CA2108176A1 - Improved lignin-based wood adhesives - Google Patents

Abstract

Novel adhesives for wood composites are described. The adhesives comprise a novel combination of an organosolv lignin and a phenol-formaldehyde resin in a weight ratio of from about 0.5:99.5 to about 70:30 based on the phenolic solids in said phenol-formaldehyde resin. The adhesives further comprise a modifier which improves the performance of the adhesive. Adhesives comprising an organosolv lignin and a liquid phenol-formaldehyde resin are also described. The organosolv lignin solution is comprised in either an alkaline solution or in a dispersion. Adhesives wherein the organosolv lignin is phenolated or methylolated prior to incorporation with the phenol-formaldehyde resin are also described. Wood composites such as plywood, waferboards and oriented strandboards were manufactured using the adhesives of the invention. Results of board testing demonstrate that the wood composites of the invention are competitive with wood composites manufactured using commercial adhesives.

Description

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IMPROVED LIGNIN-B~SED WOOD ADHESIVES

CROSS-REFERENCE TO RELATED APPLICATION

This is a continuation-in-part of application Serial No. 07/682,565, filed April 9, l991 entitled "LIGNIN-BASED WOOD AD~ESIVES".

BACKGROUND_OF THE INV~NTION

The pulp and paper industry produces tremendous quantities oE kraft and sulfite lignins which, for the most part, are either burnt as fuel in high pressure boilers or discharged as waste with a consequent negative environmental impact. Although wood chemists have for many years addressed the problem of locating useful non-fuel applications for these lignins, currently less than 2% of all lignins available from spent pulping liquors are recovered and marketed for non-fuel uses. Accordingly, there exists a long-standing and ongoing need to implement new, non-fuel ways of effectively using lignin and other biomass by-products.

Typical phenol formaldehyde adhesives which are used in the manufacture of structural wood products such as plywood, waferboard, oriented strandboard and fiberboard contain many constituents in addition to the resin. In the case of plywood, while the resin is the main constituent, various extenders, accelerators, fillers, viscosity control agents and other additives are generally added to the resin to control the properties of the formulation. While some of the added constituents are less costly than the resin itself, phenol-formaldehyde resins are not usually suitable for the formulation of low-value products. Furthermore, since the availability of WO92/1~57 PCT/US92/02963 2 ~ 0 ~ 2- ~

phenol which is one of the main constituents of phenol-formaldehyde resins, is likely to become a problem as supplies of petroleum feed stocks decline in the future and as phenol's price rises steadily, there is a need to develop substitutes for phenol such as lignin~

Much work has been reported on the use of lignins from conventional processes as a component in the formulation of phenol-formaldehyde adhesives.
Concentrated waste sulfite liquor has long been known to exhibit certain adhesive properties, and a common approach has been to substitute the spent sulfite liquor for a portion of the phenol in phenol-formaldehyde resins. The substitution is accomplished by pre-reacting the lignin with phenol prior to condensing it with the aldehyde.
This approach has generally not been successful because of the poor reactivity of the lignins with phenol-formaldehyde.

Another major disadvantage of the use of spent sulfite liquor in adhesive formulations is the high water solubility of the adhesive after curing which makes such formulations unsuitable for exterior applications.

The use of spent sulfite liquors in adhesive formulations is further limited by their high polydispersity. In order to obtain uniform lignin fractions, ultrafiltration was attempted and specialty products are available for use in wood lamination.

Attempts have been made to use kraft lignins in phenol-formaldehyde adhesive formulations. Since kraft lignins are relatively unreactive and sinter when heated, they are unsuitable for dry resin applications.
Furthermore, when compounded with li~uid phenol-formaldehyde resins, kraft lignins yield an over-viscous mixture. To enhance the reactivity of kraft lignins and , :
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WO92/18557 2 ' i, . i 7 ~ PCT/US92/02963 improve on their potential for cross-linking, methylol groups have been added by reacting kraft lignins with formaldehyde.

Different formulations of phenolic adhesives containing lignins from conventional processes have been proposed. In U.S. Patent No. 3,956,207 to Blackmore et al., a ready-to-use phenolic adhesive for the manufacture of plywood containing heat treated spent sulfite liquor solids, is described. The phenol-formaldehyde resin is intermixed under alkaline conditions with spent sulfite liquor solids which are heat treated in a dry state until 20~ to 50% of the dry heated solids are insoluble in an aqueous 0.5 molar sodium carbonate solution.

In U.S Patent No. 3,957,703 to Ludwig et al. a lS phenolic-aldehyde plywood adhesive was formulated with a water-insoluble, acid-polymerized lignosulfonate. The lignosulfonate is polymerized from spent sulfite liquor to the extent that it will increase its dry bulk volume less than seven times upon exposure to water.

In U.S. Patent No. 4,105,606 to Forss et al., an adhesive for the manufacture of plywood, fiber board, and similar products is described. The adhesive is a combina-tion of phenol-formaldehyde resin, and a lignin derivative such as lignosulfonates or alkali lignins. A minimum of 65~ by weight of the lignosulfonates and a minimum of 40%
by weight of the alkali lignins have relative molecular weights in excess of glucagon.

In U.S. Patent No. 4,127,544 to Allan, a phenol-formaldehyde resin adhesive is formulated in which a portion of the phenol ingredient is replaced with ammonium lignosulfonate.

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WO92t18~57 PCT/US92/02963 21 ~l~17~ -4-As an alternative to spent sulfite liquors and lignosulfonates, organosolv lignin such as ALCELLX lignin recovered by the process described in U.S. Patent No.
4,746,596 to Lora et al. can effectively compete with lignins produced from conventional processes in many applications. ALCELLX lignin can be used in applications such as the formulation of phenol-formaldehyde lignin-based adhesives. In the recent work of Lora et al., described in "Characteristics and Potential Applications of Lignin Produced by an Organosolv Pulping Process," ACS
Symposium Series No. 397, page 318, (1988), ALCELL~ lignin has been used in phenol-formaldehyde resin adhesive formulations.

SUMMARY OF THE INVENTION

This invention provides for adhesives for wood composites comprising an organosolv lignin and a phenol-formaldehyde resin in a weight ratio of from about 0.5:99.5 to about 70:30 based on phenolic solids in said phenol-formaldehyde resin.

In accordance with this invention, the performance of the adhesive can be improved by the addition of a modifier in a weight ratio with organosolv lignin of from about 0.5:99.5 to about 20:80. Boards manufactured with this particular adhesive have competitive properties.

In accordance with this invention, the performance of the adhesive can be improved by the addition of a low molecular weight organosolv lignin in a weight ratio with organosolv lignin of from about 5:95 to about 70:30. Boards manufactured with this particular adhesive have competitive properties.

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2~3~7 ,'j In accordance with this invention, the performance of the adhesive can be improved by extending the press time or increasing the press temperature during board manufacture. Boards manufactured with this particular adhesive have competitive properties.

In accordance with this invention, the performance of the adhesive can be improved by baking and drying the organosolv lignin prior to formulation. Boards manufactured with this particular adhesive have competitive properties.

In accordance with this invention, a liquid phenol-formaldehyde resin can be manufactured with a formaldehyde to phenol mole ratio of from about 2 to about 3 and alkali of from about 0.12 to about 0.47 moles per mole of phenol. An adhesive can be manufactured comprising organosolv lignin of from about 5:95 to 60:40 based on phenolic solids in said phenol-formaldehyde resin. Boards manufactured with this particular adhesive have competitive properties.

In accordance with this invention, a liquid phenol-formaldehyde resin can be manufactured with a formaldehyde to phenol mole ratio of from about 2 to about 4.5 and alkali of from about 0.1 to about 0.8 moles per mole of phenol. An adhesive can be manufactured comprising organosolv lignin of from about 0.5 to about 40% based on phenolic solids in said phenol-formaldehyde resin. Boards manufactured with this particular adhesive have competitive properties.

In accordance with this invention, a liquid phenol-formaldehyde resin can be manufactured with a formaldehyde to phenol mole ratio of from about 2.3 to about 3.0, alkali of from about 0.5 to about 0.8 moles per mole of phenol. An adhesive can be manufactured comprising ` ' , , .

WO9~/18557 PCT/US92/0~963 21~7~ -6-organosolv lignin from about 2 to about 30% based on phenolic solids in said phenol-formaldehyde resin. Boards manufactured with this particular adhesive have competitive properties.

In accordance with this invention, a liquid phenol-formaldehyde resin can be manufactured with a formaldehyde to phenol mole ratio of from about 2.4 to about 3.5 and alkali of from about 0.4 to about l moles per mole of phenol. An adhesive can be manufactured comprising organosolv lignin from about 0.8 to about 35%
based on phenolic solids in said phenol-formaldehyde resin. Boards manufactured with this particular adhesive have competitive properties.

In accordance with this invention, low molecular weight organosolv lignin can be used as a partial replacement for phenol in the manufacture of a liquid phenol-formaldehyde resin. The low molecular weight organosolv lignin can be added during the preparation of the resin and replace from about 0.5 to about 40% of the phenolic resin solids in the adhesive. The phenol-formaldehyde resin can be manufactured with a formaldehyde to phenol mole ratio of from about 2 to about 4.5 and alkali of from about O.l to about 0.8 moles per mole of phenol. Boards manufactured with this particular adhesive have competitive properties~

In accordance with this invention, an alkaline solution of organosolv lignin can be used as a partial replacement for phenol during the manufacture of a liquid phenol-formaldehyde resin. The alkaline solution of organosolv lignin can be prepared by addition of alkali of from about lO to about 25% on a lignin weight basis and can be added to a liquid phenol-formaldehyde resin in a weight ratio of from about 5:95 to about 60:40 based on phenolic solids in the resin. The phenol-formaldehyde ~ : ., ' :

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resin can be manufactured with a formaldehyde to phenol mole ratio of from about 2 to about 3 and alkali of from about 0.12 to about 0.47 moles per mole of phenol. Boards manufactured with this particular adhesive have competitive properties.

In accordance with this invention, the alkaline solution of organosolv lignin can be used as a partial replacement for phenol during the manufacture of a liquid phenol-formaldehyde resin and replace from about 2 to about 30~ of the phenolic resin solids. The phenol-formaldehyde resin can be manufactured with a formaldehyde to phenol ~ole ratio of from about 2.3 to about 3 and alkali of from about 0.5 to about 0.8 moles per mole of phenol. Boards manufactured with this particular adhesive have competitive properties.

In accordance with this invention, an organosolv lignin dispersion can be added to a liquid phenol-formaldehyde resin. The dispersion comprises a dispersing agent and organosolv lignin in a weight ratio of from about 0.5:99.5 to about 2:98. The organosolv lignin dispersion can be directly added to the resin in a weight ratio of from about 5:95 to about 60:40 based on phenolic solids in the resin. The phenol-formaldehyde resin can be manufactured with a formaldehyde to phenol mole ratio of from about 2 to about 3 and alkali of from about 0.12 to about 0.47 moles per mole of phenol. Boards manufactured with this particular adhesive have competitive properties.

In accordance with this invention, organosolv lignin can be phenolated by reacting the organosolv lignin of from about 10 to about 80% of total reaction weight with phenol of from about 10 to about 80% of total reaction weight with alkali of from about 1 to about 20%
of total reaction weight. The phenol-formaldehyde resin can be manufactured with a formaldehyde to phenol mole . . .
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W092/1~5~7 PCT/~S92/02963 ,. _ 2 ~ ~ ~ i 7 u --8--ratio of from about 2 to about 4.5 and alkali of from about 0.1 to about 0.8 moles per mole of phenol. The organosolv lignin can constitute for from about l to about 45% on a phenol weight basis. Boards manufactured with this particular adhesive have competitive properties.

In accordance with this invention, organosolv lignin can be phenolated by reacting the organosolv lignin of from about 10 to about 80% of total reaction weight with phenol of from about lO to about 80% of total reaction weight with alkali of from about l to about 20~
of total reaction weiyht. The phenol-formaldehyde resin can be manufactured with a formaldehyde to phenol mole ratio of from about 2.4 to about 3.5 and alkali or from about 0.4 to about 1 moles per mole o phenol. The organosolv lignin can constitute from about 1 to about 70%
on a phenol weight basis. Boards manufactured with this particular adhesive have competitive properties.

In accordance with this invention, organosolv lignin can be methylolated by reacting the organosolv lignin of from about 20 to about 60% of total reaction weight with phenol of from about 20 to about 50~ of total reaction weight. Formaldehyde of from about 5 to about 50%
of total reaction weight can be added using an acid of from about 0.01 to about 3% of total reaction weight. The phenol-formaldehyde resin can be manufactured with a formaldehyde to phenol mole ratio of from about 2 to about 4.5 and alkali of from about 0.1 to about 0.8 moles per mole of phenol. The organosolv lignin can constitute from about l to about 70% on a phenol weight basis. Boards manufactured with this particular adhesive have competitive properties.

In accordance with this invention, organosolv lignin can be methylolated by reacting the organosolv lignin of from about 20 to about 60~ of total reaction , .

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g weight with phenol of from about 20 to about 50~ of total reaction weight. ~ormaldehyde of from about 5 to about 50%
of total reaction weight can be added using an acid of from about 0.0l to about 3~ of total reaction weight. The phenol-formaldehyde resin can be manufactured with a formaldehyde to phenol mole ratio of from about 2.4 to about 3.5 and alkali of from about 0.4 to about l moles per mole of phenol. The organosolv lignin can constitute from about l to about 45% on a phenol weight basis.
Boards manufactured with this particular adhesive have competitive properties.

These and other details of the invention will be apparent from a reading of the remainder of this specification and the claims.
DESCRI~TION OF THE PREFERRED EMBODIMENTS

The lignin employed in this invention is an organosolv lignin, preferably ALCELL0 lignin which is the natural product extracted from wood with alcohol and water and is recovered as described in U.S. Patent No. 4,764,596 and U.S. Patent Application Ser. No. 07/649,683 filed February l, l99l incorporated by reference herein.
ALCELLD lignin is recovered as a free-flowing powder and resembles to a great extent native lignin.

In the present invention, organosolv lignin such as ALCELL0 lignin can be added in a variety of ways as a substitute for phenol-formaldehyde core and face resins which are suitable in the formulation of adhesives for use in the manufacture of wood composites such as structural and nonstructural wood products including plywood, waferboard, oriented strandboard, particle board, fiber board, hard board and the like.

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, WO92/18~5~ PCT/US92/02963 21 ~ ~ 1 7 ~ -lo-ALCELL~ lignin is sulfur-free and has low levels of carbohydrates and inorganic contaminants. It is also highly hydrophobic, is essentially insoluble in neutral or acidic. aqueous media, and is soluble in moderate to strong alkaline solutions and certain organic solvents.

ALCELL~ lignin can be characterized as having: a relatively low number average molecular weight of about 800 to 1500 g/mole, preferably about 900 to 1300 g/mole and a glass transition temperature which is preferably about 100 to 170C, particularly about 130 to 150C, although a glass transition temperature of preferably about 80 to 170C, particularly about 90 to 150C is also observed; a narrow molecular weignt distribution, i.e., a polydispersity of less than about 4, preferably no more than about 3, particularly only about 1.5 to 2.7;
and, a methoxyl content approximately equal to the methoxyl content of native lignin ~i.e., about 20% for hardwoods and about 14~ for softwoods). ALCELL~ lignin also has a softening temperature which is preferably about 120 to 150C, particularly about 130 to 150C.

In a preferred embodiment, in waferboard and oriented strandboard manufacture, powder phenol-formaldehyde resin and dry organosolv lignin are directly blended in a weight ratio of from about 30:70 to about 95:5, preferably of from about 70:30 to about 85:15.

The performance of the combination of dry organosolv lignin and powder phenol-formaldehyde resin can be further improved by extending the press time or by increasing the press temperature. Alternatively, baking the organosolv lignin for from about 15 to about 90 minutes and at temperatures of from about 120 to about Z00C or flash drying of the organosolv lignin at a dryer inlet temperature of from about 135 to about 250C prior to formulation, significantly improves board properties.

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The performance of the organosolv lignin/phenol-formaldehyde resin combination can be improved by the addition of a modifier, preferably of a phenolic nature.
Modifiers such as low molecular weight phenolic compounds, phenol, or low molecular weight ALCELL0 lignin can be used. Other modifiers which can be used include tris-(p-hydroxyphenyl) ethane (THPE), p-tert-butyl-phenol (PTBP), bisphenol-A (BPA), p-cresol, p-ethylphenol, p-sec-butylphenol, p-amylphenol, p-nonylphenol, p-dodecylphenol, 2,4-dimethylphenol, 2,4,6,-trimethylphenol, para-alkyl phenols with side chains of 18 to 24 and 24 to 28 carbons, polyhydroxystyrene, creosote blends and fur~ural which comprises washed furfural recovered in the process described in U.S. Patent application Ser. No. 07/643,683 filed February 1, 1991 and incorporated herein by reference.

The modifier can be directly added to the powder phenol-formaldehyde resin and the dry organosolv lignin.
A modifier such as phenol, p-tert-butylphenol (PTBP) and bisphenol-A (BPA) can be added in a modifier to organosolv lignin weight ratio o~ from about 0.5:99.5 to about 20:80, preferably 1:99 to 10:90. The combination of organosolv lignin and modifier can substitute for from about 15 to about 75% of the phenolic resin solids.

Low molecular weight ALCELL0 lignin can also be added to the organosolv lignin as a modifier in a weight ratio of from about 5:95 to about 70:30, preferably 20:80 to 50:50. Low molecular weight ALCELL0 lignin is recovered as a tarry precipitate in the process described in U.S.
Patent Application serial No. 07/649,683 filed February 1, 1991. Low molecular weight ALCELL0 lignin can be characterized by a low number average molecular weight in the range of less than 500 g/mole and a low glass transition temperature in the range of from about 24 to about 80C. Another characteristic, when hardwoods are W092~l85~7 PCT/US92/02963 ; :, ~ 7~ -12-pulped, is that the low molecular weight ALCELL~ lignin is predominantly of the syringyl type, since by nitrobenzene oxidation, it yields a syringaldehyde to vanillin molar ratio of from about 2.7:1 to about 5.3:1. The low molecular weight ALCELL~ lignin can be dried first then can be added to the organosolv lignin or alternatively, the low molecular weight ALCELL~ lignin and the organosolv lignin can be mixed first then dried simultaneously prior to use.

In another preferred embodiment, in waferboard and oriented strandboard manufacture, the dry organosolv lignin can be directly added to a liquid phenol-formaldehyde resin in a weight ratio of from about 5:95 to about ~0:40 based on the weight of dry organosolv lignin and dry solids in the phenolic resin. The phenol-formaldehyde resin can be prepared by condensation of formaldehyde and phenol in a mole ratio of from about 2 to about 3.0, preferably 2.2 to 2.5. The polymerization can be carried out under alkaline conditions, for example using sodium or potassium hydroxide in one or more alkali additions and in a mole ratio of from about 0.12 to about 0.47, preferably 0.15 to 0.3 moles of alkali per mole of phenol. Urea, ammonia or other suitable compound can be added in an amount sufficient to react with any excess formaldehyde. After resin formulation, the organosolv lignin and phenol-formaldehyde resin can be sequentially used to cover the wafers covered with about 1% by weight (based on solids of a wax emulsion) in a weight ratio of from about 2 to about 5% (resin solids to dry wafers).

In another preferred embodiment, in waferboard and oriented strandboard manufacture, the organosolv lignin can be copolymerized during the condensation reaction of phenol and formaldehyde and can replace from about 0.5 to about 40%, preferably from about 5 to about 30~ of the phenolic resin solids in the resulting W092/l8557 PCT/US92/02963 2~ ~17~

adhesive. The phenol-formaldehyde resin can be prepared with formaldehyde to phenol mole ratio of from about 2 to about 4.5, preferably from about 2~2 to about 4.2 moles of formaldehyde per mole of phenol. The polymerization can be carried out under alkaline conditions, for example using sodium or potassium hydroxide in one or more alkali additions and in a mole ratio of from about O.I to about 0.8, preferably from about 0.2 to about 0.75 moles of alkali per mole of phenol. The organosolv lignin can be added in an amount sufficient to constitute from about l to about 70~, preferably from about 10 to about 50~ on a phenol weight basis. Urea, ammonia or other suitable compound can be added in an amount sufficient to react with any excess formaldehyde. The lignin/phenol-formaldehyde resin mixture can be blended with the waferscovered with about 1% by weight (based on solids of a wax emulsion) in a weight ratio of from about 2 to about 5%
(resin solids to dry wafers).

In other applications, the organosolv lignin can be used as a partial replacement of phenol-formaldehyde resin used in plywood adhesive formulation. In a preferred embodiment, the phenol-formaldehyde resin can be prepared with a formaldehyde to phenol ratio of from about 2.3 to about 3.0, preferably from about 2.4 to about 2.6. The polymerization can be carried out under alkaline conditions in one or more alkali additions and preferably using sodium or potassium hydroxide, with a mole ratio of from about 0.5 to about 0.8, preferably of from about 0.65 to about 0.75 moles of alkali per mole of phenol. Urea, ammonia or other suitable compound can be added in an amount sufficient to react with any excess formaldehyde.
The organosolv lignin can be added to the resin during adhesive preparation and replace from about 2 to about 30~, preferably from about 15 to about 20% of the phenolic resin solids.

WO92/18~5~ PCT/US92/02~63 21 ~3 81 7 (~ -14-In another preferred embodiment, in plywood adhesive formulation, the organosolv lignin can be copolymerized during resin manufacture and replace from about 0.8 to about 35%, preferably from about 4 to about 20% of the phenolic resin solids in the resulting adhesive. The phenol-formaldehyde resin can be prepared with formaldehyde to phenol mole ratio of from about 2.4 to about 3.5, preferably from about 2.8 to about 3.1. The polymerization can be carried out under alkaline conditions, preferably using sodium or potassium hydroxide in one or more alkali additions with a mole ratio of from about 0.4 to about l, preferably of from about 0.65 to about 0.85 moles of alkali per mole of phenol. The organosolv lignin can De added in a weight ratio with phenol of from about 2 to about 45~, preferably of from about lO to about 30%. Urea, ammonia or other suitable compound can be added in an amount sufficient to react with any excess formaldehyde. The resulting resin can be used during adhesive preparation.

In another preferred embodiment, low molecular weight organosolv lignin such as ALCELL~ lignin can be used as a partial replacement for phenol in the manufacture of a phenol-formaldehyde resin for waferboard and oriented strandboard applications. The low molecular weight organosolv lignin can be copolymerized during the condensation reaction of phenol and formaldehyde and replace from about 0.5 to about 40~, preferably from about to about 30% of the phenolic resin solids in the resulting adhesive. The phenol-formaldehyde resin can be prepared with formaldehyde to phenol mole ratio of from about 2 to about 4.5, preferably from about 2.2 to about 4.2 moles of formaldehyde per mole of phenol. The polymerization can be carried out under alkaline conditions, for example using sodium or potassium hydroxide in one or more alkali additions and in a mole ratio of from about O.l to about 0.8, preferably from .

WO92/l~ss7 PCT/US92/02963 2~17~

about 0.2 to about 0.75 moles of alkali per mole of phenol. The low molecular organosolv lignin can be added in an amount sufficient to constitute from about 1 to about 70~, preferably from about 10 to about 50% on a phenol weight basis. Urea, ammonia or other suitable compound can be added in an amount sufficient to react with any excess formaldehyde.

In another preferred embodiment, an alkaline solution of organosolv lignin can be added as a partial replacement for phenol during the synthesis of a phenol-formaldehyde resin for waferboard and oriented strandboard applications. An alkaline solution of organosolv lignin can be prepared using the organosolv lignin cake prior to drying or the organosolv lignin powder after drying recovered from the pulping processes described herein. An alkaline solution can also be prepared using the low molecular weight ALCELL~ lignin. In a preferred embodiment, alkali for example sodium or potassium hydroxide can be added in one or more additions in an amount of from about 10 to about 25~, preferably from about 12 to about 22% on a lignin weight basis. Water can be added as needed such that total solids are from about 30% to about 50%, preferably of from about 35% to about 45%. The organosolv lignin can be added slowly with agitation. The resulting organosolv lignin alkaline solution can be added to a liquid phenol-formaldehyde resin in a weight ratio of from about 5:95 to about 60:40 based on the weight of dry organosolv lignin and dry solids in the phenolic resin. The phenol-formaldehyde resin can be prepared by ~ondensation of formaldehyde and phenol in a mole ratio of from about 2 to about 3.0, preferably from about 2.2 to about 2.5. The polymerization can be carried out under alkaline conditions, for example using sodium or potassium hydroxide in one or more alkali additions and in a mole ratio of from about 0.12 to about 0.47, preferably from about 0.15 to about 0.3 moles of 2 ~ 7 S -16-alkali per mole of phenol. Urea, ammonia or other suitable compound can be added in an amount sufficient to react with any excess formaldehyde.

In another preferred embodiment, the alkaline organosolv lignin solution can be added to a phenol-formaldehyde resin for plywood applications. The organosolv lisnin alkaline solution can be added to a phenol-formaldehyde resin during adhesive preparation and replace from about 2 to about 30%, preferably from about to about 20~ of the phenolic resin solids in the resulting adhesive. The phenol-formaldehyde resin can be prepared with a formaldehyde to phenol ratio of from about 2.3 to about 3.0, preferably from about 2.~ to about 2.6.
The polymerization can be carried out under alkaline conditions in one or more alkali additions and preferably using sodium or potassium hydroxide, with a mole ratio of from about 0.5 to about 0.8, preferably of from about 0.65 to about 0.75 moles of alkali per mole of phenol. Urea, ammonia or other suitable compound can be added in an amount sufficient to react with any excess formaldehyde.

In another preferred embodiment, an organosolv lignin dispersion can be prepared and can be blended with a phenol-formaldehyde liquid resin for waferboard and oriented strandboard applications. Surfactants such as sodium and ammonium polymethacrylate, alkaline compounds such as sodium and ammonium hydroxide or other compounds which have a dispersant effect on the organosolv lignin can be used as a dispersing agent. The organosolv lignin cake prior to drying or the organosolv lignin powder after drying recovered from the pulping processes referred to herein can be used. Similarly, low molecular weight ALCELL~ lignin can also be used. In a preferred embodiment, the dispersing agent can be added to water and the organosolv lignin can be added slowly with agitation and the level of dispersing agent and organosolv lignin , - . , ;
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adjusted so that the dispersion behaves thixotropically.
The solids content of the dispersion are in the range of from about 45 to about 65%, preferably in the range of from about 50 to about 55%. The weight ratio of dispersing agent to organosolv lignin can be from about 0.5:99.5 to about 2:98, preferably from about lo99 to about 1.5:98.5. The organosolv lignin dispersion can be directly added to a liquid phenol-formaldehyde resin in a weight ratio of from about 5:95 to about 60:40 based on the weight of dry organosolv lignin and dry solids in the phenolic resin. The phenol-formaldehyde resin can be prepared by condensation of formaldehyde and phenol in a mole ratio of from about 2 to about 3.0, preferably from about 2.2 to about 2.5. The polymerization can be carried out under alkaline conditions, for example using sodium or potassium hydroxide in one or more alkali additions and in a mole ratio of from about 0.12 to about 0.47, preferably from about 0.15 to about 0.3 moles of alkali per mole of phenol. Urea, ammonia or other suitable compound can be added in an amount sufficient to react with any excess formaldehyde.

In another preferred embodiment, phenolation of organosolv lignin can be used in the manufacture of a phenol-formaldehyde resin for waferboard and oriented strandboard applications. Phenolation of organosolv lignin can be achieved by reacting organosolv lignin from about to about 80~, preferably of from about 30 to about 60%
of total reaction weight with phenol of from about 10 to about 80~, preferably of from about 20 to about 60% of total reaction weight under alkaline conditions, using sodium or potassium hydroxide in one or more alkali additions of from about 1 to about 20%, preferably from about 5 to about 10% of total reaction weight at a temperature of from about 80 to about 200C, preferably of from about 110 to about 180 C and for from about 0.5 to about 2 hours, preferably from about 0.5 to about 1.5 W092/18557 PCT/US92tO2963 21. ~sl 7~ -18-hours. The phenol-formaldehyde resin can be prepared by addition of more phenol, if required, and formaldehyde sl-ch that the molar ratio of formaldehyde to phenol is from about 2 to about 4.5, preferably of from 2.2 to about 4.2 moles formaldehyde per mole of phenol. The polymerization can be carried out under alkaline conditions, for example using sodium or potassium hydroxide in one or more alkali additions in a mole ratio of from about 0.1 to about 0.8, preferably of from about 0.2 to about 0.75 moles of alkali per mole of phenol. The phenolated organosol~ lignin can constitute from about 1 to about 70%, preferably from about lO to about 50% on a phenol weight basis. ~nough water can be added such that the total solids in the resin are about 57%. Urea, ammonla or other suitable compound can be added in an amount sufficient to react with any excess formaldehyde.

In another preferred embodiment, phenolation of organosolv lignin can be used in the manufacture of a phenol-formaldehyde resin for plywood applications.
Phenolation of organosolv lignin can be achieved by reacting organosolv lignin of from about 10 to about 80~, preferably of from about 30 to about 60% of total reaction weight with phenol of from about 10 to about 80%, preferably of from about 20 to about 60~ of total reaction weight under alkaline conditions, usin~ sodium or potassium hydroxide of from about 1 to about 20%, preferably from about 5 to about 10% of total reaction weight at a temperature of from about 80 to about 200C, preferably of from about 110 to about 180 C and for about 0.5 to about 2 hours, preferably from about 0.5 to about 1.5 hours. The phenol-formaldehyde resin can be prepared by addition of more phenol, if required, and formaldehyde such that the molar ratio of formaldehyde to phenol is from about 2.4 to about 3.5, preferably of from 2.8 to about 3.1 per mole of phenol. The polymerization can be carried out under alkaline conditions, for example .
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5~7 2 ~ ~ ~,17 v PCT/US92/02963 --lg--using sodium or potassium hydroxide in one or more alkali additions in a mole ratio of from about 0.4 to about 1, preferably from about 0.65 to about 0.85 moles of alkali per mole of phenol. The phenolated organosolv lignin can constitute from about 1 to about 45%, preferably from about 10 to about 30% on a phenol weight basis. ~nough water can be added such that the total solids in the resin are about 42~. Urea, ammonia or other suitable compound can be added in an amount sufficient to react with any excess formaldehyde.

In another embodiment, organosolv lignin can be methylolated by acid catalysis and the methylolated organosolv lignin can be used in the manufacture o~
adhesives for waferboards and oriented strandboard applications. Methylolation can be incorporated as a first step during the manufacture of the phenol-formaldehyde liquid resin. To promote solubility under acidic conditions, the organosolv lignin can be solubilized using a solvent which can be used in phenol-formaldehyde resin manufacture. A solvent such as trioxane, phenol or other phenolic compounds can be used. Organosolv lignin of from about 2 to about 60%, preferably from about 20 to about 40% of total reaction weight is dissolved in phenol of from about 20 to about 50%, preferably of from about 30 to about 45% of total reaction weight. Formaldehyde of from about 5 to about 50%, preferably of from about 10 to about 30% of total reaction weight is added under acidic conditions using a mineral or organic acid, preferably using sulfuric acid of from about 0.01 to about 3%, preferably of from about 0.1 to about 2~ of total reaction weight. The mixture is heated to from about 40 to about 100C, preferably to from about 60 to about 90CC for about to about 180 minutes, preferably for about 60 to about 120 minutes~ The phenol-formaldehyde resin can be prepared by addition of more phenol, if required, and formaldehyde such that the molar ratio of formaldehyde to phenol is W092/~85~7 PCT/US92/02963 2~817~ -20-from about 2 to about 4.5, preferably of from 2.2 to about 4.2 moles formaldehyde per mole of phenol. The polymerization can be carried out under alkaline conditions, for example using sodium or potassium hydroxide in one or more alkali additions in a mole ratio of from about 0.1 to about 0.8, preferably from about 0.2 to about 0.75 moles of alkali per mole of phenol. The organosolv lignin can constitute from about 1 to about 70%, preferably from about 10 to about 50% on a phenol weight basis. Enough water can be added such that the total solids in the resin are about 57~. Urea, ammonia or other suitable compound can be added in an amount sufficient to react with any excess formaldehyde.

Similarly, acid methylolation of organosolv lignin can also be used in the manufacture of adhesive for plywood applications. Organosolv lignin of from about 2 to about 60%, preferably from about 20 to about 40% of total reaction weisht is dissolved in phenol of from about 20 to about 50%, preferably of from about 30 to about 45% of total reaction weight. Formaldehyde of from about 5 to about 50~, preferably of from about 10 to about 30% of total reaction weight is added under acidic conditions using a mineral or organic acid, preferably using sulfuric acid of from about 0.01 to about 3%, preferably of from about 0.1 to about 2% of total reaction weight. The mixture is heated to from about 40 to about 100C, preferably to from about 60 to about 90C for about 30 to about 180 minutes, preferably for about 60 to about 120 minutes. The phenol-formaldehyde resin can be prepared by addition of more phenol, if re~uired, and formaldehyde such that the molar ratio of formaldehyde to phenol is from about 2.4 to about 3.5, preferably of from 2 to about 3.1 moles formaldehyde per mole of phenol. The poly~erization can be carried out under alkaline conditions, for example using sodium or potassium hydroxide in one or more alkali additions in a mole ratio : - , -. . .. ., . ~
~; ' - ' '~ ' .
- . :
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- ': :~ .;

WO92/18~57 PCT/US92/02963 of from about 0.4 to about 1, preferably from about 0.65 to about 0.85 moles of alkali per mole of phenol. The organosolv lignin can constitute from about 1 to about 45%, preferably from about 10 to about 30% on a phenol weight basis. Enough water can be added such that the total solids in resin are about 42~. Urea, ammonia or other suitable compound can be added in an amount sufficient to react with any excess formaldehyde.

In use of the adhesives, the various known methods and procedures used in the manufacture of wood composites can be employed. The conditions of manufacture are within the conditions presently used with the variations normally encountered and obvious to those skilled in the art.

The wood composites of the invention are manufactured using standard manufacturing procedures and techniques except where specifically noted. Tables 1, 2, 3, 4 and 5 illustrate the parameters used in the manufacture of the wood composites of the invention including novel adhesive formulation techniques and methods, as more particularly set forth in the following eYamples .

WO92/18~57 PCT/US92/02963 , . . .
21 0817~ -22-Table 6 shows the physical properties of boards made by substituting about 20% of a particular powder phenol-formaldehyde resin BAKELITE 9111 (manufactured by Bakelite Thermosets Limited, Belleview, Ontario, Canada) blended with different dry lignins. The boards were manufactured according to the parameters in Table 1. The results in Table 6 indicate that organosolv lignin such as ALCELL~ lignin was the best ~ubstitute in terms of improving board properties.

When dry ALCELL~ lignin was intermixed as a partial substitute with a powder phenol-formaldehyde face resin such as GP5415 (manufactured by Georgia Pacific, Crossett, AK), improved board properties as shown in Table 7 demonstrate that ALCELL~ lignin was particularly compatible with GP5415. The waferboards were manufactured according to the parameters in Table 3.

In this example, about 50~ of a powder phenol-formaldehyde resin (e.g. ~D909) was substituted with an ALCELL~ lignin and a modifier such as phenol. About nine parts of dry ALCELL~ lignin in about ten parts of water was mixed with about one part of phenol. The mixture was air dried into a powder then used to substitute for about 50% of a phenol-formaldehyde resin. Waferboards were manufactured according to the parameters in Table 1. The ... . : . , , ,: , . ~
:
-~ ' ~: .

WO92~18~57 PCT~US92/02963 ~8~ ~;J

results in Table 8 indicate that the performance of the combination of dry ALCELL0 lignin and a phenol-formaldehyde resin was improved by a modifier such as phenol and superior board properties were obtained.

When about 2% phenol based on total adhesive weight was added to dry ALCELL0 lisnin and the mixture was blended with resin GP5415 following the procedure of Example 3, the results in Table 9 show that superior board properties were obtained relative to those obtained with un-modified ALCELL0 lignin/GP5415 resin combination. A
similar improvement in board properties was also observed with the ALCELL0 lignin/BDO23 and ALCELL0 lignin/BD802 adhesive systems made as in Example 3. Waferboards were manufactured according to the parameters in Table l.

Similarly, a modifier such as low molecular wei~ht ALCELL0 lignin can be used to improve the performance of organosolv lignin such ALCELLX lignin with for example a phenol-formaldehyde resin such as BD9O9 as shown in Table lO. The tarry low molecular weight ALCELL0 lignin was added to the ALCELL0 lignin in the proportions shown in Table lO, and the mixture was heated to about 120C. The mixture was cooled to about 25C and ground into a powder. The powder was blended with a phenol-formaldehyde resin such as BD9O9. The waferboards were ma~ufactured using the parameters in Table l.

~ ~ ;

W092/18557 PCT/US92tO2~3 2 ~ r~' -24- t In this example, about 20% of a powder phenol-formaldehyde resin (e.g. LD909) was substituted with an ALCELL0 lisnin and a modifier such as tris-(p-hydroxyphenyl) ethane (THPE), bisphenol-A (BPA), p-tert-butylphenol (PTBP), p-cresol, p-nonylphenol, para-alkyl phenol with a side chain of 18 to 24 carbons, 2,4-dimethylphenol and 2,4, 6-trimethylphenol. About nine parts of dry ALCELL0 lignin in about ten parts of water were mixed with about one part of modifier as in Example 3. The mixture was air dried into a powder then used to substitute for about 20% of the phenol-formaldehyde resin.
Waferboards were manufactured according to the parameters in Table 4 with board thickness of 3/8l'. The results in lS Tables 11 and 12 indicate that the performance of ALCELL~
lignin was improved by the modifiers of Tables ll and 12.

In this example, about 20% of a powder phenol-formaldehyde resin (e.g. GP5479) was substituted with an ALCELL~ lignin and a modifier such as p-tert-butylphenol (PTBP). In this example, a dry blend of the modifier was prepared by grinding the modifier to a particle size close to the particle size of ALCELL~ lignin. The dry ALCELL~
lignin and the modifier were combined into dry blends containing about 1, about 4 and about 10~ of the modifier on a total blend weight basis. Waferboards were manufactured according to the parameters in Table 4. The results in Table 13 indicate that the phenolic modifiers effectively increase the compatibility of the ALCELL~
lignin and superior board properties were obtained.

.

WO92/18s~7PCT/US92/02~3 2~Q~17'o _~5_ The results in Table 14 indicate that the performance of the combination of a dry organosolv lignin such as ALCELL~ lignin blended with a powder phenol-formaldehyde resin such as B~909 can be improved by increasing the press time to about 200 seconds or longer at a press temperature of about 400F. Results in Table 14 how improved board properties. The waferboards were manufactured according to the parameters in Table 3.

The performance of the combination of a dry organosolv lignin such as ALCELL~ lignin with a powder phenol-formaldehyde resin such as BD909 can also be improved by increasing the press temperature to about 415F while keeping the press time constant at about 170 seconds as shown in Table 15. Waferboards were manufactured according to the parameters in Table 3.

In this particular example, when dry ALCELL~
lignin was baked at a temperature of about 160 C and for about 60 minutes and then was blended with a powder phenol-formaldehyde resin such as BD909, a significant improvement in board properties was observed, as shown in Table 16. Waferboards were manufactured according to the parameters in Table 1.

WO92/185~7 PCT/US92/02963 2~17~ -26-When ALCELL~ lignin was flash dried at a dryer inlet temperature of from about 138 to about 235C, then was blended with a powder phenol-formaldehyde resin such as BD909 as shown in Table 17. Improved board properties were obtained. Waferboards were manufactured according to the parameters in Table l.

EXAMPLE l2 This example illustrates the procedure followed in the preparation of a liquid phenolic resin used to formulate a liquid adhesive for waferboard applications.
About one mole of phenol, about 2.2 moles of formaldehyde and about 0.2 moles of sodium hydroxide were reacted and the polymerization was carried forward at a temperature of from about 80 to 100C, and until a viscosity of about 250 cps (measured at 25C) was reached. Urea was added in an amount sufficient to react with the excess formaldehyde, and the resin was quickly cooled to about 25C or below. The final resin composition was about 57~
total solids and the viscosity was about 200 cps (measured at 25C).

EXAMPLE l3 In this example, the organosolv lignin was directly added to the condensation reaction mixture of phenol and formaldehyde and copolymerized during such reaction. Subsequently, this resin was used to formulate a liquid adhesive for waferboard applications. About 2.7 . . . .
, ' ~

~V092/18557 PCTtUS92/02963 2 ~ 9 ~

moles of formaldehyde, about 0.05 moles sodium hydroxide and about 20~ ALCELL~ lignin on a weight basis with phenol were reacted for about 90 minutes at a temperature of about 70C. The reaction mixture was cooled to about 3UC, and about one mole of phenol and about 0.2 moles of sodium hydroxide were added. The mixture was then heated to about 80~C and polymerization was continued until a target viscosity of from about 200 to about 700 cps ~measured at 25C) was reached. Urea was added in an amount sufficient to react with the excess formaldehyde, and the resin was quickly cooled to about 25C or below.
The lignin/phenolic resin composition was about 57% total solids of which about 12~ was organosolv lignin.

In this example, wood wafers (e.g. Aspen) were placed in a rotating blender and about 1% (w/w) of a wax emulsion (e.g. PARACOL 802N manufactured by Hercules, Wilmington, DE) was sprayed to cover the wafers.
Organosolv lignin, such ALCELL~ lignin in dry form and the liquid phenol-formaldehyde resin of Example 12 were used to cover the wafers in a weight ratio of about 20:80, the organosolv lignin was used to cover the wafers prior to spraying with liquid phenol-formaldehyde resin. The total phenol-formaldehyde resin and organosolv lignin solids were blended on the wafers at about 4.5~ (w/w).

The mixture of wafers of Example 14 containing about 3.6% Example 12 liquid phenol-formalde~yde resin and about 0.9% dry ALCELL~ lignin were pressed into 3/8"

WO92tl8557 ~CT/US~2/02963 21 ~ g 1 7 ~ -28- ~

boards at a temperature of about 410F, at a pressure of about 540 psig and for about 5 minutes and according to the manufacturing parameters of Table 2. These waferboards were compared to control boards manufactured with about 4.5% Example 12 liquid phenol-formaldehyde resin and no ALCELL0 lignin.

The results in Table 18 show that the ALCELL0 lignin containing boards have good properties and were competitive with control boards.

In this example, two batches of wood wafers were made according to the procedure of Example 14 without the addition of dry ALCELL0 lignin. The wafers in each batch contain about 4.5~ of Example 13 liquid phenol-formaldehyde resins at about 390 cps and at about 700 cpsviscosity. The wafers were pressed into 3/8" boards at a temperature of about 410F, at a pressure of about 540 psig and for about 5 minutes and according to the manufacturing parameters of Table 2. These waferboards were compared to control boards manufactured with about 4.5% Example 12 liquid phenol-formaldehyde resin and no ALCELL~ lignin.

The results in Table 19 show that the ALCELL0 lignin containing boards have good properties and were competitive with control boards.

,~ . .~, . .

. ' .- ~ ` ' ' 2~gl7i This example illustrates the procedure followed in the preparation of a liquid phenol-formaldehyde resin for plywood applications. The organosolv lignin was added to the liquid phenol-formaldehyde resin during plywood adhesive formulation (see Example 20). About one mole of phenol, about 2.45 moles of formaldehyde, the water and a first portion of the sodium hydroxide, preferably about 0.15 moles sodium hydroxide per mole of phenol were reacted at a temperature of from about 80 to 100C until a viscosity of from about 2000 to 2500 cps (measured at 25C~ was reached. A second portion of the sodium hydroxide, preferably about 0.2 moles were added and the polymerization was carried forward at a temperature of from about 65 to 75C, and until a viscosity of from about 2000 to 2500 cps (measured at 25C) was reached. A
third portion of sodium hydroxide, preferably 0.15 moles were added and the reaction was continued at a temperature of from about 65 to 75C until a viscosity of from about 1500 to 1800 cps (measured at 25C) was reached. Urea was added in an amount sufficient to react with the excess formaldehyde, and the resin was quickly cooled to about 25C or below. The final resin composition was about 42~
total solids and the resin viscosity was about 800 cps (measured at 25C).

In this example, the organosolv lignin was directly added to the condensation reaction mixture of phenol and formaldehyde and copolymerized during such reaction. The lignin-containing phenol-formaldehyde resin can be used to formulate an adhesive for plywood .

W092/~8557 PCT/US92/02963 ~ 7~J 30 i ~

applications (see Example 19). About 15% ALCEL~ lignin on a weight basis with phenol, about 0.28 moles formaldehyde, about 20~ of the water and about 0.08 moles of sodium hydroxide were reacted for about 90 minutes at from about 55 to 60C. The mixture was cooled to a temperature of about 30C and one mole of phenol, about 0.17 moles sodium hydroxide and about 2.52 moles of formaldehyde and the remaining water were added and the polymerization was continued until a viscosity of from about 2000 to 2500 cps (measured at 25C) was reached. The mixture was cooled to a temperature of from about 55 to 75C, about 0.23 moles of sodium hydroxide were added and the polymerization was continued until a viscosity of from about 2000 to 2500 cps. About 0.17 moles of sodium hydroxide were added and the polymerization was continued until a viscosity of from about 1700 to 2000 cps (measured at 25C) was reached.
Urea was added in an amount sufficient to react with the excess formaldehyde, and the resin was quickly cooled to about 25C or below. The lignin/phenolic resin composition was about 42% total solids and the resin viscosity was about 1000 cps (measured at 25C).

An adhesive for plywood manufacture can be prepared in a variety of ways and different techniques have been employed to formulate the adhesive depending on the application. In this particular example, about 7.11%
by weight of Example 18 phenol-formaldehyde resin, about 21.35% by weight water, about 12.09% by weight of a mixture of additives (e.g. fillers or viscosity modifiers) and about 2.49% by weight alkali, preferably sodium hydroxide, were mixed for from about 5 to 15 minutes. The balance of Example 18 resin, about 56.93% by weight was added to the mixture. The final adhesive composition was ~ . ~

WO92/18557 PCT/US92/029~3 ~l 0~17~

from about 24 to 32~ total solids of which about 1 to 7%
was organosolv lignin. The final adhesive viscosity was about 5600 cps (measured at 25C).

A commercial adhesive using for example Canadian Reichhold Chemical Company 3B-055 Resin was prepared followinq a similar procedure.

An adhesive for plywood manufacture was prepared using the procedure of Example 19. In this example, about 13.62% by we~ht of Example 17 phenol-formaldehyde resin, about 18.54% by weight water, about 11.17~ by weight of a mixture of additives (e.g. fillers or viscosity modifiers), about 3.07% by weight alkali, preferably sodium hydroxide, and about 4.78% organosolv lignin, preferably ALCELL0 lignin were mixed for from about 5 to 15 minutes. The balance of Example 17 resin, about 48.81%
by weight was added to the mixture. The final adhesive composition was from about 24 to 32~ resin solids of which about 2 to 10% was organosolv lignin. The final adhesive viscosity was about 3780 cps (measured at 25C).

In this example, about 4.7% organosolv lignin was added to a commercial adhesive (e.g. Borden 3130H).
About 13.60% of a commercial resin (e.g. Borden 3130), about 18.53% water, about 11.2% of a mixture of additives (e.g. fillers or viscosity modifiers), about 4.8%
organosolv lignin, preferably ALCELL~ lignin and about 3.06% alkali, preferably sodium hydroxide were mixed for . ~
- ;
, `

, f 2 1 ~
from about 5 to 15 minutes. The balance of the commercial resin, about 48.8% by weight was added to the mixture.
The final adhesive composition was about 26.85% resin and about 4.7~ organosolv lignin. The final adhesive viscosity was about 7200 cps (measured at 25C).

The following examples are illustrative of a testing procedure which compares the adhesion performance of the lignin-containing plywood adhesive of the invention with a commercial adhesive. The adhesives as prepared were particularly suited for use with Douglas Eir plywood and can be modified for other applications (e.g. by spray or mechanical spreader) and for use with other veneer~ (e.g.
southern pine). Test panels were prepared under extreme manufacturing conditions in order to accentuate the two major causes of panel failure, namely over-penetration and dry-out. Shear specimens were prepared and tested for over-penetration and dry-out according to an approved procedure (e.g. American Plywood Association, PS 1-83).

An adhesive for plywood manufacture was prepared using the procedure of Example 19. In this particular example, the plywood adhesive was suitable for commercial applications. In this example, about 13.62% by weight of Example 17 phenol-formaldehyde resin, about 19.11~ by weight water, about 10.62~ by weight of a mixture of additives ~e.g. fillers or viscosity modifiers), about 3.11% by weight alkali, preferably sodium hydroxide, and about 4.82~ organosolv lignin, preferably ALCELL~ lignin were mixed for from about 5 to 15 minutes. The balance of Example 17 resin, about 48.90% by weight was added to the mixture. The final adhesive composition was about 26.6%
total solids of which about 4.82% was organosolv lignin.

WO92~18557 PCT/U~92/02963 2 ~ ; 3 The final adhesive viscosity was about 7000 cps (measured at 25C).

The adhesives in Table 20 were tested by the preparation of three ply panels made with l/8" Douglas Fir veneer. The panels were pressed using a press temperature of about 300F and a pressure of about 200 psi. To accentuate over-penetration, a wet glue spread of about 70 lbs of adhesive per 1,000 square feet of double glue line was used witn an assembly time of from about 2 to 3 minutes and a pressing time of about 6 minutes. To accentuate dry-out, a wet glue spread of about 40 lbs of adhesive per l,000 square feet of double glue line was used with an assembly time of about 40 minutes and a pressing time of about 5 minutes. The press was closed immediately after loading so that there was no "fry-time".
The panels were tested using the vacuum pressure and four-hour alternate boil test and the results are summarized in Table 20. A high percent (~) wood failure indicates that the adhesive was holding and that the wood was breaking rather than the adhesive.

Three ply panels were prepared and tested as in Example 23. Results in Table 21 indicate that the adhesive of Example 20 performs better than commercial adhesives with or without lignin.

,_.
21~817~ -34- l The adhesives in Table 22 were tested by the preparation of 13/16" five ply panels made with Douglas Fir veneer. In this example, the panels were pressed for varying press times, at a press temperature or about 300P, and a pressure of about 200 psi. The wet glue spread was about 60 lbs of adhesive per 1,000 square feet of double glue line were used with an assembly time of about 15 minutes. The "fry-time" was about 0.5 minutes.
The panels were tested using the vacuum pressure and four-hour alternate boil test and the results were summarized in Table 20. A high percent t~) wood failure indicates that the adhesive was holding and that the wood was breaking rather than the adhesive.

The results in Table 22 indicate that the organosolv lignin containing adhesive has the same or faster curing properties as the commercial adhesive.

The adhesive of Example 22 was tested in a commercial mill trial by the preparation of 5/6" three ply, 21/32" five ply and 25/32" five ply panels made with Douglas Fir veneer. The panels were cold pressed at a pressure of about 150 psi and for about 5 minutes, and hot pressed using a press temperature of a~out 275~, a pressure of about 200 psi and for about 5.5 minutes. A wet glue spread of about 65 lbs of adhesive per 1,000 square feet- of double glue line was used. The press was closed immediately after loading. The panels were tested using the vacuum pressure and four-hour alternate boil tests and the results were summarized in Table 23. A high percent WO92J185~7 PCT/US92/02~63 , ~ 2 ~ 7 ~

(%) wood failure indicates that the adhesive was holding and that the wood was breaking rather than the adhesive.
The results in Table 23 indicate that Example 22 adhesive has excellent board properties.

In this example, ALCELL~ lignin dispersions were prepared and were blended with a phenol-formaldehyde resin to form the adhesive. In preparing the lignin dispersion, about 1.2~ ammonium hydroxide (ammonia basis) was used.
Ammonium hydroxide was added t~ wate. and then ALCELL~
lignin was added slowly with agitation to from a stable dispersion. The lignin dispersion contained about 51.3%
total solids.

An adhesive for waferboard manufacture was prepared with the dispersion of Example 27. About 58.6 grams of the lignin dispersion of Example 27 was mixed with 214.4 grams of a phenol-formaldehyde resin (e.g. face resin PH-102) and 4.9 grams of water. The final adhesive composition was about 54% total solids of which about 20%
was organosolv lignin. The final adhesive viscosity was about 379 cps (measured at 25C). The final adhesive composition was adjusted by addition of water to about 50%
total solids. The final adhesive viscosity was about 222 cps (measured at 25C).

W O 92/18557 PC~r/US92/02963 ~ . ~
2~ ~81 7u -36-The adhesive of Example 28 was tested by the preparation of boards manufactured according to the parameters of Table 5. The results of board testing were shown in Table 24 and demonstrate that the boards prepared were competitive with control boards.

In this example, the dispersion of Example 27 replaces about 20% of the phenol used during the synthesis of a phenol-formaldehyde resin. In preparing the adhesive, the procedure of Example 13 was followed where the lignin dispersion of Example 27 was used instead of the organosolv lignin. The final resin composition was about 54% solids of which about 12% was organosolv lignin.
The final adhesive viscosity was about 174 cps (measured at 25C).

The phenol-formaldehyde resin of Example 30 was tested as a face resin on boards manufactured according to the manufacturing conditions shown in Table 5. The results in Table 25 demonstrates that the boards have good properties.

WO92/185~7PCT/US92/02963 ,., :

In this example, alkaline ALCELL~ lignin solution was prepared by addition of sodium hydroxide and ALCELL~ lignin to water. About 1200 grams of a lignin cake containing about 65% solids were mixed with about 270 grams of an about 50% sodium hydroxide solution and about 559 grams of water to obtain a solution containing about 44.9~ solids and having a viscosity of about 1300 cps The solution composition was adjusted by addition of water to contain about 40% solids and to a viscosity of about 227 cps (measured at 25C).

The alkaline ALCELL~ lignin solution of Example 32 can be used as a partial replacement for phenol during phenol-formaldehyde resin synthesis. In preparing the resin, the procedure of Example 13 was followed and the alkaline organosolv lignin solution of Example 32 replaces the organosolv lignin used. The final adhesive composition was about 54% total solids of which about 12% was organosolv lignin. The final adhesive viscosity was about 204 cps (measured at 25C).

-The phenol-formaldehyde resin of Example 33 was tested as a face resin on boards manufactured following the parameters of Table 5. The results in Table 26 demonstrate that the boards have good properties and were competitive with control boards.

, -.:

1 " ' 21 ~ ~1 7l~ -38-In this example, the alkaline lignin solution of Example 32 was added to the phenol-formaldehyde resin of Example 17 and used in plywood applications. In this example, about 568.7 grams of Exampie 17 phenol-formaldehyde resin was blended with 128.5 grams of the alkaline lignin solution of Example 32. The final adhesive was about 42.4~ total solids of which about 15~ was organosolv lignin. The final adhesive a viscosity was about 685 cps (measured at 25C).

The adhesive of Example 35 was tested by the preparation of 3/8" three ply panels made with 1/8"
Douglas Fir veneer. In this example, the panels were pressed for about 6 minutes, at a press temperature of about 300F and a pressure of about 200 psi. The panels were tested using the vacuum pressure and four-hour alternate boil test under conditions that promote over-penetration. The adhesive was compared to a commercial phenol-formaldehyde resin. A high percent (~) wood failure indicates that the adhesive was holding and that the wood was breaking rather than the adhesive. The results in Table 27 indicate that the adhesive of Example 35 was performing equal to or better than the commercial adhesive.

:
~ ':
"' ~" ' .

WOg2~18557 PCT/US92/02963 The adhesive of Example 35 was tested by the preparation of 3/8" three ply panels made with 1/8"
Douglas Fir veneer. In this example, the panels were pressed for about 5 minutes, at a press temperature of about 300F, and a pressure of about 200 psi. The panels were tested using the vacuum pressure and four-hour alternate boil test under conditions that promote dry-out.
The adhesive was compared to a commercial phenol-formaldehyde resin. A high percent (%) wood failureindicates that the adhesive was holding and that the wood was breaking rather than tAe adhesive. The results in Table 28 indicate that the adhesive of Example 35 was performing equal to or better than the commercial adhesive.

The adhesive of Example 35 was tested by the preparation of 5/8" three ply panels made with 1/8"
Dou~las ~Fir veneer. In this example, standard production methods were simulated by using about 6.5 minutes prepress time, about one minute closed assembly time, about 0.5 minutes fry time at an assembly time ranging from about 5 to 45 minutes. The panels were pressed for about 6.5 minutes, at a press temperature of about 300F and at a pressure of about 200 psi. The panels were tested under normal conditions. The adhesive was compared to a commercial phenol-formaldehyde resin. A high percent (%) wood failure indicates that the adhesive was holding and that the wood was breaking rather than the adhesive. The results in Table 29 indicate that the adhesive of Example WO92~1855? PCT/US92/02963 211 ~3~17~
35 was performing equal to or better than the commercial adhesive.

In this example, ALCELL~ lignin was phenolated prior to phenol-formaldehyde resin synthesis for waferboards and oriented strandboard applications. About 0.67 moles phenol, about 0.14 moles sodium hydroxide and about 20~ organosolv lignin on phenol weight basis were reacted for about 60 minutes and at a temperature of about 180C. The reaction mixture was cooled tO about 45C, and about 0.33 moles phenol, about 4.1 moles formaldehyde and about 0.24 moles sodium hydroxide were added. Enough water was added such that the final adhesive has a total resin solids content of about 55~. The mixture was heated to 80C and polymerization was continued until a target viscosity of from about 200 to 400 cps (measured at 25C) was reached. Urea was added in an amount sufficient to constitute 5% of the resin liquid weight and the resin was quickly cooled to 25C or below. The final adhesive composition was about 55~ resin solids of which about 12%
was organosolv lignin. The final adhesive viscosity was about 205 cps (measured at 25C).

The adhesive of Example 39 was tested by the preparation of three layers waferboard panels. The manufacturing conditions of Table 5 were followed. The results of board testing were shown in Table 30 and demonstrate that the boards prepared were competitive with control boards.

, . ' , . . .
.:

WO92/18~57 2 ~ ~ ~ 1 7 ~ PCT/US92/02963 , In this example, ALCELL~ lignin was phenolated prior to phenol-formaldehyde resin synthesis used in plywood applications. In this example, about 15% of the total phenol used in the resin was replaced by organosolv lignin such as ALCELL~ lignin. About 0.28 moles of phenol and about 0.06 moles sodium hydroxide were reacted for about 60 minutes and at a temperature of about 180C. The mixture was cooled to about 45 and about 0.72 moles phenol, about 2.69 moles formaldehyde and water was added in an amount sufficient such that the final resin solids were about 42% solids. About 0.12 moles of sodium hydroxide were added and the mixture was refluxed for about 20 minutes. ~he mixture was then cooled to about 80C and the polymerization continued until a viscosity of about 2500 cps (measured at 25C) was reached. The mixture was then cooled to about 70C and about 0.24 moles sodium hydroxide was added. The polymerization was continued until a viscosity of about 2500 cps (measured at 25C) was reached. The mixture was cooled to about 65C
and about 0.18 moles sodium hydroxide were added. The polymerization was continued until a viscosity of from about 1500 cps (measured at 25C) was reached. Urea was added in an amount sufficient to constitute about 5% of the resin weight and the resin was cooled to 25C or below. The final adhesive composition was about 42~ total solids of which about 8% was organosolv lignin.

An adhesive for plywood manufacture was prepared using the procedure of Example 19. In this particular .

WO92/185~7 PCT/US92/02963 2~i7~

example, about 7.11% by weight of Example 41 phenol-formaldehyde resin, about 21.35% by weight water, about 12.09% by weight of a mixture of additives (e.g. fillers or viscosity modifiers) and about 2.49~ by weight alkali, preferably sodium hydroxide, were mixed for from about 5 to 15 minutes. The balance of Example 41 resin, about 56.93% by weight was added to the mixture. The final adhesive composition was from about 24 to 32~ total solids of which about 1 to 7% was organosolv lignin. The final adhesive viscosity was about 5600 cps (measured at 25C).

The adhesives in Table 31 with varying levels of ALCELL~ lignin substitution were tested by the preparation of 3/8" three ply panels made with 1/8" Douglas Fir veneer. The panels were pressed using a press temperature of about 300F and a pressure of about 200 psi. To accentuate over-penetration, a wet glue spread of about 70 lbs of adhesive per 1,000 square feet of double glue line was used with an assembly time of from about 2 to 3 minutes and a pressing time of about 6 minutes. The press was closed immediately after loading so that there was no "fry-time". The panels were tested using the vacuum pressure and four-hour alternate boil test and the results are summarized in Table 31. A high percent (%) wood failure indicates that the adhesive was holding and that the wood was breaking rather than the adhesive.

The adhesives in Table 32 with varying levels of ALCELL~ lignin substitution were tested by the preparation ,' :, . . .
:

WO92/18~57 PCT/US92/02963 2 ~
.

of 3/8" three ply panels made with 1/8" Douglas Fir veneer. To accentuate dry-out, a wet glue spread of about 40 lbs of adhesive per 1,000 square feet of double glue line was used with an assembly time of about 40 minutes and a pressing time of about 5 minutes. The press was closed immediately after loading so that there was no "fry-time". The panels were tested using the vacuum pressure and four-hour alternate boil test and the results are summarized in Table 32. A high percent (%) wood failure indicates that the adhesive was holding and that the wood was breaking rather than the adhesive.

The adhesives in Table 33 with varying levels of ALC~LL0 lignin substitution were tested by the preparation of 5/8" five ply panels made with 1/8" Douglas Fir veneer.
In this example, adhesion performance was studied under simulated normal assembly conditions at slightly high and normal wet spreads. Normal production methods were simulated by using 5 minutes prepress conditions, one minute closed assembly time and 0.5 minute fry time at different assembly times ranging from about 5 to 30 minutes. The press temperature was set at about 300F, and a pressure of about 200 psi. The wet glue spread was about 60 lbs of adhesive per 1,000 square feet of double glue line. The panels were tested using the vacuum pres-sure and four-hour alternate boil test and the results were summarized in Table 33. A high percent (%) wood failure indicates that the adhesive was holding and that the wood was breaking rather than the adhesive.

.: , ,. ; :. , ::

.,:
.

WO92tl8557 PCT/US92/02963 210817b In this example, low molecular weight ALCELL~
lignin was used as a partial replacement for phenol in the manufacture of phenol-formaldehyde resins for waferboards and oriented strandboard application. To the adhesive, the procedure of Example 13 was used and the low molecular weight ALCELL~ lignin replaces the organosolv lignin. The final adhesive composition was about 54% total solids of which about 12% was organosolv lignin. The final adhesive viscoslty was about 204 cps (measured at 25C).

The adhesive of Example 46 was tested by the preparation of three layers waferboard panels. The manufacturing conditions of Table 5 were followed. The results of board testing are shown in Table 34 and demonstrate that the boards prepared were competitive with control boards.

In this example, ALCELL~ lignin substituted for about 20% of the phenol on a phenol weight basis used in phenol-formaldehyde resin manufacture. About 1.3 moles of formaldehyde, 0.06 moles of sodium hydroxide and about 20%
ALCELL~ lignin on a weight basis with phenol were reacted for about 90 minutes and at a temperature of about 70C.
The reaction mixture wa~ cooled to about 30C, and about one mole of phenol, about 1.15 mole formaldehyde and about 0.27 moles of sodium hydroxide were added. The mixture .
.~ , .

W~92/18557 ~ ~ g 1 ~ ~ PCT/US92/02~63 ....
.~. . .

was heated to about 80C and polymerization was continued until a target viscosity of from about 200 to 700 cps (measured at 25C) was reached. Urea was added in an amount sufficient to react with the excess formaldehyde and the resin was quickly cooled to about 25C or below.
The final resin composition was about 57~ total solids of which about 12~ was organosolv lignin. The final adhesive viscosity was about 240 cps (measured as 25C).

In this example, organosolv lignin such as ALCELL0 lignin substituted for about 40~ phenol on a weight basis during phenol formaldehyde resin manufacture.
About 2.9 moles of formaldehyde, about 0.16 moles sodium hydroxide, about 40% organosolv lignin on a weight basis with phenol and water were reacted for about 90 minutes and at a temperature of about 70C. The reaction mixture was cooled to about 45C, about one mole phenol and about 0.31 moles of sodium hydroxide were added. The mixture was heated to about 80C and polymerization was continued until a target viscosity of about 200 to 400 cps (measured at 25C) was reached. Urea was added in an amount equal to about 5~ of total resin weight, and the resin was quickly cooled to about 25C or below. The final resin composition was about 57% total solids of which about 25%
was organosolv lignin. The resin viscosity was about 240 cps (measured at 25C).

The adhesives of Examples 48 and 49 have been tested as face resins for waferboards and oriented ~ , . .

:~: . . . .
, .., ~ . .
.

WO92/185~7 PCT/US92/02963 ~1~8~ 7~ -46-strandboard applications. The manufacturing conditions of Table 5 were followed. The results of board testing are shown in Table 35 and demonstrate that the boards prepared were competitive with control boards.

In this example, ALCELL0 lignin was acid methylolated as a first step in the synthesis of a phenol-formaldehyde resin for waferboard and orlented strandboard applications. About 20% on a weight basis of the phenol used in the manufacture of the phenol-formaldehyde resin was replaced by organosolv lignin. Thus 18.8 grams of lignin were dissolved in about 0.32 moles of phenol, about 0.39 moles formaldehyde and 0.003 moles of sulfuric acid.
The mixture was reacted for about 45 minutes at a temperature of about 80C. The reaction mixture was cooled to about 45C and about 0.006 moles sodium hydroxide was added to neutralize the sulfuric acid.
About 0.68 moles of phenol, about 2.36 moles of formaldehyde and about 0.31 moles of sodium hydroxide were added. Enough water was added such that the total resin solids were about 55%. The mixture was heated to about 80C and polymerization was continued until a target viscosity of from 200 to 400 cps (measured at 25C) was reached. Urea was added in an amount sufficient to constitute about 5~ of the resins liquid weight and the resin was quickly cooled to about 25C or below. The final adhesive composition was about 55% total solids of which about 12% was organosolv lignin.

, , .
' . ;~' ~

wos2/18s57 PCT/US92/02963 8 1 7 ~

The adhesive of Example 51 was tested as a face resin in waferboard applications. Results in Table 36 demonstrate that the boards prepared were competitive with control ~oards.

In this example, ALCELL~ lignin was acid methylolated as a first step in the synthesis of a phenoi-formaldehyde resin for plywood applications. About 15% on a weight basis of the phenol used in the manufacture of the phenol-formaldehyde resin was replaced by ALCELL~
lignin. About 14.1 grams of organosolv lignin, about 0.23 moles phenol, about 0.31 moles formaldehyde and about 0.002 moles sulfuric acid were reacted for about 45 minutes at a temperature of about 80C. The mixture was cooled to a temperature of about 35C and about 0.012 moles sodium hydroxide was added to neutralize the sulfuric acid. Enough water was added such that the final resin solids were about 42%. About 0.77 moles phenol and about 2.84 moles formaldehyde were added. About 0.18 moles of sodium hydroxide were added. The mixture was heated to reflux for about 15 minutes then cooled to about 80C.
The polymeriæation was continued until a viscosity of from about 2000 to 2500 cps (measured at 25C) was reached.
The mixture was cooled to about 70C. About 0.24 moles of sodium hydroxide were added and the polymerization continued until a viscosity of from about 2000 to 2500 cps ~measured at 25C) was reached. The mixture was cooled to about 65C. About 0.18 moles sodium hydroxide were added and the polymerization continued until a viscosity of about 1500 to 1800 cps (measured at 25C) was reached.

,", ~\ ~

W092/18557 PCT/US92tO2963 ~_.
2~2~ 7~ -48-Urea was added in an amount sufficient to constitute about 5~ of the final adhesive weight and the resin was cooled to 25C or below. The final resin composition was about 42~ total solids of which about 8~ was organosolv lignin.

An adhesive for plywood manufacture was prepared using the procedure of Example 19. In this particular example, about 7.11% by weight of ~xample 52 phenol-formaldehyde resin, about 21.35% by weight water, about 12.09% by weight of a mixture of additives (e.g. fillers or viscosity modifiers) and about 2.49~ by weight alkali, preferably sodium hydroxide, were mixed for from about 5 to 15 minutes. The balance of Example 52 resin, about 56.93% by weight was added to the mixture. The final adhesive composition was from about 24 to 32~ total solids of which about 1 to 7% was organosolv lignin. The final adhesive viscosity was about 5600 cps (measured at 25C).

The adhesives in Table 37 with varying levels of ALCELL~ lignin substitution were tested by the preparation of 3/8" three ply panels made with 1/8" Douglas ~ir veneer. The panels were pressed using a press temperature of about 300F and a pressure of about 200 psi. To accentuate over-penetration, a wet glue spread of about 70 lbs of adhesive per 1,000 square feet of double glue line was used with an assembly time of from about 2 to 3 minutes and a pressing time of about 6 minutes. The press was closed immediately after loading so that there was no "fry-time". The panels were tested using the vacuum - , .. ,; :.: .

2 ~ 7 ~

pressure and four-hour alternate boil test and the results are summarized in Table 37. A high percent (%) wood failure indicates that the adhesive was holding and that the wood was breaking rather than the adhesive.

The adhesives in Table 38 with varying levels of ALCELL0 lignin substitution were tested by the preparation of 3/8" three ply panels made with l/8" Douglas Fir veneer. To accentuate dry-out, a wet glue spread of about 40 lbs of adhesive per 1,000 s~uare feet of double glue line was used with an assembly time of about 40 minutes and a pressing time of about 5 minutes. The press was closed immediately after loading so that there was no "fry-time". The panels were tested using the vacuum pressure and four-hour alternate boil test and the results are summarized in Table 38. A high percent (%) wood failure indicates that the adhesive was holding and that the wood was breaking rather than the adhesive~

The adhesives in Table 39 with varying levels of ALCELL0 lignin substitution were tested by the preparation of 5/8" five ply panels made with l/8" Douglas Fir veneer.
In this example, adhesion performance was studied under simulated normal assembly conditions at slightly high and normal wet spreads. Normal production methods were simulated by using 5 minutes prepress conditions, one minute closed assembly time and 0.5 minute fry time at different assembly times ranging from about 5 to 30 minutes. The press temperature was set at about 300F, and . .

' ' ,, WO92/18~7 PCT/US92~02963 2~ 7~ -50- f a pressure of about 200 psi. The wet glue spread was about 60 lbs of adhesive per 1,000 square feet of double glue line. The panels were tested using the vacuum pres-sure and four-hour alternate boil test and the results were summarized in Table 39. A high percent (~) wood failure indicates that the adhesive was holding and that the wood was breaking rather than the adhesive.

WO92t18557 PCT/US92/02963 2 ~ 7 ~

Wafer Type commercial aspen Moisture Content(%)4.6 Additives Binder Content (~ by wafer weight) 2.5 Wax Content (% solids by wafer weight) 1.0 Press Conditions Temperature (F) 410 Time (seconds) 180 Pressure (psij 540 Board Thickness(inches)3/8+20/1000 Density (lb./cu.ft.) 39.8-43.0 No. Panels/Condition 3 Panel Dimensions15" x 15"

.
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. .

WO92/1855~ PCT~US92/02963 2 i ~17!~

Wafer Type commercial aspen Moisture Content(%)4.6 Additives Binder Content (% by wafer weight) 4.5 Wax Content (% solids by wafer weight) 1.0 Press Conditions Temperature tF) 410 Time (seconds) 300 Pressure (psi) 540 Board Thickness (inches)3/8+20/1000 Density (lb./cu.ft.) 39.8-43.0 No. Panels/Condition 3-4 Panel Dimensions15" x 15"

W~9~/l8557 PCT/~S92/02963 2, 3~

Wafer Type commercial aspen Moisture Content(%) 4.6 s Additives Binder Content (~ by wafer weight) 1.95 Wax Content (~ solids by wafer weight) 1.0 Press Conditions Temperature (F) 400 Time (seconds) 170 Pressure (psi) 550-750 Board Thickness (inches) 7/16+20/1000 Density (lb./cu.ft.) 38.0-42.0 No. Panels/Condition 4-5 Panel Dimensions 42" x 42"

' ', ' .

~092/~8S57 PCT/US~2/0~963 2~17''' ~54~

Wafer Type commercial aspen Moisture Content(%) 4.6 Additives Binder Content (~ by wafer weight) 1.95 Wax Content (% solids by wafer weight) Press Conditions Temperature (F) 400 Time (seconds) 180 Pressure (psi) 540 Board Thickness (inches)7/16+20/1000 Density (lb./cu.ft.)38.0-42.0 Panels/Condition 3 Panel Dimensions 15" X 15"

W092/~8557 PCT/US92/02963 2~ ~g~ 7~

Wafer Type commercial aspen Moisture Content(~) 4.6 Core Resin (% by wafer weight) 3.0 Face Resin (% by wafer weight) 3~3 Additives Wax Content (% solids by wafer weight) 0.9 Press Conditions Temperature (F) 400 Time ~seconds) 255 Pressure (psi) 540 Board Thickness (inches) 7/16+20/1000 Density (lb./cu.ft.) 38.0-42.0 No. Panels/Condition 3 Panel Dimensions 15" x 15"

: , ' WO~2/18557 PCT/US92~02~3 i:

2~17~

Liqnin MOR MOE IB D-4 (psi) (Kpsi) (psi) (lbs) Organosolvl 4875 846 74 198 Lignosulfonate2 4762 806 63 179 Kraft3 4066 722 74 163 Note: Figures in parenthesis are in percent (%) and based on values for board made with a 100~ phenol-formaldehyde resin.
Kev:
MORE = Modulus of Rupture (psi) MOE = Modulus of ~lasticity (Kpsi) IB = Internal Bonding (psi) D-4 - Single Cycle Bending American Plywood Association Test Method (lbs) Standards of Measurement MORE, MOE, IB: ASTM Standard D 1037-78 D-4, D-5: Cycle Bending American Plywood Association Test Method (1) ALCELL~ Lignin, Repap Technologies, Valley Forge, PA
(2) Orzan S by ITT Rayonier, Stamford, CT
(3) Indulin AT by Westvaco, New York, NY

WO92/18~57 PCT/US92/02~3 1 7 ~

MOR _ D-4 D-5_ psi psi lbs lbs (%) (%) (%) (%) 100% GP54151 3456 59.4 144 115 (100) (100) (100) (100) 80% GP5415 3654 60.1 143 141 20% ALCELL0 (106) (101) (99) (123) Lignin 10 Conditions: 400F Temperature, 170 seconds 100% BD909 used in Core Layer Kev:
D-5 = Six Cycle 3ending American Plywood Association Test Methods (lbs) (1) Face resin manufactured by Georgia Pacific (Crossett, Arkansas) .

.

W092/185~7 PCT/US92/02963 , .

2 ~ 3 psi lbs psi (%) (%) (%) 5 100% BD9091 4096 131.5 55.8 (100) (100) (100) 50% BD909 4431 130.3 59.2 5% Phenol (i08) (109) (106) 45% ALCELL0 Lignin Conditions:

100~ GP5415 used in face layer, Georgia Pacific, Crossett, Arkansas (1) Core resin by Reichhold, Bellevue, Ontario, Canada.

;~ , WO92/185~7 2 1 ~ ~3 1 ~ ~ j :` ~

psi lbs psi (%) (%) (%) 100% GP5415 4163 170 68 (100) (100) (100) 80~ GP5415 20% ALCELL0 Lignin 4015 119 50 (96) (70) (74) lQ 80% GP5415 4619 198 55 18% ALCELLX Lignin (111) (116) (81) 2% Phenol 100% BD802 2952 146 57 (100) (100) (100) 80% BD802 3138 119 50 20% ALCELL0 Lignin (106) (82) (87) 80% BD802 3114 155 55 18~ ALCELL~ Lignin (106) (106) (96) 2% Phenol 10Q% BD023 3226 190 81 (100) (100) (100) 80% BD023 2913 164 65 20% ALCELL Lignin (90) (86) ~80) ;~

.

WO92/18~57 PCT/USg2/02963 2~8~7~ -60-80% 3D023 3360 195 79 18% ALCELL Lignin (104) (103) (97) 2% Phenol Conditions:

BD023 and BD802 are both manufactured by Reichhold Ltd, 3ellevue, Ontario, Canada~

GP5415 is manufactured by Georgia Pacific, Crossett, Arkansas.

WO92/185S7 ~ PCT~US92/02963 psi psi lbs ( % ) 100% BD909 4310 81 225 (1003 (100) (100) 80% BD909 3735 68 172 20% ALCELL0 Lignin (87) (84) (76) 80% BD909 3832 73 206 16% ALCELL0 Lignin (89) (90) (92) 4% Low Molecular Weight ALCELL0 Lignin 80% BD909 4223 83 224 10% ALCELL0 Lignin (98) (102) (100) 10% Low Molecular Weight ALCELL0 Lignin - ~: , .. :...... -; . -: ,:

':

WO92/18557 PCT/US92rO2963 ., , --2~ 081 l ~i -62-psi lbs psi (~) (%) (%) 100% BD9091 4298 141 66 (100) (100) (100) 80% BD909 3443 118 42 20% ALCELL0 Lignin (80) (84) (63) 80% BD909 4343 129 51 18% ALCELL0 Lignin (101) (91) (77) 2% Phenol 80% BD909 3694 144 53 18% ALCELL~ Lignin (86) (102) (80) 2% PTBP

80% BD909 3462 86 40 18% ALCELL0 Lignin (81) (61) (60) 2% p-Cresol 80% BD909 3825 124 39 18% ALCELL0 Lignin (89) (88) (58) 2% p-Nonyl Phenol 80% BD909 4298 137 49 18% ALCELL0 Lignin (100) (97) (73) 2% p-C24-28 Phenol WO92/185~7 PCT/US92/02963 2 1 i~
!

80% BD909 3636 110 45 18% ALCELL~ Lignin ~85) (85) (68) 2% 2,4-Dimethyl Phenol 80% BD909 3876 154 50 5 18% ALCELL~ Lignin (91) (109) (76) 2% 2,4,6-Trimethyl Phenol Conditions:
-100% GP5415 in face layer manufactured by Georgia Pacific,Crossett, Arkansas.

Key:

(1) Core resin manufactured by Reichhold Ltd, Bellevue, Ontario, Canada .: .

W092/18~57 PCT/US92/0~963 ~ f:
2 ~ 6 4--psi lbs psi (%) (%) (%) 100% BD9091 4829 171 58 (100) (100) (100) 80% BD909 3723 - 194 61 18% ALCELL~ Lignin (77) 1113) (105) 2~ THPE

80% BD909 4368 193 40 18% ALCELL~ Lignin (91) (113) (83) 2% BPA

Conditions:

100% GP5415 in face layer manufactured by Georgia Pacific, Crossett, Arkansas.

Keyl (1) Core resin manufactured by Reichhold Ltd, Bellevue, Ontario, Canada :: , WO92/185~7 PCT/US92/02963 ~ 2~ ~17~

psi lbs psi (%) (%) (%) 100% GP54791 4042 157 59 (100) (100) tlOO) 80% GP5479 4147 147 54 19.8% ALCELL0 Lignin (102) (93) (92) 0.2% PTBP

80% GP5479 4243 176 56 19.2% ALCELL0 Lignin (103) (112) t96) 0.8~ PTBP

80% GP5479 3990 129 51 18% ALCELL Lignin (99) (82 (86) 2% PTBP

Conditions:

100% GP5415 in face layer manufactured by Georyia Pacific, Crossett, Arkansas.

: .
.

WO92~18557 PCT/US92/02963 2 1 ~ ~ ~ 7 S -66-Key:

(1) Core resin manufactured by Georgia Pacific, Crossett, Arkansas.

wo92~18ss7 PCT/US92/02963 2 ~ 7 ~
. , .

Press MOR IB D-4 D-5 Time psi psi psi psi (sec) (%) (%) (%) (%) 5 100% BD909 170 400958 194 177 (100)(100)(100) (100) 80% BD909 170 3503 52 159 149 20% ALCELL Lignin (87) (90) (82) ~84) 80% BD909 200 4048 64 218 198 10 20% ALCELL Lignin (100) (110) (112) (112) 80% BD909 230 4679 72 238 220 20% ALCELL Lignin (117) (124) (123) (124) Conditions:

400F temperature 100% GP5415 in face layer manufactured by Georgia Pacific, Crossett, Arkansas.

.

WO92/185~7 PCT/US9~/0~963 21 ~ ~ ~ q ~6a- t TABLE lS

Temp MOR IB D-4 D-5 psi psi lbs. lbs.
F (~ ) (%) (%) 100% BD909 400 3698 56 136 112 (100)(100) (100) (100) 80% BD909 400 3076 52 104 77 20~ ALCELL~ (83) (93) (76) (69) Lignin 80% BD909 415 3537 54 143 113 20% ALCELL~ (96) (96) (105) (101 Lignin Conditions:

100% GPS415 in face layer manufactured by Georgia Pacific, Crossett, Arkansas.

W092~185S7 PCT/US92tO2963 7 ~) . ..

psi psi lbs.
(~) (%) (%) 100% BD909 431081 225 (100) (100) (100) 80% BD909 389471 177 20% ALCELL~ Lignin (90) (88) (79) 80% BD909 4681 74 230 20% Baked ALCELL~ Lignin (109)(91) (102) 160C - 60 min.

Conditions:

100% GP5415 in face layer manufactured by Georgia Pacific, Crossett, Arkansas.

, WO92~1~5S7 PCT/US92/~2963 2 ~ ~ ~X 1 7 ~ -70-Inlet MOR IB D-4 Dryer psipsi lbs.
Temp.
(C) 100% BD909 431081 225 (100)(100)(100) 80% BD909 138 389169 184 20% ALCELL~ (90)(85) (82) Lignin 80~ BD909 157 374877 210 20% ALCELL~ (87)(95) (93) Lignin 80% BD909 192 396370 216 20% ALCELL~ (92)(86) (96) Lignin 80% BD909 235 444786 240 20% ALCELL~ (103)(106)(107) Lignin Conditions:

100% GP5415 in face layer manufactured by Georgia Pacific, Crossett, Arkansas.

WO92/18557 2 f ~ ~v? 17 ~) PCI`/US92/02963 , : ---71~

ps i ps i lbs .
(%) (%) (%) 4. S%Example 12 5138 116 279 Resin ( 100 ) ( 100 ) ( 100 ) 3 . 6% Example 12 Resin 5159 103 284 O . 9% ALCELL0 Lignin ( 100 ) ( 89 ) ( 102 ) 2 ~ ~J ~ ~ 7 ~ -72-psi psi lbs.
(%) (%) (%) Example 12 Resin 5138 116 279 (100) (100) (100)- ;

Example 13 Resin 5279 109 274 700 cps Viscosity (103) (94) (98) Example 13 Resin 4604 115 243 390 cps Viscosity (90) (99) (87) WO92/185~7 PCT/VS92/029~3 2 ~

Vacuum-Pressure 4 Hour- Alt Boil Over-penetration Dry-out Test (%) ~%) Commercial Adhesive1 56.6 77.2 Example l9 Adhesive 60.5 91.7 (1) Adhesive prepared from Canadian Reichold Chemical Company BB-055 resin as in Example l9 WO92/18~S7 PCTtUS92/02963 ... .
2~ ~17~ -74-~ABLE 21 Vacuum-Pressure4 Hour- Alt Boil Over-penetrationDry-out Test (~) (%) 5 Commercial Adhesivel 95 55.6 Example 20 Adhesive 94.3 72.1 Example 21 Adhesive2 92 49.1 (1) Borden 3130-H Adhesive (2) Borden 3130-H Adhesive containing about 4.7%
organosolv lignin WO92/18~57 ~ ~ ~gl 7 ~PCT/US92/02963 Vacuum-Pressure4 ~our- Alt Boil (%) (%) Press Time: 6 min 5 Example 20 Adhesive ---- ----Commercial Adhesivel 40 40 Press Time: 5 min Example 20 Adhesive 62 88 Commercial Adhesive1 7 15 Press Time: 4.5 min Example 20 Adhesive ---- ----Commercial Adhesivel 2 7 (1) Borden 3130H Adhesive .

W09~/1855~ PCT/US92/02963 2~ ~17'~ -76-Vacuum-Pressure 4 ~our- Alt Boil Panelsl (%) (%) 3 ply, 5/16" 93.2 94.7 5 5 ply, 21/32" 89.1 94.6 5 ply, 25/32" 93.4 93.8 ~1) Douglas Fir veneer WO92/18557 2 -~ Y3 ~ 1 7 ~ PCT/US92/02963 : -77-psi lbs psi (%) (%) (%) 5 100% PH-1021 5204 276 83 (100) (100) (100) 80% PH-102 4866 295 97 20% ALCELL~ lignin (94) (117) (107) Dispersion Conditions:

100~ SL-101 used in Core layer manufactured Dyno Polymers, Virginia, Minnesota.

~y:

(1) Face resin manufactured by Dyno Polymers, Virginia, Minnesota W092/18557 PCTtUS92/02963 '' f~'~`

21 ~17~ -78-psi lbs psi (%) (~) (%) 5 100% PH-1021 5204 276 83 (100) (100) (100) Ammonia Dispersion 5176 287 86 20% Phenol Replacement (119) (103) (104) Conditions:

100% SL-101 used in core layer manufactured by Dyno Polymers, Virginia.

Key:

(1) Face resin manufactured by Dyno Polymers, Vir~inia, Minnesota.

' .

21~g~

.

psi lbs psi (%) (%) (%) 5 100% PH-1021 5204 276 83 (100) (100) (100) ALCELL0 lignin as 4679 310 84 20% Phenol Replacement (90) (112) (101) Conditions:

100% SL-101 used in Core Layer manufactured by Dyno Polymers, Virginia, Minnesota.

Key:

(1) Face resin manufactured by Dyno Polymers, Virginia, Minnesota.

WO92/18~57 PCT/US92/02963 ~._ 2~ ~17~

Vacuum-Pressure Over-penetration (%) 5 85~ Example 17 Resin 68 15% Alkaline ALCELL~
Lignin Solution 100% Commercial Adhesive 50 Conditions:

(1) The wet glue spread is about 70 lbs of adhesive per 1,000 square feet of double glue line.
(2) The assembly time is about 2.5 minutes.

W092/185s7 21 ~ ~ ~ 7 ~ PCT/US92/02~63 4 Hour- Alt Boil Dry-out Test (%) 5 85% Example 17 Resin 78.6 15~ Alkaline ALCELL~
Lignin Solu~ion 100~ Commercial Adhesive 72 Conditions:

(1) The wet glue spread is about 40 lbs of adhesive per 1,000 square feet of double glue line.
(2~ The assembly time is about 40 minutes.

`' ` ~; ' `` ~

WO92~18557 PCT/US92/02963 21n8i ~ -82- ~' Vacuum-Pressure 4 Hr- Alt Boil Knife (%) (%) (~) 85% Example 17 Resin 78 72 96 5 15% Alkaline ALCELL~
Lignin Solution 100% Commercial Resin 74 70 97 Conditions:

(1) The wet glue spread is about 65 lbs of adhesive per 1,000 square feet of double glue line.
(2) The assembly time is about 5 to 45 minutes.
(3) The prepress time is about 6 minutes.
(4) The closed assembly time is about one minute.

W092/S85~7 2 ~ 7 ~ PCT/US92~02963 ~ . ~ . . .

psi lbs psi t%) (%) ~%) 5 100~ PH-1021 4006 182 63 (100) (100) (100) 20% Pnenol Replacement 4413 278 62 (110) (131) (98) Conditions:
, 100% GP92C60 in core layer manufactured by Georgia Pacifc, Crossett, Arkansas.

Kev:

tl) ~ace resin manufactured by Dyno Polymers, Virginia, Minnesota.

' . . ~ :

~- .. --' `' :.

2 ~ 7 ~

Vacuum-Pressure Knife (%) (%) Example 42 Adhesive 42 91 5 2.5% ALCELL0 Lignin Example 42 Adhesive 51 67 8.5~ ALCELL0 Lignin Example 42 Adhesive 72 93 2.2% ALCELL0 Lignin WO92/185~7 ~ 1 ~ g~ 7 ~PCT/US92/02963 4 Hr- Alt BoilKnife (~) (%) Example 42 Adhesive 78 81 5 2.5% ALCELL0 Lignin Example 42 Adhesive 59 77 4.9% ALCELL0 Lignin Example 42 Adhesive 57 90 4.1~ ALCELL0 Lignin WO92/18557 PCT/US92/02g63 2~ 86-Vacuum-Pressure 4 Hr- Alt Boil Knife (%) (%) (%) Example 42 Adhesive 74 72 90 5 2.5% ALCELL~ Lignin Example 42 Adhesive 66 62 88 4.9% ALCELL~ Lignin Example 42 Adhesive 80 72 93 4.1% ALCELL~ Lignin WO92/18~57 2 ~ ~ ~1 7 ~ PCT/US92/0~63 ,~ ,. .

psi lbs psi (%) (%) (%) 100~ PH-1021 4006 182 63 (100) (100) (100) 20% Phenol Replacement 4258 199 59 by Low Molecular Weight (106) (108) (94) ALCELL~ Lignin Conditions:

100% SL-101 used in core layer manufactured by Dyno Polymers, Virginia, Minnesota.

~:

(1) Face resin manufactured by Dyno Polymers, Virginia, Minnesota.

W092/185S7 PCT/US92tO2963 t._.
21~8~7~ -88-psi lbs psi (~) (%) (%) 0% Phenol Replacement 5015 205 76 ( 100 ) ~ 100 ) ( 100 ) 20% Phenol Replacement 4593 204 76 (92) (100)(100) 30% Phenol Replacement 4169 193 79 (83) (94) (104) 40% Phenol Replacement 4522 214 71 (90) (105)(94) 50% Phenol Replacement 3738 220 65 (75) (107)(85) 60% Phenol Replacement 4185 222 70 (83) (108)(92) Conditions:

100% GP92C60 in core layer manufactured by Georgia Pacific, Crossett, Arkansas.

, .

WO92/18S~7 2 ~ ~ $ 1 7 ~ PCT/US92/02963 f` ~

Key:

(1) 100~ PH-102 face resin manufactured by Dyno Polymers, Virginia, Minnesota.

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WO92/18557 PCTtUS92/02963 ~.
--90-- ~, 2 ~ 3 psi lbs psi (%) (%) ~%) 5 0% Phenol Replacement 4242 195 66 (100) 1100)(100) 20~ Phenol Replacement 4274 268 72 (101) (137)(109) Conditions:

100% PH-102 in face layer manufactured by Dyno Polymers, Virginia, Minnesota 100% SL-101 in core layer manufactured by Dyno Polymers, Virginia, Minnesota.

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WO92/18557 2 ~ 7 ~ PCTtUS92/02963 j: ~

Vacuum-Pressure Knife ~%) (%) Example 20 Adhesive 45.5 89 5 4.2% ALCELL~ Lignin Example 20 Adhesive 26.6 85 8.5~ ALCELL~ Lignin Example 19 Adhesive 39.7 81 2.2% ALCELL~ Lignin 10 Example 19 Adhesive 21.7 74 4.4% ALCELL~ Lignin Example 54 Adhesive 42.9 78 2.2~ ALCELL~ Lignin Example 54 Adhesive 31.8 69 4.4% ALCELLX Lignin WO92~18S57 PCT/US92/02963 2~17~ -92-4 Hr- Alt BoilKnife (%) (%~

Example 20 Adhesive 70 74 4.2~ ALCELL0 Lignin Example 20 Adhesive 78.1 85 8.5% ALCELL0 Lignin Example 19 Adhesive 47.4 79 2.2% ALCELL~ Lignin 10 Example 19 Adhesive 43.7 77 4.4% ALCELL~ Lignin Example 54 Adhesive 35.3 70 2.2% ALCELL0 Lignin Example 54 Adhesive 28.4 69 4.4% ALCELL0 Lignin , '.

WO92/18557 ~ 7 ~ PCT/US92/029~3 .: ~

Vacuum-Pressure 4 Hr- Alt Boil Knife (%) (%) (~) Example 20 Adhesive 57 60.2 81 4.2% ALCELL~ Lignin Example 20 Adhesive 86.4 86 96 8.5% ALCELL~ Lignin Example 19 Adhesive 48 41.8 68 2.2% ALCELL~ Lignin 10 Example 19 Adhesive 48 62.5 68 4.4% ALCELL~ Lignin Example 54 Adhesive 38.3 29.5 64 2.2% ALCELL~ Lignin Example 54 Adhesive 44 48.8 69 4.4% ALCELL~ Lignin WO92/185~7 PCTtUS~2/02963 2 1 ~ 3 ~ 7 ~ -94-The invention and many of its attendant advantages will be understood from the foregoing description, and it will be apparent that various modifications and changes can be made without departing from the spirit and scope of the invention or sacrificing all of its material advantages, the specific materials, procedures and examples hereinbefore described being merely preferred embodiments.

For example, the dry organosolv lignin could be mixed into a low viscosity liquid phenolic resin for use in waferboard manufacture and alternatively, the organosolv lignin could be formulated as a component of a wax emulsion by mixing with small amounts of a dispersing agent. In another example, the performance of the plywood adhesive could also be improved by the addition of a modifier.

In another example, at the commercial level, the organosolv lignin and the phenolic resin could be applied simultaneously by independent application means. The lignin can be applied in liquid, slurry or powder form.

In another example, the lignin in either liquid, slurry or powder form could be added to the liquid precursor of a powder phenol-formaldehyde resin and the mixture spray-dried and used to obtain a lignin/phenol formaldehyde resin blend.

In another example, it could be possible to chemically modify an organosolv lignin and use it in adhesive applications without blending with a phenol-formaldehyde resin.

Additionally, it could be possible to utilize the invention to make lignins other than organosolv lignin compatible with phenol formaldehyde resins and the WO92~185~7 PCT/~S92/02963 2~817S

invention could be used in structural and nonstructural wood products applications other than for plywood and waferboard.

Claims (70)

We claim:

1. An adhesive for wood composites comprising an organosolv lignin and a phenol-formaldehyde resin in a weight ratio of from about 0.5:99.5 to about 70:30 based on phenolic solids in said phenol-formaldehyde resin.

2. The adhesive of Claim 1 wherein said phenol-formaldehyde resin is a powder resin.

3. The adhesive of Claim 2 wherein said organosolv lignin is blended with said phenol-formaldehyde resin in a weight ratio of from about 5:95 to about 70:30 based on phenolic solids in said phenol-formaldehyde resin.

4. The adhesive of Claim 3 wherein said organosolv lignin is baked prior to blending with said phenol-formaldehyde resin for improving the performance of said phenol-formaldehyde resin and said organosolv lignin.

5. The adhesive of Claim 3 wherein said organosolv lignin is flash dried prior to blending with said phenol-formaldehyde resin for improving the performance of said phenol-formaldehyde resin and said organosolv lignin.

6. The adhesive of Claim 3 which further comprises a modifier for improving the performance of said phenol-formaldehyde resin and said organosolv lignin.

7. The adhesive of Claim 6 wherein said modifier and said organosolv lignin together substitute for from about 15% to about 75% based on phenolic solids in said phenol-formaldehyde resin.

8. The adhesive of Claim 7 wherein said modifier is selected from the group consisting of low molecular weight organosolv lignin, low molecular weight phenolic compounds, tris-(p-hydroxyphenyl) ethane, p-tert-butyl-phenol, bisphenol-A, p-cresol, p-ethylphenol, p-sec-butylphenol, p-amylphenol, p-nonylphenol, p-dodecylphenol, 2,4-dimethylphenol, 2,4,6,-trimethylphenol, para-alkyl phenols with side chains of 18 to 24 and 24 to 28 carbons, polyhydroxystyrene, creosote blends and furfural.

9. The adhesive of Claim 8 wherein said modifier is selected from the group consisting of phenol, p-tert-butylphenol and bisphenol-A.

10. The adhesive of Claim 9 wherein the weight ratio of said modifier to said organosolv lignin is from about 0.5:99.5 to 20:80.

11. The adhesive of Claim 8 wherein said modifier is a low molecular weight organosolv lignin.

12. The adhesive of Claim 11 wherein the weight ratio of said low molecular weight organosolv lignin to said organosolv lignin is from about 5:95 to 70:30.

13. The adhesive of Claim 12 wherein said low molecular weight organosolv lignin is a lignin with a molecular weight of less than about 500 g/mol, a glass transition temperature of from about 24° to 80°C and a syringaldehyde to vanillin molar ratio of from about 2.7:1 to about 5.3:1.

14. The adhesive of Claim l wherein said phenol-formaldehyde resin is a liquid resin.

15. The adhesive of Claim 14 wherein said organosolv lignin is added to said phenol-formaldehyde resin in a weight ratio of from about 5:95 to about 60:40 based on the weight of said organosolv lignin and phenolic solids in said phenol-formaldehyde resin.

16. The adhesive of Claim 15 wherein said adhesive is prepared by condensing formaldehyde and phenol in a mole ration of from about 2 to about 3 under alkaline conditions.

17. The adhesive of Claim 20 wherein said alkali is from about 0.12 to about 0.47 per mole of said phenol.

18. The adhesive of Claim 14 wherein said organosolv lignin is added during the preparation of said phenol-formaldehyde resin in a weight ratio of from about 0.5:99.5 to 40:60 based on phenolic solids in said adhesive.

19. The adhesive of Claim 18 wherein said adhesive is prepared by condensing formaldehyde and phenol in a mole ratio of from about 2 to about 4.5 under alkaline conditions and reacting said organosolv lignin with said formaldehyde and said phenol during said condensation.

20. The adhesive of Claim 19 wherein said organosolv lignin is from about 1 to about 70% on a weight basis with said phenol.

21. The adhesive of Claim 20 wherein said alkali is from about 0.1 to 0.8 per mole of said phenol.

22. The adhesive of Claim 14 wherein said organosolv lignin is added to said phenol-formaldehyde resin in a weight ratio of from about 2:80 to about 30:70 based on the weight of said organosolv lignin and phenolic solids in said phenol-formaldehyde resin.

23. The adhesive of Claim 22 wherein said adhesive is prepared by condensing formaldehyde and phenol in a mole ration of from about 2.3 to about 3 under alkaline conditions.

24. The adhesive of Claim 23 wherein said alkali is from about 0.5 to about 0.8 per mole of said phenol.

25. The adhesive of Claim 14 wherein said organosolv lignin is added during the preparation of said phenol-formaldehyde resin in a weight ratio of from about 0.8:99.2 to 35:65 based on phenolic solids in said adhesive.

26. The adhesive of Claim 25 wherein said adhesive is prepared by condensing formaldehyde and phenol in a mole ratio of from about 2.4 to about 3.5 under alkaline conditions and reacting said organosolv lignin with said formaldehyde and said phenol during said condensation.

27. The adhesive of Claim 26 wherein said organosolv lignin is from about 2 to about 45% on a weight basis with said phenol.

28. The adhesive of Claim 27 wherein said alkali is from about 0.4 to 1 per mole of said phenol.

29. The adhesive of Claim 14 wherein said low molecular weight organosolv lignin is added during the preparation of said phenol-formaldehyde resin in a weight ratio of from about 0.5:99.5 to 40:60 based on phenolic solids in said adhesive.

30. The adhesive of Claim 29 wherein said adhesive is prepared by condensing formaldehyde and phenol in a mole ratio of from about 2 to about 4.5 under alkaline conditions and reacting said organosolv lignin with said formaldehyde and said phenol during said condensation.

31. The adhesive of Claim 30 wherein said organosolv lignin is from about 1 to about 70% on a weight basis with said phenol.

32. The adhesive of Claim 31 wherein said alkali is from about 0.1 to 0.8 per mole of said phenol.

33. The adhesive of Claim 14 wherein said organosolv lignin is in alkaline solution.

34. The adhesive of Claim 33 wherein the ratio of said organosolv lignin to said alkali is from about 10 to about 25% on a weight basis with said organosolv lignin.

35. The adhesive of Claim 34 wherein said organosolv lignin alkaline solution is added during the preparation of said phenol-formaldehyde resin in a weight ratio of from about 5:95 to 60:40 based on the weight of said organosolv lignin and phenolic solids in said phenol-formaldehyde resin.

36. The adhesive of Claim 35 wherein said adhesive is prepared by condensing formaldehyde and phenol in a mole ratio of from about 2 to about 3 under alkaline conditions.

37. The adhesive of Claim 36 wherein said alkali is from about 0.12 to 0.47 per mole of said phenol.

38. The adhesive of Claim 34 wherein said organosolv lignin alkaline solution is added during the preparation of said phenol-formaldehyde resin in a weight ratio of from about 2:98 to 30:70 based on phenolic solids in said adhesive.

39. The adhesive of Claim 38 wherein said adhesive is prepared by condensing formaldehyde and phenol in a mole ratio of from about 2.3 to about 3 under alkaline conditions and reacting said organosolv lignin with said formaldehyde and said phenol during said condensation.

40. The adhesive of Claim 39 wherein said alkali is from about 0.5 to 0.8 per mole of said phenol.

41. The adhesive of Claim 1 wherein said organosolv lignin is comprised in a dispersion.

42. The adhesive of Claim 41 wherein said dispersion further comprises a dispersing agent.

43. The adhesive of Claim 42 wherein said dispersing agent and said organosolv lignin are in a weight ratio of from about 0.5:99.5 to about 2:98.

44. The adhesive of Claim 43 wherein said dispersion is added to said phenol-formaldehyde resin in a weight ratio of from about 5:95 to about 60:40 based on the weight of said organosolv lignin and phenolic solids in said phenol-formaldehyde resin.

45. The adhesive of Claim 44 wherein said adhesive is prepared by condensing formaldehyde and phenol in a mole ratio of from about 2 to about 3 under alkaline conditions.

46. The adhesive of Claim 45 wherein said alkali is from about 0.12 to about 0.47 per mole of said phenol.

47. The adhesive of Claim 46 wherein said dispersing agent is ammonium hydroxide.

48. The adhesive of Claim 14 wherein said organosolv lignin is subjected to phenolation.

49. The adhesive of Claim 48 wherein said phenolation comprises the step of reacting said organosolv lignin with phenol in a weight ratio of from about 10 to about 80% based on total reaction weight and under alkaline conditions.

50. The adhesive of Claim 49 wherein said alkali is in a weight ratio of from about 1 to about 20% based on total reaction weight.

51. The adhesive of Claim 50 wherein said phenolated organosolv lignin is added during the preparation of said phenol-formaldehyde resin.

52. The adhesive of Claim 51 wherein said adhesive is prepared by condensing formaldehyde and phenol in a mole ratio of from about 2 to about 4.5 under alkaline conditions and reacting said phenolated organosolv lignin with said formaldehyde and said phenol during said condensation.

53. The adhesive of Claim 52 wherein said phenolated organosolv lignin is from about 1 to about 70%
on a weight basis with said phenol.

54. The adhesive of Claim 53 wherein said alkali is from about 0.1 to about 0.8 per mole of said phenol.

55. The adhesive of Claim 51 wherein said adhesive is prepared by condensing formaldehyde and phenol in a mole ratio of from about 2.4 to about 3.5 under alkaline conditions and reacting said phenolated organosolv lignin with said formaldehyde and said phenol during said condensation.

56. The adhesive of Claim 55 wherein said phenolated organosolv lignin is from about 1 to about 45%
on a weight basis with said phenol.

57. The adhesive of Claim 56 wherein said alkali is from about 0.4 to about 1.

58. The adhesive of Claim 14 wherein said organosolv lignin is subjected to methylolation.

59. The adhesive of Claim 58 wherein said methylolation comprises the step of dissolving in phenol said organosolv lignin of from about 2 to about 60% based on total reaction weight.

60. The adhesive of Claim 59 which further comprises the step of adding formaldehyde of from about 5 to about 50% based on total reaction weight under acidic conditions.

61. The adhesive of Claim 60 wherein said phenol is from about 20 to about 50% based on total reaction weight.

62. The adhesive of Claim 61 wherein said acid is of from about 0.01 to about 3% based on total reaction weight.

63. The adhesive of Claim 62 wherein said methylolated organosolv lignin is added during the preparation of said phenol-formaldehyde resin.

64. The adhesive of Claim 63 wherein said adhesive is prepared by condensing formaldehyde and phenol in a mole ratio of from about 2 to about 4.5 under alkaline conditions and reacting said methylolated organosolv lignin with said formaldehyde and said phenol during said condensation.

65. The adhesive of Claim 64 wherein said methylolated organosolv lignin is from about 1 to about 70% on a weight basis with said phenol.

66. The adhesive of Claim 65 wherein said alkali is from about 0.1 to about 0.8 per mole of said phenol.

67. The adhesive of Claim 63 wherein said adhesive is prepared by condensing formaldehyde and phenol in a mole ratio of from about 2.4 to about 3.5 under alkaline conditions and reacting said methylolated organosolv lignin with said formaldehyde and said phenol during said condensation.

68. The adhesive of Claim 67 wherein said methylolated organosolv lignin is from about 1 to about 45% on a weight basis with said phenol.

69. The adhesive of Claim 68 wherein said alkali is from about 0.4 to about 1 per mole of said phenol.

70. A wood composite manufactured with the adhesive of Claim 1.