Adhesives from Renewable Resources - ACS Publications - American

Chapter 20 Carbohydrates in Adhesives Downloaded by NANYANG TECHNOLOGICAL UNIV on June 8, 2016 | http://pubs.acs.org Publication Date: December 31, 1989 | doi: 10.1021/bk-1989-0385.ch020

Introduction and Historical Perspective Anthony H . Conner Forest Products Laboratory Forest Service U. S. Department of Agriculture One Gifford Pinchot Drive Madison, WI 53705

Carbohydrates, in the form of gums, polysaccharides, oligomers, and monomeric sugars, are readily available in large quanitities from renewable biomass resources. Each of these substances, either directly or in a chemically modified form, is a source of intermediates (derivatives) that have potential use in adhesive formulation. Carbohydrates have been utilized historically for and in adhesives and are likely to be used more and more in the future as petroleum-derived chemicals become scarce and prices increase. Appropriate research emphasis can effectively further their use as adhesive raw material. T h i s section of the b o o k deals w i t h the u t i l i z a t i o n of c a r b o h y d r a t e s i n adhesives. It includes a n u m b e r o f excellent chapters t h a t give a g o o d flavor for present research i n t o the use o f c a r b o h y d r a t e s i n adhesives. A s a n i n t r o d u c t i o n t o t h i s section, I w o u l d like t o give a b r i e f overview of the use o f c a r b o h y d r a t e s i n adhesives. T h i s overview is presented f r o m a p e r s o n a l perspective. I t w i l l p r o b a b l y s k i m over some very i m p o r t a n t areas a n d m a y miss others entirely. I hope, however, t o give y o u some i n d i c a t i o n o f the b r e a d t h o f p o s s i b i l i t i e s for u s i n g c a r b o h y d r a t e s i n adhesives a n d some i n d i c a t i o n s of possible areas where future research w o u l d be a p p r o p r i a t e . C a r b o h y d r a t e s , i n the f o r m o f g u m s , p o l y s a c c h a r i d e s , o l i g o m e r s , a n d m o n o m e r i c sugars, are r e a d i l y o b t a i n a b l e f r o m renewable b i o m a s s sources. E a c h of these has p o t e n t i a l use i n the f o r m u l a t i o n o f adhesives. T h i s has been true h i s t o r i c a l l y a n d w i l l b e i n c r e a s i n g l y true i n the f u t u r e as p e t r o l e u m - d e r i v e d chemicals become scarce a n d their prices rise. C a r b o h y d r a t e p o l y m e r s are available i n large q u a n t i t i e s f r o m b o t h p l a n t a n d a n i m a l sources. T h e s e i n c l u d e cellulose a n d hemicellulose f r o m w o o d y p l a n t s , This chapter not subject to U.S. copyright Published 1989 American Chemical Society

Hemingway et al.; Adhesives from Renewable Resources ACS Symposium Series; American Chemical Society: Washington, DC, 1989.

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ADHESIVES F R O M RENEWABLE RESOURCES

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s t a r c h a n d g u m s f r o m a n u m b e r of different p l a n t s a n d m i c r o o r g a n i s m s , a n d c h i t i n f r o m a n i m a l sources. O l i g o m e r s a n d m o n o m e r s c a n be o b t a i n e d d i r e c t l y f r o m b i o m a s s , b u t generally are o b t a i n e d b y selective h y d r o l y s i s o f p o l y m e r s . T h e types o f m o n o m e r i c sugars t h a t c a n be o b t a i n e d b y h y d r o l y s i s o f the p o l y mers i n c l u d e b o t h pentoses (e.g., xylose a n d arabinose) a n d hexoses (e.g., g l u cose, g l u c o s a m i n e , a n d mannose). T h e p o l y m e r s , oligomers, a n d m o n o m e r s can be converted to a v a r i e t y o f c h e m i c a l intermediates (derivatives or d e g r a d a t i o n p r o d u c t s ) by either c h e m i c a l or b i o l o g i c a l means. These also have p o t e n t i a l as sources o f adhesive m a t e r i a l s . T h i s chapter deals w i t h each o f these types o f c a r b o h y d r a t e s , how they have been used i n adhesives, a n d how they m i g h t be used i n the f u t u r e . I n m a n y cases, I w i l l o n l y a l l u d e t o possible uses because d e t a i l e d discussion o f specific uses o f c e r t a i n c a r b o h y d r a t e m a t e r i a l s is covered b y others i n chapters t h a t follow. Carbohydrate Polymers in Adhesives C a r b o h y d r a t e p o l y m e r s are a m a j o r constituent o f a l l p l a n t s , the exoskeletons of various m a r i n e a n i m a l s , a n d some m i c r o o r g a n i s m s . Because u p to three-quarters of the d r y weight o f plants consists o f polysaccharides, i t is not s u r p r i s i n g t h a t m a n y p o l y s a c c h a r i d e s are r e a d i l y available at low cost. P o l y s a c c h a r i d e s , espec i a l l y f r o m p l a n t sources, have served a v a r i e t y of uses i n m a n k i n d ' s h i s t o r y , r a n g i n g f r o m basic necessities, such as f o o d , c l o t h i n g , a n d f u e l , to p a p e r a n d adhesives. C a r b o h y d r a t e p o l y m e r s h i s t o r i c a l l y have been used for or i n adhesives. I n deed, m y first encounter w i t h adhesives, a n d p o s s i b l y y o u r first encounter, i n volved the use o f a c a r b o h y d r a t e p o l y m e r t o glue p a p e r . A s a c h i l d , I used a paste m a d e f r o m flour a n d water t o glue p a p e r - m a c h e i n t o some very i n t e r e s t i n g f o r m s . A n d as a p a r e n t , I used t h i s same technique t o b u i l d m a n y a t u n n e l a n d h i l l for m y son's m i n i a t u r e t r a i n l a y o u t , thus passing a l o n g ( i n disguised f o r m ) a b i t o f knowledge a b o u t the use o f c a r b o h y d r a t e p o l y m e r s as a n adhesive t h a t was surely first discovered before recorded h i s t o r y . A s I have a l r e a d y i n d i c a t e d , the p o l y m e r i c c a r b o h y d r a t e m a t e r i a l s a v a i l a b l e f r o m n a t u r a l sources i n c l u d e g u m s , s t a r c h a n d d e x t r i n s , cellulose, hemicellulose, c h i t i n , a n d b a c t e r i a l polysaccharides. G u m s . G u m s are h y d r o p h o b i c or h y d r o p h i l i c p o l y s a c c h a r i d e s d e r i v e d f r o m p l a n t s or m i c r o o r g a n i s m s t h a t u p o n d i s p e r s i n g i n either hot or c o l d water p r o duce viscous m i x t u r e s or s o l u t i o n s (i.e., gels ( i ) ) . A s used i n the m o d e r n sense, the t e r m g u m includes any water-soluble or water-swellable p o l y s a c c h a r i d e or i t s d e r i v a t i v e . T h i s includes s t a r c h a n d d e x t r i n s a n d various derivatives of cellulose. T h e l a t t e r , however, are considered separately. N a t u r a l g u m s i n c l u d e p l a n t exudates, seed g u m s , p l a n t e x t r a c t s , seaweed ext r a c t s , a n d the e x t r a c e l l u l a r m i c r o b i a l polysaccharides. P l a n t exudates i n c l u d e g u m a r a b i c , g u m g h a t t i , g u m k a r a y a , a n d g u m t r a g a c a n t h . Seed g u m s i n c l u d e


20.

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Carbohydrates in Adhesives: Introduction

guar g u m , locust b e a n g u m , a n d t a m a r i n d . T h e a r a b i n o g a l a c t a n o b t a i n e d f r o m l a r c h is a n e x a m p l e o f a polysaccharide t h a t c a n be e x t r a c t e d f r o m p l a n t s . E x amples o f seaweed extracts are agar, a l g i n , a n d f u n o r a n . X a n t h a n g u m a n d d e x t r a n are m i c r o b i a l polysaccharides. T a b l e I indicates t h e d i s t r i b u t i o n o f g u m s for a n u m b e r o f i n d u s t r i a l purposes (2,3). T h e i r u t i l i z a t i o n i n adhesives is


a m a j o r e n d use. I n recent years, s y n t h e t i c p o l y m e r s a n d m i c r o b i a l l y p r o d u c e d g u m s i n c r e a s i n g l y have replaced p l a n t - d e r i v e d g u m s . H i s t o r i c a l l y , several adhesives have been derived f r o m n a t u r a l c a r b o h y d r a t e p o l y m e r s (1,4-6). I n a few cases, t h e y have been u t i l i z e d because o f t h e i r o w n p a r t i c u l a r adhesive q u a l i t y . However, n a t u r a l c a r b o h y d r a t e p o l y m e r s are u s u a l l y u t i l i z e d as modifiers for more costly s y n t h e t i c resins, especially as thickeners, c o l l o d i a l s t a b i l i z e r s , a n d flow controllers. T a b l e I I lists examples o f the use o f n a t u r a l g u m s i n adhesives (7-40).

Table I. D i s t r i b u t i o n of Polysaccharide G u m s by C o m m e r c i a l Usage Product Type

Percent

Detergents a n d l a u n d r y p r o d u c t s

16

Textiles

14

Adhesives

12

Paper

10

Paint

9

Food

8

P h a r m a c e u t i c a l s a n d cosmetics Other

7 24

SOURCE: Reprinted from ref. 2. Copyright 1977 American Chemical Society. S t a r c h a n d D e x t r i n s . S t a r c h is a r e a d i l y available m i x t u r e o f p o l y s a c c h a rides.

S t a r c h y foods have been a n i m p o r t a n t component

o f t h e h u m a n diet

f r o m p r e h i s t o r i c times t o t h e present day. I t is n o t s u r p r i s i n g , therefore, t h a t very p r a c t i c a l uses for s t a r c h p r o d u c t s developed very early a n d have c o n t i n u e d t h r o u g h o u t h u m a n h i s t o r y . T o d a y , s t a r c h has a n u m b e r o f a p p l i c a t i o n s n o t o n l y i n t h e f o o d i n d u s t r y b u t i n other industries as w e l l . I n a d d i t i o n t o i t s use i n f o o d , s t a r c h is also a source o f chemicals (41) a n d sweeteners (42) a n d is used extensively i n t h e paper i n d u s t r y (43-45) as a s i z i n g agent a n d a n adhesive. T h e u t i l i z a t i o n o f s t a r c h as a n adhesive c a n be t r a c e d a t least t o 3,500-4,000 B . C . , w h e n i t was used b y the E g y p t i a n s t o b o n d p a p y r u s s t r i p s . T o d a y , s t a r c h a n d d e x t r i n s derived f r o m s t a r c h f i n d a v a r i e t y o f a p p l i c a t i o n s i n adhesives (46). D r . H . M . K e n n e d y o f G r a i n Processing C o r p o r a t i o n presents a detailed overview o f the use o f s t a r c h a n d d e x t r i n s i n C h a p t e r 2 3 . C e l l u l o s i c s . C e l l u l o s e is t h e m a j o r c h e m i c a l constituent o f p l a n t s . I t is a h o mogeneous p o l y s a c c h a r i d e f o r m e d f r o m /?-D-glucopyranose u n i t s l i n k e d together



T a b l e I I . E x a m p l e s of the Use of N a t u r a l G u m s i n A d h e s i v e s Gum


Agar

Applications Pressure sensitive t a p e A d h e s i v e i n gloss finishing paper p r o d u c t s D e n t u r e adhesives C l e a r adhesive a p p l i c a t o r c r a y o n B i n d e r for s i l i c a gel T L C plates

Algin

Pharmaceutical tablet binder A d h e s i v e for miscellaneous paper products Adhesive i n combination w i t h a n i m a l glues W a t e r remoistenable adhesive (especially for postage s t a m p s )

Funoran

7 8 9 10 11

V i s c o s i t y s t a b i l i z e r for s t a r c h d e x t r i n a n d l a t e x - t y p e adhesives used for c o r r u g a t e d boards

G u m Arabic

References

12-14 15 4,16 17

A d h e s i v e for glassine p a p e r W a l l p a p e r paste

18 19 20

A d h e s i v e for regenerated cellulose

18

H o u s e h o l d adhesive

21-23

A d h e s i v e for w o o d a n d paper

24,25

Guar G u m

M e d i c i n a l adhesives

26-28

G u m Karaya

D e n t u r e adhesive M e d i c i n a l adhesives

28\ 31-35

Tamarind

P a p e r adhesives L a b e l pastes

36 36

L a b e l pastes E x t e n d e r for urea-formaldehyde

37

adhesives

G u m T r agaçant h

26-28

Pharmaceutical tablet binder

38 1

D e n t u r e adhesive L a b e l i n g adhesive

40

39


20.

CONNER

275


by (1—^4)-glycosidic b o n d s . I n a d d i t i o n t o cellulose use i n p a p e r a n d t e x t i l e s , a large n u m b e r o f cellulose derivatives are p r o d u c e d c o m m e r c i a l l y . T h e s e d e r i v a tives are f o r m e d by either esterification or etherification o f the a v a i l a b l e h y d r o x y l groups. A range o f p r o d u c t s w i t h a v a r i e t y of p h y s i c a l properties h a v i n g a n u m ber of i m p o r t a n t c o m m e r c i a l uses is o b t a i n e d

(47-51).

C e l l u l o s e forms the b a c k b o n e of m a n y i m p o r t a n t i n d u s t r i a l adhesives

(52).

Professor D a v i d H o n of C l e m s o n U n i v e r s i t y reviews the use of cellulosic adheDownloaded by NANYANG TECHNOLOGICAL UNIV on June 8, 2016 | http://pubs.acs.org Publication Date: December 31, 1989 | doi: 10.1021/bk-1989-0385.ch020

sives i n C h a p t e r 2 1 . H e m i c e l l u l o s e . Hemicelluloses are a n o n c r y s t a l l i n e g r o u p o f heterogeneous polysaccharides t h a t , next t o cellulose, c o n s t i t u t e the m o s t a b u n d a n t source of c a r b o h y d r a t e s i n p l a n t s . L i k e cellulose, the hemicelluloses are l o c a t e d i n the cell w a l l of p l a n t s a n d i n the bast fibers o f b a r k . O n h y d r o l y s i s , cellulose gives o n l y glucose. H y d r o l y s i s of hemicelluloses y i e l d a m i x t u r e o f D-glucose, D - m a n n o s e , D - x y l o s e , D-galactose, L-arabinose, a n d s m a l l a m o u n t s of D - g l u c u r o n i c a c i d , 4 - O - m e t h y l - D - g l u c u r o n i c a c i d , a n d D - g a l a c t u r o n i c a c i d . G . H . v a n der K l a s h o r s t of the N a t i o n a l T i m b e r Research I n s t i t u t e , P r e t o r i a , S o u t h A f r i c a , discusses the use of a s o d a bagasse hemicellulose i n a corrugated b o a r d adhesive i n C h a p t e r 22. Chitin.

C h i t i n refers t o the

fibrillar

acetamido-2-deoxy-D-glucopyranose

p o l y m e r f o r m e d f r o m /?(1—>4) l i n k e d 2-

u n i t s (53,54)-

is u s u a l l y i n c o m p l e t e . T h e t e r m chitosan

T h e N - a c e t y l a t i o n of c h i t i n

is generally used w h e n the n i t r o g e n

content is greater t h a n 7% b y weight; also, t h i s t e r m is generally used for a r t i f i c i a l l y deacetylated c h i t i n s . C h i t i n a n d chitosan are the o n l y n a t u r a l l y o c c u r r i n g polysaccharides t h a t are basic i n character. C h i t i n c a n be i s o l a t e d f r o m a large n u m b e r o f o r g a n i s m s , i n c l u d i n g insects, f u n g i , a n d crustaceans. C h i t i n is the m a j o r source of g l u c o s a m i n e , w h i c h is used i n significant q u a n tities by the p h a r m a c e u t i c a l i n d u s t r y . I n a d d i t i o n , c h i t i n a n d c h i t o s a n find a n u m b e r of other m e d i c a l uses i n c l u d i n g a r t i f i c i a l k i d n e y m e m b r a n e s , b i o d e g r a d able p h a r m a c e u t i c a l carriers, a n d b l o o d a n t i c o a g u l a n t s . I n d u s t r i a l l y , c h i t i n is used also as a c h e l a t i n g agent for t o x i c m e t a l s , as paper a n d t e x t i l e a d d i t i v e s , i n t e x t i l e finishes, i n p h o t o g r a p h i c p r o d u c t s a n d processes, a n d for d e w a t e r i n g m u n i c i p a l sludges. C h i t i n a n d i t s derivatives are k n o w n to occur i n n a t u r a l adhesive systems a n d have been suggested b y several researchers as adhesives for b o n d i n g v a r i o u s m a t e r i a l s together. B a r n a c l e s secrete a n adhesive to a t t a c h themselves to rocks, s h i p s , a n d other objects. T h i s adhesive hardens r a p i d l y , even i n seawater. T h i s adhesive, w h i c h is p r e d o m i n a t e l y c a l c i u m c a r b o n a t e i n a proteinaceous m a t r i x , c o n t a i n s c h i t i n (55).

E g g s o f lice are attached to the bristles of hogs by a very h y d r o l y s i s -

resistant adhesive t h a t contains c h i t i n a n d p-benzoquinone

(56).

S o l u t i o n s of c h i t o s a n salts are well k n o w n for t h e i r adhesive properties

(53).

C h i t o s a n itself adheres well to n o n c o n d u c t i n g surfaces, such as p a p e r , r a y o n , cellophane, w o o d , leather, r u b b e r , a n d glass, b u t not to m e t a l surfaces

(57,58).

F o r s m o o t h surfaces, a stronger b o n d is f o r m e d by first a p p l y i n g a t h i n p r i m e r



276

coat. T h e use of c h i t o s a n for the m a n u f a c t u r e o f safety glass, p l y w o o d , l a m i n a t e d p a p e r , a n d f u r n i t u r e was p a t e n t e d (59). T h e adhesive develops considerable water resistance w h e n t h o r o u g h l y d r i e d , heated at 100-150 ° C for a short t i m e , or c h e m i c a l l y t r e a t e d . C h e m i c a l t r e a t m e n t consists of either r e a c t i o n w i t h a m m o n i a or a l k a l i to f o r m a n i n s o l u b l e c h i t o s a n , w a s h i n g w i t h a n a c i d s o l u t i o n


t o f o r m the i n s o l u b l e c h i t o s a n s a l t , or i n c o r p o r a t i o n of f o r m a l d e h y d e i n t o the adhesive. C h i t o s a n has been r e p o r t e d to be a n excellent b i n d e r for p e l l e t i z e d fertilizers a n d feeds (60). X a n t h a t i o n of c h i t i n w i t h c a r b o n disulfide gives a viscous golden b r o w n s o l u t i o n t h a t some c l a i m to be useful as a n adhesive i n the p r o d u c t i o n of p l y w o o d a n d h a r d b o a r d (61). Bacterial Polysaccharides.

M a n y b a c t e r i a l species release

exopolysaccha-

rides i n t o t h e i r e n v i r o n m e n t . T h e synthesis of capsular a n d s l i m e p o l y s a c c h a rides or s i m i l a r s t i c k y surface m a t e r i a l s serves as a n adhesive to a t t a c h the b a c t e r i a t o s o l i d substrates, even i n a m a r i n e e n v i r o n m e n t . T h e s e polysaccharides range f r o m c o m p o s i t i o n a l l y s i m p l e h o m o p o l y m e r s to very c o m p l e x

heteropoly-

mers c o m p o s e d of several i n d i v i d u a l sugars l i n k e d i n a variety of ways. M o d i f i e d P o l y m e r s . F u t u r e a p p l i c a t i o n s of c a r b o h y d r a t e p o l y m e r s or o l i g o mers derived f r o m these p o l y m e r s as adhesives w i l l depend o n m o d i f y i n g the p o l y m e r p r o v i d e d b y n a t u r e to give a c o m p o n e n t t h a t c a n undergo f u r t h e r c r o s s l i n k i n g to f o r m adhesive m a t e r i a l s . C a r b o h y d r a t e p o l y m e r s t y p i c a l l y have one p r i m a r y a n d two secondary h y d r o x y l groups. P o l y m e r s like c h i t i n c o n t a i n a n a m i n e group i n a d d i t i o n t o the h y d r o x y l groups.

These groups offer positions at w h i c h reactive moieties c a n

be a t t a c h e d . If these moieties are sufficiently reactive, a n d the s u b s t i t u t i o n of the h y d r o x y l s is adequate, t h e n one c o u l d f o r m a t h r e e - d i m e n s i o n a l p o l y m e r i c network d u r i n g a c u r i n g stage t h a t w o u l d f u n c t i o n as a n adhesive. T h e c a r b o h y drate p o l y m e r is a l r e a d y formed a n d therefore the degree of s u b s t i t u t i o n for the reactive group does not have to be large. I n fact, the p h y s i c a l properties of such reactive p o l y m e r s m i g h t be t a i l o r e d for use i n a variety of adhesive a p p l i c a t i o n s . T h e t r i c k , of course, is to find a c h e m i c a l c o m p o u n d t h a t c a n be reacted r e a d i l y w i t h the c a r b o h y d r a t e p o l y m e r t o give the desired reactive moitiés a l o n g the b a c k b o n e of the c a r b o h y d r a t e p o l y m e r . Here, the adhesives chemist w i l l have to b o r r o w f r o m a n d e x t e n d the work t h a t has been a n d is now b e i n g done o n the f o r m a t i o n of m o d i f i e d starches (62),

cellulosics (48-51,63,64),

and textiles.

Professor N a r a y a n of P u r d u e U n i v e r s i t y i l l u s t r a t e s the p o t e n t i a l adhesive a p p l i cations of grafted cellulosic p o l y m e r s i n C h a p t e r 24. I n the case of adherends such as w o o d , the p o s s i b i l i t y exists t h a t the c a r b o h y d r a t e p o l y m e r s or l i g n i n , or b o t h , can be m o d i f i e d in situ t o give a c t i v a t e d surfaces (65,66)

or surfaces c o n t a i n i n g reactive groups. T h e n , the surfaces are

b o n d e d b y direct r e a c t i o n or by r e a c t i o n w i t h a reactive, g a p - f i l l i n g c o m p o u n d .


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A n o t h e r interesting a p p r o a c h used to b o n d w o o d involves the s w e l l i n g (66) or d i s s o l u t i o n ( w i t h cellulose solvents) o f the c a r b o h y d r a t e m a t r i x (67) at the surface. B o n d i n g t h e n takes place w h e n t w o surfaces are b r o u g h t i n t o contact a n d the v o l a t i l e components e v a p o r a t e d b y h e a t i n g . C r o s s l i n k s f o r m t h r o u g h r e f o r m a t i o n o f Η-bonds or possible c o m p l e x f o r m a t i o n w i t h m e t a l ions, i n the case of cellulosic solvents.


Monosaccharides, Disaccharides, a n d Oligosaccharides i n Adhesives M o n o s a c c h a r i d e s (e.g., glucose), disaccharides (e.g., sucrose), a n d oligosaccha rides c a n be o b t a i n e d r e a d i l y f r o m n a t u r a l sources, either d i r e c t l y or by h y d r o l y s i s of n a t u r a l c a r b o h y d r a t e p o l y m e r s . These can be used to either m o d i f y s y n t h e t i c adhesive resins or t o replace t h e m altogether. I n a d d i t i o n , reactive derivatives c o u l d be synthesized f r o m these c o m p o u n d s a n d used t o f o r m u l a t e adhesive p o l y m e r s . M o d i f i e d S y n t h e t i c A d h e s i v e s . P h e n o l - f o r m a l d e h y d e (68) a n d u r e a - f o r m a l dehyde (69) are i m p o r t a n t s y n t h e t i c adhesives. P h e n o l - f o r m a l d e h y d e adhesives ( P F ) f i n d a v a r i e t y o f a p p l i c a t i o n s i n c l u d i n g b o n d e d abrasives, f o u n d r y a p p l i c a t i o n s , fiber b o n d i n g , a n d w o o d b o n d i n g . U r e a - f o r m a l d e h y d e adhesive resins ( U F ) are used generally to b o n d w o o d p r o d u c t s . I w i l l i l l u s t r a t e the m o d i f i c a t i o n o f s y n t h e t i c adhesives w i t h c a r b o h y d r a t e s u s i n g b o t h these general types o f adhesives. F i g u r e 1 i l l u s t r a t e s the fact t h a t resins a n d adhesives f o r m e d by the possible c o m b i n a t i o n s o f a phenolic c o m p o u n d , a nitrogenous c o m p o u n d , a n aldehyde c o m p o u n d , a n d a c a r b o h y d r a t e have been r e p o r t e d i n the l i t e r a t u r e . T h e exact c o n d i t i o n s used to f o r m u l a t e the resins a n d adhesives represented i n F i g u r e 1 v a r y considerably. F o r e x a m p l e , a d d i t i o n a l circles representing a c i d i c , basic, a n d n e u t r a l r e a c t i o n c o n d i t i o n s c o u l d be a d d e d . I n m o s t instances, the exact c h e m i s t r y t h a t occurs d u r i n g the f o r m u l a t i o n of resins at each intersection is not k n o w n . Indeed, i n m a n y cases, the component a c t u a l l y r e a c t i n g i n t o the resin or adhesive s y s t e m m a y not be the o r i g i n a l c a r b o h y d r a t e a d d e d at the s t a r t . I n t h i s a n d other respects, these f o r m u l a t i o n s w i l l overlap w i t h those discussed i n the next section. T a b l e III lists a n u m b e r o f selected references t h a t describe the f o r m u l a t i o n of resins or adhesives at each intersection i n F i g u r e 1. P F , U F , U F m o d i f i e d w i t h phenolics, a n d P F m o d i f i e d w i t h nitrogenous c o m p o u n d s (e.g., urea) have n o t been i n c l u d e d , because they do not c o n t a i n c a r b o h y d r a t e s a n d because they are i n c o m m o n use. T h e resin a n d adhesive systems t h a t have been investigated m o s t recently are those f o r m e d by the c o m b i n a t i o n of c a r b o h y d r a t e s w i t h P F , b o t h w i t h a n d w i t h o u t the a d d i t i o n of a nitrogenous c o m p o u n d . O u r a t t e m p t s at the Forest P r o d u c t s L a b o r a t o r y to use c a r b o h y d r a t e m o d i f i e d P F to b o n d w o o d are discussed i n C h a p t e r 25. T h e i n c o r p o r a t i o n of a nitrogenous c o m p o u n d ( t y p i c a l l y u r e a or a m m o n i a ) modifies the o v e r a l l c h e m i s t r y d u r i n g adhesive f o r m u l a t i o n , a p p a r e n t l y i n a



278


F i g u r e 1. R e s i n s c a n be classified as b e i n g f o r m e d f r o m c o m b i n a t i o n s of a phen o l i c c o m p o u n d ( P ; t y p i c a l l y p h e n o l ) , a n aldehyde ( A ; t y p i c a l l y f o r m a l d e h y d e ) , a nitrogenous c o m p o u n d ( N ; t y p i c a l l y urea), a n d a c a r b o h y d r a t e ( C ) .


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beneficial m a n n e r . T h i s is especially t r u e w h e n the resins are f o r m u l a t e d under basic c o n d i t i o n s w i t h r e d u c i n g c a r b o h y d r a t e s t h a t are r e a d i l y degraded at basic p H s . D r . C h r i s t i a n s e n of the Forest P r o d u c t s L a b o r a t o r y a n d Professor K a r c h esy of O r e g o n S t a t e U n i v e r s i t y discuss t h e i r experiences w i t h c a r b o h y d r a t e p h e n o l - u r e a based adhesive resins i n C h a p t e r s 26 a n d 27.


T a b l e I I I . Selected References t h a t D e s c r i b e the F o r m u l a t i o n o f Resins and Adhesives N a m e d i n Figure 1 System

1

Phenol-Carbohydrate ( P C ) Phenol-Aldehyde-Carbohydrate ( P A C ) Phenol-Nitrogenous compound-Carbohydrate ( P N C ) Nitrogenous compound-Carbohydrate ( N C ) Nitrogenous compound-Aldehyde-Carbohydrate ( N A C ) Phenol-Nitrogenous compoundAldehyde-Carbohydrate ( P N A C ) Carbohydrate-Aldehyde ( C A ) 1

References 70- 79 80-94 70,95-98 78,99-103 99,104-113 114-123 108,124-126

A c r o n y m s c o r r e s p o n d t o those used i n F i g u r e 1.

Professor V i s w a n a t h a n o f the U n i v e r s i t y of A r k a n s a s discusses his research i n t o the f o r m u l a t i o n of formaldehyde-free, t h e r m o s e t t i n g adhesives f r o m whey permeate w i t h u r e a a n d p h e n o l or b o t h i n C h a p t e r 28. P o l y m e r i c c a r b o h y d r a t e s o f a n u n d e t e r m i n e d degree o f p o l y m e r i z a t i o n have also been used to m o d i f y s y n t h e t i c adhesive resins. I n p a r t i c u l a r , cellulosic p a p e r m i l l sludges have been used to m o d i f y P F a n d U F resins (127). A carb o h y d r a t e p o l y m e r was r e p o r t e d to be a n excellent extender a n d m o d i f i e r for p o l y v i n y l a l c o h o l adhesives (128). A t h e r m o s e t t i n g / t h e r m o p l a s t i c adhesive has been r e p o r t e d t h a t is c o m p o s e d o f a p r o t e i n (i.e., a n i m a l glue) c o n t a i n i n g lignosulfonate a n d a c a r b o h y d r a t e or p o l y h y d r i c a l c o h o l (129). A l t h o u g h t h i s is not a n e x a m p l e o f the m o d i f i c a t i o n o f a s y n t h e t i c adhesive, i t does f u r t h e r i n d i c a t e the w i d e range o f adhesive types t h a t have been m o d i f i e d w i t h c a r b o h y d r a t e s . A l s o , i t is i n t e r e s t i n g to note the further connection between a nitrogenous c o m p o n e n t (protein) a n d a carbohydrate. R e p l a c e m e n t o f S y n t h e t i c A d h e s i v e s . T o t a l replacement of s y n t h e t i c a d hesives w i t h a n adhesive s y s t e m based e n t i r e l y o n c a r b o h y d r a t e s , except as i n d i c a t e d above (i.e., N C a n d C A ) , has not been r e p o r t e d . A n d , as discussed above, i t is not clear t h a t the c a r b o h y d r a t e i n fact is r e a c t i n g as the c a r b o h y d r a t e component t h a t was o r i g i n a l l y a d d e d . C a r b o h y d r a t e - b a s e d adhesives, i n w h i c h the f o r m u l a t i o n begins w i t h the c a r b o h y d r a t e , have been r e p o r t e d (130), b u t the a c i d s y s t e m used d u r i n g form u l a t i o n r e a d i l y degrades the o r i g i n a l c a r b o h y d r a t e to f u r a n i n t e r m e d i a t e s t h a t


280


p o l y m e r i z e . T h e f o r m u l a t e d resins are subsequently m i x e d w i t h c r o s s l i n k i n g agents (formaldehyde o r t r i e t h y l e n e t e t r a m i n e ) p r i o r t o c u r i n g .


Stofko (131-133) has r e p o r t e d a n i n t e r e s t i n g adhesive s y s t e m for w o o d p r o d ucts i n w h i c h c a r b o h y d r a t e is p r e s u m a b l y converted t o f u r f u r a l a n d h y d r o x y m e t h y l f u r f u r a l in situ, r e a c t i n g w i t h b o t h t h e l i g n i n i n w o o d a n d h o m o p o l y m e r i z i n g i n t h e b o n d l i n e t o f o r m the adhesive j o i n t . R e a c t i v e D e r i v a t i v e s . A s w i t h t h e p o l y m e r i c c a r b o h y d r a t e s , one m e t h o d t h a t m i g h t l e a d t o f u t u r e u t i l i z a t i o n o f c a r b o h y d r a t e s as adhesives involves t h e f o r m a t i o n o f reactive derivatives attached a t t h e h y d r o x y Is. T h i s w o u l d give a c o m p o n e n t capable o f c r o s s l i n k i n g t o f o r m adhesive p o l y m e r s . Here a g a i n , t h e adhesives chemist w i l l have t o b o r r o w f r o m a n d e x t e n d t h e work t h a t has been a n d is n o w b e i n g done o n the f o r m a t i o n o f m o d i f i e d starches, cellulosics, a n d textiles. T w o interesting reactive groups t h a t m i g h t b e considered, at least for p u r poses o f i l l u s t r a t i o n , are the a l l y l (134) d v i n y l groups (135). T h e p r e p a r a t i o n of a l l y l ethers o f c a r b o h y d r a t e s a n d their p o l y m e r i z a t i o n have been described (136-138). T h e i r p o l y m e r i z a t i o n is slow even w i t h added c a t a l y s t s s u c h as peroxides. A l l y l s t a r c h was s t u d i e d a t the Forest P r o d u c t s L a b o r a t o r y i n t h e m i d - f o r t i e s as a n adhesive for w o o d , b u t w i t h o u t success. T h e p r e p a r a t i o n o f v i n y l cellulose (139) a n d v i n y l c a r b o h y d r a t e s (140) has been described. T h e p o l y m e r i z a t i o n o f 6- O - v i n y l - 1 , 2 : 3 , 4 - d i - O-isopropylidene-D-galactopyranose has been investigated (140). V e r y h i g h m o l e c u l a r weight p o l y m e r s were o b t a i n e d i n r e l a t i v e l y short r e a c t i o n times. C o m p o u n d s such as these o r t h e i r further react i o n p r o d u c t s (e.g., epoxides) m i g h t b e useful i n adhesives, especially i f m e t h o d s c o u l d be f o u n d for i n c r e a s i n g t h e r a p i d i t y w i t h w h i c h they p o l y m e r i z e . a

n

Carbohydrate Degradation Products i n Adhesives T h e r e a c t i o n o f c a r b o h y d r a t e s i n a c i d or a l k a l i n e s o l u t i o n results i n a n u m b e r o f p r o d u c t s , m a n y o f w h i c h have been identified over t h e past c e n t u r y (141)> W i t h the e x c e p t i o n o f anhydrosugars (e.g., l,6-anhydro-/?-D-glucopyranose) a n d oligosaccharides, w h i c h are concentration-dependent a n d e q u i l i b r i u m c o m p o nents (reversion p r o d u c t s ) f o r m e d i n a c i d s o l u t i o n , a l l o f these p r o d u c t s result f r o m reactions associated w i t h the L o b r y de B r y n - A l b e r d a V a n E k e n s t e i n t r a n s f o r m a t i o n o r intermediates f o r m e d f r o m t h i s t r a n s f o r m a t i o n . In a c i d s o l u t i o n , pentoses a n d hexoses f o r m fur an c o m p o u n d s . Pentoses give h i g h y i e l d s o f 2-furaldehyde ( f u r f u r a l ) . Hexoses give 5 - ( h y d r o x y m e t h y l ) - 2 furaldehyde ( h y d r o x y m e t h y l f u r f u r a l ) , w h i c h c a n further react t o give l e v u l i n i c acid and polymeric materials. It is interesting t o speculate t h a t these c o m p o u n d s , b o t h because o f t h e i r r e a c t i v i t y a n d t h e i r a b i l i t y t o f o r m p o l y m e r i c m a t e r i a l s , m i g h t be useful i n adhesives f o r m u l a t i o n s .


20.

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CONNER

F u r a n s . T h e last statement is c e r t a i n l y true o f furans derived f r o m sugars (142,143), p a r t i c u l a r l y f u r f u r a l a n d f u r f u r y l a l c o h o l , w h i c h is r e a d i l y derived f r o m f u r f u r a l (144)- D r . M c K i l l i p o f Q O C h e m i c a l s discusses f u r a n resin c h e m i s t r y a n d f u r a n p o l y m e r s i n C h a p t e r 29. D r . S t a n f o r d a n d h i s colleagues at t h e U n i v e r s i t y o f M a n c h e s t e r I n s t i t u t e o f Science a n d T e c h n o l o g y discuss t h e use o f a d i i s o c y a n a t e d e r i v e d f r o m f u r f u r a l for p o l y u r e t h a n e p r o d u c t i o n i n C h a p t e r 30.


L e v u l i n i c A c i d . L e v u l i n i c a c i d is f o r m e d b y t h e a c i d c a t a l y z e d d e g r a d a t i o n o f hexose sugars v i a t h e i n t e r m e d i a c y o f h y d r o x y m e t h y l f u r f u r a l (145). A l t h o u g h its f o r m a t i o n was r e p o r t e d as e a r l y as 1836 (145), the m e c h a n i s m o f i t s f o r m a t i o n has been s t u d i e d at least as recently as 1985 (147)L e v u l i n i c a c i d is a h i g h l y reactive keto a c i d t h a t is r e a d i l y a v a i l a b l e f r o m renewable m a t e r i a l s . It has been proposed as a renewable basic c h e m i c a l r a w m a t e r i a l (148-150) t h a t c a n be used for a v a r i e t y o f purposes. These uses i n c l u d e plasticizers, p h a r m a c e u t i c a l s , solvents, f o o d a d d i t i v e s ,

flavoring

compounds,

c h e m i c a l intermediates, a n d resins a n d p o l y m e r s . R e c e n t l y , a - a n g e l i c a l a c t o n e , w h i c h is f o r m e d o n d i s t i l l a t i o n o f l e v u l i n i c a c i d b y t h e loss o f a molecule o f water, h a s been p r o p o s e d as a l i q u i d fuel extender

(151).

D i p h e n o l i c a c i d , t h e condensation p r o d u c t o f l e v u l i n i c a c i d a n d p h e n o l , is useful i n the p r e p a r a t i o n o f modified p h e n o l - f o r m a l d e h y d e

resins, polyether

resins, o r as m o n o c a r b o x y l i c a c i d c h a i n stoppers i n a l k y d resins (152).

It can

be s u b s t i t u t e d for b i s p h e n o l - A , t h e p r i m a r y r a w m a t e r i a l i n the p r o d u c t i o n o f e p o x y resins

(153).

Several interesting resins a n d p o l y m e r s have been o b t a i n e d f r o m l e v u l i n i c acid.

These a n d s i m i l a r p o l y m e r s m i g h t have p o t e n t i a l a p p l i c a t i o n i n adhe-

sives.

A h e a t - s e t t i n g resin was p r o d u c e d f r o m a fusion o f l e v u l i n i c a c i d a n d

amines (154)-

T h e resins were described as h a r d a n d t o u g h w i t h g o o d adhesion

t o glass. L e v u l i n i c a c i d reacts r a p i d l y w i t h f o r m a l d e h y d e ; a h a r d , flexible, i n fusible resin is f o r m e d (155).

T h e preparation of polyamides from furfural and

l e v u l i n i c a c i d has been described (156).

Adhesive compositions having good

water resistance were prepared f r o m a t a c t i c p o l y p r o p y l e n e a n d l e v u l i n i c a c i d (157) . T h i s adhesive was used for b o n d i n g p o l y p r o p y l e n e t o itself or t o p l a s t i c s , wood, a n d paper. C o p o l y m e r i z a t i o n of butadiene w i t h dichloroallyl levulinate (158) or w i t h m e t h y l or e t h y l l e v u l i n a t e (159) gives c o p o l y m e r s w i t h r u b b e r l i k e properties. Levoglucosan.

Levoglucosan, l,6-anhydro-/?-D-glucopyranose,

is a t h e r m a l

d e g r a d a t i o n p r o d u c t o f m a t e r i a l s c o n t a i n i n g cellulose o r other polysaccharides f o r m e d f r o m D-glucose. U s u a l l y , i t is p r o d u c e d b y p y r o l y s i s in vacuo o f cellulose, s t a r c h , or w o o d . A m e t h o d for i s o l a t i n g levoglucosan f r o m lignocellulose p y r o l ysis has been p a t e n t e d (160).

T h e synthesis o f levoglucosan has been reviewed

{161). V a r i o u s reports i n t h e l i t e r a t u r e i n d i c a t e t h a t levoglucosan m i g h t b e o f i n terest i n r e l a t i o n t o adhesives. T h e i n d i c a t i o n s are t h a t levoglucosan a n d i t s derivatives c a n undergo r i n g - o p e n i n g p o l y m e r i z a t i o n , t h a t reactive derivatives


282



of levoglucosan c a n be p r o d u c e d a n d used to f o r m p o l y m e r s , a n d t h a t p h e n o l , a m a j o r adhesive c o m p o n e n t now p r o d u c e d f r o m p e t r o l e u m , c a n be synthesized f r o m levoglucosan. L e v o g l u c o s a n has been p o l y m e r i z e d either t h e r m a l l y or i n the presence of a c i d c a t a l y s t s , such as z i n c chloride a n d m o n o c h l o r o a c e t i c a c i d , t o give o l i g o - a n d polysaccharides (161,162). T h e m o l e c u l a r weight a n d y i e l d s of the final p o l y mers are s t r o n g l y dependent o n the e x p e r i m e n t a l c o n d i t i o n s . C o p o l y m e r i z a t i o n w i t h alcohols a n d ethers has been r e p o r t e d . A l t h o u g h the exact structures of the r e s u l t i n g p o l y m e r i c systems are not k n o w n , they appear t o offer p r o m i s e for the p r e p a r a t i o n of adhesives a n d lacquers (162), a l t h o u g h no specific references to the use of these p o l y m e r s as adhesives were f o u n d . R i n g - o p e n i n g p o l y m e r i z a t i o n of the 2 , 3 , 4 - t r i - O - s u b s t i t u t e d levoglucosan, esp e c i a l l y the b e n z y l ether, has generally proven m o r e successful t h a n p o l y m e r i z a t i o n o f the u n s u b s t i t u t e d levoglucosan a n d y i e l d s polysaccharides of h i g h m o l e c u l a r weight (161,162). I n either case, the p o l y m e r i z a t i o n c o n d i t i o n s rep o r t e d i n the l i t e r a t u r e , especially i n terms of t i m e , t e m p e r a t u r e , a n d c a t a l y s t s , p r o b a b l y w o u l d preclude p o l y m e r i z a t i o n w i t h i n the b o n d l i n e . However, the p o s s i b i l i t y o f r i n g - o p e n i n g p o l y m e r i z a t i o n afforded by t h i s c o m p o u n d a n d s i m i l a r anhydrosugars w o u l d suggest t h a t further research m i g h t be w a r r a n t e d . T w o i n t e r e s t i n g p o l y m e r i c systems have been f o r m e d f r o m reactive l e v oglucosan derivatives a n d w i l l serve to i n d i c a t e the p o s s i b i l i t i e s of t h i s a p p r o a c h . T h e s e two systems are l , 6 - a n h y d r o - 2 , 3 , 4 - t r i - 0 - m e t h a c r y l - / ? - D - g l u c o p y ranose a n d the c o r r e s p o n d i n g t r i - O - a c r y l derivative (163). T h e y were p o l y m e r ized w i t h b e n z o y l peroxide as r a d i c a l i n i t i a t o r to give a t h r e e - d i m e n s i o n a l s t r u c ture w i t h a t h e r m a l d e g r a d a t i o n t e m p e r a t u r e of 300 ° C . T h e second p o l y m e r i c s y s t e m c a n be f o r m e d f r o m l , 6 - a n h y d r o - 2 , 3 , 4 - t r i - i ) - g l y c i d y l - / ? - D - g l u c o p y r a n o s e u s i n g a n a m i n e c a t a l y s t (164)· T h i s c o m p o u n d is f o r m e d b y e p o x i d a t i o n of the t r i - O - a l l y l d e r i v a t i v e of levoglucosan. P h e n o l a n d s u b s t i t u t e d phenols c a n be o b t a i n e d f r o m l i g n i n by p y r o l y s i s , a l k a l i f u s i o n , a n d hydrogenolysis (165-167). T h i s m e t h o d o l o g y c o u l d be used t o prepare a n adhesive s t a r t i n g m a t e r i a l , presently o b t a i n e d f r o m p e t r o l e u m sources, f r o m a renewable source, a l t h o u g h t e c h n i c a l difficulties require s o l u t i o n t h r o u g h f u r t h e r research. T h e conversion of levoglucosan derivatives to p h e n o l i n reasonable y i e l d s has been r e p o r t e d (168-175). T h i s affords the p o s s i b i l i t y of also o b t a i n i n g p h e n o l f r o m the cellulose p o r t i o n of renewable resources. T h e r e a c t i o n is c a r r i e d out i n l i q u i d a m m o n i a w i t h s o d i u m m e t a l a n d thus p r o b a b l y is i m p r a c t i c a l o n a c o m m e r c i a l scale. B u t further research m i g h t lead to s i m p l e r , less costly, a n d m o r e efficient m e t h o d s for t h i s conversion. Conclusions C a r b o h y d r a t e s are r e a d i l y available f r o m renewable biomass sources. I n t h i s i n t r o d u c t i o n , I have given a b r o a d overview of how c a r b o h y d r a t e p o l y m e r s ,


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o l i g o m e r s , m o n o m e r s , a n d d e g r a d a t i o n p r o d u c t s h i s t o r i c a l l y have been u t i l i z e d i n a n d for adhesives. I n a d d i t i o n , I have p o i n t e d o u t some e x a m p l e s o f where research m i g h t f u r t h e r t h e use o f c a r b o h y d r a t e s as adhesive r a w m a t e r i a l s . The

replacement o f p e t r o l e u m - d e r i v e d (nonrenewable) sources o f adhesive

raw m a t e r i a l s w i t h renewable sources w i l l follow three basic strategies: 1) r e newable m a t e r i a l s w i l l be used t o replace p a r t o f the r e q u i r e d p e t r o l e u m - d e r i v e d adhesive systems, 2) n e w p o l y m e r i c adhesives w i l l b e synthesized f r o m renew Downloaded by NANYANG TECHNOLOGICAL UNIV on June 8, 2016 | http://pubs.acs.org Publication Date: December 31, 1989 | doi: 10.1021/bk-1989-0385.ch020

able m a t e r i a l s a n d t o t a l l y replace p e t r o l e u m - d e r i v e d adhesive systems, or 3) the adhesives systems n o w based o n p e t r o l e u m - d e r i v e d m a t e r i a l s w i l l continue t o be used, b u t t h e adhesive r a w m a t e r i a l s w i l l be derived f r o m renewable sources i n stead o f f r o m nonrenewable ones. C a r b o h y d r a t e s are very versatile chemicals t h a t c a n be u t i l i z e d i n a l l three strategies as d e m o n s t r a t e d b y t h e preceding discussion.

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