with the follow process: (a) a selected amount of a Reax^® 85A (Reax is a registered trademark of the MeadWestvaco Corporation, Glen Allen, VA, USA), a commercial lignosulphonate (LS) was dissolved in suitable volume of water;

(b)a selected amount of sodium hydroxide (NaOH) was mixed into the solution; (c) a selected amount of a mixture of lignin derivatives was mixed into the solution; (d) the solution was filtered to produce a filtrate; and

(e) the filtrate then was then mixed into a selected volume of a commercial slack wax emulsion (EW-58S, Hexion Specialty Chemicals, Columbus, OH, USA) to produce a stable lignin- modified wax emulsion. The EW-58S wax emulsion contained 58% solids. The lignin derivatives were produced by organosolv pulping of a batch of aspen chips. The black liquor generated during the organosolv pulping was separated from the pulp solids materials, and then was rapidly diluted with cold water which caused precipitation of lignin derivatives. The lignin derivatives were separated from the de-lignified liquor and dried prior to use. The processing conditions and physico-chemical properties of the lignin derivatives recovered after organosolv pulping of the aspen wood chips, are shown in Table 1.

Table 1:

Biomass processing parameter

Acid (% odw feed) 0

Cooking time (min) 60

Cooking temperature (⁰C) 193

Ethanol concentration in cooking liquor (% wt.) 50

Lignin derivatives yield (% total native lignin) 60 Characteristics of lignin derivatives

Primary hydroxyl groups (mmol/g) 0.95

Secondary hydroxyl groups (mmol/g) 0.79

Aliphatic hydroxyl groups (mmol/g) 1.74

Phenolic hydroxyl groups (mmol/g) 4.21

Total hydroxyl groups (mmol/g) 5.95

Methoxyl groups (mmol/g) 6.32

Ethoxyl groups (mmol/g) 0.68

Synngyl groups (mmol/g) 4.84

Guaiacyl groups (mmol/g) 1.89 Degree of condensation (DC) 33

Number-average molecular weight (Mn, g/mol) 887 Weight- average molecular weight (Mw, g/mol) 1,808 Z average molecular weight (Mz, g/mol) 3,650 Polydispersity (D) 2.04

Glass transition point (Tg, ⁰C) 61

Thermal Flow Index at 105^«C (mm) 24

Thermal Flow Index at 120⁰C (mm) 37

Thermal Flow Index at 150⁰C (mm) 69

Thermal Flow Index at 180⁰C (mm) 82

Melt Flow Index (g lignin derivatives/ 10 mm measured at 160°C) ~~50

Normalized specific Internal bond strength at 12O⁰C (MPa/cm²/mg) 2.9

Normalized specific Internal bond strength at 15O⁰C (MPa/cm²/mg)* 3.6

Normalized specific Internal bond strength at 18O⁰C (MPa/cm²/mg)* 4.9 * Measured at 30% replacement level by a kgnin derivative of a commercial OSB phenolic resin

Favourable emulsifying conditions for incorporation of the lignin derivatives into a slack wax emulsion were achieved. Several lignin-modified wax emulsion formulations were prepared by combining solutions produced by following steps (a)-(d) that incorporated mixtures of lignin derivatives recovered from different types of hardwood lignocellulosic feedstocks, with, the EW- 58S wax emulsion. Several other lignin-modified wax emulsions were prepared by proportionally increasing the amounts of mixtures of lignin derivatives incorporated into the EW-58S wax emulsions. The LS was added to all samples, as a surface tension/inter facial tension reducing agent, in a fixed amount to yield a final concentration of 0.03%. A range of solutions with varying concentrations of NaOH were prepared while mixtures of lignin derivatives were added in excess (Table 2). Excess lignin derivatives were filtered out. The remaining supernatants containing the lignin derivatives were intermixed into the EW-58S wax emulsions in a 1:1 volume ratio. The solutions were mixed thoroughly and then left to stand for 24 hrs.

Modifϊed-lignin wax emulsion samples 1 - 4 (Table 2) formed a solid black mass when intermixed into the commercial slack wax emulsion and produced a non-liquid formulation with limited suitability for wood composites applications.

Table 2:

1 12 0 0 1.0211 5.00 0 5.00 Solid broken

2 10 0 2 1.0519 4.17 ^~ 0.03 4.17 Solid broken

3 5 5 2 1.0508 2.08 0.03 2 08 Solid broken

4 2.5 7.5 2 0.9732 1.04 0.03 1.04 Solid broken 5 1.25 8.75 2 0.8626 0.52 0.03 0.52 Thick light

6 0.6 9.4 2 1.0217 0.25 0.03 0.25 ^Normal viscosity lighter

7 0.25 9.75 2 1.0020 0.10 0.03 0.10 ^Norma viscosity lighter

Modified-lignin wax emulsion sample 5 (Table 2) formed a thick coffee brown solution when intermixed into the commercial slack wax emulsion and produced a non-liquid formulation with limited suitability for wood composites applications.

Modified-lignin wax emulsion samples 6 and 7 (Table 2) formed liquid light brown solutions when intermixed into the commercial slack wax emulsion, that were stable for several dap at room temperature. These modified-lignin wax emulsions were suitable for wood composites applications. These modified-lignin wax emulsions contained about 10-25% wt. of the novel lignin derivatives.

Example 2: Preparation of lignin wax emulsions with varying NaOH & LS contents. Modified-lignin wax emulsion samples were produced according to the recipes shown in

Tables 3-6, with the following process steps:

(a) a solution comprising LS, NaOH and water was prepared following steps (a)-(b) from Example 1;

(b) a mixture of lignin derivatives was added to the solution at a ratio of about lg:2g yielding about 33% lignin (by wt) in the solution;

(c) the lignin solution was exposed to ultrasound treatments and mixed thoroughly to produce a black paste;

(d) the black paste was combined with EW-58S wax emulsion at a ratio of 3:2, mixed thoroughly, and left to stand for two days at an ambient temperature. Table 3: Preparation of the LS-NaOH solutions to produce lignin-modified slack wax emulsions with a final LS concentration of 0.3%

Sample 7.4% NaOH Water LS [Final NaOHl

[Final LS] (%) ID# added (toL) (mL) (mL) (%)

IA 2.0 8.0 2.0 0.8 1.23

IB 1.5 8.5 2.0 0.8 0.93

1C 1.0 9.0 2.0 0.8 0.62

ID 0.8 9.2 2.0 0.8 0.49

IE 0.6 9.4 2.0 0.8 0.37 ^~

IF 0.4 9.6 2.0 0.8 0.25 Table 4: Preparation of lignin-modified wax emulsions with a final LS concentration of

0.3%

Sampl LS-NaOH Lignin Wax [Final [Final

[Final lignin] [Final wax] e solution derivatives emulsion LS] NaOH]

(%) \'°)

ID# (g) (8) (0.9 g/tnL) (%) (%)

1A2 2.0 1.11 1.8 0 3 0.50 22.6 21 3

1B2 2.0 1.08 1.8 0.3 0.38 22.1 21 4

1C2 2.0 1.04 1 8 0.3 0.25 21.5 21 6

1D2 2.0 1.05 1.8 0.3 0.20 21 6 21 5

1E2 2.0 1.14 1 8 0.3 0.15 23.1 21 1

1F2 2.0 0.97 1 8 0.3 0.10 20 3 21 9

Table 5: Preparation of the LS-NaOH solutions to produce lignin-modified slack wax emulsions with a final LS concentration of 1.6%

Sample 7 4% NaOH Water LS [Final NaOH]

[Final LS] (%) ID# added (tnL) (mL) (mL) (%)

2A 2.0 8.0 2.0 2.3 1.23

2B 1.5 8.5 ^~ 2.0 ^~ 3.9 0.93

2C ^~ 1.0 9.0 ^~2.0 ^~ 3.9 0.62

^~2D^~ 0.8^{~ ~} 92 ^~ ^~ 2.Q ^"3.9 0A9

2E 0 6 9.4 ^~ 2.0 3 9 ^~ ^~ 0 37

^~2F 0.4 9.6 ^~ 2.(T^" 3.9^~ 025

Table 6: Preparation of lignin-modified wax emulsions with a final LS concentration of

1.6%

Sampl LS-NaOH Lignin Wax [Final [Final

[Final lignin] [Final wax] e solution derivatives emulsion LS] NaOH]

(%) (%)

ID# (g) (S) (0.9 g/mL) (%) (%)

2A2 2.0 1.03 1 8 1.0 0.51 21 3 21 6

2B2 2.0 0.94 1 8 1.6 0.39 19 8 22.0

2C2 2.0 1.01 1 8 1.6 0.26 21 0 21.7

2D2 2.0 1.14 1 8 1.6 0.20 23 1 21 1

2E2 2.0 1.02 1 8 1.6 0.15 21 2 21 7

2F2 2.0 1.05 1 8 1.6 0.10 21 6 21 5

Lignin-modified wax emulsion sample ID#s 1A2-1B2 resulted in black broken emulsions. Lignin-modified wax emulsion sample ID#s 1F2 resulted in a chocolate brown liquid with phase separauon. Lignin-modifϊed wax emulsion sample ID#s 1C2-1E2 conditions yielded liquid, chocolate brown formulations with evenly distributed precipitates. Lignin modified wax emulsions sample ID#1C2 appeared to be the most homogenous formulation. Ligmn-modifϊed wax emulsion sample ID#s 2A2-2B2 resulted in solid brown/black solid mass, broken emulsion. Ligmn-modified wax emulsion sample ID# 2C2 resulted in a slightly thick chocolate brown solution with precipitates, and showed some phase separation Ligmn-modified wax emulsion sample ID#s 2D2-2F2 resulted in a chocolate brown formulation containing some evenly distributed precipitates and particulate matter. Lignin-modifϊed wax emulsion sample ID# 1C2 yielded the best result formulation comprising a stable and uniform emulsion at 0.3% LS The best formulation with a 1.6% LS final concentration was the lignin- modified wax emulsion sample ID# 2C2 which had a shghdy thicker composition in comparison to the series of wax emulsions produced with a 0.3% LS final concentration. The optimal range of final NaOH concentrations was found to be about 0.25% to about

0 15% for the 0 3% LS series, and the optimal range of final NaOH concentrations in the 1.6% LS series was about 0 26% to about 0.10%.

The addition of excess NaOH appeared to break-down the kgnin-modified wax emulsion into separated phases, although the lignin derivatives remained in solution Lower final NaOH concentrations did not yield stable lignin-modifϊed slack wax formulations in view of the particle aggregation that was observed in those compositions. The addition of the LS facilitated stable lignin-modifϊed slack wax formulations. However, combinations of higher concentrations of both LS and NaOH resulted in thicker wax emulsions that are not particularly suitable for the manufacture of wood composite materials. In this example, the concentrations of LS incorporated into the compositions were relatively higher compared to those used in Example #1, but were kept constant among a given dilution series (Tables 3 and 5). The final concentration achieved of LS was 03% for the first dilution series (Table 4) and 1.6% for the second dilution series (Table 6). Both dilution series were otherwise identical The final NaOH concentration in the emulsions ranged from 0.1% to 0.5%. The concentration of lignin derivative mixtures was about 22% of the total final formulations. The final concentration of solids in the lignin -modified wax emulsions produced in this example was around 45% with the lignin derivatives comprising about half of the emulsions and the remainder comprising the commercial slack wax.

The increase in the lignin derivatives content produced stable wax emulsions suitable for use in production of OSB materials.

Example 3: Preparation of lignin-modified wax emulsions with vatying LS and lignin derivatives contents.

Fifty-mL samples of modiiied-kgnin wax emulsion samples were produced according to the recipes shown in Tables 7 10, following process steps outlined in Example 2. A first series was prepared wherein the final solids content in the modified-lignin wax emulsions was 54% solids, with approximately half comprising novel lignin derivatives solubilized and recovered from a hardwood kgnocellulosic feedstock.

A second series was prepared wherein the final solids content in the modified-lignin wax emulsions was 56%, with 25% of that composing the novel lignin derivatives.

Table 7: Preparation of the LS-NaOH solutions to produce lignin-modified slack wax emulsions with a final LS concentration of 1.0%, and comprising about 50% lignins.

7.4% NaOH Water LS [Final NaOH]

ID# [Final LS] (%) added (mL) (mL) (mL) (%)

1C 1.0 9.0 2.0 3.9 0.62

2C 1.0 9.0 2.0 3.9 0.62

2D 0.8 9.2 2.0 3.9 0.49

^{~ ~} 2E^{~ ~ ~} 0.6 ^"9.4^" 2.0 ^~3.9^~ ^{" "} 0.37 ^"

Table 8: Preparation of lignin-modified wax emulsions with a final LS concentration of about 1%

LS-NaOH Lignin Wax [Final [Final

[Final lignin] [Final wax]

ID# solution derivatives emulsion LS] NaOH

(g) (g) (0.9 g/mL) (%) (%)

1C3 12.00 12.31 26.11 0.9 0.20 24.4 30.0

2C3 12.64 12.53 24.52 1.0 0.16 ^" 252 28.6

2D3 ^" 12.18 11.93 25.16 ^"l.O 0.12 24.2^~ 29.6

2E3 12.19 11.76 24.44 1.0 0.09 ^" 24.3 29.3

Table 9: Preparation of the LS-NaOH solutions to produce lignin-modified slack wax emulsions with a final LS concentration of 1.0%, and comprising about 25% lignins.

LS-NaOH Lignin Wax [Final [Final

[Final lignin] [Final wax]

ID# solution derivatives emulsion LS] NaOH]

(⁰Z^o) (⁰Z^o)

(g) (g) (0.9 g/mL) (%) (⁰Z^o) 1C5 6.01 6.11 36.97 0.5 0.15 12.4 43.7

2C5 6.12 6.12 36.79 0.5 0.12 12.5 43.5

2D5 6.03 5.91 37.45 0.5 0.12 12.0 44.0

2E5 6.01 6.11 36.97 0.5 0.12 12.4 43.7

Table 10: Preparation of lignin-modified wax emulsions with a final LS concentration of 1.0%, and comprising about 25% lignins.

2Dl 1 117.27 116.34 240.0 1.0 0.12 24.6 29.4

„. _{1 Λ}, Total % ^/0 % lignin

Find Mass Mgnin ^₁

'^~' of total solids solids

2D11 6.01 6.11 36.97 0.5

All of the samples produced with the recipes shown in Tables 7-10 comprised liquid lignin-modified slack wax emulsions. Lignin-modified wax emulsion sample ID#s 1C3-2E3 (~ 50:50 lignin/wax) were liquid and were about the same chocolate brown color. AU samples had visually detectable particles distributed throughout emulsions. Lignin-modified wax emulsion sample ID#s 1C5— 2E5 (~25/75 lignin/wax) were almost identical in color. These samples were of a grey /brown color that was significantly lighter than the color of lignin-modified wax emulsion sample ID#s 1C3-2E3.

The preceding examples exemplify methods of the present invention for preparing lignin-modified wax emulsions comprising lignin derivatives solubilized during and recovered from organosolv pulping of lignocellulosic biomass sources. Example 4: OSB panels prepared with a lignin-modified wax emulsion

Lignin-modified wax emulsion sample ID#s 2D5 and 2Dl 1 were prepared in 250-mL volumes following the process steps outlined in Example 3, and were used for production of OSB panels. Three types of homogenous OSB panels were produced in triplicate using aspen strands as the feedstock. The strands were screened to remove fines and then dried to about 2% moisture content prior to blending with a commercial liquid OSB face phenol-formaldehyde resin (EW-58S emulsion). The EW-58S emulsion was added at 3% (dry wood basis). The target moisture content of strands after blending was 5.5%. The commingled aspen strand - EW-58S emulsion was passed through a conventional press set at a target density of 40 lb/ft³ to produce panels having a thickness of 0.4375 inches. The first set of three OSB panels were the controls produced with the EW-58S emulsion with the following process steps:

(a) aspen strands were screened to remove fines;

(b) 14 kg aspen strands were dried to about 2% moisture content (MC); (c) the liquid PF resin OSF-59LFM was warmed to 25°C;

(d) the blending was conducted using the following parameters:

• strands: 14 kg dry Aspen / blend (2% MC)

• wax emulsion: 241 g EW-58S

• phenol-formaldehyde resin: (59% solids): 711 g of OSF-59FLM resin (e) resinated furnish was checked for moisture content.

(f) each mat was formed manually with care to ensure even density distribution across the face of each panel.

(g) each panel was pressed with the following parameters:

• weight of dispensed materials: 3665 g / mat • dimensions: 28" x 28" x 7/16"

• density: 40 lb/P

• press temperature: 210⁰C

• press time: 4 minutes

(h) the control OSB panels were labeled Cl - C3 The second set of three OSB panels were produced following the same process steps listed for the control OSB panels except that the wax emulsion in step (d) was substituted with lignin-modified wax emulsion sample ID# 2Dl 1 (50%:50% lignol:wax ratio). The three OSB panels produced with lignin-modified wax emulsion sample ID# 2D5, were labeled E5 - E7.

The third set of three OSB panels were produced following the same process steps listed for the control OSB panels except that the wax emulsion in step (d) was substituted with lignin- modified wax emulsion sample ID# 2D5 (25%:75% lignobwax ratio). The three OSB panels produced with lignin-modified wax emulsion sample ID# 2D5, were labeled El - E3.

Each of the three panels from each blend was tested for: (a) density, (b) internal bond strength (IB), (c) bond durability using MOR and MOE determinations (MOR = modulus of rupture; MOE = modulus of elasticity), (d) thickness swell and water absorption after (i) a 24- hour submerged water soaking, and (ii) a 2-hour period of boiling in water. The above tests were conducted following the Canadian Standard #0437.1-93 Test Methods for OSB and Waferboard (ISSN 0317-5669, published in April 1993 by Canadian Standards Association, Toronto, ON, Canada). The testing results are shown in Tables 11 - 13. Table 11

Panel density IB density Internal bond TSWA* density

Panel ID #

(lb/fV) (Ib/ft3) strength (MPa) (Ib/ft³)

Cl 41.0 42.6 0.256 43.5

C2 40.0 38.8 0.216 41.8

C3 39.9 40.6 0.238 40.0

C1-C2 mean 40.3 40.7 0.237 41.8

El 40.3 39.7 0.212 42.0

E2 39.6 38.9 0.206 41.4

E3 40.2 40.5 0.266 42.2

E1-E3 mean 40.0 39.7 0.228 41.9

E5 39.5 39.2 0.139 41.4

E6 39.6 37.1 0.155 40.1

E7 39.5 39.9 0.132 42.7

E5-E7 mean 39.5 38.7 0.142 41.4

*TSWA is "Thickness swell and water absorption".

Table 12

% thickness swelling % water absorption % thickness swelling % water absorption

(24-h soak) (24-h soak) (24-h soak+ 2-h boil) (24-h soak+ 2-h boil)

Cl 20.3 30.3 75.3 142.3

C2 20.2 31.5 66.4 141.6

C3 19.8 31.6 64.1 142.9

C1-C2 mean 20.1 31.1 68.6 142.3

El 20.0 31.5 65.0 141.8

E2 22.9 34.1 72.0 141.6

E3 23.7 34.3 67.7 140.6

E1-E3 mean 22.2 33.3 68.2 143.1

E5 26.7 41.5 78.3 150.4

E6 30.0 44.7 79.2 155.8

E7 29.5 41.1 87.4 153.2

E5-E7 mean 28.7 42.4 81.6 153.1

Table 13

Wet bending

Dry bending density Dry MOR Dry MOE Wet bending MOR

Panel ID # density

(Ib ft³) (MPa) (MPa) (MPa) (Ib ft')

Cl 40.9 30.40 4596 41.3 11.99

C2 41.4 25.75 3824 39.9 9.25 C3 420 32 22 4510 38.5 9 25 C1-C2 mean 41.4 29.46 4310 39.9 10.16

El 42 6 31.72 4971 40.8 11.60

E2 40.7 26.16 3670 40.4 11.56

E3 40 9 33.22 4061 40.2 11.00

E1-E3 mean 41.4 30.37 4234 40.5 11.39

E5 39 7 22.86 3823 39.4 4.99

E6 41 7 26.51 3984 40.4 6.81

E7 40.0 22.16 3580 39.5 6 37

E5-E7 mean 40.5 23.84 3796 39.8 6.06

OSB panels prepared with lignin-modified wax emulsion sample ID# 2D5 (i.e., panels

E1-E3) performed similarly to OSB panels prepared with the commercial slack wax EW-58S

(i.e., panels C1-C3). Lignin-modified wax emulsion sample ID# 2D5 comprised a 25%:75% lignokwax ratio. These data indicate that 25% of a commercial slack wax emulsion used for production of OSB materials, can be replaced widi lignin derivatives.

Claims

1. A derivative of native lignin wherein said hgnin derivative has a total hydroxyl content of from about 0.1 mmol/g to about 7 mmol/g.

2. A lignin derivative according to Claim 1 wherein the derivative has a total hydroxyl content of from about 3.5 mmol/g to about 6.8 mmol/g.

3. A lignin derivative according to Claim 1 wherein the derivative has a total hydroxyl content of from about 4.5 mmol/g to about 6.5 mmol/g

4. A lignin derivative according to Claim 1 wherein the derivative comprises alkoxy groups.

5. A lignin derivative according to Claim 1 wherein the bio mass from which the lignin is derived comprises hardwood biomass.

6. A lignin derivative according to Claim 1 wherein the biomass from which the lignin is derived comprises softwood biomass.

7. A lignin derivative according to Claim 1 wherein the biomass from which the lignin is derived comprises annual fibre biomass.

8. A kgnin derivative according to Claim 1 wherein the biomass from which the lignin is derived comprises Popu/us spp, Eucalyptus spp., Acacia spp., or combinations/hybrids thereof.

9. A lignin derivative according to Claim 1 wherein the biomass from which the lignin is derived comprises pine; spruce; or combinations /hybrids thereof

10. A lignin derivative according to Claim 1 wherein the biomass from which the lignin is derived comprises wheat straw, bagasse, corn cobs, or combinations /hybrids thereof.

11. A wax composition comprising a lignin derivative according to Claim 1.

12. A composition according to Claim 11 wherein the composition is an emulsion.

13. A composition according to Claim 11 comprising, on the basis of the solid content, from about 1% to about 50%, by weight, of lignin derivative.

14. A slack wax composition comprising a lignin derivative according to Claim 1.

15. A method for preparing a lignin-modified wax emulsion, the method comprising: a. preparing an aqueous solution comprising one of a surface tension reducing agent and an interfacial tension reducing agent; b. commingling with the aqueous solution a selected amount of a base; c. commingling with the aqueous solution containing therein said base, a selected amount of a lignin derivative according to Claim 1; d. separating the aqueous solution into a filtrate and a retentate wherein the mixture of lignin derivatives is commingled with said filtrate; and e. commingling a selected volume of the filtrate with a selected volume of a wax emulsion.

16 A method according to Claim 15, where the one of a surface tension reducing agent and an interfacial tension reducing agent is selected from a group consisting of lignosulphonates, isogenic lignin derivatives, ionogenic detergents exemplified by sodium dodecyl sulfate and the like, and combinations thereof

17. A hgnin modified wax emulsion produced according to the method of Claim 15

18. A wax emulsion comprising water, an emulsified wax, one of a surface tension reducing agent and an interfacial tension reducing agent, a base, and a ligrnn derivative according to Claim 1.

19. A composite wood product comprising a lignin-modified wax composition according to Claim 11

20. A method of producing a composite wood product, said method comprising. a. Obtaining a cellulosic fibre material, b Obtaining an adhesive suitable for adhering die fibres of said material;

C. Mixing said cellulosic material widi said adhesive, forming the mixture into a suitable shape and curing; and d. Applying a wax composition according to Claim 11 to the cured article.