Journal of Polymers and the Environment, Vol. 10, Nos.

1/2, April 2002 (

2002)

Recent Industrial Applications of Lignin: A Sustainable Alternative to Nonrenewable Materials

Jairo H. Lora1 and Wolfgang G. Glasser 2,3

Lignin represents a vastly under-utilized natural polymer co-generated during papermaking and biomass fractionation. Different types of lignin exist, and these differ with regard to isolation protocol and plant resource (i.e., wood type or agricultural harvesting residue). The incorporation of lignin into polymeric systems has been demonstrated, and this depends on solubility and reactivity characteristics. Several industrial utilization examples are presented for sulfur-free, water-insoluble lignins. These include materials for automotive brakes, wood panel products, biodispersants, polyurethane foams, and epoxy resins for printed circuit boards.
KEY WORDS: Lignin; biopolymers; adhesives; biodispersants; OSB; polyurethane foams; epoxy resins; wood; pulp and paper.

INTRODUCTION Lignin is natures most abundant aromatic (phenolic) polymer. Its principle function is to provide trees with the ability to raise a crown above ground level [1, 2]. Lignin is separated from wood during pulp and papermaking operations, where it serves primarily as fuel. Only a small amount (ca. 12%) is isolated from spent pulping liquors and employed in a wide range of specialty products. These, however, amount to 1 million tons per year worldwide [3, 4]. TYPES OF LIGNINS AND THEIR PROPERTIES Lignins vary in structure according to their method of isolation and their plant source [2, 57]. Hardwoods develop a different lignin than softwoods, and annual
1 2

Granit S. A, Media, Pennsylvania 19063. Virginia Polytechnic Institute and State University, Department of Wood Science and Forest Products, Blacksburg, Virginia 24061. 3 To whom all correspondence should be addressed. E-mail: wglasser@ vt.edu

crops are different again. However, the differences are minor as far as most applications are concerned. Major differences exist between lignins derived from different pulping processes. The traditional sulfite process generates a water-soluble polymeric derivative in admixture with degraded carbohydrates. An aliphatic sulfonic acid (SO3H) function becomes part of the lignin backbone ensuring ready water-solubility in the presence of a suitable counter ion (Na, Ca, Mg, NH4, etc.). Kraft or thio lignins are generated during kraft pulping in alkaline medium. They contain a small number of aliphatic thiol groups that give the isolated product a characteristic odor, especially during heat-treatment. A very small amount of kraft lignin is isolated from pulping liquors in the United States and Europe [4]; the vast majority is used as in-house fuel required for the recovery of chemicals. Kraft lignins are dark-colored and water- and solventinsoluble products that dissolve in alkali owing to their high concentration of phenolic hydroxy groups. Neither lignin sulfonates nor kraft lignins undergo a distinctive glass-to-rubber (or fluid) transition when heated, despite the fact that lignin in wood has a Tg of under 100 C [8]. Numerous other lignin products and derivatives have been

39
1566-2543/02/0400-0039/0 2002 Plenum Publishing Corporation

40 described that originated from unusual plant sources or experimental pulping processes [6, 7]. SULFUR-FREE LIGNINS: TYPES AND SOURCES Sulfur-free lignins are an emerging class of lignin products [9, 10]. Having no sulfur and being of moderate macromolecular size, these lignins resemble more closely the structure of native lignin, and they exhibit distinct properties relative to kraft and sulfite lignins. This opens up new avenues for utilization. Sulfur-free lignins come from principally three sources: Biomass conversion technologies (mainly oriented toward alcohol production), Solvent pulping (organosolv processes), and Soda pulping, particularly of alternative biomass resources, such as agricultural harvesting residues and non-wood fiber crops.

Lora and Glasser produced on pilot scale from residues of the industrial production of furfural from sugar cane bagasse, and that is commercially available on the specialty chemicals market (see Table I, footnotes). Angiolin was the designation used for a steam explosion lignin from hardwoods. These lignins have some similarities in structure, but they differ in solubility, reactivity, and molecular weight [14]. Currently there are a number of commercial biomass to ethanol projects in the planning stages. When implemented, these projects have the potential of becoming commercial sources of sulfur-free lignins. Lignins from Solvent Pulping Solvent pulping is an alternative to kraft and sulfite pulping that is claimed to be more environmentally acceptable and less capital-intensive. In addition to cellulose pulp, solvent pulping permits the recovery of organosolv lignin and other chemical co-products. Lignin is recovered from the spent solvent by precipitation, which typically involves adjusting concentration, pH, and temperature. Organosolv lignins are usually high-purity, low molecular weight products with relatively narrow molecular weight distributions [6, 7, 14]. These lignins show a low glass transition temperature and exhibit flow when heated. They have high solubility in organic solvents and are very hydrophobic and practically insoluble in water. The properties of lignins from alcohol pulping of various raw materials are illustrated in Table II. In the 1990s, lignin from solvent pulping of hardwoods was available in industrial quantities from a Canadian demonstration plant that used the ethanol-based Alcell process. Although the Alcell technology was demonstrated to successfully produce pulp for papermaking plus lignin, and although many novel lignin applications were industrially implemented, further development of the process was suspended because of financial difficulties of the company supporting this endeavor. Currently, several private and public sector ventures continue efforts in many parts of the world to introduce either variations of the Alcell process or processes using solvents other than ethanol. Such projects may eventually lead to the commercial availability of organosolv lignins in the not-too-distant future. Lignins from Soda Pulping The fact that neither liquid fuel production from biomass nor solvent pulping have reached commercial maturity has severely limited the market penetration of sulfur-free lignins. Sulfur-free soda pulping of non-wood feedstocks such as straw, sugar cane bagasse, flax, etc., is

Lignins from Biomass Conversion Technologies The production of liquid fuels, such as ethanol, from biomass has been proposed as a strategy to alleviate dependency on foreign energy sources [3]. The biomass conversion technologies used typically involve a hydrolytic pretreatment. The pretreatment is either catalyzed by added mineral acid or autocatalyzed by biomassderived organic acids, as occurs in steam explosion or autohydrolysis [1113]. Such treatments not only make the carbohydrate component susceptible to saccharification and/or fermentation, but also have the potential of generating sulfur-free lignin. From the pretreated biomass the lignin must be extracted (for instance with an organic solvent or with aqueous alkali), and from the resulting solution, lignin is recovered normally by precipitation. The lignin recovered is largely insoluble in water under neutral or acidic conditions. It is soluble in organic solvents and in aqueous alkali; and it can be recovered with a low content of contaminants such as sugars and ash. Table I shows typical properties of lignins recovered from several biomass conversion processes [6, 14]. Various biomass conversion technologies have advanced to demonstration and pilot scale, and some lignins originating from such efforts have been available for development purposes. Among these were lignins from acid hydrolysis and steam explosion (see Table I). In the 1980s a South African company (C. G. Smith Sugar, Ltd.) offered a lignin called Sucrolin, which was

Recent Industrial Applications of Lignin

Table I. Properties of Lignins from Biomass Conversion Processes (from Refs. 6 and 14) Acid Hydrolysisa TVA Property Total Hydroxyl/C9 % Phenolic OH/C9 % Carboxyl/C9 % Carbonyl/C9 % Methoxyl/C9 % Tg ( C) Mn ( 103)e Mw ( 103)e
a

41

NYU SWc 1.2 11.2 0.5 4.1 HW 1.1 9.3 0.6 5.4

C. G. Smith Bagasse (Sucrolin) d 0.8 0.4

Steam Explosion b HW (Angiolin) e 1.1 9.69.8 0.5 4.3 Straw 1.1 8.5 0.6 5.4

HWc 1.2 10.5 0.5 4.7 0.15 3.6

1.2 19.3 NA 0.40.9 1.34.8

0.2 2.8 0.6 9.3 96 0.8 40.0

0.2 2.6 1.3 22.8 95 0.7 10.1

0.6

0.2 2.12.9 1.01.1 15.018.2 113139 0.9 2.33.0

0.3 4.7 0.6 10.3 125 0.4 1.1

Acid hydrolysis methods involve the use of catalytic amounts of mineral acids (usually H2SO4) under various conditions. The process advocated by the Tennessee Valley Authority (TVA) of Muscle Shoals, AL employs a two-stage hydrolysis with 1 and 3% H2SO4 at steam pressures of 1.2 and 1.9 MPa, respectively. The lignin is subsequently isolated by solvent or alkali extracting as described by Glasser and Strickland [13]. The data given are those of a typical ethanol extract. The process of New York University (NYU) achieves hydrolytic biomass pretreatment with 2% H2SO4 at 220 C in a twin-screw extruder. The lignin represents an alkali-soluble fraction of the combined residue [6]. The process of C. G. Smith Ltd. of South Africa involves the acid hydrolysis of sugar cane harvesting residue (bagasse) under conditions favoring the formation of furfural. The lignin has become comercially available under the trade name Sucrolin; it is marketed by the Aldrich Chemical Comp. (cat. no. 37, 107-6); it represents the alkali-soluble residue of the combined insoluble hydrolyzate. b Steam explosion is carried out on a continuous Stake Technology machine (Norval, Ontario). Conditions of steam explosion and lignin isolation have been described by Wright and coworkers [11]. The lignin from Liriodendron tulipifera has been marketed under the trade name Angiolin. c HW and SW designates hardwood and softwood resources, respectively. d Sucrolin is commercially available from Aldrich Chemical Company (cat. no. 37, 107-6). e Angiolin has been available from the Biobased Materials Center of Virginia Tech, 1650 Ramble Road, Blacksburg, VA 24061-0503. For more details of the molecular weight determination, see Glasser and coworkers [14].

practiced widely around the world and offers a potentially more readily available source of such lignins. Because of their small size and economic constraints, many of the pulp mills processing nonwood resources cannot afford the capital-intensive system developed for processing much larger quantities of spent pulping liquors, such as
Table II. Properties of Organosolv Alcell Genetic Origins Mixed Hardwood a 1.11.4 0.30.6 1.01.3 97 0.6 2.18.0 Wheat Straw 1.2 0.40.6 0.1 0.8 106122 Lignins from Different

Property Total OH/C9 Phenolic OH/C9 Carboxyl/C9 Methoxyl/C9 Tg ( C) Mn ( 103) Mw ( 103)

a

Reed 1.2 0.50.6 0.1 1.0 97 0.7 1.5

Kenaf 1.2 0.5 0.1 1.0 6670

This lignin is commercially available from Aldrich Chemical Company (cat. no. 37, 101-7).

those used in wood pulping operations for recovery of energy and recycling of cooking chemicals. Consequently, many small nonwood mills are forced to discharge their pulping effluents with little or no treatment into the environment. Lignin recovery from these effluents can significantly reduce the environmental impact of these operations. Furthermore, the remaining effluent (after lignin removal) can be more easily purified by biological treatment. Another source of nonwood lignins may come from larger nonwood mills that may have a conventional recovery process but want to incrementally expand their pulping capacity and need an economically and environmentally acceptable way to handle the excess liquor generated. Recovery of these lignins is based on precipitation, followed by liquid/solid separation and drying. Table III lists the properties of two of these products. A comprehensive review of the sources, properties, and uses of nonwood lignins has been published elsewhere [9, 10]. One of the difficulties of this type of process technology when applied to nonwood fiber sources is that the

42
Table III. Properties of Nonwood Soda Lignins of Different Origins Property Total OH/C9 Phenolic Oh/C9 Carboxyl/C9 Methoxyl/C9 Tg ( C) Mn ( 103) Mw ( 103) Wheat Straw 1.6 0.80.9 1.0 160185 1.8 3.3 Hemp 1.1 0.6 0.1 0.9 158

Lora and Glasser antiplasticizers. Some lignins do not exhibit flow with temperature, whereas others readily undergo fluid flow when heated. In general, nonwood soda lignins may have a wider range of properties than have been observed with wood lignins. This type of characterization of lignins in terms of structure and functionality reveals relatively little about those differences that are hard to assess quantitatively [8]. Among the latter are the questions of solubility in organic solvents, thermal deformability or flowability, and reactivity under specific reaction conditions. However, these characteristics can be remedied by one or several modification (derivatization) options [5, 15]. This leaves supply and variability questions as sole impediments to industrial lignin utilization in structural materials. The following provides information about a potential, industrially practical method for the improvement of solubility and thermal flow constraints by chemical modification, and it provides several examples of the use of lignins in industrial materials. ASPECTS OF LIGNIN USE AS A POLYMERIC MATERIAL Polymeric lignins can be used in thermosetting resins, in thermoplastic blends, and in surfactant applications [3, 5]. The performance in thermosetting resins requires sufficient functionality of lignin in combination with adequate compatibility with cross-linking agents to prevent phase separation [16]. Heat deformability and compatibility with other polymers represents the major obstacle for the formulation of thermoplastic blends. Some of these obstacles may be overcome by a variety of derivatization reactions [15]. Chemical Modification Examples By virtue of the inherent functionality of isolated lignins, almost endless opportunities exist for their chemical modification. However, because of the propensity of hydroxyl groups, esterification and etherification rank most prominent among the modification alternatives. These and other modification examples have been reviewed elsewhere [15, 1729]. Etherification with alkylene oxides (especially ethylene oxide) has been carried out on pilot plant scale, and hydroxyalkyl lignins have been test-marketed (WESTVACO Corp., North Charleston, SC, Hydroxyethyl Lignin, RLX 5044-21A). Most result-oriented lignin derivatizations have focused on improvements in solubility and glassiness or

soda spent pulping liquors often contain silica, which may co-precipitate with the lignin, rendering it of lower quality. Soda lignins have been available in Asia in the past, but they are normally of low and variable quality. The LPS precipitation process recently introduced commercially in Europe (Granit S.A. of Lausanne, VD, Switzerland) is claimed to have solved this problem and to have obtained soda lignins with relatively low ash and silica content. As in other recovery processes, in the LPS process there is a pH adjustment to bring the alkaline liquor to an acidic environment. This forms a dispersion, which is treated in a carefully controlled maturation step under a temperature and time schedule specific to the type of liquor being processed. In the maturation step, a filterable slurry is formed. The cake obtained after filtration is washed and dried. LPS lignins recently became commercially available in powder and solution form from a small flax specialty pulping commercial operation in France. The mill produces about 40 M 3 per day of black liquor, which is processed to generate about 250,000 kg/ year of lignin. Larger volumes of this product are expected to become available as lignin recovery is adopted by other nonwood pulp mills. In summary, sulfur-free lignins, although known for many years, are gaining new interest as a result of a diversification of biomass processing schemes. With the disappearance of the popular organosolv lignins from commercial availability, nonwood alkali extraction lignins are beginning to receive industrial attention. Soda lignins may originate from many different plant sources and process variations. The analytical data obtained with these lignins that are focused on structure and functionality often reveal remarkably few differences that are of significant consequence on generic uses. These soda lignins all have in common that they are of (1) low molecular weight, (2) high phenolic hydroxy content, and (3) relatively low (but variable) glass transition temperature. However, their properties sometimes vary significantly. For instance, the thermal behavior of these lignins seems to depend on type (process and feedstock), and on the presence of contaminants that may act as plasticizers or

Recent Industrial Applications of Lignin brittleness. It is well recognized that solubility generally follows glass transition temperature (Tg), with solubility (in organic solvents) increasing as Tg declines. Because there are not many universally accepted quantitative tools available to model solubility, but the methodology for measuring glass transition temperatures is well established, most research has focused on relating glass transition temperatures to derivatizations [30]. A previous article on this topic has employed the Fujita-Kishimoto equation that relates Tg to plasticization [30]. Because derivatization amounts to internal plasticization, this equation can be employed for predicting changes in glass transition temperature (and solubility) of modified lignins. Tg
2

43

(1)

where Tg is the difference in glass transition temperature between the unplasticized and the plasticized polymer, is a parameter representing the plasticizers contribution to increased free volume, 2 represents the difference in thermal expansion below and above Tg (i.e., 4.8 10 4 C 1 and constant for most glasses), and C is plasticizer content. Whereas the important -parameter has been found to be in the order of 0.27 for the plasticization of lignin with water, the corresponding parameter for hydroxyalkly lignin derivatives has been given as being in the range of 0.05 to 0.15 [30]. However, it must be recognized that plasticization with water is limited to 5% or less in the case of lignin, and that internal plasticization by modification with alkylene oxides avoids this limitation to narrow ranges of effectiveness. The effect of internal plasticization by reaction with ethylene oxide (EO), propylene oxide (PO), and butylene oxide (BO) is illustrated in Fig. 1 [30]. The reaction of lignin with alkylene oxides has been studied extensively [1929], and it remains one of the most attractive etherification alternatives for the following reasons [31]: (1) it can be limited to weight gains of less than 2530% by limiting the modification reaction to only phenolic hydroxy groups; (2) it can be carried out in aqueous alkali at room temperature (if it is to be limited to phenolic hydroxy groups); (3) it produces a unifunctional derivative with only aliphatic hydroxy groups [28]; (4) the hydroxyalkyl lignin derivative separates spontaneously from the alkaline, homogeneous reaction mixture as the reaction progresses, because the derivative becomes insoluble in aqueous alkali when its acidic functionality (phenolic hydroxy groups) is depleted (limited to alkyl groups larger than ethyl); (5) the derivative is easily analyzed (by NMR spectroscopy) [28]; and (6) the reaction product is highly soluble in a variety of common organic solvents, and it is melt flowa-

Fig. 1. Effect of (H2O) and internal alkylene, ethylene (EO), propylene oxide (PO), and butylene oxide (BO) plasticization of lignin on the reduction of glass transition temperature Tg [30].

ble. Nonphenolic, powderous hydroxypropyl lignins are commercially available on the specialty chemicals market (Aldrich Chemical Company, cat. no. 37,096-7). Hydroxyalkyl lignin derivatives with higher degrees of molar substitution, with extended alkyl ether chains, can be prepared, but their synthesis is significantly more complicated [21, 2527, 29].* In summary, lignin modification by derivatizing substituents offers opportunities for tayloring properties of sulfur-free lignins to specific end uses. Many derivatization reactions have been reported in the past, and these derivatives can be expected to follow similar plasticization principles as those observed with alkylene oxides.
* The propoxylation procedure initially disclosed in an 1975 article [19], which involves the heterogeneous reaction of lignin in propylene oxide suspension in the presence of solid KOH as catalyst and with agitation at 140 C, has subsequently been found to be unpredictable and dangerous. With insufficient agitation and with the catalyst sequestered by lignin in its solid state, the reaction may lead to an exothermic propylene oxide decomposition (or homopolymerization) event instead of the intended formation of a lignin-propylene oxide copolymer. Such a runaway reaction (with an amount of propylene oxide of 100 g) has resulted in a violent explosion that destroyed a laboratory used by Professor Knut Lundquist of Chalmers University of Technology in Goteborg, Sweden in the late 1970s. It was only by coincidence that nobody was injured in the incident.

44
Table IV. Wear Characteristics of Brake Pads Produced with Combinations of Organosolv Lignin and Phenolic Resin (from Nehez, Ref. 33) Inner wear (mm /g) 0.102 0.071 0.090 Outer Improvewear Average ment (mm /g) (mm /g) (%) 0.142 0.122 0.139 0.122 0.096 0.114 21.3 6.6

Lora and Glasser either powder or liquid form) or isocyanates. Organosolv lignin has been found to be beneficial in all of these types of binders [15, 34]. In phenolic powder resin systems used for OSB, lignin can be used as a direct partial replacement for the phenolic component, and the resulting boards are equal to or better than the controls (Table V) [34, 35]. A North American producer of OSB successfully used this approach in the early 1990s to industrially produce commercial construction panels that met the requirements for exterior use. Lignin was blended on-site as a 525% replacement of the powder phenolic resin normally used as the binder in the face layers of the OSB panels. In addition to the cost benefits, the use of lignin led to an improvement of the environmental conditions in the panel manufacturing facility, such as lower levels of dust in the area around the blenders where the resin is applied to the wood strands before board forming and pressing. Organosolv lignin can also be used with liquid phenolic resins for OSB-manufacture, either by incorporation during phenolic resin synthesis [36, 37] or by addition as a formulated dispersion. In this case, boards comparable to the control have been obtained (see Table V). The use of lignin in isocyanate binders for wood has been explored on several occasions in the past [3840]. Industrial tests of isocyanate binders with lignin for OSBproduction were carried out by ICI Polyurethanes (now part of Huntsman Inc.) [40]. Results have shown that, when binding lignocellulosic materials (i.e., wood) with isocyanates, the use of lignin in combination with specific lignin solvents results in improved performance relative to lignin-free isocyanates used at the same binder level.

Binder 100% phenolic 90% phenolic/10% lignin 80% phenolic/20% lignin

Examples of Industrial Utilization Conventional kraft and sulfite lignins are mature products that have traditionally been used as dispersants and binders. Most interesting new applications are related to sulfur-free lignins, because they offer greater versatility and can be heat-processed without the irritating odorrelease commonly observed with commercial kraft lignins. Sulfur-free lignins are phenolic polymeric products that can be used in many thermosetting applications, for example, in conjunction with phenolic, epoxy, or isocyanate resins [15, 32]. In addition to the cost and life cycle advantages derived from using lignin, some environmental advantages can be obtained as well. For instance, reduced formaldehyde emissions have been reported for both the resin and the finished product when using lignin in phenol-formaldehyde resin systems. Lignin in nature plays important biological roles, and its properties, such as antioxidant and antimicrobial activity, among others, are well-documented. Sulfur-free lignins, being closer in structure to native lignin, are more likely to capitalize on those properties. The following provides a summary of recent industrial lignin applications. Use of Lignin as Substitute for Phenolic Powder Resins Phenolic powder resins are used as the binder in the manufacture of friction products. The use of organosolv lignin as a partial replacement for these phenolic resins was proposed by Nehez [33], and it was later successfully implemented by a North American manufacturer of automotive brake pads and moldings on commercial scale. The use of 20% lignin/80% phenolic resin resulted in competitive advantages relative to controls prepared with 100% phenolic resin. Improvements included the stability of the friction coefficient to temperature variations and improved wear behavior (Table IV). Oriented strand board (OSB) has become the dominant construction wood panel product in North America. In its manufacture, wood strands are bonded with a binder under heat and pressure. The binders used are phenolic (in

Table V. Strength Properties of OSB-Panels Produced with Combinations of Phenolic Resin and Lignin Binder Control 100% Phenolic Lignin 80% Phenolic/20% Lignin

Property A. Powder Resin MOR (psi) a IB (psi) b D-4 (lbs) c D-5 (lbs) d B. Liquid Resin MOR (psi) a IB (psi) b D-4 (lbs) c
a b

3456 59.4 144 115 5204 83 276

3654 60.1 143 141 4866 295 97

Modulus of rupture. Internal bond. c Single cycle bending testAmerican Plywood Association. d Six cycle bending testAmerican Plywood Association.

Recent Industrial Applications of Lignin

Table VI. Strength Characteristics of OSB Panels Produced with Combinations of Isocyanates and Organosolv Lignin [40] Swelling (%) 42.5 1 pbw 32.5 977 IB b (kPa) 655

45 the purpose of achieving desired viscosity levels. The isocyanurate foams were prepared either with a commercial polyol (control), or with the lignin polyol alone. The isocyanate component constituted 4055% of the foams on a weight basis. Other components, blowing agent, water, surfactants, etc., were added to the formulation in accordance with industrial practice. Some lignin polyols were incompatible with blowing agents; these samples were not tested. The density of all foams ranged from 1.52 pounds per cubic foot (pcf) (Table VII). The compression strength of the lignin-derived foam products was found to be adequate and in line with control materials. Dimensional stability at elevated temperature and moisture conditions determines the loss of foam substance during prolonged exposure to elevated temperature and moisture condi-

Binder Isocyanate Isocyanate 2 pbw a lignin dimethylethyleneurea

a b

Pbw, parts by weight based on isocyanate. Internal bond.

As a result it is possible to reduce isocyanate requirements to achieve equal or better mechanical properties (Table VI). The use of lignin also results in improved release of the product from the press plattens, alleviating a problem that has hindered the more widespread use of isocyanate binders [40]. Use of Lignin in Polyurethane Foams Lignins may readily become liquid fluids when modified with alkylene oxides [25]. These products consist of either or both (1) hydroxy alkyl lignins dissolved in poly(oxyalkylene glycols) of low molecular weight and/ or (2) chain-extended lignin-poly(oxyalkylene ether) copolymers [2129]. These products differ in viscosity, whereby the solutions typically have lower overall shear resistance. Liquid alkoxylated lignin products are viewed as potentially useful polyols for use in rigid polyurethane foams [3, 19, 20, 23]. Their beneficial thermal degradation (fire resistant) properties have been revealed previously [41]. Industrial tests of two types of foam products were conducted by ARCO Chemical Company in the late 1980s, and the results are summarized in Table VII [31]. The two different types of foam products investigated represent a polyurethane and a polyisocyanuratetype. Whereas polyurethanes constitute materials crosslinked with diisocyantes, isocyanurate foams contain an isocyante component that has undergone some degree of homopolymerization and cyclization. Isocyanurate foams containing lignin appear to be holding greater promise than polyurethane foams because of their tolerance to the darker color inherent to most lignin-based materials. (However, it should be pointed out that nonphenolic lignin derivatives can easily be bleached to a high brightness level by the use of such oxidants as hydrogen peroxide [17, 42]). Isocyanurate foams are typically used in hidden insulation panels. The results summarized in Table VII reveal that the polyol component of all polyurethane foams was prepared by blending a lignin polyol with a commercial polyol for

Table VII. Composition and Properties of Industrial Foam Samplesa Foam Composition and Property Polyurethane Foams: Lignin polyol (%) Commercial polyol (%) c Isocyanate (%) Additives (%) d Density (pcf) Dimensional stability, V (%) e Isocyanurate Foams: Lignin polyol (%) Commercial polyol (%)f Isocyanate (%) Additives (%) Density (pcf) Dimensional stability, V (%)e Compression strength (psi)h Control Lignin Foam b

1617 2426 4244 15 1.82.1 2629

0.0 35 54 11.3 1.7 21.1 23 7.7 3.4

26 0 54 20 1.61.9 515 1824 913 1782

Friability (%)
a

Results of an Industry-University Cooperative Project between ARCO Chemical Company, Newtown Square, PA, and Virginia Tech, Blacksburg, VA [31]. b Foams contained Angiolin, steam explosion soda-lignin from yellow poplar (Liriodendron tulipifera), reacted with 30 moles of propylene oxide per kg of lignin in a pressure reactor using conditions described elsewhere [22]. The resulting polyols typically had homopolymer contents of 1922% and hydroxyl numbers of 120200. c Thanol R-470X. d Containing surfactant (0.5%), catalyst (0.2%), fire retardant (3%), water (0.3%), and blowing agent (fluorocarbon) (111%). e Measured at 158 F and 95% relative humidity for 28 days. f Chardol 336A. g Containing sulfonic N-95 (8.7%), surfactant, (0.5%), catalyst (1 2%), water (0.4%), and blowing agent (fluorocarbon) (9.2%). h Measured in parallel (II) or crosswise ( ) direction to continuous foams (belt) former.

46 tions. The results determined for the isocyanurate foams (see Table VII) reveal that all lignin-containing foams perform significantly better than the control products. Weight loss during exposure to elevated temperatures represents the ability of a foam to generate volatile, possibly toxic, gaseous degradation products; therefore any reduction in weight loss (i.e., improvement in dimensional stability at elevated temperature) represents a significant advantage. Lignin-based foams were sometimes three or four times better than control foams. Friability, however, which measures foam response to mechanical abrasion, was consistently high with all lignin-based polyols. This is of concern to the foam manufacturer, and it is unknown whether this parameter can be improved by optimization. In conclusion, the use of lignin in foam products seems to hold some promise, especially regarding the exposure response to elevated temperature and humidity conditions; but some handicaps (friability) are recognized as well. Because aromatic polyols are currently based on low-value by-products of the manufacture of PET commodity plastics, lignin may not offer a substantial cost advantage. Use of Lignin in Epoxy Resins Lignin has also been used in epoxy resins, and many different formulation approaches have been explored [15, 21, 4346]. Marginally soluble lignins were formulated with epoxy resins and cross-linked by heat; and lignins were derivatized with epoxy functional groups followed by cross-linking with anhydrides or diamines. A dropin approach has most recently been taken by IBM for the production of printed circuit board-resins (PCB) [4749]. Whereas conventional kraft and soda lignins proved to be hampered by high ionic contents, requiring extensive postisolation purification protocols, organosolv lignin could be used directly. All lignins created problems with organic solventsolubility, and they required special solvent mixtures for formulation. However, epoxy resins that contained approximately 50% lignin were successfully prepared and applied to PCB production. These PCBs held considerable promise, and test boards passed in all property categories (Table VIII). Epoxy-functional lignins were also prepared, and they could be used as solid, uncured films and powders formulated with amine crosslinkers in place and curable by heating without solvent [44]. Epoxy resins on lignin basis hold yet unexplored promise for use in printed circuit boards and many other applications where epoxy resins excel. The results of an extensive life cycle assessment revealed that (1) the total energy requirements for a lignin-

Lora and Glasser

Table VIII. Performance Comparison of Printed Circuit Boards (PCBs) between Conventional FR4-Epoxy Resins and Epoxy Resins Formulated with ca. 50% Lignin Content (According to Kosbar et al., ref. 49). FR 4 Control Resin 128.3 450 4 312.6 2.18 Lignin/Epoxy Laminate 140.4 1250 3.98 309.7 1.76

Parameter Tg after lamination ( C) Min. viscosity at 120130 C (Pa-s) Dielectric constant at 1 MHz Decomposition Temp. ( C) Moisture absorption (%) after 16 h boiling in water Total energy requirements for wiring board systems (GJ/100 kg resin solids) Non-fossil per total energy requirements for wiring board systems (%)
a b

17.8a

11.0a

3.9a

18.1a,b

Data given are for the case of 100% metal recovery. Data given are for kraft instead of organosolv lignin.

based wiring board was almost 40% less than that of a control board, and (2) the nonfossil energy requirements increased nearly five-fold when lignin was used as a component (see Table VIII) [49]. Lignin-Based Biodispersants Soda lignins recovered by the LPS process of Granit S.A. from flax pulping in France have been found to possess dispersant properties. They also have been found to exhibit bacteriostatic and biocidal properties (Fig. 2). An Austrian company (Bioconsult Gesellschaft fuer Biotechnologie mbH, Hallein, Austria) has recently developed a lignin-based formulation for control of microbial populations in industrial water circuits, such

Fig. 2. Inhibition of bacterial growth (Staphylococcus aureus) by different amounts of soda lignin from flax.

Recent Industrial Applications of Lignin REFERENCES

47

Fig. 3. Biocidal activity of various white water sludge formulations. (Data based on treatment of 5-L batches of white water containing 4.6 g/L total solids of which 65% were CaCO3. The bars represent (A) control (blank); (B) soda straw lignin; (C) soda flax lignin; (D) a commercial lignin solfonate solution as used conventionally for sludge control; (E) a commercial biocide solution containing methylene-bisthiocyanate; and (F) a commercial biocide solution containing a quaternary ammonium salt) [50].

as in paper machine recirculating (white) waters [50]. Slime deposition in the white water of paper machines is generally prevented by the addition of biocides of different origin. Both total amount of slime (in dry matter per liquid volume) and slime solids content (in percent) are critical parameters. The latter relates to the ease of resuspension of deposited slime via the shear forces of the circulating fluid when the turbulence of the flow is adjusted. Published data obtained with industrial white water samples (5-L batches) treated with different biocidal mixtures revealed high effectiveness of nonwood soda lignins (Fig. 3). The product is currently used in several paper machines in Europe, where it is displacing more toxic, less-environmentally friendly products. The product is dosed at the level of 100200 ppm (based on weight of paper produced) at a location of the water circuit where good agitation and mixing are promoted.

CONCLUSION New applications are emerging for specialty, sulfurfree lignins in diverse areas, principally as sustainable alternatives to nonrenewable products, such as phenolic and epoxy resins, and isocyanates. This is in addition to industrial efforts that aim at using lignin as the principal component of thermoplastic materials [51]. The latter represents an activity for which little published information exists so far. The ability for lignin to make significant impact in these areas, however, depends on its availability in industrial quantities as a high-purity product, preferably in a sulfur-free form.

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