Chapter 2

Lignin in Adhesives
Introduction and Historical Perspective

Norman G. Lewis and Thomas R. Lantzy

W o o d Chemistry and Biochemistry
Publication Date: December 31, 1989 | doi: 10.1021/bk-1989-0385.ch002

Department of Forest Products

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V i r g i n i a Polytechnic Institute and State University

Blacksburg, VA 24061

Lignins, complex organic polymers produced by all vascular terres-

trial plants and second in abundance only to cellulose, are the sub-
stances holding plant fibers together. They are recovered mainly
as byproducts from woodpulping operations with about 75 million
tons produced annually worldwide. Over the last hundred years or
so, there has been an enormous effort to develop lignin-based adhe-
sives, but this has met with no real commercial success principally
due to product variability, dark color, and lack of chemical reactiv-
ity. Lignin-based adhesives normally require excessively long curing
times and high curing temperatures during composite board pro-
duction. However, they can be employed as extenders in diverse
wood-composite resins with no significant deterioration in the me-
chanical properties of the board products. This is particularly true
if the lignins are activated chemically (e.g., by methylolation). Sev-
eral recent reports have been directed toward improving even further
the lignin chemical reactivity (e.g., in the synthesis of soda bagasse
lignin-formaldehyde-resorcinol and lignin-isocyanate resins). Appar-
ently, these developments surmount previous difficulties and allow
for some cautious optimism for the future.

T e r r e s t r i a l vascular p l a n t s have evolved w i t h a u n i q u e c a p a c i t y t o synthesize

l i g n i n , whose m a i n p h y s i o l o g i c a l functions are t o p r o v i d e r i g i d i t y a n d s t r e n g t h
to p l a n t cell w a l l s a n d t o act as a b a r r i e r t o i n f e c t i o n (1). N e x t t o cellulose,
l i g n i n i s n a t u r e ' s second most a b u n d a n t o r g a n i c m a t e r i a l a n d is often described
as the m a t e r i a l b i n d i n g p l a n t fibers together (#).

0097-6156/89/0385-0013$06.00/0 * 1989 American Chemical Society

In Adhesives from Renewable Resources; Hemingway, R., et al.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1989.
 14 ADHESIVES F R O M RENEWABLE RESOURCES

I n g y m n o s p e r m s , l i g n i n is f o r m e d f r o m j>-coumaryl (1) a n d c o n i f e r y l (2) a l -

cohols, whereas, i n angiosperme, s i n a p y l a l c o h o l (3) is also i n v o l v e d (3). L i g n i f i -
c a t i o n is generally viewed t o occur e x c l u s i v e l y v i a the r a n d o m , d e h y d r o g e n a t i v e
p o l y m e r i z a t i o n o f m o n o l i g n o l s (1) - (3) (^), a r e a c t i o n r e q u i r i n g b o t h H2O2 a n d
peroxidase (5) ( F i g u r e 1).
It is also w e l l k n o w n t h a t the r a t i o of m o n o l i g n o l s (1) - (3) i n v o l v e d i n
the l i g n i f i c a t i o n process is species (6), t i m e (7), l i g h t (8) a n d m o r p h o l o g i c a l
o r i g i n (9,10) dependent. L i g n i f i c a t i o n c a n a p p a r e n t l y also be influenced b y
g r a v i t a t i o n a l forces experienced b y p l a n t s d u r i n g g r o w t h (11-19).
T h e f o l l o w i n g conclusions c a n be m a d e w i t h regard t o current knowledge of
the l i g n i f i c a t i o n process: 1) s t r i c t e n z y m a t i c c o n t r o l l e a d i n g t o the f i n a l p r o d -
Publication Date: December 31, 1989 | doi: 10.1021/bk-1989-0385.ch002

u c t a p p a r e n t l y does n o t o c c u r a n d 2) b o t h r e g u l a t o r y processes c o n t r o l l i n g i t s
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d e p o s i t i o n a n d s t r u c t u r e in situ are p o o r l y u n d e r s t o o d .
L i g n i n f o r m a t i o n i n p l a n t s of m a n y f a m i l i e s of A n g i o s p e r m a e , p a r t i c u l a r l y
those i n C o m m e l i n i d a e of C r o n q u i s t (SO) (i.e., grasses), suffers f r o m a n a d -
d i t i o n a l c o m p l i c a t i o n due t o the presence of c e l l - w a l l - b o u n d h y d r o x y c i n n a m i c
acids, s u c h as p - c o u m a r i c (4) (21), ferulic (5) (22,23), 5 - h y d r o x y f e r u l i c (6) (24),
d i f e r u l i c (7) (23,25,26), a n d 4 , 4 / - d i h y d r o x y t r u x i l l i c (8) acids (27) ( F i g u r e 2).
T h e s e acids have l o n g been s p e c u l a t e d t o b e i n v o l v e d d i r e c t l y i n l i g n i f i c a t i o n ,
a n d t h i s is o n l y n o w b e i n g c l a r i f i e d . T h i s c l a r i f i c a t i o n was achieved b y a d m i n -
i s t e r i n g specifically C - l a b e l l e d forms of ferulic a c i d (5) t o wheat ( Triiicum
1 3

aestivum L . ) . Subsequent a n a l y s i s of the p l a n t tissue (28) a n d i s o l a t e d l i g n i n s

(29) b y s o l i d a n d s o l u t i o n state C - N M R , respectively, revealed t h a t these acids
1 3

were c o v a l e n t l y b o n d e d t o l i g n i n .

Lignin and Papermaking

T h e discovery of l i g n i n a n d i t s subsequent use i n adhesive f o r m u l a t i o n s are

i n t e r t w i n e d w i t h t e c h n o l o g i c a l developments i n the p u l p a n d p a p e r i n d u s t r y .
S u r p r i s i n g l y , i t is not generally a p p r e c i a t e d t h a t the massive w o r l d w i d e p r o -
d u c t i o n of p u l p a n d p a p e r , u s i n g w o o d as a resource, o n l y b e g a n a b o u t 1850
or so. T h i s is i n spite of the fact t h a t f o r m a t i o n of p a p e r f r o m w o o d (e.g.,
b y t r e a t m e n t o f m u l b e r r y b a r k w i t h lye) h a d been developed b y T s ' a i L u n i n
105 A . D . i n C h i n a (SO) a n d perhaps even earlier b y others (31). However, b y
the t i m e t h i s t e c h n o l o g y reached the W e s t e r n H e m i s p h e r e v i a the M i d d l e E a s t ,
w o o d h a d l o n g been replaced b y other p l a n t m a t e r i a l s o f higher cellulosic c o n -
tent (e.g., c o t t o n , l i n e n , flax). W o o d r e m a i n e d forgotten as a source of p a p e r
u n t i l R e n e A . F . de R e a m u r (1683-1757) n o t e d t h a t wasps p r o d u c e d a p a p e r l i k e
nest f r o m w o o d (30).
I n 1839, P a y e n discovered t h a t w o o d was n o t homogeneous b u t c o n t a i n e d
cellulose a n d a n " i n c r u s t i n g m a t e r i a F (32-34) for w h i c h S c h u l t z e coined the
t e r m l i g n i n i n 1865 (35). A s s h o w n i n T a b l e I, c h e m i c a l w o o d p u l p i n g processes
were developed t o dissolve away l i g n i n , hemicelluloses, a n d extractives (30).
T h e s e represent the m a j o r w o o d p u l p i n g processes i n o p e r a t i o n today.

In Adhesives from Renewable Resources; Hemingway, R., et al.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1989.
 LEWIS AND LANTZY Lignins in Adhesives: Introduction

-Η©·

OH

free-radical
1, R R «H
coupling
r 2

2, R «OCH ,R aH
1 3 2

3, R .R «OCH
Lignin
t 2 3

F i g u r e 1. L i g n i n f o r m a t i o n f r o m m o n o l i g n o l s (1) - (3).
Publication Date: December 31, 1989 | doi: 10.1021/bk-1989-0385.ch002
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In Adhesives from Renewable Resources; Hemingway, R., et al.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1989.
 16 ADHESIVES F R O M RENEWABLE RESOURCES

T a b l e I. M a j o r C h e m i c a l P u l p i n g Processes

Type Developer(s)
Soda Burgess a n d W a t t (1854)
Sulphite T i l g h m a n (1857)
Kraft D a h l (1884)

Sources of Lignin

E s s e n t i a l l y a l l of the l i g n i n c o m m e r c i a l l y a v a i l a b l e is i s o l a t e d as b y p r o d u c t s f r o m
either the s u l p h i t e or the k r a f t process. T a b l e II gives a very conservative i d e a
Publication Date: December 31, 1989 | doi: 10.1021/bk-1989-0385.ch002

of a n n u a l l i g n i n p r o d u c t i o n i n the U n i t e d States (2) a n d w o r l d w i d e (36).

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T a b l e I I . E s t i m a t e d A n n u a l P r o d u c t i o n of L i g n i n
( m i l l i o n s of tons)

Type U n i t e d States Worldwide

Kraft lignin 20 75
Lignosulphonates 1.5 15
(Sulphite pulping)

I n a d d i t i o n t o k r a f t or s u l p h i t e l i g n i n s , there are a n u m b e r of other p r o -

cesses w h e r e b y l i g n i n c o u l d p o t e n t i a l l y be recovered (e.g., b y a c i d o l y s i s , s t e a m -
e x p l o s i o n , organosolv, b i o l o g i c a l t r e a t m e n t , etc). T h e e x i s t i n g a n d p o t e n t i a l
processes for l i g n i n recovery are described briefly i n the f o l l o w i n g sections.
Kraft Pulping. T h i s is the m a j o r w o o d p u l p i n g process a n d p o t e n t i a l l y repre-
sents the p r i m a r y source of t e c h n i c a l l i g n i n . D u r i n g p u l p i n g , cellulosic fibers are
o b t a i n e d f r o m w o o d b y t r e a t m e n t w i t h solutions of s o d i u m h y d r o x i d e a n d s u l -
p h i d e at elevated t e m p e r a t u r e s , pressure a n d h i g h p H . T h e hemicelluloses ( a n d
some cellulose) are degraded t o give m a i n l y isosaccharinic acids, the c h e m i s t r y
of w h i c h has been adequately described elsewhere (37). O n the other h a n d ,
the l i g n i n released f r o m the cell w a l l d u r i n g p u l p i n g increases i n m o l e c u l a r size
as d e l i g n i f i c a t i o n proceeds (38) a n d is h i g h l y p o l y disperse (39). K r a f t spent
p u l p i n g l i q u o r s thus consist of l i g n i n ( « 4 7 % ) , h y d r o x y acids ( « 2 8 % , e.g.,
i s o s a c c h a r i n i c a c i d ) , i n o r g a n i c s , a n d s m a l l q u a n t i t i e s of other organics (37).
L i g n i n c a n be i s o l a t e d f r o m these spent p u l p i n g l i q u o r s as a p r e c i p i t a t e b y a c i d -
i f i c a t i o n . A l m o s t a l l k r a f t l i g n i n is b u r n e d for energy recovery; however, a b o u t
35,000 tons are p r o d u c e d a n n u a l l y i n the U n i t e d States for v a r i o u s c h e m i c a l
b y p r o d u c t s (2).

Sulphite Pulping. T h i s is a generic t e r m used t o describe various s u l p h i t e

c h e m i c a l w o o d p u l p i n g processes c a r r i e d out at different pH's a n d p u l p y i e l d s
(37). ( T h e t e r m y i e l d refers t o the q u a n t i t y o f fiber recovered f r o m the o r i g i n a l
wood.)

In Adhesives from Renewable Resources; Hemingway, R., et al.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1989.
 2. LEWIS AND LANTZY Lignins in Adhesives: Introduction 17

I n the a c i d s u l p h i t e l o w - y i e l d p u l p i n g process, w o o d is t r e a t e d w i t h s o l u t i o n s
of a m m o n i u m , s o d i u m , calcium, or magnesium s u l p h i t e / b i s u l p h i t e at low p H
( « 1-2) a n d a t elevated t e m p e r a t u r e s a n d pressures. D u r i n g t h i s t r e a t m e n t , es-
s e n t i a l l y a l l o f the l i g n i n s , hemicelluloses, a n d e x t r a c t i v e s are " d i s s o l v e d " away,
l e a v i n g b e h i n d a fiber o f very h i g h cellulosic content. T h e hemicelluloses u n d e r g o
severe h y d r o l y s i s , affording m a i n l y w a t e r - s o l u b l e monosaccharides i n t h e spent
s u l p h i t e l i q u o r ( S S L ) . T h e s u l p h o n a t e d l i g n i n fragments released i n i t i a l l y d u r -
i n g d e l i g n i f i c a t i o n ( « 3 0 - 4 0 % l i g n i n removal) are m a i n l y m o n o m e r i c compounds
c o n t a i n i n g either m o n o - , d i - , o r t r i - s u l p h o n i c acids (3,40). H o w e v e r , as d e l i g n i -
f i c a t i o n proceeds, t h e l i g n i n released f r o m t h e c e l l w a l l i s o f i n c r e a s i n g m o l e c u l a r
size a n d h i g h l y p o l y disperse (40). C o n s e q u e n t l y , l o w - y i e l d spent s u l p h i t e l i q u o r s
Publication Date: December 31, 1989 | doi: 10.1021/bk-1989-0385.ch002

( S S L ) recovered after w o o d p u l p i n g l a r g e l y consist o f l i g n o s u l p h o n a t e s ( « 5 5 % ) ,

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w o o d sugars ( « 2 5 - 3 0 % , e.g., glucose, m a n n o s e , etc.), i n o r g a n i c s , a n d other o r -

ganics i n s m a l l e r a m o u n t s (37). D e p e n d i n g u p o n the p u l p i n g process e m p l o y e d ,
l i g n o s u l p h o n a t e s c a n b e recovered as either a m m o n i u m , c a l c i u m , s o d i u m , o r
m a g n e s i u m salts (35). Currently, only about 2 0 % of a l l S S L materials pro-
d u c e d are used as c h e m i c a l p r o d u c t s (e.g., as i n e x p e n s i v e b i n d e r s f o r a n i m a l
feed a n d d i r t r o a d s , a n d as dispersants i n o i l - w e l l d r i l l i n g a n d cement/concrete
admixtures).

Acidolysis. A c i d o l y s i s l i g n i n s are recovered f r o m processes w h e r e b y p l a n t m a -

t e r i a l (e.g., w o o d ) is saccharified b y t r e a t m e n t w i t h m i n e r a l acids, s u c h as s u l -
p h u r i c o r h y d r o c h l o r i c acids (41)· T h e l i g n i n is recovered p r i m a r i l y as a n i n -
s o l u b l e residue. T h i s process h a s been used i n E u r o p e i n t h e p a s t , b u t is n o t
commercially important i n the Western Hemisphere.

Steam Explosion. S t e a m - e x p l o s i o n l i g n i n s are o b t a i n e d f r o m w o o d (or some

other p l a n t m a t e r i a l ) t h a t h a s been s u b j e c t e d briefly t o h i g h t e m p e r a t u r e s a n d
pressures followed b y r a p i d decompression (42). T h i s process i s used t o a l i m i t e d
extent t o d a y p a r t i c u l a r l y for t h e processing o f l o w - q u a l i t y h a r d w o o d s . The
l i g n i n s recovered are o f r e l a t i v e l y l o w m o l e c u l a r weight ( M « 700) a n d soluble
n

i n either a l k a l i o r c e r t a i n o r g a n i c solvents (42,43).

Organosolv. O r g a n o s o l v l i g n i n s are o b t a i n e d as r e l a t i v e l y l o w - m o l e c u l a r - w e i g h t
entities b y t r e a t m e n t o f p l a n t tissue w i t h aqueous s o l u t i o n s o f o r g a n i c solvents,
n o r m a l l y c o n t a i n i n g trace a m o u n t s o f m i n e r a l acids (44)- Solvents i n c l u d e
e t h a n o l , m e t h a n o l , b u t a n o l , acetic a c i d , e t h y l acetate, p h e n o l , e t c . T o d a t e ,
t h i s a p p r o a c h h a s n o t been c o m m e r c i a l i z e d d u e t o t h e q u a n t i t i e s o f o r g a n i c
solvents c o n s u m e d a n d t h e l o w q u a l i t y o f the p u l p fiber o b t a i n e d .
Enzymatic Liberation. T h i s is a process w h e r e b y l i g n i n - r i c h residues are o b -
tained b y treatment of plant material w i t h cellulases/hemicellulases/pectinases,
etc. T h e s e l i g n i n p r e p a r a t i o n s m a y m o r e closely resemble " n a t i v e " l i g n i n d u e
to t h e v e r y m i l d processing c o n d i t i o n s e m p l o y e d .

In Adhesives from Renewable Resources; Hemingway, R., et al.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1989.
 18 ADHESIVES F R O M RENEWABLE RESOURCES

Lignin in Wood-Composite Adhesives

It is w o r t h w h i l e t o review the U . S . m a r k e t size for the four p r i n c i p a l resins c u r ­

r e n t l y used i n w o o d - p a n e l p r o d u c t s t o d a y (^5). T h e s e are p h e n o l - f o r m a l d e h y d e
( P F ) , urea-formaldehyde ( U F ) , melamine-formaldehyde ( M F ) , and resorcinol-
f o r m a l d e h y d e ( R F ) ( T a b l e I I I ) . W h e n these p r o d u c t i o n figures are c o m p a r e d t o
the q u a n t i t i e s o f l i g n i n p o t e n t i a l l y a v a i l a b l e ( T a b l e I I ) , i t is i m m e d i a t e l y o b v i o u s
t h a t a l l w o o d adhesives c o u l d be replaced b y o n l y a very s m a l l f r a c t i o n o f the
l i g n i n p r o d u c e d a n n u a l l y d u r i n g c h e m i c a l w o o d p u l p i n g processes.

T a b l e I I I . U . S . P r o d u c t i o n of T h e r m o s e t t i n g
Publication Date: December 31, 1989 | doi: 10.1021/bk-1989-0385.ch002
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R e s i n s (1983) i n M e t r i c T o n s (χ 1 0 ) 3

Resin 1
Total Wood Products
RF 15.5 1.5
UF 586.0 440.0
MF 90.0 5.0
PF 660.0 297.0

Totals 1,351.5 743.5

* R F = resorcinol-formaldehyde
U F = urea-formaldehyde
M F = melamine-formaldehyde
P F = phenol-formaldehyde

T h e r e have been m a n y a t t e m p t s t o replace these resins w i t h l i g n i n d e r i v a ­

tives for w o o d c o m p o s i t e adhesives s u i t a b l e for p l y w o o d , p a r t i c l e b o a r d a n d
w a f e r b o a r d . M o s t of these studies have been e m p i r i c a l i n n a t u r e , a n d few have
achieved f u r t h e r c o n s i d e r a t i o n for i n d u s t r i a l a p p l i c a t i o n . A s w o o d b i n d e r s , t e c h ­
n i c a l l i g n i n s are v a r i a b l e i n q u a l i t y a n d p o o r l y reactive i n c o m p a r i s o n t o c o n ­
v e n t i o n a l resin systems s u c h as p h e n o l - f o r m a l d e h y d e ( P F ) resins. C o n s e q u e n t l y ,
t h e y are n o t u t i l i z e d o n t h e i r o w n . Indeed, i f t h e y were, t h i s w o u l d adversely
affect p r o d u c t i o n q u a l i t y a n d t i m e s , a n d necessitate e q u i p m e n t changes. I n the
w o o d c o m p o s i t e i n d u s t r y , resins h a v i n g s u c h deleterious effects are n o t l i k e l y t o
be used even if savings could be made in terms of material costs.
Progress t o w a r d p r o d u c i n g i n d u s t r i a l l y acceptable l i g n i n adhesives c a n be
b r o k e n d o w n i n t o t w o m a i n categories as either 1) l i g n i n - b a s e d b i n d e r s (by
themselves as s u c h or i n c h e m i c a l l y m o d i f i e d f o r m ) , or 2) as c o p o l y m e r s ( w i t h
other r e a c t a n t adhesives).
Lignosulphonates. C r u d e S S L c a n be o b t a i n e d as a b r o w n i s h , s p r a y - d r i e d
powder or as a viscous, hygroscopic, d a r k - c o l o r e d l i q u i d . S S L a n d the l i g n o ­
s u l p h o n a t e s present i n i t have been the focus o f n u m e r o u s efforts to p r o d u c e a n

In Adhesives from Renewable Resources; Hemingway, R., et al.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1989.
 2. LEWIS AND LANTZY Lignins in Adhesives: Introduction 19

i n d u s t r i a l l y useful adhesive. E s s e n t i a l l y , there are t w o m e t h o d s o f c u r i n g S S L -

based adhesives, n a m e l y , b y t h e r m o s e t t i n g o r b y free-radical p o l y m e r i z a t i o n .
W i t h respect t o t h e r m o s e t t i n g , i t h a s been w e l l d o c u m e n t e d t h a t crude C a -
based S S L c a n be used as a p a r t i c l e b o a r d adhesive (46)- T h i s a p p l i c a t i o n h a s
been e v a l u a t e d o n a m i l l - s c a l e basis i n D e n m a r k , F i n l a n d , a n d S w i t z e r l a n d ,
b u t h a s n o t been a d o p t e d o n a c o m m e r c i a l scale. T h i s is because resin c u r i n g
r e q u i r e d b o t h h i g h press a n d autoclave temperatures as w e l l as l o n g h e a t i n g
t i m e s . W h i l e t h i s development was a " t e c h n i c a l " success, i t was - a c c o r d i n g
to N i m z (36) - never c o m m e r c i a l i z e d due t o t h e frequency o f fires experienced
during mill-scale trials.
Subsequent a t t e m p t s t o i m p r o v e the properties (i.e., r e a c t i v i t y ) o f S S L adhe-
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sives have essentially e m p l o y e d either a c i d i f i c a t i o n o f C a - b a s e d S S L o r m e m b r a n e

filtration o f the crude p u l p i n g l i q u o r s . A c i d i f i c a t i o n o f C a - S S L w i t h concentrated
H2SO4 gave a n adhesive s u i t a b l e for p a r t i c l e b o a r d a p p l i c a t i o n s (47). However,
processing parameters s t i l l required h i g h press t e m p e r a t u r e ( « 204 ° C ) , press
t i m e s (5-7 m i n ) , a n d pressure (400 p s i ) . T h e very l o w p H ( < 1) o f t h e resin
used m a y also have a l o n g t e r m corrosive effect o n n a i l s , staples, etc., a n d engen-
der w o o d d e t e r i o r a t i o n . M e m b r a n e filtration o f S S L shows s o m e w h a t greater
p r o m i s e . T h i s a p p r o a c h was first r e p o r t e d b y Forss et a l . (48,49) * t h e de- n

velopment o f K A R A T E X , a P F / l i g n i n adhesive b i n d e r c o n t a i n i n g either l i g n o -

sulphonates o r k r a f t l i g n i n s o f n o m i n a l m o l e c u l a r weight > 5000 as d e t e r m i n e d
by passage t h r o u g h a m e m b r a n e . A p p l y i n g t h i s a p p r o a c h , S h e n a n d C a l v e (50)
e x a m i n e d t h e w a f e r b o a r d b i n d i n g properties o f a n a m m o n i u m - b a s e d S S L t h a t
h a d been subjected t o m e m b r a n e filtration. B o a r d pressing c o n d i t i o n s were
s t i l l excessive (e.g., 8 m i n at 210 ° C for 1 1 - m m - t h i c k w a f e r b o a r d ) . Best b o a r d
properties were o b t a i n e d w i t h t h e l o w - m o l e c u l a r weight permeate ostensibly o f
< 5,000 m o l e c u l a r weight a n d c o n t a i n i n g s u l p h o n a t e d l i g n i n s a n d m o n o s a c c h a -
rides. O n t h e other h a n d , t h e l i g n o s u l p h o n a t e retentate ( > 5,000 m o l w t ) gave
b o a r d s o f unacceptable m e c h a n i c a l properties.

It s h o u l d be recognized at t h i s p o i n t t h a t 1) t h e l i g n o s u l p h o n a t e s ( < 5,000

m o l w t ) l a r g e l y consist o f the m o n o m e r s c o n t a i n i n g m o n o - , d i - o r t r i - s u l p h o n i c
acids as p r e v i o u s l y described (3,40), a n d 2) t h e m e c h a n i c a l properties o f t h e
waferboards were d e t e r m i n e d largely b y monosaccharide, r a t h e r t h a n l i g n o -
s u l p h o n a t e , content (51). It was subsequently proven, under c o n t r o l l e d l a b o r a -
t o r y c o n d i t i o n s , t h a t the rate o f t h e r m o s e t t i n g o f b o t h h i g h a n d l o w m o l e c u l a r
weight l i g n o s u l p h o n a t e s can be i m p r o v e d b y increasing the m o n o s a c c h a r i d e c o n -
tent o f t h e adhesive (52). I n a n analogous m a n n e r , f o r m a l d e h y d e was s h o w n
to b e capable o f s l i g h t l y i n c r e a s i n g t h e rate o f t h e r m o s e t t i n g , p r e s u m a b l y b y
increasing the rate of crosslinking.

However, w h i l e t h e use o f f r a c t i o n a t e d NH4-SSL r e m a i n s a " t e c h n i c a l suc-

cess," t h e t h e r m o s e t t i n g rates are s t i l l very l o w i n c o m p a r i s o n t o P F resins.
Therefore, t h e l i k e l i h o o d o f p r o d u c i n g a c o m m e r c i a l l y acceptable t h e r m o s e t t i n g
l i g n o s u l p h o n a t e - b a s e d resin is s t i l l very f a r f r o m reality.

In Adhesives from Renewable Resources; Hemingway, R., et al.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1989.
 20 ADHESIVES F R O M RENEWABLE RESOURCES

L i g n o s u l p h o n a t e s i n crude S S L c a n also be o x i d a t i v e l y p o l y m e r i z e d b y either

c h e m i c a l (36,53) or b i o c h e m i c a l (54) means. I n the f o r m e r process, o x i d a n t s
such as h y d r o g e n p e r o x i d e , c a t a l y z e d b y s u l p h u r d i o x i d e (or p o t a s s i u m f e r r i -
c y a n i d e ) , c a n b e used t o cure fermented C a - b a s e d S S L . T h i s was f o u n d t o be
s u i t a b l e as a n adhesive for m e d i u m - d e n s i t y i n t e r i o r - g r a d e p a r t i c l e b o a r d (36,53).
O p t i m u m b o n d i n g c o n d i t i o n s used 2 0 % o f a t e c h n i c a l S S L ( 5 4 % ) , 9 % o f a 3 5 %
H2O2 s o l u t i o n , 4 % a m m o n i u m c h l o r i d e a n d 0.6% SO2 for b o n d i n g p a r t i c l e -
b o a r d at 120 ° C w i t h a press t i m e o f 5 m i n . D i f f i c u l t i e s experienced p r e v i o u s l y
i n c o n t r o l l i n g the e x o t h e r m i c n a t u r e o f t h i s c u r i n g r e a c t i o n have a p p a r e n t l y
been resolved. W h e t h e r t h i s development w i l l receive c o m m e r c i a l endorsement
r e m a i n s t o be seen.
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A n o t h e r a p p r o a c h t o c u r i n g S S L b y o x i d a t i v e p o l y m e r i z a t i o n e m p l o y s the
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use o f e n z y m e s (54)- I n t h a t s t u d y , S S L was t r e a t e d w i t h the w h i t e - r o t fungus

Fomes annosus a n d a l a c c a s e - i n d u c i n g phenoloxidase u n t i l the s o l u t i o n reached
a " h o n e y l i k e " consistency. T h i s viscous l i q u i d was t h e n s u b s e q u e n t l y used t o
b o n d w o o d p a r t i c l e s together at a pressure o f 0.03 k g c m " . It now needs 2

t o be e s t a b l i s h e d w h e t h e r the m e c h a n i c a l properties o f these b o a r d s s u r v i v e

accelerated a g i n g tests.
T h e a p p l i c a t i o n o f l i g n o s u l p h o n a t e s as a n extender or co-reactant i n P F or
U F resins has been w e l l s t u d i e d , i n d u s t r i a l l y a p p l i e d , a n d e x t e n s i v e l y d o c u -
m e n t e d i n a recent comprehensive review (36). Since t h a t s t u d y , waferboards
have been p r o d u c e d w i t h excellent m e c h a n i c a l properties after b e i n g b o n d e d at
204 ° C , 4 t o 5 m i n , 3375 k P a w i t h a l i g n o s u l p h o n a t e - P F resin (55). T h e p h e -
n o l i c r e s i n was m o d i f i e d b y use o f K 3 F e ( C N ) e s t a b i l i z e d l i g n o s u l p h o n a t e s ; b o t h
p h e n o l a n d the l i g n o s u l p h o n a t e s were used i n a p p r o x i m a t e l y e q u a l p r o p o r t i o n s .
W i t h r e g a r d t o p o t e n t i a l l i g n i n u t i l i z a t i o n , p e r h a p s some of the best re-
p o r t e d results have been e n u n c i a t e d by Forss et a l . (48,49). A s described
p r e v i o u s l y , spent s u l p h i t e l i q u o r ( S S L ) was s u b j e c t e d t o m e m b r a n e filtration,
a n d the l i g n o s u l p h o n a t e retentate ( > 5,000 n o m i n a l m o l e c u l a r weight cutoff)
was used t o replace f r o m 40 t o 7 0 % o f P F resin w i t h no significant d e t e r i o r a t i o n
i n m e c h a n i c a l b o a r d p r o p e r t i e s . P a r t i c l e b o a r d , p l y w o o d , a n d fiberboard were
t h e n p r o d u c e d i n F i n l a n d u s i n g resins c o n t a i n i n g h i g h m o l e c u l a r weight l i g n o -
s u l p h o n a t e s a n d P F i n m i l l - s c a l e t r i a l s under n o r m a l processing c o n d i t i o n s , a n d
t h i s use was a p p a r e n t l y successful (48,49). A w i d e l y s t a t e d advantage o f t h i s
u l t r a f i l t r a t i o n a p p r o a c h is t h a t l i g n i n derivatives can be c o m m e r c i a l l y p r o d u c e d
w i t h less p r o d u c t v a r i a b i l i t y . H o w e v e r , i t does not a p p e a r t h a t t h i s m e t h o d o l o g y
is c u r r e n t l y b e i n g used c o m m e r c i a l l y t o p r o d u c e l i g n i n - b a s e d adhesives.
T h e use o f S S L or l i g n o s u l p h o n a t e s i n other p o l y m e r i c adhesive systems has
also been e x a m i n e d [e.g., w i t h p o l y a c r y l a m i d e , p r o t e i n s / a l d e h y d e s , p o l y e t h y l e n e
o x i d e , p o l y e t h y l e n e i m i n e , epoxides, m e l a m i n e , styrene o x i d e , p o l y i s o c y a n a t e s
(36)]. S o f a r , these procedures, for different reasons, have n o t led t o a n y m a j o r
p r a c t i c a l a p p l i c a t i o n (36). It w o u l d , however, be i n t e r e s t i n g t o r e e x a m i n e some
o f these processes u s i n g n o t crude spent s u l p h i t e l i q u o r s , b u t i n s t e a d those
purified by membrane filtration.

In Adhesives from Renewable Resources; Hemingway, R., et al.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1989.
 2. LEWIS AND LANTZY Lignins in Adhesives: Introduction 21

Kraft Lignins. K r a f t l i g n i n s are n o r m a l l y o b t a i n e d as b r o w n p o w d e r s h a v i n g

very b r o a d m o l e c u l a r weight d i s t r i b u t i o n s a n d v a r i a b l e p r o p e r t i e s . B o t h color
a n d p r o d u c t v a r i a b i l i t y are disadvantages t h a t do n o t l e n d themselves t o easy
acceptance b y resin m a n u f a c t u r e r s . T h e y are m a i n l y u n s u i t a b l e as t h e r m o s e t ­
t i n g adhesives since press t i m e s r e q u i r e d are t o o l o n g , press t e m p e r a t u r e s t o o
h i g h , a n d b o a r d / p a n e l m e c h a n i c a l properties p o o r . T h i s p o o r resin r e a c t i v ­
i t y is r e a d i l y e x p l a i n a b l e ; the p h e n o l i c content o f k r a f t l i g n i n is l o w , there are
n o r m a l l y s u b s t i t u e n t s ortho a n d para t o a n y p h e n o l i c h y d r o x y l f u n c t i o n a l i t i e s ,
a n d i t s m o l e c u l a r size m a y prevent efficient c r o s s l i n k i n g reactions due t o steric
constraints.
K r a f t l i g n i n s are e s s e n t i a l l y a c i d - i n s o l u b l e , b u t u p t o 3 5 % b y weight of l i g n i n
Publication Date: December 31, 1989 | doi: 10.1021/bk-1989-0385.ch002

i n s o l u t i o n c a n be achieved u n d e r a l k a l i n e c o n d i t i o n s . H o w e v e r , as s u c h , these so­

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l u t i o n s are t o o viscous t o be of a n y p r a c t i c a l use i n l i q u i d adhesive f o r m u l a t i o n s .

O n e m e a n s t o reduce v i s c o s i t y difficulties has been t o o b t a i n h i g h solids ( « 4 0 % ) ,
l o w - v i s c o s i t y l i g n i n s o l u t i o n s b y e m p l o y i n g p h e n o l - H 2 0 or p h e n o l : H 2 Ο : N a O H
(or NH3) as solvents (56). T h i s a p p r o a c h was used t o give a p l y w o o d adhesive
w i t h excellent b o a r d p r o p e r t i e s (57). T h e adhesive was p r e p a r e d i n a t w o -
step process b y p a r t i a l l y c o n d e n s i n g p h e n o l a n d f o r m a l d e h y d e together u n d e r
alkaline conditions. T h e r e s u l t i n g condensate was t h e n reacted w i t h a l i g n i n
concentrate a n d f o r m a l d e h y d e i n the presence o f a l k a l i t o p r o d u c e a resin o f
3 7 . 2 % s o l i d s content, p H 11.4, a n d a v i s c o s i t y o f 460 c P .
L i k e l i g n o s u l p h o n a t e s , the use o f k r a f t l i g n i n as extenders or co-react a n t s
i n P F a n d U F resins has been w e l l e x p l o r e d a n d o c c a s i o n a l l y i m p l e m e n t e d
(36,58-60). R e f e r r i n g a g a i n t o the w o r k by Forss (48,49), some o f the best
results c l a i m e d , as regards P F r e p l a c e m e n t , were o b t a i n e d u s i n g h i g h m o l e c ­
u l a r weight k r a f t l i g n i n s . Indeed, p r o p e r t i e s a p p e a r e d s u p e r i o r t o those u s i n g
lignosulphonates.
I n r e a l t e r m s , t h o u g h , the p r o b l e m s t h a t k r a f t ( a n d o t h e r l i g n i n s ) face are
those o f p o o r r e a c t i v i t y , p r o d u c t v a r i a b i l i t y , a n d d i s c o l o r a t i o n . I n order for m o r e
reactive k r a f t l i g n i n adhesives t o be m a d e , t h e y m u s t be c h e m i c a l l y m o d i f i e d
i n some m a n n e r . T h i s c a n be done b y a v a r i e t y o f means (e.g., i n t r o d u c t i o n o f
reactive c r o s s l i n k i n g sites o n t o the l i g n i n molecules b y means o f h y d r o x y m e t h y -
l a t i o n , e p o x i d a t i o n , i s o c y a n a t i o n , a n d the l i k e ) .
H y d r o x y m e t h y l a t i o n ( m e t h y l o l a t i o n ) was first r e p o r t e d as a means o f a c t i ­
v a t i n g k r a f t l i g n i n s for c r o s s l i n k i n g reactions w i t h P F resins (61-63). I n these
studies, i t was d e m o n s t r a t e d t h a t b a s e - c a t a l y z e d c o n d e n s a t i o n o f f o r m a l d e h y d e
w i t h s o f t w o o d k r a f t l i g n i n i n t r o d u c e d C H O H groups m a i n l y at C - 5 of the a r o ­
2

m a t i c r i n g a n d , t o a lesser extent at Cp ( F i g u r e 3). These authors (61-63)

i n d i c a t e d t h a t o f a l l the C - 5 a n d C/j p o s i t i o n s i n softwood l i g n i n , o n l y 0.33 a n d
0.03, respectively, were a v a i l a b l e for c o n d e n s a t i o n w i t h f o r m a l d e h y d e . T h e Cp
p o s i t i o n s require a c t i v a t i o n for c o n d e n s a t i o n b y either a n adjacent C - c a r b o n y l
a

or b y the presence o f a C , / ? - d o u b l e b o n d . T h e s e findings were u n a m b i g u o u s l y

a

c o n f i r m e d i n a recent i n v e s t i g a t i o n by C h e n a n d G r a t z l (64). H o w e v e r , even

w i t h the i n t r o d u c t i o n o f these a d d i t i o n a l c r o s s l i n k i n g sites, the r a t e o f c o n -

In Adhesives from Renewable Resources; Hemingway, R., et al.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1989.
 ADHESIVES F R O M RENEWABLE RESOURCES
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F i g u r e 3. P r o p o s e d h y d r o x y m e t h y l a t i o n reactions of l i g n i n (61-64)-

In Adhesives from Renewable Resources; Hemingway, R., et al.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1989.
 2. LEWIS AND LANTZY Lignins in Adhesives: Introduction 23

d e n s a t i o n o f m e t h y l o l a t e d k r a f t l i g n i n s is s t i l l far less t h a n t h a t for P F resins

(65). C o n s e q u e n t l y , t h e y are n o t used o n t h e i r o w n a n d need t o be a p p l i e d i n
c o m b i n a t i o n w i t h P F resins (65-71).
Interestingly, s o d a bagasse l i g n i n is m u c h m o r e reactive t o w a r d f o r m a l d e h y d e
t h a n other l i g n i n s , a feature a t t r i b u t a b l e t o fewer s u b s t i t u e n t s at C - 3 a n d C - 5
(72). T h i s m a t e r i a l , after m e t h y l o l a t i o n , r e s o r c i n o l g r a f t i n g , a n d m i x i n g w i t h
p h e n o l i c r e s i n , p r o d u c e s c o l d - s e t t i n g w o o d adhesives s u i t a b l e for s t r u c t u r a l f i n -
gerjoints a n d g l u l a m .
Epoxy Resins. T h e use o f l i g n i n i n o r g a n i c p o l y i s o c y a n a t e - l i q u i d a r o m a t i c
e p o x i d e b i n d e r s has also been e v a l u a t e d ( 7 5 ) . A c c o r d i n g t o t h e a u t h o r s , the
l i g n i n served o n l y as a d i l u e n t , a l t h o u g h f a i r l y h i g h levels o f s u b s t i t u t i o n ( « 35%)
Publication Date: December 31, 1989 | doi: 10.1021/bk-1989-0385.ch002

b y l i g n i n were achieved.
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Lignin Isocyanates. I n the v e r y near f u t u r e , i s o c y a n a t e adhesives are l i k e l y

t o grow i n i m p o r t a n c e i n the w o o d p a n e l i n d u s t r y . I n t h i s r e g a r d , a n u m b e r
of i n v e s t i g a t i o n s have a t t e m p t e d t o i m p r o v e t h e w o o d - b o n d i n g p r o p e r t i e s of
l i g n i n b y r e a c t i o n w i t h isocyanates, or b y i n c l u s i o n o f i s o c y a n a t e f u n c t i o n a l -
ities i n t o t h e l i g n i n p o l y m e r . F o r e x a m p l e , G a m o (74) was able t o prepare
a n adhesive s u i t a b l e for p r o d u c i n g 3-ply p l y w o o d w i t h acceptable mechani-
cal p r o p e r t i e s . T h i s was achieved by r e a c t i n g 20 p a r t s o f i s o c y a n a t e s o l u t i o n
( m e t h y l e n e d i i s o c y a n a t e : t o l u e n e , 3:1) w i t h 100 p a r t s k r a f t l i g n i n - f o r m a l d e h y d e
resin. O t h e r approaches involve r e a c t i o n o f k r a f t l i g n i n w i t h p r o p y l e n e oxide
t o afford h y d r o x y p r o p y l l i g n i n s t h a t c a n t h e n be reacted w i t h p o l y m e t h y l e n e -
p o l y p h e n y l e n e i s o c y a n a t e or h e x a m e t h y l e n e d i i s o c y a n a t e ( 7 5 ) . In a somewhat
s i m i l a r m a n n e r , l i g n i n - m o d i f i e d p o l y u r e t h a n e adhesives have been p r e p a r e d
from 4,4/-diphenylmethane-diisocyante-lignin-maleic anhydride-propylene oxide
c o p o l y m e r s ( 76,77).
T h e use o f l i g n i n , essentially as a d i l u e n t (extender), has also been inves-
t i g a t e d (78). I n t h i s case, d i - or p o l y i s o c y a n a t e s were reacted w i t h ethylene
or p r o p y l e n e carbonates i n a s o l u t i o n c o n t a i n i n g l i g n i n . T h e s e m i x e d ethylene
and p r o p y l e n e c a r b o n a t e - c o n t a i n i n g o r g a n i c p o l y i s o c y a n a t e s were s u i t a b l e as
p a r t i c l e b o a r d adhesives.
S team-Explosion, Acidolysis, Organosolv, and Cellulase Lignins.
S t e a m - e x p l o s i o n l i g n i n s have received some a t t e n t i o n as adhesives m a i n l y be-
cause t h i s process offers some p o t e n t i a l for u t i l i z i n g l o w - q u a l i t y h a r d w o o d s . Like
k r a f t l i g n i n , these p r e p a r a t i o n s also require a c t i v a t i o n [e.g., b y h y d r o x y m e t h y -
l a t i o n (79), i s o c y a n a t i o n (75,80)] to achieve any t y p e o f acceptable w o o d c o m -
p o s i t e adhesive p r o p e r t i e s .
A c i d o l y s i s l i g n i n s , o r g a n o s o l v , a n d cellulase l i g n i n s are p r e s e n t l y l a b o r a t o r y
curiosities due t o a lack of c o m m e r c i a l i z a t i o n . W h e t h e r these l i g n i n s w i l l offer
any advantages at a l l w i t h respect t o resin adhesives c u r r e n t l y used r e m a i n s t o
be e s t a b l i s h e d . P r e l i m i n a r y e x p e r i m e n t s [e.g., w i t h a c i d o l y s i s l i g n i n s (81)] have
not d e m o n s t r a t e d a n y s u p e r i o r q u a l i t i e s t o date.

In Adhesives from Renewable Resources; Hemingway, R., et al.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1989.
 24 ADHESIVES F R O M RENEWABLE RESOURCES

Conclusions

C o n s i d e r a b l e research a c t i v i t y has been directed t o w a r d p r o d u c i n g w o o d c o m ­

posite adhesives f r o m l i g n i n , a n d t h i s has been a c c o m p a n i e d b y very l i t t l e p r a c ­
t i c a l success i n t e r m s o f c o m m e r c i a l i m p l e m e n t a t i o n . B y themselves, a n d r e ­
gardless o f source, l i g n i n s offer n o advantages i n t e r m s o f c h e m i c a l r e a c t i v i t y ,
p r o d u c t q u a l i t y , o r color w h e n c o m p a r e d t o c o n v e n t i o n a l w o o d c o m p o s i t e adhe­
sives. A t l o w replacement levels (10 t o 3 0 % ) , l i g n i n s c a n a n d w i l l continue t o be
e m p l o y e d as extenders for U F a n d P F resins. W h e n t h e y are used as extenders,
best results are o b t a i n e d w h e n c h e m i c a l l y a c t i v a t e d (e.g., b y m e t h y l o l a t i o n ) .
H o w e v e r , l i g n i n m a y f i n d a p p l i c a t i o n as a s u i t a b l e w o o d - c o m p o s i t e adhesive
Publication Date: December 31, 1989 | doi: 10.1021/bk-1989-0385.ch002

i n adhesive f o r m u l a t i o n s i f c h e m i c a l l y m o d i f i e d i n some m a n n e r . I n t h i s respect,

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the recent developments w i t h s o d a bagasse l i g n i n - r e s o r c i n o l - f o r m a l d e h y d e a n d

l i g n i n - i s o c y a n a t e adhesives a l l o w for some c a u t i o u s o p t i m i s m for the f u t u r e .

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In Adhesives from Renewable Resources; Hemingway, R., et al.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1989.