Vol. 7, No.

1, January-February 1974 Simulation of Reactions with Lignin by Computer 17

be used as an approximate measure of the extent of an
otherwise difficult to characterize compositional hetero-
geneity.
For example, copolymers A, B, and C of Table I proba-
bly contain some relatively longer sequences of acryloni-
trile since the estimate of the average acrylonitrile se-
quence length based on Rz is much larger than those
based either on Ri or the final composition. Naturally,
this kind of measure is more accurate for that range of co-
polymer composition in which very long sequences are not
likely (which is the case for the copolymers of Table I).
This is true since the actual nmr measurement is in terms
of triads. Thus, the measure of deviations from theoretical
predictions of average sequence lengths is most sen-
sitive for those lengths which are on the order of about
2-4, or approximately the length of a triad.

Simulation of Reactions with Lignin by Computer (SIMREL). I.

Polymerization of Coniferyl Alcohol Monomers1
Wolfgang G. Glasser*2 and Heidemarie R. Glasser26
3456®

Department of Forestry and Forest Products, Virginia Polytechnic Institute and State University,
Blacksburg, Virginia. Received June 6, 1973
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ABSTRACT: A computer program was written to simulate the formation of a dehydrogenation polymer of coni-
feryl alcohol starting with a monomer of the type C9H9O2OCH3 with another monomer of the same type, forming
a polymer of up to 100 units (aglomerated monomers). Coupling reactions are selected according to a statistical
distribution of predetermined values found in the literature. Coupling modes include combinations of any of four
radical species leading to previously reported interunit bonds. Tables are printed out giving the reaction sequence
and the percentage figures of the reaction types at the time of simulation. A summary with the final configura-
tion of the polymer is printed at the end of the simulation run, also listing a modified Rydholm diagram and
other tables. The simulation mechanism is based on code numbers of molecule positions in C9 units that identify
chemical elements and reactivity coefficients and that decide upon the possibility of a molecule position to per-
form a reaction. Three states of reactivity are possible: reactive, not reactive, and “latent.” A “latent reactivity”
classifies a reaction as possible with the exception that a statistical percentage figure does not permit further
reaction with this particular position because a prescribed analytical value is lower or equal to one being comput-
ed. The SIMREL program searches for a reactive position in the polymer under formation and performs a reac-
tion with a new monomer unless it is statistically impossible; then, the reactive position is converted into a latent
one. A limit on the number of units in the polymer or exhaustion of reactive positions terminates the simulation.

1. Introduction as an entirely homogeneous substance; recent indications

Lignin is known to be three-dimensionally branched
a
polyphenol, synthesized by some plants from phenylpro-
penoid precursors (for review, see ref 3-6). Enzymatically
triggered phenolic coupling has been recognized as the
motor of polymerization. Although this mechanism is
widely believed to proceed in a random manner, some
schemes have been proposed to the contrary.7·8 However,
one way or the other, there seems to be no doubt as to the
initial enzymatic control of its formation from coniferyl
alcohol and related phenylpropanes. If there is a control
mechanism that would cause lignin to form in “repeating
units,” it would be unique to the biochemistry of plants,
as other natural polyphenols such as tannins and phloba-
phenes are considered to be disordered polymers. Also, the
existence of such a control mechanism would probably
have little effect on the overall chemical makeup of lignin
and its reactions. The concept of lignin as a completely
ordered molecule might be as erroneous as that of lignin
(1) Part of the results have been presented in a paper given at the 4th
Canadian Wood Chemistry Symposium, held in Quebec, Canada,
July 4-6, 1973.
(2) (a) Assistant Professor of Wood Chemistry; (b) M. S., formerly a Re-
search Associate, College of Forest Resources, University of Washing-
ton, Seattle, Wash.
(3) K. V. Sarkanen and C. H. Ludwig, Ed., “Lignins—Occurrence, For-
mation, Structure and 'Reactions,” Wiley Interscience, New York, N.
Y„ 1971.
(4) K. Freudenberg and A. C. Neish, “Constitution and Biosynthesis of
Lignin,” Springer-Verlag, New York, N. Y., 1968.
(5) J. M. Harkin in “Oxidative Coupling of Phenols,” W. I. Taylor and A.
R. Battersby, Ed., Marcel Dekker Inc., New York, N. Y., pp 256-263.
(6) T. Higuchi, Advan. Enzymol., 34, 207 (1971).
(7) K. Forss and K. E. Fremer, Pap. Puu, 47, 443 (1965).
(8) K. Forss, K. E. Fremer, and B. Stenlund, Pap. Puu, 48, 565, 669
(1965).
obtained by several investigators are that lignin configura-
tion varies with its location in the cell structure.9"14 The
assumption that a statistical polymer formed essentially
randomly through a limited number of oxidative coupling
reactions of one, two, or three p-hydroxycinnamyl alcohol-
type phenols makes this substance well suited for mathe-
matical simulation by computer. Such mathematical
models have previously been used in the field of pulp and
paper technology to simulate pulping processes in terms of
such process parameters as liquor: wood ratio, chemical
charge, and reaction rates.15"22 These models allowed to
make reasonable predictions as to yields and lignin con-
tents of resulting pulps. However, no attempts have been
(9) B. J. Fergus and D. A. I. Goring, Holzforschung, 24, 113,118 (1970).
(10) R. Draganova and R. C. Simionescu, Cellulose Chem. Technol., 2, 359
(1968).
(11) R. Draganova, Tseluloza Khartiya, 2 (16), 17 (1971); cited in Abstr.
Bull, Inst. Pap. Chem., 43, 2790 (1973),
(12) R. Draganova, Cellulose Chem. Technol., 5, 451, 457, 463 (1971).
(13) O. P. Grushnikov and N. N. Shorygina, Usp. Khim., 40, 1394 (1971);
cited in Abstr. Bull. Inst. Pap. Chem., 42,11138 (1972).
(14) M. Matsukura and A. Sakakibara, Mokuzai Gakkaishi, 15, 35 (1969).
(15) T. J. Williams, Ind. Eng. Chem., 59, 53 (1967).
(16) J. Schmied, Papier (Darmstadt), 21 (10A), 672 (1967).
(17) A. J. Kerr, APPITA, 24,180 (1970).
(18) A. H. Morris, Pap. Traded., 152 (39), 42 (1968).
(19) Yu. N. Nepenin, I. S. Shul'man, V. P. Denisenko, . I. Ternitskii,
and I. A. Faradkhev, Mater. Nauch.’Tekh. Konf. Lesotekh. Akad., 1,
10 (1967), cited in Abstr. Bull. Inst. Pap. Chem., 41,4347 (1971).
(20) Yu. A. Makhov, Sb. Tr. TNII Bumagi, No. 4, 158 (1969); cited in
Abstr. Bull. Inst. Pap. Chem., 41,4345 (1971).
(21) I. E. V’Yukov, Sb. Tr. VNII Tsellyul.-Bumazh. Prom. No. 57, 204
(1970); cited in Abstr. Bull. Inst. Pap. Chem., 41,10268 (1971).
(22) I. E. V’Yukov, V. N. Smorodin, and I. V. Gornostaeva, Sb. Tr. VNII
Tsellyul.-Bumazh. Prom., No. 57, 245 (1970); cited in Abstr. Bull.
Inst. Pap. Chem., 41,10269 (1971),
18 Glasser, Glasser Macromolecules

Coniferyl alcohol Analytical literature data Table I

monomer Identification of Molecule Positions
steering ID Characterization
dehydrogenation
1 C
2 CH
reaction Relative frequency of 3 CH2OH
4 Radical species -
forming and coupling 4 OH
Ra> Rb’ Rc> Ra “kinetics” radical species 5 CH—OH
6 O
polymerization steering 7 CH2OR
mechanism 8 CO
9 CHD (double bond)
Content of 10 CHO
analysis^ functional groups 11 ch2
Dehydrogenation-polymer and types of 12 CHO—sugar
linkages 13 C—OCHs
Figure 1. Schematic outline of the principles of polymerization into radical species by “dehydrogenation.” The polymer is
used in the SIMREL model. subsequently formed by coupling reactions of radicals.
The distribution of such reactions in the SIMREL model
9CH.0H ‘ has been selected in accordance with analytical data pub-
I lished in the literature (cf. ref 3-5). The structural make-
8 CH
up of the polymer is monitored continuously, and the ob-
II tained analytical data are compared with the desired dis-
7 CH tribution of interunit bonds. Deviations of the two data
sets are used to influence the frequencies of formation and
types of coupling reactions of radicals in such a way that
the deviations are eliminated.
T OCH:i Monomeric phenylpropane units are coded with ten
10 0 molecule positions, as depicted in Figure 2. Each mole-
/ cule position is given an “identification” (ID) which char-
acterizes the type of substitution in this position. Identifi-
Figure 2. Codes used in phenylpropane units. cations are listed in Table I. Thus, a Cg unit is described
by molecule positions and identifications.
made to simulate the chemical reactions that are involved 2.1. Basic Types of Coupling Reactions. The simula-
in the formation and the reactions of lignin and to make tion of phenolic coupling reactions proceeds in accordance
predictions as to the chemical structure of this natural with established pathways. In Figure 3, the four presently
product. The objective of this investigation, therefore, is recognized mesomeric forms of the coniferyl alcohol radi-
to present a simulation of the formation of lignin following cal are shown which may lead to the formation of dimers
presently accepted concepts of mechanisms operative in by coupling. The theoretical number of combinations is 42
plants. This simulation is to result in a structural model =
16. However, this number is reduced to only five differ-
of lignin that satisfies analytical requirements obtained ent coupling patterns if all dimers resulting from radical
with various methods by several investigators and de-
type Rd, all “mirror images” (e.g., 8-10 vs. 10-8), and the
scribed in the literature. The success of this simulation theoretical peroxide resulting from the coupling of two Ra
will be tested by simulating reactions of lignin under a radical species are disregarded. These five inter-unit
variety of conditions and comparing observed with pre- bonds are as follows
dicted results. Since most studies with lignin have been
carried out using fragments of lignin such as model com- SARKANEN’S SIMREL
Code3 Code Synonym
pounds or mildly isolated lignin preparations comprising 8-10
0-O-4 0-aryl-ether
only small portions of the total material present in wood, 5-0-4 5-10 biphenyl ether
results cannot be applied to lignin in general. How well 0-0 8-8 pinoresinol
certain fragments represent lignin can probably best be 0-5 5-8 phenylcoumaran
judged after applying results obtained with fragments to 5-5 5-5 biphenyl
the polymer in a simulation model. By superimposing the
In the beginning stages of simulating lignin formation,
results of different reactions, degradations, and isolations
radical Ra was neglected, as its coupling behavior is large-
in a simulated lignin model, one might be able to discover
ly dependent upon side-chain substituents. It is suspected
discrepancies, interpret them, and even solve them. Sim- that the stabilization of a radical in position 1 of the
ple addition of results obtained with fragments might not is suppressed in favor of other
be representative for the macromolecule at all. Possibly,
phenylpropane monomer
positions, particularly in 8 and 10. In comparison to Ra,
changes will have to be made in the concept of lignin, as
Rb, and Rc it is expected that Ra has a low rate of forma-
much of the information on this polymer is based on the
tion. Freudenberg expressed the opinion that coupling
behavior of fragments. In addition to gaining information
with position 1 will probably occur only with those units
about the structure of lignin, the simulation model is ex-
that have already been incorporated in oligomers or poly-
pected to become a useful tool in assessing new reactions, mers.23 Therefore, Ra radicals were excluded from react-
determining theoretical yields and giving insight into in the simulation model, and its cou-
reaction kinetics. ing as monomers
pling reactions were introduced only in the higher mers.
2. Principles of Simulation Initially, polymerization was simulated by adding reac-
tive sites of monomers to reactive sites of the growing
The mathematical simulation of the polymerization of
coniferyl alcohol is schematically presented in Figure 1. (23) K. Freudenberg, K. Penzien, and H. Renner, Chem. Ber., 102, 1320
Monomeric phenylpropane units (Cg units) are converted (1969).
Vol. 7, No. 1, January-February 1974
CH2OH ch2oh
CH HC·
Figure 3. Mesomeric radicals of coniferyl alcohol.
polymer through one of the five different coupling pat-
terns resulting from Ra, Rt>, and Rc. Sites were thereby
defined as “reactive” if (1) there was a free phenolic hy-
droxyl group present, meaning position ten had identifica-
tion four, and (2) position five and/or eight was still avail-
able for coupling.
In order to prevent complete exhaustion of phenolic hy-
droxyl groups in the simulation model, through constantly
reacting all reactive sites, three different levels of REAC-
TIVITIES were introduced for molecule positions five,
eight, and ten. These three were: REAC 0: not reactive,
because the requirements described above are not satis-
fied; REAC 4: reactive; the requirements for reactive sites
are satisfied, and coupling may occur; REAC 3: latent;
the requirements for reactive sites are satisfied, but cou-
pling cannot occur because the statistical distribution of
coupling types or substituents in certain positions in the
already formed polymer does not permit a reaction. Con-
sequently each C9 unit in the simulation model was com-
pletely identified only with the codes MOLECULE POSI-
TION (1-10), IDENTIFICATION (1-13, expandable), and
REACTIVITY (0, 3, or 4).
2.2. Basic Coupling Reactions with Rd-Type Radicals
(Side-Chain Displacement Reactions). The participa-
tion of Rd-type radicals in the formation of lignin has first
been eluted from the observation of 1,2-diarylpropane de-
rivatives,24 which are apparently formed through coupling
of Rd and Rb with simultaneous displacement of the side
chain of Rd. Larsson and Miksche25 have since discovered
that the displacement of side chains is restricted to mole-
cules with benzyl alcohol groups. In addition, side-chain
displacements had also been observed with compounds
containing carbonyl groups in a position.26 Other substit-
uents in a position seem to favor coupling in position 6
rather than 1 with no elimination of the side chain, as
shown in Figure 4.25 Benzyl alcohol groups, however, are
results of coupling reactions in 0 position where the inter-
mediate quinone methide has added water. Such coupling
reactions in 0 position may be 0-0-4, 0-1, or in some in-
stances also 0-5 and 0-0. Consequently, displaced side
chains are actually not lost, but they remain attached to
(24) H. Nimz, Chem. Ber., 98, 3160 (1965); ibid., 99, 469, 2638 (1966).
(25) S. Larsson and G. E. Miksche, Acta Chem. Scand., 23, 917 (1969).
(26) J. C. Pew and W. J. Connors, J. Org. Chem., 34,585 (1969).
Simulation of Reactions with Lignin by Computer 19
C
C
Figure 4. Coupling of Rd-type radicals in dependence of substitu-
ents in the a position (after Larsson and Miksche, ref 25).
other Cg units. This mechanism also implies that side-
chain displacement reactions occur only after the Rd-
forming Cg unit has been incorporated in an oligomer or
polymer; coniferyl alcohol with a radical in position 1
would apparently couple with its position 6 (see Figure 4),
as was proposed by Larsson and Miksche.25
The computer simulation of reactions of Rd-type radi-
cals was, for the above reasons, limited to nonmonomeric
units. A further restraint was introduced in the SIMREL
program by requiring Rd-type radicals to be free of sub-
stituents in position 5 in order to guarantee a better mo-
bility of the displaced aromatic rings. This restraint, in all
probability, does not comply with lignin formation in
vivo. Theoretically, Rd-type radicals can lead to nine dif-
ferent coupling modes as illustrated in Table II. Only four
of them have been observed;25·27 these are the 1-5, 1-0-4,
0-1, and 5-6 linkage. The 6-0-4 linkage has been searched
for, but was not detected;27 it appears to be absent. Three
other coupling modes, a 1-1 link, a 6-6 link, and a 1-6 link
are improbable, as they involve either double displace-
ment or double rearrangement reactions of Rd-type radi-
cals. One other linkage (0-6) must be considered likely,
although it has not yet been detected. Thus, five different
types of linkages were included in the simulation of cou-
pling reactions with Rd-type radicals. These are the fol-
lowing
SARKANEN’S SIMREL
Code Code Synonym
1-5 1-5 biphenyl
(3-1 1-8 1,2-bis-guaiacyl propane
1-0-4 1-10 biphenyl ether
6-5 6-5 biphenyl
(3-6 6-8 1,2-guaiacyl propane
2.3. Distribution of Basic Coupling Reactions. The
structure of lignin as a statistical polymer built through
random coupling reactions of four different mesomeric
forms of one radical species depends obviously on the rela-
tive frequency with which each mesomer occurs. This fre-
quency in turn is a result of (a) how often a specific meso-
mer is formed and (b) how long it will survive under the
conditions of lignification in vivo. Freudenberg described
the average lifetime of a radical with 45 sec.28 The actual
(27) S. Larsson and G. E. Miksche, Acta Chem. Scand., 23, 3337 (1969).
(28) K. Freudenberg, in ref 4, p 86.
20 Glasser, Glasser
Table II
Theoretically Possible Coupling Reactions
of Rd-Type Radicals
R velopment of the polymer. This concept is based on the
structure of lignin suggests that the ß position of a C9 unit
is a favored position for radical formation since almost· all
Ca atoms are involved in inter-unit bonds. The assign-
ment of numerical values to express the relative abun-
dance of each mesomeric species would be a prerequisite
for a kinetically correct simulation model. However, some
doubts would remain even if such values could be devel-
oped because of differences in the coupling rate of conifer-
yl alcohol dehydrogenated in the Zulauf vs. the Zutropf
procedure, as pointed out in detail by Sarkanen.29 There-
fore, the simulation of lignin formation has to be based
upon some other mechanism in order to determine the
relative rate and consequently distribution of basic cou-
pling reactions.
In the SIMREL model this problem was solved by pre-
scribing “distributions of coupling reactions” and allowing
“reaction margins.” The “distribution of coupling reac-
tions” consisted thereby of a weighted mixture of all pos-
sible inter-unit bonds, and “reaction margins” were per-
centages of the total number of units by which fixed dis-
tributions were allowed to deviate if the propagation of
simulated lignin formation depended on it. This method
(29) K. V. Sarkanen, in ref 3, pp 146, 150.
Macromolecules
which emphasizes the result of lignin formation rather
than the kinetic forces involved, seemed to guarantee best
an even distribution of coupling types throughout the de-
idea that lignin—particularly that from softwood spe-
cies—shows only limited variation in its structure.
The distribution of basic coupling reactions was deter-
mined in accordance with data obtained from the litera-
ture, and compiled in Table III. Thus, 20% of all coupling
reactions was based on Rd-type radicals with three-fourths
of them occurring with benzyl alcohol or -carbonyl units
(CQ—R, R = OH, R = 0), and one-fourth with units having
other than benzyl or carbonyl constituents. The majority
of coupling reactions in position one occurs with Rb-type
radicals, so that about 10% of all linkages in the lignin
model will be of the d-1 type. Biphenyl ether linkages
were increased over most previously reported data to 10%
on the basis of recent results by Pew, Connors, and Kun-
ishi30 and Larsson and Miksche.31 Most other data were
kept in close agreement with data obtained from the liter-
ature.
The simulation of lignin formation was carried out by
adding monomeric coniferyl alcohol to some reactive site
in the polymer. For this purpose, the polymer was
searched by the program for a REAC 4 position of the unit
with the lowest possible unit number. If a unit was found
with one REAC 4 position—for example, in molecule posi-
tion 5—the addition of the monomer to this position was
attempted with any coupling reaction involving position 5.
This could be either a 5-5, a 5-8, or a 5-10 reaction. The
random choice between these different possibilities was
restricted by imposing an analytical templet on the model
in form of the “distribution-of-coupling-reactions” value.
Thus, for example, a 5-5 reaction was allowed if the total
number of 5-5 links which would be present after the
reaction was less than a preset limit. If this limit were ex-
ceeded the reaction was not permitted, and another reac-
tion with position 5, namely, 5-8 or 5-10, would be tested.
If none of these reactions was feasible, the REAC 4 of the
unit in the polymer was converted to a REAC 3 and the
simulation was continued with the renewed search for a
REAC 4 position. In the event a unit with two or three
REAC 4 positions was found, one of the reactive sites was
chosen randomly over the others. By this method mole-
cule positions 5, 8, and 10 were equivalent and had the
same chance of reacting. In essence, the simulation of the
lignin formation was based on the result of the unknown
selection mechanism prevailing in nature, rather than its
driving kinetic force. The result was decided to be the an-
alytical distribution of linkages listed in Table , plus
whatever margin was required to permit the simulation of
a lignin molecule with 75 or more units corresponding to a
molecular weight of about 14,000.
Side-chain displacement reactions which were defined
to be all reactions resulting from Rd-type radicals, inde-
pendently of whether the sidechain is actually displaced
or not, were simulated immediately following the attach-
ment of monomeric Cg units. Such a reaction was initiat-
ed, if, at a certain point of polymerization, it was found
that less than 20% of all reactions could be classified as
side-chain displacement reactions. Any of the five possible
reactions was chosen randomly as long as the analytical
requirements of Table III were satisfied. A reaction of
molecule position 1 required the presence of a hydroxyl or
carbonyl group in a position (ID 7 or 8 in position 7). If
such a reaction was required by the analytical templet,
but was not possible because the desired substituent was
(30) J. C. Pew, W. J. Connors, and A. Kunishi, Chim. Biochim. Lignine
Cellul. Hemiceíluí. Actes Symp. Int., 229 (1964).
(31) S. Larsson and G. E, Miksche, Acta Chem. Scand., 21,1970 (1967).
Vol. 7, No. 1, January-February 1974
CH.OH
Figure 5.0-5 coupling.
not available in the a position, the reaction was deferred
until such a substitution at molecule position 7 appeared.
In addition to directly limiting the types of reactions
that could occur in the formation of lignin, some other re-
strictions were imposed that indirectly limited certain
types of coupling reactions. These were reactions that in-
volved the formation of such end groups as coniferyl alco-
hols, aldehydes, and phenolic hydroxyls.
Considering that all coupling reactions involving mono-
meric Ra radicals, as well as most couplings of Rb with Rc,
would automatically lead to the irreversible formation of a
coniferyl alcohol or aldehyde end group, it is surprising
that softwood lignins contain only 9% of such groups.32 In
the SIMREL model all reactions producing such end
groups by depriving a unit of its reactive phenolic hydrox-
yl groups were restricted to less than 9%. On the other
hand, the survival of about 25% of phenolic hydroxyl
groups is guaranteed through assigning “latent reactivi-
ties” (REAC 3) to phenolic positions.
Obviously, nature possesses an extremely sensitive
mechanism leading to a (random) polyphenol that exhib-
its little structural variations. As already recognized by
Sarkanen,29 exclusive ß- -4 coupling will form chain
polymers without phenolic and coniferyl endgroups (ex-
cept for one at each end), and exclusive ß-ß and ß-5 reac-
tions will form polymers with plenty of such end groups.
And yet lignins seem to exhibit little variation in their
overall distribution of types of linkages and end groups.
The simulation of formation of lignin described so far
has been based on reactions of monomeric radicals of
coniferyl alcohol, exclusively. This simplification is un-
realistic in view of experiments by Freudenberg and his
group that have also been discussed by Sarkanen.29 These
experiments showed that the in vitro formation of oligom-
ers only follows the conversion of 80% of coniferyl alcohol
monomers to dimers, suggesting that polymers are formed
only after dimerization is virtually complete and mono-
mers are depleted. The prevalence of 80% dimers at some
stage of dehydrogenation makes the participation of mo-
nomers in the polymerization questionable. However, the
addition of oligomers instead of monomers to the growing
(32) Y. Z. Lai and K. V. Sarkanen, in ref 3, pp 195, 227.
Simulation of Reactions with Lignin by Computer 21
R any benzyl substitution
=
Figure 6.0-0 coupling.
polymer will require refinement of the present simulation
model.
2.4. Simulation Mechanics. After the decision has been
made how to attach a Cg unit to the polymer, some mo-
lecular changes are carried out on both reaction partners.
These changes concern “identifications” as well as “reac-
tivities” of certain molecule positions in the units. These
consequences of coupling reactions are discussed in the
following and are listed in Table IV for the example of a
ß-5 coupling reaction.
5-5 Coupling. Biphenyl structures, resulting from the
coupling of two Rc radicals, are subject to the smallest
number of constraints, as they do not contribute to the ir-
reversible formation of coniferyl end groups or to the de-
pletion of phenolic hydroxyls. The formation of 5-5 and
4-0-5 linkages is reported to occur predominantly with
higher oligomers rather than with monomers.33 However,
no such restriction was added in the SIMREL program.
ß-5 Coupling. The coupling of Rb- with Rc-type radicals
results in most instances (~75%) with internal ring clo-
sure through addition of the phenolic hydroxyl group to
the quinone methide intermediate (I, Figure 5). However,
in some cases the quinone methide stabilizes through ad-
dition of other hydroxyl-containing compounds, as indi-
cated in the case of II (Figure 5). The relative proportion
of one or the other stabilization pathway was derived from
data available in the literature and reviewed by Sarka-
nen.32 In the instance of open ß-5 derivatives, Sarkanen’s
Rydholm diagram was referred to in ref 32.
ß-ß Coupling. Pinoresinol (III) is the major result of
coupling of two Rb radicals as shown in Figure 6. Addi-
tional minor dimerization products are IV and V (Figure
6) which result from Rb-type coupling of ferulic acid in
(33) K. Freudenberg and K. C. Renner, Chem. Ber., 98,1879 (1965).
22 Glasser, Glasser
CH.OH CH—CHOH
CHOH CH—CHOH
OH
Figure 7. 0-0-4 coupling.
the case of IV, and Ca—Ce condensation in the case of V.
The remaining quinone methide intermediate of V stabili-
zes again through addition of a hydroxyl containing com-
pound like water, sugar (or carbohydrate), or phenol. The
relative distribution of the three optional derivatives was
again derived from Sarkanen’s Rydholm diagram.32
5-0-4 Coupling. The long neglected coupling of Ra and
Rb radicals leading to biphenyl ether structures is subject
to end-group constraints, as it will establish coniferyl
endgroups if the Ra-type radical couples with a REAC 4
in position 8. Recent experiments by Pew and coworkers
have shown that 5-0-4-type coupling patterns are almost
as frequent as 5-5 couplings.30 The same is indicated by
oxidation studies of Larsson and Miksche.31
0-0-4 Coupling. The coupling of Ra and Rb radicals
leads to 0-aryl ether derivatives which have been recog-
nized as the most representative dimeric structures in lig-
nin. The quinone methide intermediate which is formed
initially becomes stabilized through the addition of some
hydroxyl containing moiety as water, sugar, or phenol, as
is indicated in Figure 7. A number of additional con-
straints are imposed on 0-0-4 coupling reactions as these
reactions may establish end groups and consume phenolic
hydroxyl groups. As a consequence, coupling of Ra-type
radicals must be favored only after some side-chain sub-
stitution has previously occurred. Therefore, most 0-
ethers will result from the addition of Rb-type monomeric
radicals to Ra-type oligo- or polymeric radicals; otherwise,
a much greater number of coniferyl end groups will be
formed.
Coupling Reactions Based on Rd-Type Radicals.
Reactions resulting from Rd-type radicals involve approxi-
mately 20% of all units32 with three-fourths of them caus-
ing the displacement of side chains, and the rest of the
Macromolecules
coupling reactions taking place in position 6 of the aro-
matic ring. Displacement reactions initially require the
presence of benzyl alcohol or carbonyl groups, leaving the
a position after the displacement reaction as aldehyde
group or unconjugated carbonyl group detached from the
aromatic ring. However, the displaced side chain will not
be lost, but remains attached to whatever coupling coun-
terpart in the 0 position that had led to the secondary for-
mation of a benzyl alcohol or carbonyl function. General-
ly, coupling reactions in position 1 will take place with
positions 5, 8, and 10 (corresponding to Rc-, Rb-, and Ra-
type radicals), whereas position 6 will probably become
attached to position 5 or 8.
0- 1 Coupling. The most abundant and longest known
result of coupling with Rd-type radicals is the 1,2-diaryl-
propane derivative which is reported to be present in lig-
nin to the extent of about O.lO-O.lS/Cg unit.32 Upon cou-
pling, the quinone methide intermediate will stabilize
much in the same fashion as the 0-0-4 dimer by addition
of some hydroxyl-containing compound.
1- 5 and 1-0-4 Couplings. Coupling reactions of posi-
tion 1 with Ra- and Rc-type radicals to form 1-0-4 and 1-5
inter-unit bonds seem much less pronounced than 0-1-
type linkages. Only about one unit each in a polymer of 50
units participates in these types of reactions (cf. ref 27).
0-6 and 6-5 Reactions. The only recently discovered
coupling reactions of Rd-type radicals with units lagging
ketonic or hydroxylic benzyl carbon atoms lead to conden-
sations at the Ce atoms of the aromatic rings. In the SIM-
REL model, only 2-3% of each are assumed to occur. As
in all other coupling mechanisms of the 0 position, the 0-6
linkage may be responsible for the formation of a benzyl
alcohol and, following oxidation, an a-carbonyl group or a
lignin-carbohydrate bond or a noncyclic benzyl-aryl ether
linkage.
Carbonyl groups have received much attention in lig-
nin chemistry.34"37 They can be formed through either
disproportionation reactions occurring in cell structures38
or through autoxidation.39 Three types of carbonyl groups
are presently assumed to exist in lignins (cf. ref 3). These
are coniferyl aldehyde end groups, conjugated (a), and iso-
lated carbonyl groups. The presence of other aldehyde
groups, such as in glyceraldehyde 0-aryl ether structures40
is questionable. Also, the possibility of cinnamic acid end
groups cannot be ruled out.36-41 However, such groups
must be considered rarities and can probably be neglected
in structural schemes such as the one presented here.
Coniferyl aldehyde groups are simulated through simple
conversion of identification 3 into ID 10 in position 9 of
coniferyl end groups. A similar process generates conju-
gated carbonyl groups from benzyl alcohol groups in units
with ID 5 in position 7. Isolated carbonyl groups are as-
sumed to be the result of displaced side chains in the form
of aldehyde end groups.32 These groups are now given re-
sponsibility for the observation that borohydride-reduced
milled wood lignin is more difficult to sulfonate than gen-
uine lignin.42 Presumably, the presence of the aldehyde
group is necessary to activate the primary hydroxyl group
of the C7 atom of the displaced side chain to form a car-
(34) E. Adler and J. Marton, Acta Chem. Scand., 13, 75, 357 (1961).
(35) E. Adler, J. Marton, and K. I. Person, Acta Chem. Scand., 15, 384
(1961).
(36) J. Marton and E. Adler, Tappi, 46,92 (1963).
(37) E. Adler, Pap. Puu, 43,634 (1961).
(38) K. Freudenberg and N. Schluter, Chem. Ber., 88, 617 (1955).
(39) K. Freudenberg and B. Lehmann, Chem. Ber., 93,1354 (1960).
(40) K. Lundquist, G. E. Miksche, L. Ericsson, and L. Berndtson, Tetra-
hedron Lett., 46, 4587 (1967).
(41) T. M. VasiVeva, R. K. Boyarskaya, and G. P. Grigor’ev, Zh. Prikl.
Khim. (Leningrad), 41, 603 (1968); cited in Abstr. Bull. Inst. Pap.
Chem., 40,4693(1970).
(42) D. W. Glennie, in ref 3, p 627.
Vol. 7, No. 1, January-February 1974 Simulation of Reactions with Lignin by Computer 23

Table III
Distribution of Basic Coupling Reactions
Guidelines
Sarkanen Freudenberg Harkin Adler (Ref in SIMREL
(Ref 3) (Ref 4) (Ref 5) 34, 35 45-47) Program
/3-0-4 0.45“ 0.44“ <0.50“ 0.25' 0.45»
ß-ß 0.17“ 0.22/ 0.14-0.16'· 0.11* 0.06»
ß- 0.14“ 0.09» 0.20* 0.09' 0.11"
5-5 0.256 0.256 0.254 0.12»
4-0-5 0.05 V 0.06“ 0.061· 0.10»
Side-chain “displace-
ments”
Total 0.204 0.20"
1-5 0.025»
/3-1 0.15“ 0.10"
1-0-4 Combined with 0.025"
4-0-5
6-5 0.025"
/3-6 0.025»
Phenolic OH 0.32 0.32 0.26" 0.26
Coniferyl end groups 0.09 0.09
Lignin-carbohydrate Combined with
bonds ß-ß 0.06
Benzyl aryl ethers
noncyclic 0.08“ 0.08“ 0.12» 0.08 0.06»
Carbonyls
Total 0.20 0.20 0.20 0.22
Conjugated carbonyl 0.07 0.07 0.07
Isolated carbonyl 0.13 0.10-0.13 0.15
“
Number of units involved with side chains. b Number of units involved with aromatic rings. Described as possibly “

“grossly inaccurate.” d Number of units associated with side-chain displacement reactions. Number of phenolic oxygen in
respective aryl ethers. 1 Number of oxygen in dialkyl ethers, plus number of oxygen in lactones. » Number of phenolic oxygen
in cyclic aryl ethers. h Number of units that participate in pinoresinols and lactones. Number of units in phenylcoumarans.
*

' Number of
arylglycerol units connected to adjacent unit by a /3-aryl ether link.45 k Number of cyclic benzyl alkyl ethers in
pinoresinols.46 ' Number of cyclic benzyl aryl ethers in phenylcoumarans.46 Number of phenolic hydroxyl groups in p-
”

hydroxyarylpropane structures.46 In percentage of the total number of linkages.

”

bonium ion under the acidic conditions of the sulfonation Table IV

reaction. Change in Identification of Two Coniferyl Alcohol
Benzylic Substituents. Derivatives of quinone meth- Units through Dimerization, as Demonstrated
ides are formed following coupling reactions of Rp-type for the Case of Dehydrodiconiferyl Alcohol
radicals. These highly unstable quinoid substances tend to Mole- Before Coupling After Coupling
reestablish phenolic character through the addition of hy- cule Unit A Unit B Unit A Unit B
droxyl-containing compounds like water, carbohydrates, Posi-
and phenols, which are present at lignification sites. The tion ID REAC ID REAC ID REAC ID REAC
rate of addition of hydroxyl moieties was related to the
9 3 0 3 0 3 0 3 0
pK value of hydroxyl groups in question by Freuden- 8 9 4 9 4 2 0 9 0
berg.43 However, the mathematical formulation of this 7 9 0 9 0 2 0 9 0
process in the SIMREL, model appears at least premature. 1 1 0 1 0 1 0 1 0
Therefore, the principle of using analytical results rather 2 9 0 9 0 9 0 9 0
than kinetic forces to determine the relative rate of hy- 3 13 0 13 0 13 0 13 0
4 1 0 1 0 1 0 1 0
droxyl addition was adhered to. In the simulation, the 5 9 4 9 4 9 4 1 0
number of coupling reactions in the ß position had to be 6 9 0 9 0 9 0 9 0
balanced by the number of hydroxyl, carbonyl, (isolated) 10 4 4 4 4 4 4 6 0
aldehyde, sugar, and noncyclic aryl ether substituents in
the a position, as is shown in Table V. substituents. In Table VI all reactions are compiled that
The listing of some “miscellaneous” C—C bonds in the affect directly or indirectly the phenol concentration in
a position in most proposed Rydholm diagrams is inter-
lignin. According to the data used, 0.26 hydroxyl group/
preted as a consequence of secondary condensation reac- C9 should be located on the aromatic ring. In the present
tions of benzyl alcohol groups.44 Also, conjugated and iso- simulation model, however, in which only monomers are
lated carbonyl groups must be considered as conversion added to the polymer, noncyclic aryl ethers in the a posi-
products of benzyl alcohols. Therefore, the ratio of adding tion were excluded since they would automatically lead to
water us. carbohydrates us. phenols to quinone methides the formation of coniferyl end groups. Instead, hydroxyl
is taken to be 52:6:6, as is shown in Table V.
groups are listed.
Phenolic Hydroxyl Groups. In general, the content of
phenolic hydroxyl groups in lignin is determined as ap- 3. Analytical Evaluation
proximately O.3/C9 unit (cf. Table III). However, this Among the great advantages of computer techniques in
functional group is as much a consequence of other reac- are the simple and rapid ways of compiling and
general
tions in lignin as are the previously discussed benzylic
displaying information. In the simulation of the formation
(43) K. Freudenberg, in ref 4, p 94.
(44) K. Freudenberg and M. Swaleh, Chem. Ber., 102, 1316 (1969). (46) E. Adler, H. D. Becker, T. Ishihara, and A. Stamvik, Hoizforschung,
(45) E. Adler, K. Lundquist, and G. E. Miksche, Aduan. Chem. Sci., 59, 20,3(1966).
28(1966). (47) E. Adler and J. Marton, Acta Chem. Scand., 15,370 (1961).
24 Glasser, Glasser Macromolecules

Table V
Balance of Coupling Reactions That Cause
Addition of Extramolecular Hydroxy-Containing
Moieties to Quinone Methide Intermediates
Quinone Methide
Coupling Reactions Derived Substituents
in the #3 Position in the <* Position
Water
3-0-4 0.45 —OH 0.22
3-1, open 0.10 =0 0.07
3-5 0.04 —CHO 0.15
3-6 0.03 —Miscellaneous 0.08
3-3 with C7-Ce 0.02
condensation
Sub total 0.52
Total 0.64 Carbohydrates 0.06
Phenols 0.06
Grand total 0.64

Table VI
Balance of Substituents in the Para
Position of Phenylpropanes
Reaction Margin 3-0-4 0.45
<*-0-4, noncyclic 0.06
Figure 8. Correlation between reaction margins and degree of 0.10
<*-0-4, cyclic
completion in a polymerization. 5-0-4 0.12
of large statistical polymeric molecules, the information 1-0-4 0.01
Hydroxyl groups 0.26
should allow us to define a molecule structure as well as Total 1.00
to provide numbers that illustrate and correlate important
structural data. percentage of each type of coupling reaction which has oc-
3.1. List of Sequence of Coupling Reactions. The first curred in the polymer formed up to the last unit incorpo-
analytical data provided in the output of the SIMREL rated in the polymer. Such values are computed and list-
program concerns the sequential presentation of the units ed for the reactions 5-5, 5-8 and 8-5, 5-10 and 10-5, 8-10
coupled and their types of coupling reactions. The print- and 10-8, the phenolic hydroxyls, and the individual side-
out reads, for example: “Unit 12 Molecule 5 reacts with chain “displacement” reactions 1-5, 1-8, 1-10, 6-5, 6-8
Unit 18 Molecule 8”. The same table also contains the (these in per cent of the total number of reactions result-

(sc id
HOCH,—CH— CH=0
OCH, CH,OH

CHO

CH

CH

CH=0
Figure 9. Fragment of polymer of coniferyl alcohol with 8% reaction margin.
Vol. 7, No. 1, January-February 1974 Simulation of Reactions with Lignin by Computer 25

Table VII
Reaction Margins and Permitted Number of X rH &copy; &copy;

Reaction Types of the Simulation Model ¿ &copy; &copy; &copy;

Reaction Margins
&copy; CO
Name Std 2 3 4 5 6 7 8 9 10 tO CO

&copy;
&copy;

0-O-4 45 65 65 65 65 65 65 65 65 65
0-0 6 8 9 10 11 12 13 14 15 16
0-5 11 13 14 15 16 17 18 19 20 21 &copy;
CO &copy;

to
CO
rH rH CO
5-5 12 14 15 16 17 18 19 20 21 22 i. ~
4-0-5 10 12 13 14 15 16 17 18 19 20
Phenolic
OH 25 25 25 25 25 25 25 25 25 25 X § &copy;
CO
CO

rH &copy; &copy;

Table VIII
Permitted vs. Completed Number of Reaction
Types in Three Completed Polymer Simulations &copy; &copy;

&copy; &copy;

Margins
9 10 C9 &copy;

rH
CO
2
43 CN
O ·

Reaction P“ H ® &copy; &copy; &copy;

0-O-4 65 42 65 42 65 38 ? y

14 15 16 11 "o LO &copy;iC LO rH 4*
ß-ß 9 9 <N _ti 0 CN
&copy;

&copy; &copy; &copy; LO N rH <N N N CO N

19 17 20 16 21 14 0 o
0-5 y rH

| I
&copy; &copy; &copy; &copy;

5-5 20 14 21 18 22 19
4-0-5 18 17 19 14 20 17 ‘5
y
Phenolic 25 24 25 28 25 26 u c9 Í ^ CO H O
H
&copy;

CO NCOCl^
&copy; N
y 10
&copy; &copy; &copy; &copy;

Degree of cc
ft 8 10-8 0.65 &copy; &copy; &copy; &copy; &copy; &copy; &copy; &copy; &copy; &copy;

polymerization 1.19 1.19 1.20

h
P 3
“ =
permitted. C 6 =
completed. t> ^ rH X lO to rf
«
3
x
i
2
*1
&copy;

tO
CO LO
CO N
&copy;

N H rH
CO
H CS rH
&copy;

N O
&copy;

h 00 ^

ing from Rd-type radicals), and the total number of side-

&copy; &copy; &copy; &copy; &copy; &copy; &copy; &copy; &copy; &copy;
4»
X
chain “displacement” reactions of the number of units tN
0
calculated. For example, after completing the incorpora- &copy; X co to c·*
CO N N rH
&copy; rf CO
i-H rH CN CN rH
N &copy; X
rH M
LO rh >
rH
X
M -g
&copy; i—1

tion of unit 37 into the polymer, the statistical distribu- ti ·

¡ &copy;

LO rH &copy; &copy; &copy; &copy; &copy; &copy; &copy; &copy; &copy; &copy; &copy;

tion of types of reactions will read

53
ed
5-5 0.14 hS CO to S &copy; &copy;
tO t>
N N H
&copy; &copy;

<N
tO N X
N N <N rH
&copy;

h 23 Sh
5-8, 8-5 0.07
s &copy; &copy; &copy; &copy; &copy; &copy; &copy; &copy; &copy; &copy; &copy; &copy; &copy; &copy;

5-10, 10-5 0.06 4»

s
8-10, 10-8 0.41 ft
^ to N X to rH
phenolic OH 0.27 E &copy; &copy; &copy;
&copy;

N rH rH N N N rH
&copy;

3
o
&copy; &copy; &copy; &copy; &copy; &copy; &copy; &copy; &copy; &copy; &copy; &copy; &copy; &copy;

Side-chain displacement
0
1-5 0.12 V XtOCOtOOOrHXtOtOOOOOOOOOCOtOtO
occurred.

1-8 0.48 ti sH
1-10 0.14 5 CJ

6-5 0.13 cr ft 0000000000000000

6-8 0.13 X
total 0.18 ti OH CN 05 t>
reactions

.2 NtO'ia®nMtO)HHIiHHHS
The five side-chain displacement reactions always total V
1.00, where the “total” expresses the number of units in- id hhhhhhhhhhhhhhhh

volved in this type of reactions per total number of units. ft \ZZZZZZZZZZZZZZZZ

qqqqqqqqqqqqqqqq
3.2. Table of Substituents in Each Molecule Position. 1 HHHHHHHHHHHHHHHH
^{^^4 ^ ^ ^ ^
Information concerning the substituents of each molecule - - & - -
displacement

y HHHHHHHHHHHHHHHH
position of each unit is listed in a second table, similar to <9
y ££££££££££££££££
Table IV. All substituents are listed with one of 13 code ft
numbers (identifications, Table I). For the hand drawing QQQQQQQQQQQQQQQQ
QHWHWHHHHWHWHHWW
of a structural scheme, both the reaction sequence and y
u
HHbbbbbbhHbHHbbb side-chain

the molecule substitutions have to be known. Further ta- C

y all

bles facilitate the analytical assessment of a polymeric 3

*
«KPiaípíKwqstóasacKKKosK
of

y
lignin structure. X
3.3. Miscellaneous Analytical Tables. A compilation o o o
XHLOtOHrHlOtOHXHHHrtLOrH
o o o o cent

I
of the total number of different types of coupling reactions
that have occurred in the polymer permits evaluation of QQQQQQQQQQQQQQQQ per

OOOOOOOOOOOOOOOO
the overall distribution of interunit bonds. The total num-
in

ber of reactions taken place in thé polymerization will OHHNOIU)

generally exceed the total number of units involved. The -- - --

ratio of both numbers is a measure of the “degree of con-
zzzzzzzzzzzzzzzz
densation,” which is computed in the simulation program OOOOOOOOOOOOOOOO
Expressed

and listed.
26 Glasser, Glasser Macromolecules

Table XI
o o on ooono o Distribution of Type of Reactions
Type of Reactions That
Occurred in 77 C9 Units
to <£ tO tC to 6 6 4 6 to to to Tp to
MOLECULE 1 WITH MOLECULE 5 = 1 TIMES
MOLECULE 1 WITH MOLECULE 8=9 TIMES
MOLECULE 1 WITH MOLECULE 10 = 2 TIMES
OOOOO O OOOO o o o o o MOLECULE 5 WITH MOLECULE 5 = 11 TIMES
MOLECULE 5 WITH MOLECULE 8 = 13 TIMES
MOLECULE 5 WITH MOLECULE 10 =
1 TIMES
MOLECULE 6 WITH MOLECULE 5 = 1 TIMES
O t> O CO CO CO 3 7 3 7 CO CO CO CO CO
MOLECULE 6 WITH MOLECULE 8 = 3 TIMES
MOLECULE 8 WITH MOLECULE 8 = 7 TIMES
MOLECULE 8 WITH MOLECULE 10 = 1 TIMES
MOLECULE 10 WITH MOLECULE 5 = 12 TIMES
8
OOOOO o OOOO o o o o o MOLECULE 10 WITH MOLECULE 8 = 31 TIMES

1.19 DEGREE OF CONDENSATION

Figure

MNOINNIN N N N N tN N CS N A last table presents the lignin structure in form of a

of
modified RYDHOLM diagram. Each molecule position in
the side chain and the aromatic ring is listed with its ac-
OOOOOO OOOOO OOOO tual and theoretical substituents and the synonyms of
Scheme
compounds they represent (e.g., /3-aryl ether, coumaran,
biphenyl ether, etc.)
NNSNNO NN«3NO 10 00 O The following example will best demonstrate the me-
chanics of forming and analyzing a SIMREL model poly-
mer.

OOOOO OOOOO OOOO O 4. Example Model Polymer

Structural

of

Z In an example polymerization of coniferyl alcohol mono-

o
mers, the distribution of coupling reactions chosen was
G) ^ Gi Gi Gi Gi O) Gi
CO
G> G> G> G> G> G> G>
identical with the one listed in Table III. Additional reac-
O tion margins ranged from 2 to 10% (based on the sum of
fc
units calculated) in increments of 1% and were homoge-
Printout

hi
O OOOOO OOOOO OOOO o neous for all types of reactions except for /3-0-4 which was
set constant at 0.65. The total number of reactions per-
mitted for each type of coupling and for each polymeriza-
Computer
rH rHrHr-frlGi H rH tion attempted is listed in Table VI. If the margins are set
of
too narrow, the polymerization will be incomplete and be
terminated at a point where all reactive sites (positions
OOOOO OOOOO OOOO o
with REAC 4) are exhausted. The SIMREL program will
attempt to form a polymer of 75 or more units, with 75
units containing only REAC 0 and REAC 3 sites, and the
rest of the units carrying REAC 4 positions. The results
are presented in part in Figures 8 and 9, and in Tables
Identifications

Vni-XII. Results summarized in Figure 8 indicate that

increasing reaction margins facilitate the propagation of
OOOOO OOOOO OOOO o
and

polymerization reactions and that at least a reaction mar-

gin of 8% is required to complete a polymer of 75 units.
However, wide reaction margins seem only to guarantee
CO CO CO CO CO CO CO CO CO CO CO CO CO CO CO
the propagation of polymerization reactions, whereas they
Positions
are not used exhaustively, as is shown in Table VIII. If the
number of reactions permitted is compared to that of
OOOOO OOOOO OOOO o completed reactions, the result shows that the comple-
tions fall consistently short of their potential. This proba-
Molecule
bly means that a wider reaction margin is required at an
G) O G> CS G> G> G> OS G> G) G> OS G> G> OS
earlier stage of polymerization where only a small number
of units is linked together than at later stages.
A fragment of the structural scheme of the polymer re-
OOOOO OOOOOOOOOO O sulting from the simulation with an 8% reaction margin is
shown in Figure 9. The sequence of reactions leading to
this structure is listed in Table IX as printed out by the
computer. The simulation starts with a ß-ß coupling of
unit 1 with unit 2, followed by the formation of a biphenyl
ether linkage between units 1 and 3. Subsequently, unit 2,
position 5 enters in a ß-S coupling with unit 4. The types
of reactions involved in the polymer are calculated on the
ID
oy
73 W
ubK
73
oy
73 K basis of units listed on the left-hand side of column 1 and
[««TiuntiiDt'coaoHHNwifujio
U are listed in Table IX also. These numbers are relayed to
the “steering mechanism” of the SIMREL polymerization
Vol. 7, No. 1, January-February 1974 Simulation of Reactions with Lignin by Computer 27

Table XII
Rydholm Diagram
PERCENTAGE
POSITION ID CONFIG. ACTUAL THEORY NAME
9 C-GAMMA 3 CH20H 0.05 0.06 CONIFERYL ALCOHOL
10 CHO 0.03 0.03 CONIFERYL ALDEHYDE
3 CH20H 0.74 0.72 PRIMARY HYDROXYLS
7 CH20R 0.13 0.13 PINORESINOLS
8 CO 0.04 0.04 LACTONES
11 CH2 0.01 0.02 GAMMA-6 CONDENSATION
8 C-BETA 2 CH 0.42 0.45 BETA ETHERS
2 CH 0.04 0.03 BETA-6-CONDENSATION
2 CH 0.17 0.14 PHENYL COUMARANS
2 CH 0.18 0.19 PINORESINOLS
2 CH 0.12 0.10 BETA-l-CONDENSATION
9 CHD 0.08 0.09 END-GROUPS
7 C-ALPHA 5 CHOH 0.33 0.22 BENZYL ALCOHOLS
2 CH 0.17 0.17 PINORESINOLS
2 CH 0.17 0.10 PHENYLCOUMARANS
12 CHO-SUGAR 0.05 0.06 LIGNIN CARBOHYDRATE BOND
8 CO 0.05 0.07 ALPHA-CARBONYL
10 CHO 0.16 0.15 GLYCERALDEHYDES
9 CHD 0.08 0.09 ENDGROUPS
0 .08 MISCELLANEOUS
0 06 BENZYLARYLETHER
1 AROMATIC RING 1 C 0. 01 0. 03 5-1 CONDENSATION
1 C 0. 12 0. 10 BETA-l-CONDENSATION
1 C 0. 03 0. 02 BIPHENYLETHER CONDENSATION
1 C 0 .84 0 ,85 SIDECHAIN
2 AROMATIC RING 9 CHD 1 .00 1 .00
3 AROMATIC RING 13 C-OCH3 1 .00 1 ,00 METHOXYL GROUPS
4 AROMATIC RING 1 C 1 .00 1 .00
5 AROMATIC RING 9 CHD 0 .35 0 .37 UNCONDENSED UNITS
1 C 0 .29 0 ,25 BIPHENYLS
1 C 0. 17 0. 12 BIPHENYLETHERS
1 C 0. 17 0. 14 COUMARANS
1 C 0. 01 0. 03 5-1 CONDENSATION
1 C 0. 01 0. 03 5- 6 CONDENSATION
0. 06 SYRINGYL UNITS
6 AROMATIC RING 9 CHD 0. 95 0 94 UNCONDENSED UNITS
1 C 0. 01 0. 03 6- 5 CONDENSATION
1 C 0 .04 0 .03 BETA-6 CONDENSATION
10 PHENOLIC HYDROXYL 6 O 0 03 0 .02 BIPHENYLETHER CONDENSATION
6 O 0. 42 0. 45 BETA ARYL ETHERS
0 06 BENZYLARYLETHER
6 O 0 17 0 .12 BIPHENYL ETHERS
6 O 0 .15 0 .10 PHENYLCOU MAR AN
4 OH 0 .24 0 .25 PHENOLIC HYDROXYLS

propagation. The rationale behind the awkward basis of
units listed only on the left-hand side of column 1, Table
IX, is the following. Most units that are initially added to
the polymer represent end groups in that they contain
coniferyl alcohol or aldehyde side chains or phenolic hy-
droxyl groups. These units are first listed on the right-
hand side of column 1, Table IX, because they are added
to existing units in the polymer. Only after a unit reacts
for a second time, it will appear on the left-hand side of
column 1; then, however, it will probably also have lost its
end group and better represent the type of reactions in-
volved in the structure of the polymer. Experimentally, it
was found that this trick greatly facilitates the propaga-
tion of the polymerization reaction especially in the be-
ginning stages of the simulation.
The identifications of molecule positions of units con-
tained in the structural sketch in Figure 9 are compiled in
Table X. Displaced side chains are listed under “SC,”
where the corresponding rings can be found as “RI.” The
distribution of types of reactions as printed out by the
SIMREL program is compiled in Table XI for the com-
plete polymer, and the Rydholm diagram is shown in
Table XII.
5. Conclusion
The simulation of polymerization reactions of coniferyl
alcohol by computer appears to be feasible. Considering
the relatively small number of constraints and the many
possibilities to react, the structure of the polymer can be
considered a close approximation of the theoretical values
found in the literature. However, the results are incom-
plete in that they are based on a number of assumptions
and simplifications that have to be eliminated before an
acceptable simulation model for lignin can be presented.
In particular, there is need to incorporate the reactions of
oligomers; also, other units than only coniferyl alcohol,
such as sinapyl and coumaryl units, have to participate in
a simulated lignification; and thirdly, noncyclic a-aryl
ethers have to be introduced in order to provide a lignin
scheme suited for the simulation of reactions with lignin,
which represents a major goal of this study.